MXPA02004212A - Detergent compositions. - Google Patents

Abstract

A detergent composition which dispenses and dissolves well in aqueous solution and having good storage stability is described. The composition comprises a reactive particle which preferably comprises first and second reactants which are respectively, acid and alkali-sources and which release gas on contact with water, in which the particle number ratio of the first reactant to the second reactant (that is the ratio of number of particles of the first reactant to the second reactant) in the reactive particle is at least 50:1. The reactive particles themselves are also claimed.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD This invention relates to stable components in particles comprising two reagents, which react with each other in contact with a fluid, in particular a liquid such as water, where said particles can be exposed to said fluid in storage, before want the reaction. The invention relates to the proportion of said particulate components in a stable form, so that the reaction between the two reactants will not substantially take place until desired. The invention also relates to compositions containing said particulate components. The invention particularly relates to effervescent particles, which promote a rapid dissolution to be incorporated into compositions that need to be dissolved quickly and easily in an aqueous medium. The technology may find application in various fields, such as cleaning compositions, in particular washing and dishwashing detergent compositions, which may be in a granular form or which may have been processed to the shape of a tablet. The invention particularly relates to laundry detergent applications.

^ ^ ^ ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ In the field of detergents, problems of poor dissolution and assortment are well known. This problem has been exacerbated by the recent tendencies to produce detergents with a much higher mass density, such as above 600 g / l, to satisfy consumer needs for lower volumes of product and packaging and less waste, it is say, highly active cleaning compositions. The problem is compounded by the use of detergent formulations, which are based not only on readily soluble phosphate builders, but rather on less soluble alternatives, which overcome any environmental problems associated with phosphate builders. In addition, there is a great need to promote a rapid release of detergents into the wash water to provide, in the short term, a more efficient cleaning operation, efficient power washing cycles, wherein the contact time of the detergent solution with the Items that will be washed can be reduced to a minimum. Many solutions have been proposed to try to avoid the problems of poor dissolution and assortment. One of these solutions has been the use of effervescent systems in detergents. For example, detergent compositions comprising effervescent ingredients are described in WO 98/04687. In WO 98/04671, effervescence systems are described for use in . ^ ... Mt ^^ ..? ? ^? ^ mterients, where in an effort to improve dissolution, effervescent acid and alkaline reagents are mixed, which react after contact with water to produce a gas, with a stabilizing agent to produce a substantially anhydrous effervescence particle. , which has maximum efficiency when used in a washing step. Similarly, WO 98/35011 also discloses particles comprising reactants of sodium bicarbonate and organic acid, which react together and form a particle with a binder. EP-A-918 087 discloses co-builder particles to be added to detergent compositions, comprising bicarbonate and polycarboxylic acid, which are formed by roller compaction and which do not contain any free moisture. However, the requirements to provide good storage stability and a good effervescence in final use after contact with the wash liquor, are conflict requirements; the use of stabilizing agents can prevent or reduce the effectiveness in the washing conditions, such as the contact of the water with the effervescent reagents and the resulting reaction rate is decreased, so that the effervescence and, therefore, the effect auxiliary dissolution are undesirably reduced. Therefore, there is a need for effervescent supply systems for use in such applications, which have good storage stability and rapid dissolution and, therefore, release of effervescence upon contact with water during use. a ^^ i t ^ MwrfA,. ^ rf, ... "A ^ jt¡ | tBi ^.,. ^^ M ^ te ^^ jiftj BRIEF DESCRIPTION OF THE INVENTION The inventors herein that have surprisingly improved storage stability and maximized efficiency during use can achieve this through the careful selection of the particle sizes of the reagents in the effervescence particle. Thus, according to the present invention, there is provided a reactive particle comprising two reagents in particle, which react together on contact with a reaction promoter fluid, the ratio in particle number of the first reagent to the second reagent (is say, the ratio of the number of particles from the first reagent to the second reagent) is at least 50: 1. Preferably, the ratio of the average particle size of the second reagent to the first reagent is at least 2: 1. Thus, although a larger number of the reagent of relatively larger particle size can be used, preferably a larger number of the reagent with a relatively smaller particle size is used. It has been found that this combination of a large number of reagents with a relatively smaller particle size, and a smaller number of components with a relatively larger particle size leads to the surprising result than during a procedure for combining the first and second ones. reagents to form the Reactive particle, the reactant with the largest particle size acts as a "core", which is effectively surrounded in the reactive particle by the second component. In this way, the second component provides a barrier, so that a fluid, which promotes the reaction between the two reagents, can not penetrate the barrier layer that acts as a barrier to the ingress of moisture towards the adjoining surface between the two. reagents, so that no reaction is promoted between the first and second reagents and the storage stability is, surprisingly, significantly improved. In a preferred aspect of the invention, the particle is an effervescent particle wherein at least each of the first and second reagents are, respectively, an alkaline source and an acid source, and the fluid is a liquid, i.e. water or other water component. However, it will be evident to those experienced readers that the principle is more broadly applicable to the improved stability of any of the other reagents, where they can be exposed to a fluid (ie, a liquid or a gas), which will promote their reaction with one another, before those desired under conditions of use, where exposure to the fluid is desirable. The present invention also relates to detergent compositions comprising said effervescent particles. The present invention also relates to washing processes, wherein a detergent composition comprising particles effervescent, it is contacted with water to provide a rapid dissolution of the detergent composition in the water, and the water comprising the dissolved detergent composition is then used to wash the soiled articles. The invention is directed, in particular, to the washing of dirty household articles, particularly dishwashing and / or laundry washing applications. The invention is particularly useful for laundry procedures.

