MXPA98000273A - Detergent compositions - Google Patents

Abstract

A detergent composition suitable for use in laundry and dishwashing methods is provided which comprises: a cationic ester surfactant present at a level of 0.1% to 2.0% by weight of the detergent composition, and an anionic surfactant present at a 8% to 30% by weight level of the detergent composition, wherein less than 9.5% by weight of the detergent is an anionic surfactant selected from the group comprising linear or branched alkylbenzenesulfonates

Description

C0MP0 DETERGENT SITES TECHNICAL FIELD The present invention relates to detergent compositions containing a cationic ester surfactant and an anionic surfactant. The detergent composition is suitable for use in laundry and dishwashing methods.

BACKGROUND OF THE INVENTION The satisfactory removal of dirt / greasy stains, ie soils / stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions that are used in laundry and dishwashing methods. The surfactant components have traditionally been used in detergent products to facilitate the removal of said dirt / greasy stains. In particular, surfactant systems comprising cationic esters for use in the removal of dirt / greasy spots have been described. For example, EP-B-21,491 discloses detergent compositions containing a mixture of non-ionic / cationic surfactant and an admixture enhancing mixture. detergency comprising an aluminosilicate and polycarboxylate builder. The cationic surfactant may be a cationic ester. The improved removal of dirt in the form of particles and greasy / oily is described. EU-A-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. A problem that is commonly encountered with frequently washed fabrics is the accumulation of greasy stains / dirt, which can be caused when the greasy stains / dirt are not completely removed from the fabric during washing. This can lead to the tendency of the frequently washed fabric to obtain a "percured" appearance. Applicants have now surprisingly discovered that a solution to this problem is provided when a surfactant system comprising a cationic ester surfactant and an anionic surfactant at a relatively high level is employed in a detergent composition. It has been found that these surfactant systems have a surprisingly better cleaning performance than detergents with a high level of anionic surfactant that do not comprise cationic ester surfactants, or that detergents that they have a relatively low level of a surfactant system comprising a cationic ester surfactant and an anionic surfactant. It is believed that two mechanisms are responsible for these benefits. First, the cationic ester surfactant can reduce the deposition of "lime soaps" (formed by the alkaline earth ions and the fatty acids in the washing solution) on the fabric. The "lime soaps" can form a film on the stain / greasy dirt components, thus preventing the surfactants from interacting with these components. In this way, the removal of the "lime soaps" deposited by means of the cationic ester surfactant facilitates the removal of greasy stains / dirt by the surfactant system. Secondly, the monomers of the free cationic ester surfactant and the monomers of the free anionic surfactant in the wash solution can form miscella, which are relatively hydrophobic. Therefore, they will have a greater affinity for hydrophobic stains and greasy soils and in this way an improved cleaning performance of the surfactant system is achieved. All documents cited in the present description are, in a relevant part, incorporated herein by way of reference.

BRIEF DESCRIPTION OF THE INVENTION The detergent composition of the present invention comprises: (a) a cationic ester surfactant present at a level of from 0.1% to 2.0% by weight of the detergent composition; and (b) an anionic surfactant present at a level of from 8% to 30% by weight of the detergent composition, wherein less than 9.5% by weight of the detergent composition is an anionic surfactant selected from the group comprising linear alkylbenzenesulfonates or branched. In another preferred aspect, the cationic ester surfactant is selected from those having the formula: wherein Ri is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain or M ".N + (6R7R8) (CH2) s; X and Y, independently, are selected from the group consisting of COO, OCO, , CO, OCOO, CONH, NHCO, OCONH and NHCOO where at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R2, R3,, Re, R7 and s are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or an alkyl group of Ci-C3; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the proviso that at least some of uov must be 1; and where M is a counter anion. Preferably, the detergent composition comprises a nonionic surfactant, preferably present at a level of from 0.5% to 25% by weight of the detergent composition, wherein said nonionic surfactant and said cationic ester surfactant are present. preferably at a level of from 2.5: 1 to 8: 1, most preferably from 3: 1 to 6: 1.

