MXPA01003097A

MXPA01003097A - Solid detergent compositions

Info

Publication number: MXPA01003097A
Authority: MX
Inventors: Richard Timothy Hartshorn; Zayeed Alam; Kevin Norwood
Original assignee: Zayeed Alam; Richard Timothy Hartshorn; Kevin Norwood; Procter & Gamble; The Procter & Gamble Company
Priority date: 1998-09-25
Filing date: 1998-09-25
Publication date: 2001-10-01
Also published as: MXPA01003081A; ES2283074T3; AU9510898A; WO2000018869A1; EP1115831B1; CA2344434C; ATE357500T1; EP1115831A1; JP2002525419A; DE69837403T2; CA2344434A1; ZA996130B; DE69837403D1; MX227672B; AR026850A1

Abstract

The present invention provides a detergent granule and tablets comprising an anionic surfactant system comprising an anionic sulfate surfactant and / or an anionic sulfonate surfactant and other detergent active ingredients, the granule comprises at least one and one second particulate component and optionally a binding agent, characterized in that the ratio of sulfate anionic surfactant to sulfonate anionic surfactant in the particulate components and in the optional binder is less than 1: 4 or more than 4: 1, preferably even less than 1: 5 or more than 5: 1, the invention also relates to specific granules comprising a restricted degree of mixture of anionic sulfonate and zeolite surfactant, sulfate anionic surfactant and carbonate salts and / or a restricted degree of mixture of polymeric detergency builder and anionic surfactant co, in particular sulfa surfactants

Description

DETERGENT GRANULES TECHNICAL FIELD OF THE INVENTION This invention relates to detergent granules or tablets comprising two or more granular components and anionic surfactants which are comprised in this granule or tablet in such a way that an improved supply to the washing is obtained, a reduced formation of residue on the fabrics or the washing machine, and an improved product appearance is obtained, while a good cleaning performance is provided.

BACKGROUND OF THE INVENTION In order to meet the needs of the consumer, a detergent must not only provide good cleaning, but the product must also have good aesthetics, good flow properties, good dispersion and good dissolution in the wash water. Additionally, it is important that the same quality of product and cleaning is provided during the life of the product, and therefore, that the product is not only stable, but also can be dosed uniformly in each use. It has been found that a more uniform dosage of detergent actives can be achieved if the active substances are present in granules of a similar particle size. It has also been discovered that this contributes to the overall appearance of the product. In particular, it has been found that when the number of granular components of a composition is reduced and that therefore, for example, several detergent components are incorporated in the same granule, an improved uniform dosage to the wash is obtained. However, the inventors have discovered that certain detergent ingredients that are required to provide good cleaning performance can cause problems when mixed together in the same granule. They have discovered in particular that the product tends to gel and leave residues on the fabric and the machine when active detergents which are used in general are mixed together to form a granule or tablet. They have surprisingly discovered that this occurs in particular when anionic sulfate surfactants and anionic sulfonate surfactants are formulated together. Granules containing mixtures of these surfactants tend to form gels which do not disperse or dissolve well. This not only leads to residues in the fabric and debris in the washing machine, but also causes the surfactants not to be supplied efficiently or completely to the washing and also that the other detergent actives can be trapped in the gelled surfactant mixture. and therefore are not supplied to the washing effectively or completely.

The inventors have now discovered that when only small amounts of sulfate surfactant and sulfonate surfactant are mixed, or preferably do not mix at all, these problems are reduced or even avoided. In this manner, the anionic sulfonate and sulfate surfactants can be used in the formulations, as may be required for improved cleaning performance and foaming profile. They have discovered that this can be done more effectively by formulating a detergent granule comprising different particulate components with a reduced degree of sulfate and sulfonate surfactant mixture, or even where more preferably no component comprises both of the anionic surfactant of sulfate and the anionic sulfonate surfactant. Moreover, the inventors have discovered that other detergent ingredients such as water insoluble builders, inorganic salts and polymeric builders also can cause dispersion or dissolution problems depending on how they are mixed in the formulation. In particular, zeolite, carbonate salts and polymeric polycarboxylates were found to cause problems. The inventors also discovered a way to formulate those potentially problematic ingredients in the detergent granule component, to optimize the dispersion, dissolution and performance of the individual detergent actives.

In this way, the present invention provides an improved method for formulating known detergent actives, to provide improved overall product performance, delivery, dosage and appearance.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a detergent granule comprising an anionic surfactant system, comprising an anionic sulfate surfactant and / or an anionic sulfonate surfactant, and other detergent active ingredients, the granule comprises at least one first and one second particulate component and optionally a binding agent, characterized in that the ratio of sulfate anionic surfactant to sulfonate anionic surfactant in the particulate components and in the optional binder is less than 1: 4 or more than 4: 1, preferably even less than 1: 5 or more than 5: 1. Preferably, no anionic sulfate and sulfonate surfactant are intimately mixed with each other in the same particulate component, and therefore preferably the detergent granule does not comprise particulate components containing both sulfate anionic surfactant and anionic surfactant sulfonate co. This granule has been found to cause less gelling problems or fewer dispersion or dissolution problems and fewer waste problems.

The invention also provides detergent granules comprising specific particulate components containing specific ratios of anionic sulfonate surfactant to polymeric builder material and / or water insoluble builder material, and the invention also provides granules comprising components that they comprise specific ratios of anionic sulfate surfactant to inorganic carrier salts and / or polymeric builder material. The invention also provides methods for manufacturing the granule of the invention and detergent compositions consisting substantially of the granule. The components as described herein may also be present in a detergent tablet. By reducing the degree of mixing of anionic sulfate surfactant and anionic sulfonate surfactant to the tablet components, reduced gelling and decreased residue on the fabric and improved dissolution or dispersion of the tablet in the washing liquid is achieved.

