MXPA99003683A - Detergent compositions comprising a mixture of cationic, anionic and nonionic surfactants - Google Patents

Abstract

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

Description

DETERGENT COMPOSITIONS THAT COMPRISE A MIXTURE OF CATIONIC, ANIONIC, AND NON-IONIC SURGICAL SOCIOACTIVE AGENTS TECHNICAL FIELD The present invention relates to detergent compositions or components thereof which contain a cationic quaternary ammonium surfactant and an additional surfactant. The detergent compositions of the invention produce foam having relatively large volumes and relatively lower bubble sizes. The detergent compositions of the invention are generally for use in laundry and dishwashing processes to provide for the removal of increased oily dirt, benefits of care and good distribution.

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. Cationic surfactants are also described in combination with anionic surfactants in, for example, EP-AO 121 949. It has been found that surfactants cationics of the invention provide highly effective cleaning benefits, particularly in grease and greasy soils. Without intending to be limited by theory, the Applicant believes that the foregoing is because the particular cationic surfactants used in the detergent compositions of the present invention have surprisingly good solubility and form an association in the presence of anionic components to produce anionic complexes. surprisingly soluble cationics that lead to unexpected development benefits; The cationic surfactant rapidly penetrates the greasy stains to produce the increased rate of removal of greasy dirt. Furthermore, it is believed that the immediate dispersion of the greasy dirt of the cationic surfactants used in the present invention can also complex with the fatty acids and any other products produced from relatively charged dispersion, increasing their solubility and promoting their removal of fat, oily dirt and general cleaning development. The solubility properties of the cationic surfactant and the cationic / anionic complexes it forms are particularly beneficial when used in a solid detergent composition. It has been found that detergent compositions containing a particular class of cationic surfactants show improved distribution (by the tub of the washing machine or by a dose device inside the washing machine) and the dispersion through washing. The gelation problems that occur when using conventional detergent compositions, in particular those containing cationic surfactants, are reduced by the high and low density detergent compositions. An additional benefit of the cationic surfactants used in the detergent compositions of the invention is that they provide a benefit of care in terms of color care and fabric care. Delicate garments that are subjected to daily use and tend to repeat their washing are vulnerable to color fading and damage to the garment's fiber (error). It is known that the repeated abrasive action as the fabrics are wound on the sides of the tub of the washing machine during the washing cycle, causes damage to the fiber and fading of the color. The present invention provides a detergent composition that reduces the overall bubble size of the foam generated during the wash cycle. The reduced size of the bubble is accompanied by an increase in foam viscosity and residence time and a creaminess observed in the foam, as well as an increased ratio of wash liquor to bubble surface area. By using the detergent compositions of the invention, the viscose foam produced provides protection against the delicate garments that are wrapped in the sides of the tub of a washing machine during the wash cycle, reducing abrasion and reducing the damage to the fiber and to the color of the garment. Without intending to be limited by theory, the applicant believes that the greater stability of the foam is due to the ability of the cationic surfactant to pack well in the air / water interface. The foregoing is particularly considerable in the presence of anionic surfactants. All documents cited in the present disclosure are incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a detergent composition having good distribution / dissolution properties containing: (a) a cationic surfactant of the formula I: R 1 R 2 R 3 R 4 N + X "(I) wherein R is a hydroxyalkyl group having no more than 6 atoms of carbon, each of R and R is independently selected from the alkyl or alkenyl of -4, R is an alkyl or alkenyl of C5_j _] _ and X ~ is a counter ion, and b) an anionic and / or nonionic surfactant. invention relates in particular to solid detergent compositions, particularly a granular detergent composition having a density of 400 g / liter at 1200 g / liter. The present invention also provides a detergent composition or component thereof comprising (a) a cationic surfactant of the formula I: R 1 R 2 R 3 R 4 N + X "(I) wherein R is a hydroxyalkyl group having no more than 6 carbon atoms each of R and R is independently selected from the alkyl or alkenyl of C] __ 4, - R is an alkyl or alkenyl of 5 _] _] _ and X ~ is a counter ion, and b) an anionic and / or nonionic surfactant , the detergent composition providing a foam height of at least one 50 mm foam in a rotating test cylinder, unless otherwise specified, the alkyl or alkenyl, as used herein, may be branched, linear or substituted The substituents may be, for example, heterocyclic groups containing one or more N, S or O atoms, and halogenide substituents.

