EP1187905A1 - Detergent particles and methods for making them - Google Patents

Abstract

Detergent particles formed from irregular colour, size and shape individual particulate components. At least two particulate components, a first component of a first colour and a second component of a second colour, the first and second components are adhered to one another, the mean particle size of at least the first or second particulate component being no more than 50% of the mean particle size of the detergent particle to give particles of desirable colour. In addition, a detergent particle having sphericity index no greater than 1.7 and/or narrow particle size distribution from particulates where one has a sphericity index greater than 1.7 or at least one of the first and second particulate components has a span of at least 2. The detergent particles are produced substantially in the absence of pressure compaction. Also provided is a method for making the detergent particles described and detergent compositions comprising these detergent particles.

Description

DETERGENT PARTICLES AND METHODS FOR MAKING THEM

Field of the mvention The present invention relates to particulate detergent compositions and methods for making them Such detergent compositions may be used for any cleaning purposes, m particular for dish-washmg or laundry detergents They may be used directly in the form of particulate detergent compositions or alternatively, may be formed into tablets of detergent composition using any of the well known tablettmg methods such as compaction.

Background of the Invention In order to meet the needs of the consumer, particulate detergents must meet several criteria in addition to providing good cleaning properties Such additional cπteπa include- good flow properties so that they can be easily delivered from the container to the washing machine or washing process; good solubility/dispensing so that they will be delivered into the wash effectively; and in addition, particulate detergents must appeal to the consumer aesthetically. Most particulate detergents comprise a primarily white or pale-coloured base with optional colour-contrasting speckles. It has been found that detergents where the base particles vary in hue are judged by the consumer to be undesirable and are even thought by the consumer to provide less effective cleaning.

However, since detergent compositions generally comprise pre-processed detergent components such as agglomerates, blown powder produced by spray drying processes or extrudates, in addition to raw mateπals, and because the raw materials themselves vary so much m colour, size and or shape, significant efforts must be made to avoid non-uniformity. In order to address this, considerable efforts and high costs are required to provide detergent particulates with uniform properties. It would therefore be desirable to find a method for making detergents which enable use of a wider range of active detergent materials such as those with wide vanations of colour, shape and/or size, yet to produce detergent particles with good flow properties and good dispensing and dissolving properties in addition to good aesthetic properties.

The present inventors have now found improved particles and methods for making such particles which overcome these problems of the prior art. Summary of the Invention In accordance with the present invention, there is now provided a detergent particle compnsmg at least two particulate components, a first component of a first colour and a second component of a second colour, the first and second components being adhered to one another, the mean particle size of at least the first or second particulate component being no more than 50% of the mean particle size of the detergent particle

In accordance with a further aspect of the present invention there is provided a detergent particle having a sphericity index no greater than 1 7 compnsmg at least two particulate components, a first component and a second component, at least one of the first and second components having a sphericity index greater than 1 7, the first and second components being adhered to one another substantially in the absence of pressure compaction.

In accordance with a further aspect of the present invention there is provided a detergent particle having a geometric mean particle diameter greater than 500 microns, the detergent particle compnsmg a first particulate component and a second particulate component, the first and second particulate components being adhered to one another substantially in the absence of pressure compaction, the geometric mean particle size of at least one of the first and second components being no more than 50 % of the geometric mean particle size of the detergent particle. Preferably at least one of the first and second particulate components has a span of at least 1.7. In accordance with the present invention, there is also provided a method for making the detergent particles described, comprising contacting the first particulate component and the second particulate component, optionally in the presence of a binder in a moderate to low shear mixing step to adhere the first and second particulate components to one another and detergent composition comprising the claimed detergent particles. Detailed Descnption of the Invention

The present inventors have found that by selecting a combination of first and second particulate detergent components and forming these into a single particle, the undesirable properties and lack of uniformity can be overcome. Furthermore, these benefits can be achieved without the intensive processing steps which have been used in the prior art, such as formation of particulates from pastes which require lengthy, energy intensive mixing such as high shear mechanical mixing and even extrusion, both of which use compaction pressure to form particulates and require energy intensive drying processes.

In accordance with a first aspect of the present invention, the first and second particulates are differently coloured from one another. Colour difference as used herein refers to the ΔE value as measured using tπ-stimulus colonmetry using a D25M Colorimeter manufactured by Hunter Laboratories. In such a colonmeter, L, a and b values are generated for a sample by directing incident light onto a sample of powder at a 45° angle. Incident light is reflected from the sample and collected by photo detectors which are set vertically above the powder sample at 0°. The detectors convert the light intensity into tπ-stimulus values (X,Y,Z) as documented by Commission Internationale de l'Eclairage (CUE). These values are then used to form a descnptive colour term on a standard CIELAB colour scale. The method is well documented, for example, in "Industrial Color Technology" by R Johnston and M Saltzman, American Chemical Society, 1971. Using the CIELAB colour scale, L expresses whiteness where L=100 for white samples and L=0 for black samples; a represents red/green where positive numbers indicate redness and negative numbers indicate colours towards the green end of the spectrum; and b represents yellow/blue where positive numbers indicate yellowness and negative numbers indicate blueness. Thus for the present invention, colour difference is a positive ΔE value between samples of the first and second particulate components where

ΔE = V(ΔL² + Δa² + Δb²), where ΔL is the difference in L value between the first and second particulate components, Δa is the difference in a value between the first and second particulate components and Δb is the difference in b value between the first and second particulate components. In particular, in the invention there will generally be a ΔE value of at least 3. The invention is particularly useful for even larger colour differences such as ΔE values of at least 4, or even at least 6 or 8 or even at least 10. A further useful colour definition is whiteness which is represented by W=L-3b. A whiteness value of from 92 to 100 is preferred for the detergent particles of the invention.