DETAILED DESCRIPTION OF THE INVENTION The granule or detergent tablet of the invention comprises at least two particulate components, which comprise at least two detergent active ingredients. The particulate components can be defined as preformed particulate components, formed from the (at least two) detergent actives therein. Suitable preformed particulate components may be formed by spray drying, agglomeration, marmerization, extrusion or compaction process, all of which are methods well known in the art for combining detergent ingredients. It may be preferred to preprocess certain ingredients by spray drying and others by agglomeration or extrusion, in this way, it may be particularly preferred that at least one of the preformed particulate components be a particle of blown powder which is obtained by drying processes by spray, and at least one component is an agglomerated or extruded material. Suitable spray drying processes for forming said preformed particulate components are described, for example, in EP-A-763594 or EP-A-437888. Suitable methods for forming preformed particulate components that are agglomerated are described for example in W093 / 25378, EP-A-367339, EP-A-420317 or EP-A-506184 and suitable methods for forming preformed particulate components by extrusion. they are described, for example, in WO91 / 02047. For purposes of the invention, the ingredients in a single particle component can therefore be considered in an intimate mixture with one another, while for the purpose of the invention, the ingredients of a particulate component are considered not to be intimately mixed with the ingredients of another component in particle. The granule or tablet may also comprise particles which are not preformed particle components as defined herein, but for example particulate furnish. It may be preferred that the granule or tablet comprises particulate builders, such as organic or inorganic salts or acids, in particular polymeric or monomeric acids or particulate polycarboxylic acids or salts thereof, silicates, inorganic salts, such as alkalinity sources and salts, fillers and detergency builders, organic and inorganic bleaching particles, such as percarbonate salts and perborate salts, bleach activators, and also enzymes and perfumes. Effervescence components, such as organic acids and carbonate salts are also preferably included. However, it may be preferred that perfumes, enzymes, but also bleach activators and effervescence components are present as one or more components in preformed particles, thus containing more than one ingredient. The granule or tablet may also comprise liquid components, which may be useful as binders, as described herein. The particulate components and optionally other particulate ingredients, or delivery materials (which contain no more than active ingredients) can be formed in the granule by any known method but preferably by the use of a granulation method in which only pressure is used Reduced or no additional pressure is used. The particulate components as described herein should therefore preferably be mixed in such a manner that the ingredients of one component are not formed in an intimate mixture with the ingredients of the other component. Therefore preferably the component should not be mixed in such a way as to form a component, but in such a way that substantially all the ingredients in the core of each component in particle, more preferably in the component as a whole, remain in that component in particle . To achieve this, it is preferred to use a method in which a moderate or low shear mixer is used. In this way, high shear mixers such as the Lodige CB mixer can be used, but preferably lower shear mixers, described below as low or moderate shear mixers, are used. In a preferred process for manufacturing the granule of the invention, a first feed stream of detergent ingredients, which may contain one or more of the particulate components, is fed to the mixer and in addition a second feed stream of detergent ingredients, which may contain one or more of the particulate components, is fed to the mixer, preferably a binder is also present in the mixer. The binder can be fed directly to the mixer through a third stream or can be contacted with particulate components and other ingredients before one or both of these feed streams enter the blender. Where the mixer is divided into different zones, the three components can be fed into the same zone or optionally can be fed to different zones. In a preferred process, the particulate material will be premixed prior to the addition of the binder. The medium to low shear mixer that will be used to make the granule or the tablet herein may be for example a moderate speed Lodige KM (trademark) mixer (Ploughshare)., or a mixer manufactured by Fukae, Draes Schugi or similar brand mixers which mix with medium to low shear force. The Lodige KM (Plowshare) moderate speed mixer, which is a preferred mixer for use in the present invention, comprises a horizontal hollow static cylinder having a centrally mounted rotatable shaft around which several plow-shaped blades are mounted. Preferably, the shaft is rotated at a speed of 15 rpm at 140 rpm, more preferably at 80 rpm at 120 rpm. The crushing or pulverization is achieved by means of cutters, generally smaller in size than the rotary axis, which operate preferably at 3600 rpm. Other mixers similar in nature that are suitable for use in the process include the Lodige Ploughshare ™ mixer and the Drais ® KT 160 mixer. In general, the shear stress will not be greater than the shear produced by a Lodige KM mixer with the speed tip of plows below 10 m / s or even below 8 m / s or even lower. Preferably, the average residence time of the various starting detergent ingredients in the low to moderate speed mixer is preferably in the range of 0.1 seconds to about 30 minutes, more preferably the residence time is 0.1 to 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level. Other suitable mixers are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, tray agglomerators and fluid bed agglomerators. Particular preference is given to fluid bed agglomerators. Typical fluidized bed agglomerators are operated at a surface air velocity of 0.1 to 3 m / s, either under positive or negative pressure. The air inlet temperatures are generally in the range of -10 or 5 ° C to 250 ° C. However, the air inlet temperatures are generally below 200 ° C, or even below 150 ° C. The fluidized bed granulator is preferably operated so that the flow number FN of the fluid bed is at least 2.5 to 4.5. The flow number (FNm) is a ratio of the excess velocity (Ue) of the fluidizing gas and the particle density (pp) in relation to the mass flow (qpq) of the liquid sprinkled in the bed at a normal distance ( D0) of the spray device. The flow number provides an estimate of the operational parameters of a fluidized bed to control the granulation within the bed. The flow number can be expressed as the mass flow as determined by the following formula: FNm = log? 0 [. { PpUe} / q? ¡q] o as the volume flow as determined by the formula: FNv = log? o [. { EU} / qvi¡q] where qv? q is the volume of spray in the fluid bed. The calculation of the flow number and a description of its utility are fully described in WO 98/58046 the description of which is incorporated herein by reference. In addition, the fluidized bed is generally operated at a Stokes number of less than 2, or even less than about 1, more preferably from 0.1 to 0.5. The Stokes number is a measure of particle coalescence to describe the degree of mixing that occurs to particles in a piece of equipment such as the fluid bed. The Stokes number is measured by the formula: Stokes number = 4pvd / 9u in which p is the apparent particle density, v is the excess velocity, d is the average particle diameter 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. Thus, where the mixer is a fluid bed mixer, the components of detergent particles and other particulate ingredients of the granule or tablet are passed to the fluid bed optionally having multiple internal "stages" or "zones". A stage or zone is any small area within the fluid bed, and those terms are used interchangeably in the present. The process conditions within a stage may be different or similar to the other stages in the fluid bed / dryer. It is understood that two adjacent fluid beds are equivalent to a single fluid bed having multiple stages. The various feed streams of particulate components and other ingredients can be added at the same time or in different stages, depending on, for example, the particle size and moisture level of the feed stream. The different feed streams at different stages can minimize the heat load on the fluid bed, and optimize the particle size and increase the uniformity of the shape of the produced detergent granules. The bed is typically fluidized with hot air in order to dry or partially dry the moisture such as that of the binder liquids of the ingredients in the fluid bed. Where the binder is sprayed in the fluid bed, the spray is generally achieved through nozzles capable of delivering a fine or atomized spray of the binder to achieve intimate mixing with the particulate components and the other optional ingredients. Typically, the drop size of the atomizer is less than 2 times the particle size. This atomization can be achieved either through a conventional 2 fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle. To achieve this type of atomization, the rheology of solution or suspension may have a viscosity of less than 500 centipoise, preferably less than 200 centipoise at the point of atomization. Although the location of the nozzle in the fluid bed can be in almost any location, 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 superior spray configuration. To achieve better results, the location of the nozzle is placed at or above the fluidized height of the particles in the fluid bed. The fluidized height is typically determined by the height of the lock or the overflow gate. 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, one of skill in the art will recognize that alternate 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 1 to 20 minutes, (i) a non-fluidized bed depth of 100 to 600 mm, (ii) a spray droplet size of 2 times the average particle size in the bed, which is preferably no more than 100 microns, more preferably no more than 50 microns, (iv) dew height generally from 150 to 1600 mm in height of dew from the fluid bed plate or preferably 0 to 600 mm from the top of the fluid bed, (v) from 0.1 to 4.0 m / s, preferably 1.0 to 3.0 m / s of fluidizing velocity and (vi) of 12 to 200 ° C bed temperature, preferably 15 to 100 ° C. Again, one of ordinary skill in the art will recognize that conditions in the fluid bed may vary depending on a number of factors. The detergent granules of the invention, which are preferably produced in said low to medium shear 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 stability and / or flow capacity of the particle after the detergent particles leave the mixer or dryer if an optional drying step is added subsequently to the mixer or at a later stage in the mixer. Said optional processing step may (also) include continuously adding a coating agent such as zeolite and fuming silica to the mixer to facilitate the free flowability of the resulting detergent particles and to avoid over-agglomeration. Said coating agents generally have an average particle size below 10 microns, preferably below 60 microns, even more preferably below 50 microns. Other additional coating agents include any conventional coating agent that is used to form a protective layer, to protect the ingredients against moisture, light, or temperature or external reagents, including inorganic salts, and also additional binders, brighteners, disintegration aids. , inks, dot formers and other dyes or bleaching agents and perfumes. To form the granule or tablet of the invention, the preformed particulate components can be added in their wet or dry states, for example, it is common in the formation of detergent granules or tablets that initially the particulate components are wet and pass through a drying stage. The wet state will aid in the formation of the granule or tablet of the invention, by joining the particulate components (and optionally other ingredients) together. In the present invention, the preformed particulate component or components can be such as a preformed particle before it goes through a drying state, such that a preferred embodiment is in a form that could be described as a wet agglomerate, a wet extruded material or wet blown powder. In general, this means that a solvent or binder for processing is present in too high a quantity. Said solvent will preferably contain water; the particulate component can then have a water content of, for example, up to 35%, preferably up to 25% or even up to 15% by weight of the component. However, often, the particulate component will have already gone through a drying step before the formation of the granule or tablet of the present, so that the water content can be, for example, up to 20%, preferably up to 15% or even up to 10% or even 5% by weight of the component. It may be more preferred to use dry, dried, or partially dried particulate components to form the granule or tablet of the invention, and then use a binder. In general, said binder will comprise a liquid or be in a liquid or viscous form at processing temperature. The binder will generally be added by spraying either directly into a mixer or container containing the particulate component or components of the grain or tablet of the invention, or onto the particulate component or components as they are introduced into the mixing step. The binding agent is added for purposes of improving granulation or agglomeration by providing a binding or adhesion agent for detergent components and other particulate ingredients of the granule or tablet. The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinylpyrrolidone and derivatives thereof, polyacrylates / maleates, organic acids or their salts such as citric acid or citric salts, and mixtures thereof. the same. Other suitable binding agents include those which are listed herein and described in Beerse et al, U.S. Patent No. 5,108,646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference. If an anionic surfactant is present in the binder, it preferably comprises one or more anionic sulfate surfactants and is free of anionic sulfonate surfactants. Mixtures of branched and linear alkyl sulfates may be preferred. Nonionic surfactants, although good binders, may not be preferred in all embodiments, because they can cause gelling and dispersion problems when contacted with water. In fact, in a preferred embodiment of the invention, the granule or tablet comprises less than 3% or even less than 3% or even less than 1% or even 0% nonionic surfactants, to help reduce the problems of dispersion or dissolution. Due to the excellent performance of the anionic surfactants, when formulated according to the invention, the reduction or elimination of nonionic surfactants has no negative impact on the cleaning performance of the granule or tablet of the invention. The tablets of the invention can be manufactured by any method known in the art. In general, the individual particulate components and the other optional ingredients and optionally the binding agents are mixed by any of the steps described above, to form a mixture which is then formed into a tablet.

It may be preferred that the tablet be manufactured under limited pressure and that optionally a coating or binder be used to form a stable tablet. This will ensure a reduced mixture of the ingredients of one component with ingredients of another component. The average particle size of the detergent granule of the invention will generally be 300-2,000 microns, preferably at least 500 microns, more preferably at least 600 microns. The average particle size will generally be below 1, 700 microns or even below 1, 500 or even below 1, 300 microns. This average particle size can be determined for example by sieve analysis, for example by screening a sample of the relevant particle material herein through a series of sieves, typically 5, with sieves of various diameters or aperture sizes. Obtaining a fraction number (therefore having a particle size above, below or between the mesh sizes of the sieve sizes used) with which the weight is determined (fractions by weight) and then the average particle size. Preferably at least 70% or even at least 80% by weight of said granule has a particle size of 300 to 3,000 microns, or even at least 70% or even 80% by weight of said granules have a particle size of 400 to 2,000. microns, or even at least 70% or even 80% by weight of said granules has a particle size of 500 to 1,500 microns.

