MXPA98010094A - Detergent compositions - Google Patents

Abstract

A suitable detergent composition is provided for use in laundry and dishwashing methods, comprising a cationic ester surfactant and an alkalinity system and wherein means are provided to retard the release of said alkalinity system in connection with the release of said cationic ester surfactant

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD • The present invention relates to detergent compositions comprising a cationic ester surfactant and an alkalinity system, wherein means are provided to retard the release of the alkalinity system to the wash solution. BACKGROUND OF THE INVENTION The satisfactory removal of dirt / greasy stains, ie dirt / stains that have a high The 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 such substances. dirt / greasy spots. 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 describes 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 removal is described ^. improved dirt in the form of particles and greasy / oily. Document EU-A-4, 228, 042 discloses biodegradable cationic surfactants which include cationic ester surfactants for use in detergent compositions and provide removal of soils greasy / oily. 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 in relation to the component of the cationic surfactant. US-A-4, 239, 660 discloses laundry detergent compositions containing a cationic ester surfactant and a non-ionic surfactant at defined weight and a high alkalinity source. The source of alkalinity allows a washing solution to have a pH from 8 to 10 to be formed in 3 minutes of dissolution of the composition in water at 37 ° C and a solution of concentration of 0. fifteen%. This is achieved through the use of alkalinity sources highly soluble. Document EU-A-4, 260, 529 discloses laundry detergent compositions 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 ester surfactant component. Applicants have discovered that a problem with the use of certain cationic ester surfactants is the tendency of the ester linkage to bind hydrolytically, flk thereby breaking the surfactant molecule under the washing conditions of a typical laundry method. or dishwashing and under the conditions of alkalinity typical of said methods of laundry and washing dishes, using cationic surfactants. Precisely, the high alkalinity sources, considered by the prior art as essential for the optimal development of the surfactant of the cationic ester surfactants, can be the cause of a hydrolytic adhesion of the ester bond, which can comprise the development of the surfactant in the wash. It has been found that a solution to this problem is provided when the cationic ester surfactant is employed in a detergent composition that provides means for delay the release or establishment of alkalinity in the wash solution. Such means provide a reduced alkalinity at the start of the wash and in this way a general reduction or retardation of the hydrolytic adhesion of the ester bond is achieved during the washing. In general, the • sufficient alkalinity to wash to allow the cationic ester surfactant agent to perform the removal of greasy dirt / stain during washing. In this way, the introduction of such media in a detergent composition will optimize the overall development of the surfactant in the wash. All the documents cited in the present description are incorporated, in relevant part, herein as reference.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention there is provided a detergent composition containing: ^^ (a) a cationic ester-acting agent; and (b) an alkalinity system, wherein the means are provided to retard the release of a wash solution of said alkalinity system in relation to the release of said cationic ester surfactant, so that in the method of T50 test of the present describes the time to achieve a concentration that is 50% of the ultimate concentration of said cationic ester surfactant is at least 120 seconds less than the time to achieve a concentration that is 50% of the ultimate concentration of said alkalinity system. In a preferred aspect, the cationic ester surfactant is selected from those having the formula: R3 M wherein R] _ is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain or M ~ .N + (RgR7Rs) (CH) S; X and Y, independently, they are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, OCOO, OCONH or ^ NHCOO; R2, R3, R4, RQ, R7 and Rs are independently selected from the group consisting of alkyl, 0 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 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 5 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. The alkalinity system preferably comprises alkali salts selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate salts, crystalline layered silicate and inorganic perhydrated salts and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION Cationic ester surfactant An essential element of the detergent compositions of the invention is a cationic ester surfactant. Preferably, the cationic ester surfactant of the present invention is present at a level of from 0.1% to 20.0%, most preferably from 0.5% to 10%, more preferably from 1.0% to 5.0% by weight of the detergent composition. The cationic ester surfactant of the present invention is preferably a water dispersible compound having surfactant properties and comprising at least one ester (i.e., -C00-) bond and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 4239660 and 4260529. In a preferred aspect, the ester bond 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 ( that is, chain length of three atoms), preferably 5 of three to eight atoms, most preferably of 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 connect átk only with the carbon atoms in the chain. In this way, groups that have, for example, links -0-0- (ie, peroxide), -NN- and -NO- are excluded, but include separating groups that have, for example, -CH2 bonds -O-CH2- and -15 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. Preferred cationic ester surfactants are those having the formula: R, M wherein R ^ is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain or M ".N + (RgR7R8) (CH2) s; X and Y, independently, they are selected from the group consisting of A COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO where at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R, R3, R4, RQ, R7 and ß are independently selected from the group consisting of alkyl groups, Alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; where the values of m, n, s and ^^ t 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 u or v must be 1; and where M is a Contra anion. Preferably, M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, most preferably methyl sulfate, chloride, bromide or iodide.

In a preferred aspect, the cationic ester surfactant is selected from those having the formula: g wherein R] _ is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO; R2, R3 and R4 are independently selected from the group consisting of alkyl groups and hydroxyalkyl having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; where the value of n is on the scale from 0 to 8, the value of b is on the scale from 0 to 20, the value of a is 0 or 1, and the value of m is 3 to 8. 20 Most preferably, R 2, R 3 and R 4 are independently selected from an alkyl group of C 2 - and a hydroxyalkyl group of C 1 -C 4. In a preferred aspect, at least one, preferably only one, of R2, R3 and R4 is a hydroxyalkyl group. The hydroxyalkyl preferably has 1 to 4 carbon atoms, most preferably 2 or 3 carbon atoms, more preferably 2 carbon atoms. In another preferred aspect, at least one of R2, R3 and R4 is a C2-C3 alkyl group, most preferably two C2-C3 alkyl groups are present. The highly preferred water-dispersible cationic ester surfactants are esters having the formula: O CH 3 R ± CO (CH 2) -MN + CH 3 M ~ CH 3 wherein m is 1 to 4, preferably 2 or 3 and wherein R] _ is a linear or branched alkyl chain of C ^ -C ^ g. Particularly preferred choline esters are of the type which include the quaternary methylammonium halides of stearylcholine (R] _ = C ^ alkyl), the quaternary methylammonium halides of palmitoylcholine ester (R ^ = C15 alkyl), the halides of quaternary methylammonium ester of myristoylcholine (R) _ = C13 alkyl), the methylammonium halides of ester lauroylcholine (R ^ _ = alkyl of Cu), quaternary methylammonium halides of cocoylcholine ester (R] _ = C11 alkyl- C13), quaternary methylammonium halides of ceboylcholine ester (Rt_ = C15-C17 alkyl), and mixtures thereof. Other suitable cationic ester surfactants have the following structural formulas, wherein d can be from 0 to 20. 3 M In a "preferred aspect, the cationic ester surfactant is hydrolysable under the conditions of a washing method for laundry. The particularly preferred choline esters, mentioned above, can be prepared by direct esterification of a fatty acid or the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, water, propylene glycol or preferably an ethoxylate of fatty alcohol ^^ such as the ethoxylate of fatty alcohol of C ^ gC ^ which has a degree of ethoxylation from 3 to 50 ethoxy groups per mole 25 forming the desired cationic material. They can also be prepared by direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.

