MXPA02000030A

MXPA02000030A - Detergent particles and methods for making them.

Info

Publication number: MXPA02000030A
Application number: MXPA02000030A
Authority: MX
Inventors: Scott John Donoghue
Original assignee: Procter & Gamble
Priority date: 1999-06-21
Filing date: 2000-06-20
Publication date: 2002-07-02
Also published as: AR024427A1; AU5751200A; CA2375497A1; EP1187905A1; CN1399673A; BR0011844A; JP2003503549A; WO2000078914A1

Abstract

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

Description

PARTICLES OF DETERGENTS AND PROCEDURES TO PREPARE THEM FIELD OF THE INVENTION The present invention relates to detergent particle compositions and to an improved process for making said compositions. The detergent compositions of the invention are suitable for any cleaning process, such as laundry detergent compositions and dishwashing machines. Said particulate compositions may be used directly in their particulate form or they may be first formed in detergent tablets by any method of tablet formation such as compaction.

BACKGROUND OF THE INVENTION To meet consumer needs, particulate detergents must meet several criteria in addition to providing good cleaning properties. Said additional criterion includes: good flow properties so that these can be easily administered from the container to the washing machine or washing process; good solubility / dispensing so that these are effectively administered in the wash; and in addition, particulate detergents should attract the consumer aesthetically. Most particulate detergents comprise a mostly white or pale colored base with optional spots of contrasting color. It has been found that detergents where the base particles vary in color are judged by the consumer to be undesirable and even the consumer thinks that they provide less cleaning efficiciency. However, since the detergent compositions generally comprise pre-processed detergent components such as agglomerates, blown powder produced by spray-drying process or extrudates, in addition to the raw materials, and because the raw materials vary themselves In color, size and / or shape, significant efforts must be made to avoid non-uniformity. To address this, considerable efforts and high costs are required to provide the particulate detergent with uniform properties. It would therefore be desirable to find a method for making detergents that allow a wider range of active detergent materials such as those with wide variations in color, shape and / or size, to produce the detergent particles with good flow properties and good properties of dispensation and good dissolution in addition to good aesthetic properties.

The present inventors have now found improved particles and methods for making such particles that overcome these problems of the prior art.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, a detergent particle is provided which comprises at least two particulate components, a first component of a first color and a second component of a second color, the first and second components being adhered to each other, the average size of the particles of at least the first or second particulate component is not greater than 50% of the average particle size of the detergent particle. In accordance with a further aspect of the present invention there is provided a detergent particle having a sphericity index no greater than 1.7 comprising two particulate components, * a first component and a second component at least, at least one of the first and second components having a sphericity index greater than 1.7, the first and second components being adhered to each other substantially in the absence of compaction pressure.

According to a further aspect of the present invention there is provided a detergent particle having a geometric mean of particle diameter greater than 500 microns, the detergent particle comprising a first particulate component and a second particulate component, the first and second particulate components being adhered to each other substantially in the absence of compaction pressure, the geometric mean of the particle size of at least one of the first and second components that are not greater than 50% of the geometric mean of the particle size of the detergent particle. Preferably at least one of the first and second particulate components has an extension of at least 1.7. In accordance with the present invention, there is also provided a method for making the detergent particles described, comprising contacting the first particulate component and the second particulate component, optionally in the presence of a binder in a mixing step of moderate effort. cutting to adhere the first and second particulate components together and form the detergent composition comprising the detergent particles claimed.

DETAILED DESCRIPTION OF THE INVENTION The present inventors have found that by selecting a combination of first and second particulate detergent components and forming them into a single particle, the undesirable properties and the lack of uniformity can be overcome. In addition, these benefits can be achieved without the intensive processing steps that have been used in the prior art, such as the formation of paste particulates that require prolonged mixing, with energy intensity such as high shear mechanical mixing and even extrusion, both that use compaction pressure to form particulates and require intense energy drying procedures. According to a first aspect of the present invention, the first and second particulates are colored differently from each other. The color difference as used herein refers to the value? E as measured by using colorimetry of three stimuli using a D25M Colorimeter manufactured by Hunter Laboratories. In said colorimeter, the values L, a and b are generated from a sample by directing the incident light towards a powder sample at an angle of 45 °. The incident light is reflected from the sample and is collected by photodetectors which are fixed vertically on the dust sample at 0 °. The detectors convert the intensity of light into values of three stimuli (X, Y, Z) as documented by the Commission Internationale del l'Eclairage (CIÉ). These values are then used to form a descriptive color term on the CIELAB standard color scale. This method is well documented, for example, in "Industrial Color Technology" by R. Johnston and M. Saltzman, American Chemical Society, 1971 Chemical Society, 1971.

Using the CIELAB color scale, L expresses whiteness where L = 100 for white samples and L = 0 for black samples; a represents red / green where positive numbers indicate reddish hue and negative numbers indicate colors towards the green end of the spectrum; and b represents yellow / blue where the positive numbers indicate yellowish tone and the negative numbers indicate blue tones. Therefore for the present invention, the color difference is a positive value? E between the samples of the first and second particulate components where? E = V (? L2 +? A2 +? B2), where? L is the difference in the value L between the first and second particulate components,? a is the difference in a value between the first and second particulate components and? b is the difference in the value b between the first and second particulate components. In particular, in the invention there will generally be an? E value of at least 3. The invention is particularly useful even for large color differences such as E values of at least 4, or even at least 6 or 8 or even at least 10. An additional useful color definition is the whiteness that is represented by W = L-3b. A whiteness value of 92 to 100 is preferred for the detergent particles of the invention. As used herein, "sphericity index" refers to the average value obtained when a measurement is taken of each of 50 particles taken from a sample of particles (whether the detergent particles produced according to the invention, or the first or second particulate that forms the detergent particles), and the value for the sphericity index is calculated for each particle based on the following equation: sphericity index = p2 / (4pa), where p is the perimeter of the particle is already the area of the particle as measured by using an image analysis system Leica Q500MC image analysis system. The apparatus consists of a microscope connected to a video camera and a computer. Commercially available software such as the Q500 software supplied by Leica is used to analyze the amplified images and give the values for p and a. The sphericity index of a perfect circle is 1. Therefore, in accordance with a further aspect of the invention, the sphericity index of the detergent particle is not greater than 1.7 and the sphericity index of at least one of the first and second particulate components is at least 1.7. Preferably the standard deviation of the extension of the detergent particles of the invention is less than 0.8, preferably less than 0.5 and more preferably below 0.2. The sphericity index of the detergent particles according to the invention is preferably not greater than 1.5, more preferably not greater than 1.3 or even 1.2. The sphericity index of at least one of the first and second particulates is preferably greater than 1.9 or even greater than 2.1 or even greater than 2.5. Therefore, the invention allows highly irregular components to adhere together to form a highly regular detergent particle without the need for processes by high energy pressure compaction by aqueous pastes or suspensions such as in extrusion or high mixing processes. shear strength. The invention is even useful when both the first and second particulates comprise highly irregular particles, so that preferably, the sphericity index of both first and second particulates is greater than 1.9 or even greater than 2.1 or 2.5 or even 3. As used herein, "geometric mean of particle diameter" means the geometric mass of the average diameter of a series of discrete particles as measured by standard technique of measuring particle size based on mass, preferably by dry screening. An adequate screening method is in accordance with ISO 3118 (1976). A suitable device is the Ro-Tap Model B screening evaluation agitator which uses 20.32 cm screens of selected sizes. As used herein, the phrase "geometric standard deviation" or "extension" of a particle size distribution means the geometric width of the normal logarithm function best fit for the aforementioned particle size data which can be achieved by the diameter ratio of 84.13 percentile divided by the diameter of the 50th percentile of the cumulative distribution (D8 .13 / D50); see Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker According to a third aspect of the present invention, the geometric mean of the particle diameter of at least the detergent particle is at least 500 microns and the particle geometric diameter of at least 500 microns. one of the first and second particulate components is not greater than 50% of the geometric mean of the particle diameter of the detergent particle, preferably not greater than 25% or even not greater than 10% or 5%. Preferably, the geometric mean of the particle diameter of both the first and second particulate components is as defined. In addition, at least one of the first and second particulate components has an extension (geometric standard deviation) of at least 121, or equal to 2 or 2.5 at least or at least 3 or at least 3.5 or equal to 4 at least or at least 5. Preferably, the extent of both the first and second particulate components is as defined. The invention is particularly useful for forming detergent particles having an extension of at least 0.3, preferably of at least 0.4 or even at least 0.5 or greater, below the extent of the first and / or second particulates. Therefore, to try to achieve highly regular detergent particles, instead of using them as raw materials for processing, highly regular materials and high energy processes, the present inventors have found that the process of the present invention allows the Highly irregular raw materials with less energy intensity are used in a less energy intensive process to produce high quality, highly regular detergent particles. The sizes of the particles of the first and second components can vary widely. It has been found that the invention is useful even where there is a difference in the geometric mean of particle diameter between the first and second particulate components of at least 200 microns or even of at least 250 or 300 or even at least 400 or even at least 500 micras. Preferably one or both of the first and second particulates has a geometric mean of particle diameter below 550 μm. It is particularly preferred that at least one of the first and second particulate components have a geometric mean of particle diameter greater than 150 μm or even greater than 200 μm and preferably not greater than 450 μm or even not greater than 400 μmg. In one embodiment of the invention, the ratio of the average particle sizes of the first and second particulate components will be respectively at least 3: 2, preferably at least 2: 1 or even a high ratio of at least 5. : 1 or at least 10: 1. The proportion may even be higher such that the ratio is at least 20: 1 or even at least 50: 1. Where the ratio is high, it is preferred that the relatively smaller particulate component have a color that is more desirably related to the color of the other particulate component. It may also be preferred that as the particle diameter of the particulate component is smaller, the sphericity index is lower.

