Field of the Invention

[0001] The present invention relates to the aqueous cleaning of soiled substrates, spe- cifically textile fibres and fabrics, using a cleaning system comprising polymeric particles. More specifically, the invention is concerned with a system wherein the polymeric particles include antimicrobial agents which prevent mould and bacterial growth on the particles which may occur after repeated uses in washing procedures.

Background to the Invention

[0002] Aqueous cleaning processes are a mainstay of both domestic and industrial textile fabric washing. On the assumption that the desired level of cleaning is achieved, the efficacy of such processes is usually characterised by their levels of consumption of energy, water and detergent. In general, the lower the requirements with regard to these three components, the more efficient the washing process is deemed. The downstream effect of reduced water and detergent consumption is also significant, as this minimises the need for disposal of aqueous effluent, which is both extremely costly and detrimental to the environment.

[0003] Such washing processes, whether in domestic washing machines or their indus- trial equivalents (usually referred to as washer extractors), involve aqueous submersion of fabrics followed by soil removal, aqueous soil suspension, and water rinsing. In general, the higher the level of energy (or temperature), water and detergent which is used, the better the cleaning. The key issue, however, concerns water consumption, as this sets the energy requirements (in order to heat the wash water), and the detergent dosage (to achieve the desired detergent concentration). In addition, the water usage level defines the mechanical action of the process on the fabric, which is another important performance parameter; this is the agitation of the cloth surface during washing, which plays a key role in releasing embedded soil. In aqueous processes, such mechanical action is provided by the water usage level, in combination with the drum design, for any particular washing ma- chine. In general terms, it is found that the higher the water level in the drum, the better the mechanical action. Hence, there is a dichotomy created by the desire to improve overall process efficiency (i.e. the reduction of energy, water and detergent consumption), and the need for efficient mechanical action in the wash. For domestic washing in particular there are defined wash performance standards specifically designed to discourage the use of such higher levels in practice, in addition to the obvious cost penalties which are associated with such usage.

[0004] Current efficient domestic washing machines have made significant strides towards minimising their consumptions of energy, water and detergent. EU Directive 92/75/CEE sets a standard which defines washing machine energy consumption in kWh/cycle (cotton setting at 60°C), such that an efficient domestic washing machine will typically consume <0.19 kWh/kg of washload in order to obtain an 'A' rating. If water consumption is also considered, then 'A' rated machines use <9.7 litres/kg of washload.

[0005] Detergent dosage is then driven by manufacturer recommendations but, again, in the domestic market, for a concentrated liquid formulation, a quantity of 35 ml (or 37 g) for a 4-6 kg washload in soft and medium hardness water, increasing to 52 ml (or 55 g) for a 6-8 kg washload (or in hard water or for very dirty items) is typical (see, for example, Unilever pack dosage instructions for Persil ^® Small & Mighty). Hence, for a 4-6 kg wash- load in soft/medium water hardness, this equates to a detergent dosage of 7.4-9.2 g/kg whilst, for a 6-8 kg washload (or in hard water or for very dirty items), the range is 6.9-9.2 g/kg.

[0006] Energy, water and detergent consumptions in the industrial washing process (washer-extractors) are considerably different, however, and usages of all three resources are less constrained, since these are the principal factors in reducing cycle time - which is, of course, more of a consideration than in the case of domestic use. For a typical industrial washer extractor (25 kg washload rated and above), energy consumption is 0.30-1.0 kWh/kg, water is at 20-30 litres/kg, and detergent is much more heavily dosed than for domestic washing. The exact level of detergent used will depend on the amount of soiling, but a range of 20-100 g/kg is representative.

[0007] Thus, it can be taken from the above discussion that it is the performance levels in the domestic sector which set the highest standard for an efficient fabric washing process, and that these are: an energy consumption of <0.19 kWh/kg, a water usage of <9.7 litres/kg, and a detergent dosage of approximately 8.0 g/kg. However, as previously observed, it is becoming increasingly difficult to reduce the water (and, hence, energy and detergent) levels in a purely aqueous process, due to the minimum requirement to wet the fabric thoroughly, the need to provide sufficient excess water to suspend the soil removed in an aqueous liquor and, finally, the necessity to rinse the fabric.

[0008] Heating of the wash water is then the principal use of energy, and a minimum level of detergent becomes necessary in order for an effective concentration to be reached at the operating wash temperature. Means to improve mechanical action without increasing the water level used would, therefore, make any aqueous wash process significantly more efficient (i.e. yield further reductions in energy, water and detergent consumption). It should be noted that mechanical action itself has a direct effect on the detergent level, since the greater the level of soil removal which is achieved through physical force, the less that is required of the detergent chemistry. However, increasing the mechanical ac- tion in a purely aqueous washing process has certain associated drawbacks. Fabric creasing readily occurs in such processes, and this acts to concentrate the stresses from mechanical action at each crease, resulting in localised fabric damage. Prevention of such fabric damage (i.e. fabric care) is of primary concern to the domestic consumer and the industrial user.