As used herein, "sphericity index" refers to the mean value obtained when one measurement is taken of each of 50 particles taken from a sample of particles (either the detergent particles produced according to the invention, or the first or second partiuclates which form the detergent particles), and the value for sphericity index is calculated for each particle based on the following equation: sphericity index = p²/(4πa), where p is the penmeter of the particle and a is the area of the particle as measured usmg a Leica Q500MC image analysis system. The apparatus consists of a microscope connected to a video camera and computer

Commercially available software such as the Q500 software supplied by Leica is used to analyse the magnified images and to give values for p and a. The sphericity index of a perfect circle is 1. Thus, in accordance with a further aspect of the invention, the sphencity index of the detergent particle is no greater than 1.7 and the sphencity index of at least one of the first and second particulate components is at least 1 7. Preferably the standard deviation of the span of the detergent particles of the invention is less than 0.8, preferably less than 0.5 and most preferably below 0.2.

The sphericity index of the detergent particles according to the invention is preferably no greater than 1 5, more preferably no greater than 1.3 or even 1.2. The spheπcity index of at least one of the first and second particulates is preferably greater than 1.9 or even greater than 2.1 or even greater than 2.5 Thus, the invention enables highly irregular components to be adhered together to form a highly regular detergent particle without the need for high energy compaction pressure processing via aqueous pastes or slurries such as m extrusion or high shear mixing processes. The invention is even useful when both the first and second particulates comprise highly irregular particles, so that preferably, the sphericity index of both the first and second particulates is greater than 1.9 or even greater than 2.1 or 2.5 or even 3. As used herein, "geometric mean particle diameter" 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. A suitable sieving method is m accordance with ISO 31 18 (1976). A suitable device is the Ro-Tap testign sieve shaker Model B using 8" sieves of selected sizes. 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 50^th percentile of the cumulative distribution (D_{g4 13}/D₅₀); See Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997. In accordance with a third aspect of the present invention, the geometric mean particle diameter of at least the detergent particle is at least 500 microns and the geometric particle diameter of at least one of the first and second particulate components is no more than 50% of the geometric mean particle diameter of the detergent particle, preferably no greater than 25% or even no greater than 10% or 5%. Preferably, the geometric mean particle diameter of both the first and second particulate components is as defined. In addition, at least one of the first and second particulate components has a span (geometric standard deviation) of at least 1.7, or even at least 2 or 2.5 or at least 3 or at least 3.5 or even at least 4 or at least 5. Preferably, the span of both the first and second particulate components is as defined. The invention is particularly useful for forming detergent particles having a span at least 0.3, preferably at least 0.4 or even at least 0.5 or greater, below the span of the first and/or second particulates. Thus, in trying to achieve highly regular detergent particles, rather than using as raw matenals for the processing, highly regular matenals and high energy processes, the present inventors have found that the process of the present invention enable highly irregular, less energy intensive raw matenals to be used in a less energy intensive process to produce high quality, high regularity detergent particles.

The particle sizes of the first and second components can vary widely. The invention has been found to be useful even where there is a difference in geometric mean particle diameter between the first and second particulate components of at least 200 microns or even of at least 250 or 300 or even at least 400 or even at least 500 microns. Preferably one or both of the first and second particulates has a geometric mean particle diameter below 550μm. It is particularly preferred that at least one of the first and second particulate components has a geometric mean particle diameter greater than 150μm or even greater than 200μm and preferably no greater than 450μm or even no greater than 400μm. In one embodiment of the invention, the ratio of the mean particle sizes of the first and second particulate components respectively will be at least 3.2, preferably at least 2:1 or even a high ratio of at least 5 : 1 or at least 10:1. The ratio may be even higher such that the ratio is at least 20:1 or even at least 50:1. Where the ratio is high it is preferred that the relatively smaller particulate component has a colour which is most desirable relative to the colour of the other particulate component. It may also be preferred that the smaller particle diameter particulate component the smaller sphericity index

In addition, the process of the present invention is suitable for forming detergent particles from first and second particulates each having a wide span of bulk densities and having bulk densities which vary significantly from one that of one another. As used herein the term "bulk density" refers to the uncompressed, untapped powder bulk density, as measured by pounng an excess of particulate sample through a funnel into a smooth metal vessel (e.g. a 500ml volume cylinder) scraping off the excess off the heap above the nm of the vessel, measuπng the remaining mass of powder and dividing the mass by the volume of the vessel.

The bulk density of the first and second particulate components may differ by at least 25 g/1, or even by at least 75 g/1 or at least 100 g/1. The bulk density of the first and second particulate components, respectively is generally above 200 g/1 and may be as high as 1500 g/1. It is particularly preferred that the bulk density of at least one particulate component will be greater than 700 g/1, preferably greater than 750 g/1 or even above 800 g/1. The bulk density of the detergent particles of the invention will generally be from 400 to 1 lOOg/l, generally the bulk density will be above 550 g 1, preferably greater than 650 g/1 or even greater than 700 g/1 The invention may be particularly useful for prepaπng detergent particles having bulk density below 550g/l, or even below 500 or below 450g/l. Each of the first and second particulate components may compnse an individual detergent ingredient in particulate form or may comprise a pre-formed detergent particulate. As used herein, the pre-formed particulate may comprise any combination of two or more detergent ingredients. Suitable pre-formed particulates may have been formed by a spray-drymg, agglomeration, marumeπsation, extrusion or compaction process, all of which methods for combining detergent ingredients are well known m the art. Particularly preferred pre-formed particulates are powders obtained from spray-drymg processes, agglomerates and extrudates Spray dned powders are particularly useful.

Suitable spray-drymg processes for forming such pre-formed particulates are descnbed for example in EP-A-763 594 or EP-A- 437888. Suitable processes for forming pre-formed particulates which are agglomerates are described for example in W093/25378, EP-A-367339, EP-A-420317 or EP-A-506184 and suitable processes for forming pre-formed particulates by extrusion are described for example in W091/02047.

The pre-formed particulates may be m their wet or dry states for example, it is common in formation of detergent particulates that initially, the particulates are wet and undergo a drying stage. In the present invention, the pre-formed particulate may be a particulate before it has undergone a drying stage. Generally this means that a solvent used as a binding agent for the processing is present in higher amounts that are desirably present in a finished particulate detergent. Generally, such a solvent will be water and the particulates may have a water content for example 15 to 30 wt % of the pre-formed particulate. Often however, the pre-formed particulate will already have undergone a drying step pnor to addition to the mixer so that the water content may be below 15 wt % or even below 10 wt %.