Alkalinity system Another essential aspect of the detergent composition of the present invention is an alkalinity system, which comprises the components capable of providing alkalinity species in solution. Alkalinity species refers to the purposes of this invention: carbonate, bicarbonate, hydroxide, the various silicate anions, inorganic perhydrate anions and crystalline layered silicates. Such alkalinity species can be formed, for example, when the alkali salts selected from the alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate salts, crystalline layered silicate or inorganic perhydrated salts, preferably alkali metal percarbonate, perborate and persilicate salts. and any mixture thereof, dissolve in water. Preferably, the alkaline earth carbonates and alkali metal and bicarbonate are selected from sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate and mixtures thereof, including sodium carbonate, sesquicarbonate and mixtures thereof, with calcium carbonate. ultrafine as described in the German patent application no. 2,321,001 published November 15, 1973. Suitable mixtures include mixtures of sodium carbonate with sodium bicarbonate, sodium carbonate with potassium carbonate and sodium carbonate with sodium bicarbonate and potassium carbonate. Most preferably, the alkalinity system is substantially free of carbonate salts, but may comprise bicarbonate salts. The carbonate and bicarbonate preferably have an amorphous structure. Preferably the carbonate and bicarbonates are coated with coating materials, described later in the section "delayed release rate - media". The carbonate and bicarbonate particles can have an average particle size of 250 μm or greater, preferably 500 μm or more. It is preferred that less than 20% of the particles have a particle size below 500 μm. The average particle size of the carbonate and bicarbonate particles of the present is determined by reference with a method that involves the selection of varied sizes of sieve through which the sample is intended to pass. The average particle size of a sample is given by the sieve diameter through which half the mass of the sample will be passed, and consequently half of the sample will not pass. Suitable silicates include sodium silicates with a SiO2: Na2 ratio of 1.0 to 2.8, as with ratios of 1.6 to 2.0 being preferred, and a ratio of 20 being highly preferred. The silicates may be in the form of any anhydrous salt or a hydrated salt. Sodium silicate with a Si02: Na20 ratio of 2.0 is the most preferred silicate. Preferably, the silicates have an amorphous structure. The alkali metal percarbonate salts are also suitable alkalinity species and are described in more detail in the section "inorganic perhydrate salts" herein. The alkali metal percarbonate used may preferably be sodium percarbonate or potassium percarbonate, most preferably sodium percarbonate. Percarbonate is generally found in the particulate form. The percarbonate particles generally have a mean particle diameter ^ fc of 150-1200 μm, preferably 500-900 μm. Preferably, the percarbonate particles are coated, the alkali metal persilicates, as described in the section "inorganic perhydrated salts", are also suitable alkalinity species. Other suitable alkalinity species include a crystalline layered silicate, preferably a silicate Ü-crystalline laminate and very preferably crystalline-layered silicate is a crystalline layered sodium silicate con-20 with the general formula NaMSix02 + 1 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. The most preferred material is Ü-Na2Si2? 5, available from Hoechst AG as? aSKS-6. The crystalline layered silicate material is preferably present in granular detergent compositions as a particulate in an intimate mixture with a solid, water-soluble ionizable material. The solid, water-soluble ionizable material is selected from organic acids, salts of organic and inorganic acid and mixtures thereof. According to the invention, the stratified silicate alkalinity species is preferably coated with a coating material such as citric acid, as described in the section "delayed release media". The alkalinity system is preferably present in an amount from 1% to 75%, most preferably in an amount from 10% to 40% by weight of the detergent composition.

RELEVANT RELEASE Kinetics An essential aspect of the invention is the means, which are provided to retard the release to an alkalinity system wash solution relative to the release of a cationic ester surfactant.

Delayed release rate - media The media is preferably provided for the delayed release of the same alkalinity system to the wash solution. The delayed release media may include coating any suitable alkalinity species with a coating designed to provide delayed release. The coating can therefore, for example, comprise a material poorly soluble in water, or be a coating of sufficient thickness for the kinetics ^ P of thick coating solution provide the speed controlled release. The coating material can be applied using various methods. Any coating material typically occurs in a weight ratio of coating material to the alkalinity species from 1:99 to 1: 2, preferably from 1:49 to 1: 9. g. Suitable coating materials include triglycerides (eg partially) hydrogenated vegetable oil, soybean oil, cottonseed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixture thereof. Other suitable coating materials may comprise the alkali metal and alkaline earth metal sulfates. Another suitable coating material may comprise citric acid. A preferred coating material is sodium silicate of a ratio of Si 2: Na 2+. from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level from 2% to 10%, (usually from 3% to 5%) of percarbonate silicate solids. The magnesium silicate can also be included in the coating. Other coating materials suitable for use herein include polymers derived from amino acids such as polyglutamine acid, as described in GB 91-20653.2, and polyaspartic acid, as described in EP 305 282, and EP 351 629. EP-A-0382464 disclose coating materials such as polyacrylic acid and cellulose acetate phthalate. Such polymeric coating materials are water-soluble (acidic) polymers which are preferably used as a coating material for inorganic perhydrate salts and peroxyacid bleach precursors. Polymers suitable for use herein have a molecular weight in the range of from 1,000 to 280,000, preferably from 1,500 to 150,000. Preferably, the polymers have a melting point above 30 ° C. Any coating material can be combined with organic binder materials to provide mixed inorganic / organic salt binder coatings. Suitable binders include alcohol ethoxylates of C 2 or C 2 containing from 5-100 moles of ethylene oxide per mole of alcohol and most preferably primary alcohol ethoxylates of C 5 5 C 2 or contain from 20-100 moles. of ethylene oxide per mole of alcohol. Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, anhydridemaleic acid constitute at least 20% moles of polymer are other examples of polymeric materials useful as binders. Such polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned C-IO-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole. Other examples of binders include the mono- and diglycerol esters of C] _o-2o and also the C10-C20 fatty acids. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein. A method for applying the coating material involves agglomeration. Preferred agglomeration procedures include the use of any binder, organic material described below. Any conventional agglomerator / mixer can be used, including, but not limited to, a pan, rotating drum and vertical mixer types. The liquid coating compositions can also be applied by spraying or atomizing by spraying on a movable base of bleaching agent. Preferred methods for applying the coating materials are described in WO 93/918259. Other means to provide delayed release ~ W required include the mechanical means to alter the physical characteristics of the alkalinity system to control its solubility and release rate. Suitable means may include compaction, mechanical injection, manual injection. Other means to delay the release of alkalinity may include an adequate selection of k alkalinity species with an amorphous structure. It is known that the above dissolves in a relatively slow way compared to the alkalinity species with a crystalline structure. In this way, an adequate selection of alkalinity species amorphous will provide an alkalinity release delay. Additionally, the delayed release media may include a suitable selection of any other component of the matrix of the detergent composition so that when the composition is introduced into the wash solution, the environment provided with ionic strength in the present allows that the delayed release kinetics required is achieved.

