Detergent Compositions and Methods for Cleaning Field of the Invention This invention relates to detergent compositions and methods for cleaning which provide most effective cleaning results with least physical washing being needed. The technology may find application in various cleaning compositions, in particular laundry and dish-washing detergent compositions which may be in a fluid, such as granular, liquid or flowable gel or paste form or which may have undergone additional processing steps to be in a tablet form. The invention relates particularly to laundry detergent applications. The invention particularly relates to cleaning applications which require hand washing by the user.

Background of the Invention Poor dissolution and dispensing problems are well-known in the detergent field.

This problem has been exacerbated by recent tendencies to produce higher bulk density detergents, such as above 600g/l, or detergent tablets to meet the consumer need for lower product and packaging volumes and less wastage i. e. higher active cleaning compositions.

The problem is compounded by the use of detergent formulations which are based not on readily soluble phosphate builders, but instead on less soluble alternatives which overcome any environmental problems associated with phosphate builders.

In particular, in applications where washing is carried out by hand, it is beneficial to wait until the detergent composition has at least partially dissolved in the aqueous solution so that the cleaning properties of the active detergent ingredients can begin to take effect. In this way, the chemical cleaning which takes place, as the soil begins to be broken down can at least partially replace the need for intensive mechanical cleaning by the user. However, the user will tend to commence washing as soon as the detergent is added to water so that chemical cleaning performance is not maximised at the time of commencement of the washing action by the user. Machine-washing processes will also reduce energy consumption if the chemical cleaning has begun to take effect at the time the mechanical cleaning (e. g. agitation) has commenced.

Many suggestions have been made in an effort to increase the rate of dissolution and dispensing of detergents in aqueous solutions in an effort to overcome this problem.

One such solution has been the use of effervescent systems in detergents. For example, detergent compositions comprising effervescing ingredients are described in W098/04687. In W098/04671, effervescence systems for use in detergents are disclosed in which in an effort to improve dissolution, acid and alkaline effervescing reactants which react on contact with water to produce a gas, are mixed with a stabilising agent to produce a substantially anhydrous effervescence particle which has maximum efficacy on use in a washing step. Similarly, W098/35011 also discloses particles comprising sodium bicarbonate and organic acid reactants which react together and which are formed into a particle with a binder. EP-A-918 087 describes co-builder particles for adding to detergent compositions, comprising bicarbonate and polycarboxylic acid which are formed by roller-compaction and which contain no free moisture. However, in fact, the requirements of providing good storage stability and good end use effervescence on contact with the wash liquor are conflicting requirements; the use of stabilising agents can prevent or reduce efficacy in the wash conditions as the water contact with the effervescing reactants and the resulting reaction rate slows down, so that the effervescing and therefore, dissolution aid effect is undesirably reduced.

Furthermore, washing processes are still commenced by the end users before detergent active components have entered into the aqueous wash solution. The present inventors have now provided a washing process in which an audible signal is produced by the detergent composition to indicate to the user when the detergent composition is at least partially dissolved in the wash water, indicating that mechanical cleaning can begin.

This washing process thereby maximises the efficiency of the cleaning process by ensuring that the chemical cleaning begins prior to the mechanical cleaning applied by the user.

Summarv of the Invention In accordance with the present invention there is now provided a method for washing soiled articles comprising obtaining a detergent composition comprising a signal component, adding the detergent composition to water, and commencing mechanical cleaning of the soiled articles characterised in that on addition of the detergent composition to the water a signal is produced which indicates at least partial dissolution

of the detergent composition in the wash water. Preferably the signal lasts for a duration which indicates when the chemical cleaning by the at least partially dissolved detergent composition has commenced so that the user is directed to commence mechanical cleaning when the signal is completed. By"mechanical cleaning"herein is meant any of the conventional mechanical methods for cleaning, such as agitation, contact with jets of liquid or gas to mechanically remove soil and/or abrasion. Preferably the signal is audible. Preferably the signal is produced by an effervescence system. This is found to be particularly beneficial as the effervescence may also contribute to mechanical cleaning.

In accordance with a further aspect of the invention, there is also provided a detergent composition comprising a signal component such that on contact of the detergent composition with water, a signal is produced. Preferably the signal is audible.

Preferably the signal component comprises an effervescence system such that on contact with water effervescence is released which is audible to the user. Preferably the duration of the signal corresponds with time taken for the detergent composition to at least partially dissolve in the washing water so that the user waits for the substantial completion of the signal before commencing the mechanical washing step.

In accordance with a further aspect of the invention there is also provided use of a signal component in a detergent composition to generate a signal which provides an indicator of dissolution of the detergent composition. Preferably the signal is an audible signal.

Detailed Description of the Invention The detergent compositions of the invention comprise a signal component such that on contact with water, a signal is produced which provides an indicator of the at least partial dissolution of the detergent composition. Preferably the signal component produces an audible signal. Preferably the audible signal is produced by an effervescence system; preferred effervescence systems comprise an acid-source and an alkali-source which react with one another on contact with water. In a particularly preferred embodiment of the invention, the effervescence system comprises an effervescence particle. The audible signal produced by the signal component is preferably at a noise level of at least 42dB, more preferably at least 45dB and most preferably at least 50dB for at least part of its duration. Preferably, the noise level generated by the audible signal is

at least 3dB greater than the average ambient background noise level as measured over a five minute measurement period for background noise. Preferably the noise level will be at least 5dB greater than ambient background noise, more preferably at least l OdB greater than ambient background noise. A suitable apparatus for measuring noise levels is a CEL SoundTrack dB21 apparatus, (Model CEL-480 Version 1.8) from CEL Instruments Ltd using a microphone and run on Broadband SLM mode with the frequency weighting for RMS set at A and the frequency rating for peak set at Z. A measurement range of 20- 90 dB is generally suitable.

Preferably the effervescence system is designed so that the duration of the signal corresponds to the length of time needed for the detergent active ingredients to at least partially dissolve in the wash water so that in the preferred method of the invention, on completion of the audible signal, the mechanical washing process commences. By duration of the signal it is intended to refer to the time delay between contact of the detergent composition comprising the signal component with the wash water and completion of the signal. The audible signal may either commence immediately during this time or there may be an initial delay before the signal is produced. Preferably the audible signal has a duration of at least 5 seconds, more preferably at least 10 seconds or even at least 30 seconds or 1 minute.

Effervescence Svstem The effervescence system comprises one or more effervescence components such that on contact of the effervescence system with water, effervescence is produced. This effervescence may be as a result of gas trapped in the matrix of the effervescence system being released when the particle contacts water, or more usually, is the result of a reaction which takes place between two or more reactants present in the effervescence system which, on contact with water react with one another to produce a gas. Where the effervescence is produced by reaction of two or more reactants, preferably, the reactants are provided by an acid-source and an alkali-source.

