MXPA99003627A - Detergent compositions - Google Patents

Abstract

The present invention relates to detergent compositions or components thereof containing a proteolytic enzyme and one or more cationic surfactants of the formula:R1R2R3R4N+ X-, in which R1 is a hydroxyalkyl group having no greater than 6 carbon atoms;each of R2 and R3 is independently selected from C1-4 alkyl or alkenyl;R4 is a C5-11 alkyl or alkenyl;and X- is a counterion.

Description

DETERGENT COMPOSITION TECHNICAL FIELD The present invention relates to detergent compositions or components thereof containing cationic surfactant and a proteolytic enzyme for use in laundry and dishwashing processes to provide improved cleaning and grease removal benefits.

BACKGROUND OF THE INVENTION It is known how to use cationic surfactants in detergent compositions. For example, GB 2040990A discloses granular detergent compositions comprising cationic surfactants. Other detergent components frequently employed in detergent compositions are proteolytic enzymes, which are known to aid in the disintegration and removal of proteinaceous spots. The Applicant has found that in some cases, particularly of some body soiling, for example in neck spots and cuffs, grease and oil stains may contain proteinaceous soils which are difficult to disintegrate because the grease and oil soiling component protects the proteinaceous component of the stain.

The applicant has found that using a specific class of cationic surfactant in combination with a proteolytic enzyme removes the fat component from the stain by exposing the previously protected proteinaceous stain and making it available for enzymatic action. The combination provides improved cleaning benefits along with Improved removal of residual stains Continuous use of a detergent formulation in accordance with the invention maintains good stain removal benefits by prolonging the new appearance of laundered garments. In addition, the stain removal performance of proteolytic enzymes is generally directly related to their concentration in the detergent composition in such a way that an increase in the amount of proteolytic enzyme increases the performance of the removal of stains. However it has been observed that under stress conditions such as the use of short cycles in the washing machines or low temperatures or in the presence of very stained substrates the optimal performance of the protease enzyme is limited to a certain level The increase in the level of the protease enzyme beyond this amount does not produce benefits of improved stain removal performance. Applicant has found that these problems can be lessened by means of a detergent composition comprising a combination of a specific quaternine ammonium cationic surfactant and a proteolytic enzyme. The invention has been found to be particularly beneficial in detergent compositions further comprising agents Ammonium surfactants. Without intending to be limited by theory, the applicant considers that the particular cationic surfactants used in the detergent compositions of the present invention have a surprisingly good solubility and form an association in the presence of anionic components to produce surprisingly soluble anionic / cationic complexes which give As a result, unexpected performance benefits. Furthermore, it is considered that after the disintegration of the grease filth by the enzyme, the cationic tepsioactives used in the present invention can also complex with the fatty acids and any other negatively charged product produced by the disintegration, increasing their solubility and improving the general cleansing action and the elimination of grease and oil dirt. All documents cited in the present description are incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition or components thereof comprising: a) a proteolytic enzyme; and b) a cationic surfactant of formula I: R1R2R3R * N + X " Wherein R1 is a hydroxyalkyl group having not more than 6 carbon atoms, each of R2 and R3 is independently selected from alkyl or alkeniion of C? T, R4 is an alkyl or alkenyl of C5.H, and X "It's a counterion.

As used herein, unless otherwise indicated, alkyl or alkeniium may be branched, linear or substituted. The substituents may be, for example, aromatic groups, heterocyclic groups containing one or more N, S, O atoms, or halogen substituents.

DETAILED DESCRIPTION OF THE INVENTION A canteic surfactant In general, the cationic surfactant is present in the composition or component thereof in an amount of not more than 60% by weight, preferably not more than 10% by weight, preferably in an amount not greater than 4.5% or even 3% by weight. The benefits of the invention are obtained even with very small amounts of the cathiopic surfactant of formula I. Generally, there will be at least 0.01% by weight, preferably at least 0.05%, or at least 0.1% by weight of the surfactant cationic in the detergent compositions of the invention. Preferably, R1 in formula I is a hydroxyalkyl group which it has no more than 6 carbon atoms and preferably the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Preferred R1 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and - CH (CH 3) CH 2 OH Preferred are -CH 2 CH 2 OH and -CH 2 CH 2 CH 2 OH and particularly preferably -CH 2 CH 2 OH. Preferably, R 2 and R 3 are each selected from ethyl and methyl groups and preferably both R 2 and R 3 are methyl groups. Preferred R 4 groups have at least 6 or even at least 7 carbon atoms R 4 can have no more than 9 carbon atoms, or even no more than 8 or 7 carbon atoms Preferred R 4 groups are linear alkyl groups Preferred linear R 4 groups having from 8 to 11 atmos of carbon, or from 8 to 10 carbon atoms. Preferably each of R 2 and R 3 is selected from Cu alkyl and R 4 is C 1 - n alkyl or alkenium. Although pure or substantially pure cationic compounds are within ambit or of this invention, it has been found that the mixtures of the cationic surfactants of formula I can be particularly effective The mixtures of cationic surfactants of the present invention can comprise mixtures mixtures of compounds of formula I preferably wherein there is at least 10% , or even at least 20%, or at least 50% by weight of cationic surfactant of formula I and wherein R4 is C5-9 alkyl or alkenyl Other useful examples of mixtures of surfactants include those in which R4 it can be a combination of linear C8 and C10 alkyl groups, or C9 and Cu alkyl groups. In accordance with one aspect of the invention, a mixture of surfactants is present in the composition. cationics of formula I, the mixture comprising an alkyl surface active agent of shorter chain formula I and an alkyl surface active agent of formula I of longer chain. Preferably, in the mixture of shorter and longer chain alkyl surfactants, there will be from 5 to 95% by weight of shorter chain alkyl surfactant or at least 30% by weight of shorter chain alkyl surfactant, and preferably from 40 to 95% of the shorter alkyl chain cationic surfactant. In general, the amount of the longest chain cationic tepsioactive will be from 5 to 95% by weight, preferably from 5 to 70% by weight, preferably from 35 to 75% by weight of the cationic surfactant, preferably at least 50% by weight. % by weight of longer alkyl chain surfactant. The longer chain alkyl cationic surfactant is selected from the surfactants of formula I wherein R 4 is an alkyl group having n carbon atoms, wherein n is from 8 to 11; the shorter chain alkyl tepsioactive is preferably selected from those of formula I wherein R 4 is an alkyl group having (n-2) carbon atoms. X in formula I can be any counterion that provides electrical neutrality, but is preferably selected from the group consisting of halide, methylsulfate, sulfate and nitrate; preferably it is selected from methyl sulfate, chloride, bromide and iodide. Halide ions, especially chloride, are most preferred.

Proteolytic enzyme The granular detergent compositions or the components thereof according to the present invention also contain a proteolytic enzyme. The weight ratio between the proteolytic enzyme and the cationic surfactant is generally from 15,000 to 10 1, preferably from 1 to 15. 10000 to 5 1, preferably from 1 5000 to 1 1 based on the percentage by weight of active enzyme of the detergent composition In the detergent compositions of the present invention, the proteolytic enzyme component is generally present at levels of 0 00005% to 2% active enzyme by weight of the detergent composition, preferably 0,0001% to 0 2% by weight, preferably from 0,000% to 0 05% by weight of active enzyme in the detergent composition Examples of suitable protease enzymes for use in the detergent compositions of the present invention, are the subtilisins, which are obtained from particular strains dß ñ subtilis and 8 licheniformis (subtilisin BPN and BPN ') A suitable protease is obtained from a strain of Baciilus, which has maximum activity on the whole pH scale of 8 to 12, developed and sold as ESPERASER from Novo Industries AS of Denmark, hereinafter "Novo" The preparation of this enzyme and enzymes Analogs are deciphered in GB 1, 243,784 from Novo Other suitable proteases include ALCLASER, DURAZYMR and SAVINASER from Novo and AXATASER, AXACALR, PROPERASER and AXAPEM (protein designed by genetic engineering) of Gist-Brocades. Proteolytic enzymes also encompass modified bacterial sepna proteases such as those described in European Patent Application Serial No. 87 303761 8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and "Protease B" is dominated here and in European patent application 199,404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, here referred to as "protease A". More preferred is what is referred to herein as "protease C", which is a vanant of a Bacillus alkaline serine protease, in which lysine replaces the arginine in position 27, the tyrosome replaces valine in position 104 , serine replaces asparagm at position 123, and alanine replaces threonine at position 274. Protease C is described in EP 90915958.4, which corresponds to WO 91/06637, published on May 16, 1991. included are the genetically modified variants, particularly of protease C. A preferred protease, referred to as "protease D" is a vanant carbonyl hydrolase having an amino acid sequence not found in nature, which is derived from a carbonyl hydrolase precursor by replacing a amino acid different from a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent at the +76 position, preferably also in combination with one or more positions amino acid residue residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274, according to the numeration of the subtilisin of Bacillus amyloliquefa ßns, as described in WO95 / 10591 and in the patent application of C. Ghosh, et al., "Bleachin Compositions Comprisin Protease Enzymes", which has US number No. 08 / 322,677 , filed October 13, 1994. Also suitable for the present invention are the proteases that are deficient in patent applications EP 251 446 and WO 91/106637 and the BLAPR protease, described in WO 91/02792 and its variants described in WO 95. / 23221 See also a high pH protease from Bacillus sp. NCIMB 40338 which is deciphered in WO 93/18140 A for Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A for Novo. When desired, a protease having reduced adsorption and increased hydrolysis is available, as deciphered in WO 95/07791 for Procter & amp; amp; amp;; Gamble. A recombinant trypsin-like protease for detergents, which is suitable for the present invention, is described in WO 94/25583 to Novo. In EP 516 200 of Unilever, other suitable proteases are deciphered. The protease enzyme or porotease enzyme mixture can be added to the detergent composition as a separate ingredient (e.g., in the form of a pill, granulate, slurry liquid, etc.) or as a mixture with two or more protease or protease enzymes and an additional enzyme, for example as part of an associated granulate.