Relative Release Rate - Synthetic Parameters The release of the cationic ester surfactant relative to the alkalinity system is such that the T50 test method of the present describes the time to achieve a concentration that is 50% of the final concentration of the cationic ester surfactant, and that this is at least 120 seconds less than the time to achieve a concentration that is 50% of the ultimate concentration of said alkalinity system. Preferably, the time to achieve a concentration that is 50% of the ultimate concentration of the cationic ester surfactant is greater than 300 seconds less than the time to achieve a concentration that is 50% of the ultimate concentration of the alkalinity system .

Delayed release - test method The delayed release kinetics of the present is defined with respect to the "TA test method", which measures the time to achieve A% of the final concentration / level of the component when a composition containing the component it dissolves according to the standard conditions now established. Standard conditions involve a 1-liter glass beaker filled with 1000 ml of distilled water at 20 ° C, to which 10 g of composition are added. The contents of the vessel are agitated using a magnetic stirrer placed at 100 rpm. The final concentration / level is taken to be the concentration / level for 15 minutes after the addition of the composition to the glass filled with water. Suitable analytical methods are selected to allow reliable determination of the incidental concentrations, and ultimate in the solution of the component being treated, subsequent to the addition of the composition to the water in the vessel. Such analytical methods can include those that have to do with a continuous monitoring of the concentration level of the component, including for example photometric and conductometric methods. Alternatively, methods involving the removal of volumes from the solution at established time intervals may be employed, stopping the dissolution process by appropriate means such as rapid reduction of the volume temperature, and determining the concentration of the component in the volume by chemical volumetric methods. Suitable graphical methods, including curve coupling methods, can be used if appropriate, in order to calculate the TA value of the empirical analytical results. The particular analytical method selected to determine the concentration of the component will depend on the nature of said component, and on the nature of the composition containing said component.

Additional detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of such additional components, and levels 5 of incorporation thereof will depend on the physical form of the composition, and on the precise nature of the washing operation for which it is to be used. The compositions of the invention preferably contain one or more additional detergent components selected from the additional surfactants, bleaching agents, builders, organic polymeric compounds, enzymes, suds suppressors, lime and soap scatterers, soil slurry and soil release agents. anti-redeposition and corrosion inhibitors. 15 Additional Surfactant The detergent compositions of the invention ^^ preferably contain one or more additional surfactants selected. of anionic, nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. A typical list of anionic, nonionic, ampholytic, and switerionic classes and species of such surfactants is provided in the U.S.P. 3,929,678 issued to Laughiin and Heuring on December 30, 1975. Other examples are provided in "surface active agents and detergents" (Vol I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is provided in the U.S.P. 4,259,217 issued to Murphy on March 31, 1981. W When present, surfactants Ampholytic, amphoteric and zwitterionic ampholytics are generally used in combination with one or more anionic and / or nonionic surfactants.

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

Anionic Sulfate Surfactant The anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, ethylene oxide ether sulfates of alkyl phenol, acyl glucamin sulfates of C5-C17-N- (C1-C4 alkyl) and -N- (hydroxyalkyl) __ C] _- C2), and alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (described herein) non-sulfate nonionic compounds). The alkyl sulfate surfactants are preferably selected from the linear and branched primary alkyl sulfates, most preferably the branched chain alkyl sulphates and the salts thereof.

C ^ -C ^ alkyl sulfates of straight chain. The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of C 1 Q-C ^ Q alkyl sulfates 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 -Cis alkyl sulfate, most preferably C 1 -C 4, 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 ethoxylate surfactants. Such mixtures have been described in PCT application No. WO) 3/18124.

Sulfonate Anionic Surfactant Anionic sulphonate surfactants suitable for use herein include the linear alkylbenzene sulphonate salts of 5-C2O 'alkyl ether sulfonates, primary or secondary Cg-C22 alkan sulfonates, Cg-C24 sulfonated polycarboxylic acid olefinsulfonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Carboxylate anionic surfactant Carboxylate anionic surfactants include alkylethoxycarboxylates, the alkylpolyethoxypolycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH2O) xCH2C00"" M + wherein R is an alkyl group from Cg to C ^ sx ranges from 0 to 10, and the ethoxylate distribution is such that, in a base of weight, 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 RO- (CHR ^ -CHR2-O) -R3 wherein R is an alkyl group from Cg to C ^ s-- x is from 1 to 25, R ^ _ and R2 are selected from the group consisting of • hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid 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 ^ the secondary soap surfactants that contain a 9 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-ethyl propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R.sub.1 CO.sub.1) CH COOM, wherein R.sub.s is a linear or branched alkyl or alkenyl group of c.sub.12 ~ c.sub.17, R is a group C1-C4 alkyl and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant An additional preferred surfactant according to the detergent composition of the invention is a nonionic surfactant present from 0.1% to 20%, most preferably from 0.2% to 10% by weight, most preferably from 0.5% to 5% by weight of the detergent composition. Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

Nonionic surfactant of 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.

