DETERGENT PARTICLES AND PROCESSES FOR MAKING THEM

Abstract: Particulate detergents and methods for making them with improved process flexibility are disclosed. The detergent particulates are formed from a combination of pre-formed detergent particulates and other detergent ingredients which may also be preformed such as blown powders, extrudates or agglomerates or particulate raw materials. Selection of the feed streams into a low or moderate shear mixing process enable density of the finished detergent particle to be controlled without requiring careful control of the processing conditions.

Description: DETERGENT PARTICLES AND PROCESSES FOR MAKING THEM Field of the Invention The present invention relates to particulate detergent compositions and an improved process for making such compositions The detergent compositions of the invention are suitable for any cleaning process, such as laundry and dishwashing detergent compositions Such particulate compositions may be used directly m their particulate form or may first be formed into detergent tablets by any standard tablettmg process such as compaction Background of the Invention In order to meet the needs of the consumer, in addition to providing good cleaning, detergent compositions must meet many additional requirements including good aesthetics, good flow properties, good solubility and good dispensing performance into wash water In order to meet all of these requirements, the complexity of detergent compositions and range of products offered has grown Formulation flexibility for producing such complex compositions is therefore extremely important and many methods for formulating detergent compositions are already known In view of the high performance requirements of the consumer, achieving uniform dosage of all of the detergent actives m the composition has increased importance, in particular where sophisticated detergent ingredients present in detergents at low levels make a significant impact on one of the performance features mentioned above This problem is exacerbated by the advent of "compact" or low dosage granular detergent products These low dosage detergents are currently in high demand as they conserve resources and can be sold is small packages which are more convenient for consumers prior to use However, m a low dosage of detergent, where actives are present m very low levels, significant variability may occur in the concentration of such actives in each unit dosage Performance problems have been identified with some compact detergent products and the present inventors have now found that this may be due to formulation variability where low level detergent ingredients which give a significant impact on one or more of the performance factors mentioned above may vary considerably from dose to dose Summary of the Invention The present invention therefore reduces these problems by providing a process in which such low dosage/high impact ingredients can be dispersed uniformly throughout a detergent formulation Segregation is minimised without the need to incorporate high levels of fillers to form such low dosage/high impact ingredients into larger particles In accordance with the present invention there is now provided a method for making a detergent particles comprising selecting detergent base particles having a geometπc mean particle diameter from 500 - 2000 microns, in a moderate to low shear mixer adheπng detergent active particulates to the detergent base particles, wherein the detergent active particulates have a geometπc mean particle diameter no greater than 40% of the geometric mean particle diameter of the detergent base particles and comprise a detergent active selected from perfumes, enzymes, photobleaches. catalysts, soil release polymers, suds suppressors, bleaching compounds, whitening agents and layered silicates. The present invention also provides detergent particles produced by such a process, and detergent compositions incorporating these particles As used herein, it is intended to mean that a detergent active particulate is bound to the detergent base particulate, the two components subsequently appearing in a detergent composition as an individual detergent particle. Detailed Descπption of the Invention Physical Properties The detergent active particulates preferably have a geometric mean particle diameter which is below 200μm, preferably below 150μm and even below 100 μm. The geometπc mean particle diameter of the detergent active particulates is generally above lOμm preferably above 20 μm and may even be above 40μm or above 60μm As used herein, the phrase "geometπc 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 in accordance with ISO 31 18 (1976). A suitable device is the Ro-Tap testing sieve shaker Model B using 8 inch sieves of selected sizes. As used herein, the phrase "geometπc standard deviation" or "span" of a particle size distribution means the geometπc 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 84 , 3 /D 5 o); See Gotoh et al, Powder Technology Handbook, pp. 6-1 1 , Marcel Dekker 1997. The detergent base particles have a geometric mean particle diameter from 500 to 2000μm. The geometπc mean particle diameter of the detergent base particles is generally greater than 550μm or even greater than 600μm or 650μm. Preferably, the geometπc mean particle diameter of the detergent base particles is below 1500μm. The detergent particles produced preferably have a geometπc standard deviation of from 1 to about 2, preferably from 1.0 to 1.7. more preferably from about 1.0 to about 1 4. Preferred fully formulated detergents comprising the detergent particles also have such a geometπc standard deviation. Preferably the geometric mean particle diameter of the detergent active particulates is no greater than 20% of the geometπc mean particle diameter of the detergent base particles more preferably no greater than 10% and may even be below 5% of the geometric mean particle diameter of the detergent base particles Generally m the detergent particles, no more than 25wt% is derived from the detergent active particulates, preferably no greater than 10 wt%. The invention may even be useful where the proportion of the detergent particles derived from the detergent active particulates is no greater than 5 or even no greater than 2 wt%. As used herein the term "bulk density" refers to the uncompressed, untapped powder bulk density, as measured by pouring 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, measuring the remaining mass of powder and dividing the mass by the volume of the vessel. The bulk density of the detergent particles produced and also of the detergent base particles is generally above 200 g/1 and may be as high as 1500 g/1. It is particularly preferred that the bulk density a finished detergent composition compnsing the detergent particles produced according to the present invention is greater than 550 g/1, preferably greater than 600 g/1 or even above 650 g/1. The bulk density of the detergent particles produced is therefore generally from 400g/l to 1 100 g/1, generally above 500g/l or even above 550 or 650g/l, generally less than l OOOg/l or below 900g/l. The invention may be particularly useful for forming detergent particles having a low bulk density such as below 550 or even below 500 or 450 g 1. The detergent base particles for use m the method of the present mvention may compnse a single detergent ingredient m particulate form or may be a pre-mix of detergent ingredients. Where the detergent base particles comprise a pre-mix, the separate detergent ingredients may simply be mixed together or may comprise a pre-formed particulate compnsing any combination of two or more detergent ingredients, or mixtures thereof, optionally with single detergent ingredients. Suitable pre-formed particulates for the base particles may have been formed by spray-drymg, agglomeration, marumeπsation. extrusion or compaction, 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-dπed powders are particularly useful. Pre-formed particulates made according to at least one low shear