Additional detergent components The detergent compositions or components thereof according to the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the cleaning operation in which they are to be used The compositions or components thereof according to the invention preferably contain one or more additional detergent components selected from additional surfactants, sequestrants, bleaches, bleach precursors, bleach catalysts, organic polimépcos compounds, additional enzymes, foam suppressors, lime soap dispersants, additional suspension and antiredeposition agents for soils, perfumes and corrosion inhibitors Additional Tepsioactive Agent The detergent compositions or components thereof according to the invention preferably contain an additional surfactant selected from ammonium, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof Typical listing of ammonium classes , non-ionic, ampholytic and zwiteponic, as well as species of these surfactants, is given in US Patent No. 3,929,678, issued to Laughlin and Heupng on December 30, 1975 Additional examples are given in "Surface Active Agents and Detergents" II (Vols I and II, by Schwartz Perry and Berch) A listing of suitable cationic surfactants is given in U.S. Patent No. 4,259,217, issued to Murphy on March 31, 1981. When present, the ampholytic, amphoteric and zwitteponics are generally used in combination with one or more ammonium and / or nonionic surfactants In a particularly preferred embodiment, the detergent compositions further comprise up to 50% surfactant. Essentially any surfactant useful for detersive purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and ammonium salts). substituted such as mono-, di- and t-copolyamine salts) of ammonium sulfate, sulfonate, carboxylate and sarcosinate ammonia surfactants Sulfate ammonium surfactants are preferred Other ionic surfactants include isethionates such as acyl isethionates, N-acyltaurates , fatty acid amides of methyltamide, alkylsuccinates and sulfosuccinates, monoesters of sulfosuccina (especially saturated and unsaturated C-i2_c18 mopoesters), sulfosuccinate diesters (especially saturated Cg-C ^ saturated diesters), N-aolsarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in tallow oil or depolded therefrom.

Ammonium Surfactant Surfactant Ammonium sulfate surfactants suitable for use in the compositions of the invention include linear or branched alkyl sulphates, primary and secondary alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, acyl N- (alkyl C-1-C4) -and -N- (hydroxy-C-C2) -glucamilansulfates C5-C17, and sulfates of aikilpohsacapdos such as alkyl polyglucoside sulfates (described in present nonionic non-sulfated compounds) The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of Cg-C22 alkyl sulphates which have been ethoxylated with 0 to 20 moles of ethylene oxide per molecule. Most preferably, the surfactant of alkylethoxysulfate is an alkyl sulfate of C- | "-C- | 8, most preferably Cj 1-C15, which has been ethoxylated with from 0 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of Preferred alkyl sulfate and alkyl ethoxysulfatelate surfactants These mixtures have been described in PCT Application No. WO 93/18124 Ammonium Sulfonate Surfactant The sulfonic ammonium surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzenesulfonates, alkyl sulphonates, C6-C22 alkanesulfonates, ppb or secondary, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixture thereof. Particularly preferred compositions of the present invention further comprise an ammonium surfactant, selected from alkyl sulfate and / or alkylbenzenesulfonate surfactants of the formulas II and III, respectively R5S03-M '+ (11) 10 6S03-M' + (lll) wherein R ^ is a linear or branched alkyl or alkene portion having from 9 to 22 carbon atoms, preferably C12 to C18 alkyl or as found in secondary alkylsulfates, R6 is C- alkylbenzene; o-Cl 6 > preferably C- alkylbenzene | 1-C-13, M + and M '* can vary independently and are selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium. Particularly preferred compositions of the invention comprise both an alkyl sulphate tepsioactive agent and an alkylbenzene surfactant, preferably in ratios from ll to lll of 15 1 a 1 2, most preferably 12 1 to 2 1 The amounts of the ammonium surfactant or of the mixture of more than one ammonium surfactant in the preferred composition can be 1% to 50%, however, preferably the ammonium surfactant is present in amounts of 5% to 40% by weight of the composition. Preferred amounts of the alkyl sulfate surfactant of the formula II are from 3% to 40%, preferably from 6% to 30% by weight of the detergent composition The preferred amounts of alkylbenzenesulfonate surfactant of formula III in the detergent composition are at least 1%, preferably at least 2%, or even at least 4% by weight Preferred amounts of the alkylbenzenesulfonate surfactant are up to 23%, most preferably not more than 20%, more preferably up to 15% or even 10% The yield benefits obtained when also using ammonium surfactant up in the compositions of the invention, are particularly useful for ammonium surfactants of longer carbon chain length such as those having a carbon chain length of C 12 or greater, particulate carbon chain lengths of C-14/15 or even up to C16 is In preferred embodiments of the detergent compositions of the invention comprising surfactant to ion, there will be a significant excess of ammonium surfactants, preferably a weight ratio of surfactant to cationic ion of 50 1 to 2 1, preferably 2 1 However, the benefits of the invention are also achieved when the ratio between cationic surfactant and ammonium surfactant is substantially stoichiometric, for example from 3 2 to 4 3 In a preferred embodiment of the invention, the essential cationic surfactant of formula I is intimately mixed with one or more ammonium surfactants before the addition of the other components of the detergent composition Carboxylate Ammonium Surfactant Suitable carboxylate ammonium surfactants include alkylethoxycarboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkycarboxyls") especially certain secondary soaps such as the decays herein. Suitable alkyl ethoxycarboxylates include those with the formula RO (CH2CH2?) xCH2COO- +, wherein R is an alkyl group of CQ to C-JS. x vain from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of matepal in which x is 0 is less than 20%, and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR- | -CHR2-0) -R3 wherein R is up to C grupo to C- | 8- x alkyl group is from 1 to 25, R- | and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succimic acid radical, hydroxysuccimic acid radical and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to and 8 carbon atoms, and mixtures thereof Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to the carbon atom. a secondary carbon The preferred secondary soap surfactants for use herein are the water soluble members selected from the group consisting of the water-soluble salts of 2-meth? -1-undecano? co, 2-et acid ? 1-decane? co, 2-propyl-1 -nonanoic acid, 2-butyl-1-octane-2-acetic acid and 2-pentyl-1-heptane? co-acid. Certain soaps can also be included as suds suppressors Sarcosmate d alkali metal surfactant agent Other suitable anionic tepsioactive agents are the alkali metal sarcosmates of the formula R-CON (R1) CH2COOM, wherein R is a straight or branched C5-C17 alkyl or alkenyl group, R "! Is a C 1 -C 4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl or oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant _ Essentially any alkoxylated nonionic surfactant is suitable herein. Non-ionic ethoxylated and propoxylated surfactants are preferred. Linear or branched alkoxylated groups are suitable. The preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, ethoxylated nonionic alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated nonionic condensates with propylene glycol and non-ionic ethoxylated condensation products with ddpropylene / ethylepdiamine adducts A non-ionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can be is straight or branched, ppmapa 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 Nonionic non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ^ CO RlZ, wherein R1 is H, C1-C4 hydrocarbyl, 2-h? drox ?, ethylene, 2-hydroxypropylene, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 or C 2 alkyl, more preferably C 1 alkyl | (ie, methyl), and R2 is a C5-C31 hydrocarbyl, preferably straight chain Cs-C-ig alkyl or alkemyl, most preferably straight chain Cg-C-17 alkyl or alkemyl, more preferably alkyl or Alquemlo of C- | - | -C- | 7 straight chain or a mixture of the same, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof Z will preferably derive from a reducing sugar in a reaction of reductive ammation, most preferably Z is a glycityl A non-ionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula R6C0N (R) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and every R? is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and - (C 2 H 4) x H, wherein x is on the scale of 1 to 3 Alkylpolysaccharide Nonionic Surfactant Suitable alkyipolysaccharides which are used herein are described in U.S. Patent No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, v. g, a polyglycoside, a hydrophilic group containing from 1 3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (gl? Cos? Lo) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms n is 2 or 3, t is from 0 to 10, and x is from 1 3 to 8 Glycosyl is derived preferentially from glucose Amphotopic Surfactant Amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (? R4) xNu (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 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 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 oxide groups of Ethylene The C 8 -C 8 alkyldimethylamine oxide and the C 1 io-C 18 acylamidoalkyldimethylamine oxide are preferred. A suitable example of an alkylfodicarboxylic acid is M? Ranol (MR) C2M Conc, manufactured by Miranol, Inc, Dayton, New Jersey Zwitterionic Surfactant Zwitterionic Therapeutic Agents can also be incorporated into the detergent compositions herein These surfactants can be widely deciphered as secondary and tertiary amine derivatives derived from heterocyclic secondary and tertiary amines or quaternary phosphine quaternary ammonium derivatives or Tertiary Sulfone The sultaine and betama surfactants are examples of zwitteponic surfactants that can be used herein. Suitable betaines are those compounds having the formula R (R ') 2N + R COO- wherein R is a hydrocarbyl group of CQ -C- Q, each R1 is typically C1-C3 alkyl, and R2 is a C-1-C5 hydrocarbyl group. Preferred betaines are the betanes of C12-C18 dimethylammonium hexanoate and the acylamidopropane- (or ethane) dimethyl- (od? et? l) beta? nas of C-QC-Q Complex betaine surfactants are also suitable for use herein.

