MXPA99003629A - A detergent composition - Google Patents

Abstract

The invention relates to a detergent composition comprising:a) a hydrophobic peroxyacid bleaching component, capable of providing a hydrophobic peroxyacid compound, with the proviso the component does not comprise the sodium salt of nonanoyloxybenzene sulfonate;b) a hydrophilic nonionic component, having a Hydrophilic/Lipophilic Balance of at least 10.8, asmeasured by the HLB-test;c) a cationic surfactant component, with the proviso that the cationic surfactant is not a cationic choline ester surfactant or a salt of the cationic C12-C14 alkyl dimethyl ammonium ethanol surfactant.

Description

A DETERGENT COMPOSITION TECHNICAL FIELD The present invention relates to a detergent composition comprising cationic surfactants, bleach components of hydrophobic peroxyacid and a hydrophilic nonionic component.

BACKGROUND OF THE INVENTION Among consumers there is a need for detergents that provide improved cleaning and improved stain removal. The different spots can have different properties. Therefore, there is a need to provide detergent compositions containing various components that can together ensure the removal of all different spots. Thus, in the last few years, detergents have been developed which contain various types of surfactants, such as anionic and cationic surfactants. Additionally, since certain spots are bleachable, detergent manufacturers have Developed bleaches that can act on bleachable stains, selectively, thus eliminating bleachable stains, while not damaging the fabrics. One type of bleach that is particularly for this is a hydrophobic bleach. However, the use of the variety of different surfactants, bleaches and other detergent ingredients has increased the complexity of the detergent formulations. The various components can interact with each other, thus influencing each one with their respective properties. Applicants have discovered that a problem encountered with the more complex detergent formulations may be a reduction in the operation of the individual detergent ingredients. It has been found that the introduction of an additional ingredient to a detergent composition, which increases the complexity of the detergent composition, does not always result in an increased cleaning performance in the final composition, as would be expected. In particular, it has been found that cationic and hydrophobic components, when comprised in a detergent composition, can decrease the functioning of the counterparts. Applicants have now found that this problem can be improved or solved by the introduction of a hydrophilic nonionic component, especially certain nonionic surfactants, into the detergent composition comprising certain hydrophobic bleach components and cationic surfactant components. It has been found that the incorporation of a hydrophilic nonionic component in a detergent composition comprising certain cationic surfactants and hydrophobic bleach leads to improved performance of these latter two components, compared to detergent compositions that do not comprise the nonionic component, hydrophilic Both the bleaching operation and the cleaning performance are unexpectedly increased when a non-ionic hydrophilic component is introduced into the composition. This leads to a much improved elimination of both bleaching and non-bleaching spots. An additional benefit may be that the levels of individual components may be reduced, if is desired, because more efficient operation is obtained by the individual components. - All documents cited in the present description, in their relevant part, are incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, there is provided a detergent composition comprising: a) a hydrophobic peroxyacid bleach component capable of providing a hydrophobic peroxyacid compound, provided that the component does not comprise the sodium salt of nonanoyloxybenzenesulfonate; b) a nonionic hydrophilic component having a hydrophilic / lipophilic balance of at least 10.8, when measured by the EHL test; c) a cationic surfactant component, provided that the cationic surfactant is not a choline ester cationic surfactant, nor a cationic alkyldimethylammonium ethanol salt of 12 to 14 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION THE NON-IONIC, HYDROPHILIC COMPONENT In accordance with the present invention, a hydrophilic nonionic surfactant component having a hydrophilic / lipophilic balance (EHL) of at least 10.8 is present, when measured by the HLB test described herein. To avoid confusion, when using the term "having a hydrophilic / lipophilic balance (EHL)" or "having an EHL", herein is meant that a non-ionic, hydrophilic surfactant component has an EHL whose value is obtained by the calculation described below, or has an EHL whose value is obtained by the comparative EHL test, described later. Preferably the hydrophilic nonionic component has an EHL of at least 11, more preferably, at least 11.6, most preferably, at least 11.7. The ratio of the cationic surfactant to the hydrophilic nonionic component is generally from 100: 1 to 1: 100, preferably from 20: 1 to 1:30, better still, from 5: 1 to 1:20, and most preferably, from 1: 1 to 1:10.

The ratio of the hydrophobic peroxyacid bleach component to the hydrophilic nonionic component is generally from 150: 1 to 1: 100, preferably from 50: 1 to 1:20, more preferably from 20: 1 to 1:10, most preferably, from 15: 1 to 1: 1. It is preferred that the hydrophilic nonionic component be present at a level of from 0.01% to 40%, more preferably, from 0.5% to 20%, still more preferable from 1.0% to 14%, most preferably from 2.0% to 8% by weight. weight of the composition. It is preferred that the nonionic component have an average molecular weight of 200 to 2,000, more preferably, 250 to 1,000, most preferably 250 to 600. It is preferred that the non-ionic hydrophilic component is a nonionic surfactant, as described later.

THE PROOF EHL The EHL test is used to determine if a certain nonionic component has a hydrophilic / lipophilic balance, or EHL, of at least 10.8 and, therefore, if it is in accordance with the definition used. for this invention of a non-hydrophilic non-ionic component for use in the present invention. In the EHL test, the non-ionic components whose EHL can not be calculated by the formula that follows, are compared with one or more non-ionic components of norm, whose EHL can be obtained by calculation, to determine in this way the E? L of the first nonionic component. The procedure of comparing the nonionic components with the standard components is given below. Any linear non-ionic component, consisting of "and" ethoxylate groups, "x" carbon atoms, 2x + 1 hydrogen atoms and a hydroxy group, whose EHL can be calculated by the following formula, can be used as non-ionic components de norm, for comparison: % by weight of ethoxylate 44 and 100 EHL = • X 5 44y + 12x + 2x + l + 17 5 The comparison between the nonionic component of the standard and another component, to obtain its EHL, can be carried out by gas chromatography, as indicated by G. E. Petro s i and J. R. Vanatta. { Journal oíT American Oil Chemist's Society, August 1973, volume 50, pages 284-289). With the above formulation, the EHL of standard non-ionic components is calculated, linear, with a purity of 95%, preferably of 99%, with different values "x" and "y". For a good comparison of the EHL values, it is necessary to use several non-ionic test components (preferably at least six), whose calculated EHL is less than, equal to, or greater than 10.8. The non-ionic components of the standard and the non-ionic component are each applied to a support material (Chromosorb W-NA 60/80 mesh, Jones Chromatography, Wales, United Kingdom) and at different times the support materials are packed applied in 2 m copper columns (Jones Chromatography, Wales, United Kingdom), of a gas chromatograph (Pye Unica 204, with flame ionization detector, nitrogen gas as carrier). A mixture of two solvents, one hydrophobic and one hydrophilic, preferably n-octane and butane-1-ol, is introduced into each column. Chromatography is carried out at a constant temperature, which is selected so that, preferably, the non-ionic component is liquid.

Then, the retention time of the two solvents of the mixture, pl and p2, is calculated and the ratio (R) of the retention times pl / p2 is calculated. A graph of the In R is formed against the calculated EHL values. There is an approximately linear relationship between these two values. Then the above procedure is repeated for each nonionic component, whose EHL must be determined, applying it on the support material (Chromosorb) using the same mixture of two solvents and the same temperature. When measuring the retention times, calculate the ln R and compare the In R obtained with the graph of the nonionic components of the norm, it can be determined if the EHL of this nonionic component is above 10.8, which makes it an hydrophilic ion component according to the invention.

THE NON-IONIC SURGICAL AGENT The highly preferred hydrophilic nonionic components for use in the invention are nonionic surfactants having an EHL of at least THE NON-IONIC SURGICAL AGENT, ALCOXILATED The highly preferred hydrophilic nonionic components are the alkoxylated nonionic tertiary surfactants. Essentially any alkoxylated nonionic surfactant, having an EHL of at least 10.8, is suitable here. Preferred are ethoxylated-and propoxylated nonionic surfactants. Other highly preferred α-alkoxylated surfactants are nonionic ethoxylated alcohols and ethoxylated / propoxylated, nonionic fatty alcohols. Other preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylate / propoxylate condensates, with propylene glycol, and the condensation products of nonionic ethoxylate with propylene oxide / ethylene diamine adducts.