[0009] In the light of these challenges which are associated with aqueous washing processes, the present inventors have previously devised a new approach to the problem, which allows the deficiencies demonstrated by the methods of the prior art to be overcome. The method which is provided eliminates the requirement for the use of large volumes of water, but is still capable of providing an efficient means of cleaning and stain re- moval, whilst also yielding economic and environmental benefits.

[0010] Thus, in WO-A-2007/128962, there is disclosed a method and formulation for cleaning a soiled substrate, the method comprising the treatment of the moistened substrate with a formulation comprising a multiplicity of polymeric particles, wherein the formulation is free of organic solvents. Preferably, the substrate is wetted so as to achieve a substrate to water ratio of between 1 :0.1 to 1 :5 w/w, and optionally, the formulation additionally comprises at least one cleaning material, which typically comprises a surfactant, which most preferably has detergent properties. In preferred embodiments, the substrate comprises a textile fibre and the polymeric particles comprise, for example, particles of polyamides, polyesters, polyalkenes, polyurethanes or their copolymers but, most prefera- bly, are in the form of nylon beads.

[0011] The use of this polymeric cleaning method, however, presents a requirement for the cleaning particles to be efficiently separated from the cleaned substrate at the conclusion of the cleaning operation, and this issue is addressed in WO-A-2010/094959, which provides a novel design of cleaning apparatus requiring the use of two internal drums ca- pable of independent rotation, and which finds application in both industrial and domestic cleaning processes.

[0012] In co-pending WO-A-201 1/064581 , there is provided a further apparatus which facilitates efficient separation of polymeric cleaning particles from the cleaned substrate at the conclusion of the cleaning operation, and which comprises a perforated drum and a removable outer drum skin which is adapted to prevent the ingress or egress of fluids and solid particulate matter from the interior of the drum, the cleaning method requiring at- tachment of the outer skin to the drum during a wash cycle, after which the skin is removed prior to operating a separation cycle to remove the cleaning particles, following which the cleaned substrate is removed from the drum.

[0013] In a further development of the apparatus of WO-A-201 1/064581 , there is dis- closed in co-pending WO-A-2011/098815 a process and apparatus which provides for continuous circulation of the polymeric cleaning particles during the cleaning process, and thereby dispenses with the requirement for the provision of an outer skin.

[0014] Further benefits in terms of reduced power and consumable requirements for the cleaning method originally proposed in WO-A-2007/128962 have been disclosed in co- pending GB Patent Application No. 1018318.4, where the technology has been refined to achieve at least equivalent cleaning performance whilst employing significantly reduced levels of detergents and much lower process temperatures.

[0015] The apparatus and methods disclosed in the foregoing prior art documents have been highly successful in providing an efficient means of polymeric cleaning and stain re- moval which also yields significant economic and environmental benefits. The move to much lower wash temperatures has been particularly beneficial in this regard. As a consequence of the achievement of such lower temperatures, however, the need to control hygiene in the washing machine has become significantly more important. Hotter wash temperatures (>60°C) can provide some level of hygiene control via thermal disinfection, since heat is an efficient destroyer of mould and bacteria, and higher temperatures are increasingly beneficial. When these polymeric cleaning processes are run at lower temperatures (<40°C), however, hygiene considerations are magnified compared to the equivalent aqueous process, due to the presence of the polymeric particles. Said particles provide a large additional surface area contained within the washing machine, on which mould and bacteria can grow. The growth here can be accelerated by the fact that the particles remain moist for a considerable time after each wash process has been run, and the overall levels of mould and bacteria reached can be further increased if the machine remains unused for extended periods of time.

[0016] The hygiene problem in the polymeric cleaning machine can, of course, be con- trolled by similar means to that used in conventional aqueous domestic or industrial washing, namely the use of higher wash temperatures as noted above, and/or chemical additives in the wash water used. Suitable additives include chlorine derived bleaches (e.g. sodium hypochlorite) or oxygen derived bleaches (e.g. hydrogen peroxide), but the use of these materials has drawbacks in that they can decolour some garment types, and gener- ally promote fabric damage through chemical attack. The oxygen derived bleaches also become less effective at lower wash temperatures (<40°C), even when used in combina- tion with suitable activators, e.g. tetraacetyl ethylene diamine. Other additives based on chloro compounds (e.g. liquid chlorophenols) can also be used, but with similar drawbacks. Possibly the most benign means of achieving antimicrobial performance in the wash water is via the addition of silver containing materials (e.g. silver containing zeolite materials). Such approaches are expensive to consider, however, as they are effectively applicable for single wash use only. Furthermore, as in all cases with chemical additives in the wash water, there are effluent treatment considerations to take into account.

