The present invention relates a detergent dispensing cartridge for use with a washing machine.

The washing of clothes in automatic washing machines is well known and is practised extensively.

Ways are often sought to improve the washing action by modification of the detergent used, the nature of the washing cycle and the machine itself.

There is an ever increasing need to modify washing processes such that external resources (especially water and electricity) are used more effectively. Also the re is increasing environmental pressure on the reduction of excessive chemical use in cleaning. Further consumers are more demanding in terms of the time that they must spend in performing household chores.

According to a first aspect of the present invention there is provided a detergent dispensing cartridge for use in a washing machine.

By washing machine any vessel / machine (whether manually operated or fully / partially automated) which is capable of being used in a washing operation is intended. The washing machine is preferably an automatic clothes washing machine. Most preferably the washing machine is one which has been modified such that it operates using the technology of one or more of the co-pending patent applications WO2007/128962, GB 090261 9.6, GB 0907943.5, GB 0916249.6, GB 0916250.4, GB 0920565.9, GB 1002245.7, and GB 1006076.2 ; the disclosures of which are incorporated by reference.

According to a second aspect of the present invention there is provided a detergent dispensing cartridge for use in a washing machine, wherein the washing machine is for cleaning a soiled substrate, comprising the treatment of the moistened substrate with a formulation comprising a multiplicity of polymeric particles,.

According to a third aspect of the present invention there is provided a detergent dispensing cartridge for use in a washing machine, wherein the washing machine is for cleaning a soiled substrate, comprising the treatment of the moistened substrate with a formulation comprising a multiplicity of polymeric particles, wherein said formulation is free of organic solvents .

Preferably the ratio of beads to substrate is generally in the range of from 30: 1 to 0.1 : 1 w/w, preferably in the region of from 10: 1 to 1 : 1 w/w, with particularly favourable results being achieved with a ratio of between 5 : 1 and 1 : 1 w/w, and most particularly at around 2 : 1 w/w. Thus, for example, for the cleaning of 5 g of fabric, 10 g of polymeric particles would be employed

The polymeric particles are of such a shape and size as to allow for good flowability and intimate contact with the textile fibre. A variety of shapes of particles can be used, such as cylindrical, spherical or cuboid ; appropriate cross -sectional shapes can be employed including, for example, annular ring, dog-bone and circular. The particles may have smooth or irregular surface structures and can be of solid or hoi- low construction. Particles are preferably of such a size as to have an average mass in the region of 5 to 100 mg, preferably from 10 to 30 mg. In the case of the most preferred beads, the preferred average particle diameter is in the region of from 0.5 to 6.0 mm, more preferably from 1 .0 to 5.0 mm, most preferably from 2.5 to 4.5 mm, and the length of the beads is preferably in the range from 0.5 to 6.0 mm, more preferably from 1 .5 to 4.5 mm, and is most preferably in the region of 2.0 to 3.0 mm.

Said polymeric particles may comprise any of a wide range of different polymers. Specifically, there may be mentioned polyalkenes such as polyethylene and polypropylene, polyesters and polyurethanes, which may be foamed or unfoamed. Preferably, however, said polymeric particles comprise polyamide or polyester particles, most particularly particles of nylon, polyethylene terephthalate or polybutylene terephthalate, most preferably in the form of beads. Said polyamides and polyesters are found to be particularly effective for aqueous stain/soil removal, whilst polyalkenes are especially useful for the removal of oil-based stains. Optionally, copolymers of the above polymeric materials may be employed.

Various nylon or polyester homo- or co-polymers may be used including, but not limited to, Nylon 6, Nylon 6,6, polyethylene terephthalate and polybutylene terephthalate. Preferably, the nylon comprises Nylon 6,6 homopolymer having a molecular weight in the region of from 5000 to 30000 Daltons, preferably from 10000 to 20000 Daltons, most preferably from 15000 to 16000 Daltons. The polyester will typically have a molecular weight corresponding to an intrinsic viscosity meas- urement in the range of from 0.3-1 .5 dl/g, as measured by a solution technique such as ASTM D-4603.

Generally the polymeric particles comprise nylon chips, e.g. Nylon 6 or Nylon 6,6.

It has been found that with the use of a cartridge great benefits are provided to a consumer in terms of ease of use. The use of a cartridge allows discharge of a detersive composition into a washing machine (over multiple wash cycles) where the consumer has no need to measure the detersive composition or come into contact with same yet have the security of knowing that the correct detersive composition has been applied to the wash load of the machine.

