MXPA99003687A

MXPA99003687A - Detergent compositions

Info

Publication number: MXPA99003687A
Application number: MXPA/A/1999/003687A
Authority: MX
Inventors: Gibson Hall Robin; Wayne Heinzman Stephen; Gerard Gray Peter
Original assignee: The Procter&Ampgamble Company
Priority date: 1996-10-18
Filing date: 1999-04-19
Publication date: 1999-09-01

Abstract

The present invention relates to detergent compositions having a pH of at least 8.0 in a 0.5%by weight aqueous solution or components thereof containing 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 one or mixtures of more than one of C5-11 alkyl or alkenyl;and X- is a counterion which does not substantially exchange with a hydroxide ion at 20°C in a 0.5%by weight solution of the detergent composition.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to detergent compositions or to components thereof which contain a specific cationic surfactant to be used under alkaline washing conditions, which has a carefully selected counter-ion. The detergent compositions of the invention are to be used in any detergency field, including household cleaners, but are generally used in laundry and dishwashing processes to provide improved benefits of greasy stain removal and cleaning benefits.

BACKGROUND OF THE INVENTION The use of cationic surfactants in detergent compositions is known. For example, GB 2040990A discloses granular detergent compositions comprising cationic surfactants. EP-A-121949 discloses surfactants to be used in laundry detergent compositions. This reference describes a broad class of cationic surfactants.

Applicants have found that a particular group of cationic quaternary ammonium surfactants provide good cleaning properties, especially on greasy, oily stains. It has been found that cationic compounds are particularly beneficial in detergent compositions that additionally include anionic surfactants. Without being limited to the theory, the applicant believes that the particular surfactants used in the detergent compositions of the present invention surprisingly have good solubility. In addition, these are associated in the presence of anionic components to produce, surprisingly, anionic / cationic complexes which lead to unexpected performance benefits: the cationic surfactant is contacted quickly and effectively with the greasy spots and rapidly penetrating and breaking the stain providing effective removal of greasy stains. It is further believed that, after breaking the greasy dirt, the cationic surfactants used in the present invention also form complexes with the fatty acids and any other negatively charged product from the break, increasing their solubility and increasing the removal of oily dirt, oily and overall cleaning performance. However, it has been found that some surfactants can produce unpleasant odors during processing or use under alkaline detergent conditions in the wash solution. Without being limited by theory, applicants believe that odors arise as a result of the exchange of the counterion of the cationic surfactant with hydroxide ions in the aqueous alkaline wash solution. The resulting quaternary ammonium hydroxide product can then produce amine byproducts with unpleasant odors. To adequately avoid this problem during use in alkaline conditions, the particular cationic surfactants must have a counter ion having a higher relative selectivity towards the cationic surfactant than that of the hydroxide ion in aqueous solution under the conditions of use. All documents cited in the present description are incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention there is provided a detergent composition having a pH of at least 8.0 in an aqueous solution at a concentration of 0.5% by weight, or a component thereof, including a cationic surfactant of formula I: R1R2R3R4N + X "(I) wherein R is a hydroxyalkyl group having not more than 6 carbon atoms, each of R and is independently selected from alkyl or alkenyl of C] __ 4, - R4 is an alkyl or alkenyl of C5_ ] _? _ and X- is a counterion which is not substantially exchanged with a hydroxide ion in an aqueous solution at 0.5% by weight of the detergent composition at 20 ° C. In a further aspect of the invention, the surfactant cationic includes a mixture of cationic surfactants of formula I: R1R2R3R4N + X "(I) wherein R is a hydroxyalkyl group having not more than 6 carbon atoms; each of R and R is independently selected from alkyl or alkenyl of C] __ 4; R4 is an alkyl or alkenyl of C5_11 and X "is a counterion which is not substantially exchanged with a hydroxide ion in an aqueous solution at 0.5% by weight of the detergent composition at 20 ° C and where, in the agent mixture cationic surfactants of formula I, at least 10%, preferably at least 20% or even at least 50% by weight of the cationic surfactant whose R4 is C5..9 alkyl or alkenyl In accordance with a further aspect of the invention, the cationic surfactant includes a mixture of surfactants of formula I wherein there is a longer alkyl chain surfactant having R with n carbon atoms in which n is from 8 to 11 and a shorter alkyl chain surfactant having (n-2) carbon atoms Unless otherwise mentioned, alkyl or alkenyl as used herein can be branched, linear or substituted The substituents can be, for example, aromatic groups s, heterocyclic groups containing one or more N, S or 0 atoms, or halogen substituents. Appropriate counterions are generally counterions that are more electronegative than hydroxide ions.