DETAILED DESCRIPTION OF THE INVENTION Reactive Particle The reactive particle comprises two reagents in particles, which react together on contact with a third component, generally a reaction promoting fluid. The reaction promoter fluid can be either a third reagent, which is required for a reaction between the first and second reagents, or it can comprise a reaction medium, which both allows the penetration of a fluid from a third reagent aa particle reactive so that a reaction occurs, or that promotes contact between the first and second reagents, so that the reaction between the first and second components is enabled or promoted. The invention is particularly useful when the fluid is a liquid and in particular when the fluid is water, which can come into contact with the reactive particle either in the gaseous or liquid phase. In particular, the particle - m-aaJafcM »***. > , ___ «_ ^ __ ¿. - frfl -üiirtüi r i ?? Reactive reaction can comprise an effervescent particle, wherein the first and second reactants react with one another on contact with water to produce effervescence. Thus, in this embodiment, at least one of each first and second reagent comprises an acid source and at least one alkaline source. The ratio of the particle number of the first reagent to the second reagent (ie, the ratio of the number of particles of the first reagent to the second reagent) is at least 50: 1, preferably at least 100: 1, preferably at least 500: 1, or even very preferably at least 1000: 1 and most preferably at least 5000: 1, or even at least 10000: 1. In addition, the ratio of the average particle size of the second reagent to the first reagent is at least 2: 1, preferably at least 8: 1, most preferably at least 15: 1, or at least 20: 1, or even at least 30: 1. Preferably, the particle size extension of each reagent is no greater than 3, preferably no greater than 2, most preferably no greater than 1.5. As used herein, the phrase "average particle size" means the average geometric mass diameter of a group of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by sieving in dry. As used herein, the phrase "geometric standard deviation" or "expansion" of a particle size distribution means i ^ ?? t? .. ^ ....._ .., "., ... • ^ - • jtir? ti ^ - ^ - ÍÉfMí? TiT ^" ^ * A l? íi the geometric width of the normal record function best adjusted for the aforementioned particle size data, which can be achieved through the diameter ratio of 84.13% divided by the 50% diameter of the cumulative distribution (D84.13 / D50); , Gotoh et al., Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997. Preferably, the average particle size of the particles is from about 500 microns to about 1500 microns, preferably from about 600 microns to about 1200 microns, and most preferably from about 700 microns to about 1000 microns.The particle size distribution is defined by a geometric standard deviation or relatively tight "expansion", in order not to have too many particles outside the target size. geometric standard is pre preferably from about 1 to about 2, preferably from about 1.0 to about 1.7, still most preferably from about 1.0 to about 1.4, and most preferably from about 1.0 to about 1.2. In particular, to prepare an effervescence particle that will be used, for example, in a domestic or industrial cleaning application, the average particle size of the second reagent is preferably greater than 100 μm, preferably greater than 200 μm and most preferably higher than 300 μm. The particle size of the first reagent is preferably below 50 μm, preferably below 25 μm and m and preferably below 10 μm. When the reactive particle is an effervescent particle, the first reagent comprises either the acid source or the alkaline source, but preferably comprises the alkaline source, and the second reagent preferably comprises the acid source. The first reagent is preferably present in the reactive particles at a level of from 0.1% to 99% by weight of the total particle, preferably from 3% to 80%, most preferably from 10% to 75%, and most preferably from 15% to 70% The second reagent is preferably present in the reactive particles at a level of from 0.1% to 99% by weight of the total, preferably from 20% to 95%, preferably from 30% to 85% and most preferably from 35% to 75% by weight. the effervescent particle. For an optimal reaction, the weight ratio of the first and second reagents, in the reactive particle, is preferable and substantially stoichiometric, so that they are substantially the same moles of reactive groups. In this manner, the moles of reactive group from the first reagent to the second reagent are preferably from 5: 1 to 1: 5, preferably from 3: 1 to 1: 3, preferably from 3: 2 to 2: 3 and most preferably from 9:10 to 10: 9. Suitable acid sources include organic, mineral or solid inorganic acids, their salts or derivatives, or mixtures thereof. It is preferred that the acids are mono-, bi-, or tri-protonic acids. Such acids include mono- or polycarboxylic acids, preferably citric acid, glutamic acid, 3-ketoglutaric acid, citralic acid, acid * j *, *. * *. ^ .. ^^ iiiin f | 1TT | ¡ítlfuiJiin ijf mfj in ¡Üiilii ¡| | j | ÜhlÜ tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, masonic acid. Said acids are preferably used in their acid form. The derivatives also include esters of the acids. Preferred acids include citric acid and malic acid. Citric acid is particularly preferred. Any alkaline source can be used in the reactive particle. Alkaline carbonate sources are particularly preferred, for example, including carbonate, bicarbonate, sesquicarbonate and percarbonate salts, in particular bicarbonate and / or carbonate. Preferred carbonates that will be used herein include carbonate and acid carbonates, which must be present in the effervescence particle in a form that can react with the acid source. Generally, therefore, the alkaline source must be soluble in water, or of a very fine particle size so that a reaction with the acid source occurs easily after contact of the effervescent particle with the water. The alkali metal or alkaline ferrous metal salts are suitable. Water-soluble salts such as potassium, lithium, sodium and the like salts are preferred, among which sodium and potassium carbonate are particularly preferred. Suitable bicarbonates that will be used herein include any bicarbonate alkali metal salt such as lithium, sodium, potassium, and the like, among which sodium bicarbonate and potassium bicarbonate are preferred. The bicarbonate can be preferred to carbonate, since it is more effective in weight, that is, at a parity weight, the bicarbonate is a "CO2 deposit" greater than carbonate. However, the total detergent formulation requirements may result in a more alkaline pH, produced by carbonates, providing a more useful total detergent formulation, thus, the selection of carbonate or bicarbonate or mixtures thereof is effervescence granules. it may depend on the desired pH in the aqueous medium, where the detergent composition, comprising the effervescent particles, dissolves. For example, when a relatively high pH is desired in the aqueous medium (for example, a pH above 9.5), it may be preferred to use carbonate alone or to use a carbonate-bicarbonate combination, where the carbonate level is greater than the bicarbonate level, typically in a carbonate to bicarbonate weight ratio of 0.1 to 10, preferably 1 to 5 and most preferably 1 to 2. In one aspect of the invention, wherein the detergent composition comprises only bicarbonate as the alkaline source, preferably the effervescence particle further comprises more than 6% by weight of citric acid optionally in mixtures with other acid source components. Preferably, the reactive particle is substantially anhydrous, so that the entire moisture content (including both bound ie water of crystallization, as unbound, ie free moisture) is less than 0.5% by weight of the effervescent particle. This is particularly preferred when the reaction promoter fluid is water, or when the water promotes contact of the reaction promoter fluid with the reagents More particularly, when the effervescence component comprises both an acid source and an alkaline source, preferably at least the source of acid used to form the effervescence particle has a total moisture content of less than 0.1% by weight, preferably less 0.05% by weight and most preferably less than 0.01% by weight. Most preferably the alkaline source also has a total moisture content of less than 0.1% by weight, preferably less than 0.05% by weight, and most preferably less than 0.01% by weight. Preferably, the effervescence particles have a particle size such that the average particle size is 0.001 mm to 7 mm, preferably less than 2 mm. The mass density of the effervescent particles is preferably from 500 g / l to 1200 g / l, most preferably from 700 g / l to 1100 g / l. The reactive particles may optionally comprise additional ingredients. In general, the effervescence particles comprise not more than 50% by weight of the particle of the additional ingredient (s), preferably not more than 35% by weight, and most preferably not more than 20 or 10%. It may be particularly preferred to have a highly active particle comprising not more than 5% by weight or not more than 2% by weight of additional ingredients, in addition to the components that contribute to gas production / release. When the reactive particle is A **. + * Í * J ... i ^ ^^ - »- ^ trttili? TM ti? Mü? Í? L? Ftlf? Lf í ínti mili M? Ütl ili'i an effervescent particle to be used in a detergent composition, suitable additional ingredients may comprise any of the detergent ingredients described below, in simple form or in mixtures. Particularly suitable surfactants or organic or inorganic builder components are preferably those which are soluble in water, such as those described below. The reactive particles of the invention may optionally comprise binders or coating agents. Suitable bonding or coating materials are selected from one or more blends of more than one of the binders and coating materials known to those skilled in the art. In particular, suitable binders include anionic surfactants such as alkyl or alkylaryl sulfonates or sulfates, of 6 to 20 carbon atoms, preferably alkylbenzene sulfonates, of 8 to 20 carbon atoms, cellulose derivatives, such as carboxymethylcellulose and homogenous polycarboxylic acid. or copolymer or its salts, nonionic surfactants, preferably alcohol ethoxylates of 10 to 20 carbon atoms containing 5-100 moles of ethylene oxide per mole of alcohol and most preferably the primary alcohol ethoxylates of 15 to 20 atoms of carbon containing 20-100 moles of ethylene oxide per mole of alcohol. Of these, tallow ethoxylated alcohol is preferred with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50). Other preferred binders include polymeric materials such as polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average weight of 600 to 10,000. Copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid are other examples of binders polymeric Other binders also include mono or diglycerol ethers of 10 to 20 carbon atoms, as well as fatty acids of 10 to 20 carbon atoms. In the embodiment of the present invention, when a binder is desired, alkylbenzene sulphonates of 8 to 20 carbon atoms are particularly preferred. The reactive particles used in the present invention are preferably prepared by mixing the reactive component (s) with any additional ingredients to produce an intimate mixture and then subjecting the mixture to a granulation step to form particles. However, any granulation process can be used in order to maintain high levels of active ingredient in the finished effervescence particles, the granulation preferably must be presented substantially without the addition of any free moisture to the mixture. The agglomeration, extrusion, marumerization, compaction procedures are suitable. However, a preferred agglomeration step comprises an agglomeration step under pressure to form an agglomerate mixture, followed, if necessary, by a granulation step wherein the agglomerate is formed as reactive particles, such as effervescent particles for used in detergent compositions of the invention. In the preferred pressure agglomeration process, the substantially dry mixture comprising the reagents and any optional additional ingredients, is exposed to high external forces that carry the particles closely together thus densifying the volumetric mass of said particles and creating bonding mechanisms between the particles. components in the mixture. Actually, agglomeration under pressure results in an aggregation mechanism, which is characterized by the presence of bonds between particles, between primary effervescent particles and a structure where these effervescent particles remain identifiable and retain many of their characteristics, for example the ability to react together in the presence of water to supply carbon dioxide. The increase in density associated with the preferred methods for making the reactive particles for use in the present invention is closely linked to the applied pressure. Typically, the mass density will be increased to 200 g / l, preferably from 10 g / l to 150 g / l, starting from the density of the mixture comprising the effervescent starting materials, ie, the source of acid and carbonate , and optionally the detergency builder, before experiencing an agglomeration under pressure. The agglomeration under pressure can be carried out using different procedures, which can be classified by the level of applied forces. A preferred method that will be used herein is that of compaction. In this procedure, the reactants preferably the source of acid and the alkaline source and any additional optional ingredients after having been mixed together, are forced between two compaction rollers that apply a force to said mixture so that the rotation of the rollers transforms the mixture to a compacted sheet / flake. This compacted sheet / flake is then broken to form effervescent particles. Typical roller compactors for use herein are, for example, Pharmapaktor L200 / 50P® commercially available from Hosokawa Bepex GmbH. The variables of the process during the agglomeration step under pressure through roller compaction are the distance between the rollers, the feeding speed, the compaction pressure and the roller speed. A typical feeding device is a feed screw. The distance between the rolls is typically from 0.5 cm to 10 cm, preferably from 3 to 7 cm and most preferably from 4 to 6 cm. The pressure force is typically between 20 kN and 120 kN, preferably 30 kN to 100 kN, most preferably 50 kN to 100 kN. Typically, the roll speed is between 1 rpm and 180 rpm, preferably 2 rpm at 50 rpm, and most preferably 2 rpm at 35 rpm. Typically, the feed rate is 1 rpm and 10 rpm, preferably 5 rpm at 70 rpm, most preferably 8 rpm at 50 rpm. The temperature at which the compaction is made is not critical, typically F, varies from 0 ° C to 40 ° C. The sheet / flake produced by the process of agglomeration under pressure, is broken into effervescence particles through the appropriate method to reduce the size of the sheet / flake to form particles, for example, by cutting, crumbling or breaking the sheet / flake for producing the required length, and if necessary, through a procedure for the particles to become round, that is, to obtain round or spherical granules according to the diameter size defined hereinbefore. In the preferred embodiment, one way to break the sheet / flake after the roll compaction step is to grind the compacted sheet / flake. Grinding can typically be done with a Flake Crusher FC 200® device commercially available from Hosokawa Bepex GmbH. Depending on the particle size required for the effervescence particles, the ground material can be further sieved. Said sieving of the dry effervescent granules can be performed, for example, with a commercially available Alpine Airjet Screen® apparatus. In a preferred process for making a reactive particle where the water is a reaction promoting fluid, the processing takes place under controlled conditions to minimize the amount of moisture, which can make contact with the respective reagents as they form to a reactive particle. The inventors have found that even moisture footprint quantities can adversely affect the stability of the particle produced. In particular, when the reaction is between the first and second reactants this is a self-accelerating reaction, for example, when the reaction between the two reactants produces water as a by-product, this may be particularly important. A particular example where this factor is important, is when the particle that is being produced is an effervescent particle, which is formed from two reactants which are respectively a source of acid and an alkaline source, in particular such as acids organic (for example, citric acid) and a carbonate source, respectively. Thus, in said preferred process, the first and second reagents are formed as a reactive particle, such as an effervescent particle in copper-dried conditions, where atmospheric moisture is reduced from the processing medium. In general, this is achieved through the use of a dehumidifier. Preferably, the Relative Humidity (RH) is less than less than 40%, preferably less than 30% and most preferably less than 20%. Preferably, in addition, at least one and preferably both reagents, provided in an over-dried form, are prepared as the particles of the invention. By "over-drying" it is meant that the reagent is provided in a form that is both dry (i.e., substantially all of the free moisture is removed) and in addition, as is at least partially anhydrous (from so that at least some of the bound water, such as water of crystallization or other water attached to the structure of the reagent, has been removed). Thus, It is preferable that, when the first and second reagents make contact with each other preferably one, and most preferably the two reagents have a total moisture content (comprising both free water and crystallization). it can be measured by drying at 120 ° C for 2 hours in a drying oven) is not greater than 0-1% by weight, preferably not more than 0.05% by weight and most preferably not greater than 0.01%.