The density of the granule according to the invention will generally be above 300 g / l, preferably larger than 400 g / l or even larger than 450 g / l or even larger than 500 g / l. The detergent granule can be incorporated in any detergent composition, preferably laundry detergents. It is more preferred that the detergent granule comprises the majority of the detergent actives of a fully formulated detergent and that the granule contains 60% or even 70% or even 80 or 90% or more of the fully formulated detergent composition. It may even be preferred that the granule forms approximately 100% of the detergent composition.

Particulate Components The detergent granule or tablet comprises at least two particulate components comprising more than one active detergent. The detergent tablet or tablet preferably comprises anionic sulfate surfactant and anionic sulfonate surfactant as described herein. Then, the ratio of sulfate surfactant to sulfonate in a single component should be less than 1: 4 or even less than 1: 5, or more than 4: 1 or even more than 1: 5. It has been found that reducing the degree of mixing of sulfate surfactant and sulfonate surfactant is particularly advantageous when the sulfate surfactant is an alkyl sulfate surfactant or branched alkyl sulfate surfactant.

In this manner, the alkoxylated alkyl sulfates can be mixed with sulfonate surfactant at higher ratios, for example 4: 1 to 1: 4, than the alkyl sulfate or branched alkyl surfactants. Preferably the ratio is still less than 1: 6 or even less than 1: 7 or more than 6: 1 or even more than 7: 1 or more preferably less than 1: 10 to more than 10: 1 or even less than 1 : 15 or more than 15: 1. However, preferably there is no component in the granule or tablet of the invention comprising anionic sulfate surfactant and anionic sulfonate surfactant. Thus, it is more preferred that at least one particulate component comprises an anionic sulfonate surfactant and another detergent active ingredient and that at least one other component comprises an anionic sulfate surfactant and another detergent active ingredient. Alternatively, or in addition to, the anionic sulfate surfactant and / or the anionic sulfonate surfactant may each be present as separate ingredients. For example, the alkyl sulfate surfactant or part thereof may be present as a binding agent for binding the particulate components to form the granule or tablet, provided that the above relationship is satisfied with respect to the binding agent. Then, preferably anionic sulfonate surfactant is not present in the binder.

In addition, the anionic sulfate surfactant, but in particular the anionic sulfonate surfactant may be present as a particle consisting essentially of said sulfate or sulfonate surfactant, for example in the form of a granule or flake or extruded material of said sulfonate or sulfonate surfactant. surfactant agent. Consisting essentially of means such that the particle comprises at least 80% or even at least 90% by weight of the respective surfactant particle. The particles can therefore contain very small amounts of ingredients which are introduced for example by the process for making the particles, in particular those can include water and salt. It is more preferred that the detergent granule or tablet of the invention comprises at least a first particulate component containing the anionic sulfonate surfactant or part thereof, and a carrier material, and comprising a second particulate component comprising the agent anionic sulfate surfactant or part thereof, and a carrier material. The anionic sulfate surfactant is preferably a mixture of sulfate surfactants, preferably at least one linear alkyl sulfate surfactant and at least one branched alkyl sulfate surfactant, as described hereinafter. The ratio of linear to branched alkyl sulfates is preferably from 1: 10 to 10: 1 or more preferably from 1: 5 to 5: 1, preferably from 1: 3 to 1: 1. It is more preferred that a premix of linear and branched alkyl sulfate is used to make a particulate component or to form (part of) the binder, preferably being in the form of a paste in which the linear alkyl sulfate ratio is branched is from 1: 5 to 5: 1 preferably from 1: 3 to 1: 1, more preferably from 2: 3. The particulate component of the granule or tablet herein preferably comprises a binder material and a carrier material. This binder material (which does not necessarily comprise the same material as the binder as defined herein) can be any ingredient capable of joining or adhering together particles such as the anionic surfactants herein, except the other materials described above, in particular polyethylene glycols, polyvinyl acetyl amines, polyacrylates and / or maleates, polyvinylpyrrolidones and derivatives thereof, or mixtures thereof. The carrier material can be any particulate ingredient. Useful particulate delivery materials include inorganic or organic acids or salts and builders such as silicates. Particularly useful carrier materials include sulfate salts, carbonate salts, bicarbonate salts, inorganic peroxygen salts, organic carboxylic acids and salts thereof, amorphous silicates, layered crystalline silicates, aluminosilicates and mixtures thereof.

The inventors have also discovered that improved dissolution and dispersion and decreased residue formation on the fabrics can be achieved when the degree of mixing of anionic surfactant, in particular anionic sulfate surfactant and inorganic carrier salts, in particular salts thereof, is reduced. carbonate. In this way, to further reduce waste problems in fabrics, and to further improve dissolution and dispersion, the particle components of the granule or tablet herein preferably include a component in which the ratio of the anionic surfactant of sulfate to the inorganic salts in a component is less than 1: 5 or more than 5: 1, or even less than 1: 6 or even more than 6: 1, or even more preferably 10: 1. This is in particular the case for carbonate salts. It may be preferred that more than one component comprising alkyl sulfate surfactant is substantially free of inorganic carbonate salts. In this way, it may be preferred to incorporate some or all of the inorganic carbonate salts, if their presence is required in the granule or tablet, in a particulate component comprising anionic sulfonate surfactant, but only very small amounts or preferably none of the surfactant sulfate, within the limitations of the relationship described above. The inventors have also discovered that improved dissolution and dispersion and reduced residue formation on fabrics can be achieved when the degree of mixing of anionic surfactant, in particular anionic sulfonate surfactant, and water insoluble builder materials is reduced, in particular zeolite. In this way, to further reduce the waste problems in fabrics, and to further improve dissolution and dispersion, it is also preferred that when a first particulate component comprising an anionic surfactant, except in particular a sulfonate, the carrier material comprises only limited amounts of water-insoluble detergency builder. Examples of water insoluble builders as defined herein include silicates such as amorphous silicates, crystalline layered silicates and aluminosilicates. Thus, it may be preferred that when the water-insoluble builder material is present in the component, the ratio of the sulfonate anionic surfactant to the water-insoluble builder in said component is less than 1: 5 or more. more than 5: 1, or even less than 1: 6 or more than 6: 1 or even less than 1: 7 or more than 7: 1. It may even be preferred that no component of the granule or tablet of the present invention comprises anionic sulfonate surfactant and water-soluble builder material, in particular no aluminosilicate. In the present, improved dispersion and dissolution of the detergent ingredients can be achieved. The granule to tablet may comprise, in a preferred embodiment, a polymeric builder material. Preferred examples are described below.

The inventors have also discovered that improved dissolution and dispersion and reduced fabric residue formation can be achieved when the degree of mixing of anionic surfactant, in particular sulfate anionic surfactant and polymeric builder materials, in particular acids, is reduced. polymeric polycarboxylics or salts thereof. Thus, for the present invention, more than just a small amount or preferably none of polymeric builder material may be present in a particulate component comprising anionic surfactant, but in particular, anionic sulfate surfactant. It was found that this is particularly advantageous if the polymeric builder material is an acrylic / maleic acid copolymer or polyacrylate polymer, in particular when it has an average molecular weight of more than 3,000 or even more than 4,000 or even up to 15,000 or up to 80,000. Therefore, the polymeric builder material may be in a particulate component or binder together with the polymeric builder but herein it is preferred that the ratio of the sulfate anionic surfactant, or even of any anionic surfactant , the polymeric detergency builder material is less than 1: 3 or more than 3: 1, preferably less than 1: 4. Even more preferably, the ratio of sulfate surfactant to polymeric builder material in a component or binder is less than 5: 1 or more than 1: 5 or even less than 7: 1 or more. 1: 7 Preferably the ratio of sulfonate surfactant to polymeric builder material in one component is less than 3: 1 or more than 1: 3 or even less than 4: 1 or more than 1: 4. It may be beneficial that no polymeric detergency improver is present in a component comprising alkyl sulfate surfactant. In this way, the polymeric builder material may preferably be incorporated in the granule or tablet as a separate ingredient, or in a component that does not contain anionic sulfate surfactant, or even more preferably in components that contain substantially no surfactant anionic The granule or tablet preferably comprises from 0.5% to 50% by weight of sulfonate surfactant, preferably from 0.5% to 25% or even from 1.0% to 15% or even from 1.5% to 10% or up to 6% by weight of the granule or tablet. The granule or tablet preferably comprises from 0.5% to 60% by weight of sulfate surfactant, preferably from 1.0% to 45% or even from 3.0% to 25% or even from 5% to 20% or even from 10% to 18%. % by weight of the granule or tablet. The granule or tablet preferably comprises from 1.0% to 70% by weight of water-insoluble builder, in particular aluminosilicates such as zeolite, and crystalline layered silicates such as SKS-6, more preferably from 1.0% to 60% or even from 5.0% to 50% or even 10% to 45% by weight of the granule or tablet. The granule or tablet may comprise from 0.5% to 50% by weight of polymeric builder material, more preferably from 1.0% to 35% or even from 3.0% to 25% or even from 7% to 20% by weight of the granule or Tablet. The granule or tablet may comprise from 0.5% to 70% by weight of inorganic salts, including alkalinity sources, more preferably from 2.0% to 60% or even from 3.0% to 50% or even from 5% to 40% by weight of the granule or tablet. The granule or tablet preferably comprises 5% or even 107% to 90% or even 80% by weight of a first component comprising anionic sulfonate surfactant, more preferably from 20% to 70% or even from 25% to 65%. %-in weigh. The granule or tablet preferably also comprises 5% or even 10% to 90% or up to 80% by weight of a second component comprising anionic sulfate surfactant, more preferably from 20% to 70% or even 25% by weight. 65% by weight. In a preferred embodiment of the invention, the granule components comprise at least a first component that is a blown powder, preferably made by spray drying and at least a second component made by agglomeration or extrusion or compaction, preferably agglomeration.