mixing step, for example in a fluidised bed. for example by fluid bed agglomeration are particularly preferred. Particularly preferred particles are as described m our co-pending application filed today under reference number CM2158F. Suitable spray-drymg processes for forming such pre-formed particulates are descπbed for example in EP-A-763594 or EP-A-437888. Suitable processes for forming pre-formed particulates which are agglomerates are described for example 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. Such pre-formed particulates may be added to the mixer in their wet or dry state. They are preferably added to the mixer in their dry state as addition in their wet state may have an adverse effect on flow into the mixer. Alternatively it may be preferred that the pre-formed particulates are formed in a first stage of a moderate to low shear mixer and the detergent active particulates are added in a second stage so that the pre-formed particulates may be m a wet state when they are contacted with the detergent active particulates. Thus, the pre-formed particulate may be for example an agglomerate, blown powder or extrudate which has not yet undergone a final drying stage. Generally this means that a solvent used as a binding agent for the processing is present in higher amounts than are desirably present m a finished particulate detergent. Generally the solvent is water and wet particulates will have a free water content for example of froml5 to 30 wt % of the pre-formed particulate. Often, however, the pre-formed particulate will already have undergone a drying step prior to addition to the mixer so that the water content will be below 15 wt %, preferably below 10 wt %. Generally the free water content of the detergent base particles on entry into the mixer will be below 15 wt %, preferably below 10 wt %. It may be preferred that the detergent base particles comprise a surfactant or mixture of surfactants. Suitable surfactants are described below. The surfactant content of the detergent base particles or a pre-formed particulate component forming all or part of the detergent base particles 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 detergent base pre-formed particulate component comprises 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 m mixtures may be present m 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. The detergent base particles preferably also comprises an organic builder such as a poly carboxylic acid and/or salt such as citric acid, tartaπc acid, malic acid, succimc 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 paniculate component, preferably below 10 wt % of the particulate component Other preferred ingredients in the pre-formed particulate component are chelants such as phosphonate chelants NTA, DTPA and succi c acid derivative chelants. as descπbed below These components are preferably present in the detergent base particles m amounts below 5 wt % or even below 2 wt % Suds supressors and/or soil release polymers and/or bleach activators are also preferred ingredients m 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 polymeric materials, enzymes, bleaching components such as bleach activators or bleach salts such as peroxy salts. Highly suitable single ingredients m particulate form include inorganic components, particularly water-soluble inorganic components such as builders and bleach salts such as alkali metal percarbonates and or perborates. These ingredients are discussed more detail below . Suitable detergent ingredients for incorporation either into the detergent particles themselves, or for post-addition to formulate a fully formulated detergent composition are discussed below. The detergent active particulates are selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compounds, whitening agents and layered silicates. Perfumes Preferred detergent active particulates comprise perfume. Any perfume or perfume composition can be used. However, it must be solid or m combination with other components so that it has a solid form. For example it may be loaded onto a particulate earner such as zeolite, or any other known solid carrier, for example as described in WO94/16046, ES93000006, EP-A- 535942, and EP-A-294206. More preferably it is present m encapsulated form. Suitable encapsulates are described for example m W094/12613. EP-A-539025, EP-A-478326, EP-A- 383406, EP-A-382464, EP-A-346034, EP-A-70719. Particularly preferred encapsulates compnse starch. Preferred perfumes contain at least one component with a low molecular weight volatile component, e.g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-contammg functional group. Preferred functional groups are aldehyde, ketone. alcohol or ether functional groups or mixtures thereof. Enzymes The detergent active particulates may comprise one or more enzymes. Suitable enzymes include the commercially available lipases. cutmases. amvlases. neutral and alkaline proteases, cellulases. endolases, esterases, pectmases, 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, Savmase, Pπmase, Durazym. and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases, described m more detail m GB- 1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Preferred amylase enzymes may be those described in PCT/ US 9703635, and in W095/26397 and W096/23873. Amylase enzyme may be incorporated into the composition 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 based on the content in the final detergent composition. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcah genes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in EP-B-0218272. Another preferred lipase is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described m European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414. Huge-Jensen et al, issued March 7, 1989. Photobleaches Preferred detergent active particulates comprise photobleach particles Preferred photo- bleaches herein comprise a compounds having a porphin or porphyrin structure Porphm and porphyrin. in the literature, are used as synonyms, but conventional]} porphin stands for the simplest porphyrin w ithout any substituents. wherem porphyrin is a sub-class of porphin The references to porphin m this application will include porphynn The porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P. Ti, Cr, Zr, In. Sn or Hf, more preferably Ge, Si or Ga. or more preferably Al . most preferably Zn. It can be preferred that the photo-bleach or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyndyl-N-oxide, phenyl, naphthyl and anthracyl moieties. The photo-bleaching compound or component can have solubilizing groups as substituents Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleachmg compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof Highly preferred photo-bleachmg compounds have a phthalocyanme structure, which preferably have the metal elements or cations described above The phthalocyanmes can be substituted, suitable examples include the phthalocyanme structures which are substituted at one or more of the 1 -4, 6. 