In addition, the process of the present invention is suitable for forming the first and second particulate detergent particles each having a wide range of bulk densities and having bulk densities that vary significantly from one another. As used herein the term "bulk density" refers to the bulk density of the uncompressed, non-compacted powder, as measured by pouring an excess of particulate sample through a funnel into a smooth metal vessel ( for example a cylinder of 500 ml of volume) scraping the excess out of the pile on the margin of the glass, measuring the remaining mass of powder and dividing the mass by the volume of the glass. The bulk density of the first and second particulate components may differ by at least 25 g / l, or even by at least 75 g / l or by at least 100 g / l. The bulk density of the first and second particulate components, respectively, is genetically greater than 200 g / l and may be as high as 1500 g / l. It is particularly preferred that the bulk density of at least one particulate component is greater than 700 g / l, preferably greater than 750 g / l or even higher than 800 g / l. The bulk density of the detergent particles of the invention will generally be from 400 to 1100 g / l, generally the bulk density will be greater than 550 g / l before, preferably greater than 650 g / l or even greater than 700 g / l. The invention can be particularly useful for preparing detergent particles having bulk density below 550 g / l, or even below 500 or below 450 g / l.

Each of the first and second particulate components may comprise a single detergent ingredient in particulate form or may comprise a preformed detergent particle. As used herein, the pre-formed particulate may comprise any combination of two or more detergent ingredients. Suitable preformed particulates may have been formed by spray drying, agglomeration, marumerisation, extrusion or compaction procedures, all of which are methods well known in the art for combining detergent ingredients. Particularly preferred pre-formed particulates are powders obtained from spray-drying, agglomerating and extruding processes. Spray dried powders are particularly useful. Suitable spray drying processes are described, for example, in EP-A-763 594 or EP-A-437888. Suitable methods for forming preformed particulates are described for example in W093 / 25378, EP-A-367339, EP-A-420317 or EP-A-506184 and suitable methods for forming pre-formed particulates by extrusion are described by example in W091 / 02047. The pre-formed particulates can be for example either in their wet or dry states, it is common in the formation of detergent particulates that initially, the particulates are wet and a drying step is carried out. In the present invention, the pre-formed particulate can be a particulate before it is subjected to a drying step.