Preferably the cartridge has multiple compartments. Generally each compartment may be activated separately such that the contents of each compartment may be released separately / sequentially. Each compartment may be designed such that it holds a bespoke complete detergent formulation or a formulation that focuses upon a single active component of a detergent formulation. It is preferred that each compartment may be activated separately; either in completely individual activation or in a "program" that activates one or more compartments at pre-defined portions of a wash cycle so that a portion of the compartment content may be released . In this way it has been found that the detergent release can be tailored to suit a particular wash load in terms of its size, compositions and type of staining present thereon. Clearly it is envisaged that a particular compartment may be activated once, not at all or a plurality of occasions in a wash cycle. Separate containment and release has been found to be useful for many reasons including storage stability of compartment components, particularly for antagonistic components. For example the antagonist interaction between bleach and enzyme may be obviated . A further example is the reduction / elimination of components that have opposite ionic charges. In this regard most dye fixatives / dye transfer inhibitors (e.g. such as PVP, PVP-VI , PVNO based compounds or deri- vates thereof) (hereafter DTIs) have a positive charge. The presence of this positive charge brings about a detrimental interaction between anionic surfactants which are typically employed in detergents (especially laundry detergents to provide cleaning function) . The dye fixatives / DTIs and the anionic surfactants "couple" together because of their opposing charges, compromising their respective functions. One way to avoid this problem is to replace the anionic surfactants with nonionic surfactants which avoids the coupling effect however typically nonionic surfactants provide a poorer cleaning function that anionic surfactants. By the placement of the dye fixatives / DTI in a compartment separate from any anionic surfactant the coupling problem may be obviated .

Additionally with the containment / release in separate compartments, the temperature / heating of the wash liquor may be tailored such that it is optimized to work with the contents of the compartment being released at that juncture. As an example when a bleach / bleach activator composition is released heating of the wash liquor (e.g. to around 40-60°C) may be appropriate to ensure that optimal functioning of the bleach / bleach activator composition occurs. I n contrast many of the other detergent components require no wash liquor heating to achieve their optimal function. I n this aspect it is to be understood that the entire wash liquor or a portion thereof may be heated. Where only a portion of the wash liquor is heated the portion may be a portion of the wash liquor which is passing through r adjacent to the cartridge or the portion passing through or adjacent to any wash liquor circulation system.

Moreover the containment / release in separate compartments allows the pH of the wash liquor may be tailored such that it is optimized to work with the contents of the compartment being released at that juncture. As an example when a bleach / bleach activator composition is released raising of the pH of the wash liquor (e.g. to an alkaline pH by release of a suitable pH modifying agent) may be appropriate to ensure that optimal functioning of the bleach / bleach activator composition occurs. In contrast many of the other detergent components require no pH adjustment to achieve their optimal function.

Plus with the containment / release in separate compartments, release of individual detergent actives may be tailored such that it is optimized to work with the system of WO2007/128962.

In this regard it has been found that one preferred release profile is in the following order: - a) Release of an enzyme containing formulation;

b) Release of an oxidising formulation ;

c) Release of a builder / fabric conditioner containing formulation. Another preferred release profile is in the following order:- a) Release of a dye fixative / DTI containing formulation

b) Release of an enzyme containing formulation;

c) Release of a oxidising formulation;

d) Release of a builder / fabric conditioner containing formulation.

Composition (a) and / or (b) and / or (c) may also contain a surfactant. The oxidising formulation may contain a bleach and / or a bleach activator / catalyst.

I n accordance with the method of WO2007/128962 the polymeric particles used may be present throughout the entire laundry washing cycle or only for a portion thereof. Where the polymeric particles are only present for a portion of the washing cycle it is preferred that the polymeric particles are removed form the washing area of the washing machine at a rinse cycle (preferably a final rinse cycle) of the washing machine operation.

The cartridge may comprise compartments for release of some detersive components in a pre-wash cycle (which may be before the beads are added to the machine) of the washing machine operation. This has been found to be beneficial with certain detergent components, the activity of which may be compromised by adsorption on the polymeric particles.

Additionally or alternatively the cartridge may comprise compartments for release of some detersive components in a rinse cycle (preferably a final rinse cycle) of the washing machine operation. This has been found to be beneficial with certain detergent components, the activity of which may be compromised by adsorption on the polymeric particles. Preferred examples of detersive components for release at this stage (and for which there is preferably a compartment in the cartridge) are optical brighteners and fragrances. The cartridge compartments may be modular, e.g. one or more compartments of the cartridge may be replaceable without replacing the entire ca rtridge. Equally it is preferred that a consumer may select which compartments are most suitable for their kind of typical washing so that a complete cartridge may be constructed using the compartments that they are most like to require in their washing.

Each compartment may have a volume of from 1 to 5000 cc, more preferably from 10 to 900 cc, more preferably from 20 to 600 cc, more preferably from 20 to 400 cc, more preferably from 20 to 300 cc, more preferably from 20 to 200 cc and most preferably from 20 to T OO cc.

The positioning of the cartridge in the washing machine is flexible. Clearly it is preferred that the cartridge is positioned such that the cartridge contents can be dispensed into the area of washing of the washing machine. A conduit may be present to connect the cartridge output to the washing area. Alternatively and / or additionally the cartridge may be positioned such that its output is adjacent to or connected to fresh incoming wash fluid (e.g. water) . The cartridge may be positioned / the washing machine may be designed such that fresh incoming wash fluid / wash liquor flows over / around the device . The cartridge compartment activation may be operated by one or more of a number of mechanisms . Different activation mechanisms may be used for different compartments of the cartridge.