THE ALCOHOL ALCOHOL SURELY ALCOHOL AGENT, NON-IONIC According to the invention, the highly preferred hydrophilic nonionic components can be the condensation products of aliphatic alcohols having an EHL of at least 10.8, and having more than six, preferably 6 to 25 moles of alkylene oxide, in particular ethylene oxide, and / or propylene oxide, are suitable for use in the present. The alkyl chain of the aliphatic alcohol can be straight to branched, primary or secondary, and will generally contain from 6 to 22 carbon atoms. Particularly preferred are the condensation products of the alcohols having an alkyl group containing from 6 to 16, more preferably, from 12 to 16 carbon atoms, with 6 to 12 moles, more preferably, 7 to 9 moles, of oxide of ethylene, per mole of alcohol.

AGENT SURGICAL AMID ACID POLYHYDROXY-GRASO, NON-IONIC According to the invention, the preferred hydrophilic nonionic components can be the polyhydroxy fatty acid amides having an EHL of at least 10.8. The polyhydroxy fatty acid amides, suitable for use herein, can be those having the structural formula RzCONR1Z, wherein R1 is H, hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxyethyl, 2- hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably alkyl of 1 to 4 carbon atoms, more preferably, alkyl of 1 or 2 carbon atoms, most preferably alkyl of 1 carbon atom (ie, methyl); and R2 is a hydrocarbyl of 5 to 31 carbon atoms, preferably straight-chain alkyl or alkenyl, of 5 to 19 carbon atoms, more preferably straight alkyl or alkenyl of 9 to 17 carbon atoms, highly preferable , straight chain alkyl or alkenyl, of 11 to 17 carbon atoms, or mixtures thereof; and Z is a polyhydrosxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an -alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, Z will be derived from a reducing sugar, in a reductive amination reaction, more preferable, Z is a glycityl.

THE NON-IONIC TENSIOACT-TTO AGENT OF FATTY ACID AMID According to the invention, the preferred hydrophilic, nonionic components can be the fatty acid amide surfactants having an EHL of at least 10.8.

Suitable fatty acid amide surfactants can be those having the formula R6CON (R7) 2, wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, and each R7 is selected from the group consisting of hydrogen, alkyl of 1 to 4 atoms carbon, hydroxyalkyl of 1 to 4 carbon atoms and (C2H <? O)? H, where x is on the scale of 1 to 3.

THE NON-IDENTICAL SURFACTANT OF ALQUILPOLISACARIDE According to the invention, the preferred hydrophilic, nonionic components can be the alkylpoly-saccharides having an EHL of at least 10.8. The alkylpolysaccharides suitable for use herein may be those described in U.S. Patent 4,565,647, to Llenado, issued January 21, 1986, which has a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide. , for example, a polyglycoside, which contains a hydrophilic group of 1.3 to 10 saccharide units. Preferred alkyl polyglycosides have the formula: R20 (C "H2nO) t (glycosyl) x wherein R 'is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 8 to 10 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.

THE WHIRLING COMPONENT OF HYDROPHOBIC PEROXYACY An essential aspect of the detergent compositions of the invention is a hydrophobic peroxyacid bleach component, capable of providing a hydrophobic peroxyacid compound, provided that the component does not comprise the sodium salt of nonoyloxybenzenesulfonate. Preferably, the hydrophobic peroxyacid compound comprises at least one nitrogen atom. By "hydrophobic organic peroxyacid compound" is meant here an organic peroxyacid whose predecessor carboxylic acid has a critical micelle concentration of less than 0.5 moles / liter, and wherein said critical micelle concentration is measured in an aqueous solution at 10 ° C. 50 ° C.

Preferably the hydrophobic peroxyacid bleach component comprises a source of hydrogen peroxide and a hydrophobic peroxy acid bleach precursor compound, provided that this precursor is not the sodium salt of nonanoyloxybenzenesulfonate. Preferably, the hydrophobic peroxyacid bleach precursor compound comprises at least one nitrogen atom. The production of hydrophobic peroxyacid occurs by a m-site reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a preferred alternative embodiment, the hydrophobic peroxyacid bleach component comprises a preformed hydrophobic peroxyacid comprising at least one nitrogen atom, which is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and hydrophobic peroxyacid precursor, in combination with a preformed hydrophobic peroxyacid, are also contemplated. Preferably, the hydrophobic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms. In a preferred aspect, the Peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably, at least 8 carbon atoms, most preferably at least 9 carbon atoms.

THE INORGANIC PERHYDRATE WHITENERS Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are usually incorporated in the alkali metal form, preferably the sodium salt, at a level of from 1% to 40% by weight, more preferably, from 2% to 30% by weight and, very preferably, from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate ales are usually the alkali metal salts. The inorganic perhydrate salt may 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 salts inorganic, such as the alkali metal silicate, carbonate or borate salts, or mixtures thereof; or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB02H02 or of the tet-rahydrate -NaBOtH02.3H20.

Alkali metal percarbonates, in particular sodium percarbonate, are the preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H202, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

THE PEROXIÁCIDO WHITENER PRECURSOR Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, the peroxyacid bleach precursors can be represented by: or il X - C - L Where L is a substitutable group and X is essentially any functionality, such that by perhydrolysis, the structure of the produced peroxyacid is: OR II c OOH For the purposes of the present invention, X will contain, in such manner, at least six carbon atoms, preferably, from 9 to 25, more preferably, from 9 to 15 carbon atoms. The hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, more preferably from 0.1% to 15% by weight, most preferably from 0.2% to 10% by weight of the compositions detergents Suitable, hydrophobic, peroxyacid bleach precursor compounds typically contain one or more N-acyl or O-acyl groups, precursors that can be selected from a wide variety of classes.

Suitable classes include anhydrides, esters, the imides, the lactams and the acylated derivatives of imidazoles and oximes. Examples of useful materials within those classes are described in GB-A-1586789.

Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

SUBSTITUTE GROUPS The substitutable group, hereinafter referred to as the L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, it will be difficult to stabilize the activator for use in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 O Y -0-C = CHR4, and -N - ^ - H-R4 I "II R30 and its mixtures; where 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; R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substantially substituted by any functional group, including, for example, the alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilizing groups are the groups -S04 ^ f, -N * (R3) 4X ~ and C "-N (R3); very preferable-, the groups -S03 ~ M + and -C02T4T in which R3 is an alkyl chain containing from 1 to 4 carbon atoms; M is a cation that provides solubility to the bleach activator, and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being the most preferred; and X is a halide, hydroxide, methylsulfate or acetate anion.

THE PRECURSORS OF ALKYL-PEROXYACY REPLACED WITH AMIDA Preferred peroxyacid precursors are the amide substituted alkylperoxy acid precursor compounds, which include those having the following general formulas: wherein R1 is an aryl or alkaryl group of about 1 to 14 carbon atoms; R 2 is an alkylene, arylene and alkarylene group containing about 1 to 14 carbon atoms; and R5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L it can be essentially any substitutable group; R1 preferably contains about 6 to 12 carbon atoms; R2 preferably contains about 4 to 8 carbon atoms; R1 may be straight or branched chain alkyl, substituted aryl or alkylaryl which contains branching, substitution or both, and may be derived from synthetic sources or from natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. R2 may include alkyl, aryl, where R2 may also contain halogen, nitrogen, sulfur and other typical substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386. It may be preferred that R1 and R5 together with the nitrogen atom and the carbon atom form an annular structure. Preferred examples of bleach precursors of this type include the amide substituted peroxyacid precursor compounds, selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and most preferred, oxybenzenesulfonate from (6-nonanamido- caproyl), and mixtures thereof, such as those described in EP-A-0170386.

THE ORGANIC PEROXYACY BENZOXAZINE PRECURSES Precursor compounds of the benzoxazine type are also suitable, which are described, for example, in EP-1-332,294 and in EP-A-482, 807, in particular those having the formula: wherein Ri is an alkyl, alkaryl, aryl or arylalkyl containing at least 5 carbon atoms.

THE PRECURSORS OF LACTAMA N-ACILADA Yet another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class, generally described in GG-A-955735. Preferred materials of this class comprise the caprolactams.

Suitable caprolactam bleach precursors have the formula: wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. Preferred hydrophobic N-acyl-caprolactam bleach precursor materials are selected from benzoylcaprolactam, octanoylcaprolactam, nonanoycaprolactam, decanoylcaprolactam, undecenoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, and mixtures thereof. Most preferred of all is nonanoylcaprolactam. Suitable valerolactams have the formula: wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. It is further preferred that R1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylphenyl, decenyl and mixtures thereof. Mixtures of any of the peroxyacid bleach precursors, described hereinbefore can also be used.