DETAILED DESCRIPTION OF THE INVENTION Rotary cylinder test The rotary cylinder foam test is carried out on a graduated glass cylinder that has a height of 50 cm and a diameter of 50 cm. Add 8 g of detergent composition to 250 cm 3 of deionized water in the cylinder at 20 ° C. Then a sample of 100% white cotton woven towel, 10 cm x 10 cm, is placed in the cylinder. A cap is placed on the cylinder, which is then rotated about the central axis for twenty minutes at a rotational speed of 15 rpm. Immediately after the rotation is completed, the height of the foam is measured. The height of the foam will be at least 50 cm, preferably at least 60 cm, most preferably at least 60 cm, more preferably at least 70 cm. Preferably after a residence time of two minutes, preferably at least 5 mm and most preferably at least 10 mm of foam remain.

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% and even 3% by weight. The benefits of the invention are found even with very small amounts of the agent 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 cationic surfactant in the detergent compositions of the invention. Preferably, R in formula I 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 R groups are -CH2CH2OH, CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH. The -CH CH2OH and -CH2CH2CH2OH groups are more preferred, and -CH2CH2OH is particularly preferred. Preferably, R and R are each selected from ethyl and methyl groups, and most preferably both R and are methyl groups. The R groups that are preferred have at least 6, or even at least 7, carbon atoms. R can not have more than 9 carbon atoms or even no more than 8 or 7 carbon atoms. Preferred R groups are linear alkyl groups. Linear R groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred. Preferably, each of R and R3 is selected from C] __ 4 alkyl and R is Cg alkyl or alkenyl]. Although pure or substantially pure cationic compounds are within the scope of this invention, it has been found that the mixtures of cationic surfactants of the formula I can be example, mixtures of particularly effective surfactants, in which R can be a combination of linear alkyl groups of C3 and C ^ Q, or alkyl groups of Cg 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 comprises a shorter alkyl chain surfactant of the formula I and a longer alkyl chain surfactant. of the formula I. The longer alkyl chain cationic surfactant is selected from the surfactants of the formula I wherein R is an alkyl group having n carbon atoms wherein n is from 8 to 10; the shorter alkyl chain surfactant is preferably selected from those of formula I wherein R is an alkyl group having (n-2) carbon atoms. Generally, said mixtures will comprise from 5 to 95% by weight and most preferably 50% by weight. Generally said mixtures will contain from 5 to 95% by weight of the shorter alkyl chain surfactant, preferably from 5 to 70% by weight, most preferably from 35 to 65% by weight and more preferably at least 40% by weight. X in formula I can be any counterion that provides electrical neutrality, but is preferably selected from the group consisting of halide, methylsulfate, sulfate and nitrate, being most preferably selected from methyl sulfate, chloride, bromide and iodide. Halide ions, especially chlorine, are the most they prefer The distribution and dissolution benefits of the invention are particularly useful in solid detergent compositions such as those having a bulk density of at least 400, preferably at least 600 g / liter, most preferably from 650 g / l to 1200 g / l. liter. The volume density is measured by a simple funnel and rate device consisting of a conical funnel rigidly molded into a base and provided with a hinge valve at its lower end to allow the contents of the funnel to be emptied into an axially cylindrical cup aligned 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 so that the lower extremity is 140 mm above the upper surface of the base. The cup has a general 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 the measurement, the funnel is filled with dust by emptying by hand, the flap valve is opened and the powder is allowed to fill the cup. The filled cup is removed from the frame and the excess powder is removed in the cup when passing through an implement per straight diado, ie; a knife, on its upper edge. The filled cup is then weighed and the value obtained for the weight of the powder is doubled to provide a volume density in g / liter. Replication measurements are made as required. In this way, the detergent compositions of the present invention may have relatively low density, for example, below 700 g / liter or at a below 650 or 600 g / liter. The detergent compositions of the invention may have a relatively high density of at least 700 g / liter. The detergent compositions of the invention additionally contain a nonionic and / or anionic surfactant. The amounts of anionic and / or nonionic surfactant in the detergent compositions of the invention are generally 5% by weight of the detergent composition at 60%. Preferably, the amount of anionic and / or nonionic surfactant will be from 7 to 55% and most preferably from 10 to 50% by weight of the detergent composition.