DETAILED DESCRIPTION OF THE INVENTION Cationic Surfactant The cationic surfactant is generally present in the composition or component thereof in an amount of not more than 60% by weight, preferably not more than 10% by weight, most preferably in an amount of not more than 4.5% by weight. even 3% by weight. The maximum amount of cationic surfactant can even be as low as 1% by weight. The benefits of the invention are found even with very small amounts of the cationic surfactant of the formula I. In general, 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. In formula I, R1 is a hydroxyalkyl group having 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 (CH3) CH2OH. More preferred are the groups -CH2CH2OH and -CH2CH CH2OH, and -CH2CH2OH is particularly preferred. Preferably, R2 and R are each selected from ethyl and methyl groups, and most preferably both R and R3 are methyl groups. The R groups that are preferred have at least 6, or even at least 7, carbon atoms. R4 could have no more than 9 carbon atoms or even no more than 8 or 7 carbon atoms. R can be C5..9 or Cu The R groups that are preferred are linear alkyl groups. Linear R groups having from 8 to 11 carbon atoms, or from 7 to 9 carbon atoms are preferred. The counter ion X in formula I can be any counterion that is not substantially exchanged with the hydroxide ion in aqueous solution at 0.5% by weight of the detergent composition at 20 ° C, so as to substantially prevent the formation of malodorous compounds. . An appropriate method for determining whether the counterion is substantially or not exchanged with the hydroxide ion is described in J. Phis. Chem. 1986, 90.3366-3368 -Use of Reactive Counterion Type Micelles for the Determination of Selectivity Coefficients • by Maria da Graca Nascimento, Sebastiao A.F Miranda and Faruk Nome. Preferred counterions to be used in the present invention have a selectivity coefficient for ion exchange in the presence of the hexadecyl-trimethyl ammonium ion at 25 ° C, of at least 2.5, preferably at least 3 or even at least 3.5 (See Table I in the aforementioned reference). Generally the appropriate counterions have an electronegativity greater than that of the hydroxide ions. The preferred examples are chloride ions, bromide and nitrate, and of these the chloride ion is particularly preferred. Although pure or substantially pure cationic compounds are within the scope of this invention, it has been found that mixtures of cationic surfactants of the formula I can be particularly effective, for example, mixtures of surfactants in which R can be a combination of linear alkyl groups of Cg and IQ, O alkyl groups of C9 and C ^. According to one aspect of the invention, a mixture of cationic surfactants of the formula I is present in the composition, and the mixture is composed of a shorter alkyl chain surfactant of the formula I and a surfactant of longer alkyl chain of formula I. The longer alkyl chain cationic surfactant is preferably selected from the surfactants of formula I wherein R 4 is an alkyl group having n carbon atoms where n is from 8 to 11; the shorter alkyl chain surfactant is preferably selected from those of formula I wherein R is an alkyl group having (n-2) carbon atoms. In mixed cationic surfactant systems, there will generally be from 5 to 95% by weight of longer alkyl chain surfactants, preferably from 30 to 95%, and most preferably at least 50% by weight based on the cationic surfactant total. In general, there will be from 5 to 95% by weight, of shorter alkyl chain surfactant, preferably from 5 to 70% by weight, more preferably 35 to 65% by weight. Preferably there will be at least 40% by weight of the shorter alkyl chain surfactant based on the total cationic surfactant in the detergent composition or components thereof.

Additional detergent components The detergent compositions or components thereof according to the present 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 or component thereof, and on the precise nature of the washing operation for which it will be used.

The compositions or components thereof of the invention preferably contain one or more additional detergent components selected from additional surfactants, builders, sequestrants, bleaches, bleach precursors, bleach catalysts, organic polymer compounds, additional enzymes, suds suppressors. , lime soap dispersants, additional suspension and antiredeposition agents for soils, perfumes and corrosion inhibitors.

Additional Surfactant The detergent compositions or components thereof according to the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical list of anionic, non-ionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the US patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981.

When present, the ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant In a particularly preferred embodiment of the invention, the detergent compositions additionally include an anionic surfactant. Any anionic surfactant useful for detersive purposes is appropriate. These may include salts (including, for example, the sodium, potassium, ammonium and substituted ammonium salts such as the mono-, di- and triethanolamine salts) of the sulfate, sulfonate, carboxylate and sarcosinate surfactants. Sulfate-based surfactants are preferred. Other suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially monoesters of saturated and unsaturated CI2 ~ T_Q) sulfosuccinate diesters (especially saturated and unsaturated C5-C1 diesters), N-acyl sarcosinates. 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 or obtained from tallow oil.

Sulphonic Anion Surfactant The anionic sulfate surfactants suitable for use in the compositions of the invention include the alkyl sulfates, alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, acyl giucamin sulfates of C5-C17-N- (alkyl) of C1-C4) and -N- (hydroxyalkyl of CTL-C2), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds are described herein). The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C9-C22 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 1 -C 8 alkyl sulfate, preferably of C 11 -C 15, which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT patent application No. WO 93/18124.

Sulfonate Anionic Surfactant The sulfonic anionic surfactants suitable for use herein include the linear alkylbenzene sulphonate salts of c5_c20 'alkyl ether sulfonates, primary or secondary Cg-C22 alkan sulfonates, c6_ olefinsulfonates, < - 24 'sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof. Particularly preferred compositions of the present invention further comprise an anionic surfactant, selected from alkyl sulfate and / or alkylbenzenesulfonate surfactants of formula II and III, respectively: R5 OR S03 ~ M + (II) R6SO3"M '+ (III) wherein R is a linear or branched alkyl or alkenyl portion having from 9 to 22 carbon atoms, preferably C 1 to 2 alkyl or as found in the secondary alkyl sulfates; R ° is 10-C15 alkylbenzene, preferably C11-C13 alkylbenzene; M + and M + can vary independently and are selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium.