THE PREFORMED ORGANIC PEROXIDE The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic hydrophobic peroxyacid, typically at a level of 0.05% to 20% by weight, more preferably, 1 % to 10% by weight of the composition. A preferred class of hydrophobic organic peroxyacid compounds are the amide substituted compounds of the following general formulas: -N R¿ -OOH -R C -OOH O O Wherein R1 is an aryl or alkaryl group with about 1 to 14 carbon atoms; R 2 is an alkylene, arylene or alkylene group of 1 to 14 carbon atoms, approximately; and R5 is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R1 preferably contains about 6 to 12 carbon atoms. R2 preferably contains about 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl, substituted aryl or alkylaryl which contains branching, substitution or both, and may be derived from synthetic sources or from natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. R2 may include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulfur and other typical substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. The activating compounds of bleach, substituted with amide, of this type, are described in EP-A-0170386. Suitable examples of this class of agents include: (6-octylamino) -6-oxocaproic acid, (6-nonylamino) -6-oxocaproic acid, (6-decylamino) -6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate , the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in US 4,483,781, US 4,634,551, EP 0,133,354, US 4,412,934 and EP 0,170,386. A preferred hydrophobic, preformed peroxyacid bleaching compound for the purposes of the invention is monononylamido-peroxycarboxylic acid-Other suitable organic peroxyacids include diperoxyalkanedioic acids having more than 7 carbon atoms, such as diperoxydecanedioic acid (DPDA), diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Also suitable here are mono- and diperazelaic acids, mono- and diperbrasyl acids and N-phthaloylaminoperoxycaproic acid (PAP), nonanoylamido-peroxo-adipic acid (NAPAA) and hexanosulfenoyl-peroxypropionic acid.

Other suitable organic peroxyacids include the diaminoperoxy acids which are described in WO 95/03275, which have the following structural formula: 0 0 0 0 MOC IR- (RXN) r.-CI (NR2) "'-R3- (R2N) m' -C I (NR1) m-RIC00M wherein: R is selected from the group consisting of alkylene of 1 to 12 carbon atoms; cycloalkylene of 5 to 12 carbon atoms; arylene of 6 to 12 carbon atoms, and their radical combinations; R1 and R2 are independently selected from the group consisting of H, alkyl of 1 to 16 carbon atoms and aryl radicals of 6 to 12 carbon atoms, and a radical that can form a ring of 3 to 12 carbon atoms together with R3 and both nitrogens; R3 is selected from the group consisting of alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms and arylene radicals of 6 to 12 carbon atoms; each of n and n 'is an integer selected in such a way that its sum is 1; each of y m 'is a selected integer so that its sum is 1; Y M is selected from the group consisting of cations and radicals H, alkali metal, alkaline earth metal, ammonium and alkanolammonium, and combinations thereof. Other suitable organic peroxyacids include the amidoperoxyacids which are described in WO 95/16673, which have the following general structure: X-Ar-CO-NY-R (Z) -CO-OOH Where X represents hydrogen or a compatible substituent; Ar is an aryl group; R represents (CH2) ", wherein n = 2 or 3, and each of Y and Z independently represents a substituent selected from -hydrogen or an alkyl or aryl or alkaryl group, or an aryl group substituted with a compatible substituent, provided that at least one of Y and Z is not hydrogen if n = 3. The substituent X in the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group consisting of halogen, typically a chlorine atom, or some other non-released, non-interfering species, such as an alkyl group, conveniently up to 6 carbon atoms, for example, a methyl, ethyl or propyl group.

Alternatively, X may represent a second amido-percarboxylic acid substituent of the formula: -CO-NY-R (Z) -CO-00H where R, Y, Z and n are as-defined further back.

MOOC-R1CO-NR2-R3-NR4-CO-R5COOOM where R1 is selected from the group consisting of alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, arylene of 6 to 12 carbon atoms, and their radical combinations. It can be found that it is particularly useful to mix the preformed permeate and the cationic surfactant together before their incorporation with the other components of the detergent composition.

THE CATIÓNIC SURGICAL AGENT Another essential component of the detergent composition of the present invention is a cationic surfactant, under the condition that the cationic surfactant is not a surface active agent choline ester cationic, or a cationic alkyldimethylammonium ethanol salt of 12 to 14 carbon atoms in the alkyl. It is preferred to select the cationic surfactant from the group consisting of the cationic monoalkoxylated amine surfactants (other than the sodium salt of the cationic alkyldimethylammonioethanol surfactant, from 12 to 14 carbon atoms in the alkyl), cationic amine surfactants bis-alkoxylated and their mixtures. Preferably the cationic surfactant is present at a level of 0.1% to 20%, more preferably, 0.5% to 7%, most preferably 0.5% to 3% by weight of the detergent composition.

THE CATIÓNIC TENSIOACTIVE AGENTS OF AMINA MONO- ALCOXILADA The cationic surfactant of the present invention may be a mono-alkoxylated amine cationic surfactant having the general formula I: (I) wherein R1 is an alkyl or alkenyl portion containing from about 6 to 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to 14 carbon atoms; each of R2 and R3 is independently alkyl groups containing from 1 to about 3 carbon atoms, preferably methyl, most preferably both R2 and R3 are methyl groups; R 4 is selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylsulfate or the like, to provide electrical neutrality, A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is from 0 to 30, preferably from 2 to about 15. , very preferably from 2 to about 8, provided that if A is ethoxy and R is hydrogen and p is 1, Ri is not an alkyl group of 12 to 1-4 carbon atoms. Formula 1 has p = 1 and is a hydroxyalkyl group that has no more than 6 carbon atoms, so that the -OH group is separated from the quaternary ammonium nitrogen atom, by not more than 3 carbon atoms. Particularly preferred ApR4 groups are: -CH2-CH2OH, -CH2CH-CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH, with -CH2CH2OH being particularly preferred. Preferred R1 groups do not have more than 10 carbon atoms, or even no more than 8 or 9 carbon atoms. Preferred R1 groups are linear alkyl groups. The linear R1 groups that 'have 8 to 11 carbon atoms, or 8 to 10 carbon atoms are preferred. Said cationic surfactant which is highly preferred has a formula wherein Ri is an alkyl group of 8 to 10 carbon atoms, p is 1, A is ethoxy and R2 R3 are methyl groups. It has been discovered that the mixtures of the cationic surfactants of the formula I can be particularly effective, for example, the surfactant mixtures in which R1 can be a combination of linear alkyl groups of 8 and 10 carbon atoms or of alkyl groups of 9 and 11 carbon atoms. Other cationic mono-alkoxy amine surfactants, highly preferred for use herein are of the formula: Rl ^ (CH2CH20), - sH ^ N "X" CH3 CH, wherein R1 is hydrocarbyl of 10 to 18 carbon atoms and mixtures thereof, especially alkyl of 10 to 14 carbon atoms, preferably alkyl of 10 and 12 carbon atoms; and X is any convenient anion to provide charge balance, preferably chloride or bromide. As noted, compounds of the above type include those in which the ethoxy units (CH2CH20) (OE) are replaced by butoxy units, isopropoxy [CH (CH3) CH20] and [CH2CH (CH3) O] (i-Pr ) or n-propoxy units (Pr) or mixtures of units OE and / or Pr and / or i-Pr. When used in granular detergent compositions, monoalkoxylated amine cationic surfactants are preferred, wherein the hydrocarbyl substituent R1 is from 8 to 11 carbon atoms, especially from 10 carbon atoms. , since they increase the rate of dissolution of the laundry granules, especially under cold water conditions, in comparison with the materials of greater chain length.

The levels of cationic monoalkoxylated amine surfactants, used in the detergent compositions of the invention, are preferably 0.1% at %, more preferably, from 0.4% to 7%, very preferably, from 0.5% to 3.0% by weight of the composition.