Non-ionic 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 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 _ or C 2 alkyl, more preferably C 1 _ alkyl (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 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 hydroxyl directly connected to - F 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. A preferred polyhydroxy nonionic fatty acid amide surfactant for use herein is a C2.5-C17 alkyl N-methyl glucamide. The ratio of polyhydroxy fatty acid to ester surfactant • cationic is preferably between 1: 1 to 1: 8, most preferably 1: 2.5. It has been discovered that such surfactant systems are capable of reducing the formation of "lime-soap" and the deposition of inlay on the cloth.

Non-ionic fatty acid amide surfactant ^^ Suitable amide surfactants include ^^^ r rr * - r those having the formula: R CON (R) 2 where R 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 ^ ^ alkyl, C1-C4 hydroxyalkyl, and (C2H4?) xH, where x is on a scale of 1 to 3. 25 Non-ionic surfactant of allylpolysaccharide The appropriate alkyl polysaccharides that are used they are described herein in the US patent No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group 5 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 (CnH2nO) t (glucosyl) x 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 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose. Amphoteric Surfactant Amphoteric surfactants suitable for use herein include the surfactants of • amine oxide and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR) xN ° (R5), wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R is an alkylene group or 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. They prefer the ^ alkyl dimethylamine oxide of C ?? c18 V e "*" oxide of Acylamidodimethylamine from Cι '^ s- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant agent 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 1) 2N + R 2 COO- wherein R is a hydrocarbyl group of C -C ^ s, each R 1 is typically C 1 -C 3 alkyl, and R is a group hydrocarbyl of C ^ -? . The preferred betaines are the dimethyl ammonium hexanoate betaines of Ci2_cl8 and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C ^ o- ^ s- Also, complex betaine surfactants are suitable for use herein.

Cationic Surfactants The additional cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from N-alkyl or alkenyl ammonium mono- or cycloalkyl surfactants, preferably Cg-C] _g, in which the remaining N-positions are substituted by methyl groups , hydroxyethyl or hydroxypropyl.

Water-soluble builder compound 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 from 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, gßk tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the 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 the British Patent. No. 1,389,732 and the aminosuccinates described in the Dutch application 7205873 and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829, 1, 2, 2-etantetracarboxylates, 1, 1, 3, 3-propanetracarboxylates and the 1,1,2,3-propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. 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. In a highly preferred aspect of the invention, means are also provided for retarding a preferred water-soluble detergent builder component washing solution relative to the cationic ester surfactant. Such media may comprise equivalents of any delayed release medium described herein to achieve any of the delayed release media to achieve delayed release of the alkalinity system or species described below.

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%. % in weight, most preferably from 20% to 60% by weight of the composition. Examples of detergency builders widely ^^ soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the Unit cell formula Naz [(AIO2) z (Si02) and] "xH20 where z and y are integers of at least 6, the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably 10 to 264. The aluminosilicate material is in hydrated form and is crystalline Preferably, 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: Na12 [(A10) 12 (Si0) 12] -xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(A102) 8g (Si02) 10g] 276H20 Another preferred binder material is a crystalline layered silicate, preferably a crystalline ε-layered silicate, and most preferably the crystalline ε-layered silicate is a crystalline ε-layered sodium silicate with the general formula NaMSix02 + i and H20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is number from 0 to 20. Crystalline stratified sodium silicates of this type are described in EP-A-0164514 and methods for their preparation are described in the DE -A-3417649 and DE-A-3742043. In the present, x in the above general formula preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is Ü-Na Si2? 5, available Hoechst AG as NaSKS-6, crystalline layered silicate material it is preferably present in granular detergent compositions as a particulate in an intimate mixture with a solid, water soluble ionizable material. The solid, water-soluble ionizable material is selected from the organic acids, organic and inorganic acid salts and mixtures of the same. More preferably this material contains citric acid. Applicants have discovered that deposition on the fabric in the washing of inorganic scale (insoluble), for example, caused by the reaction of the binder material such as zeolite and crystalline layered silicate.

With alkali metal and alkaline earth metal ions, which cause hardness in water, they can be reduced by cationic ester surfactants according to the present invention. The cationic ester surfactants facilitate the suspension of the inorganic scale, thus reducing the deposition of said inorganic materials in the fabric. It is believed that the mechanisms are responsible for the above. First, the interaction of _, cationically charged ester surfactants with the negatively charged cloth surface can modify the surface of the fabric, which reduces the deposition of inorganic scale on the surface of the fabric. Second, the interaction of the cationically charged ester surfactants with the anionically charged deposited binder material (such as the zeolite and the crystalline layered silicate) can facilitate the suspension of the deposited binder material, which reduces the fouling of the fabric .

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. The production of organic peroxyacid occurs through a reaction in situ of the precursor with a source of hydrogen peroxide. The 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. I also know • 15 contemplate compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Whitening Agents 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 1% to 40% by weight, very 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 alkali metal salts of silicate, 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 NaB02H2? 2 or the tetrahydrate aB? 2H2? 2.3H20. The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates of the present. Sodium percarbonate is an addition compound having the formula corresponding to 2Na2CC > 3.3H202, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein. In a preferred aspect of the present invention, means are provided for delaying the release to a wash solution of the preferred inorganic perhydrate salts, relative to the release of the cationic ester surfactant. Such media may comprise equivalents of any delayed release medium of the present invention to achieve the delayed release of the alkalinity system or species, described herein.