DETAILED DESCRIPTION OF THE INVENTION Cationic ester surfactant An essential element of the detergent compositions of the invention is a cationic ester surfactant. The cationic ester surfactant is present at a level from 0.1% to 2.0%, preferably from 0.2% to 1.5%, very preferably from 0.3% to 1.0% by weight of the detergent composition. The anionic surfactant, as described above, and the cationic ester surfactant are present in a weight ratio of anionic surfactant to cationic ester surfactant of from 4: 1 to 40: 1, preferably 5: 1 to 20: 1 and most preferably from 6: 1 to 10: 1. The cationic ester surfactant of the present invention is preferably a water dispersible compound, which has surfactant properties comprising at least one ester linkage (ie, -C00-) 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 linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. , a chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms that form the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures of them, with the proviso that any nitrogen or oxygen atom in said chain is connected only with carbon atoms in the chain. In this way, the separating groups that have, for example, bonds -0-0- (eg, peroxide), -NN- and -NO- are excluded, while the separating groups that have, for example, bonds - CH2-0- CH2 - and -CH2-NH-CH2- are included. In a preferred aspect, the chain of the spacer group comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain. The cationic ester surfactants are those having the formula: wherein Ri is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain or M ~ .N + (R6R7R8) (CH2) ß; X and Y, independently, are selected from the group consisting of COO, OCO, 0, C0, 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, Re, R7 and Rß are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkynyl and alkaryl groups which they have from 1 to 4 carbon atoms; and R5 is independently H or an alkyl group of Ci-C3; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the proviso that at least some of uov must be 1; and where M is a counter anion. Preferably, 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: wherein Ri is an linear or branched alkyl, alkenyl or alkaryl chain of Cs -C31; or X is selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO; R2, R3 and R are independently selected from the group consisting of alkyl and hydroxyalkyl groups having from 1 to 4 carbon atoms; and Rs is independently H or an alkyl group of Ci-C3; 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 either 0 or 1, and the value of m is 3 to 8 Most preferably, R2, R3 and R- are independently selected from an alkyl group of C? -C and a hydroxyalkyl group of Ci -C¿,. In a preferred aspect, at least one, preferably only one of R2, R3 and R-i is a hydroxyalkyl group. The hydroxyalkyl preferably has from 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? 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: wherein m is from 1 to 4, p is referenced 2 or 3, and wherein Ri is an alkyl chain of C 1-19 I ineal or branched.

Particularly preferred choline esters of this type include the quaternary methylammonium halides of stearoyl choline ester (R? = C17 alkyl), the quaternary methylammonium halides of palmitoyl choline ester (R? = C15 alkyl), the halides of quaternary methylammonium ester of myristoyl choline (Realkyl of C13), quaternary methylammonium halides of lauroyl choline ester (R? = Cu alkyl), quaternary methylammonium halogenides of cocoyl choline ester (R? = C11 alkyl) -C13), the quaternary methylammonium halides of seboyl choline ester (R? = C1S-C17 alkyl) and any mixture thereof. Other suitable cationic ester surfactants have the following structural formulas, wherein d can be from 0 to 20.

In a preferred aspect, the cationic ester surfactant is hydrolysable under the conditions of a laundry method. Choline esters particularly preferred and mentioned above can be prepared by direct esterification of a fatty acid of the desired chain length with di-ethylaminoethanol, 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 ethoxylated fatty alcohol such as ethoxylated Cι-Ciß fatty alcohol having an ethoxylation degree of from 3 ° C. to 50 ethoxy groups per mole forming the desired cationic material. They can also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-halogenoethanol, in the presence of an acid catalyst material. The reaction product is subsequently quaternized with trimethylane, forming the desired cationic material.

Anionic Surfactant An essential component of the present invention is an anionic surfactant. The anionic surfactant is present at a level of from 8% to 30%, preferably from 9% to 20% and most preferably from 11% to 15% by weight of the detergent composition. The detergent composition according to the present invention comprises less than 9.5%, preferably less than 5% by weight of the detergent composition of a linear or branched alkylbenzene sulfonate surfactant.

The anionic surfactant and the cationic ester surfactant are preferably present in a weight ratio of anionic surfactant to cationic ester surfactant of from 4: 1 to 40: 1, preferably from 5: 1 to 20: 1 and very preferably from 6: 1 to 10: 1. Suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C 12 -C 18 monoesters), sulfosuccinate diesters ( especially saturated and unsaturated C-α-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.