The particle size of the particulate component will depend on the requirements and in particular the particle size and component of the final granule. In general, the components have a particle size above 30 microns, preferably 60% or even 80% have a particle size of more than 50 microns or even more than 100 or even 150 microns. It may be preferred that the particle size of the particulate components be such that at least 60% or even at least 80% have a particle size of more than 250 microns or even more than 300. The maximum particle size will be determined by the particle size of the final granule, preferably being at least half the particle size of the final granule. The volumetric density of the first and second particulate components will differ in general, usually by at least 25 g / l, or even by at least 50 g / l or at least 75 g / l. The volumetric density of the first and second particulate components, respectively, is generally above 200 g / l and can be as high as 1500 g / l. It is particularly preferred that the bulk density of at least one particulate component will be greater than 700 g / l, preferably larger than 750 g / l or even above 800 g / l. Generally speaking, the volumetric density of blown powders produced by spray drying process will be lower than the volumetric density of other components such as agglomerates and other intermediates, for example, the density of agglomerates and other intermediates can be 500 or even above 600 g / l or above 700 g / l. On the other hand, the volumetric density of the blown powder is generally 150 g / l at 500 g / l or 600 g / l. More commonly, the volumetric density of blown powder is at least 300 g / l but in general it is not greater than 550 g / l after drying and maturing for at least 24 hours under ambient conditions. Therefore, by using feed streams comprising blown and / or agglomerated blends or powders and / or feed material ingredients or other co-compacted combinations of detergent ingredients, the chemical composition of the detergent particles produced will not vary, but the density. For example, the particulate components comprising surfactant and builder can be added to delivery materials comprising builder and binder comprising surfactant so that the binder and the supply material contain builder and surfactant. in the same weight ratio as in the pre-formed agglomerate, so that the chemical composition of the finally produced detergent granule will be the same, but the density will be lower or higher than that of the pre-formed particulate component. Therefore, combinations of the supply materials can be used to give a pre-set volumetric density for the finished detergent granules. In this way, sophisticated processing control can be omitted.

Anionic Surfactant The anionic surfactant herein preferably comprises at least one sulfate surfactant and a sulfonate surfactant, preferably comprising at least one C9-C14 alkylbenzenesulfonate salt. It may be highly preferred that more than one sulfate surfactant be present, and it is preferred herein that at least one branched alkyl surfactant be present. The anionic sulfate surfactant preferably comprises one or more linear C 2 -C 24 alkyl sulfate salts and one or more branched C 2 -C 24 alkyl sulfate salts, preferably in a ratio of 1: 5 to 5. : 1, preferably from 1: 3 to 1: 1. Other possible anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides or methyl tauride, succinates and alkyl sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C 12 -C 18 monoesters) ) sulfosuccinate diesters (especially saturated and unsaturated Ce-Cu diesters) 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 in tallow oil.

Sulfonate Anionic Surfactant The sulfonic anionic surfactants according to the invention include the salts of linear or branched Cs-C2o alkylbenzene sulphonates, alkyl ester sulfonates, primary or secondary C6-C22 alkanesulfonates, C6-C2 olefinsulfonates, acids sulfonated polycarboxylics, and mixtures thereof. A linear C12-C16 alkylbenzene sulfonate is highly preferred. The preferred salts are sodium and potassium salts. The sulphonated alkyl ester surfactant is also suitable for the invention, preferably those of the formula: R1-CH (SO3M) - (A) x - C (O) - OR2 wherein R1 is a C6-C22 hydrocarbyl, R2 is a C-i-Cß alkyl, A is a C6-C22 alkylene, alkenylene, x is 0 or 1, and M is a cation. The counter ion M is preferably sodium, potassium or ammonium. The sulphonated esters of the sulphonated alkyl ether are preferably an alkylsulfo ester of the above formula, in which therefore x is 0. Preferably R 1 is an alkyl or alkenyl group of 10 to 22, preferably 16 carbon atoms. and x is preferably 0. R2 is preferably ethyl or more preferably methyl. It may be preferred that R1 of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It may also be preferred that R1 of the ester is derived from a naturally occurring fatty acid, preferably palmitic acid or stearic acid or mixtures thereof.

Alkyl Sulfate Anionic Surfactant The present anionic sulfate surfactant includes linear and branched primarys, but may also comprise secondary alkyl sulfates and disulfates, alkyl ethoxysulfates having an average ethoxylation number of 3 or lower, oleyl glycerol sulfates fatty acids, alkylphenol ether ether sulfates, sulfates of Cs-C? acyl-N- (C? -C4 alkyl) and -N- (CrC2 hydroxyalkyl) glucamine and sulfates of alkylpolysaccharides. The primary alkylsulfate surfactants are preferably selected from linear and branched primary C C to C 24 alkyl sulphates, more preferably the straight or branched chain alkyl sulfates of Cn-C-iβ, or even the C alkyl alkyl sulphates. -? 2-C? 4 linear chain. The secondary alkyl sulfate surfactant is of the formula: R3CH (S04M) -R4 in which R3 is a Cs-C2o hydrocarbyl, R4 is a hydrocarbyl and M is a cation.

The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulfates which have been ethoxylated with 0.5 to 3 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is an alkyl sulfate of Cp-C-iß, more preferably of C11-C15 which has been ethoxylated with 0.5 to 3, preferably 1 to 3, moles of ethylene oxide per molecule . A particularly preferred aspect of the invention uses mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. The preferred salts are sodium and potassium salts. Branched anionic surfactants The preferred branched primary alkyl sulfate surfactants for use herein are of the formula: R R 1 R 2 CH 3 Cl) (CH 2) w .. CCHH ((CCHH 2oy) CCHH ((CCHH 2) CCrH (CH 2) zOSO 3M These surfactants have a linear primary alkyl sulfate chain base structure (i.e. larger linear carbon chain including the sulfated carbon atom) preferably comprising from 2 to 19 carbon atoms and their branched primary alkyl moieties preferably comprise a total of at least 14 and preferably not more than 20 carbon atoms. the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl portions is preferably within the range of larger than 14.5 to about 17.5., the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longer linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including the branch must be at least 14, and in addition the average total number of carbon atoms for the branched primary alkyl portion is within the larger scale of 14.5 to 17.5. R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl group (preferably hydrogen or dC2 alkyl, more preferably hydrogen or methyl, and more preferably methyl), with the proviso that R, R1 and R2 are not all hydrogen. Also, when Z is 1, at least R or R1 is not hydrogen. M is hydrogen or a salt that forms cations depending on the synthesis method. w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. A primary alkyl sulfate surfactant branched in the middle part of its preferred chain is a C16 total primary carbon alkyl sulfate surfactant having 13 atoms carbon in the base structure and having 1, 2 or 3 branching units (ie R, R1 and / or R2) of a total of 3 carbon atoms, (whereby therefore the total number of carbon atoms Carbon is at least 16). The preferred branching units can be a propyl branching unit or three methyl branching units. Another preferred surfactant is branched primary alkyl sulfates having the formula: R1 R2 CH3CH2 (CH2)? CH (CH2) and CH (CH2) zOS03M wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of those sulfates is present, the average total number of carbon atoms in the primary branched alkyl portions having the above formula is within the larger scale of 14.5 to 17.5; R1 and R2 are each independently hydrogen or C1-C3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; with the proviso that R1 and R2 are not both hydrogen.

