EP0843715A1 - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition suitable for use in laundry and dish washing methods comprising: (a) a cationic ester surfactant; and (b) a soil release polymer selected from the group consisting of oligoester soil release polymers and polyamine soil release polymers.

Description

Laundry washing method

Technical field

This invention relates to a method of washing laundry in a domestic or industrial washing machine, and more especially to such a method wherein a detergent composition containing a cationic ester surfactant is delivered directly to the soiled fabrics in the early stages of the wash.

Background to the invention

The satisfactory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions for use in machine laundry methods. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic esters have been described for use in greasy soil/stain removal.

For example, EP-B-21 ,491 discloses detergent compositions containing a nonionic/cationic surfactant mixture and a builder mixture comprising aluminosilicate and polycarboxylate builder. The cationic surfactant may be a cationic ester. Improved particulate and greasy/oily soil removal is described.

US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide

SUBSTITUTE SH^CET (RULE 26) greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.

US-A-4,239,660 discloses laundry detergent compositions containing cationic ester surfactant and nonionic surfactant at defined weight ratios and an alkalinity source. The alkalinity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minutes of dissolution of the composition in water at 100°F (37°C) at a solution concentration of 0.15% .

US-A-4,260,529 discloses laundry detergent compositions having a pH of no greater than 11 containing cationic ester surfactant and nonionic surfactant at defined weight ratios. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic ester surfactant component.

The Applicants have now found that the in solution stability of the cationic ester surfactant is reduced in the presence of a highly alkaline wash environment. It is believed that the origin of this problem is the hydrolysis of the ester linkage of the cationic ester surfactant, which occurs more rapidly in highly alkaline conditions and which thereby leads to degradation of the surfactant.

The Applicants have now found that a solution to this problem may be achieved if the cationic surfactant is delivered directly to the soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics by an appropriately designed delivery means. The delivery means may, in a preferred execution, comprise a dispensing device enabling delivery of detergent directly to the soiled fabrics via a dispensing aperture.

Dispensing devices in the form of flexible containers, such as bags or pouches but having no distinct dispensing aperture are known in the art, but are not suitable for use in the laundry method of the current invention. The containers are typically made from water-insoluble, but water- permeable material. Dispensing of the detergent product occurs as wash water permeates the container thereby dissolving the contained detergent product which can then pass as a solution into the wash through the container walls. Such containers are not suitable herein in that the surfactant components have a tendency to gel inside the container and thus to be dispensed more slowly, as opposed to simple alkaline salt components which dissolve rapidly and thus dispense rapidly. An alkaline wash environment is thus established prior to the release of the cationic ester surfactants.

Similarly, laundry detergent dispensing means in the form of detergent impregnated fabric sheets are known in the art, but are also not suitable for use in the laundry method of the current invention. Such sheets are typically made from water-insoluble, but water-permeable material. Dispensing of the detergent product occurs as wash water contacts the sheet thereby dissolving the impregnated detergent product which is then released as a solution into the wash. One problem with such dispensing means is that the impregnated fabric sheets tend to get enfolded or trapped with the soiled laundry in the wash which hampers dispensing. Furthermore, the surfactant components again have a tendency to gel and thus form a gelatinous surface on the fabric sheet which delays dispensing, as opposed to any simple alkaline salt components which dissolve rapidly and thus dispense rapidly. This again leads to alkaline wash environment being established prior to the release of any cationic ester surfactants.

The Applicants have also found an alternative but related solution to the problem of decrease in stain removal performance as a result of cationic ester alkaline hydrolysis in the wash. Direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishment of a highly alkaline environment around the fabrics may also be achieved by appropriate pretreatment of the fabrics with a detergent containing the cationic ester surfactant. In a preferred aspect, the soiled fabrics are pretreated prior to their introduction into the washing machine with a liquid detergent composition formulated to a relatively low pH (i.e. pH < 9) and containing alkaline components having effect only during the wash. In another preferred aspect, the soiled fabrics are pretreated with a detergent composition containing cationic ester surfactant but no alkaline components. A second detergent composition including alkaline components may then be employed in the wash cycle.