Compositions Detergents Comprising an Effervescent Part In accordance with the present invention, there is also provided a detergent composition comprising a detergent matrix and an effervescent particle described above. The detergent matrix can be any conventional detergent composition. In general, however, it comprises a pre-formed detergent matrix component comprising a surfactant, and optional additional, detergent ingredients. Preferably, upon contact of the effervescent particle, the eRH value of the matrix will be no greater than 25%, preferably no greater than 20% or even no greater than 15% or 12%, or even 10%. The eRH value is measured using a Retronic ™ Hygroskop DT device calibrated according to the manufacturer's instructions as presented in the application brochure of Retronic Hygroskop 2 / E Spi / S dated January 3, 1983, using solutions from Saturated salt defined, which covers the humidity scale that will be tested. All measurements are taken at 25 ° C.

In a preferred aspect of the invention, at least one of the components in the detergent matrix is over-dried, i.e. has been dried to a level such that the water that is attached to one or more of the detergent ingredients, already either in the detergent matrix component or the optional additional ingredients, it is removed.

Detergent Matrix Component The detergent matrix generally comprises a detergent matrix component. Said component comprises a preformed particle, which may be in the form of a powder, particle, flake, or other solid form, comprising a surfactant and optional additional detergent ingredients. The surfactant may be anionic, nonionic, cationic, amphoteric, zwitterionic or mixtures thereof. Preferred detergent matrix components comprise anionic, nonionic and / or cationic surfactants. In particular, the matrix components comprising the anionic surfactant can be particularly useful. Suitable surfactants are described in more detail below. The surfactant content of a preformed matrix component is preferably 5 to 80% by weight of the matrix component. The amounts of surfactants above 10% or even more above 30% may be preferred. Also preferred are amounts of surfactant below 70% or even below 50%. 1 * ? The "detergent matrix component generally comprises a solid material which may be a ferrous agent such as sulfates, in particular sodium sulphate, but very it preferably comprises at least one detergent ingredient, in particular, an improved detergency or alkalinity components or mixtures of such components Suitable examples include phosphate, aluminosulite, crystalline layered silicates, sodium carbonate or amorphous silicates. For example, each of these components individually, or in mixtures, may be present in amounts of above 5%, preferably above 10% or even more than 20% by weight of the content of the matrix component. Preferably, the particularly preferred detergency builder components are sodium carbonate and / or zeolite, zeolite A and zeolite MPA are both suitable. Preformed matrix component preferably also comprises an organic builder, such as a polycarboxylic acid and / or salt such as citric acid, tartaric acid, malic acid, succinic acid, and its salts or a polymeric carboxylate such as polymers based on acrylics or rnaleic acids or their copolymers. Such components are generally present in the matrix component at levels below 15% by weight, preferably below 10% by weight, of the matrix component. Other preferred ingredients in the preformed matrix component are chelators, such as phosphonate chelates, NTA, DTPA, and chelates of succinic acid derivative, as described below. These components are generally present in a preformed particulate component in amounts below 5% by weight or even below below 2% by weight of the matrix component. The detergent matrix may comprise one or more preformed detergent matrix components. Suitable preformed components may have been formed through spray drying, agglomeration, marumerization, extrusion or compaction, all these methods for combining detergent ingredients are well known in the art. Particularly preferred preformed matrix components are powders obtained from spray drying processes, agglomerates and extruded products. Spray dried powders are particularly useful. Detergent matrix components made in accordance with at least one low shear mixing step, for example, in a fluidized bed, for example, via fluid bed agglomeration, are also preferred. Spray drying processes are also suitable for forming such preformed detergent matrix components are described for example in EP-A-763594 or EP-A-437888. Suitable methods for forming detergent matrix components that are agglomerated are described for example in W093 / 25378, EP-A-367339, EP-A-420317, or EP-A-506184. The mixers of suitable moderate shear stress below, for example, can be a mixer of moderate speed Lodige KM (trademark) (Ploughshare) or a mixer made by Fukae, Draes, Schugi or similar brand mixers that mix only with moderate to low shear. The Lodige KM (plougshare) moderate speed mixer, which is a preferred mixer for use in the present invention, comprises a horizontal hollow static cylinder having a centrally mounted rotation arrow, around which several blades in the shape of plow. Preferably, the shaft rotates at a speed from about 15 rpm to about 140 rpm, most preferably from about 80 rpm to 120 rpm. Grinding or spraying is achieved through cutters, generally smaller in size than the rotating shaft, which preferably operate at approximately 3600 rpm. Other mixers similar in nature that are suitable for use in the process include the Lodige Ploughshare ™ mixer and the Drais® KT 160 mixer. In general, in the methods of the present invention, the shear stress will not be greater than the shear stress produced by a Lodige KM mixer with the top speed of the plows below 10 m / s, or even more below 8 m / s, or even lower. Preferably, the average residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in the range of about 0.1 minutes to about 15 minutes, most preferably the residence time is about 0.5 to 5. minutes In this way, the density of the resulting detergent agglomerates is at the desired level. Other mixers suitable for use in the present invention are low or very low shear mixers, such as rotating bowl agglomerators, drum agglomerators, tray agglomerators and fluid bed agglomerators. Fluid bed agglomerators are particularly preferred. Typical fluidized bed agglomerators are operated at a surface air velocity of 0.4 to 4 m / s, either under positive or negative pressure. Inlet air temperatures generally vary from -10 or 5 ° C to 250 ° C. However, the inlet air temperatures are generally below 200 ° C, or even below 150 ° C. Suitable methods are described in, for example, WO 98/58046 or WO 98/03964. Suitable methods for forming detergent matrix components through extrusion are described in for example, WO91 / 02047. The detergent matrix may comprise only a deformed component as described or may comprise a mixture of components, for example, mixtures of different spray-dried powders or of different agglomerates, etc., or mixtures of combinations of agglomerates, spray-dried powders, and / or extruded products, etc., as described above. Particularly preferred detergent matrix components are spray-dried powders.

Additional Detergent Ingredients As described above, the detergent matrix will comprise surfactants and may comprise one or more additional detergent ingredients. These may comprise detergent starting materials or may be preformed particles made by processing at least one detergent ingredient with other ingredients that may be active or inactive in the detergent to form a solid particle. When the particulate components are detergent starting materials, any particulate detergent ingredient is suitable. These may be surfactants or solid soaps, or water soluble or dispersible polymeric materials, enzymes, bleaching components, such as bleach activators or bleaching salts such as peroxy salts. These surfactants and additional detergent ingredients are discussed in more detail below. Any of the ingredients listed below can be added to the claimed detergent compositions either as individual solid particles or preformed particles or through a detergent matrix component. These additional detergent ingredients must be incorporated in the detergent matrix if necessary, having undergone a drying step. The final detergent matrix has a value of eRH below 30%.