Preferred operation mechanisms may be manual or non-manual mechanisms. Preferred non-manual operation mechanisms include physical and chemical activation triggers associated with changes within the washing cycle) . Preferred examples include time, temperature / temperature changes, smell/ odour, humidity / water presence (or some other associated property of the cleaning liquor, e.g. such as ionic strength or pH) , drum rotation / centrifugal force or other force. Other operation mechanisms may arise from a result of a conduit from the cartridge to the washing machine (particularly the washing machine operating schematics) such that the operation of the washing machine, triggered by the schematics of the washing machine, influences or causes operation of one or more of the compartments or the cartridge at one or more time points within the washing cycle. In this way different washing cycles may triggers different activation / operation of the cartridge / compartments thereof. Additionally different wash loads / conditions may trigger a differential degree of operation of one or more compartments.

The cartridge may also have a manual override which can be accessed by a consumer. This manual override may overcome any normal dispense activity of the cartridge and influence the dispensing such that the release of one or more compartments is increased / reduced and / or the timing of the release is affected. The entire contents of a compartment may be discharged in a single wash cycle, either in one part of a single wash cycle or at multiple parts thereof. More preferably the contents of a compartment may be released over a plurality of wash cycles, e.g. over 10-30 wash cycles (such as about 20 wash cycles) for added convenience to a consumer. In this case the cartridge contents may still be released at multiple points over a plurality of cycles. Preferably the cartridge and / or one or each compartment thereof may have an "end-of-life" indicator to make sure that a consumer is aware that the contents of one or more compartment has been exhausted and needs to be replenished . The end-of-life" indicator may be triggered by or arise through liaison with the schematics of the washing machine

Equally in one embodiment of the device the cartridge is intended for a single washing cycle.

Compartment release operation may be by one or more of a number of mechanisms. Preferred compartment release mechanisms include manual release (e.g. opening, squeezing), gravitational release, active release (e.g. by a motor / pump, such as a powered motor, wax motor, piezo, injection or spray) and passive release driven by a flow or wash liquor / polymeric particles through or adjacent to a compartment drawing the contents of the compartment (or a portion thereof) there from. The release may be combination of active and passive mechanisms , e.g. an access means to a compartment may be opened under a certain condition to allow release of an active from a compartment. A preferred example of such an activating mechanism is a bimetallic driven opening means such that the opening means is acti- vated at a certain predetermined temperature to allow release (by whatever mecha nism) to occur.

For detersive components (and associated compartments) which make up a smaller portion of the entire detersive formulation (e.g. fragrances, optical brighteners) more active dispensing methods, e.g. spraying may be preferred. For detersive components (and associated compartments) which make up a larger portion of the entire detersive formulation (e.g. surfactants, builders) more passive dispensing methods may be preferred.

The compartment contents may be in any suitable physical form. Preferred forms include liquids (dispersions, suspensions, pastes, solutions and emulsions, gels) and solids Solidified gels, powders, tablets) . In a cartridge the content of differing compartments may be in differing physical forms.

The compartment contents may be contained in a secondary packaging, e.g. such as an encapsulation means, pouch or sachet .

The compartment contents may be refillable. The refill contents may be in the form of granules, powders, or liquids / gel dependent on the chemical / physical nature of the nature of the composition for the / each compartment . The refill composition may be in the form of a "unit-dose" composition, e.g. a compressed / solidified / moulded tablet or the refill may be package in a film pouch where in the film may be entirely water soluble / dispersible or have a water soluble potion or pierce-able section to allow release of the pouch contents. The film pouch may comprise a metallic foil or a plastics material, e.g. polypro- pylene, polyethylene, polyvinylalcoho!, ABS, PET, polyamides, PMMA or PC. Clearly the unit dose composition will be sized to fit the respective compartment and allow ease of refilling without exposing a consumer to any harmful chemicals. A plurality of unit-dose entities may fit in one compartment; such an arrangement may have a separate support frame associated therewith.

As well as conventional detersive actives (see later) the cartridge may contain one or more actives directed to increasing the activity of the polymeric particles. I n this regard one preferred active is a plasticiser for the polymeric particles. It is postulated that with the use of such a plasticiser the Tg of the polymeric particles would be lowered such that the polymeric particles would be more active at lower temperatures. The formulation may include sacrificial agents that are absorbed onto sites on the polymeric particles, wherein these sites would otherwise cause detrimental adsorption of one or more detersive active.

The cartridge may include a compartment which contains (supplementary) polymeric particles. These particles may be purely polymer or may have been physical or chemically altered to affect their activity. Preferred means of chemical alteration include polymeric particles into which a cfetersive active has been reversibly / irreversibly adsorbed (e.g. enzyme, bleach catalyst) or upon which a detersive active has been coated.