Generally this means that a solvent used as a binder for the processing is present in amounts higher than those desirably present in a finished particulate detergent. Generally, said solvent will be water and the particulates can have a water content for example 15 to 30% by weight of the pre-formed particulate. Often however, the pre-formed particulate will be subjected to a drying step before addition to the mixer so that the water content can be below 15% by weight or even below 10% by weight. It is particularly preferred that any pre-formed particulate component comprises a surfactant or mixture of surfactants. Suitable surfactants are described below. The surfactant content of a pre-formed particulate component is preferably 5 to 80% by weight of the particulate component. The amounts of surfactants greater than 10 or even greater than 30% may be preferred. The amounts of surfactant below 70% or even below 50% may be preferred. Where the pre-formed particulate component comprises surfactant, will generally comprise an additional detergency builder or alkalinity agent such as sodium carbonate, zeolite, or phosphate. For example, each of these components individually, or in mixtures may be present in amounts greater than 5%, preferably greater than 10% or even greater than 20% by weight of the volume of the pre-formed particulate component. Particularly preferred detergency builder components are sodium carbonate and / or zeolite. Zeolite A and zeolite MAP are both suitable. A pre-formed particulate component preferably also comprises an organic builder such as an acid and / or polycarboxylic salt such as citric acid, tartaric acid, malic acid, succinic acid and its salts or a polymeric polycarboxylate such as polymers based in acrylic acids or maleic acids or copolymers thereof. Said components are generally present in the particle at levels below 15% by weight of the particulate component, preferably below 10% by weight of the particulate component. Other preferred ingredients in the preformed particulate component are chelators such as phosphate binders NTA, DTPA and chelators derivative of succinic acid, as described below. These components are preferably present in a pre-formed particulate component in amounts below 5% by weight or even below 2% by weight of the first particulate component. The suds suppressors and / or soil release polymers are also preferred ingredients in pre-formed particulates. Where the particulate components are raw materials of the detergent, any particulate detergent solution is adequate. These can be solid surfactants or soaps, or water-soluble or dispersible polymeric materials, enzymes, bleaching components such as bleach activators or bleaching salts, such as peroxysal, but are generally inorganic components, particularly water-soluble inorganic components such as builders. These ingredients are discussed in more detail below. The detergent particles themselves may contain all the ingredients of a fully formulated detergent or may be mixed with the additional detergent components such as individual detergent ingredients in particulate form or as pre-formed detergent particles as described above. Preferably, the detergent compositions of the present invention comprise more than 30% by weight, more preferably more than 50% by weight or even as high as 80 or 90% by weight or even at least 95% by weight of the detergent particles in accordance with the present invention. The methods of the invention may comprise the step of adding a binder to the blender to facilitate production of the desired detergent particles. Generally said binder will be liquid in the form of a solution or it will melt and will be added when sprinkling either directly into the mixer or onto the particulate components as they travel in the mixer. Preferably the binder is added directly into the mixer for example by spraying. The binder is added for the purposes of improving agglomeration by providing a binding or tackifying agent for the detergent components. The binder can be any conventional detergent binder, preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinylpyrrolidone, polyacrylates, organic acids or their salts such as citric acid or citric salts, and mixtures thereof. from the same. Other suitable binding materials include those listed herein as described in Beerse et al, U.S. Pat. Number 5108646 (Procter and Gamble Company), the description of which is incorporated herein by reference. The binder must be compatible with the active detergent particles as will be appreciated by those skilled in the art. Therefore, where the stability of the active detergent particles is adversely affected by water, the binder will be substantially free of water. Thus, in one aspect of the invention, a first detergent feed stream feeds the low powder into the mixer and furthermore a second stream of the feed comprising a detergent the active particulate is fed into the mixer and the binder is also present in the mixer. mixer. The binder can be fed directly via a third stream into the mixer or can be connected with the detergent base particles or with the active detergent particles before one or both streams enter the mixer, for example the active detergent particles (or a of the base particles) can be those entrained in the binder. Where the mixer is divided into different zones, the three components can be fed in the same zone or optionally can be fed in different zones. In a preferred embodiment of the invention, the detergent base particles and the active detergent particles will be pre-mixed before their addition to the binder. In a further preferred aspect of the invention, after mixing the detergent base particles and the active detergent particles, so that the adhesion of the two components has taken place, an additional liquid component is applied to the outer part of the produced particles. . This additional coating can be of the same chemical composition as the binder or can be any other coating material or detergent ingredients described below. The moderate to low shear mixer to be used in the present invention may be for example a Lodige KM mixer (registered trademark) (Plowshare) of moderate speed, or a mixer made by Fukae, Draes, Schugi or mixers of similar brands which they only mix with moderate to low shear stress. The Lodige KM (Plowshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal cylinder with static holes having a pivoting blade mounted centrally around which several blades in the form of blades are attached. Preferably, the shaft rotates at a speed from about 15 rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm. The grinding or pulverization is carried out by means of cutters, generally smaller than the rotating shaft which preferably operates at approximately 3600 rpm. Other mixers of a similar nature that are suitable for use in the process include the Lodige Ploughshare ™ mixer and the Drais® KT 160 mixer. Generally, 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 tip speed of the blades below 10 m / s, or even below 8m / s or less. Preferably, the average residence time of the various initial detergent ingredients in the low to moderate speed mixer is preferably in the range of from about 0.1 minutes to about 30 minutes, more preferably the residence time is from about 0.5 to about 5 minutes . In this way, the density of the resultant agglomerates of the detergent 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, pellet agglomerators and fluid bed agglomerators. Fluid bed agglomerators are particularly preferred. The fluid bed agglomerators are operated at a surface air velocity of 0.1 to 4 m / s, either under positive or negative pressure. The inlet air temperatures generally have a range of -10 or 5 ° C to 250 ° C. However, the inlet air temperatures are generally below 200 ° C or even below 150 ° C. The fluid bed granulators are preferably operated in such a way that the flow number FN of the fluid bed is at least about 2.5 to about 4.5. The flow number (FNm) is a ratio of the excess velocity (Ue) of the fluidization gas and the particle density (pp) in - relation to the mass flow (q? q) of the liquid sprinkled on the bed at a normalized distance (D0) from the sprinkling device. The flow number provides an estimate of the operating parameters of a fluid bed to control granulation within the bed. The flow number can be expressed either as the mass flow as determined by the following formula: FNm = log10 [. { PpUc} / q, q] o as the volume flow as determined by the formula: FNv = log10 [. { Uc} / qvlqq] where qv? q is the volume of sprinkling in the fluid bed. The calculation of the flow number and a description of its utility is fully described in WO 98158046 the description of which is incorporated herein by reference. In addition, the fluid bed is usually operated at a number Stokes of less than about 1, more preferably from about 0.1 to about 0.5. The Stokes number is a measure of coalescence of the particle to describe the degree of mixing that occurs to the particles in a piece of equipment such as the fluid bed. The Stokes number is measured by the formula: number of Stokes = 4pvd / 9u where p is the apparent density of the particle, v is the excess speed, d is the average diameter of the particle and u is the viscosity of the binder. The Stokes number and a description of its utility are described in detail in WO 99/03964, the disclosure of which is incorporated herein by reference. Therefore, where the mixer is a fluid bed mixer, the base detergent particles of the present invention in a fluid bed optionally have multiple internal "stages" or "zones". A stage or zone is any discrete area within the fluid bed, and these terms are used interchangeably in the present invention. The conditions of the process within one stage may be different or similar to the other phases in the fluid bed / dryer. It is understood that two adjacent fluid beds are equivalent to a single fluid bed that has multiple stages. The detergent streams of detergent base particles and active detergent particles can either be added to the same stage or in different stages, depending on, for example, the size of the particles and the moisture level of the feed stream. The different feeders of different phases can minimize the heat load in the fluid bed, and optimize the particle size and increase the uniformity of the shape of the detergent particles produced. The bed typically becomes fluid with the heated air in order to dry or partially dry the moisture such as that of the binder liquids from the ingredients in the fluid bed. Where the binder is sprinkled in the fluid bed the sprinkling is generally achieved by the nozzles capable of administering a fine or atomized sprinkling of the binder to achieve intimate mixing with the particulates. Typically, the size of the spray droplet is less than about 2 times the size of the particle. This atomization can be achieved either through a conventional two fluid nozzle with atomized air, or alternatively by means of a conventional pressure nozzle. To achieve this type of atomization, the solution or rheology of the suspension may have a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise at the point of atomization. While the location of the nozzle in the fluid bed can be in most of any locations, the preferred location is a position that allows a downward vertical sprinkling of any liquid component such as the binder. This can be achieved, for example, by using a sprinkler configuration at the top. To achieve the best results, the location of the nozzle is placed at or above the fluid height of the particles in the fluid bed. The height of the fluid is typically determined by a spillway or overflow gate height. The zone of agglomeration / granulation of the fluid bed can be followed by an optional coating zone, followed by a drying zone and a cooling zone. Of course, a person skilled in the art will recognize that alternative arrangements are also possible to achieve the particles resulting from the present invention. Typical conditions within a fluid bed apparatus of the present invention include: (i) an average residence time of about 1 to about 20 minutes, (ii) a non-fluid bed depth of about 100 to about 600 nm, (iii) a spray droplet size less than 2 times the average size of the particles in the bed, which preferably is not more than about 100 microns, preferably is not greater than 50 microns (iv) the height of the spray is generally from 150 to 1600 height of the sprinkling from the fluid bed plate or preferably from 0 to 600 mm from the top of the fluid bed, (v) from about 0.1 to about 4.0 m / s, preferably from 1.0 to 3.0 m / s of fluid velocity and (vi) from about 12 to about 200 ° C of bed temperature, preferably from 15 to 100 ° C. Again, one skilled in the art will recognize that conditions in the fluid bed can vary, depending on several factors. The detergent particles produced in the mixer can be further processed by adding a coating agent to improve the color of the particle, increase the whiteness of the particle or improve the particle flow after the detergent particles leave the mixer or dryer if an optional dried drying step is subsequently added to the mixer or at a later stage in the mixer, to obtain high density granular detergent compositions produced by the methods of the invention. Those skilled in the art will appreciate that a wide variety of methods can be used to dry as well as to cool the finished detergent without departing from the scope of the invention. Since the mixer can be operated at relatively low temperatures, the need for a cooling apparatus in the present process is not generally required, which also reduces the costs of processing the final product. Another optional process step includes continuously adding a coating agent such as zeolite and / or fuming silica to the mixer to facilitate the free flow of the resultant detergent particles and prevent over-agglomeration. Said coating agents generally have an average particle size below 100 microns, preferably below 60 microns, more preferably preferably below 50 microns. Any coating step can take place either immediately after the formation of the detergent particles of the invention either before or after any drying step and optionally after the detergent particles have been mixed with the additional ingredients of the detergent to form a fully formulated detergent composition. Preferably any of said coating agent will also have active detergent properties. A particularly preferred coating agent is a surfactant or aqueous solution of surfactant. The detergent particles produced in accordance with the present invention preferably have a geometric mean of particle diameter of at least 500 microns or at least 600 or even at least 700 microns, Generally the average diameter of the particle will not be greater than 3000 microns, preferably not greater than 2500 or even not more than 1500 microns. The sphericity index of the detergent particles according to the present invention will preferably not be greater than 1.5 or even not greater than 1.4 or 1.3 or even not greater than 1.2. The extent of the detergent particles according to the invention is generally from 1 to 1.8, preferably not greater than 1.7., more preferably not greater than 1.6 or even 1.4. The weight percentage of the detergent particles derived from the first and second particulate components respectively can be in a ratio of 100: 1 to 1: 100. Where the geometric mean of the particle diameter of a desirably colored particulate component is not greater than 10% or even not more than 5% of the geometric mean of the diameter of an undesirably colored particle the weight ratio will be low, but the average number of particles of the desirably colored component in the detergent particle will generally be at least 50, preferably at least 100 or even 500 or 1000 times the average number of the undesirably colored component in the detergent particle. The detergent ingredients that are suitable as the ingredients of the base powder, and / or as ingredients of the active detergent particles and / or as the ingredients of any additional ingredients added to the detergent particles of the present invention to form the detergent compositions completely formulations of the invention are described below.

