WO2001030952A1 - Washing methods utilizing an effervescent product added prior to agitation - Google Patents

Abstract

A method of laundering soiled textile articles comprising an initial step of adding a granular detergent composition consisting essentially of an effervescence granule and a detergent matrix to water to form an aqueous wash liquor comprising from about 400 ppm to about 600000 ppm of the granular detergent composition. The effervescence granule comprises and alkali-source and an acid-source and upon contact of the granular detergent composition with water a reaction occurs between the alkali-source and the acid-source occurs to produce an effervescent gas. In a second step a cleaning-effective amount of the wash liquor is distributed substantially evenly and completely onto the textile articles in their substantially dry state.

Description

WASHING METHODS UTILIZING AN EFFERVESCENT PRODUCT ADDED PRIOR TO AGITATION

TECHNICAL FIELD

The present invention relates to washing methods utilizing a laundry detergent composition containing an effervescent particle system

BACKGROUND OF THE INVENTION

Granular or "dry" laundry detergent products offer a number of advantages over laundry detergent products in liquid form These advantages include enhanced formulation capability and flexibility, lower-cost packaging, higher product stability and superior overall cleaning and functional performance per unit cost

But in recent years, the popularity of liquid detergent compositions has been on the rise due primarily to the better dispersion and dissolution performance of liquid detergents in comparison to their granular counterparts These dissolution and dispersion advantages are particularly apparent in cold water conditions where typically the dissolution of granular detergents is poor The poor dissolution and dispersion performance of granular detergents has been further compromised by a number of recent trends, including a shift to higher-density, more compact granular detergents (having densities of 600g/l and greater), the gradual replacement of phosphate builders with other, alternative builder materials, which allegedly pose less danger to the environment but are also considerably less soluble in water than phosphate builders, and finally a tendency to use colder water temperatures in the wash cycle of an automatic washing machine

Granular detergent compositions have other disadvantages as well For example, when used in an automatic washing machine, liquid detergents immediately begin to mix with water to form a detergent solution By contrast, granular detergents do not readily mix with water but instead are almost entirely dependent upon the mechanical energy supplied by action of the washing machine agitator to disperse the detergent granules throughout the volume of water and to promote the dissolution and mixing of the detergent granules with water

This almost total dependence on the action of the agitator to promote dispersion and dissolution of the detergent granules is undesirable for at least two reasons first, it reduces the time available for cleaning because the granular detergent cannot provide any detersive or functional benefits until it is dispersed and dissolved by the action of the agitator This is important particularly because there is an increased need to promote the rapid release of detergents into the wash water to provide greatest cleaning performance in short, energy-efficient wash cycles where the time of contact of the detergent solution with the items to be washed may be reduced to a minimum

Moreover, the dependence on agitation for dispersion and dissolution of the detergent brings about an undesirable trade-off while vigorous agitation is necessary for the best possible dissolution and dispersion, vigorous agitation may also strain and increase the wear on the fabric and textile articles being cleaned Additionally, because conventional detergents rely on agitation for dissolution and dispersion, significant cleaning benefits are lost which could be obtained as the washing machine just begins to fill with water and the detergent concentration is highest Furthermore, in conventional wash processes, garments are cleaned only at the minimum concentration level, after the full amount of water is added, this overlooks the benefits that could be obtained by the higher concentrations of water obtained at the beginning of the wash cycle as the full dosage of the granular detergent is added to a relatively small quantity of wash water

Given the foregoing, there is a continuing need for granular detergent formulations which are readily soluble in wash-water, reduce the dependency on the agitator for dispersion and improve cleaning performance as a result of increasing the amount of time that soiled fabric articles are in contact with an aqueous solution containing detersive actives Accordingly, it is a benefit of the present invention that a cleaning method is provided, which by utilizing specially formulated detergent products promotes the rapid dissolution and dispersion of the granular detergent product Moreover, this rapid dissolution and dispersion of the granular product is not dependent on the vigorousness of the agitation

SUMMARY OF THE INVENTION It has now been determined that the use of an effervescence system provides a granular detergent composition with excellent dissolution and dispersion performance in a method for the laundering of fabrics and textile articles When these granular detergent products are used for laundering fabrics and textile articles according to the method outlined in detail below, the result is superior cleaning performance as well as other desirable attributes that greatly enhance consumer satisfaction with the product, particularly relative to comparable liquid detergent formulations