It is particularly preferred that any pre-formed particulate component compnses a surfactant or mixture of surfactants. Suitable surfactants are descnbed below. The surfactant content of a pre-formed particulate component is preferably from 5 to 80 % by weight of the particulate component. Amounts of surfactants above 10 or even above 30% may be preferred. Amounts of surfactant below 70% or even below 50% may be preferred Where the pre-formed particulate component compnses surfactant, generally it will in addition comprise a builder or alkalinity agent such as sodium carbonate, zeolite, or phosphate. 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 particulate component. Particularly preferred builder components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are both suitable.

A pre-formed particulate 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 particle at levels below 15 wt % of the particulate component, preferably below 10 wt % of the particulate component.

Other preferred ingredients in the pre-formed particulate component are chelants such as phosphonate chelants NT A, DTPA and succmic acid derivative chelants, as descnbed below. These components are preferably present in a pre-formed particulate component m amounts below 5 wt % or even below 2 wt % of the first particulate component. Suds suppressors and/or soil release polymers and/or bleach activators are also preferred ingredients in pre-formed particulates. 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 dispersable polymenc matenals, enzymes, bleaching components such as bleach activators or bleach salts such as peroxy salts, but are generally inorganic components, particularly water soluble inorganic components such as builders. These ingredients are discussed in more detail below. The detergent particles themselves may contain all of the ingredients of a full formulated detergent or may be mixed with additional detergent components such as individual detergent ingredients in particulate form or pre-formed detergent particles as descπbed above. Preferably, detergent compositions of the present invention comprise more than 30 wt%, more preferably more than 50 wt% or even as high as 80 or 90 wt% or even at least 95 wt% of the detergent particles according to the present invention.

The processes of the invention may comprise the step of adding to the mixer a binder to facilitate production of the desired detergent particles. Generally such a binder will be liquid in the form of a solution or melt and will be added by spraying either directly mto the mixer or onto the particulate components as they travel mto the mixer. Preferably the binder is added directly into the mixer for example by spraying. The binder is added for purposes of enhancing agglomeration by providing a binding or sticking agent for detergent components. The binder may be any conventional detergent binding agent, preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvmyl pyrrolidone, polyacrylates, organic acids or their salts such as citnc acid or citric salts, and mixtures thereof. Other suitable binder materials including those listed herein are described m Beerse et al, US Patent number 5108646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference.

Thus, in one aspect of the invention, a first feed stream of first particulate component is fed into the mixer and in addition a second feed stream comprising the second particulate component is fed into the mixer and binder is also present in the mixer. The binder may be fed directly via a third stream mto the mixer or it may be contacted with the first and/or second particulate component prior to one or both of these feed streams entering the mixer. Where the mixer is divided into different zones, the three components may be fed into the same zone or optionally may be fed into different zones. In a preferred embodiment of the invention, the first and second particulate components will be pre -mixed prior to addition of the binder.

In a further preferred aspect of the invention, after mixing of the first and second particulate components optionally with binder, so that adhesion of the two components has taken place, a further liquid component is applied to the outside of the particles produced. This further coatmg may be the same chemical composition as the binder or may be any of the other coatmg materials or detergent ingredients descnbed below.

In order to provide the moderate to low shear mixing which the first and second particulates are adhered to one another m the present invention, 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 compnses 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™ 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 vanous starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0.1 seconds to about 30 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 0.1 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. The fluidized bed granulator is preferably operated such that the flux number FN of the fluid bed is at least about 2.5 to about 4.5. Flux number (FN_m) is a ratio of the excess velocity (U_e) of the fluidisation gas and the particle density (p_p) relative to the mass flux (qι,_q) of the liquid sprayed into the bed at a normalized distance (D₀) of the spraying device. The flux number provides an estimation of the operating parameters of a fluidized bed to control granulation with the bed. The flux number may be expressed either as the mass flux as determined by the following formula:

FN_m = log₁₀[{PpU_e}/q_hq]

or as the volume flux as determined by the formula:

FN. = log₁₀[{U_e}/q_vι_lq]

where q_{v g} is the volume of spray into the fluid bed. Calculation of the flux number and a descnption of its usefulness is fully descπbed in WO 98/58046 the disclosure of which is herein incorporated by reference.

In addition, the fluidized bed is generally operated at a Stokes number of less than about 1, more preferably from about 0.1 to about 0.5. The Stokes number is a measure of particle coalescence for descnbmg the degree of mixing occurring to particles m a piece of equipment such as the fluid bed. The Stokes number is measured by the formula:

Stokes number = 4pvd/9u wherem p is the apparent particle density, v is the excess velocity, d is the mean particle diameter and u is the viscosity of the binder. The Stokes number and a descnption of its usefulness is described in detail in WO 99/03964, the disclosure of which is herein incorporated by reference. Thus, where the mixer is a fluid bed mixer, the first and second particulate components are passed mto a fluid bed optionally having multiple internal "stages" or "zones" A stage or zone is any discrete area with the fluid bed, and these terms are used interchangeably herem The process conditions withm a stage may be different or similar to the other stages in the fluid bed dryer. It is understood that two adjacent fluid beds are equivalent to a single fluid bed having multiple stages The various feed streams of the first and second particulate components can be added at the same or different stages, depending on, for example, the particle size and moisture level of the feed stream Feeding different streams to different stages can minimize the heat load on the fluid bed, and optimize the particle size and increase uniformity of the shape of the detergent particles produced.

The bed is typically fluidized with heated air in order to dry or partially dry moisture such as any binder liquids from the ingredients m the fluid bed Where binder is sprayed into the fluid bed the spraying is generally achieved via nozzles capable of deliveπng a fine or atomized spray of the binder to achieve intimate mixing with the particulates Typically, the droplet size from the atomizer is less than about 2 times the particle size. This atomization can be achieved either through a conventional two-fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle To achieve this type of atomization, the solution or slurry rheology is may have a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise at the point of atomization While the nozzle location in the fluid bed may be m most any location, the preferred location is a positioning that allows a vertical down spray of any liquid components such as binder This may be achieved for example, using a top spray configuration. To achieve best results, the nozzle location is placed at or above the fluidized height of the particles in the fluid bed. The fluidized height is typically determined by a weir or overflow gate height. The agglomeration/granulation zone of the fluid bed may be followed by an optional coating zone, followed by a drying zone and a cooling zone. Of course, one of ordinary skill in the art will recognize that alternative arrangements are also possible to achieve the resultant particles of the present invention.