With the use of the cartridge of the invention it has been found that the overall detersive formulation may be altered because of the presence of the polymeric particles. One example of an alteration is that the overall amount of detergent required per wash cycle is considera- bly lower. Indeed in this regard it has been found that the amount of detergent required may be as low as 50%, 40%, 30%, 20% or even 10% of the amount that would ordinarily be expected for a clothes washing operation in an automatic laundry washing machine . As an example it has been found that with the use of the cartridge of the invention an equivalent washing standard can be achieved for a 5kg load of laundry in an automatic laundry washing machine using as little as 1 5g of a liquid detergent formulation (whereas in a conventional washing process in an automatic laundry washing machine 150g of the same liquid formulation would be required) .

Where a smaller amount of detergent is used it has been found that the amount(s) of certain components typically found in a household laundry detergent may be reduced . I n particular it has been found that the amount of builder required may be lower. Another alteration is that it has been found that the detersive surfactant may be altered (in terms of amount and / or nature thereof) because the polymeric particles may form a modified detersive micelle with a polymeric particle at the centre of the micelle. A further alteration is that (due to the lower amount of wash liquor the amount of certain actives, e.g. such as fragrance, optical brightener, which would be wasted by extraction with excessive rinse water, may be dramatically reduced .

Since a smaller amount of detergent (than for conventional laundry washing) is required it has been found that the overall size of the cartridge and the individual compartments thereof may be small with enhanced convenience for a consumer. With the use of the cartridge of the invention it has been found that overall washing cycle may be altered. One example of an alteration is that higher temperatures may be used (on at least a portion of the wash liquor) , typically for brief periods, (with no detriment to the amount of energy used since the amount of wash liquor in the machine is lower) . This has been found to be beneficial in that the action of certain detersive components, e.g. bleaches, can be increased, often at a lower concentration of the active and possibly without any co- active (for bleach a co-active would be a bleach catalyst / bleach activator) .

It is understood that generally the washing cycle temperature is from 0°C to 90°C, more preferably between 5°C and 90°C, more preferably between 5°C and 70°C, more preferably between 1 5°C and 40°C _r e.g . about 30°C.

The washing cycle time is preferably between 1 5 and 150 minutes, more preferably between 15 and 120 minutes, and most preferably between 20 and 40 minutes. The rinsing proportion of the cycle is preferably up to 50% of the entire cycle time, more preferably up to 40%, more preferably up to 20%, more preferably up to 10%. The final spin may be around 5% of the entire cycle time. I ntermediate spins (e.g. between parts of the cycle) may be (individually or collectively) around 1 -2% of the entire cycle time.

The amount of washing water used in a wash cycle is preferably around 6 litres per kilo of wash load ; with around 3 liters for the washing stage(s) and 3 litres for the rinsing stage(s) . The amount of water can be lower, e.g. preferably between 2.5 : 1 and 0.1 : 1 litres per kilo of wash load; more preferably, the ratio is between 2.0: 1 and 0.8: 1 litres per kilo of wash load, with particularly favourable results having been achieved at ratios such as 1 .5 : 1 , 1 .2 : 1 and 1 .1 : 1 litres per kilo of wash load.

This compares to around 13 litres per kilo of wash load for a conventional washing machine; with around 4 liters for the washing stage(s) and 9 litres for the rinsing stage(s) .

The cartridge may be designed to be placed at a suitable locus in or on the washing machine, e.g. in the drum / drawer.

The cartridge may operate with a suitable cartridge receiving means within or associated with the washing machine . The cartridge receiving means may be entirely mechanical. Alternatively the cartridge receiving means may include an electronic component with associates with a portion of the cartridge (and optionally drives operation of a portion of the cartridge) . The cartridge receiving means may include a mechanism that identifies the presence of a cartridge (and / or individual compartments thereof), e.g. such as a radio -frequency identification (RFID) mechanism, e.g. such as a bar code on the cartridge.

The cartridge preferably comprises a plastics material, e.g. polypropylene, polyethylene , ABS, PET, polyamides, PMMA or PC. The ca rtridge / compartment material may be coated, e.g. with a barrier layer. Such a layer may be used to allow more aggressive chemical inclusion (e.g. to aid the prevention of polymer stress cracking) . In one embodiment of the invention it is preferred that a plurality of separate cartridges may be used simultaneously in a washing machine / washing machine cycle. Each cartridge may be disposed in a different part of the washing machine or the same part of the washing machine. Each cartridge may contain the same or a complementary detergent composition or compositions (e.g. in a number of compartments) .

A bead cleaning process may be carried out typically every 5-6 washes, allows the surface of the beads to remain highly active in the washing process. Preferably, bead cleaning is carried out by adding individual doses of surfactants (non-ionic and/or anionic and/or cati- onic) , and optionally other more aggressive chemicals, selected from, for example, sodium/potassium hydroxide, hypochlorates, hypochlorites or the other bleaches and activators previously recited, to an amount of water, such that the ratio of water to beads is preferably in the region of 0.5-3 litres water/kg of beads. The bead cleaning process may be facilitated by release of a suitable cleaning composition from the cartridge.