Additional Cationic Surfactants In preferred embodiments the compositions of the invention are substantially free of quaternop ammonium compounds of the formula I, but wherein one or R 1, R 2 R 3 or R 4 is a higher alkyl chain group C-11 Preferably, the composition should contain less than 1%, preferably less than 0 1% by weight or even less than 0 05% and more preferably less 0.01% by weight of compounds of formula I having a linear (or even branched) alkyl group having 12 or more carbon atoms. Another suitable group of cationic surfactants that can be used in the detergent compositions of the invention are the cationic ester surfactants The cationic ester surfactant is a compound having surfactant properties and comprising at least one ester linkage (i.e. , -COO-) and at least one cationically charged group. Preferred cationic ester surfactants are dispersible in water. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in US Patents. Nos. 422,8042, 4239660 and 4260529. In the preferred cationic ester surfactants, the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (ie, with a chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms, and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain connects only with the atoms of carbon in the chain. In this way, groups that have, for example, -O-O- bonds (ie, peroxide), are excluded, - NN- and -NO-, but include the spacer groups having, for example, -CH2-O-CH2- and -CH2-NH-CH2 bonds. In a preferred aspect, the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain Alkalinity In the detergent compositions of the present invention preferably a alkalinity system is present to achieve optimum performance of the cationic ester surfactant The alkalinity system comprises components capable of providing alkalinity species in the solution the present carbonate, bicarbonate, hydroxide, the various silicate, percarbonate, perborate, perphosphate, persulfate and persilicate amines. Such alkalinity species may be formed, for example, when the selected alkali metal salts of alkali metal carbonate, bicarbonate hydroxide or alkali metal silicate or alkaline earth, including crystalline layered silicate and mixtures thereof are dissolved in water Examples of carbonates are alkali metal and alkali metal carbonates, including sodium carbonate and sesquicarbonate and any mixture thereof with ultra-fine calcium carbonate or such as those described in German patent application No. 2,321,001, published on November 15, 1973 Suitable silicates include soluble sodium silicates with a ratio of S 2 2 -Na 2? from 1 0 to 2 8, preferring relationships from 1 6 to 2 0, and more preferred a ratio of 2 0 The silicates can be in either the anhydrous salt or a hydrated salt form Sodium silicate with a ratio of SIOO Na20 of 2 0 is the most preferred silicate . The preferred crystalline layered silicates for use herein have the general formula NaMS? X? 2? + L and H20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Crystalline stratified sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are deciphered in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, and is preferably 2. The most preferred material is d-Na2Si2? 5, available from Hoechst AG as NaSKS-6.

Water-soluble detergent composition The detergent compositions according to the present invention preferably contain a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably % to 70% by weight, more preferably from 20% to 60% by weight of the composition.

Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxy radicals separated from each other by no more than two carbon atoms borates, phosphates and mixtures of any of the forearms The carboxylate or polycarboxylate builder may be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxyl group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, acid (et? lend? ox?) acetic acid, maleic acid, diglycolic acid, tartaric acid co, tartronic acid and fumapco acid, as well as ether carboxylates and sulfinylcarboxylates Polycarboxylates containing three carboxyl groups include, in particular, citrates, acomtats and water-soluble citraconates, as well as succinate derivatives such as carboxymethyloxysuccinates which are British Patent No. 1, 379,241, the lactoxysuccinates described in the bptanica patent No. 1, 389,732 and the aminosuccinates described in the Dutch application 7205873 and the oxypolycarboxylate matepales such as 2-oxa-1, 1, 3-propantpcarboxylates, British Patent No. 1, 387,447 Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent No. 1 261, 829 1, 1, 2,2-ethane-tetracarboxylates, 1, 3, 3-propanotetracarboxylates, and 1, 1, 2,3- propanotetracarboxylates Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398,421 and 1, 398 422 and US Patent No. 3,936,448 and the sulfopated pyrolysed citrates described in the bptámca patent No 1 439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxyl groups per molecule very particularly citrates Acids of origin of carboxylate chelating agents monomepcos or oligomepcos or mixtures thereof with their salts, v gr, mixtures of citric acid or dß citrate / citric acid they are also considered as useful builder components builders borate detergepcia improvers, as well as detergency builders containing borate-forming materials which can produce borate under detergent storage or washing conditions are water-soluble builders useful in the present. Suitable examples of water-soluble phosphate builders are the phospho-phosphate buffers. alkali metal, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium pohmetaphosphate, in which the degree of polymerization is from about 6 to 21, and salts of acid Meanstock of partially soluble or insoluble detergency The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight , most preferably from 20% to 60% by weight of the composition. Examples of builders widely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(Al? 2) z (S? 2) and] XH 2 O wherein z and y are integers of at least 6 the molar ratio of z a is from 1 0 to 0 5 and x is at least 5, preferably from 7 5 to 276, most preferably from 10 to 264 The material The aluminosilicate is in hydrated form and is preferably crystalline, containing from 10% to 28%, most preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites can be materials of natural origin. but are preferably synthetically derived. Synthetic aluminosilicate ion exchange pads are available under the designations Zeolite A, Zeo ta B, Zeolite P, Zeolite X Zeolite MAP Zeolite HS and mixtures thereof. Zeolite A has the formula a12 [(Al? 2) i 2 (S? 2) i2] H2? where x is from 20 to 30, especially 27 Zeolite X has the formula Na86 [(AIO2) 86 (S ?? 2) i 06] ^ 6 H20 Another aluminosilicate zeolite that is preferred is the zeolite MAP builder. The zeolite MAP can be present at a level of 1% to 80%, most preferably from 15% to 40% by weight of the compositions. Zeolite MAP is described in EP 384070A (Unilever) It is defined as an alkali metal aluminosilicate of the zeolite P type having a silico to aluminum ratio of not more than 1 33 preferably on the scale dß 0 9 to 1 33 and most preferably on the scale of 0 9 to 1 2 Of particular interest is the zeolite MAP having a silicon to aluminum ratio of not more than 1 15 very particularly not more than 1 07. In a preferred aspect the zeolite MAP builder has a particle size expressed as a value dso from 10 0 to 10 0 microns most preferably from 2 0 to 7 0 microns more preferably from 2 5 to 5 microns The dso value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size can be determined in particular by conventional analytical techniques such as microscopic determination using a barndoar electron microscope or by means of a laser granulometer. Other methods to establish the dgo values are deciphered in EP 384070A Heavy metal ion sequestrant The detergent compositions or components thereof according to the present invention preferably contain a heavy metal ion sequestrant as an optional component. By ion sequestrant of heavy metal is intended here to mean components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferably show selectivity for binding to heavy metal ions such as iron, manganese and copper. . Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably from 0 1% to 10%, most preferably from 0.25% to 7 5% and more preferably from 0.5% to 5% by weight of The compositions. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the amidoalkylene poly (alkylene alkylene phosphonates), alkali metal ethan-1-hydroxydiophosphonates and nitrilotrimethylene phosphonates. Preferred among the above species are diethylene-propane-pentane (methylene-phosphonate), ethylene-ammonium (methylene-phosphonate), hexamethylenediamine (methylene-phosphonate) and hydroxyl-ethylene-1,1-diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotpacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutapacic acid, 2-hydroxypropylenediaminedisuccinic acid or any salt thereof. Especially preferred is et? Lendiam? No-N, N'-disuccinic acid (EDDS) or metal salts alkaline alkaline earth metal of ammonium or substituted ammonium thereof, or mixtures thereof. Other heavy metal ion sequestrants suitable for use herein are the iminodiacetic acid derivatives such as 2-hydroxyethyl-diacetic acid or glyce- lipodiacetic acid. , described in EP-A-317 542 and EP-A-399,133 The sequestrants of iminodiacetic acid-N-2-hydroxypropylsulfonic acid and of aspartic acid-N-carboxymethyl acid N-2-h? drox? prop? l-3 sulfonates described in EP A-516 102 are also suitable herein. Sequestrants of β-alanm-N N'-diacetic acid aspartic acid-N N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid deciphered in EP -A-509,382 are also suitable EP-A-476,257 discloses suitable amine-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein EP-A-528,859 discloses a suitable alkyliminodiacetic acid sequestrant o Dipicolimic acid and 2-phosphonobutan-1 2 4-tpcarboxyl acid are also suitable. Glymamida-N-N'-disuccinic acid (GADS), ethylene diamine-N-N'diglutapco acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable Organic Peroxyacid Bleach System A preferred feature of the detergent compositions or component thereof according to the invention is an organic peroxyacid bleach system. In a preferred embodiment, the system or bleach contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound Production of organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide Preferred sources of hydrogen peroxide include inorganic perhydrate bleach In a preferred and alternative embodiment, a preformed organic peroxyacid is directly incorporated into the composition. Compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated.