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 method of washing soiled laundry in a domestic or industrial washing machine wherein a delivery means is provided for dispensing an effective amount of a detergent composition directly to the drum of a washing machine before the commencement of the wash and subsequently enabling release of said detergent composition to the wash liquor during the wash wherein said detergent composition contains

(a) from 1 % to 90% by weight of the detergent composition of a cationic ester surfactant; and

(b) from 1.5% to 95% of the detergent composition of an alkalinity system comprising alkaline components selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof

characterized in that said delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of a hydrolysing alkaline wash liquor environment around the soiled laundry. In a preferred aspect, the cationic ester surfactant is selected from those having the formula:

*ι — G-f- (X)_U-( C H₂ )_m— ₍γ_)v_(CH₂ )_t-N-R₃ M

R

wherein Ri is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M". N + (R6R7R8)(CH2)_S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and Rg are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

According to another aspect of the invention, there is provided a method of washing soiled laundry having a pretreat step comprising application of an effective amount of a detergent composition directly to the soiled laundry before subjecting the soiled laundry to a washing step wherein said detergent composition contains

(a) from 0.1 % to 90% by weight of the detergent composition of a cationic ester surfactant; and

(b) from 10% to 99.9% of the detergent composition of detergent components selected from additional surfactants, bleaches, builders, alkalinity sources, organic polymeric compounds, enzymes, suds

SUBSTITUTE SHEET (RULE 20) suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors

characterized in that said pretreat step enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.

Detailed description of the invention

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 defined laundry detergent composition. By an effective amount of the detergent composition it is typically meant from 20g to 300g of product dissolved or dispersed in a wash solution of volume from 3 to 65 litres, as are common product dosages and wash solution volumes commonly employed in conventional machine laundry methods. In practice, dosage will alter in accordance with the size of the laundry load and degree of soiling.

A delivery means is employed in the washing method of the invention to directly deliver an effective amount of detergent product to the drum of φe washing machine before commencement of the wash cycle and to enable release of the detergent product into the wash liquor, particularly during the early stages of the wash, more particularly during the first two minutes of the wash. In an essential aspect, the delivery means enables the delivery of cationic ester surfactant to the soiled laundry prior to the establishment of a hydrolysing alkaline wash liquor environment around the soiled laundry.

By hydrolysing alkaline wash liquor environment herein it is meant a wash liquor environment that is sufficiently and sustainedly alkaline as to cause significant and rapid hydrolysis of the ester linkage of the cationic ester surfactant, such that its surfactant capability is reduced. In particular, this means a pH environment of greater than 9, particularly

SUBSTITUTE SHEET (RULE 20) greater than 10. Higher temperatures can also serve to promote the hydrolysis reaction.

In one preferred aspect said delivery means is a dispensing device having a defined dispensing aperture, particularly one of cross-sectional area greater than 5 cm^, preferably greater than 7 cm^. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method without having to compress the product in the device, which would reduce its release rate.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum on top of the laundry load, and preferably adjacent to the most soiled areas of the fabrics in the laundry load. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. As the drum rotates the detergent product is dispensed from the dispensing aperture and thus is delivered directly to the soiled laundry. The device may possess more than one dispensing aperture through which the product may be dispensed in response to its agitation in the rotating drum. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient lpcalised 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 in accord with the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, 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

SUBSTITUTE SHEET (RUL! device for use in accord with the invention is disclosed in PCT Patent Application No. WO 94/11562.

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 and to allow for its dispensing during the early stages of the wash cycle. 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.

In another aspect the delivery means is provided by compacting a detergent composition containing both cationic ester and alkaline components into a tablet formed such as to provide release of cationic ester surfactant to the soiled laundry prior to the full release of any alkaline components. The tablets are then introduced directly to the drum of the washing machine prior to commencement of the wash cycle.

In a preferred aspect, the tablet comprises layers of distinct product composition with the cationic ester surfactant, being present in a layer outwardly located relative to the layer comprising the alkalinity system, and preferably fully separated from that layer.

Pretreat washing method

According to another aspect of the present invention, the direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishment of a hydrolysing alkaline environment around the fabrics may also be achieved by pretreatment of the fabrics with a detergent composition containing the cationic ester surfactant. For the avoidance of doubt, pretreatment herein means the direct application of a pretreatment detergent composition to a soiled fabric prior to subjecting the soiled fabric to a washing step. The pretreatment composition is generally fluid in nature, that is a solution, liquid, gel, foam or mousse. Application may be achieved by any suitable means including pouring the fluid pretreat composition on the fabric possibly using a suitable dosing means, spray application of a mousse or foam, or applying the fluid using an applicator means such as a sponge or a brush. Preferably, the pretreatment composition is then manually rubbed into the soiled fabric. The pretreat composition is allowed to remain in contact with the soiled fabric for an effective time interval prior to subjecting the pretreated fabric to the washing step. Said time interval will typically be from 10 seconds to 1800 seconds, more preferably from 60 seconds to 600 seconds. The subsequent washing step is preferably carried out using a washing machine.