In a first aspect of the present invention, granular detergent compositions consisting essentially of an effervescence granule and a detergent matrix are utilized in a method of laundering soiled textile articles comprising an initial step of adding a granular detergent composition consisting essentially of an effervescence granule and a detergent matrix to water to form an aqueous wash liquor comprising from about 400 ppm to about 600000 ppm of the granular detergent composition The effervescence granule comprises an alkali-source and an acid-source and upon contact of the granular detergent composition with water a reaction occurs between the alkali-source and the acid-source occurs to produce an effervescent gas In a second step the wash liquor is distributed substantially evenly and completely onto the textile articles in their substantially dry state a cleaning-effective amount of the wash liquor

In a second aspect, the granular detergent composition is placed in a package along with instructions for use m a method of laundering soiled textile articles, wherein the instructions comprise performing a first step of mixing water and a granular detergent composition consisting essentially of an effervescence granule and a detergent matrix to form an aqueous wash liquor comprising from about 400 ppm to about 600000 ppm of the granular detergent composition and then distributing substantially evenly and completely onto the textile articles in their substantially dry state a cleaning-effective amount of the wash liquor

All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified All documents cited are, in relevant part, incorporated herein by reference DETAILED DESCRIPTION OF THE INVENTION The present invention consists of a method for using granular detergent compositions containing effervescence components in an aqueous wash process that is preferably performed in a conventional automatic washing machine

As discussed above, by incorporating the special granular detergent composition containing effervescent components, the method (which is outlined in detail below) provides cleaning performance superior to that provided by other granular detergent compositions Because the method employs these granular detergent formulations that readily dissolve upon contact with water, the cleaning benefits of the method and detergent begin immediately upon contacting the detergent with water without the need of mechanical agitation Thus not only does this method increase the time (by perhaps several minutes) that the cleaning benefits of the detergent composition are available, it also causes a momentary increase in the concentration of the detergent in the wash liquor at the beginning of a wash cycle which in turn increases the cleaning benefits of the detergent on clothing and fabrics items immersed in the wash liquor

In addition to the functional and detersive benefits described above, the effervescence may also provide auditory and visual signals to the consumer indicating the cleaning benefits of the detergent composition Visual signals may include the rapid and vigorous formation and movement of bubbles while the auditory signals would be a "popping" or "fizzing" resulting from the effervescence The methods in which these granular detergents may be used will now be described in more detail

In a first step of the method, a consumer configures the settings on a washing machine according to a variety of factors including the degree and type of soiling of the fabrics, the nature of the soils, the fabric type, the fabric load and the like according to the needs of the user The consumer then activates the washing machine and the first cycle of the washing process begins whereby flows into an automatic washing machine through an inlet and then into a drum positioned inside the automatic washing machine The cleaning processes described herein takes place within this drum, which has a rotating agitator arranged on either a substantially horizontal or substantially vertical axis positioned at the center of the drum The amount of water which is poured into the drum should be an amount that is at least sufficient to distribute substantially evenly and completely onto the textiles or fabrics articles to be laundered Generally the drum will be filled with about 45 liters to about 100 liters of water A measured portion of the granular detergent composition as taught herein may be added at the same time that the tub is being filled with water The water and granular detergent composition mix in the tub to form a wash liquor The wash liquor will comprise from about 400 ppm to about 600,000 ppm of the granular detergent composition as described herein

After the drum begins filling with water and an effervescent-containing detergent is added to the water to begin the formation of the wash liquor, the textiles and the fabric articles are added into the wash liquor The consumer may wait until the water level in the drum has reached a height of about 0 5 cm, preferably about 5 cm, more preferably about 30 cm inches (as measured from the base of the drum) before adding the textiles and fabric articles Alternatively, instead of monitoring the height of the water level in the drum the consumer may begin adding the textiles and fabric articles within 5 minutes, preferably within 30 seconds of adding the effervescent- containing detergent to the water in drum Additional water (up to the predetermined maximum level as set by the consumer) flows into the drum as the fabric articles are added, pieferably all of the fabric articles are added to the wash liquor before the predetermined maximum level After the drum has been filled with sufficient water to reach this maximum level, the water flow is terminated and the "wash" cycle then begins as mechanical energy is imparted to the wash liquor (and thus indirectly to the textiles themselves) by the rotating agitator The wash cycle should last at least about 6 minutes, typically from about 4 minutes to about 12 minutes