Inorganic perhydrate bleaches Inorganic salts of perhydrate are a preferred source of hydrogen peroxide These salts are normally incorporated in the form of an alkali metal, preferably a sodium salt at a level of 1% to 40% by weight, most preferably from 2% to 30% by weight and more preferably from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate salts, percarbonate, perphosphate, persulfate and persilicate. 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 granulated compositions use a coated form of the material, which provides better stability under storage for the perhydrate salt in the granulated product Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB ?2H2 ?2 or the tetrahydrate NaB ?2H2 ?2 3H2O The alkali metal percarbonates, particularly sodium percarbonate, are the perhydrates that are preferred herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3-3H2? 2 and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. The pyrroxy acid bleach precursors can generally be represented as: Or I! X - C - L wherein L is a leaving group and X is essentially any functionality, such that perhydrolysis, the structure of the peroxyacid produced is OR I I X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0% to 20% by weight, most preferably from 1% to 15% by weight, more preferably from 15% to 10% by weight of the detergent compositions. Suitable peroxyacid 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 include anhydrides, esters, linked, lactams and acylated derivatives of imidazoles and oximes. Useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The outgoing group, hereinafter referred to as group L, must be sufficiently reactive to allow the perhydrolysis reaction to occur within the optimum time frame (v gr, a wash cycle). However, if L is very reactive, it will be difficult stabilize this activator for use in a bleaching composition.

The preferred L groups are selected from the group consisting of: N ~ C -! , - -N A N, N - C p - CH - R4 1 1 1, 1 K = R3 Y \ Y R3 Y • 0 - CH = C - CH = CH2 --O - CH = C - CH = CH2 and mixtures thereof, wherein R1 is an alkyl, aryl or alkaline group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and And it is H or a solubilizing group. Any of R1, R3 and R4 can be substituted essentially with any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, mrosium, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3"M +, -C? 2" +, -SO4"M +, - N + (R3) 4X- and 0 <--N (R3) 3, and most preferably -S03-M- and -C? 2"M +, wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms carbon, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator Prefemorally, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is an anion of halide, hydroxide, methylsulfate or acetate Alauylpercarboxylic acid bleach precursors Alkylpercarboxylic acid bleach precursors form percarboxylic acids by perhydrolysis Preferred precursors of this type provide peracetic acid by perhydrolysis Preferred alkylcarboxylic acid precursor compounds of the imide type include the N-N-N-N-tetraacetylated alkylenediamines wherein 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. Particularly preferred is tetraacetylethylene diamine (TAED). Other preferred alkylpercarboxylic acid precursors include 3, 5,5-tr? Methexano? Lox? Sodium benzene sulfonate (iso-NOBS), sodium nopailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose Amide substituted alkylperoxy acid precursors Amide substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: R1-C- N-R2 -C- L R1 -N- C- R2 -C- L I I I I I I I I I O R5 OR R5 O O wherein R 1 is an alkyl group with 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 leaving group. The bleach activating compounds substituted with amide of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid by perhydrolysis. Compounds perbenzoic acid precursors O-acylated suitable include oxibencensulfonatos of substituted benzoyl and unsubstituted and products benzoylation of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoilsuccmimida, tetrabenzoiletilendiamipa and the N-benzoyl ureas substituted. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazoi and N-benzoiibenzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoylpyrrohdone, dibenzoyltaupna and benzoylpyrrollutamic acid Precursors Cationic peroxyacid precursor compounds cationic peroxyacid product peroxyacids catiomcos by pßrhidrolisis Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a compound suitable peroxyacid precursor with functional positively charged group such as an ammonium group or alkyl or, preferably an ethyl or methylammonium group The cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be cationically substituted may be a precursor compound of perbenzoic acid or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor compound of alkylpercarboxylic acid or a substituted alkylperoxy acid precursor. amide as previously described herein peroxyacid precursors Cationic are described in US patents We 4,904,406, 4,751, 015, 4,988,451, 4,397,757, 5,269,962, 5,127,852, 5,093,022, 5,106,528, UK 1, 382.594, EP 475.512, 458.396 and 284,292, and in JP 87-318,332 Examples of preferred precursors catiomcos peroxyacid are described in Patent Application UK 9407944 No 9 and in patent applications US 08/298903 We, 08/298650, 08/298904 and 08/298906 peroxyacid precursors cos catio Suitable include any of the substituted alkyl or benzoyl-oxybenzenesulphonates of ammonium or substituted alkylammonium, the N-acylated caprolactams and the benzoylperoxides of mopobenzoyltetraacetylglucose. The preferred cationic peroxyacid precursors of the N-acnate caprolactam class include the methylenebenzoyl caprolactams of tpalkylammonium and the methylene alkyl caprolactams. from tpalquilamomo Benzoxazine Organic Peroxyacid Precursors Benzoxazine-type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807 are also suitable, particularly those having the formula wherein R-] is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed Organic Peroxyacid bleach system organic peroxyacid may contain, in addition to or as an alternative to, a precursor compound of organic peroxyacid bleach, a preformed organic peroxyacid, typically at up level of 1% to 15% by weight, most preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas: R1-C- N-R2 -C- OOH R1"N- C- R2" C-OOH I I I! or I I I I I O R5 O Rd o O wherein R1 is an alkyl, aryl or alkaline group with 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R§ is H or an alkyl, aryl group or alkaryl containing from 1 to 10 carbon atoms. The organic peroxyacid compounds substituted with Amides of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl- and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Mono- and diperazelaic acid, mono- and diperbrasilic acid and N-phthaloylaminoperoxycaproic acid are also suitable herein.