Typical conditions within a fluid bed apparatus of the present mvention mclude: (l) a mean residence time from about 1 to about 20 minutes, (n) a depth of unfluidised bed of from about 100 to about 600 mm, (in) a droplet spray size of less than 2 times the mean particle size in the bed, which is preferably not more than about 100 micron more preferably not more than 50 micron, (iv) spray height generally from 150 to 1600 mm of spray height from the fluid bed plate or preferably 0 to 600mm from the top of the fluid bed , (v) from about 0.1 to about 4.0 m/s, preferably 1.0 to 3.0m/s of fluidizing velocity and (vi) from about 12 to about 200 °C of bed temperature, preferably 15 to 100°C Once again, one of ordinary skill in the art will recognize that the conditions the fluid bed may vary depending on a number of factors.

The detergent particles produced in the mixer can be further processed by adding a coating agent to improve the particle colour, increase the particle whiteness or improve the particle flowability after the detergent particles exit the mixer or the dryer if an optional drying step is added subsequently to the mixer or in a later stage in the mixer, to obtain the high density granular detergent compositions produced by the processes of the invention. Those skilled in the art will appreciate that a wide variety of methods may be used to dry as well as cool the exiting detergent without departing from the scope of the invention. Since the mixer can be operated at relatively low temperatures, the need for cooling apparatus is generally not required in the present process which thereby further reduces manufacturing costs of the final product.

Another optional processing step includes continuously adding a coatmg agent such as zeolite and or fumed silica to the mixer to facilitate free flowability of the resulting detergent particles and to prevent over agglomeration. Such coating agents generally have a mean particle size below 100 microns, preferably below 60 microns, even more preferably below 50 microns. Any coatmg stage may take place either immediately after formation of the detergent particles of the mvention either before or after any drying step and optionally after the detergent particles have been mixed with additional detergent ingredients for forming a fully formulated detergent composition. Preferably any such coating agent will also have detergent active properties. A particularly preferred coating agent is a surfactant or aqueous solution of surfactant.

The detergent particles produced according to the present invention preferably have a geometric mean particle diameter of at least 500 microns or at least 600 or even at least 700 microns. Generally the mean particle diameter will be no greater than 3000 microns, preferably no greater than 2500 or even no greater than 1500 microns. The spheπcity index of the detergent particles according to the present invention will preferably be no greater than 1.5 or even no greater than 1.4 or 1.3 or even no greater than 1.2. The span of the detergent particles according to the mvention is generally from 1 to 1.8, preferably no greater than 1.7, most preferably no greater than 1.6 or even 1.4. The weight percentage of the detergent particles derived from the first and second particulate components respectively may be in a ratio of from 100: 1 to 1 : 100. Where the geometric mean particle diameter of a desirably coloured particulate component is no more than 10% or even no more than 5% of the geometπc mean particle diameter of an undesirably coloured particulate the weight ratio will be low, but the number average of particles of the desirably coloured component in the detergent particle will generally be at least 50, preferably at least 100 or even 500 or 1000 times the number average of the undesirably coloured component in the detergent particle.

Detergent ingredients which are suitable as ingredients of the first particulate component or the second particulate component and/or as ingredients of any additional ingredients added to the detergent particles of the present invention to form the fully formulated detergent compositions of the invention, are descnbed below.

Detergent Ingredients Surfactant Suitable surfactants for use m 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 Heuπng on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and TJ 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 detergent particle of the present invention and compositions compnsmg such particles compπses an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be compπsed in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and tπethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosmate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

The anionic surfactants may be present in the detergent particle m amounts below 25 wt % or even below 20 wt % but m 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-l- undecanoic acid, 2-ethyl-l-decanoιc acid, 2-propyl-l-nonanoιc acid, 2-butyl-l-octanoιc acid and 2-pentyl-l-heptanoιc acid. Certain soaps may also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosmates of formula R-CON (R*) CH2

COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R^ is a Ci -C4 alkyl group and M is an alkali metal ion. Other anionic surfactants include lsethionates such as the acyl lsethionates, N-acyl taurates, fatty acid amides of methyl taunde, alkyl succinates and sulfosuccinates, monoesters of sulfosuccmate (especially saturated and unsaturated C. -,-C, monoesters) diesters of sulfosuccmate (especially saturated and unsaturated C_^-C, . diesters), N- acyl sarcosmates. Resin acids and hydrogenated resm acids are also suitable, such as rosin, hydrogenated rosm, and res acids and hydrogenated resm acids present in or deπved 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 C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cι -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysacchaπdes 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 Ci Q-Cj g alkyl sulfates, more preferably the C\ \ -C\_ζ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CI Q-CI g 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 Ci 1 -Cj g, most preferably

Ci 1 -Ci 5 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 C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates,

Cg-C24 olefin sulfonates, sulfonated polycarboxy c 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, pnmary 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 wherem : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable Cι -C4 alkyl, and R2 is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl havmg 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 deπved from a reducing sugar in a reductive animation reaction; more preferably Z is a glycityl.

Suitable alkylpolysacchaπdes for use herein are disclosed U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysacchaπde, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 sacchaπde units. Preferred alkylpolyglycosides have the formula: R2θ(C_nH_2nO)t(glycosyl)_x where R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxy alky lphenyl, 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 deπved from glucose. Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxyhc acids. Suitable amine oxides include those compounds having the formula is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ 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 R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C10-C1 g alkyl dimefhylamme oxide, and Cjo-lS acylamido alkyl dimethylamme oxide.

Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly descπbed as deπvatives of secondary and tertiary amines, denvatives of heterocychc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as Ci 2_18 dimethyl-ammonio hexanoate and the CJO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betames 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 Cg-Ci g, preferably Cg-

CJ O 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 am e surfactants preferably of the general formula I:

wherein R^ is CI Q-C_I g hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably Ci 0 and C 12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

The levels of the cationic mono-alkoxylated amme 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 amme surfactant such as

are also useful, where R* is C J O-CI g hydrocarbyl and mixtures thereof, preferably C J Q, C12,

Ci 4 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. Bleach Activator

The detergent particles or detergent compositions containing them preferably compnse a bleach activator, preferably compnsmg 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

It is preferred that the bleach activator is present in the detergent particle. It may be preferred that the bleach activator is present as a separate, admixed particle.

Preferably, at least one of the bleach activators, preferably a peroxy acid bleach precursor, 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. More preferably, all of the activator are present in one or more particulate components having the specified weight average particle size

Hereby, 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 compnsmg 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 compnse a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and or NACA-OBS. Preferred hydrophilic peroxy acid bleach precursors preferably compnses 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

O

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

O

X- C - OOH

For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherem 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 compnsmg 1 to 5 carbon atoms. The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur withm 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:

O O -N— C— R¹ -N Λ N — N— C— CH— R⁴

I , I

R³ R³ Y

I Y

R³ Y I I -O-CH=C-CH=CH₂ -O-CH=C-CH=CH₂

R³ O Y i ιι i

-O-C=CHR⁴ , and — N— S-CH— R⁴

R³ O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14

3 4 3 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R , and Y is

H or a solubilizing group. Any of R 1 , R3 and R 4 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 solubi zmg groups are -SO ^"M , -CO ^~M , -SO M , -N (R ) .X^" and

3 - + - + 3

0<~N(R )_ and most preferably -SO.. M and -CO-, M wherem R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a ha de, hydroxide, methylsulfate or acetate anion.

Peroxyacid bleach precursor compounds are preferably mcorporated m 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, lmides, lactams and acylated deπvatives of lmidazoles and oximes. Examples of useful materials with these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A- 0170386.

Alkyl percarboxyhc acid bleach precursors form percarboxyhc acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis. Preferred alkyl percarboxyhc precursor compounds of the lmide type mclude the N-,N,N*N* tetra acetylated alkylene diammes 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 diamme (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor. Other preferred alkyl percarboxyhc acid precursors include sodium 3,5,5-tn-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:

_R1 _c — _N — _R2 _{c L R}1 _N — _{c R}2 _{c L}

O R⁵ O or R⁵ O O wherem R^ 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 R 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. R^ may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². R2 can include alkyl, aryl, wherein said R² may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. Rl and R^ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described m EP-A-0170386. It can be preferred that

Rl and R^ forms together with the nitrogen and carbon atom a nng structure.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamιdo-caproyl)oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamιdocaproyl)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 m 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 descπbed 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 tπalkyl ammonium methylene benzoyl caprolactams and the tπalkyl 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 descnbed 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 diperbrassyhc acid and N-phfhaloylaminoperoxicaproic 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 or component.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the matenal which provides better storage stability for the perhydrate salt the granular product. Suitable coatings compnse inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic matenals such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2-3H2θ.

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

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

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 particle or final detergent composition at a level 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 mclude organic phosphonates, such as the ammo alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitπlo tnmethylene phosphonates, preferably, diethylene tnamme penta (methylene phosphonate), ethylene diamine tπ (methylene phosphonate) hexamethylene diamine terra (methylene phosphonate) and hydroxy- ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphomc acid Other suitable chelants for use herein include mtπlotπacetic acid and polyammocarboxyhc acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaπc acid, 2-hydroxypropylenedιamme disuccinic acid or any salts thereof, and lminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl muno diacetic acid, descπbed in EP-A-317,542 and EP-A-399,133. The lminodiacetic acιd-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -sulfonic acid sequestrants descπbed in EP-A-516,102 are also suitable herein The β-alanme-N,N'-dιacetιc acid, aspartic acιd-N,N'-dιacetιc acid, aspartic acid-N-monoacetic acid and lmmodisuccmic acid sequestrants described m EP-A-509,382 are also suitable. EP-A-476,257 describes suitable ammo based sequestrants. EP-A-510,331 descπbes suitable sequestrants denved from collagen, keratm or casein. EP-A-528,859 descnbes a suitable alkyl lminodiacetic acid sequestrant.

Dipicolmic acid and 2-phosphonobutane-l,2,4-tπcarboxyhc acid are alos suitable. Glycmamide- N,N'-dιsuccmιc acid (GADS), ethylenediamine-N-N'-diglutanc acid (EDDG) and 2- hydroxypropylenediamme-N-N'-disuccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetπam e pentacetic acid, ethylenedιamιne-N,N'-dιsuccmιc 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 compnsmg a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.

Water-Soluble Builder Compound The component or compositions herem preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight. The detergent compositions of the invention preferably comprise 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%.

The phosphate-containing builder material preferably compnses tetrasodium pyrophosphate or even more preferably anhydrous sodium tπpolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeπc polycarboxylates, or their acid forms, homo or copolymeπc polycarboxyhc acids or their salts in which the polycarboxyhc acid compnses 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 momomeπc or ohgomenc type although monomeπc polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycohc acid and ether derivatives thereof Polycarboxylates containing two carboxy groups include the water-soluble salts of succmic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglyco c acid, tartaric acid, tartronic acid and fumanc acid, as well as the ether carboxylates and the sulfmyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succmate derivatives such as the carboxymethyloxysuccmates descnbed in Bπtish Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and ammosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate matenals such as 2- oxa-1,1 ,3-propane tncarboxylates descπbed in British Patent No. 1,387,447. The most preferred polycarboxyhc 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 oxydisuccmates disclosed in

Bntish 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 sulfosuccmate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and m U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates descnbed in Bπtish Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

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

Suitable examples of water-soluble phosphate builders are the alkali metal tπpolyphosphates, 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.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeπc polycarboxyhc acids or their salts in which the polycarboxyhc acid compnses 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 anhydnde, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

The polyam o compounds are useful herein including those denved 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 component in accord with the present invention or the compositions herein may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level 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 aluminosihcates. As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present.