In a less preferred embodiment, the textiles to be cleaned are immersed in the wash liquor after the drum has been filled with water to its maximum, predetermined level At the conclusion of the "wash" cycle, the wash liquor is drained from the wash tub and fresh water is added to the tub to rinse the detergent suds and film which has accumulated on the textiles This water is then removed from the rotating drum and to remove as much excess water as possible, the textiles may enter a "spin" cycle whereby they can be spun dry by the high-speed rotation of the drum

Although not necessary or essential to the present invention, it is preferable to use a pretreatment procedure to improve the effectiveness of removing stains from a stained area of the garment This pretreatment piocedure comprises applying a pretreatment composition to the stained area and then applying a gentle brushing motion to distribute the pretreatment composition around the stained area of the garment The pretreatment composition may or may not then be rinsed off the stained area with water the pretreatment composition may be either a specially-formulated detergent pretreatment composition or a consumer may make a small amount of a pretreatment paste by mixing the granular detergent compositions taught herein with water and then applying the paste directly to the stained area

The granular detergent compositions of the present invention are also suitable for use in low-water wash processes, such process are most typically found in "high-efficiency" automatic washing machines In a low-water wash process the total amount of wash and rinse water employed in all cycles of a commercially available washing machine is not more than 120 liters, preferably less than 100 liters Additionally, the nonaqueous liquid detergent composition used is these low-water wash processes is used at a concentration amount in said aqueous solution of from about 2000 ppm to about 10,000 ppm, wherein the water volume during any individual cycle of the wash process is from about 10 liters to about 35 liters Generally, the water used during the wash process is always at a temperature of less than about 30°C The fabric to water weight ratio during the process is from about 1 1 to about 1 9 and said fabrics undergo a wash time of from about 8 minutes to about 16 minutes

The method and granular detergent compositions taught herein may also be used in machines without agitators, such as the horizontally-arranged machines described in U S Pat No 4,555,019, issued Nov 26, 1985, to Spendel , which is hereby incorporated by reference Other machine designs for which these granular detergents and methods are also suitable are discussed in U S Pat No 5,345,637, issued September 13, 1994, to Pastryk et al and U S Pat No 5,191,669, issued March 9, 1993, to Euler et al

The above enumeration and description of exemplary processes and devices is not meant to limit the scope of the method to these specific process embodiments, but rather only to illustrate methods for use in aqueous cleaning processes in conventional and widely-used automatic washing machines

Effervescence Particle

The effervescence particle comprises one or more effervescence components such that on contact of the effervescence particle with water, effervescence is produced This effervescence may be as a result of gas trapped in the matrix of the particle being released when the particle contacts water, or more usually, is the result of a reaction which takes place between two or more reactants present in the effervescence particle which, on contact with water react with one another to produce a gas

Where the effervescence is produced by reaction of two or more reactants, preferably, the reactants are provided by an acid-source and an alkali-source Suitable acid sources include solid organic, mineral or inorganic acids, salts or derivatives thereof or mixtures thereof It may be preferred that the acids are mono-, bi- or tπ-protonic acids Such acids include mono- or polycarboxyhc acids preferably citric acid, adipic acid, glutaπc acid, 3-chetoglutaπc acid, citrama c acid, tartaπc acid, maleic acid, fumaπc acid, malic acid, succinic acid, malonic acid Such acids are preferably used in their acidic form Derivatives also include esters of the acids Preferred acids include citric acid and malic acid Citric acid is particularly preferred

The acid-source is preferably present in the effervescence particles at a level of from 0 1% to 99% by weight of the total particle, preferably from 3% to 80%, more preferably from 10% to 75% and most preferably from 15% to 70% Preferably, at least 80 wt% of the acid- source has a particle size of from about 150 μm to about 1200μm, or up to l OOOμm or 710μm