Bleach Catalyst The compositions optionally contain a bleach catalyst containing a transition metal. A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or cationic cations. manganese, an auxiliary metal cation having very little or no catalytic bleaching activity, such as zinc or aluminum cations and a scavenger having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediammotetraacetic acid, ethacrylate ? lendiam? notetra- (met? lephosphon? co) and the water soluble salts thereof. Said catalysts are deciphered in the patent of E.U.A. No. 4,430,243. Other 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 MnlV2 (u-0) 3 (1, 4,7-trimet? L-1, 4,7-triazaciclononapo) 2- (PF6) 2, Mn! || 2 (u- 0) 1 (u-OAc) 2 (1, 4,7-trimetim, 4,7-tpazacyclononane) 2- (Cl? 4) 2, MpIV4 (u-0) 6 (, 4,7- tpazac? clononane) 4- (Cl? 4) 2 -Mn '|| Mn'V4 (u-0) - | (u-OAc) 2 (1, 4,7-tpmet? l-1, 4,7-tpazac? clononane) 2- (Cl? 4) 3 and mixtures thereof Others are described in the publication of the application for European Patent No. 549,272 Other ligands suitable for use herein include 1, 5,9-tmetmet-1, 5,9-tpazacyclododecane, 2-mt-1-l, 4,7-tr? azac? clononane, 2 -met? l-1, 4,7-tpazacyclononane, 1, 2,4,7-tetramethyl-l, 4,7-tpazac? clononane and mixtures thereof For examples of suitable bleach catalysts see the patent for US No. 4,246,612 and US Patent No. 5,227,084 See also U.S. Patent No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1, 4,7-tr? Met? L-1, 4 , 7-tpazac? Clononane) (OCH3) 3- (PFg) Yet another type of bleach catalyst as described in US Patent No. 5,114,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. plos include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn '"(u-0) 2 nl ^ N4) + and [B? py2Mn'" (u-0) 2MnlVb? py2 ] - (CI04) 3 Suitable and additional bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), European patent applications Nos. 384,503 and 306,089 (metalloporphiphane catalysts) , US Patent 4,728,455 (manganese / multidentate ligand catalyst), U.S. 4,711, 748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aminosinolate), U.S. Pat. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese / ligand catalyst), patent E.U.A. 4,119,557 (ferric complex catalyst), German Patent Disappearance 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), from E U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts) Additional Enzymes The compositions of the present invention may comprise one or more additional enzymes. Additional preferred enzyme materials include commercially available enzymes. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases , arabinosidases, hyalurodinase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes is a cleaning composition having a mixture of applicable enzymes conventional ones such as protease, amylase, cutinase and / or cellulase, together with one or more enzymes degrading the wall of the plant cell. Suitable enzymes are deciphered in the US patents. We 3,519,570 and 3,533,139. The detergent compositions of the invention may also contain one, or a mixture of more than one amylase enzyme (a and / or β). WO94 / 02597, Novo Nordisk A S published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amloses known to be used in cleaning compositions include amylases as well as β. Amylases are known in the art and include those described in US Pat. US patent 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 on August 18, 1994 and WO96 / 05295, Genencor, published on February 22, 1996, as well as the amylase variants having a further modification in the Immediate parent available from Novo Nordisk AS, available from WO 95/10603, published April 25, 1995. Also suitable are the amylases described in EP 277 216, W095 / 26397 and W096 / 23873 (all from Novo Nordisk). Examples of commercial α-amylase products are Purafect Ox AmR from Genencor and TermamylR, BanB, FungamylR and Duramyl, all available from Novo Nordisk A / S, Denmark. W095 / 26397 describes other suitable amylases: α-amylases characterized by having an activity specific at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and at a pH value on a scale of 8 to 10, as measured by the Phadebas® α-amylase activity test. The vanants of the above enzymes, described in W096 / 23873 (Novo Nordisk), are suitable. Other preferred amylolytic enzymes with improved properties with respect to activity level and combination of thermostability, as well as a higher activity level are described in W095 / 35382. Amylolytic enzymes, if present, are 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%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. Suitable lipolytic enzymes for use in the present invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1, 372, 034. Suitable lipases include those that show a positive ipmunological cross-reaction with the llpase antibody produced by the microorganism Pseudomonas Hisorescent IAM 1057. This lipase is available from Amano Pharmaceuticai Co. Ltd., Nagoya, Japan, under the trade name Lipase P " Amano, "henceforth called" Amano-P ". Other suitable commercial lipases include Amapo-CES, lipases from Chmmobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter lipases viscosum of U.S. Biochemicai Corp., E.U.A. and Disoynth Co., The Netherlands and the lipases of Pseudomonas gladioli. Especially suitable lipases are lipases such as Ml L? Pass and L? Pomax (Gist-Brocades) and Lipolase and Lipolase UltraR (Novo) which have been found to be very effective when used in combination with the compositions herein Nvention 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 can be considered as a special type of lipase, namely lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described in e.g., WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a salt that is preferred to be used in the present invention. Another lipase that is preferred to be used in the present invention is the lipolytic enzyme variant D96L of the native lipase derived from Humicola lanuginosa. Most preferably, strain DSM 4106 from Humicola lanuginosa is used. By variant of the lipolytic enzyme D96L is meant the vanishing of lipase as described in the patent application WO 92/05249, in which the native lipase of Humicola lanugmosa has the aspartic acid residue (D) in the 96 position changed to leucine (L). According to this nomenclature, said substitution of aspartic acid to leucine in position 96 is shown as: D96L. To determine the activity of the D96L enzyme, the normal LU test can be used (analytical method, internal Novo Nordisk AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying glycemap trlbutirate (Merck) and using gum arabic as an emulsifier. The activity of the lipase is tested at pH 7 using the statistical pH method. The detergent compositions of the invention may also contain one or more cellulase enzymes. Said cellulases include both bacterial and fungal cellulases. Preferably, they will have an optimum pH of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are described in the U.S. patent. 4,435,307, Barbesgoard et al., J61078384 and WO96 / 02653, which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thißlavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also deciphered in GB-A-2,075,028; GB-A-2,095,275, DE-OS-2,247,832 and W095 / 26398. Examples of said cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var, thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; an endoglucanase component that is preferred has the amino acid sequence described in PCT patent application No. WO 91/17243. Cellulases which are also suitable are the EGEIII cellulases of Trichoderma longibrachiatum described in WO94 / 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 the European patent application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also W091 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, W096 / 17994 and W095 / 24471. Pedase enzymes can also be incorporated into the detergent compositions of the invention. Pedases are used in combination with sources of oxygen, v., Percarbonate, perborate, persulfate, hydrogen pede, 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. Pedase enzymes are known in the art and include, for example, horseradish pedases, ligmcase pedase and halogen pedases, such as chlorine and bromopedases. Pedase-containing detergent compositions are described, for example, in International Patent Application WO 98/099813, WO89 / 09813 and in European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013 8, filed on February 20, 1996 Lacasa enzyme is also suitable Preferred breeders are substituted phenazine and phenoxazine and 10-phenot? az? nprop? on? co (PPT) acid ), 10-et? lfenot? az? n-4-carboxylic acid (EPC), 10-phenot? az? nprop? on? co (POP) acid and 10-met? lfenoxaz? na (described in WO 94/12621) ) and the substituted siphnates (substituted C3-C5 alkyl siphonates) and phenols Sodium percarbonate or perborate are the hydrogen peroxide sources that are preferred Said cellulases and / or peroxidases, if present, are incorporated in the detergent composition at no additional cost. levels from 0,0001% to 2% active enzyme by weight of the detergent composition Said additional enzymes, when present, are normally incorporated in the detergent composition at levels from 0,0001% to 2% active enzyme by weight of the detergent composition Additional enzymes can be added as separate ingredients. ados (pellets, granules, stabilized liquids, etc that contain an enzyme) or as mixtures of two or more systems (v gr, cogranulados) Enzyme oxidation scavengers Other suitable detergent ingredients that can be added are the enzyme oxidation scavengers that are deciphered in the co-pending European patent application 92870018 6, filed on January 31, 1992 Examples of said enzyme oxidation scavengers are the polyamines ethoxylated Enzyme materials A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in WO 9307263 and WO 9307260 from Genencor International, WO 8908694 A from Novo, and US Pat. 3,553,139, January 5, 1971 by McCarty et al. They also describe enzymes in the US patent. 4,101, 457, Place et al., July 18, 1978 and in the US patent. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in US Pat. 4,261, 868, Hora et al., April 14, 1981. The enzymes that will be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in the US patent. 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 the U.S. patent. 3,519,570. A Bacillus, AC13 useful and which gives proteases, xylanases and cellulases is described in WO 9401532 A de Novo.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof according to the invention, and are preferably present as components of any particulate components, where they can act to agglutinate the particulate component with each other. By "organic polymeric compound" is meant herein essentially any polymeric organic compound that is not an oligoester or polyamine soil remover polymer, and that is commonly used as a dispersant and anti-redeposition agent and suspension of soils in detergent compositions , including any of the high molecular weight organic polymeric compounds disclosed as clay flocculating agents herein. This organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. The polymers of the latter type are described GB-A-1596,756. Examples of such salts are MP 1000-5000 polyacrylates and their copolymers with maleic anhydride, said copolymers have a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. Polymaleate or polymaleic acid polymers and salts thereof are also suitable examples. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Also suitable for incorporation into the compositions of the present invention are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 1,000 to 30,000. Preference from 3,000 to 10,000. Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional organic polymeric compounds and useful with polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably about 4000.

Cationic compounds for removal / anti-redeposition of soils The detergent composition or components thereof according to the invention can comprise water-soluble ethoxylated ammonium compounds with removal / anti-redeposition properties of dirt / clay soils. These cationic compounds are described in more detail in EP-B-111965, US 4659802 and US 4664848. Ethoxylated cationic monoamines, diamines or triamines are particularly preferred among these cationic compounds. Ethoxylated cationic monoamines, diamines or triamines of the formula are especially preferred: wherein X is a nonionic group selected from the group consisting of d H, alkyl or hydroxyalkyl ester or C1-C4 ether groups and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (vgr ., ethylene, propylene, hexamethylene), b is 2, 1 or 0, for cationic monoamines (b = 0), n is preferably at least 16, with a typical scale of 20 to 35; for cationic diamines or tnamines, n is preferably at least about 12, with a typical scale of about 12 to about 42. These compounds, when present in the composition, are generally present in an amount of 0.01 to 30% by weight , preferably 0.05 to 10% by weight.