Preferred examples of surface active agents include anionic, non-ionic, cationic, amphoteric cr zwitterionic surface active agent or mixture thereof.

Examples of anionic surfactants are straight -chained or branched alkyl sulfates and alkyl polyaikoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be produced by the sulfation of higher C8-C20 fatty alcohols. Examples of primary alkyi sulfate surfactants are those of formula :

ROS0 ₃ ^" M ^÷ wherein R is a linear C8-C20 hydrocarbyl group and M is a water- solubilising cation.

Preferably R is C10-C16 alkyi, for example C ₁₂ -C14, and M is alkali metal such as lithium, sodium or potassium.

Examples of secondary alkyi sulfate surfactants are those which have the sulfate moiety on a "backbone" of the molecule, for example those of formula:

CH ₂ (CH2)n(CHOS0 ₃ ^" M ⁺ ) (CH2) _m CH3 wherein m and n are independently 2 or more, the sum of m + n typically being 6 to 20, for example 9 to 15, and M is a water-solubilising cation such as lithium, sodium or potassium.

Especially preferred secondary alkyi sulfates are the (2,3) alkyi sulfate surfactants of formulae :

CH2(CH ₂ )x(CHOS0 ₃ -M ⁺ )CH3 and

CH3(CH ₂ )x (CHOS0 ₃ ^" M ⁺ )CH2CH3 for the 2-sulfate and 3-sulfate, respectively, I n these formulae x is at least 4, for example 6 to 20, preferably 1 0 to 1 6. M is cation, such as an alkali metal, for example lithium, sodium or potassium .

Examples of alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula:

RO(C ₂ H ₄ 0)nS0 ₃ ^" M ⁺ wherein R is a C8-C20 alkyl group, preferably C10-C18 such as a C12-C-16, n is at least 1 , for example from 1 to 20, preferably 1 to 15, especially 1 to 6, and M is a salt -forming cation such as lithium, sodium, potassium, ammonium, alkylammonium or a!kanolammonium . These compounds can provide especially desirable fabric cleaning performance benefits when used in combination with alkyl sulfates.

The alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising varying alkyl chain lengths and, if present, varying degrees of alkoxylation.

Other anionic surfactants which may be employed are salts of fatty acids, for example Ca-Cis fatty acids, especially the sodium potassium or alkanolammonium salts, and alkyl, for example (¼-Οΐ8, benzene sulfonates.

Examples of nonionic surfactants are fatty acid alkoxylates. 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/ propoxylated condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts. Preferred fatty acid ethoxylates, are especially those of formula :

R(C ₂ H ₄ 0) _n OH wherein R is a straight or branched Ce-C-te alkyl group, preferably a Cg- Ci 5, for example C10-C14 , or Gj 2-Ci ₄ alkyl group and n is at least 1 , for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.

The alkoxylated fatty alcohol nonionic surfactant will frequently have a hydrophific-fipophilic balance (HLB) which ranges from 3 to 1 7, more preferably from 6 to 15, most preferably from 10 to 1 5.

Examples of fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially marketed under the trademarks Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful IMeodols include Neodol 1 -5, an ethoxylated fatty alcohol averaging 1 1 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12-C13 alcohol having about 9 moles of ethylene oxide; and Neodol 91 -10, an ethoxylated C9-C11 primary alcohol having about 10 moles of ethylene oxide.

Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol trademark. Dobanol 91 -5 is an ethoxylated (¼-C-n fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohol nonionic surfactants include Tergitol 1 5-S-7 and Tergitol 1 5=S-9, both of which are linear secondary alcohol ethoxylates available from Union Carbide Corporation , Tergitol 15-S-7 is a mixed ethoxylated product of a C-M -C15 linear secondary alkanol with 7 moles of ethylene oxide and Tergitol 15-S-9 is the same but with 9 moles of ethylene oxide.

Other suitable alcohol ethoxylated nonionic surfactants are Neodol 45- 1 1 , which is a similar ethylene oxide condensation products of a fatty alcohol having 14-1 5 carbon atoms and the number of ethylene oxide groups per mole being about 1 1 . Such products are also available from Shell Chemical Company.

Further nonionic surfactants are, for example, Cio-Cis alkyl polyglyco- sides, such s C12-C16 alkyl polyglycosides, especially the polygluco- sides. These are especially useful when high foaming is desired. Further surfactants are polyhydroxy fatty acid amides, such as C10-C18 N- (3-methoxypropyl) glycamides and ethylene oxide-propylene oxide block polymers of the Pluronic type.

Examples of cationic surfactants are those of the quaternary ammonium type.