Any alkali-source may be used in the effervescence particle Carbonate alkali-sources are particularly preferred, for example including carbonate, bicarbonate, sesquicarbonate and percarbonate salts, in particular bicarbonate and/or carbonate Preferred carbonates to be used herein include carbonate and hydrogen carbonates which should be present in the effervescence particle in a from which can react with the acid-source Generally, therefore, the alkali-source should be water soluble, or of very fine particle size such that a reaction with the acid-source takes place readily on contact of the effervescence particle with water Salts of alkali metals or alkaline earth metals are suitable Water-soluble salts such as salts of potassium, lithium, sodium, and the like are preferred amongst which sodium and potassium carbonate are particularly preferred Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred Bicarbonate may be preferred to carbonate, because it is more-weight effective, 1 e , at parity weight bicarbonate is a larger C0₂ "reservoir" than carbonate However, overall detergent formulation requirements may result in the more alkaline pH, produced by carbonates, providing a more useful overall detergent formulation, thus the choice of carbonate or bicarbonate or mixtures thereof in the effervescence granules may depend on the pH desired in the aqueous medium wherein the detergent composition comprising the effervescence particles is dissolved For example where a relatively high pH is desired in the aqueous medium (e g , above pH 9 5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate, typically in a weight ratio of carbonate to bicarbonate from 0 1 to 10, more preferably from 1 to 5 and most preferably from 1 to 2 In one aspect of the invention, where the detergent composition comprises bicarbonate alone as the alkali-source, preferably the effervescence particle additionally comprises greater than 6 wt% citric acid optionally in mixtures with other acid-source components

The carbonate source is preferably present in the effervescence particles at a level of from 0 1% to 99%o by weight of the total, preferably from 30% to 95%, more preferably from 45% to 85% and most preferably from 50% to 80% by weight of the effervescence particle Preferably, at least 80 wt% or more of the carbonate source has a particle size in the range of from about 50 μm to about 1200μm or even from 150 μm to 1000 μm For optimum effervescence in aqueous medium the weight ratio of acid-source to alkali-source, preferably carbonate and/or bicarbonate, in the effervescence particle is generally from 0 1 to 10, preferably from 0 5 to 2 5 and more preferably from 1 to 2

Preferably the effervescence particle is substantially anhydrous such that the overall moisture content (including both bound I e water of crystallisation, and unbound I e free moisture) is less than 0 1 wt% of the effervescence particle More particularly, where the effervescence component comprises both acid-source and alkali-source, preferably at least the acid-source used for forming the effervescence particle has an overall moisture content less than 0 1 wt%, more preferably less than 0 05 wt% and most preferably less than 0 01 wt% More preferably, the alkali-source also has an overall moisture content less than 0 1 wt% , more preferably less than 0 05 wt% and most preferably less than 0 01 wt%

Preferably, the effervescence particles have a particle size such that the mean diameter is from 0 001 mm to 7 mm, preferably less than 2 mm The diameter measurements can be determined by sieving a sample of the granules into a number of fractions (typically 5 fractions) on a series of sieves, with various diameter or aperture size The mean diameter size of the granules can be calculated by plotting the weight fractions, obtained by the sieving, against the aperture size of the sieves The mean particle size is taken to be the aperture size through which 50%o by weight of the sample would pass

The bulk density of the effervescence particles is preferably from 500 g/1 to 1200 g/1, more preferably from 700 g/1 to 1 100 g/1

The effervescence particles may optionally comprise additional ingredients Generally, the effervescence particles comprise no more than 50 wt% of the particle of additional ιngredιent(s), preferably no more than 35 wt%> and more preferably no more than 20% or 10% It may be particularly preferred to have a highly active particle comprising no more than 5 wt% or even no more than 2 wt% of additional ingredients besides the components which contribute to the gas production release Suitable additional ingredients may comprise any detergent ingredients which are described below Particularly suitable are surfactants or organic or inorganic builder components, preferably those which are water soluble such as those described below

The effervescence particles used in the present invention are preferably prepared by mixing the effervescence component(s) which contribute to gas production/release, with any additional ingredients to produce an intimate mixture and then submitting the mixture to a granulation step to form particles Any granulation process may be used, however, in order to maintain high active levels in the finished effervescence particles, the granulation should preferably take place substantially without addition of any free moisture to the mixture A preferred agglomeration step comprises a pressure agglomeration step to form an agglomerate mixture, followed if necessary by a granulation step in which the agglomerate is formed into the effervescence particles for use in the detergent compositions of the invention