Anionic Surfactant In a particularly preferred embodiment of the invention, the detergent compositions comprise an anionic surfactant. Any anionic surfactant useful for detersive purposes is suitable. Such surfactants may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and trietalonamine salts) of the agents anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other suitable anionic surfactants include isethionate such as the acyl isethionates, N-acyltaurates, fatty acid amides of methyl tauride, alkylsuccinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ^ -C ^ g monoesters) and sulfosuccinate esters (especially saturated and unsaturated c6-c14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as resin, hydrogenated resin, and resin acids and hydrogenated resin acids present in or derived from tallow acid. The development 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. ° higher, particularly of C14 15 or even up to carbon chain lengths of C] _g_? G. In the 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, very roughly 30: 1 to 8: 1, or 20: 1 to 5: 1. However, the benefits of the invention are also achieved where 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 essential cationic agent of the formula is intimately mixed with one or more surfactants prior to 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 the substantially stoichiometric amounts of the anionic and cationic surfactants before the addition of any other detergent component, including any additional surfactant.

Sulphonic Anion Surfactant The additional sulfate anionic surfactants suitable for use in the compositions of the invention include the alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, the acyl glucaminesulfates of C5-C1-N- (alkyl). C1-C4) and -N- (C1-C2 hydroxyalkyl), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds are described herein). The alkylethylsulfate surfactants are they preferably select from the group consisting of the alkyl sulfates of C ^ Q-C ^ g which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is a C 1 -C 8 alkylsulfate most preferably of C 2 -C 4, 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 ethoxylate surfactants. Such mixtures have been described in PCT 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 C5-C22 alkylene sulphonates, Cg-C24 olefin sulphonates, 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 the formulas II and III, respectively: R5 0S03 ~ M + (II) R6S03 ~ M. '+ (III) wherein R is a linear or branched alkyl or alkenyl portion having from 9 to 22 carbon atoms, preferably C ^ 2 to C] _ß alkyl or it is found in secondary alkyl sulfates; R ° is alkylbenzene of 1 to 6, preferably alkylbenzene of 4C; M + and M + can vary independently and are selected from alkali metals, alkaline earths, alkanolammonium and ammonium. Particularly preferred compositions of the invention comprise both an alkyl sulfate surfactant and an alkylbenzene surfactant, preferably in weight ratios of II to III from 15: 1 to 1: 2, most preferably 12: 1 to 2: 1. The amounts of the one or mixtures of more than one surfactant in the preferred composition can be from 1% to 50%, but preferably, the anionic surfactant is present in amounts of 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. The preferred amounts of the alkylbenzene sulfonate surfactant are up to 23%, most preferably no more than 20%, more preferably up to 15% or even 10%.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH 0) XCH2C00 ~ M + wherein R is an alkyl group from Cg to IQ, 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 is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO- (CHR) _- CHR2-O) -R3 wherein R is an alkyl group from Cg to C; j_g, x is from 1 to 25, R] _ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. The agents Preferred secondary soap surfactants 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 acid -1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-C0N (R) CH2COOM, wherein R is a linear or branched C-5-C-17 alkyl or alkenyl group, R is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant Wherein the detergent compositions of the invention contain nonionic surfactant, the ratio of nonionic to cationic surfactant is generally from 1:10 to 10: 1, preferably from 1: 5 to 5: 1. Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. The preferred alkoxylated surfactants are can be selected from the non-ionic condensate classes of alkylphenols, non-ionic ethoxylated alcohols, ethoxylated / propoxylated non-ionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and non-ionic ethoxylated condensation products with propylene oxide / ethylene diamine adducts .

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 C1-C4 alkyl, very preferably C] _ or C2 alkyl, more preferably C] _ alkyl (i.e., 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 C2-C7 chain alkyl or alkenyl straight 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: RDC0N (R) wherein R is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms; carbon and each R is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and - (C 2 H 4) x H, wherein x is on the scale of 1 to 3.