Suitable alummosilicate zeolites have the unit cell formula Na_z[(Alθ2)_z(Sιθ2)y]. xFFjO wherem 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 alummosilicate matenal are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The alummosilicate zeolites can be naturally occurnng mateπals, but are preferably synthetically deπved. Synthetic crystalline alummosilicate ion exchange mateπals are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [A10₂) i2 (Sιθ2)i2]. H2θ wherem x is from 20 to 30, especially 27 Zeolite X has the formula Nagg [(Alθ2) 6(Sιθ2)ι 06- 276 H₂0

Another preferred alummosilicate zeolite is zeolite MAP builder. The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight.

Zeolite MAP is described in EP 384070A (Unilever) It is defined as an alkali metal alumino-sihcate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably withm the range from 0.9 to 1.33 and more preferably withm 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 d5_Q 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 d5o 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, descnbed herein. Other methods of establishing d5Q values are disclosed in EP 384070A Other Detergent Ingredients

A preferred ingredients 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 dye g 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 descπbed above. The dye may also be mixed with a non-aqueous earner mateπal, such as non-aquous liquid mateπals including nonionic surfactants.

Optionally, the dye also comprising other ingredients such as organic binder matenals, which may also be a non-aqueous liquid. The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs mclude

E104 - food yellow 13 (quinohne yellow), El 10 - food yellow 3 (sunset yellow FCF), E131 - food blue 5 (patent blue V), Ultra Marine blue (trade name), El 33 - food blue 2 (bnl ant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyl ns), E141 and Pigment green 7 (chlormated Cu phthalocyanme) Preferred dyestuffs may be Monastral Blue BV paste (trade name) and or Pigmasol Green (trade name).

Another preferred ingredient of the particles or 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 compnses an oxygen-containmg functional group Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof Another highly preferred ingredient useful m the particles or compositions herein is one or more additional enzymes Preferred additional enzymatic materials include the commercially available hpases, 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, Pπmase, Durazym, and Esperase by Novo Industnes 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 mto the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition

Preferred amylases include, for example, α-amylases 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 Industπes A/S. Highly preferred amylase enzymes maybe those descnbed in PCT/ US 9703635, and m 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 hpolytic 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 , Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcahgenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is deπved from Pseudomonas pseudoalcaligenes, which is descnbed in Granted European Patent, EP-B-0218272.

Another preferred lipase herem is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as descπbed m European Patent Application, EP-A-0258 068, which is commercially available from Novo Industπ A/S,

Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also descnbed in U S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

The component or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical bπghteners, as mentioned above. Examples are Tmopal-UNPA-GX™ and Tmopal-CBS-X™ by Ciba-Geigy Corporation.

Others include Tinopal 5BM-GX™, Tinopal-DMS-X™ and Tinopal AMS-GX™ by Ciba Geigy Corporation

Photo-Bleaching Agent Photo-bleaching agents are preferred ingredients of the compositions or components herein. Preferred photo-bleachmg agent herein comprise a compounds having a porphm or porphynn structure. Porphm and porphynn, in the literature, are used as synonyms, but conventionally porphm stands for the simplest porphynn without any substituents; wherem porphynn is a subclass of porphm. The references to porphm in this application will include porphynn. The porphm 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 nng systems such as pyπdyl, pyπdyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

The photo-bleachmg compound or component can have solubi zmg groups as substituents. Alternatively, or in addition hereto the photo-bleachmg agent can compnse a polymenc component capable of solubihzmg the photo-bleachmg compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.

Highly preferred photo-bleachmg compounds are compounds having a phthalocyanme structure, which preferably have the metal elements or cations descπbed above. The phthalocyanmes can be substituted for example the phthalocyanme 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 Polymenc Ingredients Organic polymenc compounds are preferred additional herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amme 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 vmyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymenc compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymenc compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Highly preferred polymenc components herem 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, Gosselmk et al., and in particular according to US apphcation no.60/051517.

Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoammes and diammes of the formula:

wherein X is a nonionic group selected from the group consisting of H, C1-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 monoammes (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diammes (b=l), 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 descnbed m EP-B-011965 and US 4,659,802 and US 4,664,848

Suds Suppressing System The components and detergent compositions herein, when formulated for use in machine washing compositions, may compnse 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 compnse 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 sudsmg 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 vaπety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of vaπous types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having tπmethylsilyl end blocking units.

Other suitable antifoam compounds mclude the monocarboxyhc 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 mclude, for example, high molecular weight fatty esters (e.g. fatty acid tπglyceπdes), fatty acid esters of monovalent alcohols, aliphatic Ci -C4Q ketones (e.g. stearone) N-alkylated ammo triazmes such as tπ- to hexa-alkylmelammes or di- to terra alkyldiamine chlortπazines formed as products of cyanuπc chloπde with two or three moles of a pnmary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis steanc acid amide and monostearyl di-alkah metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system compnses antifoam compound, preferably compnsmg 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/sihca antifoam compound wherem said sihca/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_]g-Cι g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight

A highly preferred particulate suds suppressing system is described in EP-A-0210731 EP-A-0210721 discloses other preferred particulate suds suppressing systems. Other highly preferred suds suppressing systems compnse polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, alummosilicate and polycarboxyhc polymers, such as copolymers of laic and acrylic acid

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-vinylpyrrohdone and N-vmyhmidazole, polyv ylpyrrohdonepolymers 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 nnsing 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 ohgomenc terephthalate esters, typically prepared by processes involving at least one transesteπfication/oligomeπzation, often with a metal catalyst such as a tιtamum(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. Gosselmk. Other SRAs include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselmk et al. Other examples of SRA's include: the partly- and fully- amonic-end-capped ohgomenc esters of U.S 4,721,580, January 26, 1988 to Gosselmk; the noniomc-capped block polyester ohgomenc compounds of U.S. 4,702,857, October 27, 1987 to Gosselmk; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S 4,877,896, October 31, 1989 to Maldonado, Gosselmk et al. SRAs also include: simple copolymenc 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 Ci -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 havmg 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 SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shm-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. 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 citnc acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20%) by weight) of neutralizing agents, buffeπng agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti- oxidants, bacteπcides 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 chloπne-based bleach. However, since the detergent compositions of the invention are solid, most liquid chloπne-based bleaching will not be suitable for these detergent compositions and only granular or powder chloπne-based bleaches will be suitable. Alternatively, a chlonne based bleach can be added to the detergent composition by the user at the beginning or duπng the washing process. The chloπne-based bleach is such that a hypochlonte species is formed in aqueous solution. The hypochloπte ion is chemically represented by the formula OCI . Those bleaching agents which yield a hypochlonte species aqueous solution mclude alkali metal and alkaline earth metal hypochloπtes, hypochloπte addition products, chloram es, chloπmmes, chloramides, and chlonmides. Specific examples mclude sodium hypochloπte, potassium hypochloπte, monobasic calcium hypochloπte, dibasic magnesium hypochloπte, chlorinated tnsodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, tπchlorocyanuπc acid, 1,3- dιchloro-5,5-dιmethylhydantom, N-chlorosulfamide, Chloramme T, Dichloramine T, chloramme B and Dichloramine B. A preferred bleaching agent for use m the compositions of the instant invention is sodium hypochlonte, potassium hypochlonte, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).