Acid-Source Suitable acid sources include solid organic, mineral or inorganic acids, salts or derivatives thereof or mixtures thereof. It may be preferred that the acids are mono-, bi- or tri-protonic acids. Such acids include mono-or polycarboxylic acids preferably citric acid, adipic acid, glutaric acid, 3-chetoglutaric acid, citramalic acid, tartaric acid, maleic

acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acidic form. Derivatives also include esters of the acids. Preferred acids include citric acid and malic acid. Citric acid is particularly preferred.

Alkali-Source Any alkali-source may be used in the effervescence system. Carbonate alkali- sources are particularly preferred, for example including carbonate, bicarbonate, sesquicarbonate and percarbonate salts, in particular bicarbonate and/or carbonate.

Preferred carbonates to be used herein include carbonate and hydrogen carbonates which should be present in the effervescence system in a form which can react with the acid- source. Generally, therefore, the alkali-source should be water soluble, or of very fine particle size such that a reaction with the acid-source takes place readily on contact of the effervescence particle with water. Salts of alkali metals or alkaline earth metals are suitable. Water-soluble salts such as salts of potassium, lithium, sodium, and the like are preferred amongst which sodium and potassium carbonate are particularly preferred.

Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred. Bicarbonate may be preferred to carbonate, because it is more- weight effective, i. e., at parity weight bicarbonate is a larger CO,"reservoir"than carbonate. However, overall detergent formulation requirements may result in the more alkaline pH, produced by carbonates, providing a more useful overall detergent formulation, thus the choice of carbonate or bicarbonate or mixtures thereof in the effervescence systems may depend on the pH desired in the aqueous medium wherein the detergent composition comprising the effervescence particles is dissolved. For example where a relatively high pH is desired in the aqueous medium (e. g., above pH 9.5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate, typically in a weight ratio of carbonate to bicarbonate from 0.1 to 10, more preferably from 1 to 5 and most preferably from 1 to 2.

Preferably, the detergent composition will comprise at least 0. 5wt% total effervescence components, more preferably at least 1 wt% total effervescence components and most preferably at lesat 5wt% or even at least 10 or 20 wt% based on the weight of the detergent composition, of total effervescence components.

The delivery of the effervescence via an effervescence particle can be particularly useful in the present invention because adjustment of the parameters described below enable the duration of the audible signal to be tailored to the needs of the detergent composition. This will be clear to the person skilled in the art. Thus, for example for slower dissolving detergent compositions, an effervescence particle comprising a greater proportion of non-effervescent components such as binder or other optional ingredients, which slows dissolution, or a higher compaction pressure may be used to ensure that the signal is delivered either more slowly or after a delay period on contact with the wash water, so that the signal stops after a longer time span from contact of the detergent composition with the water.

Effervescence Particle Where the effervescence system comprises the preferred effervescence particle, suitable acid-sources and alkali-sources are as set out above. The acid-source is preferably present in the effervescence particle at a level of from 0.1% to 99% by weight of the total particle, preferably from 3% to 80%, more preferably from 10% to 75% and most preferably from 15% to 70%. The carbonate source is preferably present in the effervescence particles at a level of from 0.1 % to 99% by weight of the total, preferably from 20% to 95%, more preferably from 30% to 85% and most preferably from 35% to 75% by weight of the effervescence particle.

It may be preferred for the number ratio of the alkali-source to the acid-source (that is the ratio of number of particles of the alkali-source to the acid-source) to be at least 50: 1, preferably at least 100: 1, more preferably at least 500: 1, or even at least 1000: 1 and most preferably at least 5000: 1 or even at least 10000: 1.

In addition, the ratio of the median particle size of the alkali-source to the acid- source is preferably at least 2: 1, preferably at least 8: 1, more preferably at least 15: 1, or at least 20: 1 or even at least 30: 1. Preferably the span of the particle size of each of the acid-source and the alkali-source is no greater than 3, more preferably no greater than 2, most preferably no greater than 1.5.

As used herein, the phrase"median particle size"means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving. As used herein, the phrase"geometric standard deviation"or"span"of a particle size distribution means the

geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 5 percentile of the cumulative distribution (D84, 3/D50) ; See Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.

Preferably, the mediann particle size of the effervescence particles is from about 500 microns to about 1500 microns, more preferably from about 600 microns to about 1200 microns, and most preferably from about 700 microns to about 1000 microns. The particle size distribution is defined by a relatively tight geometric standard deviation or "span"so as not to have too many particles outside of the target size. Accordingly, the geometric standard deviation is preferably is from about 1 to about 2, more preferably is from about 1.0 to about 1.7, even more preferably is from about 1.0 to about 1.4, and most preferably is from about 1.0 to about 1.2.

In particular for preparing an effervescence particle to be used in the detergent compositions of the invention, the median particle size of the acid-source is preferably greater than 100pm, more preferably greater than 200pm and most preferably greater than 300pm. The median particle size of the alkali-source is preferably below 50pm, more preferably below 25im and most preferably below 101lu.

In the effervescence particle, the molar ratio of the reactive groups on the alkali- source and the reactive groups of the acid-source is preferably substantially stoichiometric, such that there are substantially equal moles of reactive groups. Thus, the molar ratio of reactive groups of acid-source to reactive groups of alkali-source is preferably from 5: 1 to 1 : 5, more preferably from 3: 1 to 1 : 3, more preferably from 3: 2 to 2: 3 and most preferably from 9: 10 to 10: 9.

In one aspect of the invention, where the detergent composition comprises bicarbonate alone as the alkali-source, preferably the effervescence particle additionally comprises greater than 6 wt% citric acid optionally in mixtures with other acid-source components.

Preferably the effervescence particle is substantially anhydrous such that the overall moisture content (including both bound i. e. water of crystallisation, and unbound i. e. free moisture) is less than 0.5 wt% of the effervescence particle. More particularly, where the effervescence component comprises both acid-source and alkali-source, preferably at least the acid-source used for forming the effervescence particle has an

overall moisture content less than 0.1 wt%, more preferably less than 0.05 wt% and most preferably less than 0.01 wt%. More preferably, the alkali-source also has an overall moisture content less than 0.5 or less than 0. 1 wt%, more preferably less than 0.05 wt% and most preferably less than 0.01 wt%.

The bulk density of the effervescence particles is preferably from 500 g/1 to 1200 g/l, more preferably from 700 g/1 to 1100 g/l.

The effervescence particles may optionally comprise additional ingredients.

Generally, the effervescence particles comprise no more than 50 wt% of the particle of additional ingredient (s), preferably no more than 35 wt% and more preferably no more than 20% or 10%. It may be particularly preferred to have a highly active particle comprising no more than 5 wt% or even no more than 2 wt% of additional ingredients besides the components which contribute to the gas production/release. Suitable additional ingredients may comprise any detergent ingredients which are described below. Particularly suitable are surfactants or organic or inorganic builder components, preferably those which are water soluble such as those described below.

