EP0789747A1 - Bleaching detergents containing a bleach activator in close proximity to a layered silicate or a clay - Google Patents

Abstract

There is provided a solid detergent composition adapted for use in a laundry washing method containing a surfactant system having poor dispensing characteristics and a bleach system capable of providing organic peroxyacid bleach to a laundry wash solution and a non-three dimensional phyllosilicate mineral compound wherein siad organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are in close physical proximity within said composition. The composition is useful in the bleaching of stains from stained coloured fabrics. The non-three dimensional phyllosilicate mineral compound acts to inhibit 'patchy' damage to said fabrics during the stain bleaching process.

Description

BLEACHING DETERGENTS CONTAINING A BLEACH ACTIVATOR IN CLOSE PROXIMITY TO A LAYERED SILICATE OR A CLAY

Teςhnical field

This invention relates to methods of washing laundry in a domestic washing machine and a detergent composition for use therein. More especially it relates to a detergent composition containing a relatively high level of a surfactant system, having a tendency to gel under the conditions found in the initial stages of a laundry wash cycle, and, in close contact, a bleach system capable of providing an organic peroxyacid bleach to a wash solution and a non-three dimensional phyllosilicate mineral compound.

Background to the invention

The satisfactory removal of bleachable soils/stains such as tea, fruit juice and coloured vegetable soils from stained fabrics is a particular challenge to the formulator of a bleaching composition for use in a laundry washing method. Traditionally, the removal of such bleachable stains has been enabled by the use of bleach components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids. The organic peroxyacids are often obtained by the in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor. Alternatively, organic peroxyacids may be included in the compositions as preformed bleach components.

The growth in usage of organic peroxyacid bleach precursors has enabled the use of lower fabric wash temperatures which itself has been accompanied by an increase in the proportion of coloured fabrics to be found in a typical domestic washload. There has been recognition in the art, that benefits in stain removal performance may be obtained in a laundry washing method which enables the formation of localised high transient concentrations of certain detergent species, including builder species, at the start of the wash cycle. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 describes such benefits in more detail.

The formation of such localised high transient concentrations can be, for example, enabled by the use of a dispensing device to deliver the detergent product directly to the wash solution. Typically, the dispensing device is charged with an effective amount of detergent product and then introduced into the drum of a washing machine before the commencement of the wash cycle. On commencement of the wash cycle, progressive release of the detergent occurs in response to the agitation of the device as the machine drum rotates, and also as a result of contact of the detergent product contained therein with the wash water.

Whilst the formation of localised high concentrations of certain detergent species can be beneficial, a problem that can be associated with the formation of especially high localised concentrations of bleaching species, particularly organic peroxyacids, is that of damage to fabric colours and materials exposed to these especially high localised bleach concentrations. Overloading of the machine with fabrics, and slow delivery of input water to the drum can in particular give rise to the formation of such localised high bleach concentrations. A particular problem which can be encountered is the localised 'patchy' discoloration of coloured dyes on the fabrics. Certain dyestuffs, are particularly susceptible to the "patchy" discoloration problem.

Where an organic peroxyacid bleach precursor forms a component of the composition the potential problem is increased. In addition to the potential for localised high concentrations of perhydroxyl ion arising from dissolution of the inorganic perhydrate normally contained in laundry detergent compositions, the perhydrolysis of the organic peroxyacid bleach precursor to form organic peroxyacids can give rise to significant localised organic peroxyacid bleach concentrations. The problem of 'patchy' damage can be particularly troublesome with peroxyacid bleach precursor compounds which on perhydrolysis provide a peroxyacid which is a perbenzoic acid, or non-cationic substituted derivative thereof, or a cationic peroxyacid. Precursor compounds of the benzoxazin type, in particular, have also been found to give rise to the problem.

The Applicants have found that the tendency to form especially high localised concentrations of bleaching species, and hence of 'patchy' fabric damage, may be enhanced by the presence in the detergent composition, in addition to the bleaching species, of relatively high levels of certain types of surfactant. In particular, surfactants having a propensity to gel, or otherwise form locally viscous phases, under the conditions experienced during dispensing of the detergent product in the early stages of a laundry wash cycle can give rise to the problem.

Surfactant systems containing high proportions of anionic surfactants having a low Krafft point, or alternatively high proportions of alkoxylated nonionic surfactants are particular effective in the removal and suspension of commonly encountered soils from soiled fabrics under the conditions of a domestic laundering process. However, such surfactant systems have been found to be particularly prone to gelling on dispensing, and hence can give rise to the 'patchy' damage problem. When such surfactant systems are incorporated in the detergent product in the form of surfactant agglomerates the potential for the problem is increased.

The development of high density products and their delivery via dispensing devices placed in the machine drum together with the fabric load has merely served to exacerbate the problem. Accordingly a need exists to provide laundry washing methods in which the organic peroxyacid is provided to the wash solution in a way that minimizes and preferably eliminates damage to fabric colours and materials during its dissolution and perhydrolysis in the wash liquor, whilst still providing acceptable bleachable soil/stain removal from soiled/stained fabrics.

The prior art contains numerous examples of organic peroxyacid bleach precursors coated or agglomerated so as to increase their stability on storage in detergent compositions and/or to influence their solution behaviour. EP-A-0070474 discloses granulate organic peroxyacid bleach precursors prepared by spray drying an aqueous pumpable dispersion containing an N-acyl or O-acyl compound together with at least one water soluble cellulose ether, starch or starch derivative in a weight ratio of activator to coating of from 98:2 to 90:10.

GB-A-1507312 discloses the coating of organic peroxyacid bleach precursors with a mixture of alkali metal Cg - C_2 fatty acid salts in admixture with the corresponding fatty acids. GB-A-1381121 employs a molten coating of inter alia Cj4 - Cig fatty acid mixtures to protect solid organic peroxyacid bleach precursors. GB-A-1441416 discloses a similar process employing a mixture of C12 - C14 fatty acids and CJO - C20 aliphatic alcohols. EP-A-0375241 describes stabilised organic peroxyacid bleach precursor extrudates in which C5- Ci8 alkyl peroxy carboxylic acid precursors are mixed with a binder selected from anionic and nonionic surfactants, film forming polymers fatty acids or mixtures of such binders.

