MXPA98000274A - Washing method of r - Google Patents

Abstract

A method for washing laundry is provided in a domestic or industrial washing machine where assortment means are provided to supply an effective amount of a detergent composition directly to the tub of a washing machine before starting the washing and subsequently allowing to release said laundry. detergent composition to the washing solution during washing, the detergent composition contains a cationic ester surfactant and alkalinity system comprising alkaline salts; the assortment means allow the assortment of the cationic ester surfactant to be washed before it is Establish an alkaline wash solution environment around the laundry, a washing method including a pre-treatment step is also provided

Description

WASHING METHOD OF CLOTHES TECHNICAL FIELD The present invention relates to a method of laundry washing in a domestic or industrial washing machine, and more specifically to said method in which a detergent composition containing a cationic ester surfactant is supplied directly to the soiled fabrics in the first Washing stages.

BACKGROUND OF THE INVENTION The satisfactory removal of dirt / greasy stains, ie soils / stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions that are used in laundry and dishwashing methods. The surfactant components have traditionally been used in detergent products to facilitate the removal of said dirt / greasy stains. In particular, surfactant systems comprising cationic esters for use in the removal of dirt / greasy spots have been described. For example, EP-B-21,491 discloses detergent compositions containing a mixture of nonionic / cationic surfactant and a builder mixture comprising an aluminosilicate and polycarboxylate builder. The cationic surfactant may be a cationic ester. The improved removal of dirt in the form of particles and greasy / oily is described. Document EU-A-4,228,042 discloses biodegradable cationic surfactants which include cationic ester surfactants for use in detergent compositions and provide for the removal of greasy / oily soils. The combination of these cationic surfactants with nonionic surfactants in compositions designed for the removal of particulate soils is also described. Anionic surfactants are described as optional components of the compositions, but are present at low levels relative to the cationic surfactant component. EU-A-4,239,660 discloses laundry detergent compositions containing a cationic ester surfactant and a nonionic surfactant at defined weight ratios and a source of alkalinity. The source of alkalinity makes it possible to form a wash solution having a pH of from 8 to 10 within 3 minutes of dissolution of the composition in water at 37 ° C at a solution concentration of 0.15% The document EU-A-4,260,529 describes compositions Laundry detergents having a pH not higher than 11 and containing a cationic ester surfactant and a nonionic surfactant at defined weight ratios. Anionic surfactants are described as optional components of the compositions, but are present at low levels relative to the cationic surfactant component. Applicants have now discovered that the stability of the cationic ester surfactant in the presence of a highly alkaline wash environment is reduced in the solution. It is believed that the origin of this problem is the hydrolysis of the ester bond of the cationic ester surfactant, which occurs more rapidly under highly alkaline conditions and which, therefore, leads to the degradation of the surfactant. Applicants have now discovered that a solution to this problem can be achieved if the cationic surfactant is delivered directly to the soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics by a suitably designed delivery means. The supply means may comprise, in a preferred embodiment, a delivery device which makes it possible to supply the detergent directly to the soiled fabrics by means of a supply opening. Delivery devices in the form of flexible containers are known in the art., such as bags or sacks, but which do not have a different supply opening and which are not suitable for use in the washing method of the present invention. The containers are typically made of a water insoluble material, but permeable to water. The supply of the detergent product occurs by permeating the wash water to the container, thereby dissolving the contained detergent product which can then pass as a solution to the wash through the walls of the container. Said containers are not suitable here because the surfactant components have a tendency to gel within the container and thus to be supplied more slowly, in contrast to the simple alkaline salt components which dissolve rapidly and thus they supply quickly. An alkaline wash environment is then established prior to the release of the cationic ester surfactants. Similarly, the detergent supply means for laundry in the form of fabric sheets impregnated with detergent is known in the art, but this is also not suitable for use in the laundry method of the present invention. Said sheets are typically made of a water insoluble material, but permeable to water. The supply of the detergent product occurs when the washing water makes contact with the sheet, thus dissolving the impregnated detergent product which is then released as a solution in the wash. A problem with such a supply means is that the impregnated fabric sheets tend to overlap or become trapped in the soiled fabric, which affects the supply. Moreover, the surfactant components again have a tendency to gel and thus form a gelatinous surface on the fabric sheet, which delays the delivery, unlike the simple alkaline salt components which dissolve rapidly and therefore they are supplied quickly. This again leads to the alkaline washing environment being established before the release of any cationic ester surfactant. Applicants have also discovered an alternative solution but related to the problem of decreased stain removal performance as a result of the alkaline hydrolysis of the cationic ester. Direct delivery of the cationic ester surfactant to soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics can also be achieved by proper pretreatment of the fabrics with a detergent containing a cationic ester surfactant. In a preferred aspect, the soiled fabrics are pretreated prior to their introduction to the washing machine with a detergent composition formulated at a relatively low pH (ie, pH <9) and which contains alkaline components that have effect only during washing. In another preferred aspect, the soiled fabrics are pretreated with a detergent composition containing a cationic ester surfactant but not containing alkaline components. A second detergent composition including alkaline components in the wash cycle can then be employed. All documents cited in the present description are, in a relevant part, incorporated herein by way of reference.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, a method of washing soiled laundry in a domestic or industrial washing machine is provided, wherein a supply means for supplying an effective amount of a detergent composition directly to the drum of a washing machine is provided. of the start of the washing and subsequently making it possible to release said detergent composition to the washing liquid during the washing. Said composition contains: (a) from 1% to 90% by weight of the detergent composition of a cationic ester surfactant; and (b) from 1.5% to 95% by weight of the detergent composition of an alkalinity system comprising alkaline components selected from the group consisting of carbonate, bicarbonate, hydroxide or alkali metal or alkaline earth metal silicate, including layered silicate crystalline and any mixtures thereof; further characterized in that said delivery means makes it possible to supply said cationic ester surfactant to said soiled fabric prior to the establishment of a liquid alkaline washing and hydrolyzing environment around the laundry. In a preferred aspect, the cationic ester surfactant is selected from those having the formula: R? R5 Ri - G + (CH) nO < X > u- (CH2V ~ (Y) v- (CH2) t-N-R3 M wherein Ri is an alkyl, alkenyl or alkaryl chain of linear or branched Cs -C31 or l ~. N + (R6 7 8 XCH2) s; X and Y, independently, are selected from the group consisting of COO, OCO, 0, CO, 0C00, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, 0C00, OCONH or NHCOO; R2, R3, R4, Re, R7 and Re are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; where the values of, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the condition that at least some of uov must be 1; and where M is a counter anion. According to another aspect of the invention, a laundry method is provided that has a pretreatment step comprising applying an effective amount of a detergent composition directly to the laundry before subjecting the laundry to one step. of washing. Said detergent composition contains: (a) from 0.1% to 90% by weight of the detergent composition of a cationic ester surfactant; and (b) from 10% to 99.9% of the detergent composition of detergent components selected from surfactants, bleaches, builders, alkalinity sources, organic polymeric compounds, enzymes, foam suppressants, lime soap dispersants, and detergent agents. suspension and anti redeposition of dirt and corrosion inhibitors, further characterized in that said pretreatment step makes it possible to supply said cationic ester surfactant to said soiled fabric prior to the establishment of a liquid alkaline washing environment around the soiled laundry.