THE AGENT SURGICAL CATIÓNICO DE AMINA BIS-ALCOXIIADA The cationic surfactant of the invention can be a cationic bis-alkoxylated amine surfactant having the general formula II: (II) wherein R1 is an alkyl or alkenyl portion containing about 8 to 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably about 10 to 14 carbon atoms; R 'is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen ( preferred), methyl and ethyl; X "is an anion such as -chloride, bromide, methylsulfate, sulfate or the like, sufficient to provide electrical neutrality, A and A 'can vary independently, and each is selected from alkoxy of 1 to 4 carbon atoms, especially ethoxy ( i.e., -CH2CH0-), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably about 4 and q is from -1 to about 30, preferably from 1 to about 4 and, most preferably , both p and q are 1. The bis-alkoxylated amine cationic surfactants, highly preferred for use herein have the formula: wherein R1 is hydrocarbyl of 10 to 18 carbon atoms and mixtures thereof, preferably alkyl of 10, 12 and 14 carbon atoms, and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general structure of cationic bis-alkoxylated amine noted above, since a preferred compound R 1 is -derived from fatty acids with the (coconut) alkyl moiety of 12 to 14 carbon atoms, R * is methyl and each of ApRJ and A 'qR4 is monoethoxy. Other cationic bis-alkoxylated amine surfactants, useful herein, include compounds of the formula: pH pH wherein R1 is hydrocarbyl of 10 to 18 carbon atoms, preferably alkyl of 10 to 14 carbon atoms; independently, p is 1 to about 3 and q is 1 to about 3; R2 is alkyl of 1 to 3 carbon atoms, preferably methyl, and X is an anion, especially chloride or bromide. Other compounds of the above type include those in which the ethoxy units (CH2CH20) (OE) are replaced by butoxy (Bu), isopropoxy units [CH (CH3) CH20] and. { CH2CH (CH30) (i-Pr) or n-propoxy units (Pr) or mixtures of units OE and / or Pr and / or -Pr. Also suitable here are mono- and diperazelaic acids, mono- and diperbrasyl acids and N-phthaloylaminoperoxycaproic acid (PAP), nonanoylamido-peroxoadipic acid (NAPAA) and hexanosulfenoyl-peroxypropionic acid. When used in compositions of granular detergents according to the present invention, cationic bis-alkoxylated amine cationic surfactants are preferred, in which the hydrocarbyl substituent R1 has from 8 to 11 carbon atoms, especially 10 atoms. of carbon, since they increase the rate of dissolution of the laundry granules, especially under cold water conditions, in comparison with the materials of greater chain length, the levels of cationic amine-alkoxylated amine surfactants, used in The detergent compositions of this invention may vary from 0.1% to 20%, preferably from 0.4% to 7%, most preferably from 0.5% to about 3.0% by weight of the detergent composition.

THE ADDITIONAL DETERGENT COMPONENTS The detergent compositions of the invention may also contain other additional detergent components. The precise nature of those components additional, and their level of incorporation, will depend on the physical form of the composition, as well as on the precise nature of the washing operation for which they will be used. The compositions of the invention preferably contain one or more additional detergent components, bleaches, builders, organic polymer compounds, enzymes, suds suppressants, lime soap dispersants, grime suspending agents and grime anti-redeposition agents, as well as corrosion inhibitors.

TENSIOACT AGENTS - VOS ADDITIONAL DETERGENTS Optionally, other additional surfactants may be present, selected from the group consisting of anionic, zwitterionic, ampholytic and amphoteric surfactants. The total amount of surfactants is preferably from 1% to 95%, preferably from 3% to 70%, more preferably from 5% to 40%, still more preferable, from 10% to 30%, most preferably from 12% to 25% by weight of the detergent composition.

A preferred aspect of the present invention is a granular detergent composition. One or more of the surfactants may be included in a base composition, optionally containing peroxyacid bleach component, hydrophobe, and / or nonionic, hydrophilic surfactant component. The base composition can be prepared by spray drying and by dry mixing / agglomeration. Alternatively, the hydrophobic peroxy acid bleach component and / or the hydrophilic nonionic surfactant component can be added as separate components to the detergent base composition, preferably combined with further detergent components as described herein, in granular form.

THE SURGICAL-AGENT AGENT The detergent composition of the present invention may comprise one or more anionic surfactants. Any anionic surfactant suitable for detergent purposes is suitable. Examples include salts (including, for example, the sodium, potassium, ammonium and substituted ammonium salts, such as the mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anhydrous sulfate surfactants are preferred. Other anionic surfactants include isethionates, such as acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated monoesters of 12 to 18 carbon atoms), the sulfosuccinate diesters (especially the saturated and unsaturated diesters of 6 to 14 carbon atoms), the N-acyl sarcosinates. Resin acids and resinous hydrogenated acids are also suitable, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tallow oil. The anionic surfactant is preferably present at a level of 0.5% to 60%, preferably at a level of 3% to 50%, more preferably, 5% to 35%, most preferably, 6 & to 20% by weight of the composition. The ratio of the anionic surfactant to cationic surfactant is preferably from 25: 1 to 1: 3, more preferably from 15: 1 to 1: 1, most preferably from 10: 1 to 1: 1.

THE ANIONIC SULFATE SURGICAL AGENT Suitable anionic sulfate surfactants for use herein include primary and secondary, linear and branched alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glyceroleulphate, alkylphenol ether sulphates, ethylene oxide, sulphates. of acyl C5-17-N- (Cl-4 alkyl) - and -N- (Cl-2 hydroxyalkyl) glucamine, and alkylpolysaccharide sulfates, such as alkyl polyglucoside sulfates (being the non-sulfated, non-ionic compounds described herein). The alkyl sulfate surfactants are preferably selected from the primary alkyl, linear and branched sulfates, of 9 to 22 carbon atoms, most preferably, branched chain alkyl sulfates, of 11 to 15 carbon atoms, and sulfates of straight chain alkyl, of 12 to 14 carbon atoms.

The alginate ethoxysulfate surfactants are preferably selected from the group consisting of alkyl sulfates of 10 to 18 carbon atoms which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxylate surfactant is a sulfate of alkyl of 11 to 18 carbon atoms, very preferably of 11 to 15 carbon atoms, which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred surfactants of alkyl sulfate and alkyl ethoxysulfate. Such mixtures have been described in the patent application of TCP No. WO 93/18124.

THE ANIONIC SULPHONATE SURGICAL AGENT Anionic sulphonate-surfactants, suitable for use herein, include salts of linear alkylbenzenesulfonates of 5 to 20 carbon atoms, alkyl ester sulfonates, primary or secondary alkanesulfonates of 6 to 22 carbon atoms, olefin sulphonates of 6 carbon atoms. at 24 carbon atoms, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulphonates, oleyl glycerol sulphonates and mixtures thereof.

THE-SURFACTANT AGENT OF CARBOXI ATO ANIONIC Anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps that are described herein. Suitable alkyl ethoxycarboxylates include those having the formula RO (CH2CH20) CH2COO ~ M +, where R is an alkyl group of 6 to 18 carbon atoms; x varies 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 alkyl polyethoxypolycarboxylate surfactants include those having the formula RO- (CHRi-CHR2-0) X-R3, where R is an alkyl group of 6 to 18 carbon atoms, x is from 1 to 25, and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mix.

Suitable soap surfactants include secondary soap tenectant agents 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 water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

THE ALKALINE METAL SARCOSINATE SURGICAL AGENT Other suitable anhydride surfactants are the alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched alkenyl or alkenyl group of 5 to 17 carbon atoms; R1 is an alkyl group of 1 to 4 carbon atoms and M is an alkali metal ion. Preferred examples are myristyl and oleoylmethyl sarcosinates, in the form of their sodium salts.

THE AGENT TENSIQACTGVO ANFORTERO Amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkyl-amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R (OR 4) XN ° (R 5) 2, wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5; preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing 1 to 3, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Alkyldimethylamine oxide of 10 to 18 carbon atoms in the alkyl, and acylamidoalkyldimethylamine oxide, of 10 to 18 carbon atoms are preferred. A suitable example of an alkylalanodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ, E.U.A.

THE HYBRID ION SURGICAL AGENT The zwitterionic surfactants can also be incorporated into the detergent compositions or their components according to the invention. 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 betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. Suitable betaines are those compounds having the formula R (R ') 2N + COO ~, wherein R is a hydrocarbyl group of 6 to 18 carbon atoms; each R1 is typically alkyl of 1 to 3 carbon atoms; and R2 is a hydrocarbyl group of 1 to 5 carbon atoms. Preferred betaines are dimethylammonium hexanoate of 12 to 18 carbon atoms and acylamidopropane (or ethane) dimethyl (or diethyl) -betaines of 10 to 18 carbon atoms. The betaine complex surfactants are also suitable for use herein.

THE COMPOSITE SOLUBLE DETERGENT COMPOUND IN WATER The detergent compositions of the present invention preferably contain water-soluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, most preferably 20% by weight. % to 60% by weight of the composition. Suitable water-soluble builder compounds include monomeric, water soluble polycarboxylates, or their acid forms; the homopolymeric or copolymeric polycarboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals, separated from each other by not 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 their ether derivatives. The polycarboxylates containing two carboxy groups include the water-soluble saltse of succinic acid, malonic acid (ethylenedioxy) -diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and the carboxylates of ether and the carboxylates of sulfinílo. Polycarboxylates containing three carboxy groups include, in particular, the water-soluble citrates, aconitrates and citraconates, as well as the succinate derivatives, such as the carboxymethyloxy-succinates described in British Patent No. 1,379,241, the lactoxysuccinates described in the British patent. 1,389,732, and the aminosuccinates described in the Netherlands application 7205873, * and oxypolycarboxylate materials, such as the tricarboxylates of 2-oxa-l, 1,3-propane disclosed in British Patent 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Pat. No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1, 1, 2, tetracarboxylates. , 3-propane. Polycarboxylates containing sulfonyl substituents include the sulfosuccinate derivatives described in British Patents No. 1,398,421 and 1,398,422, and in the U.S. Patent 3,936,448, and the sulfonated pyrolysed citrates, described in the British patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly, citrates.