Sulphonic Anion Surfactant The anionic sulfate surfactants used herein include the linear and branched primary and secondary alkyl sulphates, alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, acyl glucamin sulphates of C5-C17-N. - (C 1 -C 4 alkyl) and -N- (C 1 -C 2 hydroxyalkyl), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulphates (nonionic non-sulfate compounds are described herein). The alkylsulfate surfactants are preferably selected from the linear and branched Cι-Cis primary alkyl sulfates, most preferably the branched chain C 11 -C 15 alkyl sulfates and the straight chain C 12 -C 14 alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the Cι-Ciß alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is a Cu-Cry alkyl sulfate, most preferably Cn-Cis, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Said mixtures have been described in the PCT patent application No. WO 93/18124.

Anionic Sulfonate Surfactant The anionic sulphonate surfactants which are used herein include the salts of C5-C20 linear alkylbenzenesulfonates, alkylethersulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C4 olefinsulfonates, acids sulfonated polycarboxylics, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and many mixtures thereof. The detergent composition according to the present invention comprises less than 9.5% of a linear or branched alkylbenzenesulfonate surfactant.

Carboxylate Anionic Surfactant The carboxylate anionic surfactants include the alkylethoxycarboxylates, the alkylpolyethoxy polycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH2?)? CH2COO_M + where R is an alkyl group from Ce to Cie, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula R0- (CHR? -CHR2-0) -R3 wherein R is an alkyl group from Ce to Cie, x is from 1 to 25, Ri and R2 are selected from group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-methyl-1-undecanoic acid, -propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam suppressors.

Alkaline metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CONI 1 H 2 COOM, wherein R is a linear or branched Cs-Ci 7 alkyl or alkenyl group, R 1 is an alkyl group of C1-C4 and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant The detergent composition preferably comprises a nonionic surfactant. The nonionic surfactant is preferably present at a level of from 0.5% to 25%, preferably from 3.5% to 15% and most preferably from 6% to 10% by weight of the detergent composition. The nonionic surfactant and the cationic ester surfactant are preferably present in a weight ratio of nonionic surfactant to cationic ester surfactant of from 2.5: 1 to 8: 1, preferably from 3: 1 to 6: 1. . The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides which are used herein are those having the structural formula RSCO RiZ, 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 alkyl of Ci (ie, methyl); and R2 is a hydrocarbyl of CS-C31, preferably straight-chain C5-C19 alkyl or alkenyl, most preferably straight-chain C9-C17 alkyl or alkenyl, more preferably straight-chain C11-C17 alkyl or alkenyl or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R6C0N (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, Ci-Cn alkyl, Ci -CA hydroxyalkyl, and - (C2H / 0) HH, where x is on the scale of 1 to 3.

Alkylpolysaccharide Nonionic Surfactant The suitable alkylpolysaccharides which are used herein are described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R20 (Cn H2 n 0) t (COSi lo) x in which R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Alkalinity In the detergent compositions of the present invention, an alkalinity system is preferably present to achieve optimum performance of the cationic ester surfactant. The alkalinity system comprises components capable of providing alkalinity species in the solution. By species of alkalinity we try to say in the present: carbonate, bicarbonate, hydroxide, the different anions of silicate, percarbonate, perborates, perfosfatos, persulfato and persilicato. Said alkalinity species may be formed, for example, when the alkali salts selected from carbonate, bicarbonate, hydroxide or alkali metal or alkaline earth metal silicate salts, including crystalline layered silicate and mixtures thereof are dissolved in water. Examples of carbonates are alkali carbonates earth metals and alkali metal, including sodium carbonate and sesquicarbonate and any mixtures thereof with ultra fine calcium carbonate such as those described in German Patent Application No. 2,321,001, published November 15, 1973. Suitable silicates include Soluble sodium silicates with a ratio of Si? 2: a2? from 1.0 to 2.8, preferring ratios of from 1.6 to 2.0, and preferring more a ratio of 2.0. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with a ratio of Si? 2: Na2? 2.0 is the most preferred silicate. The preferred crystalline layered silicates for use herein have the general formula: NaMSi? 2x +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, and is preferably 2. The most preferred material is a2SY2? -5, available from Hoechst AG as NaSKS-6.