DETAILED DESCRIPTION OF THE INVENTION Laundry Washing Method The machine laundry methods herein typically comprise treating the laundry with an aqueous wash solution in a washing machine having dissolved or supplied therein an effective amount of a defined laundry detergent composition. An effective amount of the detergent composition is typically from 20g to 300g of product dissolved or dispersed in a wash solution of a volume of 3 to 65 liters, which are common product doses, and volumes of wash solution typically employed. in conventional machine laundry methods. In practice, the dose will be altered according to the size of the laundry load and the degree of dirtiness. A supply means is employed in the washing method of the invention to directly supply an effective amount of detergent product to the drum of the washing machine before the start of the washing cycle and to enable the release of the detergent product in the washing liquid., particularly during the first stages of washing, more particularly during the first two minutes of washing. In an essential aspect, the delivery means makes it possible to supply the cationic ester surfactant to the laundry before the establishment of a liquid alkaline washing and hydrolyzing environment around the laundry. By hydrolysing to the environment of the alkaline washing liquid is meant here a wash liquid environment which is sufficient and sustainably alkaline to cause a significant and rapid hydrolysis of the ester bond of the cationic ester surfactant, so that its surfactant capacity is reduced. In particular, this means a pH environment of no more than 9, particularly more than 10. Higher temperatures can also serve to promote the hydrolysis reaction. In a preferred aspect, said delivery means is a delivery device having a defined delivery opening, particularly of a cross-sectional area of more than 5 cm2, preferably of more than 7 cm2. The delivery device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine. Its volume capacity must be such that it can contain sufficient detergent product as would normally be used in the washing method without having to compress the product in the device, which would reduce its rate of release. Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the drum on top of the laundry load, and preferably adjacent to the dirtiest areas of the load fabrics. of clothes. At the beginning of the wash cycle of the washing machine, water is introduced into the drum and it rotates periodically. By rotating the drum, the detergent product is supplied from the supply opening and is thus delivered directly to the laundry. The device may have more than one supply opening through which the product may be dispensed in response to its agitation in the rotating drum. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized and transient concentrations of product in the drum of the washing machine 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 in accordance with 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 1989, p. 41-46, also discloses especially preferred supply devices for use with granular detergent products which are of a type commonly known as the "granulette". Another preferred delivery device for use in accordance with the invention is described in PCT patent application No. W094 / 11562. Especially preferred delivery devices are described in European patent applications Application Nos. 0343069 and 0343070. This latter application describes a device comprising a flexible liner in the form of a pouch extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the wetted and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure, in which the walls have a helical shape. In another aspect, the delivery means is provided by compacting a detergent composition containing both a cationic ester and alkaline components to make a tablet formed to provide release of the cationic ester surfactant to the laundry prior to the complete release of any component alkaline. The tablets are then introduced directly into the drum of the washing machine before the start of the washing cycle. In a preferred aspect, the tablet comprises layers of different product composition, the cationic ester surfactant being present in a layer located outward relative to the layer comprising the alkalinity system, and preferably completely separated from that layer.