Peroxyacid bleach precursors Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid sources according to the invention. Peroxyacid bleach precursors are usually incorporated at a level from 0.5% to 20% by weight, most preferably from 2% to 10% by weight, most preferably from 3% to 5% by weight of the compositions. Suitable peroxyacid bleach precursors typically contain one or more N- or O-acyl groups, whose precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and 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. Acylation products of sorbitol, glucose and all saccharides with benzoylating agents and acetylating agents are also suitable. Specific O-acylated precursor compounds include 2, 3, 3, -tri-methyl hexoyl oxybenzene sulfonates, ^ P benzoyl oxybenzene sulfonates, nonanoyl-6-amino 5-caproyl-oxybenzene sulfonates, monobenzoyltetraacetyl-benzoyl peroxide benzoyl peroxide and cationic derivatives of any of the foregoing, including alkyl ammonium and pentaacetyl glucose derivatives. The phthalic anhydride is a precursor of the suitable anhydride type. Specific cationic derivatives of the 0-acyl precursor compounds include 2- (N, N, N. -trimethylammonium) ethyl sodium 4-sulfophenyl carbonate, and any of the alkylammonium derivatives of the benzoyl oxybenzene sulfonates include the derivative of 4- (trimethyl) ammonium) methyl. Useful N-acyl compounds are described in GB-A-855735, 907356 and GB-A-1246338. Preferred precursor compounds of the imide type • include tetrabenzoyl N-benzoyl-thiamine succinimide Ethylene, substituted ureas of N-benzoyl and the diamines of N-, N, NN tetra acetylated alkylene wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1.2 and 6 carbon atoms. The diamine of Tetraacetylene ethylene (TAED) is particularly preferred. Preferably, the tetraacetyl ethylene diamine has a compressed particle structure, achieved by mechanical compression, to retard dissolution of the particles in the wash solution. N-acylated precursor compounds of the class 5 lactam are generally described in GB-A-955735. Preferred materials comprise the caprolactams and valerolactams. Suitable N-acylated lactam precursors have the formula: n wherein n is from 0 to 8, preferably from 0 to 2, and R is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms. ^^ Suitable caprolactam bleach precursors are of the formula: O CH. CH- 25 CH 2 R 1 C N CH 2 CH 2 wherein R is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably R is phenyl. Suitable valerolactams have the formula: or 1! Rl - wherein R is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In the highly preferred embodiments, R is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl, and mixtures thereof. The most preferred materials are those that are normally solid to < 30 ° C, particularly the phenyl derivatives, ie benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogs such as the chloro, amino alkyl, alkyl, aryl and alkoxy derivatives. The precursor materials of caprolactam and valerolactam where the portion of R contains at least 6, • preferably from 6 to 12 carbon atoms provide the 5 peroxyacids in the perhydrolysis of a hydrophobic character that has to do with the nucleophilic cleansing and dirtiness of the body. The precursor compounds wherein R comprises from 1 to 6 carbon atoms provide species of. hydrophilic whitening which are particularly efficient for bleaching 10 drink spots. Mixtures of caprolactams and J-valerolactams "hydrophobic" and "hydrophilic", typically at weight ratios of 1: 5 to 5: 1, preferably 1: 1, can be used herein for the benefits of mixed spot removal. The highly preferred caprolactam and valerolactam precursors include benzoyl caprolactam, nonayl capro-lactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl • valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6-octanamidocaproyl) oxybenzenesulfonate, (6- nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) -oxybenzenesulfonate, and mixtures of same. Examples of substituted benzoyl lactams 25 include methylbenzoyl caprolactam highly preferred, methylbenzoyl valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, caprolactam propilbenzoil, propilbenzoil valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, butylbenzoyl caprolactam ter-, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl. caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactam isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoyl valerolactam, butoxybenzoyl caprolactam tert-, butoxybenzoyl valerolactam tert-, pentoxibenzoil caprolactam, valerolactam pentoxibenzoil, hexoxibenzoil caprolactam, valerolactam hexoxibenzoil, 2,4,6-trichlorobenzoyl caprolactam, 2, 4 6-triciclorobenzoil valerolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-chlorobenzoyl caprolactam, 2,4-dichlorobenzoyl caprolactam, terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam ' , 2,4-dichlorobenzoyl valerolactam, terephthaloyl divalerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam and mixtures thereof. Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole and another useful N-acyl group containing peroxyacid precursors including N-benzoyl pyrrolidone, and benzoyl taurine and benzoyl pyroglutamic acid. ^ P Another preferred class of activating compounds of Bleaching peroxyacids are the substituted amide compounds of the following general formulas: R 1 - C - N - R 2 - C - L R 1 - N - C - R 2 - C - L II L II oi II II OR ^ OR 0 0 10 'where R is an aryl or alkaryl group with 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group that B contains from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L may be essentially any residual group. R preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R may be a straight or branched chain of alkyl, substituted aryl or alkylaryl containing a branching, substitution, or both and may be obtained from any synthetic or natural source including, for example, bait grease. Structural variations of analogous are permissible for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R is -1 r-25 preferably H or methyl. R and R must not contain more than 18 carbon atoms in total. Such substituted bleach activating compounds are described in EP-A-0170386. The L group must be sufficiently reactive for the reaction to occur within the optimum time frame (ie, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. Such characteristics are generally equivalent by the pKa of the conjugate acid of the residual group, although the exceptions of this convention are known.