EP-A-0356700 discloses compositions comprising a organic peroxyacid bleach precursor, a water soluble film forming polymer and 2-15% of a C3-C6 polyvalent carboxylic acid or hydroxycarboxylic acid for enhanced stability and ease of dispersion/solubility. The carboxylic acid, of which a preferred example is citric acid, is dry mixed with the organic peroxyacid bleach precursor and then granulated with the film forming polymer. The citric acid is asserted to provide an enhanced rate of dissolution of the organic peroxyacid bleach precursor granules.

EP-A-0382464 concerns a process for coating or encapsulation of solid particles including bleaching compounds and organic peroxyacid bleach precursors in which a melt is formed of coating material in which the particles form a disperse phase, the melt is destabilised and then caused to crumble to a particulate material in which the disperse phase particles are embedded in the continuous (coating) phase. A variety of coating materials are disclosed and certain materials such as polyacrylic acid and cellulose acetate phthalate are taught as being useful where release of the coated material is dependent on pH. The overall emphasis in the prior art has thus been on the protection of the organic peroxyacid bleach precursor against a hostile environment during storage and relatively little attention has been paid to the dissolution characteristics of the coated or agglomerated material in use. Where coating and/or agglomeration has been proposed with poorly soluble materials such as fatty acids, this has resulted in a rate of perhydrolysis of the organic peroxyacid bleach precursor which is slower than that which would occur if it had not been so protected. Any use of more rapidly soluble materials such as citric acid has been in the context of an agglomerate component in which more rapid solution of the organic peroxyacid bleach precursor has been the objective. In both instances, because perhydrolysis commences as soon as the detergent product starts to dissolve and form an alkaline hydrogen peroxide solution, the problem of especially high localised organic peroxyacid bleach concentrations, particularly those resulting from the presence of surfactant having a tendency to gel upon dispensing, has remained unsolved.

EP-A-0,028,432 discloses a granule-containing detergent composition comprising from 5% to 80% of a peroxyacid bleach precursor, from 15% to 60% of a water-insoluble silicate and 5% to 40% of a nonionic binder within a solid detergent composition. This water-insoluble silicate compound, of which a smectite clay is a preferred example, is mixed with the peroxyacid bleach precursor and further bound with the nonionic surfactant. This combination is asserted to provide a rapid generation of peroxycarboxyl anions when added to a source of hydrogen peroxide. EP-A-0,028,432 provides no teaching relating to surfactant systems having a tendency to gel upon dispensing in a laundry washing method, nor of any problems which might be related thereto.

JP5-7296 discloses the general problem of fabric colour fading, but not the specific problem of 'patchy' discoloration. In particular, no teaching is provided relating to the problem of 'patchy' colour damage resulting from the formation of localised high concentrations of bleaching species such as can arise from the formation of viscous surfactant phases on dispensing of the detergent product to the wash solution. Disclosed therein is a composition in which a water-insoluble mineral substance, a peroxyacid bleach precursor and a bleach compound are mixed together in a ratio of said mineral substance to said precursor and bleach compound of 1 : 99 to 90:10, preferably 20:80 to 65:35. The water-insoluble mineral substance is selected from acid clay, activated clay, kaolin, bentonite, diatomaceous earth and perlite, and is said to inhibit fading without inhibiting the bleaching action. JP5-7296 provides no teaching relating to surfactant systems having a tendency to gel upon dispensing device in a laundry washing method, nor of any problems which might be related thereto.

W092/13798 discloses the use of acidic materials having specified characteristics as coating materials for peroxyacid bleach precursors to delay the onset of perhydrolysis during the initial stages of dissolution/dispersion of the product in the aqueous wash pre-liquor.

The Applicants have now found that the problem of colour damage, and particularly of 'patchy' discoloration of fabrics, obtained for compositions containing a relatively high level of surfactant having a tendency to gel under the conditions found in the initial stages of a domestic laundry wash cycle, can be reduced by the close contact addition of defined levels of a non-three dimensional phyllosilicate, particularly a clay or a crystalline layered silicate mineral compound to the organic peroxyacid bleach providing bleach system. The inclusion of the non-three dimensional phyllosilicate mineral compound has also been found not to significantly compromise the bleachable stain removal ability of the composition.

Laundry compositions including clay mineral compounds and clay flocculating agents for the purpose of providing fabric softening effects have previously been disclosed in European Patent Applications No.s EP- A-299,575 and EP-A-313,146. These documents provide no teaching of the use of clay mineral compounds to inhibit fabric damage, including 'patchy' colour damage.

All documents cited in the present description are, in relevant part, incorporated herein by reference. Summary of the Invention

According to the present invention there is provided a solid detergent composition containing

(a) at least 8% by weight of the composition of a surfactant system containing at least 50% by weight of the surfactant system of a surfactant selected from

(i) an anionic surfactant having a Krafft point of less than 38°C;

(ii) an alkoxylated nonionic surfactant;

and any mixtures thereof;

(b) a bleach system capable of providing organic peroxyacid bleach to a laundry wash solution wherein said bleach system is selected from

{i φ §0UfC$ of hydrogen peroxide in combination with an ftffpgya i bleach precursor compound;

(ii) a preformed organic peroxyacid;

and any mixtures thereof; and

(c) a non-three dimensional phyllosilicate mineral compound

wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are in close physical proximity within said composition.

Preferably, said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are in close contact, most preferably in intimate admixture within said composition. Preferably, said detergent composition is in particulate form, more preferably in granular form.

In preferred granular compositions said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non- three dimensional phyllosilicate mineral compound are present within the same particulate component.

Also, in preferred granular compositions said surfactant system is present in an agglomerate particle.

Preferably, any granular detergent composition is of high bulk density, more preferably having a bulk density of at least 600 g/litre.

The non-three dimensional phyllosilicate mineral compound is preferably a clay mineral compound or a crystalline layered silicate mineral compound.