Although not preferred for the reasons given above, optional binders or coating agents may be incorporated into the effervescence particles. Suitable materials are selected from one or mixtures of more than one of the binders and coating materials known to those skilled in the art. In particular suitable binders include anionic surfactants like C6-C20 alkyl or alkylaryl sulphonates or sulphates, preferably C8-C20 aklylbenzene sulphonates, cellulose derivatives such as carboxymethylcellulose and homo-or co- polymeric polycarboxylic acid or their salts, nonionic surfactants, preferably C 10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol. Of these tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) are preferred. Other preferred binders include the polymeric materials like polyvinylpyrrolidones with an average molecular weight of from 12 000 to 700 000 and polyethylene glycols with an average weight of from 600 to 10 000.

Copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Others binders further include C 10- C20 mono and diglycerol ethers as well as C 10-C20 fatty acids. In the embodiment of the

present invention where a binder is desired C8-C20 alkylbenzene sulphonates are particularly preferred.

The effervescence particles used in the present invention are preferably prepared by mixing the effervescence component (s) which contribute to gas production/release, with any additional ingredients to produce an intimate mixture and then submitting the mixture to a granulation step to form particles. Any granulation process may be used, however, in order to maintain high active levels in the finished effervescence particles, the granulation should preferably take place substantially without addition of any free moisture to the mixture. A preferred agglomeration step comprises a pressure agglomeration step to form an agglomerate mixture, followed if necessary by a granulation step in which the agglomerate is formed into the effervescence particles for use in the detergent compositions of the invention. In the preferred pressure agglomeration process, the substantially dry mixture comprising the effervescence components and any optional additional ingredients is exposed to high external forces that bring the particles closely together thereby densifying the bulk mass of said particles and creating binding mechanisms between the components in the mixture. Indeed, pressure agglomeration results in an aggregation mechanism which is characterised by the presence of inter-particle bonds between primary solid effervescent particles and a structure in which these effervescence particles are still identifiable and retain many of their characteristics, e. g. the ability to react together in presence of water to deliver carbon dioxide.

The increase of density associated with the preferred processes for making the effervescence particles for use in the present invention, is closely linked to the pressure applied. Typically, the bulk density will increase up to 200g/l, preferably from 10 g/1 to 150 g/l, starting from the density of the mixture comprising the effervescent raw materials, i. e., acid and the carbonate source, and optionally the binder, before having undergone a pressure agglomeration.

Pressure agglomeration may be carried out using different processes which can be classified by the level of forces applied. A preferred process to be used herein is roller compaction. In this process the effervescence components, preferably the acid-source and the alkali-source and any optional additional ingredients after having been mixed together are forced between two compaction rolls that applies a pressure to said mixture so that the

rotation of the rolls transforms the mixture into a compacted sheet/flake. This compacted sheet/flake is then broken up to form effervescence particles.

Typical roller compactors for use herein are for example Pharmapaktor L200/50P commercially available available Hosokawa Hosokawa GmbH. GmbH. process variables variables the pressure agglomeration step via roller compaction are the distance between the rolls, the feed rate, the compaction pressure and the roll speed. A typical feeding device is a feed screw. The distance between the rolls is typically from 0.5 cm to 10 cm, preferably from 3 to 7 cm, more preferably from 4 to 6 cm. The pressing force is typically between 20 kN and 120 kN, preferably from 30 kN to 100kN, more preferably from 50 kN to 100 kN. Typically, the roll speed is between 1 rpm and 180 rpm, preferably from 2 rpm to 50 rpm and more preferably from 2 rpm to 35 rpm. Typically, the feed rate is between 1 rpm and 100 rpm, preferably from 5 rpm to 70 rpm, more preferably from 8 rpm to 50 rpm.

Temperature at which compaction is carried out is not critical, typically it varies from 0° C to 40 °C.

The sheet/flake produced by the pressure agglomeration process is broken up into effervescence particles by any suitable method for reducing the size of the sheet/flake to form particles, for example, by cutting, chopping or breaking the sheet/flake to produce the required length, and if necessary, by a process to make the particles rounded i. e. to obtain round or spherical granules according to the diameter size as defined herein before. In the preferred embodiment one way to break up the sheet/flake after the roller compaction step is to mill the compacted flake/sheet. Milling may typically be carried out with a Flake Crusher FC 2000 commercially available from Hosokawa Bepex GmbH.

Depending on the particle size required for the effervescence particles, the milled material may be sieved further. Such a sieving of the dry effervescent granules can be carried out, for example with a commercially available Alpine Airjet Screen O.

Detergent Matrix In addition to the signal component, the detergent compositions according to the invention comprise a detergent matrix which includes all of the other detergent ingredients. Generally, the detergent matrix comprises at least one pre-formed detergent matrix component which comprises surfactant, and optional additional detergent ingredients. Preferably the detergent matrix has eRH no greater than 30%. Preferably the eRH is no greater than 25%, more preferably no greater than 20% or even no greater than

15% or 12% or even 10%. The eRH can be measured using a Rotronic Hygroskop DT calibrated according to the manufacturers instructions as set out in the Rotronic Hygroskop application leaflet 2/E Spi/S dated 3.1.83, using defined saturated salt solutions which cover the humidity range to be tested. All measurements are taken at 25°C. In addition, preferably the detergent matrix has a free moisture content of no greater than 2wt%, preferably no greater than 1 wt%, and even more preferably no greater than 0.5 or 0.1 or 0.05 wt%. This low free moisture content may be achieved by drying one or more than one, or all of the components in the detergent matrix. Thus the detergent matrix component and one or more optional additional ingredients may be pre- mixed before drying or may be dried after mixing. Additional detergent matrix component and/or optional additional ingredients may then be combined with these pre- dried components without an additional drying step. In accordance with a further preferred aspect of the invention, at least one of the components in the detergent matrix (either a detergent matrix component or an additional optional detergent ingredient) is over-dried i. e. has been dried to a level such that water which is bound to one or more of the detergent ingredients either in the detergent matrix component or optional additional detergent ingredients, is removed.

In accordance with a further preferred aspect of the invention, the detergent composition comprises an effervescence system and a low density detergent matrix component having a bulk density below 400g/l.

Detergent Matrix Component The detergent matrix component comprises a pre-formed particulate which may be in the form of a powder, particle, flake or other solid form, comprising surfactant and optional additional ingredients. The surfactant may be anionic, nonionic, cationic, amphoteric, zwitterionic or mixtures thereof. Preferred detergent matrix components comprise anionic, nonionic and/or cationic surfactants. In particular matrix components which comprise anionic surfactant may be particularly useful. Suitable surfactants are described in more detail below. The surfactant content of a pre-formed matrix component is preferably from 5 to 80 % by weight of the matrix component. Amounts of surfactants above 10% by wt or even above 20 wt% or above 30 wt%, based on the total weight of the detergent matrix component, may be preferred. Amounts of surfactant below 70% or even below 50% may be preferred.

The detergent matrix component generally also comprises a solid material which may be filler such as sulphates, in particular sodium sulphate, but more preferably the detergent matrix component comprises at least one detergent ingredient, in particular, builder or alkalinity components, or mixtures of such components. Suitable examples include phosphate, aluminosilicate, crystalline layered silicates, sodium carbonate or amorphous silicates. These materials are described below in more detail. For example, each of these components individually, or in mixtures may be present in amounts above 5%, preferably above 10% or even above 20% by weight of the content of the pre-formed matrix component. Particularly preferred builder components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are both suitable.