Ordinarily, residual groups exhibiting such behavior are those in which the conjugated acid has a pKA on the scale from 4 to 13, preferably from 6 to 11 and most preferably from 8 to 11. The preferred bleach precursors are those in where R1, R2 and R5 are as defined for the susbstituted amide compounds and L is selected from the group consisting of: and mixtures thereof, wherein R is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R, and Y is H or a solubilizing group. The preferred solubilizing groups are -S? 3 ~ M +, C02 ~ M +, -S? 4 ~ M +, -N + (R3) 4X ~ and 0 < -N (R3) and most preferably-S? 3 ~ M + and -C? 2 ~ M +, where R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the activator of bleaching and X is an anion that provides QP 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. It should be noted that bleach activators with a residual group that does not contain solubilizing groups must be dispersed in the bleaching solution in order to aid in their dissolution. The preferred examples of the bleach activators of the above formulas include (6- octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) -oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof. Other preferred precursor compounds include those of the benzoxazine type, which have the formula: including substituted benzoxazines of type 25 wherein R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 3, R 4 and R 5 can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkyl amino, COORg (where Rg is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxazine type is: 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 scavenger having defined stability constants for the auxiliary metal cations and catalytic, 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 patent of E.U.A. No. 5,244,594. Preferred examples of these catalysts include Mn1 2 (u-0) 3 (1, 4, 7-trimethyl-1,4-, 7-triazacyclononane) 2- (PFg) 2. MnIII2 (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- (CIO4) 2, Mn ^ iMn1 ^ (u-0) 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, 7-triazacyclononane and mixtures thereof. For examples of suitable bleach catalysts see the patent of E.U.A. No. 4,246,612 and in the patent of E.U.A. No. 5,227,084. See also the patent of E.U.A. Do not. ,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1, 4, 7-trimethyl-1,4,4-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 5 (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear complexed Mn • with tetra-N-dentate and bi-N-toothed ligands, including N4MnI?:? :( u-0) 2MnIVN4) + and [Bipy2MnI ?: E (u-0) 2MnIvbipy2] - (C104) 3. 10 Suitable and additional bleach catalysts are They describe, for example, European Patent Application No. 408,131 (cobalt complex catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), E.U.A. 4,728,455 15 (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 20 (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 25 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 it is tried here to say 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 ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, QP 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 suitable heavy metal ion sequestrants For use herein are the jimino diacetic 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 discloses a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1,2,4-tricarboxylic acid. Glycinamide-N-N'-disuccinic acid (GADS), ethylene diamine 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. Preferred commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-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 0.001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, the alpha-amylases 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 0.0001% to 2% active enzyme by weight of the composition. The detergent composition according to the present invention preferably contains a lipolytic enzyme. It has been found that the cationic ester surfactant improves the performance of the lipolytic enzyme. It is believed that the mechanisms are responsible for the improved performance of the enzyme. First, fatty acids, which are formed by the enzymatic reaction of lipolytic enzymes with triglycerides contained in oily or fatty soils, will be removed from the surface of the fabric by the cationic ester surfactant. This will facilitate the "access" by the enzymes to the stains / greasy dirt during the washing process. Secondly, the removal of the fatty acids from the surface of the fabric by means of the cationic ester surfactant will reduce the formation and deposition in the "lime-soap" fabric, formed through the reaction of fatty acids with ions of calcium from the hardness of water. This will also facilitate the "access" by means of the enzymes of the stains / greasy dirt on the surface of the fabric. The lipolytic enzyme may be present at P levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably 0.001% to 0.5% by weight of the compositions. The lipase can 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 pseudoalcaligenes or Pseudomas fluorescens. Lipase that comes from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcalicrenes, which is described in European patent EP-B-0218272. Another preferred lipase herein is obtained by cloning the Humicola lanuqinosa gene and expressing the gene in Aspercillus oryza as host, as described in European patent application EP-A-0258 068, which is 0 commercially available from Novo. Industri A / S, Bagsvaerd, Denmark under the trade name Lipolase. Lipase is also described in the patent of E.U.A. No. 4,810,414, Huge-Jensen 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, wherein ^ p can act as to bind the component in particles together. 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 and suspending agents of soils in the 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 polycarboxylic acids soluble in water 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 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of 20,000 to 100,000 , especially 40,000 to 80,000. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable 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 in the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. fifteen . 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 suppression system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppression system present at a level of 0.01% to 15%, preferably 25.05% to 10% and most preferably from 0.1% to 5% by weight of the composition.

The foam suppression systems suitable for use herein can comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl-5-alkanol antifoaming compounds. By "antifoam compound" is meant herein 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. The antifoam compounds particularly preferred for use herein are the silicone anti-foam compounds defined herein as any anti-foam compound that includes a silicone component. Said anti-foam compounds silicones 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 units ^^ siloxane and a hydrocarbyl group of various types. The Preferred antifoam silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include Ios-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. A drawback associated with such fatty acid antifoams is their tendency to interact with any Ca ++ or Mg ++ ion present in the wash solution, to form insoluble "caljabones", which can be deposited on the fabric during washing. It has been found that this problem can be reduced by the presence of cationic ester surfactants. The cationic ester surfactant interacts with formed "lime-soaps", suspending them in this way in the washing solution, and thereby reducing the deposition of the "lime-soaps" formed in the fabric during washing. 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 ^ 8"" c40 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, bis stearic acid amide and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of 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; 15 (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 0.5% to 10% level, preferably 1% to 10% by weight; a particularly preferred silicone glycol trailing copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid composition, most preferably comprising an ethoxylated C 1 -C 4 alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% to 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof , with a melting point of 45 ° C to 80 ° C.

Clay Softening System The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent. The clay mineral compound is preferably a smectite clay compound. Smectite clays are described in the U.S. Patents. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter & 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 dye transfer inhibiting agents. 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 Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: where P is a polymerizable unit, and O O O II II II A is NC, CO, C, -O-, -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 represented by the following general structures: O A I or (R1) x-N- (R2) V A I and I (R3) z or = N- (R?) X) wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / or y or / and z is or or 1 and wherein the nitrogen of the N-O group can be fixed or where the nitrogen of the N-O group forms 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 N-oxides of polyamines in which the nitrogen of the NO group forms part of the R group. 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, heterocyclic or alicyclic group in which the nitrogen of the functional group is NOT part of said group R Examples of these classes are the polyamine oxides in which R is a compound »Heterocyclic such as pyrridine, pyrrole, imidazole and derivatives 5 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 ^ P also available from ISP Corporation. Other suitable polyvinyl pyrrolidones that are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions herein also ? ^ can use polyvinyloxazolidones as a dye transfer inhibiting polymeric agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. 15 ß) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein R] _ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula R] _ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the f brightener is 4,4 '-bis [(4-anilino-6- (N-2-bis- ~ w -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 R] _ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [( 4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular type of brightener is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R] _ is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4 '-bis [(4-anilino-6-morphino-s- triazin-2-yl) amino] 2,2 '-stilbenedisulfonic acid. This kind of particular brightener is sold commercially under the name ^ Commercial Fino Tinopal AMS-GX by Ciba-Geigy Corporation.

Cationic fabric softening agents can also be incorporated into the compositions of According to the invention, cationic fabric softening agents are used. Suitable cationic fabric softening agents include water insoluble tertiary amines or dilarga chain amide materials such as those described in US Pat.

^ GB-A-1 514 276 and EP-B-0 011 340. 20 Cationic fabric softening agents are typically incorporated at total levels of 0.5% to 15% by weight, typically 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 a preferred filler salt being sodium sulfate. p. pH of the compositions The present compositions preferably have a pH measured as a 1% solution in distilled water of at least 9.0, preferably from 9.0 to 11.5, more preferably from 9.5 to 10.5.

Form of the Compositions The compositions according to the invention can have a variety of physical forms including the granulated, tablet, bar and liquid forms. 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 laundry load dirty. The average particle size of the components of ^^ the granulated compositions according to the invention must Preferably, it is 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 sifting a sample from 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 global density is measured by means of a simple funnel device and cup consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve in its • lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed 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, a height ~ ^ internal of 87 mm and an internal diameter of 84 mm. Its nominal volume 0 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 5 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.