Detergent Ingredients Surfactant The surfactants suitable for use in the invention are of the anionic, nonionic, zwitterionic and ampholytic classes of these surfactants, and are presented in US Pat. No. 3,929,678, issued to Laughiin and Heuring, December 1975. Other examples are provided in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Beach). A list of suitable cationic surfactants is provided in U.S. Patent 4,259,217 issued to Murphy, issued March 3, 1981. Preferably, the detergent compositions of the present invention and the compositions comprising said particles, comprise an additional anionic surfactant. . Essentially any anionic surfactant useful for detersive purposes can be incorporated in the detergent composition. These surfactants may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono, di and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred. The anionic surfactants may be present in the detergent matrix component in amounts below 25% by weight, or even below 20% by weight, but in the final detergent composition, the particle comprising preferably is present in a level 0.1% to 60%, most preferably from 1 to 40%, and preferably from 5 to 30% by weight. Other anionic surfactants including anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyls") such as water soluble members are selected from the group consisting of water soluble salts of 2-methyl-1 acid. -undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1 -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched alkyl or alkenyl group of 5 to 17 carbon atoms, R 1 is an alkyl group of 1 to 4 carbon atoms and M is an alkali metal ion. Other anionic surfactants include isethionates such as the acyl isethionates, N-acyl tau ratios, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially monoesters of 12 to 18 carbon atoms especially saturated and unsaturated), diesters of sulfosuccinate (especially diesters of 10 to 14 carbon atoms saturated and unsaturated), N-acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in £ A i¿ * L * .. i.

Or derived from tallow oil. Suitable anionic sulfate surfactants for use in the present invention include linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulphates, oliolyl glycerol sulfates, alkyl phenol ethylene ether sulphates, acyl 5 to 17 carbon-N- (C 1 -C 4 -alkyl) and -N- (hydroxyalkyl of 1 to 2 carbon atoms) glucamine sulfates, and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (non-sulfated non-ionic compounds) being described here). The alkyl sulfate surfactants are preferably selected from the linear and branched primary alkyl branched alkyl sulfates, most preferably the branched chain alkyl sulphates of 11 to 15 carbon atoms and the straight chain alkyl sulfates of 12 carbon atoms. to 14 carbon atoms. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of alkyl sulfates of 10 to 18 carbon atoms which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably the alkyl ethoxy sulfate surfactant is an alkyl sulfate of 11 to 18 carbon atoms, most preferably of 11 to 15 carbon atoms, which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of oxide of ethylene per molecule. Preferred surfactant combinations are mixtures of the alkyl sulfate and / or sulphonate surfactants and alkyl ethoxy sulfate, optionally with a cationic surfactant. Said -.JhIh = ^ a ^ Maa8aia¿Siiate «» Ís ^ MBiA »» ^ jbda. "Tai-A mixtures have been described in the PCT patent application No. W093 / 18124. Suitable anionic sulphonate surfactants for use herein include alkylbenzene sulfonate salts of 5 to 20 carbon atoms, alkyl ether sulfonates, primary and secondary alloy sulfonates of 6 to 22 carbon atoms, olefin sulfonates of 6 to 24 carbon atoms. of carbon, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl sulfonates, and mixtures thereof. Essentially any alkoxylated nonionic surfactant or mixture is suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the non-ionic condensate classes of alkyl phenols, non-ionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, non-ionic ethoxylate / propoxylate condensates with propylene glycol, and condensation products of non-ionic ethoxylate with propylene oxide / ethylene diamine adducts. The condensation products of aliphatic alcohols of 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 primary or secondary alcohols, straight or branched, having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of étleno per mole of alcohol. The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula, R2CONR1Z wherein: R is H, hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy , or mixtures thereof, preferably alkyl of 1 to 4 carbon atoms; and R2 is a hydrocarbyl of 5 to 31 carbon atoms; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive tuning reaction; most preferably Z is a glycityl. Alkypolysaccharides suitable for use herein are described in the U.S.A. No. 4,565,647, to Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, for example, a polyglycoside, a hydrophilic group containing from 1.3 to 10 units of saccharide. The preferred alkyl polyglucosides have the formula: R2O (CnH2nO) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl, and mixtures thereof wherein the b # ^? á rJ ^ I ** r, ^ * - ^ - "- ^ t * - ^ 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. Glucosyl is preferably derived from glucose Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids Suitable amine oxides include those compounds having the formula R3 (OR 4) x N ° (R 5) 2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3, and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 groups of ethylene oxide Preferred are alkyl dimethylamine oxide of 10 to 18 carbon atoms ony and acylamino dimethylamine oxide of 10 to 18 carbon atoms. The detergent composition according to the invention can also incorporate zwitterionic surfactants. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as dimethyl of 12 to 18 carbon atoms-ammonium hexanoate and the acylamidopropan (or ethan) dimethyl (or diethyl) betaines of 10 to 18 carbon atoms and sultaine surfactants are illustrative zwitterionic surfactants .JteJa¿M - J.t. to be used in the present. Suitable cationic surfactants that will be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono-surface active agent, of 6 to 16 carbon atoms preferably N-alkyl or alkenyl ammonium of 6 to 10 carbon atoms, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups . Mono alkoxylated and bis-alkoxylated amine surfactants are also preferred. Cationic ester surfactants such as choline ester surfactants, for example, have been described in the U.S. Patents. Nos. 422,8042, 4239660 and 4260529 and are also suitable as mono-alkoxylated, cationic amine surfactants, preferably of the general formula I: wherein R1 is hydrocarbyl of 10 to 18 carbon atoms and mixtures thereof; especially alkyl of from 10 to 14 carbon atoms, preferably alkyl of 10 to 12 carbon atoms, and X is any convenient anion to provide a charge balance, preferably chlorine or bromine. The levels of monoamine amine surfactants ^ .. Aa..A ^^ l¡lfí- ít? Tf ^.? The alkali metal cationic alkoxylates in the detergent compositions of the invention are generally from 0.1% to 20%, preferably from 0.2% to 7%, most preferably 0.3% by weight. 3.0% by weight. The cationic bis-alkoxylated amine surfactant agent such as: it is also useful, wherein R1 is hydrocarbyl of 10 to 18 carbon atoms and mixtures thereof, preferably alkyl of 10, 12, or 14 atoms, or mixtures thereof. X is any convenient anion to provide a charge balance, preferably chloride.

Bleach Activator The detergent compositions of the invention preferably comprise a bleach activator, preferably comprising a peroxy bleach precursor organic acid. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one peroxy bleach precursor hydrophobic acid and at least one peroxy bleach precursor hydrophilic acid, as defined herein. The production of the peroxy organic acid then occurs through an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition, comprise a preformed acid peroxy bleach. Preferably, the bleach activator is present as a mixed, separated particle. Preferably, any bleach activator is present in a particulate component having an average particle size, by weight, of 600 microns to 1400 microns, preferably 700 microns to 1100 microns. It may be preferred that at least 80%, preferably at least 90% or even at least 95%, or even substantially 100% of the component or components comprising the bleach activator have a particle size of 300. microwaves at 1700 microns, preferably from 425 microns to 1400 microns. The preferred hydrophobic acid peroxy bleach precursor preferably comprises a compound containing an oxybenzene sulfonate group, preferably NOBS, DOBS, LOBS and / or NACA-OBS. Preferred preferred hydrophilic peroxyacid bleach precursors comprise TAED.

Peroxyacid Bleach Precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a hydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors can be represented as X-C (0) -L wherein L is a leaving group and X is essentially any functionality, so that in perhydrolysis, the structure of the produced peroxyacid is: "*" * •. '~ < * ^ AHifctM ^ * aifett * .- tfcja &**; O II X-C-OOH For the purpose of the invention, the hydrophobic peroxy acid bleach precursors produce a peroxy acid of the above formula, wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxy acid bleach precursor yields a peroxy acid bleach. of the above formula, wherein X is a group comprising from 1 to 5 carbon atoms. The leaving group, hereinafter the group L, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: O -N-C- R1 -N? N - N - C - CH - R4 I Y R3 I -0-CH = C-CH = CH2 -0-CH = C-CH = CH2 ^^^^^^^^^^^^^^^^^^^^^^^^^^^ Fc »aa.MMC? ^ *. Aft. ' < and mixtures thereof, wherein R1 is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilization group. Any of R1, R3 and R4 can be substituted by essentially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups. The preferred solubilization groups are -SO3 * M \ -C? 2"M +, -S04" M +, -N + (R3) 4X "and O <-N (R3) 3, and most preferably -S03" M + y - C02-M +, wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation, which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium cation or substituted ammonium, with sodium and potassium being most preferred, and X being a halide, hydroxide, methylisulfate or acetate anion. The peroxyacid bleach precursor compounds are preferably incorporated in final detergent compositions at a level of 0.5% to 30% by weight, preferably 1% to 15% by weight, most preferably 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10: 1 to 1:10 and preferably from 5: 1 to 1: 5, or even more than 3: 1 to 1: 3.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, said precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-15868789. Suitable esters are described in GB-A-836988, 846798, 1147871, 214231 and EP-A-0170386. The alkyl percarboxylic acid bleach precursors form percarboxylic acids after perhydrolysis. Preferred precursors of this type provide peracetic acid after perhydrolysis. Preferred alkyl percarboxylic acid precursor compounds of the imide type include the N, N, N 1 N 1 tetra acetylated alkylene diamines, wherein the alkylene group contains 1 to 6 carbon atoms, particularly those compounds wherein the alkylene group contains 1 to 2 carbon atoms. , and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred as a hydrophilic peroxy acid bleach precursor. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethyl-hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose. Amide-substituted alkyl peroxyacid precursor compounds are suitable herein, and include those of the following general formulas: - m? F? M?? tftftJL, Í & 3 & R1 - c - N - R2 - c - L R1 - N - c - R2 - c - L O R5 O or R5 O O wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, amylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl group or alkaryl containing from 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R 1 can be straight or branched chain alkyl, aryl or alkylaryl, containing branching, substitution or both, and can be obtained from any synthetic sources or natural sources, including for example, tallow grease. Analogous structural variations are allowed for R2. The R2 group may include alkyl, aryl, wherein said R2 group may also contain halogen, nitrogen, sulfur, and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386. It may be preferred that R1 and R5 together with the nitrogen and carbon atom form a ring structure. Preferred examples of bleach precursors of this type include amide-substituted peroxyacid precursor compounds seized from (6-octanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and the highly preferred (6-nonamidocapryl) oxybenzenesulfonate and mixtures thereof as described in EP-A-0170386. The perbenzoic acid precursor compounds, which provide perbenzoic acid in the perhydrolysis benzoxazine organic peroxyacid precursors, as described in, for example, EP-A-332294 and EP-A-482807 and cationic peroxyacid precursor compounds , which produce cationic peroxyacids after perhydrolysis, are also suitable. Cationic peroxyacid precursors are described in the U.S. Patents. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in U.S. Patent Application No. 9407944.9 and U.S. Patent Applications. Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of alkyl or benzoyl oxybenzenes substituted with ammonium or alkyl ammonium, N-acyl caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkyl ammonium methylene benzoyl caprolactams and methylene alkyl - < * ftff (** -'- '* = "* < f * & ** ~' ** .-- aa aaaiiaa, trialkyl ammonium caprolactams The particles or compositions of the present invention may contain, in addition to, or as an alternative, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of 0.1% to 15% by weight, most preferably 1% to 10% by weight A preferred class of peroxyacid compounds organic are the compounds substituted with amide as described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid.Accidomono- or diperazelaic acid is also suitable herein. - or diperbrasilic and N-phthaloylaminoperoxycaproic acid.