In a preferred aspect, the soiled fabrics are pretreated with a liquid detergent composition formulated to a relatively low pH, that is pH less than 9.5, more preferably less than 9, most preferably less than 8, but containing alkaline components capable of providing alkalinity during the wash. The alkaline components may for example be coated with a substance which remains intact during the pretreatment step but is removed, e.g. by abrasion, during the washing step.

In another preferred aspect, the soiled fabrics are pretreated with a detergent composition containing cationic ester surfactant but no alkaline components. A second detergent composition including alkaline components may then be employed in the wash cycle.

Cationic ester surfactant

The first essential element of the detergent compositions of the invention is a cationic ester surfactant. That is, a preferably water dispersible compound having surfactant properties comprising at least one ester (ie - COO-) linkage and at least one cationically charged group.

SUBSTITUTE SHEΞ1 (MULC 2 ab\ The cationic ester surfactant is present in amount from 0.1 % to 90%, preferably from 0.5% to 40%, most preferably from 1 % to 30% by weight of the detergent composition.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Preferred water dispersible cationic ester surfactants are those having the formula:

*l — O (CH)_nO (X)_u -( C H₂ )_m— (Y)_v— (C H₂ M

wherein Ri is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M~. N⁺(R6R7R8)(CH2)_S; X and Y, independently, are selected from the group consisiting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R£, R7, and Rs are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

Preferably R2,R3 and R4 are independently selected from CH3 and -CH2CH2OH.

Preferably M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide. Preferred water dispersible cationic ester surfactants are the choline esters having the formula:

wherein Ri is a C11-C19 linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoyl choline ester quaternary methylammonium halides (Rl =Ci7 alkyl), palmitoyl choline ester quaternary methylammonium halides (R* = Ci5 alkyl), myristoyl choline ester quaternary methylammonium halides (Rl = Ci3 alkyl), lauroyl choline ester methylammonium halides (R1 =CH alkyl), cocoyl choline ester quaternary methylammonium halides ( ^ =Cn_Ci3 alkyl), tallowyl choline ester quaternary methylammonium halides (Rl = Ci5_Ci7 alkyl), and any mixtures thereof.

Most preferred choline ester compounds among the above disclosed are cocoyl choline ester quaternary methylammonium halides.

The particularly preferred choline esters, given above, may be prepared b,y the direct esterification of a fatty acid of the desired chain length with dimethy laminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2- haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.

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

Alkalinity system

The second essential component of the detergent compositions is from 1.5% to 95% , preferably from 5% to 60% , most preferably from 10% to 40% by weight of the composition of an alkalinity system comprising components capable of providing alkalinity species in solution. By alkalinity species it is meant carbonate, bicarbonate, hydroxide and the various silicate anions. Such alkalinity species can be formed for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof are dissolved in water. Alkali metal percarbonate and persilicate salts are also suitable sources of alkalinity species.

Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973. Alkali metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the section 'inorganic perhydrate salts' herein.

Sodium hydroxide is a preferred alkali metal hydroxide herein.

Suitable silicates include the water soluble sodium silicates with an Siθ2: Na2θ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 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. Alkali metal persilicates are also suitable sources of silicate herein.

Preferred crystalline layered silicates for use herein have the general formula

NaMSi_xθ2χ+ ι .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 δ-Na2SΪ2θ5, 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 also contain additional detergent components at a level of from 10% to 99% by weight. 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 washing operation for which it is to be used.

The compositions of the invention contain one or more additional detergent components selected from additional surfactants, bleaches, builders, organic polymeric compounds, 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 anionic, nonionic, non-ester cationic, amphoteric and zwitterionic surfactants and mixtures thereof. The additional surfactant is preferably 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.

Anionic surfactant

A preferred component of the detergent compositions is an anionic surfactant. The weight ratio of anionic surfactant to cationic ester surfactant in the surfactant system is preferably from 3:1 to 15:1, more preferably from 4:1 to 12:1, most preferably from 5:1 to 10:1.