Nonionic surfactant of algilpolysaccharide Suitable alkylpolysaccharides which are used herein are described in US Pat. No. 4,565,647, Filling, issued on January 21, 1986, they have a group hydrophobic containing from 6 to 30 carbon atoms, and a polysaccharide, e.g. , a polyglycoside, a hydrophilic group containing 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R20 (CnH2n0) t (glucosyl) x or wherein R 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.

Additional detergent components The detergent compositions or components thereof according to the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition or component thereof, and on the precise nature of the washing operation for which it will be used. The compositions or components thereof according to the invention preferably contain one or more additional detergent components selected from additional surfactants, sequestrants, bleaches, bleach precursors, bleach catalysts, organic polymer compounds, additional enzymes, suds suppressors, dispersants. of lime soap, suspension agents and of antiredeposition of additional dirt, 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.

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 group, acylamidopropyl and alkylphenyl or mixtures thereof, containing from 8 to 26 carbon atoms; R is an alkylene group 0 hydroxyalkylene containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing 1 to 3 carbon atoms, or a group of polyethylene oxide containing 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of IQ-C ^ SY "acylamidodimethylamine oxide of C] _g-C] _ 3. A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated 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 + R C00- where R is a hydrocarbyl group of Cg-C ^ g, each R1 is typically C ^ alkyl- C3, and R is a C1-C5 hydrocarbyl group. Preferred betaines are the betaines of dimethyl ammonium hexanoate of Ci2"Cl8 and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C? Or ~ Cl8- 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 formula I, but wherein one or R, R, R or R is a longer alkyl chain group of C ^. Preferably, the compositions 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 that has 12 or more carbon atoms. Another suitable group of cationic surfactants that can be used in the detergent compositions of the invention are the cationic ester surfactants. The cationic ester surfactant is a compound having surfactant properties and comprising at least one ester linkage (i.e., -COO-) and at least one cationically charged group. Preferred cationic ester surfactants are water dispersible. Cationic ester surfactants Suitable excipients, including choline ester surfactants, have been described, for example, in US Patents. Nos. 422,8042, 4239660 and 4260529. In the preferred cationic ester surfactants, the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (ie, with a chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms, and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain connects only with the atoms of carbon in the chain. In this way, groups that have, for example, links -0-0- (ie, peroxide), -NN- and -N-0- are excluded, but include the separating groups that have, for example, links -CH2-O-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 preferably a system of alkalinity to achieve optimum performance of the cationic ester surfactant. The alkalinity system comprises components capable of providing alkalinity species in the solution. By species of alkalinity we try to say in the present: carbonate, bicarbonate, hydroxide, the different anions of silicate, 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. from 1973. Suitable silicates include soluble sodium silicates with a ratio of Si? 2: Na2? from 1.0 to 2.8, preferring ratios of from 1.6 to 2.0, and preferring more a ratio of 2.0. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with a ratio of Si? 2: Na2? 2.0 is the most preferred silicate. The preferred crystalline layered silicates to be used in the present have the general formula: NaMSix02x + l YH2? 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, and is preferably 2. The material that is most preferred is a2SÍ2Ü-5, available from Hoechst AG as NaSKS-6.

Water-soluble builder composition The detergent compositions according to the present invention preferably contain a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight , more preferably from 20% to 60% by weight of the composition. Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more of 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 sulfinylcarboxylates. 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 Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-l, 1,3-propane tricarboxylates 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. The polycarboxylates that contain 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 acids of origin 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 detergency builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight. 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 [(AIO2) z (SÍO2) y] "XH2O 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% of water in bound form The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form.The 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) i2l 'xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula: Na8 [(A102) 86 (si02) 106 ^ '276H20. Another preferred aluminosilicate zeolite 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 dso value of 1.0 to 10.0 microns, most preferably 2.0 to 7.0 microns, more preferably 2.5 to 5.0 microns. The dso 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 dso 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 is meant here components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, 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 diethylenetriaminpenta (methylene phosphonate), 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 acid ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediamine disuccinic acid, ethylene diamine diglutharic acid, 2-hydroxypropylenediamindisuccinic 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- acid N'diglutaric (EDDG) and 2-hydroxypropylenediamine-N-N'-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 from 2% to 30% by weight and more preferably from 5% to 25% by weight of the salts. 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. 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 aB02H2? 2 or the tetrahydrate NaB02H2? 2-3H20. 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 2Na2C03.3H20 and 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. Peroxyacid bleach precursors can generally be represented as: O II X-C-L wherein L is a residual group and X is essentially any functionality, such that in perhydrolysis, the structure of the produced peroxyacid is: II XC-OOH The hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, most preferably from 0.1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more groups N- or O-acyl; precursors that 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: Or go -N- -N A N -N- C- -CH- • «R3 U I,! RJ V Y 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 R, 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 -C? 2 ~ +, in which 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. an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X being a halide, hydroxide, methylsulfate or acetate anion.