Peroxide Source Inorganic perhydrate salts are a preferred source of peroxide. Preferably, these salts are present at a level of 0.01% to 50% by weight, most preferably from 0.5 to 30% by weight of the composition. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. In general, these materials are prepared through crystallization or fluidized bed processes. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain salts of AtatHk? A .. ^ l ^ a * J ku * * ± h * »* ftJefi * 1L? ~ ~, * ..« afr. For perhydrate, the preferred embodiments of said granulated compositions use a coated form of the material that provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts, or mixtures thereof, or inorganic materials such as waxes, oils or fatty soaps. The preferred perhydrate salt is sodium perborate and may be in the form of the monohydrate of the nominal formula NaBO2H202 or the tetrahydrate NaB02H2? 2 * 3H2 ?. The alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates herein. Sodium percarbonate is an additional compound having a formula corresponding to 2Na2C? 3 * 3H2O2, and is commercially available as a crystalline solid. Potassium peroxymonosulfate is an inorganic perhydrate salt for use in the detergent compositions herein.

Chelating Agents As used herein, chelating agents refer to detergent ingredients that act to sequester (chelate) heavy metal ions. These components may also have capacity for calcium and magnesium chelation, but preferentially show selectivity to the binding of heavy metal ions such as iron, manganese and copper. Chelating agents are usually present in the detergent matrix component and / or as additional dry aggregate detergent ingredients, so that they are present in the final detergent composition at total levels of 0.005% to 10%, preferably from 0.1% to 5%, preferably 0.25% at 7.5%, and most preferably from 0.3% to 2% by weight of the compositions or component. Suitable chelators include organic phosphonates such as amino alkylene poly (alkylene phosphonate), 1 -hydroxy diphosphonates ethan-alkali metal phosphonates and nitrilo trimethylene preferably diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methyl phosphonate), and hydroxy ethylene-1, 1- diphosphonate, 1,1-hydroxyethane diphosphonic acid and 1,1-hydroxyethane dimethylene phosphonic acid. Other chelators agents suitable for use in the present nitrile acid triacetic and polyaminocarboxylic acids such acid dome ethylenediaminetetraacetic, ethylenediamine disuccinic acid, ethylenediamine acid diglutaric acid, 2-hidroxipropilenodiamina disuccinic and any salts thereof, and iminodiacetic acid derivatives such as 2- -hydroxyethyl diabetic or glyceryl imino diabetic acid, described in EP-A-317,542 and EP-A-399,133. The chelator agents iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516.102 are also suitable herein. Also suitable are chelating or acid sequestering agents - alanine-N, N'-diacetic, acid aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid, described in EP-A-509,382. EP-A-476,257 describes suitable amino-based chelating sequestrants. EP-A-510,331 discloses suitable sequestering or chelating agents derived from collagen, keratin, or casein. EP-A-528,859 discloses a suitable alkyl iminodiacetic acid kidnapping or chelating agent. Also suitable are dipicolinic acid and 2-phosphonobuthane-1,2,4-tricarboxylic acid. They are also suitable N'- disuccinic (GADS) N-N'-diglutaric ethylenediamine (EDDG) glycinamide-N, acid and 2-hidroxipropilenodiamina-N- N'- disuccinic (HPDDS) acid. Especially preferred are N'-disuccinic acid (EDDS) diethylenetriamine pentaacetic acid, ethylenediamine-N, and 1,1-hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. In particular, chelating agents comprising an amino or amine group can be sensitive to bleaching and are suitable in the compositions of the invention.

Water Soluble Detergent Metorator Compound The detergent compositions herein preferably contain a water soluble builder compound, typically present in the detergent compositions at a level of 1% a 80% by weight, preferably from 10% to 60%, most preferably from 15% to 40% by weight.

A preferred detergent composition of the invention, comprising a phosphate-containing builder material, preferably has a level of 0.5% to 60%, preferably 5 to 50%, and most preferably 8% to 40% by weight. Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium pyrophosphate, potassium and ammonium pyrophosphate, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate in where the degree of polymerization varies from about 6 to 21 and salts of phytic acid. The phosphate-containing builder preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more than two carbon atoms, borates, mixture of any of the above. The carboxylate or polycarboxylate builder may be monomeric or oligomeric in type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water-soluble salts of lécaic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, masonic acid, diabetic acid (ethylenedioxy), maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as carboxymethyloxysuccinates described in British Patent No. 1, 379,241, Lactoxysuccinates described in the British Patent. No. 1, 389,732 and aminosuccinates described in Dutch Application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in British Patent No. 1, 387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of 0.1% to 15%, most preferably 0.5% to 8% by weight. Polycarboxylates containing four carboxy groups include oxydisuccinates described in British Patent No. 1, 261, 829, 1,1, 2,2-ethane tetracarboxylates, 1,1, 3,3-propane tetracarboxylates and 1, 1, 2, 3-propan tetracarboxylates. Polycarboxylates containing sulfa substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398,421 and 1, 398,422 and in the US patent. No. 3,936,448 and the sulfonated, pyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, particularly citrates. The acids of origin of the chelating agents of íl, i ^,. M + »?? .. á * ñL 3« ír1 * ¿? monomeric or oligomeric polycarboxylate or mixtures thereof with their salts, for example mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or washing conditions, are water soluble builders, of the present. Examples of polymeric, organic compounds include organic, homo- or co-polymeric polycarboxylic acids or their salts wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described in GB-1, 596,756. Examples of such salts are polyacrylates with a molecular weight of 1000-5000 and their copolymers with maleic anhydride, said copolymers having a molecular weight of from 2,000 to 100,000, especially from 40,000 to 80,000. The polyamino compounds are also useful herein and include those derived from aspartic acid as described in EP-A-305283 and EP-A-351629.

Partially Soluble or Insoluble Detergent Meavator Compound The compositions of the invention may contain a partially soluble or insoluble builder compound present in the detergent matrix component and / or the ingredients hriftiAÉ lt tJMttJ »*» ^ - optional extras. When present, they will typically be present in the detergent compositions in a total amount of 0.5% to 60% by weight, preferably 5% to 50% by weight, most preferably 8% to 40% by weight. Examples of highly soluble detergency builders in water include sodium aluminosilicates. As mentioned above, it may be preferred in one embodiment of the invention that only small amounts of the aluminosilicate builder are present. Suitable aluminosilicate zeolites have the unit cell formula; Naz [(AIO2) 2 (SiO2) and] xH2O, where z and y are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated and preferably crystalline form, containing from 10% to 28%, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations of Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na12 [(AI02)? 2 (Si? 2) i2] -xH2? ®n where x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AIO2) 86 (Si? 2)? O6-276 H2O.

Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP can be present in amounts of 1 to 80%, most preferably 15 to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). This was defined as an alkali metal aluminosilicate of the P type zeolite having a silicon to aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33 and most preferably within the range of 0.9 to 1.2. Of particular interest is zeolite MAP having a silicon to aluminum ratio not greater than 1.15, more particularly, not greater than 1.07. In a preferred aspect, the detergent builder of the zeolite MAP detergent has a particle size, expressed as a d50 value of average particle size of 1.0 to 10.0 microns, most preferably 2.0 to 7.0, preferably 2.5 to 5.0 microns . The value of d5o indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size, in particular, can be determined by conventional analytical techniques, such as microscopic determination using a scanning electron microscope or through a laser granulometer, described herein. Other methods to establish the values of dso are described in EP 384070A.