Borate builders, as well as enhancers containing aiae materials form borate, which can produce borate under the conditions of detergent storage or under washing conditions, are water soluble builders useful in the present. Suitable examples of water-soluble phosphate builders are alkaline metal, sodium pyrophosphate, potassium and ammonium pyrophosphate, sodium and potassium ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, where the degree of polymerization varies from around 6 to 21; and the salts of phytic acid.

THE PARTIALLY SOLUBLE DETERGENT IMPROVEMENT COMPOUND OR INSOLUBLE The detergent compositions of the present invention may contain an improving compound of partially soluble or insoluble detergency, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, most preferably, 20% to 60% by weight of the composition. Examples of largely water-insoluble detergency builders include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Na2 [(A10 z (SiO--,) y]. XH20, where "z" and "y" are at least 6, the molar ratio of "z" to "y "is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferable, from 10 to 264. The aluminosilicate material is in hydrated form and preferably crystalline, containing from 10% to 28%, more preferable , from 18% to 2% water in bonded form The aluminosilicate zeolites may be materials that occur in nature, but are preferably synthetically derived.The synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite ™ and their mixtures Zeolite A has the formula: Na? 2 [(A102) 12 (Si02) 12]. xH20 Where x is from 20 to 30, especially 27. Zeolite X has the formula: Na66 [(A10_) a6 (YES02)? O6: .276H20 Preferred crystalline layered silicates for use herein have the general formula: NaMSix02 * -? . and H20 wherein N is sodium or hydrogen; x is a number from 1.9 to 4 and "y" is a number from 0 to 20. Laminated sodium silicates, crystalline, of this type, eethan 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 a value of 2, 3 or 4 and, preferably, is 2. The most preferred material is delga-Na2Si205, obtainable from? Oesst AG as NaS S-6.

THE BLEACH CATALYST The compositions optionally contain a bleach catalyst containing 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 bleach activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, in particular ethylene diamine tetraacetic acid, ethylenediaminetetra (methylene phosphonic acid) and water soluble salts. Said catalysts are described in U.S. Patent 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include MnIV2 (uO) (1, 4, 7-trimethyl-1,4,7-triazacyclononane) -2- (PF6) 2, MnlxI (uO) i (u-OAc) 2 (1, 4, 7-trimethyl-1,4-, 7-triazacyclo-nonane)) - (C10) 2, MnIV (u- O) 6 (1, 4, 7-triazacyclononane) 4- (C104) 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-l, 5, 9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4-, 7-triazacyclononane, 1,2,4,7-tetramethyl-l-4,7-triaza-cyclononane and mixtures thereof. For examples of suitable bleach catalysts see U.S. Patents 4,246,612 and 5,227,084. Also see U.S. Patent 5,194,416, which teaches mononuclear manganese (IV) complexes, such as Mn (1, 4, 7-trimethyl-1,4,7-triazacyclononane) (0CH3) 3. (PF6). Yet another type of bleach catalyst, such as that described in US Patent 5,114,606, is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a polyhydroxy compound without carboxylate., which has at least three consecutive C-OH groups. Other examples include binuclear Mn formed to complex with ligands of tetra-N-dentate and bi-N-dentate, "including N4MnII ?: tu-Cl 2MnIVN4) + and [Bipy2Mn111 (uO) 2MnIvbipy2] - (C104) 3. Other catalysts Suitable bleach agents are described, for example, in European Patent Application 408,131 (complex cobalt catalysts), European patent applications Publication No. 384,503 and 306,089 (metallo-porphyrin catalysts); US 4,728,455 (manganese catalyst / ultidentate ligand), US 4,711,748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), US 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), US 4,626,373 (manganese catalyst / ligand), US 4,119,557 (ferric complex catalyst), German patent specification 2,054,019, (Cobalt chelant catalyst), Canadian patent 866,191 (salts containing transition metal), US 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and US 4,728,455 (manganese gluconate catalysts.

THE ACID SOURCE An acid source may be present in the detergent composition of the invention, such that it is capable of reacting with an alkali source, preferably a carbonate or bicarbonate salt, in the presence of water, to produce a gas.

Preferably the acid source is present at a level of 0.1% to 50%, more preferably, 0.5% to 25% ~, still more preferable, 1% to 12%, better still, 1% to 7%, very preferable, from 2% to 5%, by weight of-- the composition. In a preferred embodiment of the present invention, the source of acidity is present in the approximate scale of 1% to 3%, very preferably, about 3% by weight of the composition. The acid source can be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source can be a mono-, bi or triprotonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, the onohydrate acid source can be useful here. Organic acids and their derivatives are preferred. Preferably the acid is soluble in water. Suitable acids include: citric acid, glutaric acid, tartaric acid, succinic acid or adipic acid; monosodium phosphate, sodium bieulphate, boric acid or a salt or ester thereof. Citric acid is especially preferred.

THE HEAVY METAL ION SEQUESTRANT The detergent compositions of the invention preferably contain, as an optional component, a heavy metal ion sequestrant. By heavy metal ion sequestrant is meant here the components that act to sequester (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably show selectivity for binding heavy metal such as iron, manganese and copper. Heavy metal ion samplers are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, more preferable, from 0.25% to 7.5% and, most preferably, from 0.5% to 5% in weight of the compositions. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxydiphosphonates, and nitrile-trimethylene phosphonates. Preferred among the above species are diethylenetriamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Other heavy metal ion sequestrants suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids, such as ethylenediaminetetraacetic acid, ethylenetriacetic acid, ethylenediamine disuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred are ethylene diamine N, N 'disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. Other suitable heavy metal ion sequestrants, for use herein, are the iminodiacetic acid derivatives, such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid, described in EP-A-317,542 and EP-A-399, 133. The sequestrants of iminodiacetic acid-N-2- acid hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid, described in EP-A-516, 102, are also suitable in the. I presented. Sequents of beta-alanine-N, N'-diacetic acid, aspartic acid-acid are also suitable.

N, N'-diacetic, aspartic acid-N-monoacetic acid and iminodisuccinic acid, described in EP-A-509, 382. EP-A-476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestrants, derivatives of collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyliminodiacetic acid sequestrant. The dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Also suitable are glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylidene diamine-N, N'-disuccinic acid (HPDDS).

THE ENZYME Another preferred ingredient, useful in detergent compositions, is one or more "additional enzymes." Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulase, pectinases, lactases and peroxidases. conventionally incorporated in detergent compositions, suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark); those sold under the Maxatase, Maxacal and Maxapem trademarks, by Gist-Brocades; those sold by Genencor International and those sold under the Opticlean and Optimaee brands by Solvay Enzymee. The enzyme protease can be incorporated in the compositions according to the invention at a level of 0.0001% to 4% of active enzyme in the composition 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 amylases, available commercially, include, for example, those sold under the trademark Rapidase by Gist-Brocadee and those sold under the trademarks Termamyl and BAN by Novo Industries A / S. The enzyme A ilase can be incorporated into the composition according to the invention at a level of 0.0001% to 2% of active enzyme, by weight of the composition.

The lipolytic enzyme may be present at levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably from 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, obtained, for example, from a lipase-producing strain of Humicola sp. , Thermomyces sp. or Pseudomonas sp. , including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. The lipase of the chemically or genetically modified mutants of those 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 here is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergill us oryzeae as host, as described in European patent application EP-A-0258, 068, which is commercially available from Novo Industri AS, Bagsvaerd , Denmark, under the trademark Lipolase. This lipase is also described in U.S. Patent 4,810,414, to Huge-Jensen and co-inventors, issued March 7, 1989.