DIANIONIC SURFACTURING AGENTS Dianionic surfactants are also anionic surfactants useful for the present invention, in particular those of the formula: wherein R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length of Ci to C28, preferably of C3 to C24, more preferably of C8 to C20 or hydrogen; A and B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amidoalkylene groups of chain length C1 to C2s preferably from C1 to C5, more preferably C1 or C2 or a covalent bond, and preferably A and B they contain in total at least two atoms; A, B and R contain a total of 4 to 31 carbon atoms; X and Y are anionic groups selected from the group consisting of carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably 1; and M is a cationic portion, preferably a substituted or unsubstituted ammonium ion, or an alkaline or alkaline earth metal ion. The most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from C 10 to Cie, A and B are independently Ci or C2, both X and Y are sulfate groups, and M is an ion of potassium, ammonium or sodium. Preferred dianionic surfactants herein include: a) straight or branched chain 3-disulfate compounds, preferably 1,3-C23 alkyl or alkenyl disulfate (ie, the total number of carbons in the molecule), more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length of C4 to C2o; b) 1,4-disulfate compounds, preferably 1.4 straight or branched chain C8-C22 alkyl or alkenyl disulfate, more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length of C4 to C-is; the preferred R is selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and c) 1,5-disulfate compounds, preferably 1.5 straight or branched chain alkyl or C9-C23 alkyl disulfate, more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length C4 to C-iß. It may be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants. The alkoxylated dianionic surfactants of the invention comprise a structural backbone of at least five carbon atoms, to which two anionic substituent groups spaced at least three separate atoms are adhered. At least one of said anionic substituent groups is a sulfate or sulfonate group chained to alkoxy. Said structural backbone may for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferred alkoxy portions are ethoxy, propoxy, and combinations thereof. The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, more preferably from 12 to 24 atoms. Preferably the structural skeleton comprises only carbon containing groups and more preferably comprises only hydrocarbyl groups. More preferably, the structural skeleton comprises only straight or branched chain alkyl groups. The structural skeleton is preferably branched.

Preferably at least 10% by weight of the structural backbone is branched and the branches are preferably 1 to 5, more preferably 1 to 3, more preferably 1 to 2 atoms in length (not including the sulfate or sulfonate group attached to the branch. ). A preferred alkoxylated dianionic surfactant has the formula: wherein R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Ci to C28 > preferably from C3 to C24, more preferably from Cs to C2o or hydrogen; A and B are independently selected from, optionally substituted alkyl and alkenyl group, of chain length of C C28, preferably Ci to C5, more preferably Ci to C2 or a covalent bond; EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, in which n and m are independently within the range of 0 to 10, with at least m or n being at least 1; A and B contain in total at least two atoms; A, B and R contain a total of 4 to 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, with the proviso that at least one of X or Y is a sulfate group; and M is a cationic portion, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion. The most preferred alkoxylated dianionic surfactant has the formula as above wherein R is an alkyl group of chain length from Cio to Cie; A and B are independently Ci or C2, n and m are both 1, both of X and Y are sulfate groups, and M is a potassium, ammonium or sodium ion. Preferred alkoxylated dianionic surfactants herein include: ethoxylated and / or propoxylated disulfate compounds, preferably ethoxylated and / or propoxylated alkyl or alkenyl disulphates of C10-C14 straight or branched chain, more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length of C6 to C18; EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups; and n and m are independently within the range of 0 to 10 (preferably 0 to 5), with at least m or n being 1.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH2?) XCH2COO-M + in which R is an alkyl group of CQ to C- | 8. ? it varies from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR- | -CHR2-0) -R3 in which R is an alkyl group of CQ to CJ S. * is from 1 to 25, Rj and R2 are they are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants containing a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the 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 acid -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (RI) CH2COOM, in which R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is a C-1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Aluminosilicate The aluminosilicates suitable herein are zeolites having the unit cell formula Naz [(Al? 2) z (Si? 2) and] -xH2 ?, wherein z and y are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicates are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form. However, it may be useful to incorporate coated aluminosilicates.

Aluminosilicates can be naturally occurring materials, but preferably are derived in synthetic form. The ion exchange materials of synthetic crystalline aluminosilicates are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na < | 2 [(Al? 2) i2 (Si? 2) - | 2] -xH2? wherein x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(AI02) 86 (Si02) i 06? -276H2O. The preferred stratified crystalline silicate herein has the general formula: NaMSi? 02? +? And H20 in which M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. The silicates Laminated sodium crystallites of this type are described in EP-A-0164514 and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof, preferably Na. The most preferred material is o.-Na.sub.2 Si.sub.2.sub.5 ,.sub.S-Na.sub.2 Si205, or d-Na.sub.2 Si205, or mixtures thereof, preferably being at least 75% -Na2Si205, for example available from Clariant as NaSKS-6. The crystalline layered silicate material, in particular of the formula -Na2SY2? 5, may optionally comprise other elements such as B, P, S, which are obtained by processes as described in EP 578,986-B. The crystalline layered silicate may be in intimate admixture with other materials, including one or more surfactants of the surfactant system herein. Small levels of another silicate material, including amorphous silicate, meta-silicates, may also be preferred, as described herein.

Water-soluble detergent builders The detergent granules of the present invention may comprise one or more water-soluble or partially water-soluble builders. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two atoms of carbon and mixtures of any of the above. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. In addition to these water-soluble builders, polymeric polycarboxylates including homo and copolymers of maleic acid and acrylic acid and their salts may be present. 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 and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates 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, the lactoxysuccinates described in British Patent No. 1 , 389,732 and the aminosuccinates described in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1, 387,447. The polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-etantetracarboxylates, 1,1, 3,3-propanetracarboxylates and the 1, 1, 2, 3-propan-tetracarboxyíatos. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398, 441 and 1, 398, 422 and 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 most preferred may be citric acid, malic acid, and fumaric acid, or their salts or mixtures thereof. The original acids of the moriomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example mixtures of citric acid or citrate / citric acid are also contemplated as useful detergency builder ingredients.

Effervescence system Preferably, a source of effervescence is present in the granule or tablet of the invention. Any effervescence system known in the art can be useful in the granule or tablet or ingredient of the invention to provide even better dispersion and dissolution of the granule or tablet. A preferred effervescence system comprises an acid source, capable of reacting with an alkali source in the presence of water to produce a gas. The acid source is preferably present at a level 0.5% to 35%, more preferably 1.0% or even 2% to 20% or even 4% to 20% by weight of the granule or tablet. It may be preferred that the acid source or part thereof and the alkali source or part thereof be comprised in an intimate mixture, for example in the form of a compact particle.

The molecular ratio of the acid source to the alkali source is preferably from 50: 1 to 1: 50, more preferably from 20: 1 to 1: 20, more preferably from 10: 1 to 1: 10, whereby when an intimate mixture of the acid source and the alkali source is present, this ratio is more preferably from 5: 1 to 1: 3, more preferably 3: 1 to 1: 2, more preferably from 2: 1 to 1: 2 . The acid source can be any organic, mineral or inorganic acid, or a derivative thereof. Preferably the acid source comprises an organic acid. The acid compound is preferably substantially anhydrous or non-hygroscopic and the acid is preferably soluble in water. It may be preferred that the source of acid be overdrawn. Suitable acid sources include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric, succinic, or adipic acid, monosodium phosphate, boric acid, or derivatives thereof. Citric acid, maleic acid or malic acid are especially preferred. More preferably, the acid source provides acidic compounds having an average particle size in the range of 75 microns to 1180 microns, more preferably 150 microns to 710 microns, calculated by sieving a sample of the source of acidity over a series of sieves Tyler As discussed above, the effervescence system preferably comprises an alkali source, however, for the purpose of the invention, it should be understood that the alkali source may be part of the effervescent particle or may be incorporated in the granule or tablet of the invention separately. Any alkali source that has the ability to react with the acid source to produce a gas can be present in the particle, which can be any gas known in the art, including nitrogen, oxygen, and carbon dioxide gas. Preferred may be peridrate bleaches, including perborate, and silicate material. The alkali source is preferably substantially anhydrous or non-hygroscopic. It may be preferred that the alkali source be overdrawn. Preferably this gas is carbon dioxide, and therefore the alkali source is preferably a carbonate source, which can be any carbonate source known in the art. In a preferred embodiment, the carbonate source is a carbonate salt. Examples of preferred carbonates are alkaline earth metal and alkali metal carbonates, including sodium or potassium carbonate, bicarbonate and sesqui-carbonate, and any mixtures of the mimes with ultra fine calcium carbonate such as described in German Patent Application No. 2,321. , 001 published November 15, 1973. Alkali metal percarbonate salts are also suitable sources of carbonate species, which may be present in combination with one or more other carbonate sources.

The carbonate and bicarbonate preferably have an amorphous structure. The carbonate and / or bicarbonate may be coated with coating materials. It may be preferred that the carbonate and bicarbonate particles may have an average particle size of 75 microns or preferably 150 microns or larger, more preferably 250 μm or larger, preferably 500 μm or larger. It may be preferred that the carbonate salts be such that less than 20% (by weight) of the particles have a particle size below 500 μm, calculated by sieving a sample of the carbonate or bicarbonate in a series of Tyler sieves. Alternatively or in addition to the previous carbonate salt, it may be preferred that less than 60% or even 25% of the particles have a particle size below 150 μm, while less than 5% have a particle size of more than 1.18 mm, more preferable less than 20% have a particle size of more than 121 μm, calculated by sifting a carbonate or bicarbonate sample over a series of Tyler sieves.