Colorants Perfumes Enzymes Optical Brighteners A preferred ingredient of the compositions herein are colorants and colored particles or specks, which may be sensitive to bleaching. The colorant, as used herein, may be a pigment or an aqueous or non-aqueous solution of a pigment. It may be preferred that the colorant be an aqueous solution comprising a pigment, at any level to obtain a suitable coloration of the detergent particles or specks, preferably so that the levels of coloring solution are obtained up to 2% by weight of the colored particle, or most preferably up to 0.5% by weight, as described above. The colorant can also be mixed with a non-aqueous carrier material, such as non-aqueous liquid materials including nonionic surfactants. Optionally, the dye also comprising other ingredients, such as organic builder materials, can also be a non-aqueous liquid. The pigment can be any suitable pigment. Specific examples of suitable pigments include food yellow 13 E104 (quinoline yellow) E110-food yellow 3 (sunset yellow FCF) E-131-food blue 5 (blue patent B), ultramarine blue (trademark), E133 -blue food 2 (bright blue FCF), E140-natural green 3 (chlorophyll and chlorophyllins), E141 and green pigment 7 (chlorinated copper oftalocyanine). Preferred pigments can be Monastral Blue BV (trade name) and / or Pigmasol Green (trade name). Another preferred ingredient of the compositions of the invention is a perfume or perfume composition. Any perfume composition can be used herein. The perfumes may also be ** £ & ** ? S J? encapsulated Preferred perfumes contain at least one component with a volatile low molecular weight component, for example, having a molecular weight of 150 to 450, or preferably 350. Preferably the perfume component is an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or functional ether groups or mixtures thereof. Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated in the detergent compositions. Said suitable enzymes are described in the patents of E.U.A. 3,159,570 and 3,533,139. Preferred protease enzymes, commercially available include those sold under the trademarks of Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade names of Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the trade name Opticlean and Optimase by Solvay Enzymes. The protease enzyme can be incorporated into the compositions according to the invention at a level of 0.0001% to 4% of the active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases described in greater detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A / S. Highly preferred amylase enzymes may be those described in PCT / US 9703635, and in WO 95/26397 and WO 96/23873. The amylase enzyme can be incorporated in the composition according to the invention at a level of 0.0001% to 2% by weight of the active enzyme. The lipolytic enzyme may be present at levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight. The lipase can be of fungal or bacterial origin, being obtained from, for example, a strain of lipase production from Humicola sp., Thermomvces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. The lipase of chemically or genetically modified mutants of these strains is also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in the European Patent Issued, EP-B-0218272. Another preferred lipase of the present is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus orvza. as a guest, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name of Lipolase. This lipase is also described in the patent of E.U.A. 4,810,414, Hu§e-Jensen et al., Issued March 7, 1989. The compositions herein also preferably contain from about 0.05% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above. The examples are Tinopal-UNPA-GX ™ and Tinopal-CBS-X ™ by Ciba Geigy Corporation. Others include Tinopal 5BM-GX ™, Tinopal DMS-GX ™, and Tinopal AMS-GX ™ by Ciba Geigy Corporation.

Photo-Bleaching Agent Photo-bleaching agents are preferred ingredients of the compositions or components herein. The preferred photobleaching agent of the present invention comprises compounds having a porphyrin or porphyrin structure. Porphyrin and porphyrin, in the literature, are used as synonyms, but conventionally the porphine represents the simplest porphyrin without any substituent; where porphyrin is a sub-class of porphine. References to porffin in this application will include porphyrin. The porphine structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn, or Hf, most preferably Ge, Si or Ga, or most preferably Al, and preferably Zn. It may be preferred that the photobleaching compound or component be substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl and aromatic ring systems such as pyridyl, pyridyl N-oxide, phenyl, naphthyl and anthracil. The compound or component photo- H | g ¡j £££ ^ fj | i £ igi bleach can have solubilization groups as substituents. Alternatively, or in addition, the photobleaching agent may comprise a polymer component capable of solubilizing the photobleaching compound, for example, PVP, PVNP, PVI or its copolymers or mixtures thereof. Highly preferred photobleaching compounds are compounds having a phthalocyanin structure, which preferably has the metal elements or cations described above. The phthalocyanines can be substituted, for example, the phthalocyanine structures which are substituted at one or more of the atom positions 1-4, 6, 8-11,13,15-18, 20, 22-25, 27.

Organic Polymeric Ingredients Organic polymeric compounds are preferred herein, and are preferably present as components of any particulate component, such as the detergent matrix component, where they can act as binders. By "organic polymeric compound" is meant essentially any polymeric organic compound used as a dispersant, and agents against the network of position and suspension of stains in detergent compositions, including any of the high molecular weight organic polymer compounds described as agents clay flocculants in the present, including a clay / dirt removal agent against ethoxylated (poly) amine, quaternized, according to the invention. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions or components. Terpolymers containing selected monomer units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000, are also suitable herein. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Other useful organic polymeric compounds are polyethylene glycols, particularly those with a molecular weight of 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. The highly preferred polymer components herein are cotton and cotton soil release polymers. which is not cotton, according to the US patent 4,968,451, Scheibel et al., And the patent of E.U.A. 5,415,807, Gosselink et al., And in particular in accordance with the application d * E.U.A. No. 60/051517. Another organic compound, which is a preferred clay / antiscalant dispersing agent® for use herein, may be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, alkyl groups of 1 to 4 carbon atoms or hydroxyalkyl ester or ether, and mixtures thereof, a is 0 to 20, preferably 0 to 4 ( for example, ethylene, propylene, hexamethylene), b is 1 or 0; for cationic monoamines (bs = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least about 12 with a typical scale of about 12 to about 42. Other dispersing / counter redepository agents for use herein are described in EP-B-011965 and E.U.A. 4,664,848. Polymeric dye transfer inhibiting agents when present are generally in amounts of 0.01% to 10%, preferably 0.05% to 0.5%, and are preferably selected from polyamine N-oxide polymers, N-vinylpyrrolidone copolymers, and N-vinylimidazole, polyvinylpyrrolidone polymers and combinations thereof, so these polymers can be cross linked polymers. Polymeric soil release agents, hereinafter "SRA", may optionally be used in the components or compositions herein If the SRAs are used they will generally be used in amounts of 0.01% to 10.0%, typically 1.0%. at 5%, preferably 0.2% to 3.0% by weight Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on and remain adhered to hydrophobic fibers after the terms of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments.This may allow spots that appear subsequent to the SRA treatment to be more easily cleaned in subsequent washing procedures. include polymeric terephthalate esters, typically prepared through procedures that do not they contain at least one transesterification / oligomerization, usually with a metal catalyst such as titanium (IV) alkoxide. Said esters can 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 intertwined total structure. SRA agents, for example, are described in the U.S. patent. No. 4,968,451, dated November 6, 1990, by Scheibel and E.P. Gosselink. Other SRAs include the 1, 2-polypropylene / polyoxylene terephthalate, end blocked, nonionic polyesters of the U.S. patent. No. 4,711, 730 of December 8, 1987, Gosselink et al. Other examples of SRAs include: the oligomeric esters blocked at their end, partially and totally anionic, from the I ^ M ^ M ^,!, ^ ... ^^ .. ^^^^^ E.U.A. No. 4,721, 580, of January 26, 1988 of Gosselink; the nonionic crosed block polyester oligomeric compounds of the U.S.A. No. 4,702,857, dated October 27, 1987, from Gosselink et al .; and the anionic blocked esters of terephthalate, especially sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 by Maldonado, Gosselink and others. The SRAs agents also include; simple copolymer blocks of ethylene terephthalate and propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see patent of E.U.A. No. 3,959,230 to Hays, May 25, 1976 and patent of E.U.A. No. 3,893,929 of Basadur, July 8, 1975; cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the alkyl celluloses of 1 to 4 carbon atoms and hydroxyalkyl celluloses of 4 carbon atoms, see patent of E.U.A. No. 4,000,093, December 28, 1976, by Nicol et al .; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3, and a solution viscosity of about 80 to about 120 centipoise, measured at 20 ° C as an aqueous solution to the cellulose. 2%. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are trademarks of methyl cellulose ethers femi-manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRAs include those described in the US patent. No. 4,201, 824, Violland et al., And US patent. No. 4,240,918 to Lagasse et al .; patent of E.U.A. No. 4,525,524 to Tung et al. And US patent. No. 4,201, 824 of Violland et al.