Pretreatment washing method According to another aspect of the present invention, direct delivery of the cationic ester surfactant to soiled fabrics prior to the establishment of an alkaline hydrolyzing environment around the fabrics can also be achieved by pretreating the fabrics with a detergent composition containing the cationic ester surfactant. For the avoidance of doubt, pretreatment means in the present the direct application of a pretreatment detergent composition to a soiled fabric before subjecting the soiled fabric to a washing step. The pretreatment composition is generally of a fluid nature, i.e. a solution, liquid, gel, foam or mousse. The application can be accomplished by any suitable means, including emptying the fluid pretreatment composition onto the fabric using possibly a suitable dosing medium, the spray application of a foam or mousse, or the application of the fluid using an applicator means such as like a sponge or a brush. Preferably, the pretreatment composition is then manually rubbed into the soiled fabric. The pretreatment composition is allowed to remain in contact with the soiled fabric for an effective time interval before subjecting the soiled fabric to the wash step. Said time interval will typically be from 10 seconds to 1800 seconds, most preferably from 60 seconds to 600 seconds. The subsequent washing step is preferably carried out using a washing machine. In a preferred aspect, the soiled fabrics are pretreated with a liquid detergent composition formulated at a relatively low pH, i.e. a pH of less than 9.5, most preferably less than 9, more preferably less than 8, but containing alkaline components capable of provide alkalinity during washing. The alkaline components can, for example, be coated with a substance that remains intact during the pretreatment step, but is removed, eg, by abrasion, during the wash step. In other preferred aspect, the soiled fabrics are pretreated with a detergent composition containing cationic ester surfactant but not containing alkaline components. A second detergent composition that includes alkaline components can then be used in the wash cycle.

Cationic ester surfactant A first essential element of the detergent compositions of the invention is a cationic ester surfactant. That is, a compound preferably soluble in water having surfactant properties and comprising at least one ester linkage (ie, -C00-) and at least one cationically charged group. The cationic ester surfactant is preferably present in an amount of 0.1% to 90.0%, preferably 0.5% to 40%, most preferably 1% to 30% by weight of the detergent composition. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 4239660 and 4260529. Preferred water-dispersible cationic ester surfactants are those having the formula: wherein Ri is a straight or branched Cs-C31 alkyl, alkenyl or alkaryl chain or M- .N + (R6R7R8 XCH2) s; X and Y, independently, are selected from the group consisting of COO, OCO, 0, CO, 0C00, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, 0C00, OCONH or NHCOO; R 2, R 3, R 3, R 7 and Re are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs is independently H or an alkyl group of O-C3; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the proviso that at least some of uov must be 1; and where M is a counter anion. Preferably, R2, R3 and R * are independently selected from CH3 and -CH2CH2OH. Preferably, M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, most preferably methyl sulfate, chloride, bromide or iodide. Preferred water-dispersible cationic ester surfactants are choline esters having the formula: wherein Ri is a linear or branched C11-C19 alkyl chain. Particularly preferred choline esters of this type include the quaternary methylammonium halides of stearoyl choline ester (C17 reakyl), the quaternary methylammonium halides of palmitoyl choline ester (R? = Cis alkyl), the quaternary methylammonium halides of myristoyl choline ester (R? = C13 alkyl), the quaternary methylammonium halides of lauroyl choline ester (R? = Cu alkyl), the quaternary methylammonium halides of cocoyl choline ester (R? = C11 alkyl) -C13), the quaternary methylammonium halides of seboyl choline ester (R? = C15-C17 alkyl) and any mixture thereof. The most preferred choline ester compounds among those described above are the quaternary methylammonium halides of cocoyl choline ester. Particularly preferred choline esters, mentioned above, can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. They can also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-halogenoethanol, optionally in the presence of an acid catalyst material. The reaction product is subsequently quaternized with trimethylamine, forming the desired cationic material. Other suitable cationic ester therapeutic agents have the following structural formulas, wherein d can be from 0 to 20.

In a preferred aspect, the cationic ester surfactant is hydrolysable under the conditions of a laundry method.

Alkalinity System The second essential component of the detergent compositions is from 1.5% to 95%, preferably from 5% to 60%, most preferably from 10% to 40% by weight of the composition, of an alkalinity system comprising capable components to provide alkalinity species in the solution. By species of alkalinity we try to say in the present: carbonate, bicarbonate, hydroxide and the different silicate anions. Said alkalinity species can be formed, for example, when the alkali salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or alkali metal salts, including crystalline layered silicate and mixtures thereof are dissolved in water. The percarbonate and alkali metal persilicate salts are also suitable sources of alkalinity species. Examples of carbonates are the alkali earth and alkali metal carbonates, including carbonate and sodium sesquicarbonate and any mixture thereof with ultra-fine calcium carbonate, such as those described in German Patent Application No. 2,321,001, published on November 15, 1973. Alkali metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the "inorganic perhydrate salt" section herein. Sodium hydroxide is an alkali metal hydroxide which is preferred herein. Suitable silicates include water-soluble sodium silicates with a ratio of Si 2: Na 2? from 1.0 to 2.8, with the relationships from 1.6 to 2.0 being preferred, and the ratio of 2.0 being preferred. The silicates may be in the form of the anhydrous salt or the hydrated salt. Sodium silicate with a ratio of Si? 2: a2? 2.0 is the most preferred silicate. The alkali metal persilicates are also suitable sources of silicate herein. Preferred crystalline layered silicates for use herein have the general formula: NaMSix? 2- < +? and H20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, and is preferably 2. The material that is most preferred is Na2Si2? -5, available from Hoechst AG as NaSKS-6. The crystalline layered sodium silicate material is preferably present in the granular detergent compositions as particles intimately mixed with a water soluble and solid ionizable material. The water soluble and solid ionizable material is selected from organic acids, salts of organic and inorganic acids and mixtures thereof.