Additional ingredients The granule or tablet and the components thereof may contain additional detergent actives. The precise nature of these additional ingredients, and the levels of incorporation thereof will depend on the physical form of the granule or tablet comprising the builder ingredient and the precise nature of the washing operation for which it is to be used.

Additional ingredients include additional detergency builders, additional surfactants, bleach, enzymes, suds suppressors, lime soap, dispersants, soil suspending and anti-redeposition agents, soil release agents, perfumes, brighteners, photobleaching agents and additional corrosion inhibitors. Disintegration aids are highly preferred, such as water-flammable polymers or clays and paste-forming agents, which aid in the breakdown of the structure of the tablet or granule.

Non-ionic alkoxylated surfactant Essentially, any non-ionic alkoxylated surfactant is suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. However, as discussed above it may be preferred that only limited amounts of nonionic surfactants are used in the granules or tablets herein. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, non-ionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with propylene oxide / ethylenediamine adducts.

Nonionic surfactant of alkoxylated alcohol The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z, wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, -hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 alkyl or C 2, most preferably C 1 alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably CI alkyl or alkenyl < ] -C < | 7 straight chain or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R ^ CON (R ^) 2 wherein Rβ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C-1-C4 alkyl, hydroxyalkyl of C? -C4, and - (C2H4?) XH, wherein x is on the scale of 1 to 3.

Alkylpolysaccharide Nonionic Surfactant The alkylpolysaccharides suitable for use herein are described in the U.S.A. No. 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 polyglycoside, a hydrophilic group containing from 1.3 to 10 units of saccharide . Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (glucosyl) x in which R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Cationic Surfactants Cationic surfactants suitable for use in the present detergent include the quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a N-alkyl or alkenyl ammonium mono-surfactant of CQ-C-?, Preferably C5-C10. wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. The mono-alkoxylated and bis-alkoxylated amine surfactants are also preferred. Another suitable group of cationic surfactants that can be used in the granule or detergent tablets or components thereof herein are cationic ester surfactants. The ester cationic surfactant is preferably a water dispersible compound having surfactant properties comprising at least one ester linkage (ie, -COO-) and at least one cationically charged group. Cationic ester surfactants, including choline ester surfactants, have been described for example in the U.S. Patents. Nos. 4,228,042, 4,239,660 and 4,260,529.

In a preferred aspect the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain that it comprises at least three atoms (ie chain length of three atoms), preferably from three atoms to eight atoms, more preferably from three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain is connected only with carbon atoms. In the chain. In this way the spacer groups that have, for example links -OO- (ie peroxide), NN-, and -NO- are excluded, while spacers having links, for example -CH2-0-CH2- and -CH2-NH-CH - are included. In a preferred aspect the chain of the spacer group "comprises only carbon atoms, more preferably the chain is a hydrocarbyl chain.

Mono-alkoxylated cationic amine surfactants Most preferred herein are the cationic mono-alkoxylated amine surfactants preferably of the general formula I: (O) wherein R1 is an alkyl or alkenyl portion containing from 6 to 18 carbon atoms, preferably from 6 to 16 carbon atoms, more preferably from 6 to 14 carbon atoms, R2 and R3 are each independently alkyl groups containing from one to three carbon atoms, preferably methyl, more preferably both R 2 and R 3 are methyl groups, R 4 is selected from hydrogen (preferred), methyl and ethyl, X "is an anion such as chlorine, bromine, methyl sulfate; , sulfate, or the like, to provide electrical neutrality, A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is from 0 to 30, preferably from 2 to 15, more preferably from 2 to 8. Preferably the group ApR4 in formula I it has p = 1 and is a hydroxyalkyl group, which has no more than 6 carbon atoms whereby the -OH group is separated from the quaternary ammonium nitrogen atom by not more than three carbon atoms. in particular the ApR4 groups that are - CH2CH2OH, - CH2CH2CH2OH, - CH2CH (CH3) OH and - CH (CH3) CH2OH, with --CH2CH2OH being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are preferred. Other highly preferred mono-alkoxylated amine cationic surfactants for use herein are of the formula: Wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge equilibrium, preferably chlorine or bromine. As noted, compounds of the type mentioned above include those in which the ethoxy (CH2CH2O) (EO) units are replaced by butoxy, isopropoxy units [CH (CH3) CH2?] And [CH2CH (CH30] (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units. The levels of mono-alkoxylated amine cationic surfactants that are used in the granules or detergent tablets of the invention are preferably from 0.1% to 20%, more preferably from 0.2% to 7%, more preferably from 0.3% to 3.0% by weight of the granule or tablet.

Cationic bis-alkoxylated amine cationic surfactant The cationic bis-alkoxylated amine surfactant preferably has the general formula II: (II) Wherein R1 is an alkyl or alkenyl portion containing from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms, more preferably from 10 to 14 carbon atoms; R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X "is an anion such as chlorine, bromine, methyl sulfate, sulfate or the like, sufficient to provide electrical neutrality. they can vary independently and each is selected from Cr C4 alkoxy especially ethoxy, (i.e., -CH2CH2? -), propoxy, butoxy and mixtures thereof, p is from 1 to 30, preferably from 1 to 4 and q is from 1 to 30, preferably 1 to 4, and more preferably p and q are 1. The highly preferred cationic bis-alkoxylated surfactants for use herein are of the formula: Wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C2, C14 alkyl, and mixtures thereof. X is any convenient anion to provide charge balance, preferably chlorine. With reference to the general structure of the bis-alkoxylated cationic amine noted above, because in a preferred compound R1 is derived from a fatty acid fraction of C12-C14 (coconut) alkyl, R2 is methyl and ApR3 and A ' qR4 are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: In which R1 is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is from 1 to 3 and q is from 1 to 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chlorine or bromine. Other compounds of the type mentioned above include those in which the ethoxy (CH2CH2O) (EO) units are replaced by butoxy units (Bu), isopropoxy [CH (CH3) CH20] and [CH2CH (CH30] (i-Pr) or units n-propoxy (Pr) or mixtures of units EO and / or Pr and / or i-Pr.

Peridrate Bleaches A further highly preferred ingredient of the granule or tablets or component herein is an oxygen bleach, preferably comprising a source of hydrogen peroxide and a bleach or activator precursor. A preferred source of hydrogen peroxide is a perhydrate bleach, such as metal perborate, more preferably metal percarbonates, particularly sodium salts. Perborate can be mono or tetrahydrated. Sodium percarbonate has the formula corresponding to 2Na2C03 »3H2? 2, and is commercially available as a crystalline solid.

In particular, the percarbonate salts are preferably coated. Suitable coating agents are known in the art, and include silicates, magnesium salts and carbonate salts. Potassium peroximonopersulfate, sodium persulfate, is another optional inorganic perhydrate salt for use in the granule or detergent tablet herein.

Organic Peroxyacid Bleach System A preferred feature of the granule or tablet or even components herein is an organic peroxyacid bleach system. In a preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the invention claimed. In a preferred and alternative embodiment, a preformed organic peroxyacid is incorporated directly into the granule or tablet. Also contemplated are granules or tablets or particulate components containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. The peroxyacid bleach precursors can generally be represented as: O II X-C-L where L is a residual group, and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is: O II X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the granules or tablet detergents. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within those classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Residual groups The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrollsis reaction occurs within the optimum time frame (for example, a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleach granule or tablet.

The preferred L groups are selected from the group consisting of: A or II -N-C-R1 - N N - N - C - CH - R4 I I R3 I Y R3 I -0-CH = C-CH = CH, -0-CH = C-CH = CH, R3 OY 1 ^ LI 'I ^ A - 0-C = CHR4, and - N- S-CH-R4 I, II R3 O and mixtures thereof, in which R1 is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R ^ is H or R3 and Y is H or a solubilizing group. Any of R1, R ^ and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. Preferred solubilizing groups are -S? 3"M +, -C? 2" M +, - S? 4"M +, -N + (R3) 4? - and 0 <-N (R3)., And more preferably -S? 3"M + and -CO2" 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, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate or acetate anion.

Precursors of bleaching of alkylpercarboxylic acid The bleach precursors of alkylpercarboxylic acid form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarboxylic acid bleach precursors of the metric type include the tetraacetylated N-NN.sub.N.sub.2 N.sub.2 N alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. TAED is preferably not present in the agglomerated particle of the present invention, but preferably is present in the detergent granule or tablet, which comprises the particle. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-substituted alkylperoxy acid precursors Amide-substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: Rt 0-N ~ R2- C-L R1-N- C ~ R2 ™ C- L ff I c H t ^ || O R ° O or R-- > or 6 wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R ^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be • essentially any residual group. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl midazole and N-benzoyl benzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl p-glutamic acid.

Preformed Organic Peroxyacid The detergent granule or tablet 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 granule or tablet. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R1-C-N- 2- C-OOH II l and II O R5 O R1- N- C- R2-C-OOH l? II II R5 OO in which R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or a alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are 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.