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

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

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (0R1) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, which contains to 26 carbon atoms; R * is an alkylene group 0 hydroxyalkylene containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing 1 to 3 carbon atoms, or a group of polyethylene oxide containing 1 to 3 ethylene oxide groups. The alkyl dimethylamine oxide of Cio-Ciß and the acylamido dimethylamine oxide of Oo-Cis are preferred. A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein.

These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2C00- where R is a hydrocarbyl group of Ce-Ciß, each R1 is typically Ci-C3 alkyl, and R2 is a hydrocarbyl group of Ci-Cs. Preferred betaines are the betaines of C12-C18 dimethyl ammonium hexanoate and the cyclo-Ciß acyl amidopropane (or ethane) dimethyl (or diethyl) betaines. Also suitable for use herein are complex betaine surfactants.

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

Water-soluble builder composition The detergent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, more preferably from 20% to 60% by weight of the composition. Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymer-rich polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more than two carbon atoms, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, alonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . The polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates described in the Dutch application 7205873 and the oxypolycarboxylate materials such as 2-oxa-l, l, 3-propantricarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261,829, 1,1,2,2-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.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight. weight, most preferably from 20% to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Nax [(AIO2)? (SÍO2) and] • XH2O where z and y are integers of at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Nai2C (Al? 2) i2 (Si? 2) i2] - H2O where x is from 20 to 30, especially 27. Zeolite X has the formula: Naße C (AIO2) se ( Si02)? Oe] • 276H20 Organic Peroxyacid Bleach System A main feature of the detergent compositions of the invention is an organic peroxyacid bleach system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of organic peroxyacid occurs through an in. Reaction. of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a Preferred and alternative embodiment is an organic peroxyacid preformed directly into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal salt, preferably sodium, at a level of from 1% to 40% by weight, most preferably from 2% to 30% by weight and more preferably from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perfosphate, persulfate and persilicate. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salts can be included as the crystalline solid without additional protection. However, for certain perhydrate salts the preferred embodiments of said granulated compositions use a coated form of the material that provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as the alkali metal salts of silicate, carbonate or borate, or mixtures thereof, or the materialsorganic substances 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 aB? 2H2? or the tetrahydrate NaB02 H2O2.3H2O. 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 2Na2C? 3.3H2O2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. The peroxyacid bleach precursors can generally be represented as: 0 X-C-L wherein L is a starting group and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is: The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, most preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or 0- groups, which may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Starting groups The starting group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: R4 and mixtures thereof, wherein R1 is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, RA is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R * can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S03 ~ M +, -C02"M +, -SOA ~ M +, -N + (R3) AX_ and 0 <-N (R3) and most preferably -S? 3 ~ M + and -C02 ~ M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator.Preferably, M is a metal cation alkali, ammonium or substituted ammonium, with more sodium and potassium being preferred, and X being a halide, hydroxide, methylsulfate or acetate anion.

Precursors of bleaching of alkylperearboxic acid The precursors of bleaching of alkylpercarboxylic acid form perearboxylic acid in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarbaryl bleach precursors of the imide type include the tetraacetylated N-, N, N1Ni alkylenediamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose. '5 Precursors of Alkyl Epoxy Acid With Amide The amide-substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: 0 RL L wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any starting group. Amide-substituted alkylperoxy acid-activating compounds of this type are described in EP-A-0170386. 0 Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates 5 and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoylethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzyl idazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pi roglutamic acid.