Preferably, the clay mineral compound is a smectite clay compound.

Preferably, the weight ratio of the non-three dimensional phyllosilicate mineral compound to organic peroxyacid bleach precursor compound or said preformed organic peroxyacid is from 1 :1 to 1 :99.

In a preferred aspect the detergent composition is employed in a method of washing laundry in a domestic or industrial washing machine in which a dispensing device containing an effective amount of the solid detergent composition in accord with the invention is introduced into the drum of the washing machine before the commencement of the wash, wherein said dispensing device permits progressive relase of said detergent composition into the wash liquor during the wash. Detailed description of the invention

Surfactant system

In an essential aspect the solid detergent composition of the invention contains a surfactant system present at a level of at least 8% by weight, more preferably from 9% to 40% by weight, most preferably from 10% to 20% by weight of the composition.

The surfactant system contain at least 50% by weight, more preferably at least 60% by wieght, most preferably at least 70% by weight of the surfactant system of surfactant selected from an anionic surfactant having a Krafft point of less than 38 °C, an alkoxy lated nonionic surfactant and any mixtures thereof. Preferably the surfactant system contains both anionic and nonionic surfactants. The weight ratio of said anionic surfactant having a Krafft point less that 38 °C to said alkoxylated nonionic surfactant is preferably less that 5:1 , more preferably less than 4: 1 , most preferably from 3:1 to 1:1.

Surfactant agglomerate particles

In a preferred aspect the surfactant system is present as a particle formed by an agglomeration process, as described in more detail hereinafter. Such an agglomerated particle preferably contains at least 30%, more preferably at least 50% by weight of the particle of said surfactant system in combination with other detergent components such as builders and organic polymeric compounds.

Low Krafft point anionic surfactant

Anionic surfactant for use herein has a Krafft point of less than 38°C, more preferably less than 35°C, most preferably less than 32°C. The anionic surfactant is selected on the basis of this Krafft point criteria from any of those anionic surfactants listed in general hereinafter.

Krafft point can be measured by mixing lg of an anionic surfactant into 100 mis of distilled water and cooling the mixture in an ice bath, allowing it to become cloudy. The solution is then slowly heated and the temperature at which it becomes transparent is recorded. This temperature is the Krafft point.

Mixtures of low Krafft point (i.e. less than 38 °C) anionic surfactant and high Krafft point (i.e. more than 38 °C) may be used in the present invention, although the low Krafft point anionic preferably represents at least 50% by weight of the total surfactant present in the surfactant system.

Anionic surfactant

Essentially any anionic surfactants useful for detersive purposes can be included in the compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated ^-C_jg monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg-C_j^ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N- (C1-C4 alkyl) and -N-(Cι-C2 hydroxy alkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary Cio-Cig alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cio-Cjg alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cj i-Ci , most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefm sulfonates, sulfonated poly carboxy lie acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carbox late surfactant

Anionic carboxylate surfactants suitable for use herein include the alkyl ethoxy carboxylates, the alkyl poly ethoxy poly carboxy late surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Preferred alkyl ethoxy carboxylates for use herein include those with the formula RO(CH2CH2θ)_x CH2COO-M+ wherein R is a C6 to Cig alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 %, and the amount of material where x is greater than 7, is less than 25 %, the average x is from 2 to 4 when the average R is C13 or less, and the average x is from 3 to 10 when the average R is greater than C13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C12 to Ci alkyl group.

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula RO-(CHRι-CHR2-0)-R3 wherein R is a > o Cig alkyl group, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxy succinic acid radical, and mixtures thereof, wherein at least one Rj or R2 is a succinic acid radical or hydroxysuccinic acid radical, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Preferred soap surfactants are secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. The secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl- substituted cyclohexyl carboxylates. The secondary soap surfactants should preferably contain no ether linkages, no ester linkages and no hydroxyl groups. There should preferably be no nitrogen atoms in the head-group (amphiphilic portion). The secondary soap surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.

The following general structures further illustrate some of the preferred secondary soap surfactants:

A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials of the formula R3 CH(R4)COOM, wherein R is CH3(CH2)x and R⁴ is CH3(CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8.

B. Another preferred class of secondary soaps comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R5-R6- COOM, wherein R5 is C⁷-C¹⁰, preferably C8-C⁹, alkyl or alkenyl and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R^ can be in the ortho, meta or para position relative to the carboxyl on the ring.)

C. Still another preferred class of secondary soaps comprises secondary carboxyl compounds of the formula CH3(CHR)j_c- (CH2)_m-(CHR)_n-CH(COOM)(CHR)₀-(CH2)p-(CHR)_q-CH3, wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.

In each of the above formulas A, B and C, the species M can be any suitable, especially water-solubilizing, counterion.

Especially preferred secondary soap surfactants for use herein are water- soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-proρyl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R S a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxy lated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxy lated/propoxy lated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts as listed in detail hereinafter.

Nonionic condensates of alkvl phenols

The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 18 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.

Nonionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated/propoxylated fattv alcohol surfactant

The ethoxylated C -Cig fatty alcohols and Cό-Cig mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the Cio-Cig ethoxylated fatty alcohols with a degree of ethoxy lation of from 3 to 50, most preferably these are the Ci2-Cιg ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Nonionic EO/PO condensates with propylene elvcol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available Pluronic^M surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.

Organic peroxvacid bleaching system

An essential feature of the invention is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged. Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most 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 salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate can be in the form of the monohydrate of nominal formula NaBθ2*H2θ2 or the tetrahydrate NaBO2.H2O2.3H2O.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention. Compositions containing percarbonate, have been found to have a reduced tendency to form undesirable gels in the presence of surfactants and water than similar compositions which contain perborate. It is believed that this is because typically percarbonate has a lower surface area and lower porosity than perborate monohydrate. This low surface area and low porosity acts to prevent the co-gelling with fine particles of surfactant agglomerates and is therefore not detrimental to dispensing.

Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in product stability. A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB- 1,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2Sθ4.n.Na2Cθ3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Peroxvacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

O

I!