Most of the above-described hypochloπte-yielding bleaching agents are available in solid or concentrated form and are dissolved water dunng 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 lOg 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 fabπcs. 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 CI 1-13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate Branched AS branched sodium alkyl sulfate as descnbed m 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 pπmary alcohol condensed with an average of z moles of ethylene oxide -32-

QAS R2.N+(CH3)2(C2H40H) with R2 = C12 - C14 QAS 1 R2.N+(CH3)2(C2H40H) with R2 = C8 - C 1 1 APA C8 - CIO amido propyl dimethyl amme 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 C16-C18 alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tnpolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium alummosilicate of formula

Nal2(A102Sι02)12.27H20 having a primary particle size m the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d- Na2Sι205 Citric acid Anhydrous citπc acid Borate Sodium borate Carbonate Anydrous sodium carbonate: particle size 200μm to 900μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distπbution between

400μm and l200μm

Silicate Amorphous sodium silicate (Sι02:Na20 = 2.0:1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tπ-sodium citrate dihydrate of activity 86.4% with a particle size distnbution between 425 μm and 850μm

MA AA Copolymer of 1 :4 maleic/acryhc acid, average m. wt. about 70,000 MA/AA (1) Copolymer of 4:6 maleic/acryhc 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 polymenzation of 650 available from Shm Etsu Chemicals

Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by

NOVO Industries A/S under the tradename Savmase 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 Industnes A/S

PB4 Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H202-

PB1 Anhydrous sodium perborate bleach of nominal formula NaB02.H 202

Percarbonate Sodium percarbonate of nominal formula 2Na2C03.3H202

NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt

NAC-OBS (6-nonamιdocaproyl) oxybenzene sulfonate

TAED Tetraacetylethylenediamine

DTPA Diethylene tπam e pentaacetic acid

DTPMP Diethylene tπamme penta (methylene phosphonate), marketed by

Monsanto under the Tradename Dequest 2060

EDDS Ethylenedιamme-N,N'-dιsuccιnιc acid, (S,S) isomer sodium salt. Photoactivated bleach Sulfonated zmc phthlocyanme encapsulated in bleach (1) dextπn soluble polymer

Photoactivated bleach Sulfonated alum o phthlocyanme encapsulated in bleach (2) dextnn soluble polymer

Bπghtener 1 Dιsodιum 4,4'-bιs(2-sulphostyryl)bιphenyl Bnghtener 2 Dιsodιu 4,4'-bιs(4-anιlιno-6-mo holmo-1.3.5-tπazm-2-yl)ammo) stιlbene-2:2'-dιsulfonate

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 Polyvmyl lmidosole, with an average molecular weight of 20,000

PVP Polyvmylpyrohdone polymer, with an average m. wt. of 60,000

PVNO Polyvinylpyπdme N-oxide polymer, with an av. m. wt. of 50,000

PVPVI Copolymer of polyvmylpyrohdone and vmyhmidazole, with an average molecular weight of 20,000

QEA bιs((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3) bιs((C2H50)-

(C2H4 0))n, wherein n = from 20 to 30

SRP1 Aniomcally end capped poly esters SRP2 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 :Polydιmefhylsιloxane 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 Hexamethylenediamme tetra(ethylene oxιde)24

EXAMPLE I

This Example illustrates a process according to this invention which produces uniform free flowing, good dispensing and dissolving detergent particles with uniformity of colour and particle shape. Multiple detergent starting ingredients are dry mixed in an orbital vertical screw mixer of 200kg batch size, and several batches prepared. This premix is conveyed at 500kg/hr into a horizontal plate fluidised bed drier with outlet weir to maintain a constant static bed depth of 20cm. Fluidismg mlet air at 120°C is blown into the bed to maintain a fluidisation velocity of typically 2.0 ms-1. Fines are elutπated from the top of the bed, are collected in a hopper and recycled back to the bed. Air atomised spray nozzles are installed in the bed in a specific arrangement - typically 2 manifolds each with 3 nozzles aligned along the hoπzontal axis of the bed, positioned above the surface of the static bed. Bmder is made by weighing PEG 4000 into an agitated hot water jacketed tank of water at 60°C, to create a 30% PEG solution. Binder is pumped to the spray nozzle at 100 kg hr and atomised with 3 bar air withm the fluid bed Product is collected from the fluid bed and is screened on Mogensen vibratory screening units using three decks with 1250μm, 710μm and 425μm screens installed Oversize particles are ground and recycle to the fluid bed with the fines stream. Collected product (yield between the 1250μm and 425μm screens) is of density 445 g/L and mean particle size 570μm. The sphericity index is 1 4 with a standard deviation of 0.4. The product has a high whiteness vlaue of W=98.5. Other standard detergent matenals are post dry- added to the product in a mixing drum - including enzymes, perfume and dyed carbonate speckles. Spray -on materials such as perfume or nonionic surfactant may also be added at this stage to make a fully formulated detergent product.