Particularly preferred compositions of the invention include an alkyl sulfate surfactant and an alkylbenzene surfactant, preferably in ratios II to III from 15: 1 to 1: 2, more preferably from 12: 1 to 2: 1. The amounts of an anionic surfactant or mixtures of more than one anionic surfactant in the preferred compositions can be from 1% to 50%, however, preferably the anionic surfactant is present in amounts ranging from 5% to 40% by weight of the composition. The preferred amounts of the alkyl sulfate surfactant of the formula II are from 3% to 40%, or most preferably from 6% to 30% by weight of the detergent composition. The preferred amounts of the alkylbenzenesulfonate surfactant of the 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 performance benefits that result when an anionic surfactant is also used in the compositions of the invention are particularly useful for longer carbon chain length anionic surfactants such as those having a carbon chain length of C] _2 or greater, particularly of C14 / 15 or even up to carbon chain lengths of C ^ Q - Q. In preferred embodiments of the detergent compositions of the invention comprising an anionic surfactant there will be a significant excess of anionic surfactants, preferably an anionic to cationic surfactant weight ratio of 50: 1 to 2: 1, most preferably 30: 1 to 8: 1. However, the benefits of the invention are also achieved when the ratio of cationic surfactant to anionic surfactant is substantially stoichiometric, for example from 3: 2 to 4: 3. In a preferred embodiment of the invention, the cationic surfactant of the essential formula I is intimately mixed with some or all of the anionic surfactants before the addition of the other components of the detergent composition to provide an easily soluble anionic / cationic complex. It may be useful to intimately mix substantially stoichiometric amounts of anionic and cationic surfactant prior to the addition of any other detergent components, including any additional anionic surfactant.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps such as those described herein. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00"M + where R is an alkyl group from Cg to C] _g, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis , the amount of material 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 an alkyl group from Cg to Cig, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof Suitable soap surfactants include secondary soap surfactants containing a carboxyl unit connected to a carb The secondary soap surfactants preferred for use herein are the water soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid , 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CONIR1) CH2COOM, wherein R is a straight or branched C5_C17 alkyl or alkenyl group, R1 is a C1-6 alkyl group C4 and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Linear or branched alkoxylated groups are suitable. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

Nonionic surfactant of alkoxylated alcohol 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 may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONR Z, wherein: R is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably lower alkyl, most preferably lower alkyl or C2, more preferably lower alkyl] (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, most preferably straight-chain C9-C17 alkyl or alkenyl, more preferably straight-chain C ±±-C yy alkyl or alkenyl or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Non-ionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: RdCON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 atoms of carbon and each R7 is selected from the group consisting of hydrogen, C ^ -C4 alkyl, hydroxyC1-4 alkyl, and - (C2H4?) xH, where x is on the scale of 1 to 3.

Alkylpolysaccharide Nonionic Surfactant The suitable alkylpolysaccharides which are used herein are described in the US patent. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 1.3 to 10. saccharide units. Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (glucosyl) 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 atoms of carbon; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 as carbon; R is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of Cl? -A8 and the acylamidoalkyldimethylamine oxide of C? O ~ C] _g. A suitable example of an alkylalanodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- where R is a Cg-C hydrocarbyl] _8 group, each R is typically C ^ -C3 alkyl, and R is a group C1-C5 hydrocarbyl. The preferred betaines are the betaines of dimethyl ammonium hexanoate of c12_c18 and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C] _Q-CI8. Also suitable for use herein are complex betaine surfactants.

Additional Cationic Surfactants Preferably, the compositions of the invention are substantially free of quaternary ammonium compounds of the formula I, but wherein one or R, R, R or R4 is a longer alkyl chain group of Cu-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 than 0.01% by weight of compounds of the formula I having a linear (or even branched) alkyl group have 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 (i.e., -C00-) linkage and at least one cationically charged group. Preferred cationic ester surfactants are water dispersible. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. 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 any nitrogen or oxygen atom in said chain connect only with the atoms of carbon in the chain. In this way, groups that have, for example, links -0-0- (ie, peroxide), -NN- and -N-0-, are excluded, while the separating groups are included, which have, for example, links -CH2-0-CH2- and -CH2-NH-CH2. In a preferred aspect, the chain of the spacer group only comprises carbon atoms, most preferably the chain is a hydrocarbyl chain.

Alkalinity In the detergent compositions of the present invention an alkalinity system is present for supplying a detergent composition having a pH of at least 8.0 or at least 8.5 at a concentration of 0.5% by weight of the detergent composition in aqueous solution. The composition can be more closely alkaline and can have a pH of at least 9.0 or even 9.5 or 10.0 in a 0.5% by weight aqueous solution. The alkalinity system includes components capable of providing alkalinity species in solution. Examples of alkalinity species include carbonate, bicarbonate, hydroxide, different silicate anions, percarbonate, perborates, perfosfatos, persulfato and persilicato. Said alkalinity species may be formed, for example, when the alkali salts selected from carbonate, bicarbonate, hydroxide or alkali metal or alkaline earth metal silicate salts, including crystalline layered silicate and mixtures thereof are dissolved in water. Examples of carbonates are alkaline earth metal and alkali metal carbonates, including carbonate and sodium sesquicarbonate and any mixtures thereof with ultra fine calcium carbonate such as those described in German Patent Application No. 2,321,001, published on November 15, 1973. Suitable silicates include the soluble sodium silicates with a Si02: Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and a ratio of 2.0 being more preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with a ratio of Si02: Na2? 2.0 is the most preferred silicate. The preferred crystalline layered silicates for use herein have the general formula: NaMSix02x +? 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 layered sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, is preferably 2. The most preferred material is Na2Si20-5, available from Hoechst AG as NaSKS-6.