Detergent Ingredients Surfactant The surfactants for use in the invention are anionic, nonionic, cationic, ampholytic, amphoteric and kinds of these zwitterionic surfactants, which are given in U.S.P. 3,929,678, issued to Laughiin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Volumes I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217, issued to Murphy on March 31, 1981. Preferably the detergent particle of the present invention and the compositions comprising said particles comprise an anionic surfactant. Essentially any surfactant useful for detersive purposes can be understood in the detergent composition. These 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 surfactant. Anionic sulfate and sulfonate surfactants are preferred. The anionic surfactants may be present in the detergent granule in amounts of less than 25% by weight or even less than 20% by weight but in the final detergent composition comprising the particle, it is preferably present at a level of 0.1% to 60%. %, preferably from 1 to 40%, particularly from 5% to 30% by weight. Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate and soaps ("alkylcarboxyls") such as water soluble members selected from the group consisting of the water soluble salts of 2-methyl- 1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1 -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched alkyl or branched alkyl group of Cs-Cu, R 1 is a C 1 -C 4 alkyl group, and M It is an alkali metal one. Other possible anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C? 2-C-18 monoesters) , sulfosuccinate diesters (especially saturated and unsaturated Ce-C diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in, or derived from, tallow oil. Suitable anionic sulfate surfactants for use herein include linear and branched alkyl and secondary sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide sulphates, acyl-N- (CrC4 alkyl) ) and -N- (CrC2 hydroxyalkyl) glucamine sulfates, and alkylpolysaccharide sulfates such as the alkyl polyglucoside sulfates (the non-sulfated nonionic compounds are described herein). Preferably, the alkyl sulfate surfactants are selected from the linear and branched C 1 or C 8 alkylsulphates, preferably the straight or branched chain alkyl sulfates of C 11 -C 15, and the straight chain alkyl sulphates of C 12. C14 The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C-io-C-is alkyl sulfates, which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkylethylsulfate surfactant is a C 11 -C 18 alkyl sulfate, more preferably C 11 -C 15, which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule.

Preferred combinations of surfactants are mixtures of the alkyl sulfate and / or sulfonate surfactants and alkyl ethoxysulfate optionally with cationic surfactant. Such mixtures have been described in PCT patent application No. WO 93/18124. Sulfonate anionic surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzenesulfonates, alkyl ester sulfonates, primary or secondary alkanesulfonates of C6-C22 > Cβ-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, oleyl glycerol sulfonates and any mixture thereof. Essentially any alkoxylated nonionic surfactant or mixture is suitable for the present. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the condensate classes of nonionic alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylated / propoxylated condensates with propylene glycol, and the nonionic ethoxylate condensation products. with propylene oxide / ethylenediamine adducts. The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are particularly suitable for use herein. Especially 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 2 to 10 moles of ethylene oxide per mole of alcohol. The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2-CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl; 2-hydroxypropyl; ethoxy, propoxy, or a mixture thereof, preferably C1-C4 alkyl; and R2 is a C5-C3 hydrocarbyl ?; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, Z will be derived from a reducing sugar in a reductive amination reaction; preferably, Z is a glycityl. Alkypolysaccharides suitable for use herein are described in the U.S.A. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, for example a polyglucoside, hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula: R20 (CnH2nO) t (glucosyl)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Suitable amphoteric surfactants for use in the present invention include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (? R4)? N? (R5) 2, wherein R is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, which contains to 26 carbon atoms; R ^ is an alkylene or hydroxyalkylene group containing from 2 to 3 - carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ^ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are the 10"C18 alkyl dimethylamine oxide and the acylamido-alkyldimethylamine oxide of C? O-id. Zwitterionic surfactants can also be incorporated into the detergent compositions according to the invention. * These surfactants can be broadly described as amine derivatives secondary and tertiary, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as sultaine and betaine dimethylammonium hexanoate surfactants of C-12-18 and acrylamidopropane (or ethane) dimethyl (or diethyl) betaines of C10-? S are examples of zwitterionic surfactants which can be used herein .

Cationic surfactants suitable for use herein include the quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a C6-Ci6 N-alkyl or alkenyl ammonium mono, preferably Ce-Cio, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are monoalkoxylated and bisalkoxylated amine surfactants. Ester cationic surfactants, such as choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 4239660 and 4260529 and monoalkoxylated amine surfactants, preferably of the general formula I, are also suitable as are: wherein R1 is C-io-C-is hydrocarbyl, and mixtures thereof, preferably Cι-C alkyl, especially C alquilo? and C? 2 alkyl, and X is any convenient anion that provides charge balance, preferably chloride or bromide. The levels of the cationic monoalkoxylated amine surfactants in the detergent compositions of the invention are generally from 0.1% to 20%, preferably from 0.2% to 7%, particularly from 0.3% to 3.0% by weight.

The cationic surfactant based on bis-alkoxylated amine, such as it is also useful, wherein R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, preferably C 1 0 alkyl, C 2, C and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride.

Bleach Activator The detergent particles or detergent compositions containing them preferably compra bleach activator, which preferably compr an organic precursor of peroxyacid bleach. It may be preferred that the composition compr at least two organic peroxyacid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxyacid bleach precursor, as defined herein. The production of the organic peroxyacid then occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition compra pre-formed bleaching peroxy acid.

It is preferred that the bleach activator be present in the detergent particle. It may be preferred that the bleach activator be present as a separate, mixed particle. Preferably, at least one of the bleach activators, preferably a peroxyacid bleach precursor, is present in a particulate component having an average particle size, by weight, of 600 microns at 1400 microns, preferably 700 microns to 1100 microns. mieras More preferably, the entire activator is present in one or more particulate components having the specified weight of the average particle size. Here, 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 microns to 1700 microns, preferably from 425 microns to 1400 microns. Preferred hydrophobic precursors of peroxyacid bleach preferably compra compound having a suifonated oxybenzene group, preferably NOBS, DOBS, LOBS and / or NACA-OBS.