[0017] In looking to further develop the method of the cleaning process from WO-A- 2007/128962 and co-pending GB Patent Application No. 1018318.4, therefore, the present inventors have now sought to provide a process which allows the aforementioned hygiene deficiencies with polymeric cleaning to be overcome, particularly at low wash temperatures (<40°C). Hence, in the presently claimed invention, the inventors, by means of the addition of an antimicrobial agent to the polymeric particles, seek to provide a process in which lower levels of mould and bacterial growth occur within the washing machine at all times. The introduction of the antimicrobial agent in this way overcomes the drawbacks which would be associated with single use addition into the wash water (i.e. fabric damage, expense and effluent treatment considerations), and the action of the antimicrobial agent is continuous over the lifetime of the polymeric particles, which are re-used many times in subsequent washes, as is common practice with this technology.

Statements of Invention

[0018] Thus, according to a first aspect of the present invention, there is provided a method for cleaning a soiled substrate, said method comprising the use of a detergent dispensing cartridge in the treatment of the moistened substrate with a formulation comprising a multiplicity of polymeric particles, wherein said polymeric particles comprise at least one antimicrobial agent.

[0019] Said substrate may comprise any of a wide range of substrates, including, for example, plastics materials, leather, paper, cardboard, metal, glass or wood. In practice, however, said substrate most preferably comprises a textile fibre or fabric, which may comprise either a natural material, such as cotton, or a synthetic textile material, for example nylon 6,6 or a polyester.

[0020] Said antimicrobial agent inhibits the growth of microbes such as mould and bacteria, and may comprise any readily commercially available product which is suitable for such purposes, and which would be well known to the skilled person. Particularly suitable agents include solid chlorophenol derivatives, such as 5-chloro-2-(2,4- dichlorophenoxy)phenol, which is commercially available as Triclosan or Microban ^® , or its derivatives, and silver containing materials, most particularly silver containing zeolite materials, including products from the Bio-Gate ^™ Irgaguard ^® or HyGate ^™ ranges including, for example, Bio-Gate ^™ BG-Tec Plus, Irgaguard ^® B 5000, Irgaguard ^® B 7000, HyGate ^™ 4000 and HyGate ^™ 9000.

[0021] 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. Preferably, however, said polymeric particles comprise polyester or polyamide particles, most particularly particles of polyethylene terephtha- late, polybutylene terephthalate, nylon 6, and nylon 6,6, most preferably in the form of beads. Said polyesters and polyamides 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 for the purposes of the invention.

[0022] Specifically, the properties of the polymeric materials may be tailored to particular requirements by the inclusion of monomeric units which confer desired properties on the copolymer. Thus, the polymers may be adapted to attract particular staining materials by comprising co-monomers which, inter alia, are ionically charged, or include polar moieties or unsaturated organic groups. Examples of such groups may include, for example, acid or amino groups, or salts thereof, or pendant alkenyl groups.

[0023] Furthermore, the polymeric particles may comprise either foamed or unfoamed polymeric materials. Additionally, the polymeric particles may comprise polymers which are either linear or crosslinked, and said particles may be solid or hollow.

[0024] Said antimicrobial agent is most conveniently introduced into said polymer parti- cles during extrusion of said polymer. Thus, the antimicrobial agent is especially preferably added to the molten polymer prior to extrusion. In an alternative embodiment, said polymer particles may be coated with said antimicrobial agent after extrusion.

[0025] Preferably, said antimicrobial agent is added to said polymer at a level of 0.1- 5.0%, (w/w), most preferably 0.5-2.5% (w/w), especially preferably 1.5-2.0% (w/w).

[0026] Whilst, in one embodiment, the method of the invention envisages the cleaning of a soiled substrate by the treatment of a moistened substrate with a formulation which essentially consists only of a multiplicity of polymeric particles which comprise at least one antimicrobial agent, in the absence of any further additives, optionally in other embodiments the formulation employed may further comprise at least one additional cleaning agent. Preferably, the at least one additional cleaning agent comprises at least one sur- factant. Preferred surfactants comprise surfactants having detergent properties and said additional cleaning agents preferably comprise detergent formulations. Said surfactants may comprise anionic, non-ionic, cationic, ampholytic, zwitterionic and/or semi-polar non- ionic surfactants. Optionally, said at least one additional cleaning agent comprises at least one enzyme and/or bleach. Preferably, said at least one additional cleaning agent is mixed with said polymeric particles but, in an alternative embodiment, each of said polymeric particles is coated with said at least one additional cleaning agent. Further additives may be incorporated with said additional cleaning agent, as appropriate; said additives may include, for example, anti-redeposition additives, optical brighteners, perfumes, sof- teners and starch, which can enhance the appearance and other properties of the cleaned substrate.

[0027] As previously stated, various polyester and/or polyamide homo- or co-polymers may be used for the polymeric particles, including polyethylene terephthalate, polybutylene terephthalate, nylon 6 and nylon 6,6. Preferably, the nylon comprises nylon 6,6 ho- mopolymer 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 measurement in the range of from 0.3-1.5 dl/g as measured by a solution technique such as ASTM D-4603.