In the preferred pressure agglomeration process, the substantially dry mixture comprising the effervescence components and any optional additional ingredients is exposed to high external forces that bring the particles closely together thereby densifying the bulk mass of said particles and creating binding mechanisms between the components in the mixture Indeed, pressure agglomeration results in an aggregation mechanism which is characterised by the presence of inter-particle bonds between primary solid effervescent particles and a structure in which these effervescence particles are still identifiable and retain many of their characteristics, e g the ability to react together in presence of water to deliver carbon dioxide

The increase of density associated with the preferred processes for making the effervescence particles for use in the present invention, is closely linked to the pressure applied Typically, the bulk density will increase up to 200g/l, preferably from 10 g/1 to 150 g/1, starting from the density of the mixture comprising the effervescent raw materials, 1 e , acid and the carbonate source, and optionally the binder, before having undergone a pressure agglomeration

Pressure agglomeration may be carried out using different processes which can be classified by the level of forces applied A preferred process to be used herein is roller compaction In this process the effervescence components, preferably the acid-source and the alkali-source and any optional additional ingredients after having been mixed together are forced between two compaction rolls that applies a pressure to said mixture so that the rotation of the rolls transforms the mixture into a compacted sheet/flake This compacted sheet/flake is then broken up to form effervescence particles

Typical roller compactors for use herein are for example Pharmapaktor L200/50P® commercially available from Hosokawa Bepex GmbH The process variables during the pressure agglomeration step via roller compaction are the distance between the rolls, the feed rate, the compaction pressure and the roll speed A typical feeding device is a feed screw The distance between the rolls is typically from 0 5 cm to 10 cm, preferably from 3 to 7 cm, more preferably from 4 to 6 cm The pressing force is typically between 20 kN and 120 kN, preferably from 30 kN to l OOkN, more preferably from 50 kN to 100 kN Typically, the roll speed is between 1 rpm and 180 rpm, preferably from 2 rpm to 50 rpm and more preferably from 2 rpm to 35 rpm Typically, the feed rate is between 1 rpm and 100 rpm, preferably from 5 rpm to 70 rpm, more preferably from 8 rpm to 50 rpm Temperature at which compaction is carried out is not critical, typically it varies from 0° C to 40 °C

The sheet/flake produced by the pressure agglomeration process is broken up into effervescence particles by any suitable method for reducing the size of the sheet/flake to form particles, for example, by cutting, chopping or breaking the sheet/flake to produce the required length, and if necessary, by a process to make the particles rounded l e to obtain round or spherical granules according to the diameter size as defined herein before In the preferred embodiment one way to break up the sheet/flake after the roller compaction step is to mill the compacted flake/sheet Milling may typically be carried out with a Flake Crusher FC 200® commercially available from Hosokawa Bepex GmbH

Depending on the particle size required for the effervescence particles, the milled material may be sieved further Such a sieving of the dry effervescent granules can be carried out, for example with a commercially available Alpine Airjet Screen ® Detergent Matrix

The present inventors have found that for stability and maximum efficacy of effervescence in water in the wash conditions, it is not simply the properties of the effervescence particle which are critical. Thus, by careful selection and processing of the detergent matrix itself, improved properties can be achieved. This enables binders, which may adversely affect dissolution rates of the effervescence particle, to be used in reduced amounts or preferably omitted altogether.

Thus, in accordance with the present invention, the detergent matrix which comprises a pre-formed detergent matrix component comprising surfactant, and optional additional detergent ingredients, has an eRH no greater than 30%. Preferably the eRH is no greater than 25%, more preferably no greater than 20% or even no greater than 15% or 12% or even 10%. The eRH is measured using a Rotronic™ Hygroskop DT calibrated according to the manufacturers instructions as set out in the Rotronic Hygroskop application leaflet 2/E Spi/S dated 3.1.83, using dilute solutions of sodium chloride. All measurements are taken at 25°C.

The low eRH of the detergent matrix has a surprising effect on the stability of the effervescence particles. Whilst not wishing to be bound by theory, it is believed that this is because the detergent matrix not only does not contribute moisture to the effervescence particle leading to release of effervescence on storage, but in addition acts as a moisture sink so that moisture from the atmosphere contacting the detergent on storage, has a diminished adverse effect on the stability of the effervescence particle.