The finished detergent has the following composition Component % Weight of Total Feed

Dry materials added to the premix Spray dried blown powder* 76.6%

TAED as agglomerate 4.2%

Silicone based antifoam 4.0% as agglomerate Sodium carbonate 3.1% Polymeric soil release agent 0.5%

Na2Sι205 layered silicate (SKS-6) 5.8% Binder, sprayed onto the premix in the fluid bed Polyethylene glycol (RMM = 4000) 5.7% (delivered via a 30% active solution) * = compnsmg of sodium linear alkyl benzene sulphonate (13.4wt%), zeolite A (40%), sodium sulphate (23.5%), sodium carbonate (8.4%), magnesium sulphate (0.7wt%), EDDS (0.4wt%), MA/AA (2.5wt%), soap (1.5wt%), QAS l(2.0wt%), HEDP(0.3wt%), optical bnghtener(0.5wt%), water (5.3 wt%), diamme hexamethylene terra (ethylene oxide) 24 (1.5wt%).

EXAMPLE II This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent mateπals is prepared as in example 1, of composition as listed below. The mix is fed mto a continuous Lodige KM 600 plough-share mixer, which is a hoπzontally-positioned moderate speed mixer, at 200kg/hr feedrate. The rotational speed of the shaft the mixer is about 100 rpm and the rotational speed of the cutters is about 3000 rpm Water, at 60°C, is pumped from a hot water jacketed tank, as binder at 20 kg/hr The water is atomised using air atomised nozzles positioned withm the Lodige KM.

Product from the Lodige KM is fed continuously mto a horizontal plate fluidised bed dner, which reduces the free moisture content to about 6% (Mettler mfra-red oven method). Product is collected from the fluid bed and is screened on Mogensen vibratory screening units using three decks with 1180μm, 710μm and 500μm screens installed Oversize particles are ground and recycled to the fluid bed with the fines stream Collected product (yield between the 1180μm and

500μm screens) is of density 620 g/L and mean particle size 610μm The sphencity index is 1.21 with a standard deviation 1.2 and a whiteness value W=97 0. Other standard detergent mateπals are post dry -added to the product in a mixing drum - including enzymes, perfume and dyed carbonate speckles. Spray -on materials such as perfume or nonionic surfactant may also be added at this stage to form a fully formulated detergent.

Component % Weight of Total Feed

Dry matenals added to the premix Spray dried blown powder* 70.4%

Na2Sι205 layered silicate (SKS-6) 12.7%

QAS 1 2.4%

TAED as agglomerate 4.0%

Silicone based antifoam 0.8% as agglomerate sodium carbonate 5.0% sodium sulphate 4.6%

Binder, sprayed onto the premix in the Lodige KM

Water 10.0% Water removed in drying process -10.0%

Bπghtener 15 0.1%

* = formulation as described in example 1 above.

Further example compositions In the following examples all levels are quoted as % by weight of the composition: TABLE

The following compositions are in accordance with the invention.

SUBSTITUTE SHEET (RULE2&) -38-

SUBSTITUTE SHEET (RULE--6) -39-

SU--S-TπJTESrEErpLE26) -40-

SUBSTITUTE SHEET (RUl£2^

Claims

WHAT IS CLAIMED IS:

1. A detergent particle comprising at least two particulate components, a first component of a first colour and a second component of a second colour, the first and second components being adhered to one another, the geometric mean particle diameter of at least one of the first or second particulate component being no more than 50% of the geometric mean particle diameter of the detergent particle.

2. A detergent particle according to claim 1 in which the colour difference (ΔE) between the first and second particulate components as measured using tri-stimulus colorimetry on a D25M Hunter Lab. Colorimeter is at least 3, where ΔE = V(ΔL² + Δa² + Δb²), where ΔL is the difference in L value between the first and second particulate components, Δa is the difference in a value between the first and second particulate components and Δb is the difference in b value between the first and second particulate components.

3. A detergent particle according to claim 1 or claim 2 in which the colour difference (ΔE) between the first and second particulate components is at least 5.

4. A detergent particle according to any preceding claim in which the first particulate component has a geometric mean particle diameter greater than 150 microns.

5. A detergent particle according to any preceding claim in which both the first and second particulate components have a geometric mean particle diameter greater than 150 microns.

6. A detergent particle having a sphericity index no greater than 1.7 comprising at least two particulate components, a first component and a second component, at least one of the first and second components having a sphericity index greater than 1.7, the first and second components being adhered to one another substantially in the absence of pressure compaction.

7. A detergent particle according to claim 6 having a sphericity index no greater than 1.5.

8. A detergent particle according to claim 6 or claim 7 in which the sphericity index of at least the first or second component is greater than 2.

9. A detergent particle having a geometric mean particle diameter greater than 500 microns, the detergent particle comprising a first particulate component and a second particulate component, the first and second particulate components being adhered to one another substantially in the absence of pressure compaction, the geometric mean particle size of at least one of the first and second components being no more than 50 % of the geometric mean particle size of the detergent particle and at least one of the first and second particulate components having a span of at least 2.

10. A detergent particulate according to claim 9 in which at least one of the first and second particulate components has a span at least 3.

11. A detergent particle according to claim 9 or claim 10 in which at least one of the first and second particulate components has a geometric mean particle diameter no more than 25% of the geometric mean particle size of the detergent particle.

12. A detergent particle according to any preceding claim having a span less than 1.8.

13. A detergent particle according to any preceding claim in which at least the first particulate component has a geometric mean particle diameter from 200-500 microns.

14. A detergent particle according to any preceding claim having a geometric mean particle diameter from 500-2500 microns

15. A detergent particle according to any preceding claim in which there is a difference in geometric mean particle diameter between the first and second particulate components of at least 250 microns.

16. A method for making a detergent particle according to any preceding claim comprising contacting the first particulate component and the second particulate component, optionally in the presence of a binder in a moderate to low shear mixing step to adhere the first and second particulate components to one another.

17. A method according to claim 16 in which the mixing step is a low shear mixing step which takes place in a pan granulator, drum mixer, rotating bowl mixer or fluidised bed.

18. A method according to claim 16 in which the mixing step is a moderate shear mixing step which takes place in a Ploughshare mixer having a tip speed for the ploughs of below lOm/s.

19. A method according to any of claims 16 to 18 in which a binder is added during or immediately preceding the mixing step.

20. A detergent composition comprising detergent particles according to any of claims 1 to 15.