[0028] The ratio of polymeric particles to substrate is generally in the range of from 0.1 : 1 to 10: 1 w/w, preferably in the region of from 0.5: 1 to 5: 1 w/w, with particularly favourable results being achieved with a ratio of between 1 :1 and 3:1 w/w, and especially at around 2:1 w/w. Thus, for example, for the cleaning of 5 g of substrate, typically textile fabric, 10 g of polymeric particles, optionally coated with surfactant, would be employed in one em- bodiment of the invention. The ratio of polymeric particles to substrate is maintained at a substantially constant level throughout the wash cycle.

[0029] The polymeric particles are of such a shape and size as to allow for good flowabil- ity and intimate contact with the soiled substrate, which typically comprises a textile fibre or fabric. A variety of shapes of particles can be used, such as cylindrical, spherical or cu- boid; appropriate cross-sectional shapes can be employed including, for example, annular ring, dog-bone and circular. In preferred embodiments of the invention, said particles are in the form of beads and, most preferably, comprise cylindrical or spherical beads.

[0030] The particles may have smooth or irregular surface structures and can be of solid or hollow construction. Particles are of such a size as to have an average mass of 1-50 mg, preferably from 10-30 mg, more preferably from 12-25 mg. [0031] In the case of cylindrical beads, the preferred particle diameter is in the region of from 1.0 to 6.0 mm, more preferably from 1.5 to 4.0 mm, most preferably from 2.0 to 3.0 mm, and the length of the beads is preferably in the range from 1.0 to 5.0 mm, more preferably from 1.5 to 3.5 mm, and is most preferably in the region of 2.0 to 3.0 mm.

[0032] Typically, for spherical beads, the preferred diameter of the sphere is in the region of from 1.0 to 6.0 mm, more preferably from 2.0 to 4.5 mm, most preferably from 2.5 to 3.5 mm.

[0033] The method of the invention may be applied to a wide variety of substrates, as previously stated. More specifically, it is applicable across the range of natural and syn- thetic textile fibres and fabrics, but it finds particular application in respect of nylon 6,6, polyester and cotton fabrics.

[0034] Prior to treatment according to the method of the invention, the substrate is moistened by wetting with water, to provide additional lubrication to the cleaning system and thereby improve the transport properties within the system. Thus, more efficient transfer of the at least one cleaning material to the substrate is facilitated, and removal of soiling and stains from the substrate occurs more readily. Most conveniently, the substrate may be wetted simply by contact with mains or tap water. Preferably, the wetting treatment is carried out so as to achieve a substrate to water ratio of between 1 :0.1 to 1 :5 w/w; more preferably, the ratio is between 1 :0.2 and 1 :2, with particularly favourable results having been achieved at ratios such as 1 :0.2, 1 : 1 , 1 : 1.2 and 1 :2. However, in some circumstances, successful results can be achieved with substrate to water ratios of up to 1 :50, although such ratios are not preferred in view of the significant amounts of effluent which are generated.

[0035] Suitable examples of apparatus for the execution of this method are disclosed in WO-A-2010/094959, WO-A-201 1/064581 and WO-A-201 1/098815. In preferred embodiments of the invention, the claimed method additionally provides for separation and recovery of the polymeric particles, which are then re-used in subsequent washes.

[0036] As a consequence of employing the cleaning method of the present invention, excellent cleaning performance may be achieved whilst using significantly reduced levels of detergents and much lower process temperatures. Thus, cleaning operations according to the invention, whilst possible at temperatures up to 95°C, are typically carried out at temperatures not exceeding 65°C, and optimum performance is generally achieved at 5-35°C. It is at this lower end of the operational temperature range that the antimicrobial polymeric particles ensure improved hygiene in the washing machine used. According to a second aspect of the present invention, there is provided a detergent dispensing cartridge for use with 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 polymeric particles comprise at least one antimicrobial agent.

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, the cartridge having multiple compartments; a first compartment holds an antimicrobial formulation.

Preferably a portion of the contents of the first compartment are released after a plurality wash cycles have been completed.

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 wash- ing 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 0902619.6, 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.

It will be understood that features of the first aspect of the invention shall be taken to apply mutatis mutandis to the second and third aspects of the invention.

It has been found that with the use of a cartridge great benefits are provided to a consumer. Furthermore it has been observed that a reduction in any detrimental antimicrobial growth on the polymeric particles is achieved. Such an effect is not always visi- ble to a consumer. Indeed in this regard it has been observed that through use of cartridge of the present invention at least 3 log kill efficacy, preferably at least 4 log kill efficacy at 60 seconds contact time of at least two, preferably at least three and most preferably at least four of microorganisms selected from the group consisting of: S. aureus, E. coli, P. aeruginosa and E.hirae, according to the protocols of prEN 12054. Thus according to a fourth aspect of the 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, the cartridge having multiple compartments; a first compartment holds an antimicrobial formulation; wherein a portion of the contents of the first com- partment are released after a plurality wash cycles have been completed, wherein at least 3 log kill efficacy, preferably at least 4 log kill efficacy at 60 seconds contact time of at least two, preferably at least three and most preferably at least four of microorganisms selected from the group consisting of: S. aureus, E. coli, P. aeruginosa and E.hirae, according to the protocols of prEN 12054, is observed on the polymeric particles.