Heavy metal ion sequestrant Heavy metal ion sequestrants are also useful additional ingredients herein. By heavy metal ion sequestrant is meant in the present ingredients that act to sequester (chelate) heavy metal ions. These ingredients may also have calcium and magnesium chelating ability, but preferably show selectivity for binding heavy metal such as iron, manganese and copper. Therefore, they are not considered as detergency builders for purposes of the invention. Heavy metal ion sequestrants are generally present at a level from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the granule or tablets Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxydiphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminopenta (methylenephosphonate), ethylenediaminotri- (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate, 1,1-hydroxyethoediphosphonic acid and 1,1-hydroxyethanedimethylenephosphonic acid. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid, or any salt thereof. Other heavy metal ion sequestrants suitable for use herein are the minodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid 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. Sequestrants of β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1, 2,4-tricarboxylic acid. Glycine-N-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable. Especially preferred are ethylenediamine-N, N'-disuccinic acid (EDDS) and 1,1-hydroxytenediphosphonic acid or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof.

Enzyme Another preferred ingredient useful in the detergent granules of the invention, is one or more additional enzymes. Additional preferred enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases and conventionally incorporated in granules or detergent tablets. Suitable enzymes are also described in the patents of E.U.A. Nos. 3,519,570 and 3,533,139.

Organic polymeric compound The organic polymeric compounds, not being the polycarboxylic acidic acid or its salts described above, are preferred additional components of the granules or tablets herein. By organic polymeric compound is meant essentially any polymeric organic compound commonly used as a binder, dispersant and anti-redeposition agents and suspension of soils in detergent granules or tablets, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including ethoxylated quatemized (poly) amine anti-redeposition / dirt removal agents. The organic polymeric compound is typically incorporated in the detergent granules or tablets of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, more preferably from 0.5% to 10% by weight of the granule or tablet. Other organic polymeric compounds suitable for incorporation into the detergent granules or tablets herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Additional useful organic polymeric compounds are polyethylene glycols, particularly those with a molecular weight of 1000 to 10000, more particularly from 2000 to 8000, and most preferably of about 4000. The highly preferred polymeric ingredients herein are soil release polymers. cotton and not cotton in accordance with the US patent No. 4,968,451, Scheibel et al, and the patent of E.U.A. No. 5,415,807, Gosselink et al, and in particular in accordance with the application of E.U.A. No. 60/051517. Another organic compound, which is a preferred clay anti-redeposition / dispersant agent for use herein, may be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ether or ester groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. , ethylene, propylene, hexamethylene), b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least about 12, with a typical scale of about 12 to about 42.

Other dispersing / anti-redeposition agents useful for use herein are described in EP-B-011965, U.S.A. 4,659,802 and U.S.A. 4,664,848.

Foam suppression system The detergent granules or tablets or components thereof, when formulated for use in granules or tablets for machine washing, preferably comprise a foam suppression system present at a level of 0.01% to 15%, preferably from 0.02% to 10% and more preferably from 0.05% to 3% by weight of the granule or tablet. The foam suppression systems suitable for use herein may comprise essentially any known antifoam compound including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds. By "antifoam compound" is meant any compound or mixtures of compounds that act to depress the foaming produced by a solution of a granule or detergent tablet., particularly in the presence of the agitation of that solution. Particularly preferred antifoam compounds for use herein are the silicone anti-foam compounds defined herein as any antifoaming compound that includes a silicone component. Said silicone anti-foam compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred antifoam silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the patent of E.U.A. No. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof for use as foam suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (eg, stearone), N-alkylated aminotriazines such as tri- or hexa-alkylmelamines or di- to tetraalkyldiaminoclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and di-alkali metal monostearyl phosphates (eg, sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, more preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably from 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of 1% to 50%, preferably from 5% to 25% by weight of 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; (b) a dispersing compound, more preferably comprising a glycol silicone hardener copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide from 1: 0.9 to 1: 1.1, at a 0.5% to 10% level, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid composition, more preferably comprising an ethoxylated Ci ß-Ci alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably from 10% to 70% by weight. A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof. same, with a melting point of 45 ° C to 80 ° C. Other highly preferred foam suppressor systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of secular and acrylic acid.

Polymeric Dye Transfer Inhibitory Agents The granules or tablets or components herein may additionally comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

Polymeric dye transfer inhibiting agents are preferably selected from copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or combinations thereof, in which those polymers can be entangled polymers.

Optical Brightener The granules or tablets herein also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as is known in the art. It may be preferred to use a mixture of brighteners, for example a brightener on the surface of the tablet or granule and another in the core of the tablet or granule.

Polymeric dirt release agent Polymeric soil release agents, hereinafter "SRA" can optionally be used in the granules or tablets herein. If used, the SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the granule or tablets. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on hydrophobic fibers and remain adhered thereto until completing the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This may allow spots that occur subsequent to treatment with SRAs to be more easily cleaned in subsequent washing procedures. SRA's include oligomeric terephthalate esters, typically prepared by methods involving at least a large esterification / oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. These esters can be made using additional monomers capable of being incorporated into the ester structure through a, two, three, four or more positions without, of course, forming a densely intertwined total structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer comprising an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and sulfonated terminal portions derived from allyl covalently attached to the base structure, e.g. as described in the USA 4,968,451, from November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the blocked end 1, 2-propylene / polyoxyethylene terephthalate polyesters of E.U.A. 4,711, 730 of December 8, 1987 to Gosselink et al, for example those produced by transesterification / oligomerization of methyl ether of poly (ethylene glycol), DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRA's include: the partially blocked and fully anionic oligomeric esters of E.U.A. 4,721, 580, from January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-blocked oligomeric polyester block compounds of E.U.A. 4,702,857, from October 27, 1987 to Gosselink, produced for example from DMT, PEG blocked by methyl (Me) and EG and / or PG, or a combination of DMT, EG and / or PG, PEG blocked by Me and Na-dimethyl-5-sulfoisophthalate; and the anionic terephthalate esters, especially sulfoaroyl, of blocked end of E.U.A. 4,877,896, from October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in laundry and fabric conditioning products, an example being an ester granule or tablet made from monosodium salt of acid m-sulfobenzoic, PG and DMT, optionally but preferably further comprising added PEG, for example PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate oxide, see EUA 3,959,230 to Hays, of May 25, 1976 and E.U.A. 3,893,929 to Basadur, July 8, 1975; cellulose derivatives such as the cellulosic hydroxyether polymers available from METHOCEL of Dow; C 1 -C 4 alkyl celluloses and C 4 hydroxyalkyl celluloses, see E.U.A. 4,000,093 of December 28, 1976 to Nicol et al; and the methylcellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of 1.6 to 2.3 and a solution viscosity of 80 to 120 centipoise measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200 which are the commercial names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) non-ionic terephthalates that use diisocyanate coupling agents to chain polymeric ester structures, see E.U.A. 4,201, 824, Violland et al. and E.U.A. 4,240,918 Lagasse et al. and (II) SRA's with terminal carboxylate groups by manufacturing by adding trimellitic anhydride to known SRA's to convert the terminal hydroxyl groups to trimellitate esters. With the appropriate selection of catalysts, the trimellitic anhydride forms bonds with the polymer terminals through a carboxylic acid ester isolated from trimellitic anhydride instead of through anhydride bond opening. Nonionic or anionic SRAs can be used as starting materials as long as they have terminal hydroxyl groups that can be esterified. Consult E.U.A. 4,525,524 Tung et al. Other classes include: (lll) anionic SRAs based on terephthalate of the urethane-bound variety, see E.U.A. 4.201, 824 Violland et al.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the granule or tablet of the invention include perfumes, spot detectors, colorants and inks. In addition, small amounts (eg, less than 20% by weight) of neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, anti-oxidants, etc. may be present. 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). Encapsulated perfumes are highly preferred, preferably comprising an encapsulated starch.

Abbreviations used in the examples In granules or detergent tablets, the identifications of abbreviated components have the following meanings: LAS: Linear sodium alkylbenzenesulfonate of C ^ _? 3 LAS (I): Scale containing C1_3 linear sodium alkylbenzenesulfonate (9u%) and sodium sulfate and moisture.