Essentially any anionic surfactants useful for detersive purposes are suitable. 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. Anionic sulfate surfactants are preferred.

Suitable 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 iesters of sulfosuccinate ters), N-acyl id d h d d i 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 and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) 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 C10-C18 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 C10-C18 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 Cn-Ci8, 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 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x CH2COO-M + wherein R is a Cβ to Cis 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 M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRι-CHR2-0)-R3 wherein R is a C6 to Cis 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, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R¹) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is 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 propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxy late condensation products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxylated alcohol surfactant

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol 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 polyhvdroxy fattv acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R²CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2- hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci 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 C1 -C17 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 fatty acid amide surfactant

Suitable fatty acid amide surfactants include those having the formula: R6C0N(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4θ)_xH, where x is in the range of from 1 to 3.

Nonionic alkylpolysaccharide surfactant Suitable alkylpolysaccharides 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 and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R²0(C_nH_2nO)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 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactant

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

Suitable amine oxides include those compounds having the formula R3(OR )_XNO(R5)₂ wherein R is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C10-C18 alkyl dimethy lamine oxide, and C10-I8 acylamido alkyl dimethylamine oxide.

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

Zwitterionic surfactant

SUBSTITUTE SHEET (RULE 25) 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.

Suitable betaines are those compounds having the formula R(R')2N+R²COO" wherein R is a C6-C18 hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R² is a C1-C5 hydrocarbyl group. Preferred betaines are Ci 2- 18 dimethy 1-ammonio hexanoate and the CiO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

Additional cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C -Ciό, preferably Cβ-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, borates, phosphates, 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 oxypoly carboxy late 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. Preferred polycarboxylates are hydroxycarboxylates 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 are useful water-soluble builders herein.

Suitable 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.

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 Na_z[(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 2 [A10₂) 12 (Si0₂)l2]- xH₂0 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na₈₆ [(AlO₂)86(Siθ2)l06]. ?6 H₂0.

Organic peroxyacid bleachin system

A preferred feature of detergent compositions 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 perhvdrate 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. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps. Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2.3H2θ.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid.

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

Peroxyacid 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

II

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.

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:

-oftTT Y , and

-N-C-R¹ - N _M_i °__CH_R4

R³ Y

I 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 -SOg^'M^-1-, -Cθ2^~M ⁺ , -S0₄ ^"M ⁺ , -N ⁺ (R³)4X^" 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.

Alkyl 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 hexanoyloxybenzene 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 suitable herein, including those of the following general formulae:

_R1 — _c — _N — _R2 — _c — _{L R}1 — _N — _c — _R2 — _c — _L

O R⁵ 0 or R⁵ 0 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. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including 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. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyro lutamic acid.

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.

SUBSTITL-ΪL i-iil i t.. - i i 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 oxy benzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

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:

wherein R^ is H, alkyl, alkaryl, aryl, or arylalkyl.

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:

wherein Rl 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. 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.

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 MnrV^T2(u-0)3(l,4,7-trimethyl-l,4,7- triazacyclononane)2-(PF6)2, MnHl2(^u"0)l(^u"0^Ac)2(l ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)2, Mn^IV4(u-0)6(l ,4,7- triazacyclononane)4-(C104)2 , MnHlMn^^-O) i (u-0 Ac)2-( 1,4,7- 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-

SUBSTΠ JTE SHEET (RULE 26) 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 (DI), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnHI(u-0)2MnIVN4)⁺and

[Bipy2Mnπi(u-0)2Mnrv^τbipy2]-(Clθ4)3.

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (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).

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.

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.

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.

Enzvme

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

Preferred additional enzymatic materials include the commercially available lipases, cutinases, 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 Opticiean 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, -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

SUBSTITUTE SHEET (RULE 2C) composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.

Lipolytic enzyme 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., Thermomvces 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 components 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.

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 alkanolammomum 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 C18-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.

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 a Ci6- C 8 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 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.

Clay softening system

The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

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

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 Polyamine N-oxide polymers

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

(I) Λx

R

wherein P is a polymerisable unit, and

O O O

II II II

A is NC, CO, C, -0-, -S-, -N-; x is 0 or1;

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

0

wherein Rl, 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-0 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.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic 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.

The polyamine N-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.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N- vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polwinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. 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.

d) Polwinyloxazolidone

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.

e 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.