Preferred hydrophilic precursors of peroxyacid bleaching preferably comprTAED.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors can be represented as O X-C- L wherein L is a residual group and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is O X- C-OOH For the purpose of the invention, the peroxyacid hydrophobic bleach precursors produce a peroxy acid of the above formula wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxy acid bleach of the above formula in where X is a group comprising from 1 to 5 carbon atoms. The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, 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: R3 OR Y - O-C = CHR4 .y - N- S- CH- R4 and mixtures thereof, in which R "is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that contains 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a group solubilizer. Any of R1, R ^ and R4 can essentially be substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilizing groups are -S? 3"M +, -C? 2" M +, - S? 4"M +, -N + (R3) 4X- and 0 <-N (R3) and most preferably -S? 3" M + and -C? 2"M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. Peroxyacid bleach precursor compounds are preferably present in the final detergent compositions at a level of from 0.5% to 30% by weight, more preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic whitening precursors, when present, is preferably from 10: 1 to 1:10, more preferably from 5: 1 to 1: 5 or even from 3: 1 to 1: 3. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, midas, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

The bleach precursors of alkylpercarboxylic acid form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylpercarboxylic type precursor compounds include the N- N 4 N-tetraacetylated alkylene diamines in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms, particularly tetraacetylethylenediamine (TAED). as precursors of hydroxylic peroxyacid bleach Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose. Peroxyacid which are preferred are the amide-substituted alkylperoxy acid precursor compounds, including those having the following general formulas: R1- C- N- R2- C- L R1- N- C- R2- C- L L II II R5 O O wherein R1 is an aryl or alkaryl group with about 1 to about 14 carbon atoms, R2 is an alkylene, arylene and alkarylene containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms and L may be essentially any residual group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or aAs and can originate from synthetic sources or natural sources including for example bait grease. Analogous structural variations for R2 are permissible. R 2 may include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulfur or other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R2 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 form a ring structure together with the nitrogen and carbon atom. Preferred examples of bleach precursors of this type include amide-substituted peroxyacid precursor compounds selected from (6-octamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and the most highly preferred (6-nonamido-caproyl) oxybenzenesulfonate , and mixtures thereof as described in EP-A-0170386. Also suitable are perbenzoic acid precursor compounds that provide perbenzoic acid in the perhydrolysis of organic benzoxazin peroxyacid precursors, as described for example in EP-A-332,294 and EP-A-482,807, and cationic peroxyacid precursor compounds which produce cationic peroxyacids. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; R.U. 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 United Kingdom patent application No. 9407944.9 and in US patent applications. Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams. The particles or compositions of the present invention may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amine substituted compounds as described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecane-dioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Peroxide source Inorganic salts of perhydrate are a preferred source of peroxide. Preferably, these salts are present at a level of 0.01% to 50% by weight, preferably 0.5% to 30% by weight of the composition or component. Examples of inorganic salts of perhydrate include salts of perborate, percarbonate, perfosphate, persulfate and persilicate. The inorganic salts of perhydrate are usually the alkali metal salts. The inorganic salt of perhydrate can be included as the crystalline solid without additional protection. Nevertheless, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material which provides better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as alkali metal borate, carbonate or silicate salts or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaBO2H2O2 or the tetrahydrate NaB02H2O2.3H2 ?. The alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates of the present. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H2O2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the present invention.

Chelators As used herein, chelants refers to detergent ingredients that act to sequester (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably, they show selectivity to bind heavy metal ions such as iron, manganese and copper. The chelants are generally present in the detergent particle or final detergent composition at a level of 0.005% to 10%, preferably from 0.1% to 5%, particularly from 0.25% to 7.5% and preferably from 0.3% to 2% by weight of the compositions or component.

Suitable chelants include phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxydiphosphonates and nitrilotrimethylenephosphonates, preferably, diethylenetriaminpenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene 1,1-diphosphonate, acid 1, 1-hydroxyethyl-diphosphonic acid and 1, 1-hydroxyethanedimethylenephosphonic acid. Other chelants suitable for use in the present invention include nitrilotriacetic acid, and polyaminocarboxylic acids such as ethylenediamintetraacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamindisuccinic acid or any of the salts thereof, and iminodiacetic acid derivatives such as 2-hydroxy acid. hydroxyethyl diacetic or glyceryliminodiacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. Also suitable are β-alanine-N, N'-diacetic acid sequestrants, 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 sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528, 859 describes a suitable alkyliminodiacetic acid sequestrant. The dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid are also suitable. In addition, glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-di-glutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are suitable. Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N, N'-disuccinic acid (EDDS) and 1, 1-hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. 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 composition compound The component or compositions of the present invention preferably contain a builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 60% by weight, preferably 15% to 40% by weight. The detergent compositions of the invention preferably comprise a phosphate-containing builder material. Preferably, present at a level of from 0.5% to 60%, especially from 5% to 50%, particularly from 8% to 40%. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate, or more preferably anhydrous sodium tripolyphosphate. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo and copolymeric polycarboxylic acids or their salts wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, borates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric typealthough monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid, and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) d-acetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, malic acid and fumaric acid, as well as ether carboxylates and the sulfinylcarboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, Lactoxysuccinates described in British Patent No. 1, 389,732, and aminosuccinates described in the Netherlands application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1, 3-propane tricarboxylates described in British Patent No. 1, 387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of 0.1% to 15%, preferably 0.5% to 8% by weight. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1, 3,3-propane tetracarboxylates and 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo 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 pyrolysed citrates described in British Patent No. 1, 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The parent acids of the monomeric or oligomeric polycarboxylate chelating agents, or mixtures thereof with their salts, for example, citric acid or citrate / citric acid mixtures, 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 detergent wash conditions, are water soluble builders useful herein. Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, polymeta / sodium phosphate in which the degree of polymerization is in the range of about 6 to 21, and salts of phytic acid. Examples of organic polymeric compounds include homo- or co-polymeric water-soluble polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates of 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. Polyamino compounds are useful in the present invention including those aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Partially soluble or insoluble detergency enhancing composition The detergent particles or compositions of the present invention may contain an insoluble or partially soluble builder compound, typically present in detergent compositions at a level of 0.5% to 60% by weight, preferably 5% at 50% by weight, particularly from 8% to 40% by weight. Examples of detergents mainly water-insoluble builders include sodium aluminosilicates. As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of aluminosilicate builder are present. Suitable aluminosilicate zeolites have the formula of unit cell Naz [(Al? 2) z (Si? 2) y], XH2O, where z and y are at least 6; the molar ratio of z: y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrated form, and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but preferably are derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS, and mixtures thereof. Zeolite A has the formula: Nai2 [Al? 2) i2 (Si? 2) i2]. XH20 where x is from 20 to 30, especially 27. The zeolite of X has the formula Na86 [(Al? 2) 86 (SiO2)? O6] .276 H2O Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP can be present at a level of 1% to 80%, preferably 15% to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon: aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33, and more preferably within the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon: aluminum ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect, the zeolite MAP builder has a particle size, expressed as a d5o value of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns. The dso value indicates that 50% by weight of the particles have a smaller diameter than that number. The particle size can be determined, in particular, by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by a laser granulometer, described herein. Other methods for establishing the dso values are described in EP 384070A.