Additional detergent components The detergent compositions of the invention may also contain additional detergent components at a level of from 10% to 99% by weight. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition and the precise nature of the cleaning operation for which it will be used. The compositions of the invention contain one or more additional detergent components selected from additional surfactants, bleaching agents, builders, organic polymer compounds, enzymes, foam suppressors, lime soap dispersants, suspending and anti-redeposition agents. corrosion inhibitors.

Additional Surfactant The compositions of the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic non-ester, amphoteric and zwitterionic surfactants, and mixtures thereof. The additional surfactant is preferably present at a level of from 0.1% to 50%, most preferably from 1% to 40% by weight, more preferably from 5% to 30% by weight of the surfactant system.

A typical list of anionic, nonionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the U.S. patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant A preferred component of the detergent compositions is an anionic surfactant. The weight ratio of anionic surfactant to cationic ester surfactant in the surfactant system is preferably from 3: 1 to 15: 1, most preferably from 4: 1 to 12: 1, more preferably from 5: 1 to 10: 1 Essentially any surfactants useful for detersive purposes may be comprised in the detergent composition. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Suitable anionic surfactants include the acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (especially C6-diesters) C14 saturated and unsaturated), N-acyl sarcosinates. Reeine acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in tallow oil or derivatives thereof.

Sulphonic Anion Surfactant The anionic sulfate surfactants which are used herein include the linear and branched primary and secondary alkyl sulphates, alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, the acyl glucamin sulfates of C5-C17-N - (C 1 -C 4 alkyl) and -N- (C 1 -C 2 hydroxyalkyl), and alkylpolysaccharide sulfates such as the alkyl polyglycoside sulphates (the non-sulphonated nonionic compounds are described herein). The alkyl sulfate surfactants are preferably selected from linear and branched primary Cι-Cis alkyl sulfates, most preferably branched chain Cn-Cs alkyl sulfates and straight chain C12-C14 alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 1 -C 5 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is a Cu-Cie alkyl sulfate, most preferably Cn-Cis, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Said mixtures have been described in the PCT patent application No. WO 93/18124.

Sulfonate Anionic Surfactant The anionic sulphonate surfactants used herein include the salts of C5-C20 linear alkylbenzenesulfonates, alkyl ether sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates. , fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and many mixtures thereof.

Carboxylate Anionic Surfactant The carboxylate anionic surfactants include the alkylethoxycarboxylates, the alkylpolyethoxy polycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkylethoxycarboxylates include those with the formula R0 (CH2CH20)? CH2C00 ~ M + where R is an alkyl group of C? To Cie, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis , the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula R0- (CHR? -CHR2-0) -R3 wherein R is an alkyl group of Cß to Cie, x is 25, Ri and R2 are selected from the group which consists of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. 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-methyl-1-undecanoic acid, -propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam suppressors.

Alkaline metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CONIR1) CH2C00M, wherein R is a linear or branched Cs-Ci7 alkyl or alkenyl group, R1 is an alkyl group of C1-C4 and M is an alkali metal ion. Preferred examples are the iristyl or oleoyl methyl sarcosinates in the form of their sodium salts.

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

Nonionic Surfactant of Ethoxylated 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 which are used herein are those having the structural formula R2C0NR! Z, wherein: R1 is H, hydrocarbyl of Ci-G- ,, 2 -hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably Ci or C 2 alkyl, more preferably Ci alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, most preferably straight chain C9-C17 alkyl or alkenyl, more preferably straight chain C11-C17 alkyl or alkenyl or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; very preferably 1 is a glycityl.

Non-ionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C 1 -C alkyl, hydroxyalkyl of Ci -CA, and - (C 2 H 2) X H, wherein x is on a scale of 1 to 3. 5 Nonionic surfactant of alkylspolysaccharide Suitable alkyl polysaccharides that are used herein are described in the US patent No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R20 (Cn H2nO) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (0R1) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, which contains 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 5 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. Alkyl dimethylamine oxide of Cio-Ciß and acylamido dimethylamine oxide of Cio-Ciß- are preferred. 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 + R2C00- where R is a hydrocarbyl group of Cß-Ciß, each R1 is typically Ci-C3 alkyl, and R2 is a hydrocarbyl group of C1-C5. The preferred betaines are the betaines of C12-C18 dimethyl ammonium hexanoate and the cyclo-Cβ acyl amidopropane (or ethane) dimethyl (or diethyl) betaines. Also suitable for use herein are complex betaine surfactants.

Cationic Surfactants The additional cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include quaternary ammonium surfactants selected from N-alkyl or alkenyl ammonium surfactants of Cß-Ciß, preferably Cß-Cio, in which the remaining N positions are substituted by methyl, hydroxyethyl groups or hydroxypropyl.

Water-soluble builder composition The detergent compositions of 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 depletion enhancer may be of monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates described in the Dutch application 7205873 and the oxypolycarboxylate materials such as 2-oxa-l, l, 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-propanecarboxylates and the 1,1,2,3-propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. Relative acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, eg, mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components.

Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or wash conditions are water soluble builders useful herein. Suitable examples of phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from about 6 to 21, and the salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 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 N i [(AIO2)? (SÍO2) and] • 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% water in bound form. The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Nai 2 [(A102) 12 (S02) 12] -XH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(Al? 2) 86 ( Yes? 2)? Oß] - 276H20 Organic Peroxyacid Bleach System A main feature of the detergent compositions of the invention is an organic peroxyacid bleach system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Production of the organic peroxyacid occurs by an iri-situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a preferred and alternative embodiment, a preformed organic peroxyacid is incorporated directly into the composition. Also contemplated 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 form of the alkali metal salt, preferably sodium, at a level of from 1% to 40% by weight, most preferably from 2% to 30% by weight and more preferably from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perfosphate, persulfate and persilicate. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salts 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 that provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as the silicate alkali metal salts, carbonate or borate, or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB 2 H 2 o 2 or the tetrahydrate Na B 2 H 2 2.3 2.3 H 2 O. Alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates herein. Sodium percarbonate is an addition compound having the formula corresponding to 2Na2C? 3.3H2O2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. The peroxyacid bleach precursors can generally be represented as: XCL wherein L is a starting group and X is essentially any functionality, such that in the hydrolysis, the feed material of the product is produced. be : O XC-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, most preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or 0- groups, which may 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.

Starting groups The starting 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: and mixtures thereof, wherein R1 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, R * is H or R3, and Y is H or a solubilizing group. Any of R1, 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 -S03 ~ M +, -C02 ~ M +, -S0 * -M +, -N + (R3) AX ~ and 0 < -N (R3) and most preferably -S03 ~ M + and -C02 * M +, wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate or acetate anion.

Precursors of bleaching of alkylpercarboxylic acid The bleach precursors of alkylpercarboxylic acid form perearboxylic acid in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarbaryl bleach precursors of the imide type include the tetraacetylated N-, N, N 1 N alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-substituted alkylperoxy acid precursors Amide-substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: wherein R 1 is an alkyl group having from 1 to 14 carbon atoms, R 2 is an alkylene group containing 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any starting group. Amide-substituted alkylperoxy acid-activating compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable 0-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, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinbefore. 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 the patent applications of E.U.A. 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 onobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium ethylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein Ri 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, 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: wherein R 1 is an alkyl, aryl or alkaryl group having from 1 to 14 carbon atoms , R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and RS is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbranic acid and N-phthaloylaminoperoxycaproic acid.

Bleach catalyst The compositions optionally contain a bleach catalyst containing a transition metal. A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or 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 ethylenediaetetraacetic acid, ethylenediaminetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the patent of E.U.A. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Preferred examples of this catalyst include MnIV2 (u-0) 3 (1,4,7-trimethyl-l, 4,7-triazacyclononane) 2- (PFß) 2, Mn1112 (u-O)? (u- 0Ac) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (C10A) 2, MnIV4 (uO) β (1, 4,7-triazacyclononane) 4- (C10A 2, Mnin nIV4 (u-0)? (U-0Ac) 2 (l, 4,7-trimethyl-l, 4,7-triazacyclononane) 2- (C104) 3 and mixtures thereof The other is described in the publication of European Patent Application No. 549,272 Other suitable ligands for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1, 4,7-t-riazacyclononane, 2-methyl -l, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-l, 4,7-triazacyclononane and mixtures thereof For examples of suitable bleach catalysts see U.S. Patent No. 4,246,612 and in US Pat. U.S. Patent No. 5,227,084 See also U.S. Patent No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1, 7-trimethyl-1, 4,7-triazacyclononane) (0CH3) 3 - (PFß) Another further type of bleaching catalyst as described in US Patent 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 N «nHi (u-0 2 niVN + V [Bipy2MnH? (U-0) 2MniVbipy2] - (C104 3. Catalyst Suitable and additional bleaching are described, for example, in the European patent application No. 408,131 (cobalt complex catalysts), European patent applications Publication Nos. 384,503 and 306,089 (metalloporfinium catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4,711,748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U.A. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts).

Heavy metal ion sequestrant The detergent compositions of the 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 the ability to chelate calcium and magnesium, but preferably show selectivity to bind heavy metal ions such as iron, manganese and copper.

The peeled metal ion samples are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, most preferably 0.25% at 7. 5% and more preferably from 0.5% to 5% by weight of the compositions. Sequences of heavy metal ionee suitable for use herein include organic phosphonates, such as the aminoalkylenepolypicalkylene phosphonate), alkali metal ethane-1-hydroxy diphosphonates, and nitrilotri ethylene foefonatee. Preferred among the foregoing are diethylenetriaminpenta (methylene foefonate), ethylenediaminetri- (methylene foefonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1 diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyalkylcarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedieuccinic acid, or any 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. Sequencers of iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and of aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid 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-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in detergent compositions is one or more additional enzymes. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases and incorporated in conventional manner in the detergent compositions. Suitable enzymes are also described in the patents of E.U.A. Nos. 3,519,570 and 3,533,139. The commercially available protease enzymes that are preferred include those sold under the tradenames Alcalase, Savinase, Primaee, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxape by Giet-Brocades, those sold by Genecor International and those sold under the trade name Opticlean and Optimase by Solvay Enzimes. The protease enzyme can be incorporated in the compositions according to the invention at a level of from 0.001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, alpha-alases obtained from a special strain of B. licheniformis, described in greater detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the trade name Termamyl and BAN by Novo Industries A / S. The amylase enzyme can be incorporated in the composition according to the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition. The lipolytic enzyme may be present at active lipolytic enzyme levels of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase may be of fungal or bacterial origin, being obtained, for example, from a lipase-producing strain of the Humicola species, the Thermomyces species or the Pseudomonas species, including Pseudomonas pseudoacaligenes or Pseudomas fluorescens. Lipaea that comes from chemically or genetically modified strains of these strains are also useful in the present. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in European patent EP-B-0218272. Another preferred lipase in the present ee obtains cloning the gene of Humicola lanuginosa and expressing the gene in Aspergillus oryza as host, as described in the European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark under the trade name Lipolase. Lipaea is also described in the patent of E.U.A. No. 4,810,414, Huge-Jeneen et al, issued March 7, 1989.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent compositions according to the invention and are preferably present as components of any particulate components, where they can act such as to bind the particulate component together. By "organic polymeric compound" is meant herein essentially any polymeric organic compound that is not an oligoester or polyamine soil release polymer, and which are commonly used as a dispersant and anti-redeposition agent and suspension of soils in detergent compositions. , including any of the high molecular weight polymeric organic compounds described as clay flocculating agents in the preeent. The organic polymeric compote is typically incorporated into 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 the organic homo- or copolymeric polycarboxylic acids soluble in water or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described GB-A-1,596,756. Examples of said saltse are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful herein, including those derived from tartar aspartic acid as described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable herein are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives 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.