X-C-L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

O

II

X-C-OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A-0170386.

The Applicants have found that 'patchy' damage can be particularly associated with peroxyacid bleach precursor compounds which on perhydrolysis provides a peroxyacid which is

(i) a perbenzoic acid, or non-cationic substituted derivative thereof; or

(ii) a cationic peroxyacid.

Benzoxazin precursors have also been found to be particularly susceptible to the problem.

Leaving groups

The leaving group, hereinafter 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, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

R³ I -0-CH=C-CH=CH₂ -0-CH=C-CH=CH₂

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups

The preferred solubilizing groups are -SO ^'M , -Cθ2~M , -SO^^"M , -N⁺(R³)^X^" and 0 < -N(R³)₃ and most preferably -S0₃ ^"M⁺ and -Cθ2~M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.

Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

Ac = COCH3; Bz = Benzoyl

Perbenzoic acid precursor compounds of the imide type include N- benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N- benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

@ $

Suitable N-acylated lactam perbenzoic acid precursors have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R is a benzoyl group.

Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups. A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:

R¹ — C — N — R² — C — L R¹ — N — C — R² — C — L

1 1 i gr ι ι i — 1 1

O R⁵ 0 or R⁵ O 0

wherein R is an aryl or alkaryl group with from 1 to 14 carbon atoms, R² is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. Rl may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R* and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acy lated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

/

A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:

where n is from 0 to 12.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkvl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5- tri-methyl hexanoyloxy benzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:

R¹ C — N — R² C — L R¹ — N — C — R² C-

O R⁵ 0 or R⁵ O 0

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R* and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

including the substituted benzoxazins of the type

wherein R_j is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2. R . R4, and R^ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR^ (wherein R^ is H or an alkyl group) and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is:

Preformed organic peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

— OOH

wherein R* is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R² is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Rl preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. Rl and R^ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Non-three dimensional phyllosilicate mineral compound

The detergent compositions of the invention contain a non-three dimensional phyllosilicate mineral compound. In an essential aspect, the non-three dimensional phyllosilicate mineral compound and the organic peroxyacid bleach precursor compound or preformed organic peroxyacid are in close physical proximity, more preferably in close contact, most preferably in intimate admixture within said composition.

The non-three dimensional phyllosilicate mineral compound is preferably present such that the weight ratio of the non-three dimensional phyllosilicate mineral compound to organic peroxyacid bleach precursor compound or said preformed organic peroxyacid in the bleaching composition is from 1:1 to 1:99, preferably from 1:3 to 1:49, more preferably from 1:4 to 1:19.

By non-three dimensional phyllosilicate mineral compound it is meant herein a silicate mineral compound in which essentially flat (two dimensional) sheets are formed by the sharing of three of the four oxygen atoms in each silicate tetrahedron with neighbouring tetrahedrons. This definition excludes those silicates having a more complex three dimensional silicate linking structure which are occasionally referred to as "framework minerals". Preferred non-three dimensional phyllosilicate mineral compounds herein include clay mineral compounds and the crystalline layered silicates. For clarity, it is noted that the term non- three dimensional phyllosilicate mineral compound, as used herein excludes sodium aluminosilicate zeolite builder compounds, which however, may be included in the compositions of the invention as optional builder components.

The non-three dimensional phyllosilicate mineral compound is preferably present as a component of an agglomerate particle containing the organic peroxyacid bleach precursor compound or the preformed organic peroxyacid, and optionally other detergent compounds, including polymeric organic binders.

By clay mineral compound (or in abbreviation, "clay") it is meant herein a hydrous phyllosilicate, typically having a two or three layer crystal structure. Further description of clays may be found in Kirk-Othmer, Encyclopaedia of Chemical Technology, 4th edition, Volume 6, page 381, as published by John Wiley and Sons.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A- 299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.

The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula Al2(Si2θ5)2(OH)2.nH2θ and the compounds having the general formula Mg3(Si2θ5)2(OH)2-nH2θ. Smectite clays tend to adopt an expandable three layer structure. Specific examples of suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Sodium or calcium montmorillonite are particularly preferred.

Suitable smectite clays, particularly montmorillonites, are sold by various suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin and Colin Stewart Minerals.

Preferred smectite clays are sold under the tradename of White Bentonite STP by Fordamin and Detercal P7 by Laviosa Chemical Mineria SPA.

Clays for use herein may be subjected to an acid washing treatment with any suitable mineral or organic acid. Such clays give rise to an acid pH on dissolution in distilled water. A commercially available "acid clay" of this type is sold under the tradename Tonsil P by Sud Chemie AG.

Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays.

The crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein. Such substituted clays have been termed 'hydrophobically activated' clays. The cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1:200 to 1:10, preferably from 1:100 to 1:20. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

A preferred commercially available "hydrophobically activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quaternary ammonium salt sold under the tradename Claytone EM by English China Clays International. Preferred crystalline layered silicates for use herein have the general formula

NaMSi_xθ2χ+ i.yH2θ

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is 5-Na2Si2θ5, available from Hoechst AG as NaSKS-6.

The crystalline layered silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

Additional detergent components

The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the laundering operation for which it is to be used.

The compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.

Additional surfactant The detergent compositions of the invention preferably contain an additional surfactant selected from cationic, non-alkoxy lated nonionic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

The additional surfactant can be present at a level of from 0.1 % to 50% , more preferably from 1 % to 40% by weight, most preferably from 5% to 30% by weight of the surfactant system.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Non-alkoxylated nonionic surfactant

Exemplary, non-limiting classes of useful non-alkoxylated nonionic surfactants are listed below.

Nonionic polyhydroxy fattv acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^ONR^ wherein : RI is H, C1-C4 hydrocarbyl, 2- hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cl or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5- C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Cn-Cπ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fattv acid amide surfactant

Fatty acid amide surfactants suitable for use herein are those having the formula: R6C0N(R?)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, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)_xH, where x is in the range of from 1 to 3.

Nonionic alkvlpolysaccharide surfactant

Suitable alky .polysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.