8-1 1, 13, 15-18, 20, 22-25, 27 atom positions One preferred group of photobleaches comprise a polymeric component and a photobleaching component integrated with one another, whereby the weight ratio of polymeπc component to photobleaching component is from 1.1 to 1000.1, preferably 20:1 to 100:1 Particularly preferred polymenc compounds are formed from monomeπc units selected from N- vmylpyrolidone, N-vmylacetamide, N-vmyl lmidazole, N-vmyl oxazohdone, N-v yltnazole, 4- vmylpyridme and 4-vιnylpyπlιdme-N-oxιde. Preferred photo-bleachmg compounds are metals, preferably zmc, phthalocyammes or aluminium Such photo-bleaches are described in GB 2329397A. Soil Release Polymers Preferred soil release polymers (SRPs) typically have hydrophihc segments to hydrophihze 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 rmsmg cycles, thereby serving as an anchor for the hydrophihc segments This can enable stams occurring subsequent to treatment with the SRP to be more easily cleaned in later washing procedures Preferred SRPs include o gomeπc terephthalate esters, typically prepared b\ processes involving at least one transesteπfication/oligomeπzation. often with a metal catalyst such as a tιtanιum(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 crosshnked overall structure. Suitable SRPs include a sulfonated product of a substantially linear ester ohgomer comprised of an ohgomeπc ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-deπved sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E P Gosselmk. Such ester ohgomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesteπfication/oligomeπzation procedure; and (c) reacting the product of (b) with sodium metabisulfite in water Other SRPs include the nonio c end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S 4,71 1 ,730. December 8, 1987 to Gosselmk et al., for example those produced by transesteπfication oligomenzation of poly- (ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anio c-end-capped oligomeπc esters of U.S. 4,721,580, January 26, 1988 to Gosselmk, such as ohgomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dιoxa-8-hydroxyoctanesulfonate; the nonio c-capped block polyester o gomenc compounds of U.S. 4,702,857. October 27, 1987 to Gosselmk. for example produced from DMT, methyl (Me)-capped PEG and EG and or PG, or a combination of DMT, EG and/or PG, Me- capped PEG and Na-dιmethyl-5-sulfoιsophthalate: and the anionic. especially sulfoaroyl, end- capped terephthalate esters of U.S. 4,877,896, October 31 , 1989 to Maldonado, Gosselmk et al., the latter being typical of SRPs useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400. SRPs also include: simple copolymeπc 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 C ] -C alkyl celluloses and C_\ hydroxyalkvl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00™ and METOLOSE SM200™. which are methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRPs include those described U.S 4,201.824. Violland et al. and U.S 4.240,918 Lagasse et al . and SRA's with carboxylate terminal groups made by adding tnmellitic anhydride to known SRP's to convert terminal hydroxyl groups to tnmellitate esters With the proper selection of catalyst, the tnmellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of tnmellitic anhydπde rather than b> opening of the anhydπde linkage. Either nonio c or anionic SRPs may be used as starting mateπals as long as they have hydroxyl terminal groups which may be esteπfied. See U.S 4,525.524 Tung et al.. and U.S. 4.201 ,824, Violland et al Suitable soil release polymers may be selected from: (a) alkyl and hydroxyalkvl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of from 1.5 to 2.7 and a number average molecular weight of from 2000 to 100000; (b) polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1 : 10; (c) polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1 : 10 to 10.1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight of from 500 to 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000; and (d) polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide many ratio such that the mole ratio of eth y lene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from 1 : 10 to 10: 1. said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight of from 250 ti 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000: and mixtures thereof; as descπbed in more detail m EP-A-271312. Suds Supressors The detergent active particulates may comprise suds supressors. Suitable suds suppressing systems may comprise essentially any known antifoam compound, including, for example sihcone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution Particularly preferred antifoam compounds for use herein are sihcone antifoam compounds defined herein as any antifoam compound including a sihcone component. Such sihcone antifoam compounds also typically contain a silica component. The term "sihcone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred sihcone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having tπmethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxyhc fatty acids and soluble salts thereof as descπbed in US Patent 2,954,347, issued September 27. 1960 to Wayne St. John. The monocarboxyhc fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C] g-C4o ketones (e.g. stearone) N-alkylated amino tπazmes such as tn- to hexa-alkylmelammes or di- to tetra alkyldiamme chlortriazmes formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkah metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system compnses: (a) antifoam compound, preferably sihcone antifoam compound, most preferably a sihcone antifoam compound comprising in combination polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the sihcone antifoam compound; and silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/si ca antifoam compound; wherein said silica/sihcone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight; (b) a dispersant compound, most preferably comprising a sihcone 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 DCO544, commercially available from Dow Corning; and (c) an inert carrier fluid compound, most preferably compnsing a Cj g-Cj 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 and compnses a sihcone antifoam compound and an organic earner material having a melting point m -l i ¬ the range 50°C to 85°C, wherein the organic carrier mateπal compnses a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic earner material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C. Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of sihcone. such as polydimethylsiloxane. aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid. Bleaching Compounds The detergent active particulates may comprise one or more bleaching compounds. Suitable bleaching compounds include bleach activators, pre-formed peracids and peracid salts such as alkali metal percarbonate and/or perborate. The chemical nature of these components is discussed in more detail below the section entitled "Detergent Ingredients". Preferred bleach compounds are bleach activators such as TAED, NOBS, ISONOBS etc. as discussed below, and the persalts such as alkali metal percarbonate and/or perborate. Sodium salts are particularly preferred. Whitening Agents Suitable whitening agents include hydrophihc optical bπghteners such as include those having the structural formula: wherein Rj is selected from anilmo, N-2-bιs-hydroxyethyl and NH-2 -hydroxy ethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamιno. morphilino, chloro and ammo: and M is a salt-forming cation such as sodium or potassium. When in the above formula, R ] is anilmo, R2 is N-2-bιs-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilιno-6-(N-2-bιs-hydroxyethyl)-s-tnazιne-2- yl)amιno]-2,2'-stilbenedιsulfonιc acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tmopal-UNPA-GX by Ciba-Geigy Corporation. Tmopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophihc optical brightener useful in the detergent compositions herein. When in the above formula, R j is anil o, R2 is N-2-hydroxyethyl-N-2-methylammo and M is a cation such as sodium, the brightener is 4.4'-bιs[(4-anιhno-6-(N-2-hydroxyethyl-N- methylammo)-s-tπazιne-2-yl)amιno]2,2'-stιlbenedιsulfonιc acid disodium salt. This particular brightener species is marketed as Tinopal 5BM-GX™ by Ciba-Geigy Corporation. When in the above formula, R ] is anilmo. R2 is morphihno and M is a cation such as sodium, the brightener is 4.4'-bιs[(4-anιlιno-6-morphιlιno-s-tπazιne-2-yl)ammo]2,2'- stilbenedisulfo c acid, sodium salt. This particular brightener species are sold by Ciba Geigy Corporation as Tinopal-DMS-X™ and Tinopal AMS-GX™. Lavered Silicates Suitable cry stalline layered silicates are described for example in US 4.664,839 Crystalline layered silicates rich in delta-phase are preferred such as those described in W097/19156 Catalysts The detergent active particulates may also comprise catalyst particulates Suitable catalysts include transition metal-containmg bleach catalyst One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant/chelant