Foam suppressing system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppressor system 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. Suitable foam suppressor systems for use herein can comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds.

By "antifoam 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 antifoam compositions 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 silicone antifoams are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the patent of E.U.A. 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 antifoams include, for example, high molecular weight esters (e.g., triglycerides of fatty acid), ethoxylate of alcoholic acid onovalentee, C18-C40 aliphatic ketone (e.g., etheone), amino triazine N-alkylasee talents as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminchlortriazines 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% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and '(ii) silica, at a level of from 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 from 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 from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising an ethoxylated Ciß-Cis alcohol with an ethoxylation degree of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10 % to 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises an antilick compound of eylicon and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof , with a melting point of from 45 ° C to 80 ° C.

Clay Softening System The detergent compositions may contain a clay softening system comprising a mineral clay compound and optionally a clay flocculating agent. The clay mineral compound is preferably a clay compound is ectite. The clay eectites are described in the U.S. Patents. Noe 3,862,058, 3,948,790, 3,954,632 and 4,062,647. Lae patentee europeae Noe. EP-A-299,575 and EP-A-313,146 in the name of the Procter & Gamble Company describes suitable organic polymeric clay flocculating agents.

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 agents and dye transfer inhibitors. The polymeric dye transfer inhibiting agents are preferably selected from copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof. a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: P (1) Ax A wherein P is a polymerizable unit, and 0 0 A is NC, CO, C, -0-, -S-, -N-; x is o 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 repreened by the following general structures: 0 wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / oyo / yz ee or or 1 and wherein the nitrogen of the NO group can be fixed or in which the Nitrogen from the NO group is 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 groups, aromatic, alicyclic or heterocyclic. A class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxide are the polyamine oxides in which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the functional group is NOT part of said group R. Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The copolymers of N-vinylimidazole and N-vinylpyrrolidone suitable in the present invention have an average molecular weight scale of 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight from 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones that 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 from 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The optical hydrophilic brighteners useful herein include those having the structural formula: wherein Ri 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 ee an eal-forming cation such as sodium or potassium. When in the above formula Ri is anilino, R2 is N-2-bie-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2- bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfone 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 Ri is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of the acid 4,4'-bis [(4-indigo ino-6- (N-2-hydroxyethyl-N-methyl lami) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is commercially available under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morph ilino-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.

Cationic Fabric Softening Agents The telae-cationic builders can also be incorporated into the compositions according to the invention. Suitable cationic fabric softening agents include water insoluble tertiary amines or dilarga chain amide materials such as those described in GB-A-1 514 276 and EP-B-0011 340. Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with sodium sulfate being a filler salt. pH of the compositions The present compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably 10.0 to 12.5, more preferably 10.5 to 12.0.

Fof the compositions The eolid composition according to the invention can have a variety of physical f including the granulated and tablet f. In particular, the so-called concentrated detergent compositions are adapted to be added to a washing machine by means of a supply die placed in the drum of the washing machine with the load of laundry. The average particle size of the components of the granular compositions according to the invention should preferably be such that no more than 5% of the particles are more than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15. mm in diameter. The term "average particle size" as defined herein is calculated by screening a sample of the composition in a number of fractions (typically 5 fractions) in a series of 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. The overall density of the detergent compositions according to the present invention is typically an overall density of at least 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve on its lower end to allow the contents of the funnel to be emptied into a cylindrical cup aligned axially below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder is removed from the cup by passing a straight edge implement, eg, a knife, through its upper edge. The full cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required. Tablet f are generally manufactured by compressing granular compositions to ftablets using any of the rattling procedures commonly known in the art. With the proper selection of the shape of the component and the pressure employed in the pressing operation of the tablet, the hardness of the tablet can be varied. The size of the tablets is selected to facilitate dosing to the wash solution. Typically, a tablet will comprise from 5 to 100g, preferably from 10 to 50g of detergent product. The tablet can have essentially any shape including cubes and spheres. In a preferred aspect, the tablet is fd so that it has at least two distinct and spaced layers, wherein an inner layer contains a cationic ether-containing surfactant and an inner layer has the alkalinity system.