The preferred alkylpolyglycosides have the formula

R²0(C_nH2_nO)t(glycosyl)_x

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.

Amphoteric surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

A suitable example of an alkyl aphodicarboxylic acid for use herein is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Amine Oxide surfactant

Amine oxides useful herein include those compounds having the formula R3(OR )_XNO(R5)₂ wherein R³ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1 , ethylene oxide groups. The R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include Cio-Cis alkyl dimethyl amine oxides and Cg-Cig alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are Cio-Ci alkyl dimethylamine oxide, and CiO-18 acylamido alkyl dimethylamine oxide.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. 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. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Betaine surfactant

The betaines useful herein are those compounds having the formula R(R')2N+R²COO- wherein R is a C6-C g hydrocarbyl group, preferably a jo-Ci6 alkyl group or C o_i6 acylamido alkyl group, each RMS typically C1-C3 alkyl, preferably methyl, m and R² is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C1-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; Cj2-14 acylamidopropylbetaine; Cg.14 acylamidohexyldiethyl betaine; 4[Cj4_i6 acylmethylamidodiethylammonio]- 1 -carboxy butane; C 16_ 1 g acylamidodimethylbetaine; Cj2-16 acylamidopentanediethyl-betaine; [C12-I6 acylmethylamidodimethylbetaine. Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C jθ-1 g acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Sultaine surfactant

The sultaines useful herein are those compounds having the formula (R(R*)2N + R S03" wherein R is a C6-Cιg hydrocarbyl group, preferably a Cjo-C 6 alkyl group, more preferably a C12-C13 alkyl group, each RMS typically C1-C3 alkyl, preferably methyl, and R² is a Ci-C-ό hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group.

Ampholytic surfactant

Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. Cationic surfactants

Cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono >-Ci6, preferably Cδ-Cio N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Water-soluble builder compound

The detergent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran - cis - dicarboxylates, 2,2,5 ,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxy methyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C, especially less than about 40°C.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Suitable silicates include the water soluble sodium silicates with an SiO '. Na2θ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Siθ2: Na2θ ratio of 2.0 is the most preferred silicate.

Silicates are preferably present in the detergent compositions in accord with the invention at a level of from 5% to 50% by weight of the composition, more preferably from 10% to 40% by weight.

Partially soluble or insoluble builder compound

The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na₂[(Alθ2)_z(Siθ2)y]. XH2O wherein 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 from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na 12 [A10₂) 12 (Siθ2)ι₂]. xH₂0

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag₆ [(Alθ2)g6(SiO₂)l06L ²?6 H₂0.

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 it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.

Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy- ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na3EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399,133.

The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'- diacetic acid, aspartic acid-N,N' -diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A- 510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l ,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N '-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.

Bleach catalyst

The compositions optionally contain a transition metal containing bleach catalyst.

One 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 bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mnr^v2(^u"0)3(1.4,7-trimethyl-l ,4,7- triazacyclononane)2-(PF6)2, MnHl2(u-0)ι(u-OAc)2(l ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)2, Mn^rV4(u-0)6(l ,4,7- triazacyclononane)4-(Clθ4)2, Mn^IIIMn^rV4(u-0)ι(u-OAc)2-(l ,4,7- trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1 ,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl-l ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl-l ,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- l,4,7-triazacyclononane)(OCH3)3-(PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso- inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)- cyclic ligand. Said ligands are of the formula:

R² R³

R -N=C-B-C=N-R⁴

wherein Rl, R², R3, and R⁴ can each be selected from H, substituted alkyl and aryl groups such that each R!-N=C-R² and R3-C=N-R⁴ form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6, NR? and C=0, wherein R^, R°, and R? can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'- bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,- bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (ID, trisdipyridylamine- cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis-(2,2'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn^ιπ(u-0)2Mn^IVN4)⁺and [Bipy2MnHI(u-0)2MnrVbipy2]-(C104)3. Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo- porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.

Enz me Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into 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 tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.

Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Organic polymeric compound

Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as cc nponents of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, preferably from 0.5% to 15%, most preferably from 1 % to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.

Other suitable organic polymeric compounds include the copolymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, and the acrylate/fiimarate copolymers having a molecular weight of from 2,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Suds suppressing system

The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05% to 10%, most preferably from 0.1 % to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds. By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, I960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor 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 sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cιg-C40 ketones (e.g. stearone) N- alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

Copolymers of ethylene oxide and propylene oxide, particularly the mixed ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10, are also suitable antifoam compounds for use herein.

Suitable 2-alky-alcanols antifoam compounds for use herein have been described in DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to Ci6 alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in the a position by a Ci to Cio alkyl chain. Mixtures of 2-alkyl-alcanols can be used in the compositions according to the present invention.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78 % and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;

(c) an inert carrier fluid compound, most preferably comprising - C\ - Cig ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A preferred particulate suds suppressor system useful herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.

The solid silica can be a fumed silica, a precipitated silica or a silica, made by the gel formation technique. The silica particles suitable have an average particle size of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface area of at least 50m /g. These silica particles can be rendered hydrophobic by treating them with dialkylsilyl groups and/or trialkylsilyl groups either bonded directly onto the silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered hydrophobic with dimethyl and/or trimethyl silyl groups. A preferred particulate antifoam compound for inclusion in the detergent compositions in accordance with the invention suitably contain an amount of silica such that the weight ratio of silica to silicone lies in the range from 1: 100 to 3:10, preferably from 1 :50 to 1 :7.

Another suitable particulate suds suppressing system is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50m /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.

A highly preferred particulate suds suppressing 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 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45 °C to 80 °C. Other highly preferred particulate suds suppressing systems are described in copending European Application 91870007.1 in the name of the Procter and Gamble Company which systems comprise silicone antifoam compound, a carrier material, an organic coating material and glycerol at a weight ratio of glycerol : silicone antifoam compound of 1:2 to 3:1. Copending European Application 91201342.0 also discloses highly preferred particulate suds suppressing systems comprising silicone antifoam compound, a carrier material, an organic coating material and crystalline or amorphous aluminosilicate at a weight ratio of aluminosilicate : silicone antifoam compound of 1:3 to 3:1. The preferred carrrier material in both of the above described highly preferred granular suds controlling agents is starch.