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

Precursors of alkylperoxyacid substituted with amide The preferred peroxyacid precursors are the amide substituted alkylperoxy acid precursor compounds, including those having the following general formulas: RJ -N- -R- = RJ -N- -R ii f p- icn OROROO wherein R is an aryl or alkaryl group with from 1 to about 14 carbon atoms, R is an alkylene, arylene and alkarylene group containing from about 1 to 14 carbon atoms, and R is H or an alkyl group, aryl or alkaryl 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.

Precursor of perbenzoic acid Precursor compounds of perbenzoic acid they provide perbenzoic acid in the 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 a group of ammonium or alkylammonium, 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 can be a precursor compound of perbenzoic acid or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,751,015; 4,988,451; 4,397,757; 5,269,962; 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.

Precursors of benzoxazine organic peroxyacid Also suitable are the precursor compounds of the benzoxazine type 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 Ó i || || OROROO in which R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R is H or an alkyl group, aryl or alkaryl containing 1 to 10 carbon atoms. The substituted organic peroxyacid compounds with amide 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. Examples Preferred of these catalysts include Mn1 2 (u_ °) 3 (1 4, 7-trimethyl-1,4-, 7-triazacyclononane) 2- (PFd) 2 > Mn 112 (u_ °) 1 (u_ OAc) 2 (1,4, 7-trimethyl-1,4-, 7-triazacyclononane) 2- (CIO4) 2 / MnIV4 (u-0) g (1,4,7-triazacyclononane) 4- (C104) 2, MnIIIMnIV4 (u-O) 1 (u-OAc) 2 (1,4, 7-trimethyl-1,4, 7-triazacyclononane) 2- (CIO 4) 3 and mixtures thereof. Others are 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-1,4,7,7-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-dentate and bi-N-toothed ligands, including ^ Mn111 (u-0) 2MnIVN4) + and [Bipy2MnI3 :? (u-0) 2MnIVbipy2] - (C104) 3. Suitable and additional bleach catalysts 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 catalyst / 1igand), 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 cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, lipases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes in a cleaning composition has a mixture of conventional applicable enzymes such as protease, lipase, 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 adequate is the one here it 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 replaces threonine in position 274. Protease C is described in EP 90915958: 4, which corresponds to WO 91/06637, published on May 16, 1991. Also included are genetically modified variants, particularly of protease C. A protease which is preferred 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 for a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent to the position +76, preferably also in combination with one or more equivalent amino acid residue positions entities selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166 , +195, +197, +204, +206, +210, "216, +217, +218, +222, +260, +265, and / or +274 according to the numeration of the subtilisin of Bacillus 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 on October 13, 1994.

Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637, BLAPR protease described in WO91 / 02792 and their variants described in WO 95/23221. 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 & 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. The detergent composition of the invention can also contain lipolytic enzymes. Suitable lipolytic enzymes 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 reaction positive immunological cross-over 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," hereinafter referred to as "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. Especially suitable lipases are lipases such as MI Lipase and Lipoma (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 enzyme LIPOLASE 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 the D96L enzyme, the normal LU test can be used (analytical method, internal Novo Nordisk AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying 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. 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% by weight, most preferably from 0.0002% to 0.05% by weight of active enzyme in the detergent composition. The detergent compositions of the invention may also incorporate one or more cellulase enzymes. Said cellulases they 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 grisea var, thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; an endoglucanase component that is preferred has the amino acid sequence described in PCT patent application No. WO 91/17243. Cellulases which are also suitable are the EGEIII cellulases of Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases which have color care benefits.