Foam suppression system The detergent compositions of the invention, when formulated for use in compositions for machine washing, comprise preferably a foam suppression system present at a level of from 0.01% to 15%, preferably from 0.05% to 10% and most preferably from 0.1% to 5% by weight of the composition. The foam suppression systems suitable for use herein can comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkylolcancanol antifoaming compounds. By "antifoaming compound" is meant any compound or mixtures of compounds which act to reduce the foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred antifoaming compounds for use herein are the silicone defoaming compounds defined herein as any antifoam compound that includes a silicone component. Said silicone anti-foaming compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred antifoaming silicone compounds are siloxanes, particularly polydimethylsilsxanes having trimethylsilyl end blocking units. Other suitable defoaming compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are disclose in the patent of E U No 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and the salts thereof for use as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms., preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (v. G., Fatty acid tglicpepds), fatty acid esters of monovalent alcohols, C- | 8-C4o aliphatic ketones (e.g. stearone), N-alkylated ammo tpazines such as tp- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortpazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene, bis stearic acid amide and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of silicone antifoam compound; and (i) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; where said Silica / silicon antisweat compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight (b) a dispersion compound most preferably comprising a copolymer of Silicon glycol with a polyoxyalkylene content of 72-78 % and a ratio of ethylene oxide to propylene oxide of from 1 to 9 to 1 to 1 at a level of from 0 to 10%, preferably 1 to 10% by weight, a particularly preferred glycol silicone hardener copolymer of this type is DC0544 commercially available from DOW Corning under the tradename DC0544, (c) an inert carrier fluid composition, most preferably comprising an ethoxylated C-ig-Cj alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80% preferably 10% to 70% by weight, A highly preferred particulate foam suppressor system is deciphered in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material which has a melting point in the range of 50 ° C to 85 ° C, in which the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof, with a melting point of 45 ° C to 80 ° C Polymer dye transfer inhibiting agents The detergent compositions herein can 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 copolymers of N-vinylpyrrolidone and N-vimlimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be entangled polymers. a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: (I) Ax wherein P is a pollmepable unit, and O R 1 R 1 O O R 1 I I I I I I I A is -C-N-, -N- C-, CO, C, -O-, -S-, -N-; x is 0 or 1; R1 is H or straight or branched alkyl of C? .d; or it can form a heterocyclic group with R; R are aliphatic, aliphatic, ethoxylated, aromatic groups, heterocyclic or alicyclic, or any combination thereof, to which the nitrogen of the N-O group may be attached, or wherein the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: 0 O 1 I (R,) x - N - (R2) i = N- (R1) XI (R3) z wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xy / oyy / oz is 0 or 1, and wherein the nitrogen of the NO group may be attached, or where the nitrogen of the NO group forms part of these groups. The N-O group may be part of the pollmepzable unit (P) or it may be attached to the polymeric backbone, or a combination of both. Suitable N-oxide polyamines, wherein the N-O group forms part of the polymerizable unit, comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamipa N-oxides wherein the nitrogen of the NO group is part of the R group. The preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pipdine , pyrrole, imidazole, pyrrolidine, piperazine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the amine oxides to which the NO group is attached to the polymembrane unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) where R is an aromatic group, heterocyclic or hydrocyclic wherein the nitrogen of the functional group is NOT part of said group R Examples of these classes are polyamide oxides wherein R is a heterocyclic compound such as pipdine pyrrole imidazole and derivatives thereof Polyamide oxides can be obtain at almost any degree of popopulation The degree of polymerization is not critical, as long as the material has the desired water solubility and the desired dye suspension power. Typically the average molecular weight is within the range of 500 to 1,000,000 b) Copolymers of N-vimlpyrrolidone and N-vinylimidazole The N-vinylimidazole-N-vinylpyrrolidone polymers used herein have an average molecular weight scale of 5,000 to 50,000, or 5,000 to 50,000 Preferred copolymers have a molar ratio of N -vim midazole to N-vinylpyrrolidone from 1 to 0 2 c) Polyvinylpyrrolidone The detergent compositions herein can also use polyvinylpyrrolidone ("PVP"), which has an average molecular weight of from about 2,500 to about 400,000 polyvinylpyrrolidones. suitable are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trademarks PVP K-15 (molecular weight of 10,000 with viscosity), PVP K-30 (average molecular weight of 40,000), PVP K-60 (weight average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000) PVP K-15 is also available from ISP Corporation Other suitable polyvinylpyrrolidones that are commercially available from BASF Corporation, include Sokalan HP 165 and Sokalan HP 12 d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent Said polyvinylloxazolidones have an average molecular weight of 2,500 to 400,000 Polyvinylimidazole The detergent compositions of the present invention can also use polyvinylimidazole as a dye transfer inhibiting agent. Said polyvinyl imidazoles have an average molecular weight of 2,500 to 400,000.

Optical Brightener The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein are those that have the structural formula: wherein R-] is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 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-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bis [(4-anilino-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbene-disulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Clba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

When in the above formula R1 is anilmyl, R2 is N-2-hydroxyl and N-2-methylamino and M is a cation such as sodium the brightener is the disodium salt of acid 4.4, -b? s [(4-an? l? no-6- (N-2-h? drox? et? l N-met? lam? no) -s-tpaz? n-2-? l) am? no] -2 , 2'-stilbene-disulphonate This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX from Ciba-Geigy Corporation When in the above formula R i is am no, R2 is morphine and M is a cation such as sodium the brightener is the sodium salt of acid 4 4'-b? s [(4-an? l? no-6-morphyl? no-s-tpaz? n-2-? l) am? no] 2 2 ' -est? lben-d? sulfon? co This particular brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation POLYMENIC POLISHING AGENT OF SOILS Polymeric agents removing soils known, hereinafter "SRA", may be optionally employed in the present detergent compositions. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically of about 0 1% to 5%, preferably from about 0 2% to 30% by weight, of the compositions Preferred SRA's typically have hydrophobic segments to hydrophobicize the surface of the hydrophobic fibers such as polyester and nylon, and the hydrophobic segments to be deposited on hydrophobic fibers and remain adhered to them until the washing cycles are completed and Rinsing, thus serving as an anchor for the hydrophilic segments This can make it possible to more easily clean the spots that occur after treatment with the SRA in subsequent washes Preferred SRAs include oligomepic terephthalate esters, typically prepared by procedures that include less a transestepfication / oligomeation commonly with a metal catalyst such as a tantalum alkoxide (IV). Such esters can be manufactured using additional monomers capable of being incorporated into the structure of the ester through one, two three four or more positions without, of course, forming a densely intertwined overall structure Suitable SRAs include a sulphonated product of a substantially linear ester oligomer formed from an ester backbone or gomecop from terephthaloyl and oxyalkylenoxy repeating units and sulphonated terminal portions derived from aillo covalently attached to the skeleton, po Example as it is disclosed in US Pat. No. 4 968,451, dated November 6, 1990, by JJ Scheibel and EP Gosselmk. Such ester oligomers can be prepared by (a) ethoxylating alcohol to lico, (b) by reacting the product of (a) ) with dimethyl terephthalate ("DMT") and 1,2-prop? legl? col ("PG") in a two step transestepfication / oligomeation process, and (c) reacting the product of (b) with metabisulfite of sodium in water Other SRA's include the 1, 2-prop? lnno / pol? ox? et? le? terephthalate end-blocked nonionic poyesters of US Patent No. 4,711, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transestepfication / oligomepzacion of polyethylene glycol methyl ether DMT, PG and polyethylene glycol ("PEG") Other examples of SRAs include the oligomepc esters of ammonium blocked ends partially and completely from the US patent No 4 721 580, of January 26, 1988 a Gosselink, such as oligomers of ethylene col ("EG"), PG, DMT and Na-3,6-d? Oxa-8-hydrox? Octansulfonate, the non-ionic blocked block polyester oligomeric compounds of the US 4,702,857 from October 27, 1987 to Gosselink, for example produced from DMT PEG and EG and / or PG (Me) -block of methyl or a combination of DMT EG and / or PG, PEG Me-blocked and Na- d? met? l-5-sulfoisophthalate, and the blocked terphthalate esters of the ammonium ends, especially of sulfoaroyl of US Pat. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others, the latter being a typical SRA's both in fabric and lava conditioning products Example of an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably also comprising added PG, vg, PEG 3400 The SRA's also include simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US Patent No. 3,959,230 to Hays of May 25, 1976 and US Patent No. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such such as the hydroxyether cellulosic polymers available as METHOCEL from Dow, the C1-C4 alkyl celluloses and C4 hydroxyalkylcellules of US Pat. No. 4,000,093, from December 1976 to Nicol, et al., and methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit of about 1 6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoises measured at 20 ° C as an aqueous solution ai 2%. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) non-ionic terephthalates using dnsocyanate coupling agents to bind the polymeric ester structures, see E.U. 4,201, 824, Violland et al. And E.U. 4,240,918 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding methyl pyridyl anhydride to known SRA's to convert terminal hydroxyl groups to t-methylate esters. With the proper selection of the catalyst, the tmethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the tmethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be labeled, see E.U. No. 4,525,524 Tung and others. Other classes include (lll) SRA's based on non-ammonium terephthalate of urethane bonded vapors, see E.U. 4,201, 824, Violland and others, Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include colored perfumes and filler salts, with a preferred filler salt being sodium sulfate.