Foaming Suppressor System The detergent compositions herein, in particular when formulated for use in washing compositions for machines, may comprise a foam suppressor system present at a level of 0.01% to 15%, preferably from 0.02% to 10% , most preferably from 0.05% to 3% by weight of the composition or component. The foam suppressor systems suitable for use herein can comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds, and 1-alkyl alkanol antifoaming compounds, or soap. By antifoaming compound, it is meant any compound or mixture of compounds that act in order to decrease the foam or foaming produced by a solution of a detergent composition, particularly in the presence of agitation of that solution. Particularly preferred defoaming compounds for use herein are silicone anti-foaming compounds defined herein as any defoaming compound including a silicone component. Said silicone antifoaming compounds also typically contain a silica component. The term "silicone" as used herein, and generally throughout the industry, encompasses a ll ti II r | p | ^ * ^ * & ^ - * ^^? tt ^ m? ^ ?? ^? i. varißEted of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred silicone antifoaming compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoaming compounds include monocarboxylic fatty acids and soluble salts thereof as described in the U.S.A. 2,945,347, issued September 27, 1960 by Wayne St. John. Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of 18 to 40 carbon atoms (eg, stearone), amino N-alkylated triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis-stearic acid amide and phosphates and phosphate esters of di-alkali metal of monostearyl (eg, sodium, potassium, lithium). A preferred foam suppression system comprises an antifoam compound, preferably comprising in combination, polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and silica, at a level of from 1% to 50%, preferably from 5% to 25% by weight of the antifoaming agent d # silicone / silica, wherein said antifoaming compound of silica / silica is l Lé ** j üÉ i ****. incorporated at a level of 5% to 50%, preferably 10% to 40% by weight of a dispersing compound, most preferably comprising a silicone-glycol copolymer with a polyoxyalkylene content of 72-78% and an oxide ratio of ethylene to propylene oxide from 1: 0.9 to 1: 1.1, at a level of 0.5% to 10% such as DC0544, commercially available from DOW Corning, and an inert carrier fluid composition, most preferably comprising an alcohol ethoxylate of 16 to 18 carbon atoms with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5 to 80%, preferably 10 to 70% by weight. A highly preferred particle suppression system is described in EP-A-0210731. The application EP-A-0201721 describes other preferred particle suppression systems. Other highly preferred foam suppression systems comprise polydimethylsiloxane or silicone blends, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of secular and acrylic acids. Other optional ingredients suitable for inclusion in the compositions of the invention include colors and filler salts, with a preferred filler salt being sodium sulfate. 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 (eg, less than about 20% by weight), neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids may be present. , foam regulators, opacifiers, antioxidants, bactericides and colorants, as described in the US patent No. 4,285,841, Barrat et al., Issued August 25, 1981 (incorporated herein by reference). The detergent compositions may include as an additional component, a bleach based on chlorine. However, since the detergent compositions of the invention are solid, a mostly liquid chlorine bleach will not be suitable for these detergent compositions and only granular or granular chlorine bleaches will be suitable. Alternatively, a chlorine-based bleach can be added to the detergent composition by the user at the beginning or during the washing process. Chlorine-based bleach is such that a kind of hypochlorite is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI. Those bleaching agents which produce a kind of hypochlorite in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides and chlorimides. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, dihydrate sodium dichlorocyanurate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dicloramine T, chloramine B and Dicloramine B. A preferred bleaching agent for use in the compositions of the present invention is hypochlorite of sodium, potassium hypochlorite or a mixture thereof. A preferred chlorine-based bleach may be Triclosan (tradename). Most of the above-described hypochlorite bleaching agents are available in solid or concentrated form, and are dissolved in water during the preparation of the compositions of the present invention. Some of the above materials are available as aqueous solutions.

Laundry Washing Method The washing machine methods of the present typically comprise treating laundry with an aqueous washing solution in a washing machine having dissolved or dispersed therein an effective amount of a washing machine detergent composition in accordance with the invention. By an effective amount of the detergent composition is meant from 10 g to 300 g of the product dissolved or dispersed in a volume wash solution of 5 to 65 liters, as are the typical product doses and volumes of wash solution commonly used in conventional washing machine methods. The preferred washing machines can be so-called low filling machines.

"MUhhit-l '(?") In a preferred use aspect, the composition is formulated so that it is suitable for hard surface cleaning or hand washing In another preferred aspect, the detergent composition is a pre-treatment composition or soaking, which will be used to treat or soak stained and dirty fabrics.

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

Abbreviations used in the Examples The detergent compositions, the abbreviated component identifications have the following meanings: SODIUM linear alkylbenzene sulfonate of 11 to 13 carbon atoms.

TAS tallow alkyl sodium sulfate. CxyAS Clx sodium alkyl sulphate - Cly. Branched AS branched sodium alkyl sulfate as described in WO99 / 19454. C46SAS (2,3) secondary sodium sulphate of 14 to 16 carbon atoms. CxyEzS Clx-Cly sodium alkyl sulphate condensed with z moles of ethylene oxide. CxyEz predominantly linear primary alcohol of Clx - Cly condensing with an average of z moles of ethylene oxide. QAS R2.N + (CH3) 2 (C2H4OH) with R2 = C12 - C14. QAS 1 R2.N + (CH3) 2 (C2H4OH) with R2 = C8-Cl 1. APA amido propyl dimethyl amide of 8 to 10 carbon atoms. Sodium linear alkyl carboxylate soap derived from a mixture of 80/20 fatty acids of tallow and coconut. STS toluene sodium sulfonate. CFAA (coconut) alkyl-N-methyl glucamide from C12 to C14 carbon atoms.

TFAA alkyl N-methyl glucamide of 16 to 18 carbon atoms. TPKFA total cut fatty acids of 12 to 14 carbon atoms. STPP anhydrous sodium tripolyphosphate. TSPP tetrasodium pyrophosphate. Zeolite A hydrated sodium aluminosilicate of the formula Nal2 (A102SiO2) 12.27H20 having a primary particle size on the scale of 0.1 to 10 micrometers (weight expressed on an anhydrous basis). NaSK.S-6 crystalline layered silicate of the formula d- Na2Si205. Citric acid anhydrous citric acid. Borate sodium borate. Carbonate sodium carbonate anhydrous: particle size from 200 μm to 900 μm. Baking soda anhydrous bicarbonate with a particle size distribution between 400 μm and 1200 μm. Amorphous sodium silicate silicate (SiO2: Na2O = 2.0: 1). Anhydrous sodium sulfate sulfate. MG sulfate anhydrous magnesium sulfate. Trisodium citrate dihydrate citrate of activity of 86.4% with a particle size distribution of between 425 μm and 850 μm. MA / AA Copolymer of maleic / acrylic acid 1: 4, average molecular weight of approximately 70,000. MA / AA Copolymer of maleic / acrylic acid 4: 6, average molecular weight of approximately 10,000. AA sodium polyacrylate polymer with an average molecular weight of 4,500. n. * ffi.ftL.4j. ,. *** .. .A¡f f > . . ^ - «if ^ ü CMC Carboxymethyl cellulose sodium. 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 under the trade name of Satinase. Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO95 / 10591, sold by Genencor Int. Inc. Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A / S. Cellulase Enzyme cellulite, having 0.23% by weight of active enzyme, sold by NOVO Industries A S under the trade name of Carezyme. Amylase Enzyme amylolitic; having 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name of Termamyl 120T. Lipase Lipolytic Enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name of Lipolase. Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name of Lipolase Ultra. Endolase Enzyme endoglucanase, having 1.5% by weight of active enzyme, sold by NOVO Industries A / S. PB4 Sodium perborate tetrahydrate of the nominal formula NaB02.3H2 O.H202- PB1 Anhydrous sodium perborate bleach of the nominal formula Na2B02.H 202. Percarbonate Sodium percarbonate of the nominal formula 2Na2CO3.3H2O2. NOBS Nonanoyloxybenzene sulfonate in the form of sodium salt. NAC-OBS (6-nonamidocaproyl) oxybenzenesulfonate. TAED tetraacetylethylene diamine. DTPA Diethylene triamine pentaacetic acid. DTPMP Diethylene triamine penta (methylene phosphonate), sold by Monsanto under the trade name Dequest 2060. EDDS Ethylenediamine-N, N'-disuccinic acid, sodium salt of the isomer (S, S). Sulfonated zinc phthalocyanine bleach encapsulated in a soluble polymer photoactivated in bleach dextrin (1). 1 4,4'-bis (2-sulfostyril) biphenyl disodium brightener. 2 4,4'-bis (4-anilino-6-morpholino-l, 3,5-triazin-2-yl) amino) stilben-2: 2'-disulfonate disodium brightener. HEDP 1,1-hydroxyethane diphosphonic acid. PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000). PEO polyethylene oxide, with an average molecular weight of 50,000. TEPAE tetraethylenepentamine ethoxylate PVI Polyvinyl imidazole, with an average molecular weight of 20,000. PVP Polyvinylpyrrolidone polymer with an average molecular weight of 60,000.

FVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000. PVP VI Copolymer of polyvinylpyrrolidone and vinylimidazole (average molecular weight of 20,000). QEA bis ((C2H50) (C2H4O) n) (CH3) -N + C6H12-N + (CH3) bis ((C2H5O) - (C2H4O) n, where n = from 20 to 30. SRP 1 Polyesters anionically blocked in their end SRP 2 Short block copolymer of poly (1, 2 propylene terephthalate) diethoxylate PEI Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Defoamer Polydimethylsiloxane foaming controller with copolymer of siloxane-oxyalkylene silicone as the dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Opacrator A mixture of water-based mono-styrene latex sold by BASF Aktiengesellschaft under the trade name of Lytron 621. Wax paraffin wax HMEO Hexamethylenediamine tetra (ethylene oxide) 24.