A pre-formed matrix component preferably also comprises an organic builder such as a poly carboxylic acid and/or salt such as citric acid, tartaric acid, malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or maleic acids or co-polymers thereof. Such components are generally present in the matrix component at levels below 15 wt %, preferably below 10 wt % of the matrix component.

Other preferred ingredients in the pre-formed matrix component are optical brighteners or chelants such as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as described below. These components are preferably present in a pre-formed particulate component in amounts below 5 wt % or even below 2 wt % of the matrix component.

The detergent matrix may comprise one or more pre-formed detergent matrix components. Suitable pre-formed components may have been formed by spray-drying, agglomeration, marumerisation, extrusion or compaction, all of which methods for combining detergent ingredients are well-known in the art. Particularly preferred pre- formed matrix components are powders obtained from spray-drying processes, agglomerates and extrudates. Spray-dried powders are particularly useful. Detergent matrix components made according to at least one low shear mixing step, for example in a fluidised bed, for example by fluid bed agglomeration are also preferred.

Suitable spray-drying processes for forming such pre-formed detergent matrix components are described for example in EP-A-763594 or EP-A-437888. Suitable processes for forming detergent matrix components which are agglomerates are described

for example in W093/25378, EP-A-367339, EP-A-420317 or EP-A-506184. Suitable moderate to low shear mixers may be for example a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes, Schugi or similar brand mixers which mix with only moderate to low shear. The Lodige KM (ploughshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached. Preferably, the shaft rotates at a speed of from about 15 rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm. The grinding or pulverizing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm. Other mixers similar in nature which are suitable for use in the process include the Lodige Ploughshare TM mixer and the Drais K-T 160 mixer. Generally, in the processes of the present invention, the shear will be no greater than the shear produced by a Lodige KM mixer with the tip speed of the ploughs below 10 m/s, or even below 8m/s or even lower.

Preferably, the mean residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0.1 minutes to about 15 minutes, most preferably the residence time is about 0.5 to about 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.

Other suitable mixers for use in the present invention are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators.

Fluid bed agglomerators are particularly preferred. Typical fluidised bed agglomerators are operated at a superficial air velocity of from 0.4 to 4 m/s, either under positive or negative pressure. Inlet air temperatures generally range from-10 or 5°C up to 250°C. However inlet air temperatures are generally below 200°C, or even below 150°C. Suitable processes using a fluid bed agglomerator are described for example in W098/58046 or W099/03964. Suitable processes for forming detergent matrix components by extrusion are described for example in W091/02047.

The detergent matrix may comprise only one pre-formed component as described or it may comprise a mixture of components, for example mixtures of different spray dried powders or of different agglomerates etc or mixtures of combinations of agglomerates, spray dried powders and/or extrudates etc. as described above. In order to

obtain a detergent matrix having the desired low eRH, the detergent matrix component or mixture thereof, will have undergone drying to provide the required low moisture content.

Such drying may be provided in any conventional drying step, or may be the result of more thorough drying than is conventional using the usual processing route. For example, in the spray drying process the spray drying tower may be operated at higher air inlet temperatures for example from 300°C to 350°C or even 400°C. Alternatively, an extra drying step may be provided in which the agglomerates/spray dried powders/extrudates etc are dried by any convenient means. Suitable examples include drying ovens and fluidised bed dryers. For example, in a drying oven, the detergent matrix powder may be passed through such a drying oven on a conveyor or other convenient means. Preferably the free moisture in the detergent matrix component will be dried to below 1 wt%, more preferably below 0.5 wt%, or even below 0.1 or 0.05 wt% of the detergent matrix component. There is not necessarily a direct correlation between the free moisture content of the detergent matrix component and the eRH, so the eRH for a particular detergent matrix must be measured in order to ensure the appropriate eRH is achieved. In a particularly preferred aspect of the invention, the detergent matrix component is over-dried (i. e. at least some of the bound water which is naturally associated with one or more of the chemical constituents of the component is at least partially removed). Particularly preferred detergent matrix components are spray dried powders.

In particular in detergent compositions which comprise the effervescence system in the form of effervescence particles, the incorporation of a low density surfactant- containing detergent matrix component surprisingly promotes effervescence of the detergent, and in particular promotes both the initial effervescence and the duration of the effervescence. This can be particularly advantageous as it enables lower amounts of effervescence particle to be used in the detergent compositions of the invention to achieve the same effervescence effect. The low density detergent matrix component preferably has a bulk density of at least 100g/1, more preferably at least 120g/1.

Preferably the bulk density is below 350g/1 or even below 300g/1 or 250g/l. The median particle size of the low bulk density detergent matrix component is preferably at least 50 jj. more preferably at least 75pm and most preferably at least 100pm. Generally, the

median particle size will be below 500um, preferably below 450, um and even below 400 or 350, um.

Preferably the surfactant content in the low density detergent matrix component is at least 20 wt%, more preferably at least 25wt% and most preferably at least 30 wt% based on the total weight of the detergent matrix component. Any of the surfactants described below are suitable, preferred are any suds-generating surfactants. Anionic and/or nonionic surfactants are particularly preferred. Cationic surfactants which have good foaming properties may also be preferred. As for the other detergent matrix components described, the low density detergent matrix component preferably comprises additional ingredients which may be fillers such as sulphate or more preferably comprises additional detergent ingredients as described below. Particularly preferred additional ingredients are alkali metal carbonates, preferably sodium carbonate, silicates which may be either amorphous or crystalline, zeolites, brighteners and polymeric materials such as acrylate polymers which may be either homo or copolymers, for example copolymers of acrylic and maleic acids are particularly preferred.

Preferably the low density detergent matrix component is incorporated into the detergent compositions of the invention in amounts greater than 0.1 wt% based on the total weight of the detergent composition, more preferably in amounts greater than 2 wt% or even greater than 5 wt% or 10 wt%. Generally, the detergent compositions of the invention will contain no more than 20 wt% of the low density detergent matrix component, preferably no more than 15 wt%, or even no more than 10 wt% based on the total weight of detergent composition. Preferably the weight ratio of effervescence components to the low density detergent matrix component is from 10: 1 to 1: 10, preferably being from 5: 1 to 1: 3 and most preferably from 3: 1 to 1 : 2.

The low density detergent matrix component can be prepared by any of the methods for making the detergent matrix component as described above as long as they permit a sufficiently low density to be achieved. Spray drying processes and fluid bed agglomeration processes are particularly suitable. Spray drying processes are particularly preferred.

Additional Detergent Ingredients As described above, the detergent matrix may comprise one or more additional detergent ingredients. These may comprise detergent raw materials or may be pre-formed

particulates made by processing at least one detergent ingredient with other ingredients which may be active or inactive in the detergent to form a solid particulate. Where the particulate components are detergent raw materials, any particulate detergent ingredient is suitable. These may be solid surfactants or soaps, or water soluble or dispersible polymeric materials, enzymes, bleaching components such as bleach activators or bleach salts such as peroxy salts. Surfactants and additional detergent ingredients are discussed in more detail below. Any of the ingredients listed below may be added to the detergent compositions claimed either as individual solid particulates or as pre-formed particulates or via a detergent matrix component. These additional detergent ingredients may be incorporated into the detergent matrix if needed, having undergone a drying step.