Detergent formulation with an almost neutral wash pH Although the detergent compositions of the present invention are operative within a wide range of wash pHs (v. G, from about 5 to about 12), they are particularly suitable when formulated to provide a pH almost neutral washing, ie, an initial pH of about 7 0 to about 10 5 at a concentration of about 0 1 to about 2% by weight in water at 20 ° C. Formulations with an almost neutral wash pH are better for enzyme stability and to prevent stains from depositing In said formulations, the washing pH is preferably from about 7 0 to about 10 5, most preferably from about 8 0 to about 10 5, more preferably from 8 0 to 9 0 Detergent formulations with an almost neutral wash pH are described in European patent application 83 200688 6, filed May 16, 1983, JHM Wertz and PCE Goffinet Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (v. Gr, less than about 20% by weight). weight) of neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, opacifying foam regulators, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in the patent from EU 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference) Form of the compositions The compositions according to the invention can have a variety of physical forms including granulated forms, in tablets, flakes, bars, sticks and liquids. The liquids can be aqueous or non-aqueous and can be in the form of a gel. . The compositions may be pretreatment compositions or conventional laundry detergents. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a delivery device placed in the tub of the washing machine with the load of laundry. Said granular detergent compositions or components thereof according to the present invention can be made by a variety of methods, including dry blending, spray drying, extrusion, agglomeration and granulation. The quaternized surfactant can be added to the other detergent components by mixing, agglomeration (preferably combined with a carrier material) or as a spray-dried component. The compositions according to the present invention may also be used in or in combination with bleaching additive compositions, for example comprising chlorine bleach. In an aspect of the invention, the average particle size of the components of the granulated compositions according to the invention should preferably be such that no more than 15% of the particles are more than 1.8 mm in diameter and not more than 15 mm in diameter. % of the particles are less than 0.25 mm in diameter. Preferably, the average particle size is such that 10% to 50% of the particles have a particle size of 0.2 mm to 0.7 mm in diameter. The term average particle size as defined herein is calculated by screening a sample of the composition in a number of d fractions (typically 5 fractions) in a series of sieves, preferably Tyler sieves. The fractions of weight thus obtained are plotted against the size of the opening of the sieves. The average particle size sß considers the size of the opening through which 50% by weight of the sample would pass.

In a further aspect of the invention, at least 80%, preferably at least 90% by weight of the composition comprises particles with an average particle size of at least 0.8 mm, most preferably at least 1.0 mm and more preferably of 1.0, or 1.5 to 2.5 mm, More preferably at least 95% of the particles will have said average particle size. Said particles are preferably prepared by an extrusion process. Preferably, the cationic surfactant and the proteolytic enzyme are contained in the same particle. The overall density of the granular detergent compositions according to the present invention is typically an overall density of at least 400, preferably 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve on its lower end to allow the contents of the funnel to be emptied into a cylindrical cup aligned axially below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder is removed from the cup by passing a straight edge implement, eg, a knife, through its upper edge. The filled cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required.

The compacted solids can be manufactured using any suitable compaction process, such as rattling, agglomeration or extrusion, preferably tableting. Preferably, the tablets that will be used in dishwashing processes are manufactured using a normal rotary tapping press and using compression forces of 5 to 13 KN / cm2, most preferably 5 to 11 KN / cm2 for the solid compacted has a minimum hardness of 176N to 275N, preferably 195N to 245N, measured by a C100 hardness test as provided by I Holland Instruments. This method can be used to prepare homogeneous or stratified tablets of any size or shape. Preferably, the tablets are symmetrical to ensure uniform dissolution of the tablet in the wash solution.

Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a laundry detergent composition in accordance with the present invention. with the invention. For an effective amount of the detergent composition it is tried to say from 10g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. The dosage depends on the particular conditions such as water hardness and degree of soiling of the laundry.

The detergent composition may be supplied, for example, from the assortment box of a washing machine or it may be sprinkled on the dirty laundry placed on the machine. In one aspect of use a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product and used to introduce the product directly into the drum of the washing machine before starting the wash cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product that would normally be used in the washing method. washing The delivery device containing the detergent product is placed inside the drum before the start of the washing cyclebefore, simultaneously with or after the washing machine has been loaded with clothes At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the latter rotates in a pepodical manner. The design of the delivery device must be such as to allow the product to be contained dry detergent but then allow this product to be released during the wash cycle in response to its agitation when rotating the drum and also as a result of its contact with the washing liquid To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass Alternately, the device can be made of a material that is liquid permeable but impermeable to the solid product, which will allow to release the dissolved product Preferably, the detergent product will be released quickly at the beginning of the wash cycle, providing localized transient concentrations of the product in the drum of the washing machine in this stage of the washing cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2, 157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP- A-0288346 An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granular laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in PCT patent application No. W094 / 11562. Essentially preferred delivery devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This application describes a device comprising a flexible liner in the form of a bag extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the opticium to the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprises radial walls extending from a protuberance in a spoke wheel configuration or similar structure, in which the walls have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in the published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material Water-insoluble provided with an edge or seal seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of frangible water closure comprises a soluble adhesive in water disposed along the edge of a sack, sealing it, formed of a waterproof polymeric film such as polyethylene and polypropylene.

Automatic dishwashing method Any suitable methods for automatic dishwashing or the cleaning of dirty cutlery, particularly dirty silverware, are envisioned. An automatic dishwashing method that is preferred comprises treating selected items of earthenware, glassware, pots, silverware and cutlery and mixtures thereof with an aqueous liquid having dissolved or dispersed therein an effective amount of a composition for automatic dishwashing according to the invention. By an effective amount of the composition for automatic dishwashing is attempted say 8g to Og of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are typical product washings and wash solution volumes commonly used in conventional automatic dishwashing methods Packing for compositions Commercially sold embodiments of bleaching compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastics and any suitable laminates. A preferred packaging mode is described in European application No. 94921505.

Abbreviations used in the examples In the detergent compositions, the identifications of abbreviated components have the following meanings Sodium Alkylbenzenesulfonate linear C-) 2 TAS Sodium tallow alkyl sulfate CxyAS Sodium alkyl sulfate C- | X-C? C46SAS. Sodium alkylsulfate of secondary C ^ -C-j g (2.3) CxyEzS: Sodium alkylsulfate of C? x-C- | and condensed with z moles of ethylene oxide CxyEz. A predominantly linear C- | x-C? V primary alcohol condemned with an average of z moles of ethylene oxide. QAS 1: R2 + (CH3) 2tC2H4OH) with R2 = linear alkyl of Cg-C-j - | QAS 2: R2 N + (CH3) 2 (C2H4OH) with about 50% R2 = linear alkyl of CQ; about 50% of R2 = C-IQ QAS 3: R2.N + (CH3) 2 (C2H4OH) with about 40% of R2 = linear alkyl of C- | - about 60% of R2 = linear alkyl of Cg QAS 4: R2-N + (CH3) 2 (C2H4? H) with R2 = linear alkyl of CQ QAS 5: R2.N + (CH3) 2 (C2H4? H) with R2 = linear alkyl dß C-JQ Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils CFAA: N-methylglucamide from (coconut) C-12-C 4 alkyl TFAA: N- alkyl methylglucamide of C- | 6-C- | 8 TPKFA: Whole cut fatty acids of C-12-C14 STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na- | 2 (A1? 2Si? 2) l2-27H2? It has a ppmario particle size on the scale of 0.1 to 10 microns.