Further benefits are provided in terms of ease of use. The use of a cartridge allows dis- charge 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 derivates 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. In contrast many of the other detergent components require no wash liquor heating to achieve their optimal function. In 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 de- tergent 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 an enzyme containing formulation;

b) Release of a oxidising formulation;

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

d) Release of a dye fixative / DTI 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.

Preferably step (d) occurs at the end of the washing machine cycle, during the rinse phase. This for two reasons: dye fixative / DTI are generally "quaternary" molecules (i.e. including at least one N ⁺ moiety), as such they could cause precipitation in presence of anionic surfactants. Also if added before the cleaning phase, dye fixative / DTI could fix the stains (e.g. to the material being cleaned).

In 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 cartridge. 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 pref- erably from 20 to 300 cc, more preferably from 20 to 200 cc and most preferably from 20 to 100 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 car- tridge 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, tempera- ture / temperature changes, smell/ odour, humidity / water presence (or some other asso- dated 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 sche- matics 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 activated at a certain predetermined temperature to allow release (by what- ever mechanism) 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 wherein the film may be entirely water soluble / dis- persible 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. polypropylene, polyethylene, polyvinylalcohol, 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. In 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 detersive active has been reversibly / irreversibly adsorbed (e.g. en- zyme, 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 considerably 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 15g 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. In particular it has been found that the amount of builder required may be lower. Another altera- tion 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 with- out 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 15°C and 40°C, e.g. about 30°C. The washing cycle time is preferably between 15 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. Intermediate 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 litres 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 litres 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 as- sociates 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 cartridge / 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 car- tridge 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 or zwitterionic surface active agent or mixture thereof.

Examples of anionic surfactants are straight-chained or branched alkyl sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be pro- duced by the sulfation of higher C ₈ -C ₂ o fatty alcohols.

Examples of primary alkyl sulfate surfactants are those of formula:

ROS0 ₃ ^" M ⁺

wherein R is a linear C ₈ -C ₂ o hydrocarbyl group and M is a water-solubilising cation.

Preferably R is Ci ₀ -Ci ₆ alkyl, for example C12-C14, and M is alkali metal such as lithium, sodium or potassium.

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

CH ₂ (CH2)n(CHOS03 ^" M ⁺ )(CH2) _m CH ₃

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 alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae:

CH ₂ (CH ₂ )x(CHOS03 ^" M ⁺ )CH3 and

CH ₃ (CH2)x(CHOS03 ^" M ⁺ )CH ₂ CH3

for the 2-sulfate and 3-sulfate, respectively. In these formulae x is at least 4, for example 6 to 20, preferably 10 to 16. 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) _n S0 ₃ ^" M ⁺

wherein R is a C ₈ -C ₂₀ alkyl group, preferably C1 ₀ -C18 such as a Ci ₂ -Ci ₆ , 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 alkanolammonium. 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 C ₈ - Ci8 fatty acids, especially the sodium potassium or alkanolammonium salts, and alkyl, for example C ₈ -Ci ₈ , benzene sulfonates.

Examples of nonionic surfactants are fatty acid alkoxylates. The ethoxylated and propoxy- lated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic 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 C ₈ -Ci ₆ alkyl group, preferably a C ₉ -Ci ₅ , for example C10-C14, or C12-C14 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 hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably from 10 to 15.

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 Com- pany. Other useful Neodols 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 Cg-Cn primary alcohol having about 10 moles of ethylene oxide.

Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company un- der the Dobanol trademark. Dobanol 91-5 is an ethoxylated Cg-Cn 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 15-S- 7 and Tergitol 15-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 Cuds 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 simi- lar ethylene oxide condensation products of a fatty alcohol having 14-15 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, Ci ₀ -Ci ₈ alkyi polyglycosides, such s Ci ₂ -Ci ₆ alkyi polyglycosides, especially the polyglucosides. These are especially useful when high foaming is desired. Further surfactants are polyhydroxy fatty acid amides, such as Ci ₀ -Ci ₈ 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 (I) or (la), or include a mix- ture thereof;

[RHCOy-O-R-N^-R' -CRO^^C-R-O-CCOy-R')^ ^" (I)

[RHCOy-NH-R-N^-R^HRO^^C-R-NH-CCOy-R^PC CIa)

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.

Non-limiting examples of softener-compatible anions (X ^" ) include chloride, formate, nitrate, 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 14 carbon atoms, more preferably at least 16 carbon atoms. The group may be straight or branched.

A specific example of quaternary ammonium compound is di-(tallow car- boxyethyl)hydroxyethyl methyl ammonium X ^" .