Agglomerated Surfactant Particles The surfactant system herein is preferably presented in granular compositions in the form of agglomerated particles of surfactant, which may take the form of flakes, pills, marumas, noodles, tapes, but preferably take the form of granules. The most preferred way to process the particles is by the agglomeration powders (ie aluminosilacate, carbonate) with highly active surfactant pastes and to control the size and particle of the resulting agglomerates within specific limits. Said process has to do with mixing an effective amount of powder with a highly active surfactant paste in one or more agglomerators such as the pan agglomerator, or a Z-sheet mixer or very preferably in an in-line mixer. as the one manufactured by Schugi (Holland) BV, 29 Choomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1. Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a diverter mixer is used, such as a Lodige CB (tradename). Applicants discovered that the flow properties of the cationic ester surfactant containing granules is enhanced by the addition of a desiccant during the granulation process. The desiccant absorbs water ^ P during the granulation process and also absorbs the atmospheric humidity during storage of the finished product. Said absorption of atmospheric moisture also improves the stability of the cationic ester surfactant which can be hydrolyzed under wet conditions. The preferred desiccants are (anhydrous) MgS? 4 and aluminosilates of dry sodium, such as zeolite A, silicates. The applicants also discovered that the stability of the cationic ester surfactant containing particles can be improved when the level of heavy metal ions is reduced in the manufacturing process of particle, since heavy metal ions can catalyze the hydrolysis of cationic ester surfactants.

This can be achieved by limiting the possible contact of the cationic ester surfactants and the ^^ Heavy metal ions through the manufacturing process of the particle, for example through the use of vessels, which are free or substantially free of heavy metal ions, such as glass cups or plastic-lined cups. The stability of the cationic ester surfactant contains particles that can also be improve by dividing trace levels of heavy metal ion inhibitors during the process and manufacture of the particle or by spraying the heavy metal ion inhibitors in. the particles once formed. Suitable heavy metal ion inhibitors, which may be aspersion or added to particles of trace levels up to 3% by weight of the particles, including any of those described herein. Other suitable inhibiting agents include certain organic polymeric compounds, including acrylic / maleic acid copolymers. icro-pastillation of the surfactant agent particle. Cationic ester surfactants can be included in the form of micro-lozenges, formed by the so-called "pastillation process". A preferred process for the manufacture of detergent micro-pellets of a surfactant paste which is substantially in the solid phase at temperatures of 25 ° C and below, comprises the steps of: (i) mixing the surfactant paste to a temperature above the softening point, the surfactant paste comprises at least 50% by weight of nonionic surfactant; (ii) the formation of the surfactant paste fused into drops of a cooling belt; (iii) the formation of solid pellets by cooling drops of the fused surfactant paste; and (iv) the removal of solidified pellets from the cooling belt. F} In the procedure, the surfactant paste The melt is preferably formed in droplets by a continuous rotary droplet former comprising external and internal coaxial cylinders, both cylinders comprising a series of openings, at least one of the cylinders being rotatable. The drops of melt surfactant are conveniently formed in a continuous steel cooling belt and, optionally, cooled by spraying a cooling liquid on the good side of the belt to the side in which the drops are formed. The micro-pellets characteristically have a generally round surface profile and at least one and a substantially flat surface. To improve the flow properties of the granules and to improve the stability of the surfactant, the particle size of the granules must be controlled to achieve the most ideal size. Therefore, the surfactant paste is preferably subcooled before the melting process step and a crystal growth carrier such as choline chloride can be added. In this way it will be achieved that the granules, tablets or pills have the preferred size, preferably the so-called "powdering agent" is added to the micro-tablets, to prevent the product from becoming clogged and to improve the flow properties and the stability of the surfactant. Preferably, a hydrophobic powdering agent is used, such as hydrophobic silica. To improve the flow properties of the granules during the process (ie, the flow of a stage / vessel / container from one procedure to another) the powder must be essentially free of water or moisture, therefore a desiccant is preferably added during the micro-pastillation procedure.

Morphology of the particle The cationic ester surfactant containing particles or micro-pellets formed during the granulation process or the pelleting process are susceptible to decomposition when they are alkaline, under wet conditions. The stability of the particle or micro-pellet, however, can be improved, when the particle has a specific morphology, which can be defined by an MI morphology index. The morphology index can be calculated with the following formula: MI = (0.0448 x CV) + (3.61 x 106 / d3) where CV is the coefficient of variation of weight of the distribution of average particle size and d is the average weight of the particle size in microns. Preferably M is less than 0.06, most preferably less than 0.04 and most preferably less than 0.03.

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 40 g to 3 OOg 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 employed. commonly in conventional laundry washing methods. In a preferred use aspect a dispensing 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. Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and it rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation when the drum is rotated and also as a result of its contact with the washing liquid. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is liquid permeable but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the washing machine drum at this stage of the wash cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2,157,717, GB-B-2,157, 718, EP-A-0201376, EP-A-0288345 and EP- A-0288346 An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granular laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in the 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 , 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 medium. washing. 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 W bulge in a wheel configuration with spokes or similar structure, in which the walls have a helical shape. Alternatively, the delivery device can 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 polymeric material water-insoluble synthetic 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 an adhesive soluble in water disposed along and sealing an edge of a sack formed of a waterproof polymeric film such as polyethylene and polypropylene.

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.

Altalinity requirement and relative delay of alkalinity release. In the following examples 1 to 9 an alkalinity system is provided. In each example, the means for delaying the release to a washing solution of the alkalinity system relative to the cationic ester surfactant are provided. The means to retard the release of alkalinity is such that the time to achieve a concentration of 50% of the ultimate concentration of the cationic ester surfactant is at least 120 seconds less than the time to achieve a 50% concentration of the ultimate concentration of the alkalinity system, as described herein in the T50 test method.