havmg defined stability constants for the catalytic and auxiliary metal cations, particularly ethyl enediamine tetraacetic acid, ethylenediamme tetra(methvlenephosphonιc acid) and water-soluble salts thereof Such catalysts are disclosed in US 4,430,243 Other types of bleach catalysts include the manganese-based complexes disclosed US 5,246,621 and US 5.244,594 Preferred examples of these catalysts include MnTV2(u-0)3( 1,4,7- tnmethyl-l,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-0)l(u-Oac)2(l J 4.7-tπmethul- 1,4,7- tnazacyclononane)2-(C104)2, MnIV4(u-0)6( 1 ,4,7-tπaxacyclononane)4-(C104)2, MnπTMnrV4(u-0)l(u-Oac)2-(l ,4,7-tπmethyl-l ,4,7-trιazacyclononane)2-(C104)3, and mixtures thereof Others are described in EP-A-549272 Other suitable ligands include 1,5,9-tnmethyl- 1,5,9-triazacyclododecane, 2 -methyl- 1 ,4,7-tπazacyclononane, 2-methyl-l ,4,7-tnazacyclonanone, l,2,4,7-tetramethyl-l ,4,7-tπazacyclononane, and mixtures thereof For examples of suitable bleach catalysts see US 4,246,612 and US 5.227,084 See also US 5,194,416 which teaches nononuclear manganese (IV) complexes such as Mn(l,4,7-tπmethyl- l,4,7-tnazacyclonanone)(OCH3)3-(PF6) Still another type of bleach catalyst as disclosed in US 5,1 14,606 is a water-soluble complex of manganese (ITJ) and/or (TV) with a gand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups Other examples include bmuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-0)2MnIVN4)+and [Bιpy2MnIIl(u-0)2MnIVbιpy2]-(C104)3 Further suitable bleach catalysts are described for example in EP 408131 (cobalt complex catalysts) EP 384503 and 306089 (metallo-porphyπn catalysts) US4,728,455 (manganese/multidentate gand catalyst) US 4.711 ,748 and EP 224952 (absorbed manganese on aluminosilicate catalyst) US 4.601.845 (aluminosilicate support with manganese and zinc or magnesium salt) US 4,626,373 (manganese/hgand catalyst), US 4,1 19,557 (feme complex catalyst). German Patent specification 2054019 (cobalt chelant catalyst), Canadian 866191 ( transition metal-contaming salts), US 4.430.243 (chelants with manganese cations and non- catalytic metal cations), and US 4,728.455 (manganese gluconate catalysts). The preferred detergent active particulates comprise perfume, photobleach and/or catalyst. Perfume and or photobleaches are particularly preferred. In a particularly preferred aspect of the invention, the detergent active particulates comprise encapsulated perfume. In a further particularly preferred aspect of the invention, the detergent active particulates compπse photobleach. The preferred proportion of detergent active particulates to detergent base powder will vary dependent upon the relative particle sizes of these two components. Preferably in the final detergent composition the weight percentage of any one of the detergent active particulates will be no greater than 10wt%, preferably below 5 wt% or even below 2 or 1 wt% of the detergent base particles In particular where the proportion of detergent active particulates is as low as 5 or 2 or 1 wt% of the detergent base powder, preferably the geometric mean particle size of the detergent active particulates is no greater than 20%, preferably no greater than 10 % or even below 5 or even 2 or 1% of the geometric mean particle size of the detergent base particles. 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 which may form part of the detergent base particles. The individual detergent ingredients in particulate form may be any of the detergent ingredients descπbed below, in a particulate form. 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 95 wt% of the detergent particles according to the present invention. The higher the level of detergent particles of the present invention, the greater the benefits of the invention terms of promoting uniform dosages of detergent from a package of particulate detergent or a unit dosage which is formed into a tablet. 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 into the mixer or onto the paniculate components as they travel into 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, nonio c surfactants, polyethylene glycol, polyvmyl pyrrohdone. polyacrylates. organic acids or their salts such as citric acid or citπc 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 The binder must be compatible with the detergent active particulate as will be appreciated by persons skilled in the art Thus, where the stability of the detergent active particulate is adversely affected by water, the binder will be substantially water- free Thus, m one aspect of the invention, a first feed stream of detergent base powder is fed into the mixer and in addition a second feed stream comprising a detergent active particulates is fed into the mixer and binder is also present m the mixer The binder may be fed directly via a third stream into the mixer or it may be contacted with the detergent base particles or detergent active particulates prior to one or both of these feed streams entering the mixer, for example the detergent active particulate (or a proportion of the base particles) may be entrained in the binder 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 detergent base particles and detergent active particulates will be pre-mixed prior to addition of the binder. In a further preferred aspect of the invention, after mixing of the detergent base particles and detergent active particulates, 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 coating may be the same chemical composition as the binder or may be any of the other coating matenals or detergent ingredients described below The moderate to low shear mixer to be used m the present invention 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 m 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 minutes 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 m 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 fiuidized 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 (q q ) of the liquid sprayed into the bed at a normalized distance (D 0 ) of the spraying device. The flux number provides an estimation of the operating parameters of a fiuidized bed to control granulation within the bed. The flux number may be expressed either as the mass flux as determined by the following formula: FN m = log 10 [{PpU e }/q lιq ] or as the volume flux as determined by the formula- FN, = log 10 [{U e }/q vlιq ] where q v g is the volume of spray into the fluid bed Calculation of the flux number and a description of its usefulness is fully described in WO 98/58046 the disclosure of which is herein incorporated by reference. In addition, the fiuidized 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 describing the degree of mixing occurring to particles in a piece of equipment such as the fluid bed. The Stokes number is measured by the formula: Stokes number = 4pvd 9u wherein 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, detergent base particles of the present invention are passed into a fluid bed optionally having multiple internal "stages" or "zones" A stage or zone is any discrete area within the fluid bed. and these terms are used interchangeably herein The process conditions within a stage may be different or similar to the other stages 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 detergent base particles and detergent active particulates can be added either at the same or at the 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 fiuidized with heated air m order to dry or partially dry moisture such as the 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 delivenng a fine or atomized spray of the binder to achieve intimate nixmg 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 m the fluid bed may be in 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 fiuidized height of the particles the fluid bed. The fiuidized 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 m 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 invention include: (l) a mean residence time from about l 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 m the bed, which