THE 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 in such a manner that they bind the particulate component together. By organic polymeric compound is meant here essentially any polymeric organic compound commonly used as a dispersant, and the anti-redeposition agents and for the slurry suspension, in the detergent compositions, including any of the high molecular weight organic polymeric compounds, described herein as clay flocculating agents The organic polymeric compound is typically incorporated into the detergent compositions of the invention at a level of 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of lae compositions. Examples of organic polymeric compounds include homo- or copolymeric, organic, water-soluble polycarboxylic acids, or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than one carbon atom. Polymers of this last type are described in GB-A-1, 596, 756. Examples of these salts are polyacrylates with molecular weight 2,000 to ,000, and its copolymers with maleic anhydride; said copolymers having a molecular weight of 20,000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful herein, including aspartic acid derivatives, such as those described in EP-A-305282, EP-A-305283 and 3'-A-351629. Also suitable here are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, in particular those having an average molecular weight of 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives, such as methylcellulose, carboxymethylcelluloses, hydroxypropylmethylcellulose and hydroxyethylcellulose. Other useful organic polymeric compounds are polyethylene glycols, in particular those having molecular weight from 1,000 to 10,000, more in particular, from 2,000 to 8,000 and, most preferable, around 4,000. Another organic compound which is a clay dispersing / anti-redeposition agent, preferred for use herein, may be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group, selected from the group consisting of H, alkyl ester group or alkyl or hydroxyalkyl ether of 1 to 4 carbon atoms, and mixtures thereof; a is from 0 to 20, preferably from 0 to 4 (for example, ethylene, propylene, hexamethylene); b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least about 12, with a typical scale of about 12 to 42. Other heat releasing / anti-redeposition agents for use herein are described in EP-B-011965 and US Pat. 4,659,802 and US 4,664,848.

THE SUPPRESSOR FOAM SYSTEM The detergent compositions of the invention, when formulated for use in washing machine compositions, preferably comprise a foam suppressant, present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, very preferable , 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-foaming compounds and 2-alkylalcanol antifoaming compounds. By "antifoaming compound" is meant here any compound or mixture of compounds which acts as such, to depress the formation of foam or the production of foam in a solution of a detergent composition, in particular in the presence of agitation of that solution.

Particularly preferred defoaming compounds for use herein are silicone anti-foaming compounds, defined herein as any defoaming compound that includes a silicone component. These silicone antifoam compounds also typically contain a silica component. He The term "silicone", as used herein, and generally throughout the industry, comprises a variety of relatively high molecular weight polymers, which contain siloxane units and hydrocarbyl groups of various types. Preferred silicone antifoaming compounds are siloxanes, in particular polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoaming agents include the monocarboxylic fatty acids and their solubble salts. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and their salts, for example as suds suppressors, typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.

Suitable salts include the alkali metal salts, such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of from 18 to 40 carbon atoms (eg. stearone), the N-alkylated aminotriazines, as tri-a hexalalkylmelan or the di- to tetraalkyldiaminoclorotriazines, formed as cyanuric chloride products with two or ten moles of a primary or secondary amine containing from 1 to 24 carbon atoms; propylene oxide, bis-eetheric acid amide and dialkali metal phosphate esters and phosphates (eg, sodium, potassium, lithium). A preferred foam suppressor system comprises: a) antifoam compound, preferably silicon antifoam compound, highly preferable, an antifoam silicone compound comprising, in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably from 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 the silicone / silica antifoam compound; wherein said silica / silicone antifoam composition is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; b) a dispersant compound, which comprises, most preferably, a rake copolymer of silicone glycol, with a polyoxyalkylene content of 72-78% ", and a ratio of ethylene oxide to propylene oxide from 1:09 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% at 10% by weight, a copolymer of Particularly preferred silicone glycol rake, of this type, is DC0544, commercially available from DOW Corning, under the trademark DC0544; c) an inert carrier fluid compound, most preferably comprising an ethoxylated alcohol from 16 to 18 carbon atoms, with a degree of ethoxylation of 5 to 50, preferably from 8 to 15, at a level of 5% to 80%, preferably 10% to 70% by weight. A highly preferred particulate suppressor system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C; wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 - describes other sevenmae preferred particulate foam suppressors, in which the organic carrier material is a fatty acid or an alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of 45 to 80 ° C.

THE CLAY SOFTENING SYSTEM 5 The detergent co-polishes may contain a clay softening system comprising a mineral clay compound and, optionally, a clay flocculating agent. The clay mineral compound is preferably a smectite clay compound. Smectitic clays are described in U.S. Patent Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents No. EP-A-299,575 and EP-A-15 313,146, in the name of The Procter and Gamble Company, describe suitable polymeric clay-flocculating agents.

THE INHIBITED AGENTS OF TRANSFER OF DYE, 20 POLYMERIC The detergent compositions herein can also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibitors. Preferably, the polymeric dye transfer inhibiting agents of the polyamide N-oxide polymers, the copolymers of N-vmilpirrolidone and N-vmilimidazole, polyvinylpyrrolidone polymers or combinations thereof. a) Polymers of polyamine N-oxide The polyamine N-oxide polymers, suitable for use herein, contain units having the following structural formula: P I Ax I R wherein P is a polymerizable unit; and A is O O NC, CO, C, -O-, -S-, -N-; x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination of them, to which the nitrogen of the N-O group can be bound, or where the nitrogen of the N-O group is part of those groups. The N-O group can be represented by the following general structures: 0 (Ri) X-N- (R2) and 0 (R3) - or = N- (R?) X wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x and / or "y" and / or z is 0 or 1; and where the nitrogen of the N-O group may be attached or where the nitrogen of the N-O group forms part of those groups. The N-O group may be part of the polymerizable unit (P) or it may be attached to the polymer backbone, or a combination of both possibilities. 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 the aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the N-O group forms part of the group R. Preferred polyamine N-oxides are those in which R is a heterocyclic group, such as plrpdin, pyrrole, lmidazole, pyrrolidine, piperidma, quinolma, acddma and their derivatives. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the poly-epzable 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 functional group is NOT part of said Group R. Examples of such classes of polyamine oxides are those in which R is a heterocyclic compound, such as pyrridine, pyrrole, imidazole and their derivatives. The polylamin N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, provided that it has desired water solubility and desired dye suspension potency. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Copolymers of N-vinylimidazole and N-vinylpyrrolidone having a scale average molecular weight from 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinyl-pyrrolidone from 1 to 0.2. c) - Polyvinylpyrrolidone The detergent compositions herein can also use polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500 to 400,000. Suitable polyvinyl pyrrolidones can be obtained commercially from ISP Corporation, New York, NY, USA, and Montreal, Canada, under the product names PVP K-15 (average molecular weight of 10,000), PVP-30 (average molecular weight of 40,000), T? VP K -60 (average molecular weight of 160,000) and PVP-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other polyvinylpyrrolidones that are commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12. d). - Polyvinyloxazolidone The detergent compositions herein can also use polyvinyloxazolidones as polymeric agents inhibitors of dye transfer.

Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e). - Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as the polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of 2,500 to 400,000.

THE OPTICAL POLISHER The detergent compositions herein also optionally contain about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners, useful herein include those having the structural 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, morpholino, 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 ee a cation such as sodium, the brightener is 4,4 '-bis [(4-anilino-6- (N- 2-bie-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid, and the disodium salt. This particular polishing species is sold in the trade under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener, useful in the detergent compositions of the present.

When, in the above formula, i is anilino, R is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as eodium, the brightener is the disodium salt of 4,4'-bis [( 4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2, 2'-stilbenedisulfonic acid. This particular brightener species is sold in commerce under the trademark Tinopal 5BM-GX by CibarGeigy Corporation. When, in the above formula, Ri is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is the sodium salt of acid 4, '-bis [(4-anilino-6-morpholino-s-triazin -2-il) amino] -2, 2'-stilbenedisulfonic acid. Eeta particular brightener species is sold in the trade under the trademark Tinopal AMS-GX by Ciba-Geigy Corporation.

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

OTHER OPTIONAL INGREDIENTS Other optional ingredients, suitable to be included in the compositions of the invention, include perfumes, dyes and filler salts, sodium sulfate being a preferred filler salt.

THE pH OF THE COMPOSITIONS The compositions herein preferably have a pH, measured as a 1% solution in distilled water, of at least 10.0, preferably 10.0 to 12.5, most preferably, 10.5 to 12.0.

THE FORM OF COMPOSITIONS The detergent compositions of the invention can be prepared by a variety of methods, including dry mixing and agglomeration of the various compounds comprised in the detergent composition. The acid source of the invention is preferably added dry, as a separate component.

The compositions according to the invention can take a variety of physical forms, including the granulated, tablet, bar and liquid forms. The compositions in particular are so-called concentrated, granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the tub of the machine, with the load of soiled fabric. The average particle size of the base composition of the granular compositions according to the present invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more than 5% of the particles have more than 1.7. mm in diameter, and no more than 5% of the particles have less than 0.15 mm in diameter.