Other detergent ingredients Preferred ingredients of the compositions herein are colorants and dyed or speckled particles, which may be sensitive to bleaching. The colorant as used herein may be a pigment or an aqueous or non-aqueous solution of a colorant. It may be preferred that the colorant be an aqueous solution comprising a pigment, at any level to obtain adequate staining of the detergent particles or specks, preferably said levels of staining solution are obtained up to 2% by weight of the stained particle, or preference 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 colorant also comprises other ingredients such as organic binder materials, which may also be a non-aqueous liquid. The pigment can be any suitable. Specific examples of suitable pigments include E104 - yellow 13 food grade (yellow quinoline), E110 - yellow 3 grade food (sunset yellow FCF), E131 - blue 5 food grade (patent blue V), Ultra Marine blue (trade name), E133 - blue 2 food grade (bright blue FCF), E140 - natural green 3 (chlorophyll and chlorophyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). The preferred pigments can be Monastral Blue BV paste (trade name) and / or Pigmasol Green (trade name). Another preferred ingredient of the particles or compositions of the invention is a perfume or perfume composition. Any perfume composition can be used herein. Perfumes can also be encapsulated. Perfumes containing at least one component with a volatile low molecular weight component, for example, having a molecular weight of 150 to 450, or preferably 350 are preferred. Preferably, the perfume component comprises a functional group containing oxygen. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral or alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated in detergent compositions. Suitable enzymes are exemplified in the patents of E.U.A. Nos. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A / S (Denmark), those sold under the trademarks Maxatase, Maxaeal and Maxapem by Gist-Brocades , those sold by Genencor International, and those sold under the trademark Opticlean and Optimase by Solvay Enzymes. The protease enzymes can be incorporated into the compositions according to the invention at a level of 0.0001% to 4% active enzyme per weight of the composition. Preferred amylases include, for example, α-amyiases described in greater detail in GB-1, 269, 839 (Novo). Preferred commercially available amylases include, for example, those sold under the trademark Rapidase by Gist-Brocades, and those sold under the trademark Termamyl, Duramyl and BAN by Novo Industries A / S. Highly preferred amylase enzymes may be those described in PCT / US 9703635, and WO95 / 26397 and WO96 / 23873. The amylase enzyme can be incorporated into the composition according to the invention at a level of 0.0001% to 2% active enzyme by weight. The lipolytic enzyme may be present at a level of active lipolytic enzyme from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, more preferably from 0.001% to 0.5% by weight. The lipase can be fungal or "bacterial in origin being obtained, for example, from a lipase-producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.

* Including Pseudomonas pseudoalcaliqenes or Pseudomonas fluorescens. Lipase from mutants of these chemically or genetically modified strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes which is described in the European patent granted, EP-B-0218272. Another specific lipase here is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza, as a host, as described in the European patent application, EP-A-0258 068, the cell is commercially available at from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This is also described in the US patent. 4,810,414, to Huge-Jensen et al, issued March 7, 1989. The component or composition herein also preferably contains from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.

Examples are Tinopal-UNPA-GX ™ and Tinopal-CBS-X ™ by Ciba-Geigy Corporation. Others include Tinopal-5BM-GX ™, Typal-DMS-X ™ and Typal-AMS-GX ™ by Ciba-Geigy Corporation.

Photobleaching agent Photobleaching agents are preferred ingredients of the compositions or components herein. The preferred photobleaching agent herein comprises compounds having a porphyrin or porphyrin structure. Porphine and porphyrin, in the literature, are used as synonyms, but conventionally porffin is established for the simplest porphyrin without any substituent; wherein the porphyrin is a subclass of porffin. References to porfin 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, more preferably Ge, Si or Ga, or more preferably Al, more preferably Zn. It may be preferred that the photobleach or component be substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, N-pyridyl oxide, phenyl, naphthyl and anthracil. The photobleaching compound or component may have the solubilizing groups as substituents. Alternatively, or in addition to this the photobleaching agent may comprise a polymeric component capable of solubilizing the photobleaching compound, for example PVP, PVNP, PVI or copolymers thereof or mixtures thereof. The highly preferred photobleaching compounds have a phthalocyanine structure, which preferably has the metal elements or cations described above. The phthalocyanines may be substituted, for example the phthalocyanine structures which are substituted in one or more of positions 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 of the atom.

Polymeric organic ingredients Organic polymeric compounds are preferred additional components of the compositions herein and are preferably present as components of any particulate components where these can act as to bind the particulate components together. By "organic polymeric compound" is meant essentially any organic polymeric compound commonly used as a dispersant, anti-redeposition agents and soil suspension in detergent compositions, including any of the high molecular weight organic polymer compounds described as clay flocculating agents. according to the present invention, including quaternized ethoxylated (poly) amine clay as dirt removal / anti-redeposition agent.

An organic polymeric compound is typically incorporated in the detergent compositions at a level of from 0.01% to 30%, preferably from 0.1% or to 15%, most preferably from 0.5% to 10% by weight of the compositions or component. Also suitable in the present invention are terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional and useful organic polymeric compounds are polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably around 4000. The highly preferred polymeric components herein are cotton and cotton soil release polymers. no cotton according to the US patent 4,968,451, Scheibel et al., And patent of E.U.A. 5,415,807, Gossellnk et al., And in particular in accordance with US application No. 60/051517.

Another organic compound, which is a preferred clay dispersing agent / anti-redeposition agent, for use herein, may be monoamines and ethoxylated cationic diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (eg, ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least 12 with a typical scale of 12 to 42. Other dispersing agents / anti-redeposition agents to be used herein are described in EP-B-011965 and US 4,659,802 and EUA 4,664,848.