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

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

Preferred Organic Peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, highly preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R C C N R C C H H R N N C R C C H A R 5 4 R 5 4 4 where R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. The substituted organic peroxyacid compounds with amide of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Bleach catalyst The compositions optionally contain a bleach catalyst containing a transition metal. A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity , such as zinc or aluminum cations and a sequestrant having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the patent of E.U.A. No. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Examples Preferred of these catalysts include Mn * v (u-0) 3 (1,4,7-trimethyl-l, 4,7-triazacyclononane) 2- (PFe) 2, Mn ?? i2 (u-O)? (u-0Ac) (1,4, 7- trimethyl-1,4, 7- riazacyclononane) 2 - (CIOA), nIV4 (uO) e (1, 4,7-triazacyclononane) A - (CIOA 2, Mn ^ iMn1 ^ (u-0)? (u-0Ac) 2 (1,4, 7- trimethyl-1,4, 7-tiazacyclononane) 2 - (CIO *) 3 and mixtures thereof. European Patent Application Publication No. 549,272 Other suitable ligands for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2- methyl-l, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-l, 4,7-triazacyclononane and mixtures thereof For examples of suitable bleach catalysts see U.S. Patent No. 4,246,612 and in U.S. Patent No. 5,227,084, See also U.S. Patent No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (0CH3). ) 3- (PF6) Another yet another type of bleach catalyst as described in US Patent No. 5,114,606 is a water soluble mangane complex so (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-toothed ligands and bi-N-toothed ligands, including N Mni? I (u-0) 2MniVN4) + V [Bipy2Mni 11 (u-0) 2MniVbipy2] - (C10A) 3 . Suitable and additional bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), European patent applications Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4,711,748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U.A. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts).

Heavy metal ion sequestrant The detergent compositions of the invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrant is meant here components that act to sequester (chelate) heavy metal ions. These components may also have 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 from 0.005% to 20%, preferably from 0.1% to 10%, most preferably 0.25% at 7. 5% and more preferably from 0.5% to 5% by weight of the compositions. 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, ethylene diamine disuccinic acid, ethylene diamine diglutharic acid, 2-hydroxypropylenediamine diuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Other heavy metal ion sequestrants suitable for use herein are the inodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or acid. glyceryl diamine, 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. Sequestrants of β-alanine-N, β-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1, 2,4-tricarboxylic acid. Glycinamide-N-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in detergent compositions is one or more additional enzymes. Additional preferred enzyme materials include lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases, and commercially available peroxidases. incorporated conventionally 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 from 0.001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, 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 from 0.0001% to 2% active enzyme by weight of the composition. The lipolytic enzyme may be present at active lipolytic enzyme levels of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0. 001% to 0.5% by weight of the compositions. The lipase can be of fungal or bacterial origin, being obtained, for example, from a lipase-producing strain of the Humicola species, the Thermo yces 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 pseudoalcaligenes, which is described in European patent EP-B-0218272. Another preferred lipase herein is obtained by cloning the Humicola lanuginosa gene and expressing the Aspergillus oryza gene as a host, as described in the European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark under the trade name Lipolase. 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, where they can act such as to bind the particulate component together. By organic polymeric compound it herein essentially means any polymeric organic compound that is not an oligoester or polyamine soil release polymer, and which are commonly used as dispersants and anti-redeposition agents and suspension of soils in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of the latter type are described GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Terpolymers are also suitable herein which contain selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional organic polymeric compounds and useful with polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably about 4000.

Foam suppressing system The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppressor system present at a level of from 0.01% to 15%, preferably from 0.05% to 10% , most preferably from 0.1% to 5% by weight of the composition. Suitable foam suppressor systems for use herein can comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds.

By "antifoaming compound" is meant any compound or mixtures of compounds which act to depress the foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred antifoam compounds for use herein are the silicone anti-foam compounds defined herein as any antifoam compound that includes a silicone component. Said silicone anti-foam compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred antifoam silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the 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 salts of sodium, potassium and lithium, and the ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic CIS-CAO ketones (e.g., stearone), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, amide of bis-stearic acid and the di-alkali metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a silicone glycol copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising an ethoxylated Cie-Ciß alcohol with an ethoxylation degree of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10 % to 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises 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 from 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 Suitable polyamine N-oxide polymers for use herein contain units having the following structural formula: P (1) x wherein P is a polymerizable unit, and 0 0 0 A is NC, CO, C, -0-, -S-, -N-; x is o or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: 0 wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / oyo / yz is or or 1 and wherein the nitrogen of the NO group can be fixed or in which the Nitrogen from the NO group is part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric base structure or to a combination of both. The suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the N-polyamine oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the functional group is NOT part of said group R. Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpirolidone and N-vinylimidazole The copolymers of N-vini l imidazole and N-vinylpirolidone suitable in the present invention have a molecular weight scale of from 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpirolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight from 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones that are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions herein can also use polyvinyloxazolidones as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the strual formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 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 Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N-2- bis-hydroxyethyl) -s-triazin-2-yl) amino] -2, 2'-styrylisulfonic 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 Ri is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-ani 1 i non-6- (N-2-hydroxyethyl-N-methylamino) -st riazin-2-yl) ami no] -2,2'-stilbenedisulfonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morph ilino-s-triazin -2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Cationic Fabric Softening Agents Cationic fabric softening agents can also be incorporated into the compositions according to the invention. Suitable cationic fabric softening agents include water insoluble tertiary amines or dilarga chain amide materials such as those described in GB-A-1 514 276 and EP-B-0 011 340. Cationic fabric softening agents are incorporated typically at total levels of from 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with sodium sulfate being a filler salt. pH of the compositions The present compositions preferably have a pH measured as a 1% solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, more preferably from 9.5 to 11.0.