An exemplary particulate suds suppressing system for use herein is a particulate agglomerate component, made by an agglomeration process, comprising in combination

(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in combination polydimethyl siloxane and silica;

(ii) from 50% to 90%, preferably from 60% to 80% by weight of the component, of carrier material, preferably starch;

(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of agglomerate binder compound, where herein such compound can be any compound, or mixtures thereof typically employed as binders for agglomerates, most preferably said agglomerate binder compound comprises a Ci^-Cig ethoxylated alcohol with a degree of ethoxylation of from 50 to 100; and

(iv) from 2 % to 15 % , preferably from 3 % to 10% , by weight of C \2- C22 hydrogenated fatty acid. Clav flocculating agent

The compositions of the invention may contain a clay flocculating agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably from 0.1 % to 2% by weight of the composition.

The weight ratio of clay mineral compound to clay flocculating agent is preferably from 300: 1 to 1:1, more preferably from 80:1 to 10:1, most preferably from 60: 1 to 20: 1.

The clay flocculating agent functions such as to bring together any particles of clay compound in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash. This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution.

Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.

Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are preferred.

European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.

Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum. S3

Polymeric dve transfer inhibiting agents

The detergent compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polvamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :

(I) Ax

R

wherein P is a polymerisable unit, and

O O O

A is NC, CO, C, -0-, -S-, -N-; x is O or 1;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.

The N-O group can be represented by the following general structures : 0

wherein RI, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-0 group forms part of these groups. The N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.

Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups. Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are poly vinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1 :1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.

The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpvrrolidone and N-vinvlimidazole

Preferred polymers for use herein may comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000. The preferred N-vinylimidazole N-vinylpyrrolidone copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .

c Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP" having an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K- 90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidone may be incorporated in the detergent compositions herein at a level of from 0.01 % to 5% by weight of the detergent, preferably from 0.05% to 3% by weight, and more preferably from 0.1 % to 2% by weight. The amount of polyvinylpyrrolidone delivered in the wash solution is preferably from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.

The amount of polyvinyloxazolidone incorporated in the detergent compositions may be from 0.01 % to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1 % to 2% by weight. The amount of polyvinyloxazolidone delivered in the wash solution is typically from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.

έ) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.

The amount of polyvinylimidazole incorpoarted in the detergent compositions may be from 0.01 % to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1 % to 2% by weight. The amount of polyvinylimidazole delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.

Optical brightener

The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01 % to 1 % by weight of such optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, morphilino, 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-hydroxy ethyl and M is a cation such as sodium, the brightener is 4,4^*,-bis[(4-anilino-6-(N- 2-bis-hydroxyethy l)-s-triazine-2-yl)amino]-2 ,2 ' -stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, Ri is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2, 2 '-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, Ri is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-aniIino-6-morphilino- s-triazine-2-yl)amino]2 ,2 '-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic fabric softening agents

Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. These may be present as distinct components or as components of the, hereinbefore described, hydrophobically activated clay materials. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340. Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1 % to 5% by weight.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

Form of the compositions

The solid compositions in accordance with the invention can take a variety of physical forms. The compositions are particularly the so-called concentrated detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load. Concentrated granular detergent compositions dispensed into the wash liquor via a dispensing device are more subject to dissolution problems than compositions added via the dispensing compartment of a washing machine because, in the initial stages of a wash cycle, the agitation in the immediate environment of the product is inhibited by the presence of the fabric load. Whilst this can constitute a benefit in permitting the development of high transient concentrations of builder, the development of high transient organic peroxyacid concentrations can, as noted previously, lead to 'patchy' fabric colour damage.

The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass. The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Surfactant agglomerate particles

The surfactant system herein is preferably present in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of 50°C to 80°C is typical.

A particularly suitable process of making surfactant particles from high active surfactant pastes is more fully described in EP-A-510 746, published on 28th October, 1992.

In a preferred aspect the surfactant containing granules have a mean particle size of less than 480 micrometers, preferably less than 400 micrometers, and most preferably less than 350 micrometers.

Clav/organic peroxyacid precursor particles

Preferably, the organic peroxyacid bleach precursor or preformed organic peroxyacid and clay mineral compound are present in combination as particulate components, which preferably include additional components to aid the cohesion of the particles and optimize their storage stability and flowability characteristics. Particularly preferred additional components, which help to provide good particle structure, are binders, which, for example, may comprise any of the organic polymeric compounds described herein.

The particulate components can have any suitable form such as granules, flakes, prills, marumes or noodles but are preferably granular. The granules themselves may be agglomerates formed by pan or drum agglomeration, by in-line mixers or may be formed as spray dried particles produced by atomising an aqueous slurry of the ingredients in a hot air spream which removes most of the water. Laundry washing method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle. Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash 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-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/11562.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene. Packaging for the compositions

Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in copending European Application No. 93970141.4.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

XYAS Sodium Cιχ - Cιγ alkyl sulfate

XYEZ A Cι_x - Ciy primary alcohol condensed with an average of Z moles of ethylene oxide

XYEZS Cιχ - Cιγ sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole

LAS C12 linear alkyl benzene sulfonate

TFAA Ci6-Cιg alkyl N-methyl glucamide.

Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio = 2.0)

NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2θ5

Carbonate Anhydrous sodium carbonate MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000

Zeolite A Hydrated Sodium Aluminosilicate of formula Na 2(Alθ2Siθ2)i2- 27H20 having a primary particle size in the range from 1 to 10 micrometers

Citrate Tri-sodium citrate dihydrate

Percarbonate Anhydrous sodium percarbonate bleach coated with a coating of sodium silicate (Si2θ:Na2θ ratio = 2:1) at a weight ratio of percarbonate to sodium silicate of 39:1

TAED particle Tetraacetylethylenediamine particle formed by agglomerating TAED with a copolymer of 1 :4 maleic/acrylic acid having an average molecular weight of about 70,000 at a weight ratio of TAED: copolymer of 85: 10 and then coating said agglomerate with a coating of said copolymer at a weight ratio of agglomerate: coating of 95:5.