Examples of said cellulases are the cellulases described in the European patent application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also W091 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, W096 / 17994 and W095 / 24471. Peroxidase enzymes can also be incorporated into the detergent compositions of the invention. Peroxidases are used in combination with oxygen sources, e.g., 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 phenazine and fenoxazine 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), acid 10- phenothiazinopropionic (POP) and 10-methylphenoxazine (described in WO 94/12621) and the substituted syringates (substituted C3-C5 alkylarykates) 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 European co-pending patent application 92870018.6, filed on January 31, 1992. Examples of such enzyme oxidation scavengers are 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 as such agglutinate the particulate component with each other. 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 GB-A-1, 596, 756. Examples of such salts are polyacrylates of MW 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 are useful herein, including those aspartic acid derivatives such as 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 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional organic polymeric compounds and useful with polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably about 4000.

Cationic 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. Particularly preferred among these cationic compounds are the Ethoxylated cationic monoamines, diamines or triamines. Ethoxylated cationic monoamines, diamines or triamines of the formula are especially preferred: CH, CH, X - (- OCH2CH2) n - N CH- CH- CH2) a j- N + CH2CH2O - X (C ^ C ^ O - ^ X (CH2CH2O -) ñ-X wherein X is a nonionic group selected from the group consisting of H, C1-C alkyl or hydroxyalkyl ester or alkyl ether groups and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (vgr ., ethylene, propylene, hexamethylene), b is 2, 1 or 0; for cationic monoamines (b = 0), n is preferably at least 16, with a typical scale of 20 to 35; for cationic diamines or 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 compositions for machine washing, preferably comprise a system for suppressing foams present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, 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 antifoaming compounds include 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 C 13 -C 40 ketones (e.g., stearone), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, amide of bis-stearic acid and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% a 99%, preferably 75% to 95% by weight of the compound silicone antifoams; 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 alcohol of ethoxylated Cg with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10 % to 70% by weight; A highly preferred particulate foam 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 describes other foam suppression systems in preferred particles 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: PI (I) Ax IR wherein P is a polymerizable unit, and 0 0 0 II II II A is NC, CO, C, -O-, -S-, -N-; x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: O wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / oyo / yz is or 1 and wherein the nitrogen of the NO group can be fixed or where the nitrogen of the group 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 the 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 as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derived from them. 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 group, alicyclic heterocyclic or in which the nitrogen of the functional group N-O is part of said group R. Examples of these classes are the 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 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 IC90 (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. Sayings 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, R is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4, 4 '-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2 '-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) acid -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 acid 4,4 '-bis [(4-antilino-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 agent for removing dirt The polymeric agents known to release soils, hereinafter "SRA", can optionally be used in the present detergent compositions. If used, the SRA's 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 segments hydrophilic to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and the 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 attached 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 prepare: (a) ethoxylate 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, of 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 products of conditioning of fabrics such as laundry, an example being an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably also 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 C1-C4 alkylcelluloses and C4 hydroxyalkylcells of the U.S. patent. 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. These 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 SRAs include: (I) non-ionic terephthalates using coupling agents from diisocyanate for bonding 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.

Detergent formulation with an almost neutral wash pH Although the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g., from about 5 to about 12), they are particularly suitable when formulated to provide an almost neutral wash pH, ie, an initial pH of from about 7.0 to about 10.5 at a concentration of about 0.1 to about 2% by weight in water at 20 ° C. Formulations with an almost neutral wash pH are better for enzyme stability and to prevent stains from depositing. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, most preferably from about 8.0 to about 10.5, more preferably from 8.0 to 9.0. Detergent formulations with an almost neutral wash pH are described in European patent application 83.200688.6, filed on May 16, 1983, J.H.M. Wertz and P.C.E Goffinet. Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, pH regulating agents. , phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in the US patent 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference).