A cationic fabric co-softener may be present. Examples of amphoteric surfactants are C10-C18 amine oxides and the C12-C18 betaines and sulfobetaines.

Suitable builders are alkali metal or ammonium phosphates, polyphosphates, phospho- nates, polyphosphonates, carbonates, bicarbonates, borates, polyhydroxysulfonates, poly- acetates, carboxylates such as citrates and other polycarboxylates / polyacetyl carboxy- lates 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) aluminosili- cates either crystalline, amorphous or a mixture of the two. Such aluminosilicates generally have a calcium ion exchange capacity of at least 50 mg CaO per gram of aluminosilicate, comply with a general formula:

0.8-1.5 Na ₂ 0. Al ₂ 0 ₃ . 0.8-6 Si0 ₂

and incorporate some water. Preferred sodium aluminosilicates within the above formula contain 1.5-3.0 Si0 ₂ units. Both amorphous and crystalline aluminosilicates 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 1429143 (Procter & Gamble). The preferred sodium alumi- nosilicates 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 0 _2x+ 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 Glas- techn. Ber. 37,194-200 (1964), Zeitschrift fur Kristallogr. 129, 396-404 (1969), Bull. Soc. Franc. Min. Crist., 95, 371-382 (1972) and Amer. Mineral, 62, 763-771 (1977). These ma- terials 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, polycarboxylate 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 polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxy- malonates, dipicolinates, hydroxyethyliminodiacetates, phosphonates, iminodisuccinates, polyaspartic acids, BHT, phosphonate stabilisers such as, diethylenetriaminepenta (methylene phosphonic 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. 66019-18-9 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, allyloxybenzenesulphonic acid, methallyloxybenzensulphonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulphonic acid, 2-methyl-2-propene-1 -sulphonic acid, styrene sulphonic acid, vinylsulphonic acid, 3-sulphopropyl acrylate, 3-sulphopropyl methacrylate, sulphomethylacrylamid, sulphomethylmethacrylamide, 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, Alcalase, Savinase, Termamyl, Lipolase and Celluzyme by Nova Nordisk 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%.

Suitable bleaches / oxidising agents / bleaching agents usually compsies a source of active oxygen, e.g. hydrogen peroxide; urea / hydrogen peroxide; percarboxyiic adds, peroxy / per- acids suich as phthalimido-peroxy-hexanoic-acid (PAP); per-salts such as; perborate, perphosphaie, percarbonate, persulphate, persi!icate. The bleaching agent may be based on alternative chemistry, e.g. chlorine based bleaching agents, such as hypochlorite bleaches, sodium dichloro-isocyanurate or NaDCC.

Other examples of suitable bleaches include N-acyiate lactam bleach precursors, per- benzoic add precursors, perbenzosc add derivative precursors and cationic peroxyacid precursors, or mixtures thereof

Suitable bleach activators include tetraacetylethylendiamine (TAED), acetylated triazine derivatives, in particular 1 ,5-Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), acetylated glycoluriles, in particular Tetraacetylglycolurile (TAGU), acylimides, in particular n- nonanoylsuccinimide (NOSI), acetylated phenolsulfonates, in particular n-nonanoyloxi or n- lauroyloxibenzolsulfonate (NOBS and/or PRAISE), acetylated phenol carbonic acids, in particular nonanoyloxi or decanoyloxibenzoesaeure (NOBA and/or DOBA), carbonic acid anhydrides, acetylated sugar derivatives, in particular pentaacetylglucose (PAG), pen- taacetylfructose, tetraacetylxylose and octaacetyl lactose as well as acetylated N-alkylated glucamine and gluconolactone, and/or N- acetylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted ecyl acetals and ecyl lactams are likewise preferentially used. Particularly preferential bleach activators are TAED and DOBA.

Bleaching catalysts may be present. Preferred examples include complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.

When using metal salts in particular manganese salts are in the oxidation state +2 or +3 preferentially, for example manganese halides, whereby the chloride is preferential. Man- ganese sulfate, manganese salts of organic acids such as manganese acetates, acety- lacetonate, oxalates as well as manganese nitrates are suitable.

The bleach / oxidising agent constituent may comprise one or more of the foregoing compounds or materials which are described above, which may be present in any effective amount in order to provide a sanitizing or disinfecting benefit to surfaces upon which they have been applied. Advantageously, the bleach / oxidising agent agent constituent is preferably present (in a solid formulation) in amounts of from 0.0001 %wt. to 60%wt., preferably from 30%wt. to 50%wt., more preferably 40%wt. to 50%wt., and particularly preferably about 45%wt. based on the total weight of the composition of which they form a part.