Agglomerated Surfactant Particles The cationic ether surfactant herein, preferably with additional surfactants, is preferably present in the granulated compositions in the fof agglomerated particles of surfactant, which may be in the fof flakes, pellets, disks, noodles, ribbons, but preferably they have the form of granules. The most preferred form for processing the particles is by agglomerating powders (e.g., aluminosilicate, carbonate) with highly active surfactant pastes and controlling the particle size of the resulting agglomerates within specific limits. Said process includes mixing an effective amount of powder with a highly active surfactant paste in one or more agglomerators such as a container agglomerator, a Z-shaped paddle mixer or most preferably an in-line mixer such as those manufactured by Schugi (The Netherlands). ) BV, 29 Chroomstraat 8211 AS, Leyland, The Netherlands, and Gebruder Lodige Maschinebau GmbH, D-4790 Paderborn 1, Elseneretraße 7-9, Poetfach 2050, Germany. Most preferably a high shear mixer, such as a Lodige CB (tradename), is used. A highly active surfactant paste comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of surfactant is typically used. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to prevent degradation of the used anionic surfactants. A pulp operating temperature of 50 ° C to 80 ° C is typical.

Packaging for the compositions Commercially sold executions of the washing compositions can be packaged in any suitable container including those made of paper, cardboard, plastic materials 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: C12 linear sodium alkylbenzene sulfonate TAS: Sodium alkyl sulfate C45AS: Sodium linear alkylsulfate of C? - C? S CxyEzS: Sodium alkylsulfate branched from C? XC? And condensed with z moles of ethylene oxide C45E7: A predominantly linear primary C14-C15 alcohol condemned with an average of 7 moles of ethylene oxide C25E3: A branched C12-C15 primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5: A branched C12-C15 primary alcohol condensed with an average of 5 moles of ethylene oxide CEO: R1COOCH2CH2.N + (CH3) 3 with R = C11-C13 QAS: R2 .N + (CH3) 2 (C HAOH) with R2 = C12-C14 Soap: Linear eodium alkylcarboxylate derived from a mixture of 80/20 tallow oil and coconut oil TFAA: Ci-Cis alkyl N-methylglucamide TPKFA: C12-C1-4 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (Al? 2Si? 2) i2. 27H20, which has a primary particle size on the scale of 0.1 to 10 microns. NaSKS-6: Crystalline layered silicate of the formula d-Na2 YES2? S Crystalline acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a distribution particle size between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2: Na2? 2.0 ratio) Eodium sulfate: Anhydrous sodium sulfate 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 CMC: Sodium carboxymethylcellulose Protease: Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme activity 3AU / g sold by Novo Industries A / S Cellulase: Activity cellulite enzyme lOOOCEVU / g sold by r Novo Industries A / S under the trade name Carezyme Amylase: 60 kNU / g activity amyolitic enzyme sold by Novo Industries A / S under the trade name Termamyl 60T Lipase: Lipolytic enzyme activity of 100kLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa: Endoglunase enzyme activity 3000CEVU / g sold by Novo Industriee A / S PB4: Anhydrous ehydrous perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PBl: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2 .H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H2O2 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (ethylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in polymer soluble in dextrin Brightening 1: 4,4 '-bie (2-eulfoeeti ril) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-t riazin-2-yl) amino) stilbene-2: 2'-disulfonate disulfonate HEDP: 1,1-hydroxyethanophosphonic acid PVNO: N-oxide of polyvinylpyridine PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole SRP 1: Esters of end blocked with sulfobenzoil with base structure of oxyethyleneoxy and terephthaloyl SRP 2: Polymer of short block of poly (l) , 2-propylene terephthalate) diethoxylated Silicon Anti-Foams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1.

In the following examples all levels are cited as% by weight of the composition: EXAMPLE 1 The following laundry detergent compositions A to F according to the invention were prepared Set 1 Set 2 Set 3 Set 4 The following detergent formulations containing indigo bleach of particular use were prepared in the washing of garments with color, according to the invention: Set 5 The following detergent formulations were prepared according to the present invention: Set 6 The following detergent formulations according to the present invention were prepared: Set 7 The following high density detergent and bleach-containing detergent formulations were prepared according to the present invention: Set 8 The following high density detergent formulations were prepared according to the present invention: Washing method Each of the compositions A to AA of sets 1 to 8 was used in a laundry method in which a Miele 820 automatic washing machine was used, and the short cycle program of 40 ° C was selected. At the beginning of the laundry method, 100g of detergent was placed in a granulette supply device of the type known as "Arielette" and is commonly supplied with Ariel detergent products (trade name), manufactured by the Procter and Gamble Company for sale throughout Europe. The loaded granulette was then placed on top of the washing load in the drum of the washing machine. The wash load comprised 2.4 kg of a 60/40 mixture of slightly eucias cotton, polycotton and polyester fabrics. A good washing performance was obtained.