EXAMPLE 1 Preparation of the Effervescent Particle A batch of 2 kilograms of citric acid and sodium carbonate having a composition of 64% by weight of citric acid / 36% by weight of sodium carbonate was prepared by mixing in a rotary screw mixer of Hosokawa Micron 'Nautamix' DBY- 5R for 5 minutes at a fixed speed of 9 (maximum): 1280 g of anhydrous citric acid Citrique Beige (Grade of 10 fine granules: 16/40) having a particle size of 200-4000 μm, and 720 g of carbonate of Anhydrous sodium (Light Soda Ash ex Brunner Mond) were pre-milled using a Hosokawa Micron Air-Classifiying Mill mill (ACM 15) at a particle size of 5 μm. The mixture was then compacted in a compaction unit Bepex Compactation Unit (Roller diameter 200 mm, width 50 mm): the premixed powders were emptied into the feed hopper above the compaction rollers. The feed hopper has a vertical screw, which feeds the powder to the rollers. The force applied to push these two rollers together known as the compaction force was adjusted to 80 kN by adjusting the speed of the feed screw. The compacted material was collected in the form of broken and unbroken corrugated sheets, which were then ground in a Hosokawa Bepex F200 Flake Breaker apparatus at a speed set at 1. This equipment consists of a roller box with a 1000 sieve μm. The material produced by the Flake beaker was then placed in a vibration screening device (Retsch model AST200) with a sieve size of 355 μm. The material retained in the sieve was the desired finished particle (effervescence particle A in the table below) with an average particle size of 620 μm, and the fine powders were removed for recirculation. The procedure was repeated using the following mixtures of components in the amounts (the respective amounts are given in% by weight based on the effervescent particle) given in Table 1, to make alternative effervescent particles B-E.

TABLE 1 These effervescent particles are then incorporated into the detergent compositions as set forth in Examples 2 to 6.

EXAMPLE 2 A spray-dried granule having the composition presented in Example 3 below, produced by forming an aqueous slurry, which was then formed into particles in a spray-drying tower, then mixed with 5% by weight of TAED, % by weight of foam suppressant, 7.5% by weight of calcium carbonate and 2.5% by weight of sodium sulfate, as additional detergent ingredients in an Eirich mixer. An aqueous solution of PEG-4000 (35% by weight solids) was then sprayed onto the mixture, which was allowed to granulate for 5 minutes. The resulting product was sieved to collect the particles between 300 and 1200 microns. Then 10% by weight of calcium percarbonate, 0.5% by weight of perfume and 1% by weight of enzymes were added and mixed (comprising a mixture of pips comprising amylase, cellulase, pfifease and lipase). The mixture produced has an eRH value of 59%. Then, 10% by weight of effervescent particles of any of the formulations A to E or mixtures of these, were added to this mixture in a Nautamix conical mixer and subsequently packed in detergent boxes.

EXAMPLE 3 A spray-dried granule was produced in a countercurrent spray drying tower with an air inlet temperature of 300 ° C. The agglomerates or other mixtures (see Table 3) were mixed with the spray-dried granule in an intermittent rotating drum mixer. The detergent matrix has an eRH value of 38%. The effervescent particle A is then added, and the product is then packed in detergent boxes. Other examples of detergent compositions according to the invention can be prepared through the use of effervescent particles B to E or mixtures of any of the particles A to te E.

TABLE 2 50% spray-dried granule Composition of spray-dried granules% / P of total power LAS 10.4 Tallow alkyl sulfate 1.6 EDDS 0.4 Rinse aid 15 0.1 Magnesium sulphate 0J Sokalan CP5 2.5 HEDP 0.3 Sodium carbonate 8.4 Sodium sulfate 23.5 Zeolite A 40.0 Miscellaneous (water, perfume, etc.) 12.07 100. 0 Agglomerate of 10% anionic surfactant Composition of agglomerate% / P of total power Alkyl ethoxylate sulfate C45 (EO 0.6) 29.1 Zeolite A 45.0 Sodium carbonate 15.1 Polyethylene glycol (MW 4000) 1.3 Miscellaneous (water, perfume, etc.) £ 5 100.0 l ^ 1 ¿l iÉii liEffMiifi Percarbonate 10% TAED 5% Effervescent Granule 10% Minor 15% EXAMPLE 4 Example 3 was repeated, except that the spray-dried granule was dried at the highest tower inlet temperature of 350 ° C and some of the bound moisture was removed. In this case, the eRH value of the detergent matrix was 24%.

EXAMPLE 5 The detergent matrix of Example 3 was reproduced and added 5% of zeolite overdried in a conical Nautamix mixer. (The overdried zeolite is a Zeolite A, which had more than half the water of crystallization removed through further drying). The resulting detergent matrix has an eRH value of 12%. Then, 10% of the effervescent particle B was added to this matrix and the product was packed in detergent boxes. Alternative examples can be prepared through the use of any effervescent particles B to E or mixtures of any of particles A to E.

EXAMPLE 6 The spray-dried, agglomerated and agglomerated builder particles of the formulation described in Tables 3A and 3B, which are presented below, were first fed to a Lodige KM ™ mixer at 660 kg, with drum rotation at 100 ° C. RPM and a cutter speed of 3600 RPM. The resulting mixture was fed to a fluid bed dryer. Optionally, an aqueous solution of PEG-4000 (30% by weight solids) is sprayed onto the mixture in the first of three stages in the fluid bed dryer. The resulting product is sieved to collect the particles in the range from about 600 to about 1100 μm. The finer particles were recirculated to the Lodige KM mixer and the large particles were milled and recirculated to the fluid bed dryer. The detergent components added in dry and sprinkled by spray, from the tables presented later, were then added. The eRH value of the detergent matrix was typically around 14%. É4? ^ Y¡ e ^ TABLE 3A The following compositions are according to the invention. * • •. í '.

TABLE 3B The following compositions are according to the invention. iiiii iltlíjfi rlp .itÉfflt í n k * x. ¿¿¿¿X. * k AJdUi A¿ÜU * iAft, «, fa« A.? ^. Ñ. ^^. & ^ ^ S ^^^ ^^ m¡ i, í.t¿tol.? jr- > > ~ * - ". ~? ~ + .Jí ~?

Claims (21)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A reactive particle characterized in that it comprises two particulate reagents, which together react on contact with a reaction promoting fluid, wherein the ratio of the particle number of the first reagent to the second reagent (ie, the ratio of the number of particles of the first reactive to the second reagent) is at least 50: 1. 2. A reactive particle according to claim 1, further characterized in that the ratio of the average particle size of the second reagent to the first reagent is at least 2: 1. 3. A reactive particle according to claim 1 & claim 2, further characterized in that the reaction promoting fluid comprises water, either in the gas or liquid phase. 4. A reactive particle according to any of the preceding claims, further characterized in that the particle is an effervescent particle and at least each of the first and second reagents are respectively an alkaline source and an acid source. 5. A reactive particle according to any of the preceding claims, further characterized in that the ratio of the particle number of the first reagent to the second reagent (ie, the ratio of the number of particles from the first reagent to the second reagent) is at least 500: 6. A reactive particle according to any of the preceding claims, further characterized in that the ratio of the average particle size of the second reagent to the first reagent is at least 8: 1. 7. A reactive particle according to any of the preceding claims, further characterized in that the expansion of the particle size of each reagent is not greater than 2. 8. A reactive particle according to any of the preceding claims, further characterized because the average particle size of the second reagent is preferably greater than 100 μm. 9. A reactive particle according to any of the preceding claims, further characterized in that the average particle size of the first reagent is preferably below 50 μm. 10. A reactive particle according to any of the preceding claims, further characterized in that which is an effervescent particle and the first reagent comprises the alkaline source, and the second reagent comprises the source of acid. 11. A reactive particle according to any of the preceding claims, further characterized in that the first reagent is present in an amount of 15% to 70% by weight of the particle. 12.- A reactive particle in accordance with any of the > - * - preceding claims, further characterized in that the second reagent is present in an amount of 35% to 75% by weight of the particle. 13. A reactive particle according to any of the preceding claims, further characterized in that one of the first and second reagent comprises citric acid and the second the first and second reagents comprises an alkaline source selected from sodium carbonate and sodium bicarbonate, or mixtures thereof. 14. A reactive particle according to any of the preceding claims, further characterized in that it comprises a total moisture content that is less than 0.5% by weight of the effervescent particle. 15. A detergent composition comprising a reactive particle according to any of the preceding claims, further characterized in that it is an effervescent particle and a detergent matrix. 16. A detergent composition according to claim 15, further characterized in that the detergent matrix has a value of eRH not greater than 30%. 17. A method for making a composition according to claim 15 or claim 16, characterized in that the detergent matrix comprises a detergent matrix component, which is first prepared through a spray-drying process and then mixed with the reactive particle. 18. - A method for making a reactive particle according to any of claims 1 to 17, characterized in that after mixing the first and second reagents they are formed to a particle through a pressure agglomeration process. 19. A method according to claim 18, further characterized in that the pressure agglomeration step occurs at a Relative Humidity below 35%. 20. A method according to claim 19, further characterized in that the mixing of the first and second reagents is also presented at a Relative Humidity below 35%. 21. A method for washing dirty surfaces, particularly a laundry washing process, characterized in that it comprises dissolving a detergent composition comprising effervescent particles to form an aqueous solution and contacting the solution with the soiled surfaces for washing. i ^ i ^ S - ^ ,,,,., i. .to? atfi ^ aa ^ Baafaáafaa