Whether a drying step is needed depends upon the form and level of incorporation of the individual additional ingredient materials and the eRH which they and the detergent matrix component and other ingredients provide in the overall detergent matrix. In accordance with the first embodiment of the invention, the final detergent matrix must have an eRH below 30%.

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

Preferably, the particles and detergent compositions of the present invention comprises an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

The anionic surfactants may be present in the detergent matrix component in amounts below 25 wt % or even below 20 wt % but in a final detergent composition

comprising the particle, is preferably present at a level of from 0.1 % to 60%, more preferably from 1 to 40%, most preferably from 5% to 30% by weight.

Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyls") such as water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a C-C17 linear or branched alkyl or alkenyl group, RI is a C1-C4 alkyl group and M is an alkali metal ion.

Other anionic surfactants include isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(CI-C4 alkyl) and-N-(CI- C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 10-C 18 alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl sulfates and the C12-Cl4 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C l o-C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11-C 1g, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants optionally with cationic surfactant. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

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

Essentially any alkoxylated nonionic surfactant or mixture is suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

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

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are particularly suitable for use herein. Particularly preferred are the condensation products of straight or branched, primary or secondary alcohols having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: RI is H, CI-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable Cl-C4 alkyl ; and R2 is a Cs-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Suitable alkylpolysaccharides for use herein are disclosed in U. S. Patent 4,565,647, Llenado, issued January 21,1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e. g., a polyglycoside, hydrophilic group

containing from 1.3 to 10 saccharide units. Preferred alkylpolyglycosides have the formula: R20 (CnH2nO) t (glycol) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) XN0 (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof ; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C l o-C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.

Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C 16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Cationic ester surfactants such as choline ester surfactants, have for example been disclosed in US Patents No. s 4228042,4239660 and 4260529 are also suitable as are

cationic mono-alkoxylated amine surfactants preferably of the general formula I : R' ((CH2) 24o) l-5H N+ xe CH3 CH3 wherein RI is C 1 p-C 1 g hydrocarbyl and mixtures thereof, especially C10-Cl4 alkyl, preferably C I o and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

The levels of the cationic mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0.1 % to 20%, preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight.

Cationic bis-alkoxylated amine surfactant such as are also useful, wherein R 1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C12, C14 alkyl mix thereof. X is any convenient anion to provide charge balance, preterabiy-cnionde.

Bleach Activator The detergent compositions of the invention preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach. Preferably, the bleach activator is present as a separate, admixed particle.

Preferably, any bleach activator is present in a particulate component having an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. It may be preferred that at least 80%, preferably at least

90% or even at least 95 % or even substantially 100% of the component or components comprising the bleach activator have a particle size of from 300 microns to 1700 microns, preferably from 425 microns to 1400 microns. Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/or NACA-OBS. Preferred hydrophilic peroxy acid bleach precursors preferably comprises TAED.

Peroxyacid Bleach Precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as X-C (O)-L where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms. The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e. g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of :

and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R, R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.

The preferred solubilizing groups are-SO3 M,-CO'M,-SO'M,-N(RX' and 0<--N (R3) 3 and most preferably-SOoMand-CO.-,MwhereinR is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.

Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Peroxyacid bleach precursor compounds are preferably incorporated in final detergent compositions at a level of from 0.5% to 30% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10: 1 to 1: 10, more preferably from 5; 1 to 1: 5 or even from 3: 1 to 1: 3. Suitable peroxyacid bleach precursor compounds typically contain one or more N-or O-acyl groups, which

precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes.

Examples of useful materials within these classes are disclosed in GB-A-1586789.

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

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

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

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: wherein RI is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach

activator compounds of this type are described in EP-A-0170386. It can be preferred that RI and R5 forms together with the nitrogen and carbon atom a ring structure.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido- caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene-sulfonate, and the highly preferred (6-nonanamidocaproyl) oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.

Perbenzoic acid precursor compounds which provide perbenzoic acid on perhydrolysis benzoxazin organic peroxyacid precursors, as disclosed for example in EP- A-332294 and EP-A-482807 and cationic peroxyacid precursor compounds which produce cationic peroxyacids on perhydrolysis are also suitable.

Cationic peroxyacid precursors are described in U. S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U. K.

1,382,594; EP 475,512,458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No.

9407944.9 and US Patent Application Nos. 08/298903,08/298650,08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

The particles or compositions of the present invention may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 0.1% to 15% by weight, more preferably from 1% to 10% by weight. A preferred class of organic peroxyacid compounds are the amide substituted compounds as described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono-and diperazelaic acid, mono-and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Peroxide Source

Inorganic perhydrate salts are a preferred source of peroxide. Preferably these salts are present at a level of from 0.01% to 50% by weight, more preferably of from 0.5% to 30% by weight of the composition.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. Generally these materials are prepared by crystallisation or fluidised bed processes. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps. Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBO2H202 or the tetrahydrate NaBO2H202. 3H20. Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3. 3H202, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Chelants As used herein, chelants refers to detergent ingredients which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. Chelants are generally present in the detergent matrix component and/or as dry added additional detergent ingredients so that they are present in the final detergent composition at total levels of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component Suitable chelants include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine

tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1, 1 hydroxyethane dimethylene phosphonic acid.

Other suitable chelants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N- carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A- 516,102 are also suitable herein. The-alanine-N, N'-diacetic acid, aspartic acid-N, N'- diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.

Dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid are alos suitable.

Glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine- N, N'-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. In particular the chelating agents comprising a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.

Water-Soluble Builder Compound The detergent compositions herein preferably contain a water-soluble builder compound, typically present in the detergent compositions at a level of from I % to 80% by weight, preferably from 10% to 60%, most preferably from 15% to 40% by weight.

One preferred detergent composition of the invention comprises phosphate- containing builder material, preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40% by weight. Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium

polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.

Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1, 1, 3-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1,1,2,2-ethane tetracarboxylates, 1,1,3,3- propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U. S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxy-carboxylates containing up to three carboxy groups per molecule, particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e. g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.

Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000. The polyamino compounds are also useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Partially Soluble or Insoluble Builder Compound The compositions of the invention may contain a partially soluble or insoluble builder compound present in the detergent matrix component and/or the optional additional ingredients. Where present, typically they will be present in the detergent compositions in a total amount of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight. Examples of largely water insoluble builders include the sodium aluminosilicates. As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present.

Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO2) z (SiO2) y]. xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1. 0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na 12 [AlO2) 12 (Si02) xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [ (AI02) g6 (Si02) i06]. 276H20.

Another preferred aluminosilicate zeolite is zeolite MAP builder. The zeolite MAP may be present in amounts from 1 to 80%, more preferably from 15 to 40 wt%. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a median particle size dso value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The dso value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer, described herein. Other methods of establishing dso values are disclosed in EP 384070A.