Comparative performance test The performance in the removal of greasy stains from composition I when used in a washing method that included supplying granulette in a washing machine was compared to that obtained when the detergent was delivered through the supply drawer using The following test method: Three white cotton sheets were prewashed three times with a heavy duty detergent free of bleach and non-biological at 60 ° C. Margarine stains were then uniformly applied to a leaf using a paintbrush, butter stains to the second leaf and drops of flesh to the third. Sets of test samples with a size of 6cm x 6cm were cut from each sheet. The sets of cloth samples were subjected to a washing cycle in an automatic washing machine with the detergent euminietrado or from a granulette or from the drawer of supply of the washing machine. The samples were then inspected to verify removal of the different grease stains by a four person grading panel using the well-known Scheffe four-point scale. In greater detail, a Miele 820 automatic washing machine was used and the short cycle program of 40 ° C was selected. Water of 10 ° of Clark hardness (= 1.5 mmoles of Ca 2+ / liter) was used. One lOOg of detergent was used. A sample of each type of fabric was washed together with a load comprising 2.4 kg of a mixture of 60/40 synthetic fabrics and lightly soiled cotton. The load was placed before starting the wash cycle to ensure uniform distribution around the test samples. In the case of the supply with granulette, the detergent was placed in a granulette supply device of the type known as an "Arielette" and which is commonly provided with Ariel detergent products (trade name), manufactured by the Procter and Gamble Company for its sale throughout Europe. The loaded granulette was then placed on top of the wash load and adjacent to the stained samples in the drum of the washing machine, initiating the washing cycle. In the case of the supply of the drawer, the 100g of detergent was placed in the drawer of the washing machine and the washing cycle was started. The following results were obtained: Supply from Supply with granulette drawer Margarine Removal (PSU) Ref. 1.0 * Removal of butter (PSU Ref, 0.9 * Removal of meat drops (PSU) Ref. 1.2 * * = statistically significant at a 95% confidence level.

EXAMPLE 2 The following liquid detergent formulations were prepared with a pH < 9: Each of the detergent products AB to AI was used separately in a pretreatment washing method that included the following steps: A load of 2 kg of polycotton and cotton fabrics was taken. In the pretreatment step, approximately 5ml aliquots of detergent product were applied directly to the area encrusted with grease, until the area was at least moistened with the detergent. The detergent was allowed to remain in contact with the dirty area for 5 minutes. In each wash step, the load was then placed in a Mielle 820 washing machine and the short cycle program of 40 ° C was selected. One lOOml of the same detergent product was used in the wash cycle. The detergent was supplied from a solid plastic dosage ball. A good washing performance was obtained for each of the products AB to AI.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A method of washing laundry in a domestic or industrial washing machine, further characterized in that a supply means is provided to supply an effective amount of a detergent composition directly to the drum of a washing machine before the start of washing and subsequently making possible the release of said detergent composition in the washing liquid during washing, wherein said detergent composition contains: (a) from 1% to 90% by weight of the detergent composition of a cationic ester surfactant; and (b) from 1.5% to 95% by weight of the detergent composition of an alkalinity system comprising alkali salts selected from the group consisting of carbonate, bicarbonate, hydroxide or alkali metal or alkaline earth metal silicate salts, including salts of crystalline layered silicate and any mixtures thereof; further characterized in that said delivery means makes it possible to supply said cationic ester surfactant to said soiled fabric prior to the establishment of a liquid alkaline wash environment around the laundry.

2. A method according to claim 1, further characterized in that said supply means is provided by a supply device that has a supply opening and that is loaded with the detergent composition and then placed in the drum of the washing machine before the start of the wash cycle.

3. A method according to claim 1, wherein said euminium medium is formed by forming said detergent composition as a tablet, thus formed to provide release of the cationic ester surfactant in the laundry prior to release. complete of said alkalinity system, wherein the tablets are introduced into the drum of the washing machine before the start of the washing cycle.

4. A method according to claim 3, further characterized in that said tablet comprises layers of different product composition, the cationic ester surfactant being located in a layer located outwardly relative to the layer comprising the alkalinity seventh. .

5. A method according to any of claims 1 to 4, further characterized in that said cationic ester surfactant is selected from those having the formula: wherein Ri is an alkyl, alkenyl or alkaryl chain of linear or branched Cs -C31 or M ~. N + (R6R7R8) (CH2) s; X and Y, independently, are selected from the group consisting of COO, OCO, 0, CO, OCOO, CONH, NHCO, OCONH and NHCOO where at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R2, R3, R, Rβ, R? and Rs are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs is independently H or an alkyl group of Ci-C3; where the values of, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the condition that at least some of uov must be 1; and where M is a counter anion.

6. A detergent composition according to claim 5, further characterized in that R2, R3 and R4 are independently selected from the group consisting of -CH3 and -CH2CH2OH.

7. A detergent composition according to claim 5, further characterized in that the cationic ester is selected from the choline esters having the formula: wherein m is 1 to 4 and Ri is a linear or branched C 11 -C 19 alkyl chain.

8. A laundry washing method having a pretreatment step comprising applying an effective amount of a detergent composition directly to the laundry prior to subjecting the laundry to a washing step, further characterized in that said composition detergent contains: (a) from 1% to 90% by weight of the detergent composition of a cationic ester surfactant; and (b) from 10% to 99.9% by weight of the detergent composition of detergent components selected from surfactants, bleaches, builders, alkalinity sources, organic polymer compounds, enzymes, foam supra-ores, lime soap dispersants, suspeneion and anti redeposition agents for dirt and corrosion inhibitors, further characterized in that said pretreatment step makes it possible to supply said cationic ester surfactant to said soiled fabric prior to the establishment of a liquid alkaline washing environment around the clothes dirty

9. A method according to claim 8, further characterized in that said detergent composition is a fluid composition formulated at a pH of less than 9.5.

10. A method according to any of claims 8 or 9, further characterized in that the detergent composition contains no alkaline components.