Water-soluble detergent-enhancing compound 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 10% to 70% by weight , more preferably from 20% to 60% by weight of the composition. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more than two carbon atoms, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates described in the Dutch application, 7205873 and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829, 1, 1, 2, 2-etanttracarboxylates, 1, 1, 3, 3-propanetracarboxylates and the 1,1,2,3-propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. The parent acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, eg, mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or wash conditions are water soluble builders useful herein. Suitable examples of phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from about 6 to 21, and the salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions or components thereof, 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% by weight. % to 70% by weight, most preferably from 20% to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(A102) z (Si0) y] 'xH20 where z and y are integers of at least 6; the molar ratio of zay 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 aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%. %, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but preferably are derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na12 [(A102) 12 (Si02) 12- * xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(A102) 86 (Si02) 106] "276H20 Another aluminosilicate zeolite which is preferred is the zeolite MAP builders The zeolite MAP can be present at a level of 1% to 80%, most preferably 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 silicone to aluminum ratio of not more than 1.33, preferably in the range of 0.9 to 1.33 and most preferably in the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicone to aluminum ratio of no more than 1.15, most particularly no more than 1.07. In a preferred aspect, the zeolite MAP builders have a particle size, expressed as a dc value, Q of 1.0 to 10.0 microns, most preferably 2.0 to 7.0 microns, more preferably 2.5 to 5.0 microns. The dsg value indicates that 50% by weight of the particles have a diameter smaller than that number. The particle size can be determined in particular by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods to establish the d5Q values are described 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 heavy metal ion sequestrant here is meant components that act to sequester (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably show selectivity to bind 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 0.1% to 10%, most preferably 0.25% to 7.5% and more preferably 0.5% to 5% by weight of the compositions .

Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpent (methylenephosphonate), ethylenediaminetri- (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1 diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylene diamine disuccinic acid, ethylene diamine diglutharic acid, 2-hydroxypropylenediamine diuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts 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 glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1,2,4-tricarboxylic acid. The glycinamide-N-N1-disuccinic acid (GADS), ethylenediamine-N-N'-diglutharic acid (EDDG) and 2-hydroxypropylenediamine-N-N1-disuccinic acid (HPDDS) are also suitable.

Organic peroxyacid blanching system A preferred feature of the detergent compositions or components thereof according to the invention is an organic peroxyacid bleaching system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrated bleaches. In an alternative preferred embodiment, a preformed organic peroxyacid is incorporated directly into the composition. Also disclosed are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the alkali metal form, preferably sodium salt at a level of 1% to 40% by weight, most preferably 2% to 30% by weight and more preferably 5% to 25% by weight of The compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material, which provides better storage stability for the perhydrate salt in the granulated product and / or delayed release of the perhydrate salt. when putting the granulated product in contact with the water. 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 NaB02H20 or the tetrahydrate NaB02H202.3H20. 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 2 a2CO3.3H202 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 peroxyacid bleach precursors can generally be represented as: wherein L is a leaving group and X is essentially any functionality, such that in perhydrolysis, the structure of the produced peroxyacid is: O II XC-OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, most preferably from 1.0% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups; whose predecessors can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Residual groups The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: Y R 3 Y I I -0-CH = C-CH = CH 2 -O-CH = C-CH = CH and mixtures thereof, wherein R is an alkyl, aryl or alkaryl 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, R is an alkenyl chain containing 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R, R3 and R can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilizing groups are -S? 3 ~ M +, C02 ~ M +, -S04"M +, -N + (R3) 4X" and 0 <-N (R3) and most preferably -S? 3 ~ M + and -C02 ~ +, where R is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Precursors of bleaching of albuterolcarboxylic acid The alkylcarboxylic acid bleach precursors form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylpercarboxylic type precursor compounds include the N-, N, N-N ^ tetraacetylated alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 to 2 carbon atoms. and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of allylperoxy substituted with amide Preferred peroxyacid precursors are the amide substituted alkylperoxy acid precursor compounds, including those having the following general formulas: R 1 CN R 2 CL R 1 NC R 2 CLO R 5 0 R 5 OO wherein R is a group alkyl having from 1 to 14 carbon atoms, R is an alkylene group, containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl group, containing 1 to 10 carbon atoms and L can be essentially any residual group. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, the cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. 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 so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,751,015; 4,988,451; 4,397,757; ,269,962; ' 5,127,852; 5,093,022; 5,106,528; R.U. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in United Kingdom patent application No. 9407944.9 and in US patent applications. Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482, 807, particularly those having the formula: wherein R] _ is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, very preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R 1 C N R 2 C OOH R 1 N C R 2 C OOH II l 5 II OR II II OROROO in which R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R ^ is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and Rb is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds 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. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Bleach catalyst The compositions of the invention 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 manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity , such as zinc or aluminum cations and a sequestrant having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the U.S. patent. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S. patent. No. 5,246,621 and in the U.S. patent. No. 5,244,594. Preferred examples of these catalysts include Mn (u_ °) 3 (1/4, 7-trimethyl-1,4,7-triazacyclononane) 2- (PFg) 2, MnIi 2 (u-0)] _ (u-OAc) 2 (1,4, 7-trimethyl-1,4-, 7-triazacyclononane) ~ (CIO4) 2, MnIV4 (uO) g (1, 4, 7-triazacyclononane) 4- (C104) 2 / Mn -'- jjMn1 ^ (u-0) (u-OAc) 2 (1, 4, 7-trimethyl-1,4-, 7-triazacyclononane) 2- (CIO 4) 3 and mixtures thereof. Othare described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1, 5, 9-trimethyl-1, 5, 9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1 , 2,4,7-tetramethyl-l, 4,7-triazacyclononane and mixtures thereof. For examples of suitable bleach catalysts see the US patent. No. 4,246,612 and in the U.S. patent. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 _ (PFg). Yet another type of bleaching catalyst such as that described in the U.S.A. No. 5,114,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-toothed and bi-N-toothed ligands, including N4Mnip (uO) 2MnIVN4) + and [Bipy2MnII: i: (u-0) 2MnIVbipy2] - (C104) 3. Bleaching catalysts Suitable and additional are described, for example, in European Patent Application No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), E.U. 4,728,455 (manganese / multidentate ligand catalyst), E.U. 4,711,748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U. 4,626,373 (manganese / ligand catalyst), E.U. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U. 4,728,455 (manganese gluconate catalysts).