Dyes, Perfumes, Enzymes, Optical Brighteners A preferred ingredient of the compositions herein are dyes and dyed particles or speckles, which can be bleach-sensitive. The dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle, or more preferably up to 0.5% by weight, as described above. The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nonionic surfactants. Optionally, the dye also comprising other ingredients such as organic binder materials, which may also be a non- aqueous liquid. The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E 104-food yellow 13 (quinoline yellow), E 110-food yellow 3 (sunset

yellow FCF), E131-food blue 5 (patent blue V), Ultra Marine blue (trade name), E133- food blue 2 (brilliant blue FCF), E140-natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/or Pigmasol Green (trade name).

Another preferred ingredient of the compositions of the invention is a perfume or perfume composition. Any perfume composition can be used herein. The perfumes may also be encapsulated. Preferred perfumes containing at least one component with a low molecular weight volatile component, e. g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition. Preferred amylases include, for example, a -amylases described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in W095/26397 and W096/23873. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight. Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by

weight, most preferably from 0.001% to 0.5% by weight. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272. Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U. S. Patent 4,810,414, Huge-Jensen et al, issued March 7,1989.

The compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above. Examples are Tinopal-UNPA-GX and Tinopal-CBS-X by Ciba-Geigy Corporation. Others include Tinopal 5BM-GXTM, Tinopal-DMS-XTM and Tinopal AMS-GXTM by Ciba Geigy Corporation.

Photo-Bleaching Agent Photo-bleaching agents are preferred ingredients of the compositions or components herein. Preferred photo-bleaching agent herein comprise a compounds having a porphin or porphyrin structure. Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin. The porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn. It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl- N-oxide, phenyl, naphthyl and anthracyl moieties. The photo-bleaching compound or component can have solubilizing groups as substituents. Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co- polymers thereof or mixtures thereof. Highly preferred photo-bleaching compounds are

compounds having a phthalo-cyanine structure, which preferably have the metal elements or cations described above.

The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4,6,8-11,13,15-18,20,22-25,27 atom positions.

Organic Polymeric Ingredients Organic polymeric compounds are preferred additional herein and are preferably present as components of any particulate component such as the detergent matrix component where they may act as binders. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/anti- redeposition agent in accord with the invention. Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions or component. Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein. Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U. S. Patent 4,968,451, Scheibel et al., and U. S. Patent 5,415,807, Gosselink et al., and in particular according to US application no. 60/051517. Another organic compound, which is a preferred clay dispersant/anti- redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:

wherein X is a nonionic group selected from the group consisting of H, C 1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e. g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.

Other dispersants/anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Polymeric dye transfer inhibiting agents when present are generally in amounts from 0.01% to 10 %, preferably from 0.05% to 0.5% and are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.

Polymeric soil release agents, hereinafter"SRA", can optionally be employed in the present components or compositions. If utilized, SRAs will generally be used in amounts from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures. Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRAs are for example as described in U. S. 4,968,451, November 6,1990 to J. J. Scheibel and E. P. Gosselink. Other SRAs include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U. S. 4,711,730, December 8,1987 to Gosselink et al. Other examples of SRA's include: the partly-and fully-anionic-end- capped oligomeric esters of U. S. 4,721,580, January 26,1988 to Gosselink; the nonionic- capped block polyester oligomeric compounds of U. S. 4,702,857, October 27,1987 to Gosselink; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U. S.

4,877,896, October 31,1989 to Maldonado, Gosselink et al. SRAs also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U. S. 3,959,230 to Hays, May 25,1976 and U. S. 3,893,929 to Basadur, July 8,1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U. S. 4,000,093, December 28,1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRAs include those described in U. S. 4,201,824, Violland et al. and U. S. 4, 240, 918 Lagasse et al.; U. S. 4,525,524 Tung et al., and U. S. 4,201,824, Violland et al.

Suds Suppressing System The detergent compositions herein, in particular when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition or component. Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component.

Such silicone antifoam compounds also typically contain a silica component. The term "silicone"as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof as described in US Patent 2,954,347, issued September 27,1960 to Wayne St.

John. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e. g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40 ketones (e. g. stearone) N-alkylated amino triazines such as tri-to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e. g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises antifoam compound, preferably comprising in combination polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound ; and silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1: 0.9 to 1 : 1. 1, at a level of from 0.5% to 10% such as DC0544, commercially available from DOW Corning, and an inert carrier fluid compound, most preferably comprising a C I 6-C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of 5 to 80%, preferably 10 to 70% by weight.

A highly preferred particulate suds suppressing system is described in EP-A- 0210731. EP-A-0210721 discloses other preferred particulate suds suppressing systems.

Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.

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

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e. g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25,1981 (herein incorporated by reference), can be present.

The detergent compositions can include as an additional component a chlorine- based bleach. However, since the detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable. Alternatively, a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process. The chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI-. Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides.

Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1, 3-dichloro-5,5- dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).

Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the

compositions of the instant invention. Some of the above materials are available as aqueous solutions.

Laundry Washing Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from l Og to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Preferred washing machines may be the so- called low-fill machines.

In a preferred use aspect the composition is formulated such that it is suitable for hard-surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.

EXAMPLES The following examples are presented for illustrative purposes only and are not to be construed as limiting the scope of the appended claims in any way.

Abbreviations used in the Examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: Sodium linear Cl 1-13 alkyl benzene sulfonate TAS: Sodium tallow alkyl sulfate CxyAS: Sodium C 1 x-C 1 y alkyl sulfate Branched AS: branched sodium alkyl sulfate as described in W099/19454 C46SAS: Sodium C14-C16 secondary (2,3) alkyl sulfate CxyEzS: Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz: Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS: R2. N+ (CH3) 2 (C2H40H) with R2 = C12-C14 QAS 1 : R2. N+ (CH3) 2 (C2H40H) with R2 = C8-C 11 APA: C8-C10 amido propyl dimethyl amine

Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluene sulphonate CFAA: C12-C14 (coco) alkyl N-methyl glucamide TFAA : C 16-C 18 alkyl N-methyl glucamide TPKFA. C 12-C 14 topped whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of formula Nal2 (A102Si02) 12.27H20 having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 : Crystalline layered silicate of formula d-Na2Si205 Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anydrous sodium carbonate: particle size 200m to 900pm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400pm and 1200go Silicate : Amorphous sodium silicate (Si02 : Na20 = 2.0: 1) Sulfate : Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425pm and 850pm MA/AA: Copolymer of 1: 4 maleic/acrylic acid, average m. wt. about 70,000 MA/AA (1): Copolymer of 4: 6 maleic/acrylic acid, average m. wt. about 10,000 AA: Sodium polyacrylate polymer of average molecular weight 4,500 CMC : Sodium carboxymethyl cellulose Cellulose ether : Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I: Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.

Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase: Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1): Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4: Sodium perborate tetrahydrate of nominal formula NaB02. 3H2 O. H202- PB 1 : Anhydrous sodium perborate bleach of nominal formula NaB02. H 202 Percarbonate: Sodium percarbonate of nominal formula 2Na2CO3. 3H202 NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt NAC-OBS: (6-nonamidocaproyl) oxybenzene sulfonate TAED: Tetraacetylethylenediamine DTPA: Diethylene triamine pentaacetic acid DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDS : Ethylenediamine-N, N'-disuccinic acid, (S, S) isomer sodium salt.

Photoactivated bleach: Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin-sol. pol.

Photoactivated bleach: Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis (2-sulphostyryl) biphenyl Brightener 2 : Disodium 4,4'-bis (4-anilino-6-morpholino-1.3.5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate HEDP : 1, 1-hydroxyethane diphosphonic acid PEGx : Polyethylene glycol, with a molecular weight of x (typically 4,000)

PEO: Polyethylene oxide, with an average molecular weight of 50,000 TEPAE: Tetraethylenepentaamine ethoxylate PVI: Polyvinyl imidosole, with an average molecular weight of 20,000 PVP: Polyvinylpyrolidone polymer, with an average m. wt. of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with an av. m. wt. of 50,000 PVPVI: Copol of polyvinylpyrolidone and vinylimidazole (av. m wt of 20,000) QEA: bis ( (C2H50) (C2H40) n) (CH3)-N+-C6H 12-N+-(CH3) bis ((C2H50)- (C2H4 O)) n, wherein n = from 20 to 30 SRP 1 : Anionically end capped poly esters SRP 2: Diethoxylated poly (1,2 propylene terephthalate) short block polymer PEI: Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1 Opacifier : Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax: Paraffin wax HMEO: Hexamethylenediamine tetra (ethylene oxide) 24 Example 1: Preparation of Effervescence Particle A 2 kg batch of citric acid and sodium carbonate having a composition of 64wt% citric acid/36 wt% sodium carbonate was prepared by mixing in a Hosokawa Mikron 'Nautamix'DBY-5R rotating screw mixer for five minutes at a speed setting of 9 (maximum): 1280 g anhydrous citric acid ex Citrique Belge (Fine Granular Grade: 16/40) having a particle size of from 200-400pm and 720g anhydrous Sodium Carbonate (Light Soda Ash ex Brunner Mond) pre-milled using a Hosokawa Mikron Air- Classifying Mill (ACM 15) to a median particle size of 5 urn. The mixture was then compacted in a Bepex Compaction Unit (Roll 200mm Diameter, 50mm Width): the pre- mixed powders were poured into the feed-hopper above the compacting rolls. The feed- hopper has a vertical screw which feeds the powder into the rolls. The force applied to push these two rolls together known as compaction force was adjusted to 80kN by adjusting the feed-screw speed. The compacted material was collected in the form of

broken and unbroken corrugated sheets which were then milled in a Hosokawa Bepex F200 Flake Breaker at speed setting 1. This equipment consists of a Rolling Cage with a 1000pm Screen.

The material produced by the Flake breaker was then placed on a Vibrating Sieving device (Retsch model AST200) with sieve size of 355pm. The material retained on the screen was the desired finished particle (effervescence particle A in the table below) with median particle size 620ßm, and the fines were removed for recycle.

The process is repeated using the following mixtures of components in the quantities (respective amounts are given in wt% based on the effervescence particle) given in table 1, to make alternative effervescence particles B-E.

Table 1 Effervescence B C D E Particle Citricacid 40 10 55 Malicacid 20 30-35 Tartaric acid---15 Sodium 25 70-40 carbonate Sodium 15-45 10 bicarbonate l riese ettervescence particles are then incorporated into detergent compositions as set out in Examples 2 to 6.

Example 2 A spray dried granule, having the composition set out in example 3 below, produced by forming an aqueous slurry which is then formed into particulates in a spray-drying tower is then mixed with, 5 wt% TAED, 1 wt% suds suppressor, 7.5 wt% sodium carbonate and 2.5 wt% sodium sulphate, as additional detergent ingredients in an Eirich mixer. An aqueous solution of PEG-4000 (35% by weight solids) is then sprayed onto the mixture, which is allowed to granulate for 5 minutes. The resultant product is screened to collect particles between 300 and 1200 microns. 10 wt% sodium percarbonate, 0.5 wt% perfume and 1 wt% enzymes (comprising a mixture of prills comprising amylase, cellulase, protease and lipase) are then dry added and mixed. The mixture produced has an eRH of

59%. 10 wt% effervescence particles of any of formulations A to E or mixtures of these are then added to this mixture in a Nautamix conical mixer and subsequently packed into detergent cartons.

Example 3 A spray dried granule is produced on a counter-current spray drying tower with an air inlet temperature of 300°C. Agglomerates and other admixes (see Table 2) are mixed with the spray dried granule in a batch rotating drum mixer. The detergent matrix has an eRH of 38%. The effervescence particle A is then added, and the product is then packed into detergent cartons. Further examples of detergent compositions according to the invention may be prepared by the use of effervescence particles B to E or mixtures of any of the particles A to E.

Table 2 Spray dried Granule 50% Spray dried granule composition % Weight of Total Feed LAS 10.4 Tallow Alkyl Sulphate 1.6 EDDS 0.4 Brightener 15 0.1 Magnesium sulphate 0.7 Sokalan CP5 2.5 HEDP 0.3 Sodium carbonate 8.4 Sodium sulphate 23.5 Zeolite A 40.0 Misc. (water, perfume, etc.) 12.07 100.0 Anionic surfactant agglomerate 10% Agglomerate composition % Weight of Total Feed C45 alkyl ethoxylate sulfate (EO 0.6) 29.1 Zeolite A 45. 0 Sodium carbonate 15.1 Polyethylene glycol (MW 4000) 1.3

Misc. (water, perfume, etc.) 9. 5 100.0 Percarbonate 10% TAED 5% Effervesence granule 10% Minors 15% Example 4 Example 3 is repeated except that the spray dried granule is dried at the higher tower inlet temperature of 350°C and some of the bound moisture is removed. In this case the detergent matrix eRH was 24%.

Example 5 The detergent matrix of example 3 is reproduced and to it is added 5% of overdried zeolite in a Nautamix conical mixer. (Overdried zeolite is a Zeolite A which has had more than half of the water of crystallisation removed by additional drying). The resulting detergent matrix has an eRH of 12%. 10% of effervesence particle B is then added to this matrix and the product packed into detergent cartons. Alternative examples can be prepared by the use of any of effervescence particles B to E or mixtures of any of particles A to E.

Example 6 Spray dried particles, agglomerates and builder agglomerates of the formulation described in Tables 3A and 3B below are fed first into a Lodige KM 600 mixer at 660 kg, with the drum rotation at 100 RPM and cutter speed at 3600RPM. The resulting mixture is fed into a fluid bed dryer. Optionally an aqueous solution of PEG-4000 (30% by weight solids) is sprayed onto the mixture in the first of three stages in the fluid bed dryer. The resulting product is screened to collect the particles in the range of about 600 to about 1100. The fines are recycled to the Lodige KM and the large particles are ground and recycled to the fluid bed dryer. The dry-add detergent components and spray- on from the tables below are then added. The detergent matrix eRH was typically around 14%.