Form of the compositions The compositions according to the invention can have a variety of physical forms including 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 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 no 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 compacted solids can be manufactured using any suitable compaction process, such as rattling, agglomeration or extrusion, preferably tableting. Preferably, the tablets that will be used in dishwashing processes are manufactured using a normal rotating tableting press and using compression from 5 to 13 KN / cm, most preferably from 5 to 11 KN / cm so that the compacted solid 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 can be be splashed on dirty clothes 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 quickly at the start of the wash cycle, thus 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 inside the bag, dissolves the product and the solution then passes down through the hole to the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure, in which the walls They 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 the automatic washing of dishes or cleaning of dirty cutlery, particularly dirty silverware. 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: Sebum sodium alkylsulfate CxyAS: Sodium alkylsulfate of C] _x-Ciy C46SAS: Sodium alkylsulfate of secondary C ^ -C ^ (2.3) CxyEzS: Sodium alkylsulphate of C] _x-C; j_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 ethylene oxide QAS 1: R2 -N + (CH3) 2 (C2H4OH) with R2 = linear alkyl of Cg- Cn QAS 2: R2 -N + (CH3) 2 (C2H4OH) with about 50% of R2 = linear alkyl of Cg; about 50% of R 2 = C 10 QAS 3: R -N + (CH 3) 2 (C 2 H 4 OH) with about 40% of R 2 = linear alkyl of Cu; about 60% of R2 = linear C9 alkyl 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 ClO Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils CFAA: N-methylglucamide from (coconut) Ci2 alkyl-cy4 TFAA: Alkyl N-methylglucamide of C ^ -C ^ TPKFA: C, _2_c_4 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of formula Na12 (102Si? 2) 12 • 7H2O, which has a primary particle size on the scale 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 Ü- a2SÍ2? 5 Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with an average particle size of 200 μm and 900 μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (ratio Si02: Na2? = 2.0) Sodium sulphate: Anhydrous sodium sulphate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425μm and 850μm MA / AA: 1: 4 copolymer of maleic acid / acrylic acid with an average molecular weight of approximately 70,000 AA: Polyacrylate polymer sodium 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 tradename Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme of activity 3AU / g sold by Novo Industries A / S Cellulase: Cellulite enzyme of activity lOOOCEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: Activity amyolitic enzyme 120 KNU / g sold by Novo Industries A / S under the trade name Termamyl 120T Lipase: Lipolytic enzyme of activity lOOkLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa: Enzyme endoglunase enzyme of 3000CEVU / g sold by Novo Industries A / S PB4: Sodium perborate anhydrous tetrahydrate of nominal formula NaBO2.3H2O .H2O2 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2-H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H202 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraaceti1e ilendiamine Catalyst of Mn: MnIV2 (m-0) 3 (1,4, 7-trimethyl-1,4,7- triazaciclononano) (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. B photo-activated sealant: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer 1: 4, 4'-bis (2-sulphotrisyl) biphenyl disodium brightener Brightener 2: 4, 4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disodium disodium HEDP: 1,1-hydroxydanediphosphonic acid EDDS: Acid ethylenediamine-N, N-disuccinic QEA: bIS ((C2H50) (C2H4On) (CH3) -N + -CgH12 -N + - (CH3) bis ((C2H50) - (C H40n), 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 tetraethylenepentamine PVP: Polyvinylpyrrolidone polymer PVNO: Polyvinylpyridine N-oxide PVPVI: Polyvinylpyrrolidone copolymer and vinylimidazole SRP 1: Ester-blocked esters with sulfobenzoyl with oxyethyleneoxy base structure and terephthaloyl SRP 2: Poly (1, 2-propylene terephthalate) diethoxylated short block polymer Silicone 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 l 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: ! () fifteen 0 EXAMPLE 8 The following detergent formulations are examples of the present invention: EXAMPLE 9 The following bar laundry detergent compositions are examples of the present invention.