Protease Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S with an activity of 13 KNPU/g.

Amylase Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S with an activity of 300 KNU/g

Cellulase Cellulosic enzyme sold by Novo Industries A/S with an activity of 1000 CEVU/g Lipase Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S with an activity of 165 KLU/g

CMC Sodium carboxymethyl cellulose

HEDP 1,1-hydroxyethane diphosphonic acid

EDDS Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt.

PVNO Poly (4-vinylpyridine)-N-oxide polymer having an average molecular weight of 10,000.

PVPVI Copolymer of N-vinylpyrollidone and N- vinylimidazole, at a molar ratio of 1:0.5, having an average molecular weight of 10,000.

Granular Suds 12% Silicone/silica, 18% stearyl alcohol,70% Suppressor starch in granular form

DETPMP Diethylene triamine penta (methylene phosphonic acid)

Example 1

TAED/clav particle 1

An agglomerate having the following formulation was made in an Eirich Mixer model RV02 (tradename)

Wt%

TAED 85

Clay** 5

MA/AA* 10

Ϊ00

*supplied as Sokolan 45 (tradename) ex BASF

**supplied as Bentonite (tradename) ex Colin Stewart Minchem Ltd

The TAED and the clay were added to the Eirich mixer and pre-mixed. The temperature of the powder was 25 °C. An aqueous solution of the MA/AA binder, which was at a temperature of 60°C, was added to the powder mix, with the Eirich blades and pan rotating, over a period of 30 seconds. The resulting mass was further mixed for 30 seconds. The mixing was then stopped and the agglomerate product removed from the Eirich mixer and further dried in a fluid bed dryer to a moisture content of 2%. The product was then sieved and materials that were greater than 1180 micrometers and smaller than 250 micrometers were removed.

TAED/clav particle 2

The same procedure as above was repeated with the exception of the clay being replaced with an acid clay (Tonsil P (tradename) sold by Sud Chemie AG) in the same amount. TAED/clav particle 3

An agglomerate having the following formulation was made in an Eirich Mixer model RV02 (tradename)

Wt%

TAED 80

Clay** 5

MA/AA* 10

95

*supplied as Sokolan 45 ex BASF

**supplied as Bentonite ex Colin Stewart Minchem Ltd

The TAED and the clay were added to the Eirich mixer and pre-mixed. The temperature of the powder was 25°C. The molten binder, which was at a temperature of 60°C, was added to the powder mix, with the Eirich blades and pan rotating, over a period of 30 seconds. The resulting mass was further mixed for 30 seconds. The mixing was then stopped and the agglomerate product removed from the Eirich mixer and further dried in a fluid bed dryer. The product was then sieved and materials that were greater than 1180 micrometers and smaller than 250 micrometers were removed. The resulting agglomerate was then coated with MA/AA at a level of coating '.agglomerate of 5:95.

The following laundry detergent compositions A, B, C, D and E were prepared, A and B are comparative compositions and C to E are in accord with the invention:

Lipase 0.15 0.15 0.15 0.15 0.15

Cellulase 0.28 0.28 0.28 0.28 0.28

Amylase 0.27 0.27 0.27 0.27 0.27

MA/AA 3.1 3.1 3.1 3.1 3.1

CMC 0.4 0.4 0.4 0.4 0.4

PVNO 0.03 0.03 0.03 0.03 0.03

Granular suds suppressor 1.5 1.5 1.5 1.5 1.5

Minors/misc to 100%

Surfactant Krafft points

The following Krafft points for anionic surfactants were measured using the method outlined in the present description:

Surfactant Krafft point

45AS <38°C 25 AS <38°C 35AE3S 5°C 25AE3S <5°C LAS <2°C Comparative Performance Testing

Test protocol 1 - patchv colour fading testing

The formulations A to E were subjected to a full scale washing machine test using 12 Miele automatic washing machine (Model WM W698) set to the short wash cycle at 40°C for each formulation. Water of 12° Clark hardness ( = 1.8 mmol Ca²+ /litre) was used. The fabric swatches to be placed in the washing machines by pairs were numbered from 1 to 24 and made from garments obtained from High Street stores as detailed below:

Swatches Type of Garment Colour Type of fabric Number

1&4 Wool Cardigan Navy Blue 50/50% Wool/Acrylic

2&3 Mens' Shirt Dark green 100% Cotton

5&8 Tee Shirt Black 100% Cotton

6&7 Mens Sweat Shirt Black 10/90% Cotton/polyester

9&12 Tee Shirt Black 100% Cotton

10&11 Denim Shirt Navy 100% Cotton

13&16 Long Sleeve Black 50/50% Sweatshirt Cotton/polyester

14&15 Jeans Black 100% Cotton

17&20 Mens' Trousers Black 65/35% Polyester/Viscose

18&19 Mens' Cord Shirt Green 100% Cotton

21&24 Mens' Shirt Dark 100% Cotton Green

22&23 Leggings Black 97/3% Cotton/Lycra

Each machine was loaded with a ballast of 41bs (approx. 1.9kg) of clean sheets, with on top of it the following materials: a fabric swatch, lOOg of the formulation dispensed from a granulette dispensing device, of the type 72

disclosed in EP-A-343,070 and commonly supplied for use with the Ariel Ultra (tradename) granular laundry detergent as sold by The Procter and Gamble Company and a second fabric swatch on top of it. The swatches of size 30cm x 30cm were folded together so as to cause entrapment of the granulette during the first stages of dissolution/dispersion of the detergent composition containing the detergent composition. At the end of the cycle, the swatches were retrieved and dried in the open air.

The swatches were then graded visually for fabric discoloration using a grading system in which three coloured swatches demonstrating differing degrees of colour damage are used as standards to establish a 6 point scale in which 0 represents 'no discoloration' and 5 represents 'extreme discoloration' . The three standards are used to define the mid points between the various descriptions of colour discoloration viz

0 no discoloration

1 very slight discoloration 2 slight discoloration 3 clearly noticeable discoloration 4 very discolored 5 extreme discoloration

Two expert panellists are used and their results are averaged.