Form of the compositions The compositions according to the invention can have a variety of physical forms including the forms granulated, in tablets, in bars and liquids. The compositions are particularly so-called compositions Concentrated granular detergents adapted to be added to a washing machine by means of a supply device placed in the drum of the washing machine with the load of laundry. The average particle size of the components of the granular compositions according to the invention should preferably be such that no more than 5% of the particles are more than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15. mm in diameter. The term "average particle size" as defined herein is calculated by screening a sample of the composition in a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions of weight thus obtained are plotted against the opening size of the sieves. The average particle size is considered the size of the opening through which 50% by weight of the sample would pass. The overall density of the detergent compositions according to the present invention is typically an overall density of at least 600 g / liter, very preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve 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, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder is removed from the cup by passing a straight edge implement, eg, a knife, through its upper edge. The full cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required.

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

Laundry washing method The laundry washing methods of the present they typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a washing detergent composition in accordance with the invention. For an effective amount of the detergent composition is meant from 40g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of washing solution commonly used in conventional laundry washing methods. 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 turned and also as a result of its contact with the washing liquid. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is liquid permeable but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the washing machine drum at this stage of the wash cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A- 0288346. An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granular laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in PCT patent application No. W094 / 11562.

Essentially preferred delivery devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This application describes a device comprising a flexible liner in the form of a pouch extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a protrusion in a spoke wheel configuration or similar structure, in which the walls They have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water provided with an edge seal or seal designed to break in the aqueous medium as described in the applications European Patent Publication Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water-curable closure comprises a water-soluble adhesive disposed along and sealing an edge of a sack formed of a water-impermeable 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.

Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: C12 linear sodium alkylbenzene sulfonate TAS: Sodium alkyl sulfate C45AS: C14-C15 linear sodium alkyl sulfate CxyEzS: Branched sodium alkyl sulphate of Ci? -Cy condensed with z moles of ethylene oxide C45E7: A predominantly linear Ci-i-Os primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3: A branched C12-C1S primary alcohol condensed with a average of 3 moles of ethylene oxide C25E5: A branched C12-C1S primary alcohol condensed with an average of 5 moles of ethylene oxide CEQ I: R1COOCH2.N + (CH3) 3 with Ri = C11-C13 CEO II: R- ? C00CH2CH2CH2N + (CH3) 3 with Ri = C11-C13 CEQ III: R? C00CH2CH2N + (CH3) 2 (CH2CH20H) with Ri = C11-C13 CEO IV: R? C00CH2CH2 + R2R3 (CH3) with Ri = C11-C13 and R2 and R3 = C2-C3 QAS: R2 -N + (CH3) 2 (C2H OH) with R2 = C12-C14 Soap: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils TFAA: Ci-Ciß alkyl N-methylglucamide TPKFA: C12-C14 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (AIO2SÍO2) i2. 27H20, which has a primary particle size on the scale of 0.1 to 10 mieras NaSKS-6: Crystalline layered silicate of the formula d-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: 2? 2.0 ratio) Sodium sulfate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425μm and 850μm MA / AA: 1: 4 copolymer of maleic acid / acrylic acid with an average molecular weight of approximately 70,000 CMC: Sodium carboxymethylcellulose Protease: Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Alcalase: Proteolytic enzyme activity 3AU / g sold by Novo Industries A / S Cellulase: Activity cellulite enzyme lOOOCEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: Activity amyolitic 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 name commercial Lipolase Endolase: Enzyme endoglunase activity 3000CEVU / g sold by Novo Industries A / S PB4: Anhydrous sodium perborate tetrahydrate of nominal formula NaBO2.3H O.H2O2 PB1: Bleaching of sodium chloride anhydrous sodium monohydrate with a nominal formula NaB? 2. H? 2 Percarbonate: Sodium bicarbonate of nominal formula 2Na C? 3. 3H2 O2 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tet raacetylethylenediamine 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-sulfoesti ril) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-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: Esters of end blocked with sulfobenzoil with base structure of oxyethyleneoxy and terephthaloyl SRP 2: Polymer of short block of poly (l) , 2-propylene terephthalate) diethoxylated Silicon Anti-Foams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1.