is preferably not more than about 100 micron more preferably not more than 50 microns, (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 recognise that the conditions in the fluid bed may vary depending on a number of factors. The detergent particles produced 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 coating 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 coating stage may take place either immediately after formation of the detergent particles of the invention 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 detegent 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. Detergent ingredients which are suitable as ingredients of the base powder, and/or as ingredients of the detergent active particulates 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 mvention are described below. Detergent Ingredients Surfactant Suitable surfactants for use in the invention are a onic, noniomc, ampholytic, and zwitteπonic classes of these surfactants, is given in U.S.P. 3,929.678 issued to Laughlm and Heunng on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and U 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 comprising such particles comprises an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate. sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred. The anionic surfactants may be present m the detergent particle in amounts below 25 WT % or even below 20 wt % but in a final detergent composition comprising the particle, is preferably present at a level of from 0.1 % to 60%. more preferably from 1 to 40%. most preferably from 5% to 30% by weight. Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyls") such as water- soluble members selected from the group consisting of the water-soluble salts of 2-methyl-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 sarcos ates of formula R-CON (R^) CH2 COOM, wherem R is a C5-C17 linear or branched alkyl or alkenyl group, R^ is a C1-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 tauπde, alkyl succmates and sulfosuccmates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ~-C. - monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C . . diesters), N- acyl sarcosmates. Res acids and hydrogenated res acids are also suitable, such as ros , hydrogenated rosm, and resm acids and hydrogenated resin acids present m or derived from tallow oil. Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates. the C5-C17 acyl-N-(C j -C4 alkyl) and -N-(C]-C2 hydroxyalkyl) glucamme sulfates. and sulfates of alkylpolysacchaπdes such as the sulfates of alkylpolyglucoside (the noniomc nonsulfated compounds being descπbed herein). Alkyl sulfate surfactants are preferably selected from the linear and branched pnmary Cj Q-Cj alkyl sulfates, more preferably the C ] \-C\ <_ 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 o-C j 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 C j J -C J g. most preferably C] ]-C ] 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 catiomc surfactant. Such mixtures have been disclosed 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. C - _\ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates. and any mixtures thereof Essentially any alkoxylated nonionic surfactant or mixture is suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamme 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 R 2 CONR 1 Z wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C j -C4 alkyl: and R2 is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar m a reductive animation reaction; more preferably Z is a glycityl. Suitable alkylpolysacchaπdes for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysacchande. e.g., a polyglycoside, hydrophihc group containing from 1.3 to 10 sacchaπde units. Preferred alkylpolyglycosides have the formula: R2θ(C n H 2n O)t(glycosyl) x wherem R*- is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl. and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10. and x is from 1.3 to 8. The glycosyl is preferably derived from glucose. Suitable amphoteπc surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxyhc acids. Suitable amine oxides include those compounds having the formula R^(OR 4 ) λ N^(R^)2 wherem R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 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. Prefeπed are C ] j -Cι g alkyl dimethylamine oxide, and C\<_,.\ acylamido alkyl dimethylamine oxide. Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as denvatives of secondary and tertiary ammes, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as Ci 2- ] dimethyl-ammonio hexanoate and the Cj Q -i g acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultame surfactants are exemplary zwittenonic surfactants for use herein. Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cβ-Cjβ, preferably Cg- C J 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 cho ne ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as are cationic mono-alkoxylated amme surfactants preferably of the general formula I: R' \ ((CH 2 ) 2 . 4 O),. 5 H CU 3 CH 3 wherem R * is Cj -Cj g hydrocarbyl and mixtures thereof, especially C \ Q-C _ alkyl, preferably CJ Q and Ci 2 alkyl. and X is any convenient anion to provide charge balance, preferably chlonde or bromide The levels of the cationic mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0 1% to 20%, preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight Cationic bis-alkoxylated amine surfactant such as are also useful, wherem R 1 is C j Q -C j hydrocarbyl and mixtures thereof, preferably C J O, C\2, C]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 comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophihc 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 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. Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy- benzene sulphonate group, preferably NOBS, DOBS, LOBS and or NACA-OBS Preferred hydrophihc 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 i 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 l! 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 hydrophihc peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherem X is a group comprising 1 to 5 carbon atoms. The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use m a bleaching composition. Preferred L groups are selected from the group consisting of: R 3 Y I I -O-CH=C-CH=CH 2 -O-CH=C-CH=CH 2 R 3 O Y i II i -O-C=CHR 4 , and — N— S— CH— R 4 R 3 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 , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, mtrosyl, amide and ammonium or alkyl ammmonium groups The preferred solubilizing groups are -SO- ' M , -CO- ' M , -SO " M , -N (R ) 4 X " and 0<-N(R ), and most preferably -SO " M and -CO- " M where R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. Peroxyacid bleach precursor compounds are preferably present 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 hydrophihc 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 anhydπdes, esters, lmides, lactams and acylated denvatives of lmidazoles and oximes. Examples of useful matenals within these classes are disclosed GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 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 imide type include the N-,N,N^N' tetra acetylated alkylene diam es wherem 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 hydrophihc peroxy acid bleach precursor Other prefeπed 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- R 1 — C — N — R 2 — C — L R 1 N — C R 2 — C — L O R 5 O or R 5 O O wherein R' is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R 2 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. R 1 preferably contains from about 6 to 12 carbon atoms R 2 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 vanations are permissible for R^. R2 can include alkyl, aryl, wherem said R 2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R* and R^ should not contain more than 18 carbon atoms total Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that R and R-> forms together with the nitrogen and carbon atom a ring structure Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamιdo-caproyl)oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamιdocaproyl)oxy benzene sulfonate, and mixtures thereof as descnbed m EP-A-0170386 Perbenzoic acid precursor compounds which provide perbenzoic acid on perhydrolysis benzoxazm organic peroxyacid precursors, as disclosed for example in EP-A-332294 and EP-A- 482807 and cationic peroxyacid precursor compounds which produce cationic peroxyacids on perhydrolysis are also suitable Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015, 4.988,451 ; 4,397,757; 5.269,962; 5, 127.852. 