Foam suppressing system The detergent components and compositions herein, when formulated for use in machine wash compositions, may comprise a foam suppression system at a level of from 0.01% to 15%, preferably from 0.02% to 10% , still most preferably 0.05 to 3% by weight of the composition or component. The suds suppressor systems suitable for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone-based antifoam compounds and 2-alkyl alkanol or soap antifoaming compounds. By antifoam compound in the present invention it refers to any compound or mixtures of compounds which act to reduce the foaming or sudsing produced by a solution of a detergent composition, particularly when stirring 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 anti-foaming compounds also typically contain a silica component. The term "silicone" as used herein, and in general in the industry, comprises a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoaming compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable defoaming compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to 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 C? 8-C 0 (eg, stearone) amino triazines N -alkylated such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamin-clortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms, propylene oxide, amide of bis stearic acid and di-alkali metal phosphates of monostearyl (eg, sodium, potassium, lithium) and phosphate esters. A preferred foam suppression system comprises antifoam compound, preferably comprising in combination polydimethyl siloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound, wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50% , preferably 10% to 40% by weight; a dispersant compound, most preferably comprising a tilted copolymer of silicon glycol with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of about 1: 0.9 to 1: 1.1, at a level of 0.5 % to 10% such as DCO544, commercially available from DOW Corning, and an inert carrier fluid composition, most preferably comprising an ethoxylated C 16 -C 8 alcohol 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 particulate foam suppression system is described in EP-A-0210731. EP-A-0210731 describes other preferred particle foam 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 acid. 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 or combinations thereof, whereby these polymers can be cross-linked polymers. The polymeric soil release agents, hereinafter "SRA", can optionally be used in the components or compositions herein. If used, SRAs will generally be used in amounts from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain adhered thereto through the completion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can enable stains that ocsubsequent to treatment with the SRA to be cleansed more easily in later washing procedures. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that involve at least one transesterification / oligomerization, often with a metal catalyst such as a 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 crosslinked overall structure. The SRAs are for example as described in E.U.A. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other SRAs include polyesters of 1, 2-polypropionic / nonionic polyoxyethylene blocked at the terminus of E.U.A. 4,711, 730, on December 8, 1987 to E.P. Gosselink et al. Other examples of SRAs include: partially and completely anionic oligomeric esters blocked at the E.U.A. 4,721, 580, on January 26, 1988 to Gosselink; the oligomeric compounds of non-ionic polyesters blocked at the end of E.U.A. 4,702,857, on October 27, 1987 to Gosselink; and the anionic terephthalate esters, especially sulfoaroyl, blocked at the end of E.U.A. 4,877,896, on October 31, 1989 to Maldonado, Gosselink et al. SRAs also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see E.U.A. 3,959,230 to Hays of May 25, 1976 and the patent E.U.A. No. 3,893,929 to Basadur, July 8, 1975; cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; C 1 -C 4 alkylcelluloses and C 4 hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al., And methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA include those described in E.U.A. 4,201, 824, Violland et al. and E.U.A. 4,240,918 Lagasse et al .; E.U.A.4,525,524 Tung et al., And E.U.A. 4,201, 824, Violland et al. Other optional ingredients suitable for inclusion in the compositions of the invention include colors and filler salts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. In addition, smaller amounts (for example, less than about 20% by weight) of neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, can be presented, preferably combined with a carbonate salt, polyacids, foam regulators, opacifiers, antioxidants, bactericides and colorants, such as those described in the US patent 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference). The detergent compositions may include as an additional component a chlorine-based bleach. However, because the detergent compositions of the invention are solid, bleaching based on liquid chlorine will not be suitable for these detergent compositions and only bleaching granules based on chlorine or powder will be suitable. Alternatively, the user may add a chlorine-based bleach to the detergent composition at the start or during the washing process. The chlorine-based bleach is such that a kind of hypochlorite is formed in aqueous solution. The hypochlorite ion is chemically represented by the OCT formula. Those bleaching agents that 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, calcium monobasic hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5 , 5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dicloramine T, Chloramine B and Dicloramine B. A preferred bleaching agent for use in the compositions of the present invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. . A preferred chlorine-based bleach may be Triclosan (tradename). The majority of the hypochlorite bleaching agents described above are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the present invention. Some of the above materials are available as aqueous solutions.

Washing method for laundry The machine washing methods herein, usually comprise treating laundry with an aqueous washing solution in a washing machine having dissolved or dispersed therein an effective amount of a detergent composition for washing machine according to the invention. For an effective amount of the detergent composition, from 10 g to 300 g of dissolved or dispersed product in a wash solution of 5 to 65 liters in volume is referred to, since they are typical dosages of product and volumes of wash solution commonly employed in conventional machine washing methods. The preferred washing machines can be so-called low filling machines. In a preferred use aspect, the composition is formulated to be suitable for hard surface cleaning or hand washing. In another preferred aspect, the detergent composition is a pretreatment or soaking composition, to be used in order to pre-treat or soak soiled or stained fabrics.

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

Abbreviations used in the examples In the detergent compositions, the abbreviated identifications of the components have the following meanings: LAS: Linear sodium alkylbenzene sulphonate of Cn-13 TAS: Sebo sodium alkylsulfate CxyAS: Sodium alkylsulfate of C-? X-C < and branched AS: Branched sodium alkyl sulfate as described in W099 / 19454 C46SAS: (2,3) Cu-Ci6 secondary sodium alkyl sulfate CxyEzS: Sodium alkylsulfate of C-jx-C-? and condensed with z moles of ethylene oxide. CxyEz: Primary alcohol of C < | xC- | and predominantly linear condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C? 2-C14 QAS 1: R2.N + (CH3) 2 (C2H4OH ) with R2 = C8-Cn Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of coconut and tallow fatty acids STS: Sodium toluene sulfonate CFAA: (coconut) a! quil (C-i2-C-j4) - N-methyl glucamide - TFAA: C 16 -C 8 alkyl N-methyl glucamide - TPKFA: Whole cut fatty acids of C12-C 4 STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrous sodium aluminosilicate of the formula Na-12 (Al? 2Si? 2) i2-7H2 ?, which has a primary particle size in the range of 1 to 10 microns (weight expressed on an anhydrous basis) NaSKS-6: Crystalline layered silicate of formula d-Na 2 Si 2? Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm. • Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425 μm and 850 μm. MA / AA: Copolymer 1: 4 of maleic / acrylic acid, average molecular weight * of about 70,000 - MA / AA (1): Copolymer 4: 6 of maleic / acrylic acid, average molecular weight of about 10,000 AA: Polyacrylate polymer sodium of average molecular weight of 4,500 CMC: Sodium carboxymethyl cellulose Cellulose ether: Cellulose methyl ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, which has 3.3% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Savinase. Protease Proteolytic enzyme, which has 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: Cellulolytic Enzyme, which has 0.23% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Carezyme Amylase: Amylolytic enzyme, which has 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T Lipase: iipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Lipase (1): Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra Endolasa: Enzyme endoglucanase, which has 1.5% by weight of active enzyme, sold by NOVO Industries A / S. PB4: Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 PB1: Anhydrous sodium perborate with nominal formula NaB? 2-H2? 2 Percarbonate: Anhydrous sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt, which optionally comprises a disintegrating agent. - NACA-OBS: (6-nonamidocaproyl) oxybenzenesulfonate, which optionally comprises a disintegrating agent. TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminpentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 EDDS: Ethylenediamine-N, N'-disuccinic acid, isomer (S, S) in • form of its sodium salt - Photoactivated bleach: zinc phthalocyanine encapsulated in dextrin-soluble bleach polymer (1) Photoactivated bleach: aluminum phthalocyanine encapsulated in dextrin-soluble bleach polymer (1) Brightener 1 4,4'-bis (2-sulphotryl) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5- disodium triazin-2-yl) stilben-2,2'-disulfonate HEDP: 1,1-hydroxydanediphosphonic 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: Polyvinylimidazole, with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA: bis ((C2H5?) (C2H4?) n) (CH3) -N + -C6H12-N + - (CH3) bis ((C2H5?) - (C2H4? n)), where n = 20 to 30 SRP1: Anionically blocked polyesters at the ends SRP 2: Poly (terephthalate 1, 2propylene) diethoxylated polystyrene short block polymer PEI: Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone antifoam : Foam controller based on polydimethylsiloxane with siloxane-oxyalkylene copolymer as dispersion agent with a ratio of said controller to said dispersing agent from 10: 1 to 100: 1 Opacifi er: Mixture of monostyrene-latex with aqueous base, sold by BASF Aktiengesellschaft under the trade name Lytron 621 Wax: Paraffin wax HMEO: Hexamethylenediamine tetra (ethylene) oxide 24 EXAMPLE I This example illustrates a process according to this invention which produces uniform, free-flowing detergent particles with good dispersion and dissolution with uniformity of color and particle shape. Multiple initial detergent ingredients are mixed dry in an orbital vertical screw blender of 200 kg batch size, and several lots are prepared. This premix is fed to a 500 kg / hr horizontal plate fluid bed dryer without outlet weir to maintain a constant static bed depth of 20 cm. The fluid air inlet at 120 ° C is blown into the bed to maintain a fluid velocity of typically 2.0 ms-1. The fine particles are eluted from the top of the bed, collected in a hopper and recycled back to bed. The atomized air spray nozzles are installed in the bed in a specific arrangement - typically 2 double outlet nozzles are * installed in the bed along the horizontal axis of the bed, located above the surface of the static bed. The binders are made by weighing peg 4000 inside a tank of hot water jacket at 60C, to create a 30% PEG solution. The binder is pumped into the spray nozzle at 100 kg / hr and sprayed with 3 bars of air into the fluid bed. The product is collected from the fluid bed and selected on Mogensen vibratory selection units using three covers with installed screens of 1250 μm, 710 μm and 425 μm. The larger particles are mixed and recycled in the fluid bed with the flow of finer particles. The product collected (yield between sieves of 1250 μm and 425 μm) is of a density of 445 g / L the average particle size is 570 μm. The sphericity index is 1.4 with a standard deviation of 0.4. The product has a high whiteness value of W = 98.5. Other standard detergent materials are then dry added to the product in a mixing drum - including enzymes, perfume and dried carbonate specks. Sprayed materials such as perfume or nonionic surfactants can also be added in this step to make a fully formulated detergent product. The finished detergent has the following composition: Component% of weight of the total added Dry materials added to the premix Dry powder spray dried 76.6% TAED as agglomerate 4.2% Antifoam with silicone base as agglomerate 4.0% Sodium carbonate 3.1% Polymeric agent for dirt release 0.5% Laminated silicate Na2Si2O5 (SKS-6) 5.8% Binder, sprinkled on the premixture in the fluid bed Poiiethylene glycol (RMM = 4000) 5.7% (derived by a 30% active solution) * = comprising linear sodium alkylbenzenesulfonate (13.4% by weight), zeolite A (40%), sodium sulfate (23.5%), sodium carbonate (8.4%), magnesium sulfate (0.7% by weight), EDDS (0.4% by weight), MA / AA (2.5% by weight) , soap (1.5% by weight), QAS 1 (2.0% by weight), HEDP (0.3% by weight), optical brightener (0.5% by weight), water (5.3% by weight), hexamethylene diamine tetra (ethylene) oxide ) 24 (1.5% by weight).