Optical brightener

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

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

wherein Ri is selected from anilino, N-2-bis-hydroxy ethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methy lamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R is anilino, R2 is N-2-bis-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-y l)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-anilino-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. 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 Oil 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.

pH of the compositions

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

Form of the compositions

The solid compositions in accordance with the invention can take a variety of physical forms including granular and tablet 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.

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 500 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.

Tablet forms are generally made by compressing granular compositions into tablet shape using any of the tabletting process commonly known in the art. By appropriate selection of the compositional form and of the pressure employed in the tablet pressing operation the hardness of the tablet may be varied. The size of the tablets is selected to enable ease of dosing to the wash solution. Typically, a tablet will comprise from 5 to lOOg, preferably from 10 to 50g of detergent product.

SUBSTITUTE SHEET (RULE 25) The tablet may be of essentially any shape including cubes and spheres. In a preferred aspect the tablet is formed such as to have at least two distinct and separate layers, wherein an outer layer contains cationic ester surfactant and an inner layer the alkalinity system.

Surfactant agglomerate particles

The surfactant system herein is preferably present in granular compositions 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.

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 European Application No. 94921505.7. Abbreviations used in Examples

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

LAS Sodium linear C12 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate C45AS Sodium C14-C15 linear alkyl sulfate CxyEzS Sodium Cι_x-Ciy branched alkyl sulfate condensed with z moles of ethylene oxide

C45E7 A Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide

C25E5 A C 12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide

CEQ RlCOOCH2CH2.N+(CH3)3 with Ri = Cπ-

Cl3

QAS R2.N + (CH3)2(C₂H₄OH) with R₂ = C12 - C14

Soap Sodium linear alkyl carboxylate derived from an

80/20 mixture of tallow and coconut oils.

TFAA C16-C18 alkyl N-methyl glucamide

TPKFA C12-C14 topped whole cut fatty acids

STPP Anhydrous sodium tripolyphosphate

Zeolite A Hydrated Sodium Aluminosilicate of formula

Nai2(A102Siθ2)l2- 27H20 having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5

Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm

SUBSTITUTE SHEET (RULE 2δ) Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

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

Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850 μm

MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.

CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/g sold by

NOVO Industries A/S under the tradename

Savinase

Alcalase Proteolytic enzyme of activity 3AU/g sold by

NOVO Industries A/S Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename

Carezyme

Amylase Amylolytic enzyme of activity 60KNU/g sold by

NOVO Industries A/S under the tradename

Termamyl 60T

Lipase Lipolytic enzyme of activity lOOkLU/g sold by

NOVO Industries A/S under the tradename

Lipolase

Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2

PB1 Anhydrous sodium perborate monohydrate bleach of nominal formula NaBθ2-H2θ2

Percarbonate Sodium Percarbonate of nominal formula

2Na2Cθ3.3H2θ2 NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED Tetraacetylethylenediamine

SUBSTITUTE SHEET (RULE 23) DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the

Trade name Dequest 2060

Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2 : 2 ' -disulfonate .

HEDP 1,1-hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole

SRP1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

In the following Examples all levels are quoted as % by weight of the composition:

Example 1

The following laundry detergent compositions A to F were prepared in accord with the invention:

Se l

Set2

Ss .

Set 4

The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing were prepared:

SUBSTITUTE SHEET (RULE 2G) Set 5

The following detergent formulations were prepared:

Set 6

The following detergent formulations were prepared:

Set 7

The following high density and bleach-containing detergent formulations, were prepared:

&LS

The following high density detergent formulationswere prepared:

Washing method

Each of the compositions A to AA of Sets 1 to 8 was employed in a laundry washing method L which a Miele 820 automatic washing machine was employed, and the 40°C short cycle programme selected. At the start of the laundry wash method, lOOg of detergent was placed in a granulette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) detergent products, as made by the Procter and Gamble Company, for sale across Europe. The charged granulette was then placed on top of the wash load in the drum of the washing machine. The wash load comprised 2.4Kg of 60/40 mixture of lightly soiled cotton, polycotton and polyester fabrics. Good washing performance was obtained.

Comparative performance testing

The greasy stain removal performance of Composition I when used in a washing method involving granulette dispensing into a washing machine was compared to that obtained when the detergent was dispensed through a dispensing drawer using the following test method:

Three white cotton sheets were prewashed three times in a non-biological bleach-free heavy duty detergent at 60°. Margarine stains were then ςvenly applied using a paint brush to one sheet, lard stains to the second sheet and beef dripping stains to the third one. Sets of 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 with the detergent dispensed either from a granulette or from the dispensing drawer of the washing machine. The swatches were then assessed for removal of the various fatty stains by a four person grading panel using the well-known four-point Scheffe scale.