TABLE 3 A The following compositions are in accordance with the invention. Spi G Spray-dried Granules AS 10.0 10.0 15.0 5. 0 8. 0 10. 0 TAS - 1.0 - - - - MBAS - - 5.0 8.0 - - - C45AS - - 1.0 1.0 2.0 - - - C45AE3S - - 1.0 - - - QAS 1.0 1.0 - - - DTPA, HEDP and/or 0. 3 0. 3 0. 5 0. 3 EDDS gSO4 0.5 0.5 0.1 Sodium citrate - - - 3.0 5. 0 Sodium carbonate 10.0 7.0 15.0 10.0 10.0 Sodium sulphate 5.0 5.0 - - 5. 0 3.0 Sodium silicate 1.6R----2. 0 ZeoliteA 16.0 18.0 20.0 20.0 SKS-6 - - - 3.0 5.0 MA/AA or AA 1. 0 2. 0 11. 0 2. 0 EG 4000 - 2.0 - 1.0 - 1. 0 QEA 1.0 - - - 1.0 - - - - Brightener 0.05 0.05 0.05 - 0.05 - - - - Silicone oil 0. 01 0. 01 0. 01 - - 0.01 lomerate LAS 2. 0 2. 0 BAS - - - - - - 1.0 C45AS. 0 E3 - - - - - 1.0 0.5 Carbonate - - - 1.0 1.0 1.0 Sodium citrate - - - - - - 5.0 0 CFAA - - - - - Citric acid - - - 4.0 - 1.0 1.0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1. 0 1. 0 0. 2 Zeolite A - - - 15. 0 26. 0 15.0 16.0 Sodium silicate EG - - - - - - 4. Agglomerates uilder A lomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10. 0 AS 4.0 5.0 - - 5.0 3.0 - 10.0 12. 0 -add particulate components Effervescence Particle 8. 0 10. 0 12. 0 2. 0 4. 0 Effervescence Particle 10. 0 Effervescence Particle 4. 0 C Effervescence Particle 8.0 Effervescence Particle 2. 0 QEA - - - 0.2 0.5 NACAOBS 3. 0 1. 5 2. 5 OBS - 3.0 3.0 - - - - - 5.0 AED 2.5 - - 1.5 2.5 6.5 - 1.5 - BAS - - - 8.0 - - 8.0 - 4. 0 LAS (flake) 10. 0 10. 0 8. 0 Spray-on rightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 ye - - - 0.3 0.05 0.1 - - AE7 0. 5 0. 7 Perfume 0. 8 0. 5 0. 5 Dry-ad Citrate 0. 0. 0 5. 0 15. 0 5. 0 Percarbonate 15.0 3.0 6. 0 10.0 - - - 18. 0 5. 0 Perborate----6. 0 18. 0 hotobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0. 03 Enzymes (cellulase, 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, lipase) Carbonate 0.0 10.0 - - - 5. 0 8.0 10. 0 5. 0 Perfume (encapsulated) 0. 6 0. 5 0. 5-0. 3 0. 5 0. 2 0. 1 0. 6 Suds suppressor 1.0 0.6 0.3 - 0. 10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 Citric acid 6. 0 6. 0 5. 0 Dyed carbonate (blue, 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 green) SKS-6. 0 6. 0 Fillers up to 100% TABLE III B The following compositions are in accordance with the invention. C F G Spray-Dried Granules @AS 10.0 10.0 16.0 5.0 5.0 10.0 TAS - 1.0 - MBAS 5 0 5. 0 C45AS 1. 0 2. 0. 0 C45AE3S 1. 0 QAS - - 1.0 1.0 DTPA, HEDP and/or 0. 3 0. 3 0. 3 0. 3 EDDS gSO4 0.5 0.4 0.1 Sodiumcitrate 10.0 12.0 17.0 3.0 5.0 Sodiumcarbonate 15. 0 8. 0 15. 0 10. 0 Sodium sulphate 5.0 5.0 - - 5.0 3. 0 Sodium silicate 1.6R---2. 0 ZeoliteA. 0 SKS-6 - - - 3.0 5.0 MA/AA or AA 1. 0 2. 0 10. 0 - - 2. 0 EG 4000 - 2.0 - 1.0 - 1. 0 PEG 4000 - 2.0 - 1.0 - 1.0 - - - QEA 1.0 - - - 1.0 - - - - Brightener 0.05 0.05 0.05 - 0.05 - - - - Siliconeoil 0.01 0.01 0.01 - - 0.01 Agglomerate LAS - - - - - - 2.0 2.0 - MBAS - - - - - - - - 1.0 C45AS 0- AE3 - - - - - - - 1.0 0.5 Carbonate - - - - 4.0 1.0 1.0 1.0 - Sodium citrate 5. 0 CFAA Citric acid - - - - - 4.0 - 1.0 1.0 QEA - - - - - 2.0 2.0 1.0 - SRP - - - - - 1. 0 1.0 0. 2 Zeolite A 15. 0 26. 0 15.0 16.0 Sodium silicate PEG 4 0 Builder Agglomerate SKS-6 6.0 5.0 - - 6.0 3.0 - 7.0 10.0 AS. 0 5. 0 5. 0 3. 0 10. 0 12. 0 -add particulate components Effervescence Particle 8.0 4.0 4.0 - 2.0 2.0 4.0 Effervescence Particle 10. 0 Effervescence Particle 8.0 QEA - - - 0.2 0.5 - - - - MACAOBS 3.0 - - 1.5 - - - 2.5 - NOBS - 3.0 3.0 - - - - - 5.0 TAED 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (flake) 8. 0 Spray-on rightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 Dye - - - 0.3 0.05 0.1 - - - AE7 0. 5 0. 7 erfume - - - 0.8 - 0.5 - 0.5 dry-sadd Citrate 4.0 - 3.0 4.0 - 5.0 15.0 5. 0 ercarbonate 15. 0 3. 0 6. 0 10. 0 18. 0 5. 0 Perborate 6. 0 18. 0 hotobleach 0. 02 0.02 0.02 0. 1 0.05 - 0.3 - 0.03 Enzymes (cellulase, 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, lipase) Carbonate - - - - - 5.0 8.0 10.0 5.0 Perfume (encapsulated) 0. 6 0. 5 0. 5 0. 3 0. 5 0. 2 0. 1 0. 6 Suds suppressor 1.0 0.6 0.3 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 Citric acid 6. 0 6. 0 5. 0 Dyed carbonate (blue, 0.5 0.5 - 2.0 - 0.5 0.5 0.5 1.0 green) SKS-6 - - - 4.0 - - - 6.0 Fillers up to 100%

Noise data was obtained for the examples of the invention and it was found that using levels of effervescence particle A as low as 1 wt% based on the weight of the detergent composition, the noise level rose to approximately 49 dB and that for use of levels of effervescence particle A at 10 wt% based on the weight of the detergent composition, the noise level rose to as high as 55dB.