Preferred quaternary ammonium compounds have the formula (1) or (l a), or include a mixture thereof; [R'-(CO)-0-R-N ⁺ (-R")(-(RO) _n H) (-R-0-(CO)-R')]X ^~ (I )

[R'-(CO)-NH-R-N ⁺ (-R ¹ )(-(RO) _n H)(-R-NH-(CO)-R')]X ^" (la) wherein :

R is an alkylene or alkenylene group having 2 to 4 carbon atoms;

R' is an alkyi or alkenyl group having 8 to 22 carbon atoms;

n is an integer having a value of 1 to 4;

R" is an alkyi group having 1 to 4 carbon atoms; R ¹ is an alkyi group having 1 to 4 carbon atoms or hydrogen; and

X ^" is a softener-compatible anion . l\lon -limiting examples of softener-compatible anions (X ^" ) include chloride, formate, ritrate, sulfate or Ci _-4 alkyi sulfate, preferably methyl sulfate.

The alkyi or alkenyl R' ideally must contain at least 10 carbon atoms, preferably at least 1 4 carbon atoms, more preferably at least 1 6 carbon atoms. The group may be straight or branched.

A specific example of quaternary ammonium compound is di-(tallow carboxyethy hydroxyethylmethyl ammonium X ^" .

A cationic fabric co-softener may be present,

Examples of amphoteric surfactants are Cio-C-is amine oxides and the C12-C18 betaines and sulfobetaines.

Suitable builders are alkali metal or ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, bicarbonates, borates, pol hydroxysulfonates, polyacetates, carboxylates such as citrates and other polycarboxylates / polyacetyl carboxylates such as succinate, malonate, carboxymethyl succinate.

There are three main types of method of action for water-softening agents, described below.

1 ) Ion exchange agents - such agents include alkali metal (preferably sodium) aluminosiiicates either crystalline, amorphous or a mixture of the two. Such aluminosiiicates generally have a calcium ion exchange capacity of at least 50 mg CaO per gram of aluminosilicate, comply with a genera! formula :

0.8-1 .5 Na ₂ 0. Al ₂ 0 ₃ . 0.8-6 Si0 ₂ and incorporate some water. Preferred sodium aluminosiiicates within the above formula contain 1 .5-3.0 S1O2 units. Both amorphous and crystalline aluminosiiicates can be prepared by reaction between sodium silicate and sodium aluminate, as amply described in the literature.

Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429143 (Procter & Gamble) . The preferred sodium aluminosiiicates of this type are the well known commercially available zeolites A and X, and mixtures thereof. Also of interest is zeolite P described in EP 384070 (Unilever) . Another class of compounds are the layered sodium silicate builders, such as are disclosed in US-A-4464839 and US-A-4820439 and also referred to in EP-A-551375.

These materials are defined in US-A-4820439 as being crystalline layered, sodium silicate of the general formula

NaMSi _x 02x+i . YH ₂ 0 wherein

M denotes sodium or hydrogen,

x is from 1 .9 to 4 and y is from 0 to 20.

Quoted literature references describing the preparation of such materials include Glastechn. Ber. 37,194-200 (1964), Zeitschrift fur Kristal- logr. 1 29, 396-404 (1969), Bull . Soc. Franc. Min. Crist., 95, 371 -382 (1972) and Amer. Mineral, 62, 763-771 (1977). These materials also function to remove calcium and magnesium ions from water, also covered are salts of zinc which have also been shown to be effective water softening agents.

2) Ion capture agents - agents which prevent metal ions from forming insoluble salts or reacting with surfactants, such as polyphosphate, monomeric polycarboxylates, such as citric acid or salts thereof, poly- carboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, EDTA, algins, alginates. 3) Anti-nucleating agents - agents that prevent seed crystal growth, such as polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, and sulfonates. Such polymers may also act as ion capture agents as well.

Preferred organic water-soluble water softening agents which may be present include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric poly- carboxylates such as citrates, gluconates, oxydisuccinates, glycero l mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxy- methyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, phosphonates, iminodisuccinates, polyaspartic acids, BHT, phospho- nate stabilisers such as, diethylenetriaminepenta (methylene phos- phonic acid and its corresponding pentasodium salt) available under the trade names Dequest 2060 and Dequest 2066 Monsanto Chemical Co) , DTPMP and DTPMA (Dequest 2010) and HEDP.

Preferably the water-soluble water softening agent is a neutralised or partially neutralised carboxylic acid, such as citric acid, succinic acid or maleic acid, and/or a neutralised or partially neutralised polycarboxylic acid, such as a polyacrylate of Mw: 4000-8000 (such as Acusol 445N (Rohm & Haas) CAS REG Nr. 66019 -1 8-9 or Sokalan from BASF) .

Further examples of such suitable polymers include polymers based on an unsaturated sulphonic acid monomer. The unsaturated sulphonic acid monomer is preferably one of the following : 2-acrylamido methyl - 1 -propanesultonic acid, 2-methacrylamido-2-methyl-1 - propanesulphonic acid, 3-methacrylamido-2-hydroxypropanesulphonic acid, allysulphonic acid, methallysulphonic acid, allyloxybenzenesul- phonic acid, methallyloxybenzensulphonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulphonic acid, 2-methyI -2-propene-1 -sulphonic acid, styrene sulphonic acid, vinylsulphonic acid, 3-sulphopropyl acry- !ate, 3-sulphopropyl methacrylate, sulphomethylacrylamid, sul- phomethylmethacrylamide, and water soluble salts thereof.