Zeolite MAP: Zeo ta MAP of hydrated sodium alummosilicate having a silicon to aluminum ratio of 1.07 microns. NaSKS-6: Stratified silicate not of the formula d-Na2Si2? 5 Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate 'Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0 ratio) Sodium sulphate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425μm and 850μm MA AA: 1: 4 copolymer of maleic acid / acrylic acid with an average molecular weight of about 70,000 AA: Pohacplato polymer of sodium with molecular weight average of 4,500 CMC: Sodium Carboxymethylcellulose Cellulose ether: Methylcellulose ether with a degree of capacity of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme of activity 3AU / g sold by Novo Industries ACE Cellulose Enzyme cellulite activity 1000CEVU / g sold by Novo Industries A S under the trade name Carezyme Amylase Activity amyolitic enzyme 120KNU / g sold by Novo Industries A / S under the trade name Termamyl 120T Lipase Activity lipophilic enzyme 100kLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa Enzyme endoglossase activity 3000CEVU / g sold by Novo Industries A / S PB4 Anhydrous sodium perborate tetrahydrate of nominal formula aB? 2 3H2? H2O2 PB1 Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2 H2O2 Percarbonate Percarbonate of sodium of nominal formula 2Na2C? 3 3H2O2 NOBS Nopanoyloxybencepsuifonate in the form of sodium salt TAED Tetraacetylethylenediamine Catalyst of Mn n'V2 (m-0) 3 (1, 4,7-tpmet? L-1, 4,7-tpazac? Clononane) 2 (PF6) 2, as US Pat. Nos. 5,246,621 and 5,244,594 DTPA Diethylene glycosylaminopentaacetic acid DTPMP D? et? lentr? ampentane (methalenphosphonate) marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach sulfonated zinc phthalocylamine encapsulated in soluble polymer dextppa Brightener 1 4,4'-b? s (2-sulfoest? pl) b? disodium Polisher 2 4,4'-b? S (4-an? L? No-6-morfol? No-1 3 5-tpaz? N-2-? L) am? No) est? Lben- 2.2'-d HEDP acidic disodium sulfonate 1, 1-H? Drox? Etand? Fosfón? Co EDDS Ethylendiamino-N N-disuccmico acid QEA b? S ((C2H5?) (C2H4? N) (CH3) -N + -C6H12-N + - (CH3) - b? s ((C2H5?) - (C2H4? n), where p = 20 to 30 PEGX Poethylene glycol with a molecular weight of x PEO Polyethylene oxide with a molecular weight of 50,000 TEPAE Ethoxylated tetraethylene pentaamine PVP Polyvinylpyrrolidone polymer PVNO N-oxide dß polyvinylpipdine PVPVI Copolymer of polyvinylpyrrolidone and vimlimidazole SRP 1 Esters of ends blocked with sulfobenzoil with skeleton of oxyethyleneoxy and terephthaloyl SRP 2 Polymer of short block of pol? (1, 2-prop? lene-terephthalate) diethoxylated Silicon Antifoam Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10 to 100 1 Wax. Paraffin wax In the following examples, all levels are cited as% by weight of the composition EXAMPLE 1 The following laundry detergent compositions A to F of particular utility under European automatic washing conditions are examples of the present invention EXAMPLE 2 The following granular laundry detergent compositions G a I, of particular utility under European automatic washing conditions, are examples of the present invention: EXAMPLE 3 The following detergent formulations, of particular utility under washing conditions in European Aquia, are examples of the following invention.

EXAMPLE 4 The following detergent formulations are examples of the present invention Formulation N is particularly suitable for use under Japanese automatic washing conditions. Formulations O to S are particularly suitable for use under US automatic washing conditions.

EXAMPLE 5 The following granular detergent formulations are examples of the present invention. Formulations W and X are particularly suitable for use under US automatic washing conditions. And it is of particular utility under Japanese conditions of automatic washing.

EXAMPLE 6 The following granular detergent compositions of particular utility under European washing conditions are examples of the present invention EXAMPLE 7 The following detergent compositions are examples of the present invention.

And Z AA Blown powder | , Zeollta A 15.0 15.0 15.0 Sodium Sulfate 0.0 0.0 0.0 MA / AA 4.0 2.0 2.0 LAS 3.0 3.0 3.0 QAS2 1.0 - "QAS5 3.0 2.0 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 Clusters LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 QEA - 1.0 0.6 Catalyst Mn 0.03 - - Zeolite A 8.0, 8.0 8.0 Carbonate 8.0 | 8.0 4.0 Spray Perfume, 0.3 0.3 0.3 C25E3 2.0 - - C45E7 2.0 2.0 2.0 Dry additives > I 1 Citrate 5.0 - - Bicarbonate "3.0 - Carbonate 8.0 15.0 8.0 Percarbonate - 7.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 8.0 EDDS "2.0 - Polyethylene oxide of MW 5,000,000 - - 0.2 Beptonite clay - 10.0 Protease 1.0 3.3 3.3 Cellulase 0.6 0.6 - Lipasa 0.4 0.1 1.0 Amylase 0.6 0.6 - Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 EXAMPLE 8 The following detergent formulations are examples of the present invention.

EXAMPLE 9 The following bar laundry detergent compositions are examples of the present invention.

Claims (19)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: (a) a proteolytic enzyme; and a cationic surfactant of formula I: R 1 R 2 R 3 R 4 N + X "(I) wherein R 1 is a hydroxyalkyl group having not more than 6 carbon atoms, each of R 2 and R 3 is independently selected from C 1 alkyl or alkene, R4 is an alkyl or alkemyl of Cs-n; and X "is a counterion.

2. A detergent composition according to claim 1, characterized in that the cationic surfactant is present in an amount of 0.01% to 20% by weight of the composition.

3. A detergent composition according to claim 2, characterized in that the cationic surfactant is present in an amount of 0.05% to 5% by weight of the composition.

4. A detergent composition according to claim 1, characterized in that the weight ratio between the active proteolytic enzyme in the detergent composition and the cationic tepsioactive agent is from 1: 10000 to 5: 1.

5. A detergent composition in accordance with the claim 1, characterized in that in the cationic compound of formula I, R1 is -CH2CH OH or -CH2CH2CH2OH; R2 and R3 are each methyl; R4 is C6-11 alkyl.

6. - A detergent composition according to claim 5, characterized in that in the cationic compound of formula I, R4 is a linear alkyl group of C6-n.

7. A detergent composition according to claim 1, characterized in that it comprises mixtures of detergent compositions of formula I, wherein at least 10% by weight of the cationic surfactant has alkyl R4 or C5-9 alkepyl 8.- A detergent composition in accordance with the claim Wherein the cationic surfactant comprises a compound of formula I in which R 4 is a higher alkyl group having n carbon atoms, wherein n is from 8 to 11, and a compound of formula I in which R 4 is a lower alkyl group having (n-2) carbon atoms. 9. A detergent composition according to claim 8, characterized in that the cationic surfactant comprises from 5 to 95% by weight of a compound of formula I having a higher alkyl group, and from 5 to 95% of a compound of Formula I having a lower alkyl group. 10. A detergent composition according to claim 1, further characterized in that it comprises at least 0.5% by weight of anionic surfactant. 11. A detergent composition according to claim 10, characterized in that the anionic surfactant is selected from anionic surfactants having the formula II or III: R5O S 03"M + (II) R6 S 03"'* (III), in which R5 is a linear or branched alkyl portion having from 9 to 22 carbon atoms, R6 is C10-20 alkylbenzene, M +, M' + are each selected from metals alkaline, alkaline earth metals, alkanolamome and ammonium 12. A detergent composition according to claim 11, characterized in that the anionic surfactant comprises both an anionic surfactant of formula II, and an anionic surfactant of formula III in a ratio of weight of II: III from 15: 1 to 1: 2. 13.- A detergent composition according to claim 11, characterized in that the anionic surfactant II is a ppmario or secondary, linear or branched alkyl sulphate of C1ß-? s. , and in which the anionic surfactant III is a Cn-13 alkylbenzene sulphonate 14. A detergent composition according to claim 1, further characterized in that it comprises a non-active surfactant. nico selected from the group consisting of etoxiiatos alcohol, alkylphenol, fatty acid amides polihidroxíllco, alquilpollglucósidos and mixtures thereof. 15. A detergent composition according to claim 11, comprising: (a) from 0.25% to 3% by weight of up cationic surfactant of formula I: R1 R2 R3 R4 N + X "(I) in which R1 is an optionally substituted phenol or hydroxyalkyl group having not more than 6 carbon atoms, each of R2 and R3 is selected independently of C 1-4 alkyl or alkenyl; R 4 is an alkyl or alkenyl of Cß-n; and X "is a counterion, and (b) from 3% to 40% by weight of straight or branched chain alkyl sulfate, primary or secondary, as surfactant 11 (c) from 6% to 30% by weight of alkylbenzene sulfopate as surfactant III, and optionally, (D) from 0.5% to 20% by weight of a nonionic surfactant 16. A composition according to claim 1, characterized in that it is substantially free of bleach. detergent which is formed by combining a proteolytic enzyme and cationic surfactant of formula I: R 1 R2 R 3 R 4 N + X "(I) wherein R 1 is an optionally substituted phenol or hydroxyalkyl group having not more than 6 carbon atoms; each R2 and R3 is independently selected from alkyl or alkenyl of R4 is an alkyl or alkenyl of C-5-11; and X "is a counter-ion, with one or more optional detergent components 1

8. A laundry washing method in a domestic washing machine, into which a dispensing device containing an effective amount of a detergent composition is introduced into the washing machine. solid according to claim 1 before starting the washing, wherein said dispensing device allows the progressive release of said detergent composition towards the washing solution during the washing operation 1

9. A detergent composition according to claim 1, in the shape of a gel, bar or tablet.