The term average particle size, as defined herein, is calculated by sieving a sample of the composition to a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions by weight obtained in this way are plotted against the opening size of the sieves. The average particle size is taken as the aperture size through which 50% by weight of the sample would pass. The bulk density of the granular detergent compositions according to the present invention is typically a bulk density of at least 600 g / liter, more preferably, from 650 g / liter to 1,200 g / liter. The volumetric density is measured by means of a simple funnel and cup device consisting of a conical funnel, rigidly molded on a base and provided with a hinge valve at its lower end, to allow the contents of the funnel to be emptied into a Cylindrical cup aligned, arranged below the funnel. The funnel is 130 mm high and internal diameters of 130 mm and 40 mm, respectively, at its upper and lower ends. It is mounted so that the lower end is 140 m 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 m. Its nominal volume is 500 ml.

To make a measurement the funnel is filled with dust, pouring it by hand; the flap valve is opened and the powder is allowed to fill the cup. Remove the full cup from the frame and remove excess powder from the cup by passing a straight edge implement, "for example a blade, through its top edge.

Then the filled cup is weighed and the value obtained for the weight of powder is doubled, to provide the volumetric density in g / liter. Measurements are made in duplicate, when required.

THE AGGLOMERATED PARTICLES OF SURGICAL AGENT The surfactant system of the present invention is preferably present in the granulated compositions in the form of agglomerated particles of surfactant, which may take the form of flakes, lumps, bones, sticks, tapes, but preferably take the form of granules. The most preferred way of processing the particles is by agglomerating the powders (eg, aluminosilicate, carbonate) with high activity surfactant pastes, and controlling the size of. particle of the resulting agglomerates within specified limits. This procedure involves mixing a effective amount of powder with a paste of high content of high activity surfactant in one or more agglomerators, such as a tray agglomerator, a Z-blade mixer or, more preferably, an in-line mixer, such as those manufactured by Schugi ( Holland) BV, 29 Chroo straat 8211 AS, Lelystad, The Netherlands; and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. A high shear mixer, such as a Lodige CG (trademark), is most preferably used. A highly active surfactant paste comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% surfactant is typically used. The paste can be pumped to the agglomerator at a sufficiently high temperature to maintain a viscosity capable of being pumped, but low enough to avoid degradation of the anionic surfactants used. A pulp operating temperature of 50 ° C to 80 ° C is typical. In an especially preferred embodiment of the present invention, the detergent composition has a density of more than about 600 g / liter and is in the form of a powder or a granulate containing more than about 5% by weight of the alkali, preference (bi) carbonate or percarbonate. The carbonate material is added dry or supplied by means of agglomerates. The acid, preferably citric acid (preferable up to %), can be introduced into the product as a dry additive, as a separate compound, or as part of the agglomerate mixture.

THE METHOD OF WASHING FABRICS The methods for washing fabrics in the washing machine here typically comprise treating the soiled fabrics with an aqueous washing solution in a washing machine, which has dissolved or supplied therein an effective amount of a washing detergent composition in accordance with the invention. By an effective amount of the detergent composition is meant from 40 g to 300 g of product, dissolved or dispersed in a washing solution with volume of 5 to 65 liters, as are the typical product doses and the typical volumes of the product. Washing solution employed in conventional methods of washing clothes in washing machine. In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product and Use to introduce the product directly into the drum of the washing machine, before starting the washing cycle. Its volumetric capacity must be such that it is capable of containing sufficient detergent product, such as would normally be used in the washing method. Once the washing machine is loaded with the laundry load, the dispensing device containing the detergent product is placed inside the tub. At the beginning of the washing cycle of the washing machine, water is introduced into the tub and the tub is rotated periodically. The design of the dispensing device must be such that it allows the containment of the dry detergent product, but allows the release of this product during the wash cycle, in response to its agitation, as the tub turns and also as a result of its contact with the wash water. To allow the release of the detergent product during washing, the device may have numerous openings through which the product may pass. Alternatively, the device may be made of a material that is permeable to the liquid, but impermeable to the solid pro-gas; that allows the release of the dissolved product. Preferably the detergent product will be released quickly at the beginning of the cycle washing, thus providing high, localized, transient concentrations of product in the washing tub, in this stage of the washing cycle.

The dispensing devices are usable again and are designed in such a way that the integrity of the container is maintained both in the dry state and during the washing cycle. Especially preferred dispensing 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-1 -0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 1989, pages 41-46, also discloses especially preferred dispensing devices for use with granular laundry products, which are of a type commonly known as "granule". Another preferred dispensing device for use with the compositions of the invention is described in PCT patent application No. 2094/11562. Especially preferred dispensing devices are described in European Patent Application Publication Nos. 0343069 and 0343070. This latter application describes a device comprising a flexible sheath, in the form of a bag, extending from a support ring defining a hole; the hole being adapted to admit sufficient product in 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 exits through the hole, into the washing medium. The support ring is provided with a masking device to prevent "the discharge of wet, undissolved product, this device typically comprises radially extending walls, which extend from a central protrusion in a spoke wheel configuration., or a similar structure, in which the walls have a helical shape. Alternatively, the dispensing device may be a flexible container, such as a bag or bag. The bag may be of fibrous construction, coated with a waterproof protective material, so as to retain the contents, as described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymer material, insoluble in water, provided with a seal or edge seal, designed to break in the aqueous medium, as described in published European patent applications No. 0011500, 0011501, 0011502 and 0011968. A convenient form of frangible container with water comprises a water soluble adhesive disposed along, and sealing an edge of a bag formed of a waterproof polymeric film, such as polyethylene or polypropylene.

THE PACKAGING FOR THE COMPOSITIONS The commercially sold executions of the bleaching compositions can be packaged in any suitable container, including those made of paper, cardboard, plastic materials and any suitable laminates. A preferred packaging embodiment 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: linear, sodium, alkyl, 12-carbon atoms. TAS sodium seboalkyl sulfate C45AS linear sodium alkyl sulfate of 14 a carbon atoms. CxyEzS branched sodium alkyl sulphate, of C, - Civ, condensed with z moles of ethylene oxide. C45E7 A predominantly linear primary alcohol, of 14 to 15 carbon atoms, condensed with an average of 7 moles of ethylene oxide. CxyEz A branched primary alcohol, of C x - y, condenses with an average z mole of ethylene oxide. QAS I R2.Nt (CH3) 2 (C2H4OH), with R2 = C8 QAS II R2.N (CH3) i (C2H4OH), with Rt = 50% -60% C9; 40% -50% Cll. QAS III R2.Nt (CH2) _ (C2H., OH), with R2 = 30% at 70% CIO, 30% at 70% C8. QAS IV R1.NT (CH3) (C.H4OH) 2, with Ri = C12-C14.

QAS V R20 (C2H-, 0) x (gl? Cos? Lo) 2, where R2 is an alkyl group of 8 to 10 carbon atoms; t is from 2 to 8. Linear sodium alkylcarboxylate soap, derived from an 80/20 mixture of ebo-and coconut oils.

TFAA alkyl-N-methylglucamide of 16 to 1 £ carbon atoms in the alkyl. TPKFA Full-cut fatty acids, topped with C12-C14. STPP Anhydrous sodium tripolyphosphate. Zeolite A Aluminosilicate hydrated sodium of the formula Na? 2 (A102Si02)? 2.27H20, which has a primary particle size on the scale of 0.1 to 10 microns. NaSKS-6 Stratified crystalline silicate of the formula delta-Na2Si205. Citric acid anhydrous citric acid. Carbonate Anhydrous sodium carbonate, with particle size between 200 microns and 900 microns. Bicarbonate Anhydrous sodium bicarbonate, with a particle size between 400 microns and 1,200 microns. Silicate: Amorphous sodium silicate (Si02 ratio: Na20 = 2.0) Sodium sulphate: Anhydrous sodium sulfate. Citrate Trisodium citrate dihydrate, with activity of 86.4%, with a particle size distribution between 425 microns and 1,850 microns. ', - - MA / AA Copolymer 1: 4 maleic / acrylic acid, average molecular weight around 70 000. CMC Carboxymethylcellulose sodium Protease Proteolytic enzyme with activity of 4 KUNP / g, sold by NOVO Industries A / S, under the trademark Savinase. Alcalase Proteolytic enzyme with 3 AU / g activity, sold by NOVO Industries, A / S. Cellulose Enzyme cellulite with activity 100D UCEV / g, sold by NOVO Industries A / S, under the brand name Carezyme. Amylase Amylolytic enzyme with activity of 60 KUN / g, sold by NOVO Industries A / S, under the brand name Terma-myl 60T Lipase Lipolytic enzyme with activity of 100 kUX / g, sold by NOVO Industries A / S, under the brand name Lipolase Endolasa Enzyme endoglunase with activity of 3000 UCEV / g, sold by NOVO Industries A / S.