Claims (21)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: (a) a cationic surfactant of the formula I: R 1 R2 R 3 R 4 N + X "(I), wherein R is a hydroxyalkyl group having no more than 6 carbon atoms, each R 2 and R3 is independently selected from alkyl or alkenyl of C ± -, R is an alkyl to alkenyl of C5-11, and X ~ is a counter ion, and (b) an anionic and / or nonionic surfactant. - A granular detergent composition according to claim 1, further characterized in that it has a volume density of less than 700 g / l 3. - A granular detergent composition according to claim 1, further characterized by having a volume density from 700 g / liter to 1200 g / liter 4.- A detergent composition containing: (a) a cationic surfactant of the formula I: R 1 R2 R 3 R 4 N + X ~ (I), wherein R is a hydroxyalkyl group which has no more than 6 3 carbon atoms, each R and R is selected independently With alkyl or alkenyl of 0.4-4, R is an alkyl to alkenyl of Cs- ±±; And X ~ is a counter-ion; and (b) an anionic and / or nonionic surfactant, the composition detergent providing a foam height of at least 50 mm foam in a rotating cylinder foam test. 5. A detergent composition according to claim 1, further characterized in that the cationic surfactant is present in an amount of 0.01% to 20% by weight of the composition. 6. A detergent composition according to claim 5, further characterized in that the cationic surfactant is present in an amount of 0.05% to 5% by weight of the composition. 7. A detergent composition according to claim 1, further characterized in that in the cationic compound of the formula I, R1 is -CH2CH2OH or -CH2CH2CH20H; R2 and R3 are each methyl; is Cg-n-8 alkyl. - A detergent composition according to claim 1, further characterized in that in the cationic compound of formula I, R 4 is a linear alkyl group of C_ 6"11- 9.- A detergent composition according to claim 1, further characterized in that it has a mixture of cationic surfactants of the formula I, at least 10% by weight having R C5-9. 10. - A detergent composition according to claim 1, further characterized in that the cationic surfactant comprises a compound in the formula I, wherein R is a higher alkyl group having n carbon, wherein n is from 8 to 11 and a compound of the formula I in which R is a lower alkyl group having (n-2) carbon atoms. 11. A detergent composition according to claim 10, further characterized in that the cationic surfactant comprises from 5% to 95% by weight of a compound of the formula I, having an upper alkyl group and from 5 to 95% by weight. weight of a compound of the formula I, having a lower alkyl group. 1

2. - A detergent composition according to claim 4, further characterized in that it provides a foam height of at least 10 mm having a residence time of at least two minutes in a rotary cylinder foam test. 1

3. - A detergent composition according to claim 1, further comprising at least 1% by weight of anionic surfactant. 1

4. A detergent composition according to claim 13, further characterized in that the anionic surfactant is selected from anionic surfactants having the formula II or III: R5 0S03 -M + (II), R6 SO3-M, + (III), wherein R is a linear or branched alkyl portion having from 9 to 22 carbon atoms; R6 is Cin-2n alkylbenzene; M + M '+ each of the alkali metals is selected, alkaline earth metals, alkanolammonium and ammonium. 1

5. A detergent composition according to claim 14, further characterized in that the anionic surfactant comprises an anionic surfactant of the formula II and an anionic surfactant of the formula III in a weight ratio of II: III of 15: 1 to 1: 2. 1

6. - A detergent composition according to claim 14, further characterized in that the anionic surfactant II is a primary or secondary linear or branched alkyl sulphate of C] _g _] _ and wherein the anionic surfactant III is an alkylbenzene sulfonate of Cll-13- 1

7. A detergent composition according to claim 1, comprising a nonionic surfactant selected from the group consisting of alcoholetoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides and mixtures thereof. 1

8. A composition according to claim 14 containing: (a) from 0.25% to 3% by weight of a cationic surfactant of the formula I: R1 R2 R3 R4 N + X "(I), wherein R is an optionally substituted phenol or hydroxyalkyl group having not more than 6 carbon atoms, each R ^ and R is independently selected from the alkyl or alkenyl of C4_4, R is an alkyl or alkenyl of Cg _] _] _, and X- is a against ion; (b) from 3% to 40% by weight of straight or branched chain primary or secondary alkyl sulfate as surfactant II; (c) from 6% to 23% by weight of alkylbenzenesulfonate, active agent III; and (d) from 0.5% to 20% by weight of a nonionic surfactant. 1

9. A composition according to any of the preceding claims, further characterized in that it is substantially free of bleach. 20. A detergent composition formed by the combination of a cationic surfactant of the formula I: R1R2R3R4 N +? - (I) f wherein R1 is an optionally substituted phenol or p-hydroxyalkyl group having no more than 6 carbon atoms; each R and R is independently selected from the alkyl or alkenyl of C] __ 4; R is an alkyl or alkenyl of Cg_n; and X ~ is a counterion and an anionic and / or nonionic surfactant with one or more optional detergent components. 21. A method for laundry in a domestic washing machine in which a dispensing device contains 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 because the dispensing device allows the progressive release of said detergent composition in the wash liquor during washing.