The unsaturated sulphonic acid monomer is most preferably 2- acrylamido-2-propanesulphonic acid (AMPS) .

Suitable enzymes include peroxidises, proteases, lipases, amylases and cellulase enzymes. Such enzymes are commercially available and sold, for example, under the registered trade marks Esperase, Alca- lase, Savinase, Termamyl, Lipolase and Celluzyme by Nova IMordisk A/S. When present desirably the enzymes are present (as a proportion of the cartridge contents) in an amount of from 0.5 to 3 wt , especially 1 to 2 wt% .

A thickening agent or gelling agent may be used. Suitable thickeners are polyacrylate polymers such as those sold under the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and Hass Company. Other suitable thickeners are xanthan gums.

The thickener, if present, is generally present in an amount of from 0.2 to 4 wt%, especially 0.2 to 2 wt%.

One or more additional ingredients may optionally be comprised. These include conventional detergent components such as further surfactants, bleaches, bleach enhancing agents, builders , suds boosters or suds suppressors, anti-tarnish and anti -corrosion agents, organic solvents, co -solvents, phase stabilisers, emulsifying agents, preservatives, soil suspending agents, soil release agents, germicides, anti microbial / anti -bacterial agents, phosphates such as sodium tripoly- phosphate or potassium tripolyphosphate, pH adjusting agents or buffers, non-builder alkalinity sources, chelating agents, clays such as smectite clays, enzyme stabilizers, anti-limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners, and perfumes. If used, such optional ingredients will generally constitute no more than 10 wt%, for example from 1 to 6 wt%, the total weight of the cartridge contents.

Where an enzyme is present materials may optionally be present to maintain the stability of the enzyme. Such enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers generally constitute from 0.1 to 1 wt% the total weight of the cartridge contents.

Materials which serve as phase stabilizers and/or co-solvents may be used. Example are C1 -C3 alcohols or diols such as methanol, ethanol, propanol and 1, 2-propanediol. Q -C3 alkanolamines such as mono-, di- and triethanolamines and monoisopropanolamine can also be used, by themselves or in combination with the alcohols.

The detersive components, if in liquid form, may be anhydrous, or, for example, contain up to 5 wt% water. Desirably the aqueous substances contain more than 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt% water, but desirably less than 80 wt% water, more desirably less than 70 wt%, 60 wt%, 50 wt% or 40 wt% water. They may, for example, contai n from 30 to 65 wt% water.

Optionally components which adjust or maintain the pH levels may be used . Examples of pH adjusting agents are NaOH and citric acid. The pH of the cartridge contents / wash liquor may be from, for example, 1 to 1 3.

The invention is illustrated with referent to the following examples.

Examples

Example 1

Cleaning trials were carried out using a set of trial and control conditions (see Table 1 ) . Thus, the trials involved the use of a preferred cleaning apparatus as described in FCT application GB2011 /050243, run according to the method of the invention ("Xeros Plus" ulti Dose), whilst the control was carried out in the same apparatus but using a single detergent dose approach added at the start of the main wash ("Xeros Plus" Single Dose) . The wash load was an identical composition of mixed garments totalling 12 kg in both cases. The detergent components were: surfactant - ulan 200S supplied by Christeyns; hydrogen peroxide - the oxidising component - ACE B supplied by Procter & Gamble; tetraacetylethylenediamine (TAED) - the oxidising component activator - supplied by Warwick Chemicals; optical brightener - Leucophor BMB supplied by Clariant; and perfume - Amour Japonais supplied by Symrise ^® AG. Stains were added to the wash load to stress the detergent - 6 off WFK PCMS-55_05-05x05 Standard I ndustry /Commercial Laundry Stain Monitors, plus 12 off WFK SBL2004 simulated sebum grease stain sheets. The latter were used to generate sebum levels of ~8 g/kg of wash load, and thereby stress the detergent used.

Test # DeterDosage Wash- DeterWash Cycle gent Timing load gent TemTime

Dosage (kg) Dosage pera(mins)

(g) (g/kg) ture

(°C)

Xeros Surfactant At main 12 2.74 28 90

Plus 32.9 wash start

Multi (Time t =

Dose Hydrogen 0) 1 .75

Peroxide

Table 1. CLEA I G TRIALS

Both the Xeros Plus Multi Dose and Xeros Plus Single Dose cycles were run at equivalent wash temperatures of 28°C. In the Xeros Plus Multi Dose cycle however, advantage was taken of the ability with this approach to heat the oxidising component and its activator separately from the main wash in a mixing tank at 60°C, thereby allowing it to become more active chemically prior to addition. As stated above however, the wash temperature during this cycle only reached 28°C, since although a small quantity of 60°C water was added, the ambient temperature of the other wash components kept the overall temperature down. Note that the same amount of 60°C heated water was added at the same time during the wash cycle of the Xeros Plus Single Dose cycle, but without any oxidising component or activator (this having already been added at the start of the main wash as shown in Table 1 ) . The purpose of this additional heated water in the Xeros Plus Single Dose cycle therefore, was to ensure an identical temperature profile throughout to the Xeros Plus Multi Dos e case, up to the same final wash temperature of 28°C. Hence, the only difference between these two cycles was the means of detergent addition (i.e. multidosing of components throughout the cycle, versus single dosing of all components at the start of the main wash) . The overall cycle times of both cycles including main wash, bead separation and rinse were identical at 90 mins. A three rinse programme was used for both, with the optical brightener and perfume added in the final rinse for the Xeros Plus Multi Dose cycle as shown in Table 1 .