PB4 Sodium perborate tetrahydrate, with nominal formula NaBO..3H2O.H.O .. PBl Sodium perborate whitener - anhydrous, with nominal formula NaBO..H202. Percarbonate Sodium percarbonate with nominal formula 2Na2C03.3H202. NAC-OBS (Nonamidocaproil) oxybenzenesulfonate, in the form of the sodium salt. DPDA Diperoxidodecandioic acid. PAP acid F-phthaloyl idoperoxycaproic acid - NAPAA nonanoylamido-peroxoadipic acid. NACA 6-Nonylamino-6-oxocapronic acid TAED Tetraacetylethylenediamine DTPMP diethientriamine-penta (methylene phosphonate), sold by Monsanto under the brand name Dequest 2060. Photo-activated sulfonated zinc phthalocyanine, encapsulated in polymer soluble in bleaching dextrin. - 1 4, 4 '-bis (2-sulphotrisyl) biphenyl disodium brightener.

Brightener 2 4, 4 '-bis (4-an? L? No-6-morfo-l-? No-l, 3, 5- tpazm-2-? L) apuno) est? Lben-2, 2' - disulfone-to disodium HEDP aciao i, 1-hydroxyethane phosphine. PVNO N-oxide of polyvinylpipdine PVPVl Copolymer of polyvinylpyrrolidone and vinylimidazole. QEA b? S ((C.H50) (C2H40) n) (CH3) -N + -C6H12-N + - (CH3) b? S ((C.H50) - (C¿H40) n), where n = 20 to 30. SRP1 Esters crowned at the end with sulfobenzoyl, with skeleton of oxyethyleneoxy and terephthaloyl. SPR2 Short block polymer of poly (1, 2-propylene) diethoxylated terephthalate. Silicone antifoam: Polydimethylsiloxane foam controller, with siloxane-oxyalkylene copolymer as a dispersing agent, with a ratio of foam controller to dispersing agent from 10: 1 to 100: 1.

In the following examples, all levels are consigned as parts by weight of the composition, or as percent by weight of the composition, as indicated.

EXAMPLE 1 The following high density, granular laundry detergent compositions A to F were prepared having particular utility under washing conditions in a European washing machine, in accordance with the present invention.

EXAMPLE 2 The following granular laundry detergent compositions, G a l, with a bulk density of 750 g / l, are compositions according to the invention: Protease 0.26 0.85 0.85 EXAMPLE 3 The following are detergent formulations, according to the present invention, wherein J is a phosphorus-containing detergent composition, K is a detergent composition containing zeoiite and L is a compact detergent composition.

Perfume 0.3 0.3 0.3 0.3 EXAMPLE 4 The following are detergent formulations according to the present invention: PBl 6.0 2.0 EXAMPLE 5 The following are detergent formulations according to the present invention: Cellulase 0.1 0.1 0.1 EXAMPLE 6 The following are high density detergent formulations, which contain bleach, according to the present invention. 0. 4 EXAMPLE 7 The following are high density detergent formulations, according to the present invention: Zeolite A 15,0 6.0 Amylase I 0.6 0.6 EXAMPLE 8 The following are liquid detergent formulations according to the present invention.

EXAMPLE 9 The following granular detergent formulations are examples of the present invention: Rinse aid I 0.3 0.3 0.3 Cellulase 0.2 0.2

Claims (22)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition, characterized in that it comprises: a) a hydrophobic peroxyacid bleach component, capable of providing a hydrophobic peroxyacid compound; conditional on the component not comprising the sodium eal of nonanoyloxybenzenesulfonate; b) a non-ionic hydrophilic component, having a hydrophilic / lipophilic balance (EHL) of at least 10.8, when measured by the EHL test; c) a cationic surfactant component, provided that the cationic surfactant is not a cationic ester ester of cationic surface active agent, nor a salt of the cationic surfactant C12-14 alkyl dimethylammonioethanol.

2. A detergent composition according to claim 1, further characterized in that the non-ionic hydrophilic component is a nonionic surfactant.

3. A detergent composition according to claim 2, further characterized in that the Nonionic surfactant is an alkyl of 6 to 16 carbon atoms, with 6 to 12 moles of alkylene oxide.

4. A detergent composition according to claim 2, further characterized in that the nonionic surfactant is an alkyl of 12 to 16 carbon atoms, with 7 to 9 moles of ethylene oxide.

5. A detergent composition according to claim 2, further characterized in that the nonionic surfactant is an alkyl polyglycoside having the formula: R :: 0 (CnH2l, 0) t (glycosyl) » wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from 8 to 10 carbon atoms; n is 2 or 3; t is from 0 to 10 and x is from 1.3 to 8, and glycosyl is derived from glucose.

6. A detergent composition according to claim 1, further characterized in that the non-ionic hydrophilic component is present at a level of 0.5% to 20% by weight of the detergent composition.

7. - A detergent composition according to any of the preceding claims, further characterized in that the non-ionic hydrophilic component has a hydrophilic / lipophilic balance (EHL) of at least 11.6, which is measured by the test of EHL

8. A detergent composition according to claim 1, further characterized in that the hydrophobic peroxy acid bleach component comprises a source of hydrogen peroxide and a hydrophobic organic peroxyacid precursor.

9. A detergent composition according to claim 8, further characterized in that the hydrophobic organic peroxyacid precursor comprises at least one nitrogen atom.

10. A detergent composition according to claim 8, further characterized in that the hydrophobic organic peroxyacid precursor is present at a level of 0.05% to 20% by weight of the detergent composition.

11. A detergent composition according to claim 8, further characterized in that the organic peroxyacid precursor compound is a amide-substituted alkylperoxy acid precursor, selected from the group consisting of: R1-C- -R2 C-L- R1- -C-R2-C-L 0 R5 0 or R5 0 0 wherein L can be essentially any substitutable group; R * is an aryl or alkaryl group, with 1 to 14 carbon atoms; R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms; and R5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms, such that R1 and R5 in total do not contain more than 18 carbon atoms.

12. A detergent composition according to claim 1, characterized in that the bleach component of hydrophobic peroxyacid comprises a preformed organic peroxyacid.

13. A detergent composition according to claim 12, further characterized in that the preformed organic peroxyacid is present at a level of 0.05% to 20% by weight of the detergent composition.

14. A detergent composition according to claim 12, further characterized in that the Preformed organic peroxyacid is selected from the group that contains: R1-C-N-R2-C-OOH R1-N-C-R2-C-OOH 0 R5 O and R5 O 0 wherein R1 is an aplo or alkaplo group, with about 1 to 14 carbon atoms; R 2 is an alkylene, arylene and alkarylene group containing about 1 to 14 carbon atoms; and R = is H or an alkyl, aplo or alkaryl group containing from 1 to 10 carbon atoms, such that R1 and R5 do not contain more than 18 carbon atoms in total.

15. A detergent composition according to claim 1, further characterized in that the cationic surfactant is present at a level of

0. 1% to 20% by weight of the composition.

16. A detergent composition according to claim 1, further characterized in that the cationic surfactant is selected from the group consisting of monoalkoxylated amine and bisalkoxylated amine.

17. A detergent composition according to claim 16, further characterized in that the The cationic monoalkoxylated amine contains a positively charged amine group, which is substituted with two methyl groups, an alkyl group of 6 to 18 carbon atoms and an alkoxy group.

18. A detergent composition according to claim 17, further characterized in that the positively charged amine group is substituted with an alkyl group of 8 to 11 carbon atoms and a hydroxyalkyl group having no more than 6 carbon atoms.

19. A detergent composition or a component thereof, according to claim 16, further characterized in that the bis-ethoxylated, catidnic amine surfactant contains a positively charged amine group, which is substituted with a methyl group, an alkyl group of 8 to 18 carbon atoms and two (poly) alkoxy groups.

20. A detergent composition, or a component thereof, according to claim 1, further characterized in that the ratio of cationic surfactant to hydrophilic nonionic component is from 20: 1 to 1:30.

21. A detergent composition or a component thereof, according to claim 1, further characterized in that the component ratio Hydrophobic peroxyacid bleach to the hydrophilic nonionic component is from 50: 1 to 1:20.

22. A method for washing clothes in a domestic washing machine, characterized in that it comprises: introducing into a dispensing device that is placed in the tub of the washing machine; or introducing into the dispenser drawer of a washing machine, an effective amount of the detergent composition of claim 1.