In more detail, a Miele 820 automatic washing machine was employed, and the 40°C short cycle programme selected. Water of 10° Clark hardness ( = 1.5 mmol Ca^{2 +} /litre) was used. lOOg of detergent was employed. One swatch of each fabric type was washed along with a ballast load comprising 2.4Kg of 60/40 mixture of lightly soiled synthetic and cotton fabrics. The ballast load was positioned prior to commencement of the wash cycle to ensure an even distribution around the test swatches.

In the case of the granulette dispensing, the detergent was placed in a granulette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) detergent products, as made by the Procter and Gamble Company, for sale across Europe. The charged granulette was then placed on top of the ballast wash load and adjacent to the stained swatches in the drum of the washing machine and the wash cycle started.

In the case of the drawer dispensing, the lOOg of detergent was placed in the drawer of the washing machine and the wash cycle started.

The following results were obtained:

* = statistically significant at 95 % confidence level Example 2

The following liquid detergent formulations of pH < 9 were prepared:

SUBSTITUTE SHEET (RULE 26}

Each of the detergent products AB to Al was used separately in a pretreatment washing method involving the following steps:

A load of 2 Kg of soiled polycotton and cotton fabrics was taken. In the pretreatment step, approximately 5ml aliquots of detergent product were applied directly to fatty soiled areas, until the area was at least wetted with the detergent. The detergent was allowed to remain in contact with the soiled area for 5 minutes. In the wash step, the load was then placed in a Miele 820 automatic washing and the 40°C short cycle programme selected. 100ml of the same detergent product was employed in the wash cycle. The detergent was dispensed from a solid plastic dosing ball. Good washing performance was obtained for each of products AB to A

Claims

WHAT IS CLAIMED IS:

1. A method of washing soiled laundry in a domestic or industrial washing machine wherein a delivery means is provided for dispensing an effective amount of a detergent composition directly to the drum of a washing machine before the commencement of the wash and subsequently enabling release of said detergent composition to the wash liquor during the wash

wherein said detergent composition contains

(a) from 0.1 % to 90% by weight of the detergent composition of a cationic ester surfactant; and

(b) from 1.5% to 95% of the detergent composition of an alkalinity system comprising alkaline salts selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof characterized in that said delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.

2. A method according to Claim 1 wherein said delivery means is provided by a dispensing device having a dispensing aperture which is charged with the detergent composition and then placed into the drum of the washing machine prior to the commencement of the wash cycle.

3. A method according to Claim 1 in which said delivery means is provided by forming said detergent composition as a tablet formed such as to provide release of cationic ester surfactant to the soiled laundry prior to the full release of said alkalinity system wherein the tablets are introduced into the drum of the washing machine prior to commencement of the wash cycle.

4. A method according to Claim 3 wherein said tablet comprises layers of distinct product composition with the cationic ester surfactant being located in a layer outwardly located relative to the layer comprising the alkalinity system.

5. A method according to any of Claims 1 to 4 wherein said cationic ester surfactant is selected from those having the formula:

wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkaryl chain or M-. N⁺(R₆R₇R₈)(CH₂)_s; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇, and R₈ are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R₅ is independently H or a C₁-C₃ alkyl group;

wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

6. A detergent composition according to Claim 5 wherein R₂,R₃ and R₄ are independently selected from the group consisting of CH₃ and -CH₂CH₂OH.

7. A detergent composition according to Claim 5 wherein the cationic ester is selected from the choline esters having the formula: wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.

8. A method of washing soiled laundry having a pretreat step comprising application of an effective amount of a detergent composition directly to the soiled laundry before subjecting the soiled laundry to a washing step wherein said detergent composition contains

(a) from 1 % to 90% by weight of the detergent composition of a cationic ester surfactant; and

(b) from 10% to 99.9% of the detergent composition of detergent components selected from additional surfactants, bleaches, builders, alkalinity sources, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors characterized in that said pretreat step enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.

9. A method according to Claim 8 wherein said detergent composition is a fluid composition formulated to a pH of less than 9.5.

10. A method according to either Claim 8 or 9 wherein the detergent composition contains no alkaline components.