Abbreviations used in examples 10 In detergent compositions, the Abbreviated component identifications have the following meanings: LAS: C1 linear sodium alkylbenzenesulfonate TAS: Sodium alkyl sulfate 15 C45AS: C14-C15 linear sodium alkyl sulfate CxyEzS: Clx-C branched sodium alkyl sulfate] and condensed with z moles of ethylene oxide C45E7: A primary alcohol of C14-C15 predominantly ^ _ linear condensed with an average of 7 moles of Q Ethylene oxide C25E3: A branched C? 2-C:? 5 primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5: A primary alcohol of ^ 2 ~ C? branched 25 condensed with an average of 5 moles of ethylene oxide CEQ I: R1C00CH2. N + (013) 3 with R = Cn -C13 CEQ II: R1COOCH2CH2CH2N + (CH3) 3 with Rx = Cn-C13 CEQ III: R1COOCH2CH2N + (CH3) 2 (CH2CH20H) with R = Cn-C13 CEQ IV: R1COOCH2CH2N + R2R3 (CH3) with R = C ^ - C ^ and R2 and R3 = C2-C3 QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C12-C14 Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils TFAA: N-methylglucamide of alkyl of C ^ gC ^ s TPKFA: Whole cut fatty acids of C 2 ~ cl'í STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na? 2 (A102Si02) 12 • 27H2O, which has a size of primary particle on the scale of 0.1 to 10 microns. NaSKS-6: Crystalline layered silicate of the formula Ú-Na2SÍ2? 5 Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0 ratio) Sodium sulphate Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425μm and 850μm MA / AA: 1: 4 maleic acid / acrylic acid copolymer with an average molecular weight of about 70, 000 CMC: Sodium carboxymethylcellulose Protease: Proteolytic activity enzyme 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 Novo Industries A / S under the trade name Carezyme Amylase: Activity amylolytic enzyme 60KNU / g sold by Novo Industries A / S under the trade name Termamyl 60T Lipase: Lipolytic activity enzyme lOOkLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa; Enzyme endoglucose activity 3000CEVU / g sold by Novo Industries A / S PB4 Anhydrous sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PBl Anhydrous sodium perborate bleach monohydrate of nominal formula NaB02.H2? 2 Percarbonate: Sodium percarbonate nominal formula 2Na2C03.3H202 Percarbonate: Coated sodium percarbonate bleach (particle with a slow-release sodium silicate coating) (ratio of Si20: Na2O = 2: 1) to a weight ratio of percarbonate to sodium silicate of 30 : 1 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (methylene phosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Brightening 1: 4.4 '-bis (2-sulphotryryl) biphenyl disodium Brightener 2: 4, 4' -bis (4-anilino-6-morpholino-l) 3. 3-triazin-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 End esters blocked with sulfobenzoyl with base structure of oxyethyleneoxy and terephthaloyl SRP 2: Polymer block short polymer (1, 2) -propylene terephthalate) diethoxylated Silicone Antifoams: 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: EXAMPLE 1 (CONTINUED) EXAMPLE 2 The following granular laundry detergent compositions G a l were prepared with an overall density of 750 g / liter according to the invention: EXAMPLE 2 (CONTINUED) EXAMPLE 2 (CONTINUED) EXAMPLE 3 The following detergent formulations were prepared according to the present invention, wherein J is a phosphorus-containing detergent composition, K is a detergent composition containing zeolite and L is a compact detergent composition: EXAMPLE 3 (CONTINUED) EXAMPLE 3 (CONTINUED) EXAMPLE 4 The following detergent formulations containing indigo bleach of particular use were prepared in the washing of garments with color, according to the invention: EXAMPLE 4 (CONTINUED) EXAMPLE 4 (CONTINUED) EXAMPLE 5 The following detergent formulations were prepared according to the present invention: EXAMPLE 5 (CONTINUED) EXAMPLE 6 The following detergent formulations were prepared according to the present invention: EXAMPLE 6 (CONTINUED) EXAMPLE 7 (CONTINUED) EXAMPLE 7 (CONTINUED) EXAMPLE 8 The following high density detergent formulations were prepared according to the present invention: EXAMPLE 8 (CONTINUED)

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. A detergent composition containing (a) a cationic ester surfactant, and (b) an alkalinity system, wherein means are provided to retard the release of a wash solution of said alkalinity system with respect to to the release of said agent 10 cationic ester surfactant, so that in the method dk T50 test of the present describes that the time to achieve a concentration of 50% of the ultimate concentration of said cationic ester surfactant is at least 120 seconds less than the time to achieve a concentration of 15 50% of the final concentration of said alkalinity system.

2. - A detergent composition and in accordance with claim 1, further characterized in that said ^^ media are retarding means of the release to a washing solution of said alkalinity system in relation to the 20 release of said cationic ester surfactant, so that the T50 test method of the present invention describing the time to achieve a concentration of 50% of the ultimate concentration of said cationic ester surfactant is at least 300 seconds less that the time for 25 achieve a concentration of 50% of the final concentration of said alkalinity system.

3. - A detergent composition according to claim 1, further characterized in that said cationic ester surfactant is selected from those having the formula R R < Ri O + (CH) nO (X) "(CH,) r (Y) v- (CH,) t-N-R3 M" J b J wherein R ^ is a linear or branched alkyl of C5-C31, alkenyl or alkaryl chain or M-. N + (RgR7R8) (CH2) s. x YY, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO where at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R 2, R 3 R 4, R g, R 7, and R g are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkenyl 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 m, n, s, and t independently are 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 independently are 0 or 1 with the condition that at least one of uov must be 1; and where M is a counter-union.

4. - A detergent composition according to claim 3, further characterized in that R2, R3 and R4 are independently selected from the group consisting of C1-C3 alkyl and hydroxyalkyl groups.

5. - A detergent composition according to claim 3, further characterized in that the cationic ester is selected in the choline esters having the formula: 0 CH3 Rl c - - 0 - - (CH2) m • - N + - -CH- -3 M CH3 wherein m is from 1 to 4 and Ri is a linear or branched alkyl chain of C ^ i-C ^ g.

6. - A detergent composition according to claim 1, further characterized in that the cationic ester surfactant is present in an amount from 0.1% to 20% by weight of the detergent composition.

7. A detergent composition according to claim 1, further characterized in that the cationic ester surfactant is present in an amount from 0.5% to 5% by weight of the detergent composition.

8. - A detergent composition according to claim 1, further characterized in that the alkalinity system is present in an amount from 1% to 75% by weight of the detergent composition.

9. - A detergent composition according to claim 1, further characterized in that the alkalinity system is present in an amount from 10% to 40% by weight of the detergent composition.

10. A detergent composition according to claim 1, further characterized in that said alkalinity system comprises alkali salts selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate salts, crystalline layered silicate and any mixture thereof.

11. A detergent composition according to claim 1, further characterized in that said alkalinity system comprises alkali salts selected from the group consisting of inorganic perhydrate salt.

12. - A method for laundry washing in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to claim 1, is introduced into the drum of the washing machine before the start of washing, characterized in that said dispensing device allows the progressive release of said detergent composition in the washing liquid during washing.