The level of cleaning was assessed using colour measurement. Reflectance values of the WFK stain monitors were measured using a Data- color Spectraflash SF600 spectrophotmeter interfaced to a personal computer, employing a 10° standard observer, under illuminant ¾, with the UV component included and specular component excluded ; a 3 cm viewing aperture was used. The CI E L* colour co-ordinate was taken for each stain on the stain monitors, and these values were then averaged for each stain type. Note that higher L* values show better cleaning . The results are shown in Table 2.

TABLE 2. CLEAN I NG RESULTS

As can be seen from Table 2, the Xeros Plus Multi Dose cycle gives overwhelmingly superior cleaning to the Xeros Plus Single Dose cycle. Of the 13 stain types tested, 10 show superior cleaning with Xeros Plus Multi Dose, 1 shows parity cleaning for both cycles, and only 2 show superior cleaning with Xeros Plus Single Dose.

Analysis was then carried out on the stain monitor backing material for background whiteness, and also on the sebum grease removal for stains 10D and 20D (see Table 1 ) to check the wavelength dependency of these across the visible spectrum (400 - 700 nm) . Grease removal at low wash temperature is a key advantage of cleaning with polymeric beads, and in particular when combined with this mulitcomponent dosing approach to detergency. With the same spectrophotometer arrangement described above, reflectance was measured as a function of visible wavelength to determine the colour strength values (K/S) which are shown in Figures 1 - 3. Note that lower K/S values show better background whiteness and cleaning, at any given wavelength. As can be seen in Figure 1 , the background whiteness of the backing material of the stain monitors was improved with the Xeros Plus Multi Dose cycle. This is an effect of the late addition of the optical bright - ener in the final rinse (see Table 1 ) . Critically here, the K/S va lues for the 420 - 480 nm range are improved, thereby giving the material a bluer hue (this being the blue end of the visible spectrum), and users typically see this as a considerable performance enhancement. It obviously also indicates that there is scope to reduce the level of optical brightener by using a multicomponent dosing approach to detergency, versus a single dose. A visual assessment test was also carried out, with 6 volunteers assessing this effect. All coding was covered on the test stain monitors to prevent bias, and all 6 volunteers ^" indicated a superior background whiteness for the backing material of the stain monitors when washed using the Xeros Plus Multi Dose cycle.

The cleaning performance on sebum/pigment (see Figures 2 & 3), with the Xeros Plus Multi Dose cycle was again shown to be superior on both the cotton (stain 10D) and polyester/cotton substrates (stain 20D) . There is particular interest in this stain as its low temperature removal is a key driver for laundry applications, it being extremely important but very ^" difficult to remove at low wash temperatures (as used here). Such performance improvements therefore, again clearly show the benefits of multicomponent dosing for the detergency.

Finally, a sensory test was carried out with the same 6 volunteers as above to assess the freshness/perfume of the stain monitors used for both cycles. All coding was again covered on the test stain monitors to prevent bias, and 4 volunteers thought the Xeros Plus Multi Dose cycle had produced a fresher smell on these monitors; 1 was unable to dis- tinguish any difference; and 1 thought the Xeros Plus Single Dose cycle had produced a fresher smell. Here too therefore, the evidence was strongly in favour of the multicomponent dosi g approach for de- tergency.

Example 2

The same washing conditions as Example 1 were used to test performance of different beads with respect to different dyes. The results were assessed using a spectrometer (as above) .

Example 3

The same washing conditions as Example 1 were used to test performance of different beads with respect to different dyes. A visual assessment test was also carried out, with 6 volunteers assessing this effect Dye Class Dye Nr. Type of Dye Fabric

Sulphur Dyes 1 Sulphur Black Cotton

Vat Dyes 3 Vat Green Cotton

5 Vat Blue Cotton

Direct Dyes 8 Direct Yellow Cotton

Reactive Dyes 16 Reactive Red A1 Cotton

20 Reactive Black, pale shade Cotton

21 Reactive Black, heavy shade Cotton

22 Reactive Orange Cotton

24 Reactive Blue B2 Cotton

26 Reactive Violet Cotton

27 Procion H-EXL Trichromatic Mixture 1 Cotton

29 Remazol Trichromatic Mixture 3 Cotton

Disperse Dyes 33 Disperse Navy Mi xture Polyester

Acid Dyes 39 Acid Red E Polyamide