Additional Enzymes The compositions of the present invention may comprise one or more additional enzymes. Additional enzyme materials that are preferred include commercially available enzymes. Said enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, puiulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes in a detergent composition of the present invention comprises a mixture of conventional applicable enzymes such as lipase, protease, amylase, cutinase and / or cellulase, in conjunction with one or more plant cell wall degrading enzymes. . Suitable enzymes are also described in the US patents. Nos. 3,519,570 and 3,533,139.

Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a strain of Bacillus, which has a maximum activity along the pH scale of 8-12, developed and sold as ESPERASE by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASER, DURAZYMR and SAVINASER from Novo and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (manipulated protein Maxacal) from Gist-Brocades. The proteolytic enzymes also include modified bacterial serine 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 which is called here "Protease B", and in European patent application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" here. The one that is suitable here is called "Protease C", which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine in position 123 and alanine replace threonine at position 274. Protease C is described in EP 90915958: 4, which corresponds to WO 91/06637, published May 16, 1991. Also included are genetically modified variants, particularly of protease C. A preferred protease called "Protease D" is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, and which is derived from a precursor carbonyl hydrolase by substituting a different amino acid by a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more positions of amino acid 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 numbering of the subtilisin of Bacillus amyloliquefaciens, as described in WO95 / 10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes", which has the EU serial number 08 / 322,677, filed October 13, 1994. Proteases described in patent applications EP 251 446 and WO 91/06637, BLAPR protease described in WO91 / 02792 and their variants described in WO 95 are also suitable for the present invention. / 23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other different enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & amp;; Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever. One or a mixture of proteolytic enzymes may be incorporated into the detergent compositions of the present invention, generally at a level of from 0.0001% to 2% preferably from 0.001% to 0.2%, most preferably from 0.005% to 0.1% pure enzyme by weight of the composition. If present in the detergent compositions of the present invention, the lipolytic enzyme component is generally present at levels of 0.00005% to 2% active enzyme by weight of the detergent composition, preferably from 0.001% to 1%, most preferably 0.0002 % to 0.05% by weight of active enzyme in the detergent 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 immunological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas Hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P " Amano, "henceforth called" Amano-P ". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co. , Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands and the lipases ex Pseudomonas gladioli. Particularly suitable lipases are lipases such as MI Lipase and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra (Novo) which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which 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 lipase which 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 it is tried to say the lipase variant as described in the patent application WO 92/05249, in which the native lipase ex Humicola lanuginosa has the residue of aspartic acid (D) in position 96 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 enzyme D96L, the normal LU test (analytical method, internal number of .Novo Nordisk AF 95/6-GB 1991.02.07) can be used. A substrate for D96L was prepared by emulsifying glycerin tributyrate (Merck) and using gum arabic as an emulsifier. The activity of the lipase is tested at pH 7 using the static pH method. The detergent compositions of the invention may also contain one, or a mixture of more than one amylase enzyme (Á and / or β). WO94 / 02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both Á and β amylases. The α-amylases are known in the art and include those described in the U.S. patent. Do not. ,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 stability-enhanced amylases described in W094 / 18314, published 18 August 1994 and WO96 / 05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk a / S, disclosed in WO 95/10603, published 25 April 1995. also suitable are amylases described in EP 277 216, W095 / 26397 and W096 / 23873 (all by Novo Nordisk). Examples of commercial α-amylase products are Purafect Ox Am from Genencor and Termamyl, Ban, Fungamyl and Duramyl, all available from Novo Nordisk A / S, Denmark. W095 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl at a temperature range of 25 ° C to 55 ° C and a pH value in scale from 8 to 10, measured by the Phadebas A-amylase activity test. The variants of the above enzymes, described in W096 / 23873 (Novo Nordisk), are suitable. Other preferred amylolytic enzymes with improved properties with respect to the level of activity 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. The detergent compositions of the invention may also incorporate 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, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also described 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 the cellulases originated from Humicola insolens which have a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and which contain 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 lonqibrachiatum 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. Peroxidase enzymes can also be incorporated into the detergent compositions of the invention. Peroxidases are used in combination with oxygen sources, eg. , percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidases, ligninase peroxidase and halogen peroxidases, such as chlorine and bromoperoxidases. Peroxidase-containing detergent compositions are described, for example, in International Patent Application WO 98/099813, WO89 / 09813 and European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996. The laccase enzyme is also suitable. Preferred builders are substituted fentiazine and fenoxazine 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenothiazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and the substituted syringates (substituted C3-C5 alkylsalicylates) and phenols. Percarbonate or sodium perborate are the preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases, if present, are normally incorporated in the detergent composition at levels of 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 of 0.0001% to 2% active enzyme by weight of the detergent composition. Additional enzymes can be added as separate individual ingredients (pellets, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more systems (eg, cogranulates).