Indeed a preferred solid formulation for the antimicrobial formulation (comprising a solid bleach based formulation) is below:-

The bleach / oxidising agent constituent may comprise one or more of the foregoing compounds or materials which are described above, which may be present in any effective amount in order to provide a sanitizing or disinfecting benefit to surfaces upon which they have been applied. Advantageously, the bleach / oxidising agent agent constituent is preferably present (in a liquid formulation) in amounts of from 0.0001 %wt. to 60%wt., preferably from 0.1 %wt. to 20%wt., more preferably 2%wt. to 10%wt., and particularly preferably about 5%wt. based on the total weight of the composition of which they form a part.

Indeed a preferred solid formulation for the antimicrobial formulation (comprising a liquid bleach based formulation) is below:-

Metal complexes with macromolecular ligands may be used such as1 ,4,7-Trimethyl-1 ,4,7- triazacyclononane (me-TACN), 1 ,4,7-Triazacyclononane (TACN), 1 ,5,9-Trimethyl-1 ,5,9- triazacyclododecane (me-TACD), 2-Methyl-1 ,4,7 trimethyl-1 ,4,7-triazacyclononane (Me- MeTACN) and/or 2-Methyl-1 ,4,7 triazacyclononane (Me/TACN) or ligands such as 1 ,2-bis (4,7-Dimethyl 1 ,4,7-triazacyclonono-i-yl) ethane (Me4-DTNE).

The bactericidal / antimicrobial agents are generally cationic. nitrogen compounds. Among, these cationic compounds there may be mentioned by way of example: diisobutyl- phenoxyethoxyethyidimethyibenzyiammonium chloride, dodecyltrimethylammonium bromide, 15 dodecyidimethyi(2-:phenoxyethyl)ammonium bromide, benzyidimethyistearylam- monium chloride, cetylpyridinium chloride, quaternized 5-amino-1 ,3-bis(2-ethylhexyl)-5- methyl-hexahydroxypyrimidine, trimethylcetylammonium bromide, alkyidimethylhy- droxyethylammonium bromide (where alkyl denotes a mixture of radicals derived from copra fatty acids), chlorhexidine, alexidine, and cationic tertiary aliphatic amines.

The bactericidal / antimicrobial agent constituent may include one or more organic acids providing an antimicrobial benefit. Exemplary organic acids are those which generally include at least one carbon atom, and include at least one carboxyl group (-COOH) in its structure. Derivatives of said organic acids are also contemplated to be useful. Exemplary organic acid include linear aliphatic acids such as acetic acid; dicarboxylic acids, acidic amino acids, and hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, al- pha-hydroxybutyric acid, glyceric acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids. Of these, glycolic acid, lactic acid and salicylic acid and/or derivatives thereof, e.g., salicylic acid derivatives such as esters of salicylic acid, such as ethylhexyl salicylate, dipropylene glycol salicylate, TEA salicylate, salicylic acid 2- ethylhexylester, salicylic acid 4-isopropyl benzylester, salicylic acid homomenthylester are preferred.

Particularly useful quaternary bactericidal / antimicrobial agents include quaternary com- pounds, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the BARDAC®, BARQUAT®, HYAMINE®, LONZABAC®, and ONYXIDE® trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below. When one or more cationic surfactants which provide an appreciable germicidal benefit are present, they may be present as a co-antimicrobial agent, as the antimicrobial agent described hereinafter is necessarily present in order to provide the primary antimicrobial benefit. Further when one or more cationic surfactants which provide an appreciable germicidal benefit are present, preferably anionic surfactants and further optionally, amphoteric surfactants are omitted from the compositions of the invention. However, as noted previously, in certain preferred embodiments, cationic surfactants which provide an appreciable germicidal benefit are expressly excluded from the compositions of the invention, and thus, anionic surfactants as well as amphoteric surfactants may be used in such compositions.

The bactericidal / antimicrobial agent constituent may include one or more of: pyrithiones such as zinc pyrithione, halohydantoins such as dimethyldimethylol hydantoin, methyl- chloroisothiazolinone/methylisothiazolinone sodium sulfite, sodium bisulfite, imidazolidinyl urea, diazolidinyl urea, benzyl alcohol, 2-bromo-2-nitropropane-1 ,3-diol, formalin (formaldehyde), iodopropenyl butylcarbamate, chloroacetamide, methanamine, methyldibromoni- trile glutaronitrile, glutaraldehyde, 5-bromo-5-nitro-1 ,3-dioxane, phenethyl alcohol, o- phenylphenol/sodium o-phenylphenol, sodium hydroxymethylglycinate, polymethoxy bi- cyclic oxazolidine, dimethoxane, thimersal dichlorobenzyl alcohol, captan, chlorphenene- sin, dichlorophene, chlorbutanol, glyceryl laurate, halogenated diphenyl ethers such as 2,4,4-trichloro-2-hydroxy-diphenyl ether (Triclosan®) and 2,2-dihydroxy-5,5-dibromo- diphenyl ether, phenolic antimicrobial compounds such as mono- and poly-alkyl and aromatic halophenols, such as p-chlorophenol, methyl p-chlorophenol, 4-chloro-3,5-dimethyl phenol, 2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-terabromo-2-methylphenol, 5-methyl-2- pentylphenol, 4-isopropyl-3-methylphenol, para-chloro-meta-xylenol, dichloro meta xylenol, chlorothymol, and 5-chloro-2-hydroxydiphenylmethane, resorcinol and its derivatives, bisphenolic compounds such as 2,2-methylene bis (4-chlorophenol) and bis (2-hydroxy-5- chlorobenzyl)sulphide, benzoic esters (parabens), halogenated carbanilides such as 3- trifluoromethyl-4,4'-dichlorocarbanilide (Triclocarban), 3-trifluoromethyl-4,4- dichlorocarbanilide and 3,3,4-trichlorocarbanilide.