Comparative testing - patchv discoloration

Using the above test protocol 1 to compare colour damage resulting from use of formulations A to E the following results were obtained

% of swatches having grade

Formulation 0 1 2 3 4 5 Overal Grade

A 67 17 8 8 0 0 0.5

B 58 13 13 12 4 0 0.91

C 84 0 8 8 0 0 0.4

D 80 4 4 12 0 0 0.4 75 8 13 0 0 0.59

It can be seen that Compositions C to E in accordance with the invention produces appreciably less fabric discoloration than Compositions A and B.

Test protocol 2 - stain removal

Three white cotton sheets were prewashed in a non-biological bleach-free heavy duty detergent. Tea stains were then applied to one sheet, wine stains to the second sheet and coffee stains to the third one. Sets of six test swatches of size 6cm x 6cm were cut from each sheet.

The sets of fabric swatches were subjected to one wash cycle in an automatic washing machine. The swatches were then assessed for removal of the tea, wine and coffee stains using a well-established lightness measurement method.

In more detail, a Miele 756 WM automatic washing machine was employed, and the 40°C short cycle programme selected. Water of 12° Clark hardness ( = 1.8 mmol Ca²+ /litre) was used. lOOg of detergent, dispensed from a granulette dispensing device was employed. One swatch of each fabric type was washed along with a ballast load of 41bs (approx 1.9Kg) of lightly soiled sheets.

Stain removal was assessed by making LAB (lightness) measurements using the X-rite (tradename) colour eye spectrophotometer. An unstained cotton sheet was used as the reference. A stain removal index, ΔR, was calculated as follows:

ΔR ⁼ (I-washed ~ L_unwashed)^(Lunwashed " ^reference) x 100 Comparative testing - stain removal

The above test protocol 2 was followed in comparing the efficiency of Compositions B and C in removing different type of stains. The results obtained were as follows:

ΔR (%) B C

Tea 78 76

Wine 82 83

Coffee 75 74

The stain removal obtained for each of Compositions B and C is thus shown to be comparable.

Example 2

The following granular laundry detergent compositions F to I of bulk density 750 g/litre were prepared in accord with the invention:

EDDS - - 0.3 0.75

Protease 0.55 1.27 0.55 1.27

Lipase 0.15 0.15 0.15 0.15

Cellulase 0.28 0.28 0.28 0.28

Amylase 0.27 0.27 0.27 0.27

MA/AA 3.1 3.1 3.1 3.1

CMC 0.4 0.4 0.4 0.4

PVNO 0.01 0.01 0.01 0.01

PVPVI 0.01 0.01 0.01 0.01

Granular suds suppressor 1.5 1.5 1.5 1.5

Minors/misc to 100%

Claims

WHAT IS CLAIMED IS:

1. A solid detergent composition containing

(a) at least 8% by weight of the composition of a surfactant system containing at least 50% by weight of the surfactant system of a surfactant selected from

(i) an anionic surfactant having a Krafft point of less than 38⁰C;

(ii) an alkoxylated nonionic surfactant;

and any mixtures thereof;

(b) a bleach system capable of providing organic peroxyacid bleach to a laundry wash solution wherein said bleach system is selected from

(i) a source of hydrogen peroxide in combination with an organic peroxyacid bleach precursor compound;

(ii) a preformed organic peroxyacid;

and any mixtures thereof; and

(c) a non-three dimensional phyllosilicate mineral compound including layered silicates and clay mineral compound.

wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are in close physical proximity within said composition.

2. A detergent composition according to Claim 1 wherein the weight ratio of said anionic surfactant to said alkoxylated nonionic surfactant is less than 5:1.

3. A detergent composition according to either of Claims 1 or 2 wherein said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are in intimate admixture within said composition.

4. A detergent composition according to any of Claims 1 to 3 wherein said detergent composition is in particulate form and said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid and said non-three dimensional phyllosilicate mineral compound are present in the same particulate component.

5. A detergent composition according to any of Claims 1 to 4 wherein the weight ratio of the non-three dimensional phyllosilicate mineral compound to said organic peroxyacid bleach precursor compound or said preformed organic peroxyacid is from 1:1 to 1 :99.

6. A detergent composition according to either of Claims 4 or 5 wherein said detergent composition is in granular form and has a bulk density of at least 600 g/litre.

7. A detergent composition according to any of Claims 1 to 6 wherein said non-three dimensional phyllosilicate mineral compound is a clay mineral compound.

8. A detergent composition according to Claim 7 wherein said clay mineral compound is a smectite clay compound.

9. A detergent compound according to any of Claims 1 to 6 wherein said non-three dimensional phyllosilicate mineral compound is a crystalline layered silicate mineral compound.

10. A detergent composition according to Claim 9 wherein said crystalline layered silicate mineral compound has the general formula: NaMSi_xθ2χ+ i yH2θ

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20

11. A detergent composition according to any of Claims 1 to 10 wherein the hydrogen peroxide source is an inorganic perhydrate salt.

12. A detergent composition according to Claim 11 wherein said inorganic perhydrate salt is an alkali metal percarbonate salt.

13. A detergent composition according to any of Claims 1 to 12 wherein said organic peroxyacid bleach precursor compound provides peracetic acid on perhydrolysis.

14. A detergent composition according to Claim 13 wherein said organic peroxyacid bleach precursor compound is tetraacetylethylenediamine.

15. A detergent composition according to any of Claims 1 to 12 wherein said organic peroxyacid bleach precursor compound provides on perhydrolysis an organic peroxyacid which is

(i) a perbenzoic acid, or non-cationic substituted derivative thereof; or

(ii) a cationic peroxyacid.

16. A method of washing laundry in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to any of Claims 1 to 15 is introduced into the drum of the washing machine before the commencement of the wash, wherein said dispensing device permits progressive relase of said detergent composition into the wash liquor during the wash.