In the following examples all levels are cited as% by weight of the composition: EXAMPLE 1 The following laundry detergent compositions A to F according to the invention were prepared: EXAMPLE 2 The following granular laundry detergent compositions G a I were prepared with an overall density of 750 g / liter according to the invention: 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 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 5 The following detergent formulations were prepared according to the present invention: EXAMPLE 6 The following detergent formulations were prepared according to the present invention: EXAMPLE 7 The following high density detergent and bleach-containing detergent formulations were prepared according to the present invention: EXAMPLE 8 The following high density detergent formulations were prepared according to the present invention: EXAMPLE 9 The following high density detergent formulations were prepared according to the present invention:

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: (a) a cationic ester surfactant present at a level of from 0.1% to 2.0% by weight of the detergent composition; and (b) an anionic surfactant present at a level of from 8% to 30% by weight of the detergent composition, wherein less than 9.5% by weight of the detergent composition is an anionic surfactant selected from the group comprising linear alkylbenzenesulfonates or branched.

2. A detergent composition according to claim 1, further characterized in that said anionic surfactant is present at a level of from 9% to 20% by weight of the detergent composition.

3. A detergent composition according to any of claims 1 or 2, further characterized in that said anionic surfactant and said cationic ester surfactant are present in a weight ratio of anionic surfactant to cationic ester of cationic ester surfactant. : 1 to 40: 1.

4. A detergent composition according to any of claims 1 to 3, further characterized in that the anionic surfactant and the cationic ester surfactant are present in a ratio of weight of anionic surfactant to cationic ester surfactant of 6: 1 to 10: 1.

5. A detergent composition according to any of claims 1 to 4, further characterized in that the cationic ester surfactant is selected from those having the formula: wherein Ri is an alkyl, alkenyl or alkaryl chain of linear or branched Cs-C31 or M-. N + (R6R7R8 KCH2) ß; X and Y, independently, are selected from the group consisting of COO, OCO, 0, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R 2, R 3, R 4, R b, R 7 and R b are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy alkynyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs is independently H or an alkyl group of Ci-C3; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the condition that at least some of u or v must be 1; and where M is a counter anion.

6. A detergent composition according to claim 4, further characterized in that R, R3 and R-i are independently selected from the group consisting of -CH3 and -CH2CH2OH.

7. A detergent composition according to claim 4, further characterized in that R2 and R3 are C2-C3 alkyl groups.

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

9. A detergent composition according to any of claims 1 to 7, further characterized in that the cationic ester surfactant is present at a level of from 0.3% to 1.0% by weight of the detergent composition.

10. A detergent composition according to any of claims 1 to 8, further characterized in that a nonionic surfactant is present.

11. A detergent composition according to claim 9, further characterized in that said nonionic surfactant is present at a level of from 0.5% to 25% by weight of the detergent composition.

12. A detergent composition according to any of claims 9 or 10, further characterized in that the nonionic surfactant and said cationic ester surfactant are present in a weight ratio of nonionic surfactant to cationic ester surfactant from 2.5: 1 to 8: 1.

13. A detergent composition according to any of claims 1 to 11, characterized in that an alkalinity system is present.

14. A method of washing clothes in a domestic washing machine, in which a delivery device containing an effective amount of a solid detergent composition according to any of claims 1 to 12 is introduced into the drum of the washing machine before the start of washing, wherein said delivery device allows the progressive release of said detergent composition in the washing liquid during washing.