Enzyme oxidation scavengers Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers described in co-pending European patent application 92870018.6, filed on January 31, 1992. Examples of such enzyme oxidation scavengers are tetraethylene polyamines ethoxylated Enzyme materials A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 A to Novo, and E.U. 3,553,139, January 5, 1971 to McCarty and others. Enzymes are also described in E.U. 4,101,457, Place et al., July 18, 1978 and in E.U. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in E.U. 4,261,868, Hora et al., April 14, 1981. Enzymes to be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in E.U. 3,600,319, August 17, 1991, Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U. 3,519,570. A Bacillus, sp.

AC13 useful and which gives proteases, xylanases and cellulases is described in WO 9401532 A to 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 such as to bind the particulate component each. By "organic polymeric compound" is meant essentially any polymeric organic compound that is not an oligoester or polyamine soil release polymer, and which are commonly used as dispersants and anti-redeposition agents and suspension of soils in detergent compositions , including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein. The 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. Polymers of the latter type are described in GB-A-1, 596, 756. Examples of such salts are polyacrylic acid or polyacrylates of molecular weight 1000-5000 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. The polyamino compounds useful herein include those derivatives of aspartic acid including polyaspartic acid and those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable herein 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, preferably from 3,000 to 10,000 for incorporation into the compositions of the present invention. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose 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 removal / anti-redeposition compounds of dirt The detergent composition or components thereof according to the invention may comprise water-soluble ethoxylated cationic amine compounds with removal / anti-redeposition properties of particulate / 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 H, C1-C4 alkyl or hydroxyalkyl ester or alkyl 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 triamines, 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 machine wash compositions, preferably comprise 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 may comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds.

By "antifoaming compound" is meant any compound or mixtures of compounds which act to depress the foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred antifoam compounds for use herein are the silicone anti-foam compounds defined herein as any antifoam compound that includes a silicone component. Said silicone anti-foam 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 antifoam silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the U.S. patent. No. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof for use as foam 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 (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci8 ~ C ^ Q ketones (e.g. stearone), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminchlorotriazines 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 alkali metal di-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 (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a silicone glycol copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, at a level of 0.5% 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 compound, most preferably comprising an ethoxylated C alcohol gC ^ g alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% at 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein 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.

Polymeric Dye Transfer Inhibitory Agents The detergent compositions herein may additionally comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. Polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, wherein 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: P (I) Ax R where P is a polymerizable unit, and A is -; x is 0 or 1; R1 is H or linear or branched C? _g alkyl; or it can form a heterocyclic group with R; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the group N-0 may be attached or in which the nitrogen of the group N-0 is part of these groups. The group N-0 can be represented by the following general structures:, OR A. I (R?) X-N- (R2) and A (R3) z or == M- (R1) ?} wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xy / oy / yz is o or 1 and wherein the nitrogen of the N-0 group may be fixed or wherein the nitrogen The group is NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric base structure or to a combination of both. Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the functional group is NOT part of said group R Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the 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-vinylpyrrolidone and N-vinylimidazole The copolymers of N-vinylimidazole and N-vinylpyrrolidone suitable in the present invention have an average molecular weight scale of 5,000 to 100,000 or 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight from 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (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 polyvinyl pyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions herein can also use polyvinyloxazolidones as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein 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 4,4 '-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2 '-stilbenedisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula Rj_ is anilino, R 2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2 '-stilbenedisulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R ^ is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4 '-bis [(4-anilino-6-morphino-s-triazin -2-yl) amino] 2,2 '-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Polymeric dirt-releasing agent Polymeric soil-releasing agents known, hereinafter "SRA", can optionally be used in the present detergent compositions. If used, the SRAs will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the compositions. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered to them through the completion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through uan, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and sulfonated terminal portions derived from allyl covalently bonded to the base structure, for example, as described in the US patent 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include polyesters of 1,2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by the transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, PEG Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others, the latter being a typical SRA's useful in both fabric conditioning and laundry products with one example being an ester composition made from the monosodium salt of the acid m-sulfobenzoic, PG and DMT, optionally but preferably further comprising added PG, e.g. , PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see U.S. Pat. No. 3,959,230 to Hays of May 25, 1976 and the US patent. No. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such as the cellulosic hydroxyether polymers available as METHOCEL from Dow; the alkylcelluloses of A-C4 and hydroxyalkylcellulas of C4 of the patent of E.U.A. No. 4,000,093, from December 28, 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 a 2% aqueous solution. 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 diisocyanate coupling agents to link 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 trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl 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 esterified, see E.U. No. 4,525,524 Tung and others. Other classes include (III) non-anionic terephthalate-based SRAs of the urethane-linked variety, see E.U. 4,201,824, Violland et al .; Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with a preferred filler salt being sodium sulfate.