The bactericidal / antimicrobial agent constituent may include one or more of: biguanides such as polyhexamethylene biguanide, p-chlorophenyl biguanide; 4-chlorobenzhydryl biguanide, 1 ,6-bis-(4-chlorobenzylbiguanido)-hexane (Fluorhexidine®), halogenated hexi- dine including, but not limited to, chlorhexidine (1 , T-hexamethylene-bis-5-(4-chlorophenyl biguanide) (Chlorohexidine®), as well as salts of any of the foregoing, e.g. polyhexamethylene biguanide hydrochloride.

The bactericidal / antimicrobial constituent may comprise a peroxygen compound which may be essentially any compound containing a dioxygen (O-O) bond. Dioxygen bonds, particularly bivalent 0-0 bonds, are readily cleavable, thereby allowing compounds containing them to act as powerful oxidizers. Non-limiting examples of classes of peroxygen compounds include peracids, peracid salts, and peroxides such as hydrogen peroxide. The peroxygen can be any aliphatic or aromatic peracid (or peroxyacid) that is functional for disinfectant purposes in accordance with embodiments of the present invention. While any functional peroxyacid can be used, peroxyacids containing from 1 to 7 carbons are the most practical for use. These peroxyacids can include, but not be limited to, peroxyformic acid, peroxyacetic acid, peroxyoxalic acid, peroxypropanoic acid, perlactic acid, peroxybu- tanoic acid, peroxypentanoic acid, peroxyhexanoic acid, peroxyadipic acid, peroxycitric, and/or peroxybenzoic acid. Exemplary peracid salts include permanganates, perborates, perchlorates, peracetates, percarbonates, persulphates, and the like. Exemplary peroxide compounds include hydrogen peroxide, metal peroxides and peroxyhydrates. The metal peroxides that can be used include, but are not limited to, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, and/or strontium peroxide. Other salts (for example sodium percarbonate) have hydrogen peroxide associated therewith are also considered to be a source of hydrogen peroxide, thereby producing hydrogen peroxide in situ.

The bactericidal / antimicrobial constituent may comprise one or more polyols in amounts which are effective in imparting a sanitizing or disinfecting benefit to surfaces upon which the compositions are applied. By way of non-limiting example, preferred are polyols containing from 2 to about 6 hydroxyl groups. Preferred polyols are water soluble. Specific al- beit non-limiting examples of polyols include, but are not limited to, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, butylene glycol and when present, the polyols should be present in a sufficient concentration such the antimicrobial constituent of which they form at least a part, provides an effective sanitizing or disinfecting benefit to surfaces being treated with the compositions. Advantageously the one or more polyols comprise up to 100% of the antimicrobial constituent of the present invention.

The bactericidal / antimicrobial constituents may also comprise one or more monohydric alcohols, especially C C ₄ monohydric alcohols and/or C C ₄ ketones wherein such are present in should be present in a sufficient concentration such the antimicrobial constituent of which they form at least a part, provides an effective sanitizing or disinfecting benefit to surfaces being treated with the compositions. Advantageously the one or more monohydric alcohols and/or ketones comprise up to 100% of the antimicrobial constituent of the present invention. Further, when present, the one or more alcohols or ketones may also function as an organic solvent.

The bactericidal / antimicrobial constituent may comprise a halogenated compound or species. By way of non-limiting example such include halogens, and especially l ₂ , as well as iodophors such as povidone-iodine, or any substance comprising iodine and a solubiliz- ing agent that releases free iodine when in solution. While other halogen species are contemplated as being potentially useful as the antimicrobial constituent of the invention, l ₂ , as well as iodophors are preferred for use as being relatively safe from a toxicological perspective.

The bactericidal / antimicrobial agent constituent may comprise one or more of the foregoing compounds or materials which are described above, which may be present in any effective amount in order to provide a sanitizing or disinfecting benefit to surfaces upon which they have been applied. Advantageously, the antimicrobial agent constituent is preferably present in amounts of from 0.0001 %wt. to 40%wt., preferably from 0.001 %wt. to 25%wt., more preferably 0.001 %wt. to 20%wt., and particularly preferably from 0.001 %wt. to 10%wt. based on the total weight of the composition of which they form a part.

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 ACU- SOL 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 tripolyphosphate 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. C C ₃ 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, contain 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 13.