EXAMPLE II This example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in Example 1, of composition as listed below. The mixture is fed into a Lodige KM 600 Plow-share mixer, which is a moderate speed mixer located horizontally, at 200 kg / hr feeding speed. The rotational speed of the blade in the mixer is about 100 rpm and the rotational speed of the cutters is about 300 rpm. The water, at 60 ° C, is pumped from a tank with a warm water jacket, as a binder at 20 kg / hr. The water is atomized using atomized air nozzles located in the Lodige KM. The Lodige KM product is continuously fed into a horizontal plate fluid bed dryer, which reduces the free moisture content to approximately 6% (Mettler infrared red method). The product is collected from the fluid bed and sieved in Mogensen vibratory screening units using three covers with installed sieves of 1180 μm, 710 μm and 500 μm. The larger particles are mixed and recycled in the fluid bed with the flow of finer particles. The collected product (yield between sieves of 1180 μm and 500 μm) is of a density of 620 g / L the average particle size is 610 μm. The sphericity index is 1.21 with a standard deviation of 1.2. The product has a high whiteness value of W = 97.0. Other standard detergent materials are then added dry to the product in a mixing drum - including enzymes, perfume and dried carbonate specks. Sprayed materials such as perfume or nonionic surfactants may also be added in this step to make a fully formulated detergent product.

Component% of weight of the total added Dry materials added to the premix Dry spray dried powder 70.4% Laminated silicate Na2Si205 (SKS-6) 12.7% QAS 1 2.4% TAED as agglomerate 4.0% Antifoam with silicone base as agglomerate. 0.8% Sodium carbonate 5.0% Sodium sulphate 4.6% Binder, sprayed on the premix in the Lodige KM Water 10.0% Water removed in the drying process-10.0% Polisher 15 0.1% * = formulation as described in example 1 above .

Additional exemplary compositions In the following examples all levels were quoted as% or of the completely finished detergent composition: TABLE The following compositions are in accordance with the invention.

Claims

NOVELTY OF THE INVENTION CLAIMS 1. A detergent particle comprising at least two particulate components, a first component of a first color and a »Second component of a second color, the first and second components being adhered to each other, the geometric mean of the particle diameter of at least one of the first and second particulate components not being greater than 50% of the geometric mean of the diameter of particle of the detergent particle. 2. The detergent particle according to claim 1, further characterized in that the color difference (? E) between the first and second particulate components is measured using a colorimetry of three J5 stimuli in a Hunter Lab D25M colorimeter. Which is at least 3, where? E = (? L2 +? A2 +? B2), where? L is the difference in the L value between the first and second particulate components,? a is the difference in value a between the first and second particulate components and? b is the difference in the value b between the first and second particulate components. 20 3.- The detergent particle in accordance with the claim 1, further characterized in that the color difference (? E) between the first and second particulate components is at least 5. 4. - The detergent particle according to any preceding claim, further characterized the first particulate component has a geometric mean of particle diameter greater than 150 microns. 5. The detergent particle according to any preceding claim, further characterized both the first and second »particulate components have a geometric mean of particle diameter greater than 150 microns. 6. A detergent particle having a sphericity index not greater than 1.7 comprising at least two particulate components, a first component and a second component, at least one of the first and second components having a sphericity index greater than 1.7 , the first component and a second component being substantially adhered to each other in the absence of compaction pressure. j5 7.- The detergent particle in accordance with the claim 6, further characterized because it has a sphericity index no greater than 1.5. 8. The detergent particle according to claim 6 or claim 7, further characterized in that the sphericity index of at least the first or second component is greater than 2.0. 9. The detergent base particle having a geometric mean of particle diameter greater than 500 microns, the detergent particle comprises a first particulate component and a second particulate component, the first and second particulate components being adhered to each other substantially in the absence of pressure of compaction, the geometric mean of the particle size of at least one of the first and second components being no greater than 50% of the geometric mean of the particle size of the detergent particle and at least one of the first and second particulate components having an extension of at least 2. 10. The detergent particle according to claim 9, further characterized in that at least one of the first and second particulate components has an extension of at least 3. 11. The detergent particle in accordance with claim 9 or 10, further characterized in that at least one of the first and second Particulate components have a geometric mean particle diameter no greater than 25% of the geometric mean particle size of the detergent particle. 12. A detergent particle according to any preceding claim, further characterized by having an extension smaller than 1.8. 13. A detergent particle according to any preceding claim, further characterized in that at least the first particulate component has a geometric mean particle diameter of 200-500 microns. 14. - A detergent particle according to any preceding claim, further characterized in that it has a geometric mean of the particle diameter of 500-2500 microns. 15. A detergent particle according to any preceding claim, further characterized in that there is a difference in the geometric mean of the particle diameter between the first and second * particulate components of at least 250 microns. 16. A method for making a detergent particle according to any preceding claim, further characterized in that it comprises contacting the first particulate component and the second particulate component, optionally in the presence of a binder in a moderate mixing step. under shear stress to adhere the first and second particulate components together. 17. The method according to claim 16, further characterized in that the mixing step is a mixing step, of low shear that takes place in a granulator vessel, tamboe mixer, rotary bowl mixer or fluid bed. 18. The method according to claim 16, further characterized in that the mixing step is a low shear mixing step 20 which takes place in a Ploughshare mixer having a tip speed for the blades below 10m. / s. 19. - The method according to any of claims 16 to 18, further characterized in that a binder is added during or immediately preceding the mixing step. 20. The detergent composition comprising detergent particles according to any of claims 1 to 15.