LAS (II): Linear potassium alkylbenzene sulfonate of C-i _ 3 MES: C18 fatty acid a-sulphomethyl ester TAS: Sodium alkyl sulphate CxyAS: Sodium alkyl sulfate of C-jx-C < | and C46SAS: (2,3) C14-C16 secondary sodium alkylsulfate CxyEzS: C- | x-C || sodium alkyl sulphate and condensed with z moles of ethylene oxide CxyEz: Predominantly linear primary alcohol of C? x-C < and condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C < | 2-Cl4 QAS 1: R2.N + (CH3) 2 (C2H4? H) with R2 = Cs-C-] - | SADS: C14-C22 sodium alkyldisulfate of formula 2- (R) .C4H .- 1, 4- (S0 -) 2 wherein R = C10-C18. SADE2S: C14-C22 sodium alkyldisulfate of formula 2- (R) .C4H7.- 1, 4- (S04-) 2 where R = C10-C? 8 condensed with z moles of ethylene oxide APA: Amidopropyl dimethylamine of Cs-Cio. Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluene sulfonate CFAA: (coconut) C12-C14 alkyl N-methylglucamide. TFAA: N-methylglucamide of C < \ QC] Q TPKFA: Whole cut fatty acids of C- | 6_Ci8 STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (A1? 2S¡? 2) i2-27H20, which it has a primary particle size on the scale of 0.1 to 10 microns, (weight expressed on anhydrous basis). NaSKS-6 (I): Crystalline stratified silicate of the formula d-Na 2 Si 2 s of average weight particle size of 18 micras and at least 90% by weight with particle size below 65.6 micras. NaSKS-6 (ll): Crystalline layered silicate of the formula d-Na 2 Si 2? 5 of average particle size by weight of 18 microns and at least 90% by weight with particle size below 42.1 microns. Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with an average particle size between 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (Yes? 2: Na2? = 2.0) Sulfate: Anhydrous sodium sulfate Mg sulfate: Magnesium sulfate anhydrous Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425μm and 850μm MA / AA: Copolymer of 1: 4 maleic acid / acrylic acid with an average molecular weight of approximately 70,000 MA / AA (1) : Maleic acid / acrylic acid 4: 6 copolymer with an average molecular weight of about 10,000 AA: Sodium polyacrylate polymer of average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: Ethermethylcellulose with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme having 3.3% by weight of active enzyme sold by Novo Industries A / S under the trade name of Savinase. Protease I: Proteolytic enzyme having 4% by weight of active enzyme as described in WO 95/10591, sold by Genecor Int. Inc.

Alcalase: Proteolytic enzyme having 5.3% by weight of active enzyme marketed by Novo Industries A / S Cellulase: Cellulite enzyme having 0.23% by weight of active enzyme marketed by Novo Industries A / S under the trade name of Carezyme Amylase: Amylocytic Enzyme having 1.6% by weight of active enzyme marketed by Novo Industries A / S under the trade name of Termamyl 60T Amylase II: Amylolytic enzyme, as described in PCT / US9703635 Lipase: Lipolytic enzyme having 2.0% by weight of active enzyme sold by Novo Industries A / S under the tradename of Lipolase Ultra Endolase: Enzyme endoglunase having 1.5% by weight of active enzyme marketed by Novo Industries A / S PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1: Bleach of anhydrous sodium perborate monohydrate of the nominal formula NaB 2-H 2 O 2 Percarbonate: Sodium percarbonate of nominal formula 2Na 2 C 3 3.3 H 2 O 2 DOBS: Decanoyl xibencenesulfonate in the form of sodium salt DPDA: Diperoxydecanedioic acid NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt NACA-OBS: (6-nonamidocaproyl) oxybenzenesulfonate LOBS: Dodecanoyloxybenzenesulfonate in the form of sodium salt DOBS: Decanoiloxybenzenesulfonate in the form of sodium salt DOBA: Decanoyl oxobenzoic acid TAED: Tetraacetylethylenediamine DTPA: Dietelentriamine pentaacetic acid DTPMP: Diethylenetriaminepenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060.

EDDS: Ethylenediamine-N'-disuccinic acid, isomer (S, S) in the form of its sodium salt Photoactivated bleach: Sulfonated zinc phthalocyanine or sulfonated aluminum phthalocyanine encapsulated in or coated by a soluble polymer Brightening 1: 4, 4'-bis (2-sulphotrisyl) b-phenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) ester-2: 2 , disodium disulfonate HEDP: 1, 1-hydroxyethyl-diphosphonic acid PEGx: Polyethylene glycol, with a molecular weight of x (typically 4,000). PEO: Polyethylene oxide, with an average molecular weight of 50,000. TEPAE: Ethoxylated tetraethylenepentamine PVI: Polyvinylimidozole, 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) bs ((C2H50) - (C2H4?)) N, in which n = from 20 to 30 SRP 1: Anionically blocked end polyesters SRP 2: Poly (1, 2-propylene terephthalate) dietoxylated short block polymer PEI: Polyethylenimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethylene residues per nitrogen . Silicone antifoams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Opacifier: Mix of water-based monostyrene latex, marketed by BASF Aktiengesellschaft under the trademark Lytron 621 Wax: Paraffin wax EXAMPLE 1 The following example relates to a granule or tablet which is formed from individually blown and agglomerated powders and dry additives blended together and stirred with the illustrated binder ingredients, following any of the procedures as described herein. The granules are preferably manufactured by fluidized bed agglomeration. The ingredient that is sprinkled is sprinkled on the granule or tablet. In addition to the Ingredients below, the illustrated tablets and granules may be coated with a coating agent to protect them from breaking or abrasion, water, temperature changes and / or to aid in the disintegration of the tablet or granule.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A granule or detergent tablet comprising an anionic surfactant system comprising an anionic sulfate surfactant and an anionic sulphonate surfactant and other detergent active ingredients, the granule comprises at least a first and a second particulate component and optionally a binding agent, characterized in that the ratio of anionic sulfate surfactant to the anionic sulfonate surfactant in the particulate components and when present in the binder is less than 1: 4 or more than 4: 1 or even less than 1: 5 or even more than 5: 1.

2. The granule or detergent tablet according to claim 1, further characterized in that no particulate component contains both the anionic sulfate surfactant and the anionic sulfonate surfactant.

3. The granule or detergent tablet according to claim 1 or 2, further characterized in that the first particulate component comprises an anionic sulfonate surfactant and a carrier material and the second particulate component comprises a carrier material and a surfactant. sulfate anion, preferably a mixture of branched alkyl sulfate anionic surfactant and a linear alkyl sulfate surfactant.

4. The granule or detergent tablet according to claim 3, further characterized in that the first particulate component comprises a carrier material selected from inorganic salts, water-soluble builder material and water-soluble builder material or mixtures thereof, with the proviso that the ratio of anionic sulfonate surfactant to water insoluble builder material in the component is less than 1: 5 or more than 5: 1, or even less than 1 : 6 or more than 6: 1.

5. The granule or detergent tablet according to claim 3 or 4, further characterized in that the second particulate component comprises a carrier material selected from inorganic salts, water-soluble builder material and water-soluble builder material. or mixtures thereof, with the proviso that the ratio of the sulfate anionic surfactant to the inorganic salt in the component is less than 1: 5 or more than 5: 1, preferably more than 10: 1.

6. The granule or detergent tablet according to any of the preceding claims, further comprising a polymeric detergency builder material with the proviso that when the polymeric builder material is present in a particulate component or binder comprising an anionic sulfate surfactant or even any anionic surfactant, the ratio of the anionic surfactant or sulfate anionic surfactant to the polymeric builder material is less than 1: 3 or more than 3: 1, preferably less than 1: Four.

7. The granule or detergent tablet according to any of the preceding claims, further characterized in that the binder comprises an anionic sulfate surfactant, polymeric material or nonionic surfactant or mixtures thereof.

8. The granule or detergent tablet according to claim 1 or 2, further characterized in that it comprises a particulate component comprising at least 90% by weight of the component of an anionic sulfonate surfactant.

9. The granule or detergent tablet according to any of the preceding claims, further characterized in that the anionic sulfonate surfactant comprises a salt of a linear or branched C9-C14 alkylbenzene sulfonate.

10. The granule or detergent tablet according to any of the preceding claims, further characterized in that the anionic sulfate surfactant comprises one or more salts of linear C 2 -C 24 alkyl sulfate and one or more sulphate salts of C12-C24 branched alkyl in a ratio of 1: 5 to 5: 1, preferably 1: 3 to 1: 1.

11. - The granule or detergent tablet according to any of the preceding claims, further characterized in that it comprises one or more additional particulate components or ingredients of starting materials, selected from enzymes, perfumes, bleaching agent, effervescence systems, suds suppressors, brighteners and coating agents.

12. A process for manufacturing a granule or tablet according to any of the preceding claims, further characterized in that at least two particulate components are mixed with a binding agent, characterized in that the ratio of anionic sulfate surfactant to anionic surfactant of sulfonate in the particulate components, and when present, in the binder, is less than 1: 4 or more than 4: 1, or even less than 1: 5 or more than 5: 1.

13. The process for manufacturing a granular material according to any of the preceding claims in which at least two particulate components and optionally a binder are mixed in a moderate to low shear mixing step, further characterized in that ratio of sulfate anionic surfactant to sulfonate anionic surface active agent in the particulate components and, when present, in the binder, is less than 1: 4 or more than 4: 1 or even less than 1: 5 or more than 5: 1.

14. - The method according to claim 13, further characterized in that the mixing step is a low shear mixing step which takes place in a tray granulator, drum mixer or fluidized bed or a shear mixing step moderated which takes place in a mixer Km.

15. The process according to any of claims 13 or 14, further characterized in that a binder is added during or immediately preceding the mixing step.

16. The process according to any of claims 12 to 15 further characterized in that the binder or part thereof is present in the detergent particle and comprises water or an aqueous solution of surfactant having a concentration below 25% in weigh.

17. A detergent composition comprising 80-100% by weight of the granule composition according to any of claims 1 to 11.