Form of the compositions The compositions according to the invention can have a variety of physical forms including the 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 can also be used in or in combination with bleaching additive compositions, for example comprising chlorine bleach. In one 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% 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 sieving a sample of the composition in a number of fractions • (typically 5 fractions) in a series of sieves, preferably Tyler sieves. The fractions of weight thus obtained are plotted against the opening size of the sieves. The average particle size is considered 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. The bulk density of the granular detergent compositions according to the present invention is typically a bulk density of at least 400, preferably 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve at its lower end to allow the contents of the funnel to be emptied into a cup axially aligned cylindrical arranged 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, v.gr. , 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 bulk density in g / liter. Repeated 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 to be used in dishwashing processes are manufactured using a normal rotary clack press and using compression forces of 5 to 13 KN / cm, 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 lOg 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 can be supplied, for example, from the assortment box of a washing machine or it can be sprinkled on the dirty laundry placed on the machine. In one aspect of use, a delivery device is employed in the washing method. The delivery device is loaded with the detergent product and used to introduce the product directly into the drum of the washing machine before starting the washing 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. The delivery device containing the detergent product is placed inside the drum before the start of the washing cycle, before, 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 it rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation when the drum is rotated 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. Alternatively, the device may be made of a material that is liquid permeable but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the washing machine drum at this stage of the wash 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 pouch 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 orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the wetted and undissolved product, this arrangement typically comprising radial walls extending from a protrusion 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 published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water provided with an edge seal or closure designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water-curable closure comprises a soluble adhesive in water disposed along and sealing an edge of a sack 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 articles 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 the automatic dishwashing according to the invention. For an effective amount of the composition for the automatic dishwashing, it is tried to say of 8g to Og of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are product doses and volumes of solution of typical washing and commonly used in conventional automatic dishwashing methods.

Packaging for the compositions Commercially sold executions of the bleaching compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastics and any suitable laminates. A preferred packaging modality is described in European application No. 94921505.7.

Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: Linear sodium alkylbenzenesulfonate of C] _2 TAS 1: Sodium alkyl sulfate CxyAS: Sodium alkylsulfate of C ^ -C ^ and C46SAS : Sodium alkylsulfate of i ^ -Ci? secondary (2.3) CxyEzS: Sodium alkylsulfate of C] _x-C] _ and condensed with z moles of ethylene oxide CxyEz: A primary alcohol of C] _x-C] _ and predominantly linear condensed with an average of z moles of oxide of ethylene QAS 1: R2.N + (CH3) 2 (C2H 0H) with R2 = linear alkyl of Cg-Cn QAS 2: R .N + (CH3) 2 (C2H ÜH) with about 50% of R2 = linear alkyl of Cg; about 50% of R2 = Ao QAS 3: R2 -N + (CH3) 2 (C2H4OH) with about 40% of R2 = linear alkyl of u; about 60% of R2 = linear alkyl of C9 QAS 4: R2.N + (CH3) 2 (C2H4OH) with R2 = linear alkyl of C6 QAS 5: R2.N + (CH3) 2 (C2H4OH) with R2 = linear alkyl of C14 Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils CFAA: N-methylglucamide of (coconut) C] _2 ~ C14 alkyl TFAA: C-Cs alkyl N-methylglucamide TPKFA: C12-C14 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Sodium aluminosilicate hydrate of the formula Na12 (A102Si02) 12 • 27H 0, which has a primary particle size in the range of 0.1 to 10 microns. Zeolite MAP: Zeolite MAP of hydrated sodium aluminosilicate having a silicon to aluminum ratio of 1.07 microns. NaSKS-6: Crystalline layered silicate of the formula S-Na2Si 05 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 distribution particle size between 400μm and 1200μm Silicate: Amorphous sodium silicate (ratio Si02: Na 0 = 2.0) Sodium sulfate 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 maleic acid / acrylic acid copolymer with an average molecular weight of approximately 70,000 AA: Sodium polyacrylate polymer with average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: methylcellulose ether with a degree of polymerization 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 A / S Cellulase: Activity cellulite enzyme lOOOCEVU / 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: Enzyme lipolytic activity lOOkLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa: Endoglunase enzyme activity 3000CEVU / g sold by Novo Industries A / S PB4: Sodium perborate anhydrous tetrahydrate of nominal formula NaB02.3H20. H202 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB0 .H202 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03 -3H202 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylene diamine Catalyst of Mn: MnIV2 (m-O) 3 (1, 4, 7-trimethyl-1,4,4-triazacyclononane) 2 (PF6) 2, as described in the US patents. Nos. 5,246,621 and 5,244,594.

DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer 1: 4, 4'-bis (2-sulphotrisyl) biphenyl disodium brightener Brightener2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilben-2: 2'-disulfonate disulfonate HEDP: 1, 1-hydroxydanediphosphonic acid EDDS: Ethylenediamine-N, N-disuccinic acid QEA: bis ((C2H50) (C2H4On) (CH3) -N + -CgH12-N + - (CH3) bis ((C2H50) - (C2H4On) , where n = from 20 to 30 PEGX: Polyethylene 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: Polyvinylpyridine N-oxide PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole SRP 1: Esters of sulfobenzoyl blocked ends with oxyethyleneoxy and terephthaloyl base structure SRP 2: Short block polymer of poly (1,2-propylene terephthalate) diethoxylate Silicon Anti-foams: 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: 1 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 European automatic washing conditions are examples of the present invention: EXAMPLE 4 The following detergent formulations are examples of the present invention. The 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: 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