5.093.022, 5,106,528, U.K 1 ,382.594: EP 475,512, 458.396 and 284,292; and in JP 87-318,332 Examples of preferred cationic peroxyacid precursors are described m 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 described m 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-phthaloylammoperoxicaproic acid are also suitable herein Peroxide Source Inorganic persalts 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 particle or composition of the invention. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persi cate salts. The inorganic perh y drate 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 m 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 herein Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use 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 preferably selectively bind heavy metal ions such as iron, manganese and copper. Chelants are generally present 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 include organic phosphonates, such as the ammo alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably, diethylene tπamme penta (methylene phosphonate), ethylene diamine tn (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy- ethylene 1 ,1 diphosphonate, 1 ,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid. Other suitable chelants for use herein include nitrilotnacetic acid and polyammocarboxyhc acids such as ethylenediammotetracetic acid, ethylenediamine disuccimc acid, ethylenediamine diglutaπc acid, 2-hydroxypropylenedιamme disuccimc acid or any salts thereof, and lmmodiacetic acid denvatives such as 2-hydroxyethyl diacetic acid or glyceryl immo diacetic acid, described in EP-A-317,542 and EP-A-399,133. The lmmodiacetic acιd-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonιc acid sequestrants described 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 immodisuccmic acid sequestrants descnbed m EP-A-509,382 are also suitable. EP-A-476.257 descnbes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen. keratin or casem. EP-A-528,859 descnbes a suitable alkyl lmmodiacetic acid sequestrant Dipico nic acid and 2-phosphonobutane-l ,2,4-tπcarboxylιc acid are alos suitable. Glycmamide- N,N'-dιsuccmιc acid (GADS). ethylenediamme-N-N'-diglutaπc acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccimc acid (HPDDS) are also suitable. Especially preferred are diethylenetnam e pentacetic acid, ethylenediamine-N.N'-disuccimc acid (EDDS) and 1,1 hydroxyethane diphosphomc acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof In particular the chelating agents comprising a ammo or am e group can be bleach-sensitive and are suitable m the compositions of the invention Water-Soluble Builder Compound The component or compositions herein 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 may comprise phosphate-contam g 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 matenal preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tπpolyphosphate Suitable water-soluble builder compounds include the water soluble monomenc polycarboxylates, or their acid forms, homo or copolymeπc polycarboxylic acids or their salts which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing The carboxylate or polycarboxylate builder can be momomenc or o gomenc in type although monomenc 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 deπvatives thereof Polycarboxylates containing two carboxy groups include the water-soluble salts of succimc acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycohc acid, tartaπc acid, tartronic acid and fumaπc acid, as well as the ether carboxylates and the sulfinyl carboxylates Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succmate derivatives such as the carboxymethyloxysuccmates descnbed Bπtish Patent No. 1 ,379,241, lactoxysucc ates descnbed in Bπtish Patent No 1 ,389,732, and ammosuccmates descnbed in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2- oxa- 1,1 , 3 -propane tπcarboxylates descnbed in British Patent No 1,387,447 The most preferred polycarboxylic acid containing three carboxy groups is citnc 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 sulfosuccinate deπvatives disclosed in British Patent Nos 1.398,421 and 1.398,422 and in U.S Patent No 3.936.448. and the sulfonated pyrolysed citrates descπbed in British Patent No 1,439.000. Preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, more particularly citrates The parent acids of the monomenc or oligomeπc polycarboxylate chelatmg agents or mixtures thereof with their salts, e g citric acid or citrate/citric acid mixtures are also contemplated as useful builder components Borate builders and 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 tnpolyphosphates. 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-polymeric polycarboxylic acids or their salts in which the polycarboxylic 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 m 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 polyammo compounds are useful herein including those deπved from aspartic acid such as those disclosed m EP-A-305282, EP-A-305283 and EP-A-351629 Partially Soluble or Insoluble Builder Compound The particles or detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present 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 alummosihcates As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alummo silicate builder are present. Suitable aluminosilicate zeolites have the unit cell formula a z [(Alθ2) z (Sιθ2)v]- XH2O where z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264 The aluminosilicate matenal are hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water m bound form The aluminosilicate zeolites can be naturally occurnng matenals. but are preferably synthetically denved. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A. Zeolite B, Zeolite P. Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [A10 2 ) 12 (Sι0 2 )i2] xH 0 wherem x is from 20 to 30, especially 27 Zeolite X has the formula Nagg [(Alθ2)g6(Sιθ2)i06] 276 H 2 0 Another preferred aluminosilicate 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 m 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 within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2 Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and. more particularly, not greater than 1.07 In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a median particle size 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 d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, m particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer, described herein Other methods of establishing d5ø 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 dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle. or more preferably up to 0.5% by weight, as described above The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid matenals 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 include E104 - food yellow 13 (quinolme yellow), El 10 - food yellow 3 (sunset yellow FCF), E131 - food blue 5 (patent blue V), Ultra Maπne blue (trade name). El 33 - food blue 2 (bnlhant blue FCF). El 40 - natural green 3 (chlorophyll and chlorphyll s). El 41 and Pigment green 7 (chlorinated Cu phthalocyanme) Prefeπed dyestuffs may be Monastral Blue BV paste (trade name) and or Pig asol 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 comprises an oxygen-contaming functional group Preferred functional groups are aldehyde, ketone alcohol or ether functional groups or mixtures thereof Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes Preferred additional enzymatic materials include the commercially available lipases, cutmases, amylases, neutral and alkaline proteases cellulases. endolases, esterases, pectmases, lactases and peroxidases conventionally incorporated into detergent compositions Suitable enzymes are discussed m US Patents 3,519,570 and 3,533,139 Preferred enzymes are discussed above with respect to the detergent active particulates The same enzymes are preferred as components of the detergent base powder or as additional detergent ingredients added to the detergent particles of the invention to form a fully formulated detergent The detergent particles or compositions herein also preferably contain from about 0 005% to 5% by weight of certain types of hydrophihc optical bnghteners, preferably as a detergent active particulate component as mentioned above Examples are commercially marketed by Ciba Geigy Corporation as Tmopal-UNPA-GX™ and Tmopal-CBS-X™ Others include T opal 5BM-GX™, Tmopal-DMS-X™ and Tmopal AMS-GX™ by Ciba Geigy Corporation Photo-Bleachmg Agent As descnbed above, photo-bleachmg agents are preferred ingredients of the compositions and are preferably present in the form of the detergent active particulates as discussed above However, they may optionally be present m the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for forming the fully formulated detergnet compositions of the invention Organic Polymeric 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 paniculate 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 polymeπc compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) am e clay-soil removal/ anti-redeposition agent in accord with the invention Organic polymeric compound is typically incorporated in the finished 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 polymeric compounds suitable for incorporation m 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 polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselmk et al., and m particular according to US application no.60/051517. Another organic compound, which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoammes and diammes of the formula- where X is a nonionic group selected from the group consisting of H, C] -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 described in EP-B-01 1965 and US 4.659,802 and US 4.664.848. Suds Suppressing System The suds supressmg system is preferably also present in the form of the detergent active particulates as described above. Such components may however be present m the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition. Polymeric dye transfer inhibiting agents may also be present in the detergent particles or compositions of the invention When present they are generally in amounts from 0.01% to 10 %, preferably from 0.05% to 0.5% based on the final detergent compositions and are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrohdone and N- vmyhmidazole, polyvmylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers. Polymeric soil release agents, which are described above are also preferably present as detergent active particulates. However they may be present alternatively or in addition, in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition. Other optional ingredients suitable for inclusion in the compositions of the mvention include colours and filler salts, with sodium sulfate being a preferred filler salt. Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffenng 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 chlonne-based bleach. However, since the detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlonne-based bleaches will be suitable. Alternatively, a chlonne based bleach can be added to the detergent composition by the user at the beginning or dunng the washing process The chlonne-based bleach is such that a hypochloπte species is formed m aqueous solution The hypochlonte ion is chemically represented by the formula OCI . Those bleaching agents which yield a hypochloπte species m aqueous solution include alkali metal and alkaline earth metal hypochloπtes, hypochlonte addition products, chloramines. chlonmmes, chloramides, and chloπmides. Specific examples include sodium hypochloπte, potassium hypochlonte. monobasic calcium hypochlonte. dibasic magnesium hypochlonte. chloπnated tπsodium phosphate dodecahydrate, potassium dichloroisocyanurate. sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, tnchlorocyanuπc acid, 1.3- dιchloro-5.5-dιmethylhydantom. N-chlorosulfamide, Chloram e T, Dichloram e T. chloramme B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlonte. potassium hypochlonte. or a mixture thereof. A preferred chlonne-based bleach can be Tnclosan (trade name) Most of the above-described hypochloπte-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention Some of the above materials are available as aqueous solutions. Laundrv 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 Abbreviations used in the Examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS Sodium linear Cl 1 -13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate branched AS branched Sodium alkyl sulfate as described in W099/19454 CxyAS : Sodium C 1 x - C 1 y alky 1 sulfate C46SAS : Sodium C14 - Cl 6 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz C 1 x-C 1 y predominantly linear pnmary alcohol condensed with an average of z moles of ethylene oxide QAS R2.N+(CH3)2(C2H4OH) wιth R2 = C12 - C14 QAS 1 R2 N+(CH3)2(C2H40H) with R2 = C8 - C 1 1 APA C8 - CIO amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an 80 '20 mixture of tallow and coconut fatty acids STS Sodium toluene sulphonate CFAA C12-C14 (coco) alkyl N-methyl glucamide TFAA C16-C18 alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tπpolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium aluminosilicate of formula Nal2(A102Sι02)12.27H20 having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d- Na2Sι205 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm 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 425μm 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 polymerization of 650 available from Shin Etsu Chemicals Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as descnbed in WO 95/10591. sold by Genencor Int. Inc Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industnes A S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A S under the tradename Carezyme Amvlase 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 Tetraacetylethylenediamme DTPA Diethylene tπamme pentaacetic acid DTPMP Diethylene tπamme penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDS : Ethylenedιamιne-N,N'-dιsuccιnιc acid, (S,S) isomer sodium salt. Photoactivated : Sulfonated zinc phthlocyanme encapsulated m bleach (1) dextπn soluble polymer Photoactivated Sulfonated alummo phthlocyanme encapsulated in bleach (2) dextπn soluble polymer Bnghtener 1 : Disodium 4,4'-bιs(2-sulphostyryl)bιphenyl Brightener 2 : Disodium 4,4'-bιs(4-anιlmo-6-morpholmo-l .3.5-tπazιn-2-yl)ammo) stιlbene-2.2'-dιsulfonate HEDP 1 , 1 -hydroxyethane diphosphomc acid PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO Polyethylene oxide, with an average molecular weight of 50,000 TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl lmidosole. with an average molecular w eight of 20.000 PVP Polyvinylpyrohdone polymer, with an average molecular weight of 60.000 PVNO Polyvinylpyπdme N-oxide polymer, with an average molecular weight of 50,000 PVPV1 Copolymer of polyvinylpyrohdone 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, wherem n = from 20 to 30 SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Sihcone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1 Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax Paraffin wax HMEO hexamethylene diamme tetra(ethylene oxιde)24 The following are examples of the present invention 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 an orbital vertical screw mixer of 200kg batch size, and several batches prepared This bulk