NOVELTY OF THE INVENTION J CLAIMS 1. A detergent composition having a pH of at least 8.0 in an aqueous solution at a concentration of 0.5% by weight, or component thereof comprising a cationic surfactant of the formula I: R1R2R3R4N + X ~ (I ) Wherein R is a hydroxyalkyl group having no more than 6 carbon atoms; each of R 2 and R 3 J is independently selected from alkyl or alkenyl of G] __ 4; R4 is an alkyl or alkenyl of C5-.11 and X ~ is a counterion that is not * Substantially exchanges with the hydroxide ion in a 15 aqueous solution at 0.5% by weight of the detergent composition at 20 ° C. 2. - A detergent composition having a pH of at least 8.0 in an aqueous solution at a concentration of 0.5% by weight, or component thereof comprising a mixture of 20 cationic surfactants of the formula I: R 1 R 2 R 3 R 4 N + X "(I) wherein R 1 is a hydroxyalkyl group having no more than 6 carbon atoms, each of R and R 3 is independently selected from C 4 alkyl or alkenyl; R4 is a C5.11 alkyl or alkenyl and X "is a counterion that is not substantially exchanged with the hydroxide ion in an aqueous solution at 0.5% by weight of the detergent composition at 20 ° C, and further characterized in that in the mixture of cationic surfactants of the formula I, at least 10% by weight have R as an alkyl or alkenyl of C. 3. A detergent composition according to claim 1, characterized in that the counterion X ~ is selected from the group which consists of chloride, bromide and nitrate ions 4. A detergent composition according to claim 1, characterized in that the counterion X- is the chloride ion 5. A detergent composition according to claim 1, characterized in that the cationic surfactant is present in an amount of 0.01% up to 20% by weight of the composition 6.- A detergent composition according to claim 5, characterized in that the The cationic surfactant is present in an amount of 0.05% up to 5% by weight of the composition. 7. A detergent composition according to claim 1, characterized in that in the cationic compound of the formula I, R1 is -CH2CH2OH or -CH2CH2CH2OH; R2 and R3 are each methyl and R is Cg_n alkyl. 8. - A detergent composition according to claim 1, characterized in that in the cationic compound of the formula I, R4 is a group of Cg_g or Cu. 9. - A detergent composition according to claim 1, characterized in that in the cationic compound of the formula I, R4 is an alkyl or alkenyl group of C6_9. 10. A detergent composition according to claim 1, characterized in that it comprises a mixture of cationic surfactants which are compounds of the formula I which comprise a compound of the formula I, wherein R is a higher alkyl group having carbon atoms, wherein n is from 8 to 11 and a compound of formula I, wherein R is a lower alkyl group having (n-2) carbon atoms. 11. A detergent composition according to claim 10, characterized in that the cationic surfactant includes from 5 to 95% by weight of a compound of the formula I having a higher alkyl group and from 5 to 95% of a compound of Formula I having a lower alkyl group. 12. A detergent composition according to claim 1, further comprising an anionic surfactant selected from anionic surfactants having the formula II or III: R5 0S03"M + (II) R6S03" M '+ (III) characterized in that R5 is a linear or branched alkyl portion having from 9 to 22 carbon atoms; R6 is alkylbenzene of C Q_2O; M +, M + are each selected from alkali metals, ferrous alkali metals, alkanolammonium and ammonium. 13. - A detergent composition according to claim 12, characterized in that the anionic surfactant includes an anionic surfactant of the formula II and an anionic surfactant of the formula III in a weight ratio of II: III from 15: 1 to 1: 2. 14. A detergent composition according to claim 12, characterized in that the anionic surfactant II is a linear or branched alkyl sulphate of primary or secondary C3, and in which the anionic surfactant III is a C3 3 alkylbenzene sulphonate. A detergent composition according to claim 1, further comprising a nonionic surfactant selected from the group consisting of ethoxylated alcohols, ethoxylated alkylphenols, polyhydroxy fatty acid amides, alkyl polyglycosides and mixtures thereof. 16. A composition according to claim 12, comprising: (a) from 0.25% to 3% by weight of a cationic surfactant of the formula I: R1R2R3R4N + X "(I) wherein R is a phenol group or optionally substituted hydroxyalkyl having no more than 6 carbon atoms; each of R2 and R3 is independently selected from C3-4alkyl or alkenyl, - R4 is an alkyl or alkenyl of Cn and X- is a counterion; (b) from 3% to 40% by weight of a straight or branched chain primary or secondary alkyl sulfate such as surfactant II; (c) from 6% to 23% by weight of an alkylbenzene sulfonate as the surfactant III; and (d) from 0.5% to 20% by weight of a nonionic surfactant. 17. A detergent composition according to claim 1, which is substantially free of bleach. 18. - A detergent composition having a pH of at least 8.0 in an aqueous solution at a concentration of 0.5% by weight or component thereof, formed by combining a cationic surfactant of the formula I: RlR2R3R4N +? - (-, - ) wherein R1 is an optionally substituted phenol or optionally substituted hydroxyalkyl group having no more than 6 carbon atoms; each of and RJ3 is independently selected from C 1 alkyl or alkenyl; R4 is an alkyl or alkenyl of Cg_n and X ~ is a counterion that is not substantially exchanged with the hydroxide ion in an aqueous solution at 0.5% by weight of the detergent composition at 20 ° C, and an alkalinity system with one or more optional detergent components. 19. - A method of washing clothes in a domestic washing machine, in which a delivery device containing an effective amount of a solid detergent composition according to claim 1 is introduced into the washing machine before the start of washing, further characterized in that said delivery device allows the progressive release of said detergent composition in the wash solution during washing. - *