premix is added into a honzontal rotating drum type mixer with internal baffles - a laboratory scale example having batch size 40kg A proportion of premix is sampled and added to the mixer The smaller particles which pose a segregation nsk are dry mixed into the mixer Binding agent. C45AE7, is sprayed into the mixer using an air atomised nozzle The product is left to mix for 2 minutes and anti-cakmg agent (zeolite A) is added into the mixer and mixed for a further 1 minute The product is run into a storage box Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added m a mixing step with other liquid additives such as perfume, to form the final detergent Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 98 48% Photobleach 0 02% Perfume encaps type 1 0.5% Perfume encaps type 2 0.2%o Binding agent C45AE7 alcohol ethoxylate 0.7% Anti-cakmg agent Zeolite A 0.1% * = comprising 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 1 (2 0wt%), HEDP (0.3 wt%), optical brightener (0.5wt%), water (5.3wt%), diamme hexamethylene tetra (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 materials is prepared as in example 1 , of composition as listed below. A proportion of premix is sampled and added to the mixer. Binding agent, C45AE7 mixed with PEG 4000, is sprayed into the mixer using an air atomised nozzle The premix of increased cohesivity is left to mix for 1 mmute The smaller particles which pose a segregation risk are dry mixed into the mixer. The product is left to mix for 2 minutes and anti- cakmg agent (zeolite A) is added into the mixer and mixed for a further 1 mmute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added m a mixing step with other liquid additives such as perfume, to form the final detergent Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 98.48% Photobleach 0.02% Perfume encaps type 1 0.5% Perfume encaps type 2 0.2% Binding agent C45AE7 alcohol ethoxylate 1 0% PEG4000 0.5% Anti-caking agent Zeolite A 0.2% EXAMPLE III This Example also illustrates the process of the invention and incorporates the parameters of Example I A premix of dry detergent materials is prepared as example 1. of composition as listed below A proportion of premix is sampled and added to the mixer. Binding agent, C45AE5, is sprayed into the mixer using an air atomised nozzle The premix of increased cohesivity is left to mix for 1 mmute. The smaller particles which pose a segregation risk are dry mixed into the mixer The product is left to mix for 2 minutes and anti-cakmg agent (zeolite A) is added into the mixer and mixed for a further 15 seconds The product is run into a storage box Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post- added m a mixing step with other liquid additives such as perfume, to form the final detergent Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 97.78% Photobleach 0.02% Perfume encaps type 1 0.4% Perfume encaps type 2 0.1% Binding agent C45AE5 alcohol ethoxylate 1.5% Anti-cakmg agent Zeolite A 0.2% EXAMPLE IV This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent matenals is prepared as m example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer. Bonding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for 1 minute. The smaller particles which pose a segregation nsk are dry mixed into the mixer. A further spray-on of bonding agent is applied to fix the small particles firmly to the surface of the larger host particles. The product is left to mix for 2 minutes and anti- cakmg agent (zeolite A) is added into the mixer and mixed for a further 1 mmute. The product is run into a storage box Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent Component % \λ eight of T Drv materials added to the premix Detergent premix* 98.2% Photobleach 0 02% Perfume encaps type 1 0.5% Perfume encaps type 2 0.2% Binding fluid C45AE7 alcohol ethoxylate 1.0% Anti-cakmg agent Zeolite A 0.08% EXAMPLE V This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer. The fine segregatable particles are dispersed into a earner fluid such as C45AE7 in a tank, using low shear agitation, mixed for 10 minutes. The suspension of fine particles in fluid is pumped to a spray nozzle and atomised onto the premix particles m the mixer The product is left to mix for 2 minutes and anti-cakmg agent (zeolite A) is added into the mixer and mixed for a further 1 mmute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added a mixing step with other liquid additives such as perfume, to form the final detergent. Component % Weight of Total Feed Drv matenals added to the premix Detergent premix* 96.48% Photobleach 0.02% Binding fluid C45AE7 alcohol ethoxylate 3.0% Anti-cakmg agent Zeolite A 0.5% Further example compositions In the following examples all levels are quoted as % by weight of the full finished detergent composition: TABLE Having thus described the invention in detail, it will be obvious to those skilled in the art that vaπous changes may be made without departing from the scope of the mvention and the invention is not to be considered limited to what is described the specification.

Claims: WHAT IS CLAIMED IS: 1. A method for making a detergent particle comprising selecting detergent base particles having a geometric mean particle size from 500 - 2500 microns and, in a moderate to low shear mixing step, adhering detergent active particulates to the detergent base particles, the detergent active particulates having a geometric mean particle diameter no greater than 40% of the geometric mean particle diameter of the detergent base particles and comprising a detergent active selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compound, whitening agents and layered silicates. 2. A method according to claim 1 in which the geometric mean particle diameter of the detergent active particulates is below 200μm. 3. A method for making a detergent composition according to claim 1 or claim 2 in which a first stream of detergent base particles is added to the mixer; a second stream comprising the detergent active particulates is added to the mixer and binder also present in the mixer effects adhesion of the detergent active particulates to the detergent base particles. 4. A method according to claim 3 in which the binder is added by a third stream directly into the mixer. 5. A method according to any preceding claim in which a binder is added to the detergent base particles or the detergent active particulate prior to their addition to the mixer. 6. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulate is no greater than 20% of the geometric mean particle diameter of the detergent base particles. 7. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 10% of the geometric mean particle diameter of the detergent base particles. 8. A detergent composition according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 5% of the geometric mean particle diameter of the detergent base particles. 9. A method according to any preceding claim in which the detergent active particulates comprise photobleach. 10. A method according to any preceding claim in which the detergent active particulates comprise solid particles comprising perfume. 1 1. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 150 microns. 12. A method according to any preceding claim in which the low shear mixer comprises a rotating drum mixer. 13. A method according to any preceding claim in which the detergent base particles comprise agglomerates, particulate detergent raw materials, spray dried powders or mixtures thereof. 14. A detergent particle obtainable by a method according to any preceding claim. 15. A detergent composition comprising detergent particles according to claim 14.

Inventors: DONOGHUE SCOTT JOHN, MORRISON CHRISTOPHER ANDREW, SIMPSON GRAHAM, DONOGHUE, SCOTT, JOHN, MORRISON, CHRISTOPHER, ANDREW, SIMPSON, GRAHAM
Applicants: DONOGHUE SCOTT JOHN, MORRISON CHRISTOPHER ANDREW, PROCTER & GAMBLE, SIMPSON GRAHAM, DONOGHUE, SCOTT, JOHN, MORRISON, CHRISTOPHER, ANDREW, SIMPSON, GRAHAM, THE PROCTER & GAMBLE COMPANY
Application year: 2000
Main classification: C11D11
IPC codes: C11D3, C11D11, C11D17