Although there is not necessarily a direct correlation between free moisture content and eRH, preferably the detergent matrix has a free moisture content of no greater than 2wt%, preferably no greater than 1 wt%, and even more preferably no greater than 0.5 or 0.1 or 0.05 wt%o. This low free moisture content may be achieved by drying one or more than one, or all of the components in the detergent matrix. Thus the detergent matrix component and one or more optional additional ingredients may be pre-mixed before drying or may be dried after mixing. Additional detergent matrix component and/or optional additional ingredients may then be combined with these pre-dried components without an additional drying step. However, the overall eRH of the detergent matrix (all those ingredients in the detergent composition with the exception of the effervescence particle) should be below 30%. Preferably in addition, the free moisture content of the detergent matrix should be below 2wt% or even 1 wt% or 0.5 or 0.01 wt%.

In a preferred aspect of the invention, at least one of the components in the detergent matrix is over-dried i.e. has been dried to a level such that water which is bound to one or more of the detergent ingredients either in the detergent matrix component or optional additional detergent ingredients, is removed. Detergent Matrix Component The detergent matrix comprises a detergent matrix component Such component comprises a pre-formed particulate which may be in the form of a powder, particle, flake or other solid form, comprising surfactant and optional additional detergent ingredients

The surfactant may be anionic, nomonic, catiomc, amphoteπc, zwitteπonic or mixtures thereof Preferred detergent matrix components comprise anionic, no onic and/or catiomc surfactants In particular matrix components which comprise anionic surfactant may be particularly useful Suitable surfactants are described in more detail below The surfactant content of a pre-formed matrix component is preferably from 5 to 80 % by weight of the matrix component Amounts of surfactants above 10 or even above 30% may be preferred Amounts of surfactant below 70% or even below 50% may be preferred

The solid material may be filler such as sulphates, in particular sodium sulphate, but more preferably comprises at least one detergent ingredient, in particular, builder or alkalinity components, or mixtures of such components Suitable examples include phosphate, alummosihcate, crystalline layered silicates, sodium carbonate or amorphous silicates These materials are described below in more detail For example, each of these components individually, or in mixtures may be present in amounts above 5%, preferably above 10% or even above 20% by weight of the content of the pre-formed matrix component Particularly preferred builder components are sodium carbonate and/or zeolite Zeolite A and zeolite MAP are both suitable

A pre-formed matrix component preferably also comprises an organic builder such as a poly carboxylic acid and/or salt such as citric acid, tartanc acid, malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or maleic acids or co-polymers thereof Such components are generally present in the matrix component at levels below 15 wt %, preferably below 10 wt % of the matrix component

Other preferred ingredients in the pre-formed matrix component are chelants such as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as described below These components are preferably present in a pre-formed particulate component in amounts below 5 wt % or even below 2 wt % of the matrix component

The detergent matrix may comprise one or more pre-formed detergent matrix components Suitable pre-formed components may have been formed by spray-drying, agglomeration, marumeπsation, extrusion or compaction, all of which methods for combining detergent ingredients are well-known in the art Particularly preferred pre-formed matrix components are powders obtained from spray-drymg processes, agglomerates and extrudates Spray-dried powders are particularly useful Detergent matrix components made according to at least one low shear mixing step, for example in a fluidised bed, for example by fluid bed agglomeration are also preferred

Suitable spray-drymg processes for forming such pre-formed detergent matrix components are described for example in EP-A-763594 or EP-A-437888 Suitable processes for forming detergent matrix components which are agglomerates are described for example in W093/25378, EP-A-367339, EP-A-420317 or EP-A-506184 Suitable moderate to low shear mixers may be for example a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes, Schugi or similar brand mixers which mix with only moderate to low shear The Lodige KM (ploughshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached Preferably, the shaft rotates at a speed of from about 15 rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm The grinding or pulverizing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm Other mixers similar in nature which are suitable for use in the process include the Lodige Ploughshare™ mixer and the Drais® K-T 160 mixer Generally, in the processes of the present invention, the shear will be no greater than the shear produced by a Lodige KM mixer with the tip speed of the ploughs below 10 m s, or even below 8m/s or even lower

Preferably, the mean residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0 1 minutes to about 15 minutes, most preferably the residence time is about 0 5 to about 5 minutes In this way, the density of the resulting detergent agglomerates is at the desired level

Other suitable mixers for use in the present invention are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators

Fluid bed agglomerators are particularly preferred Typical fluidised bed agglomerators are operated at a superficial air velocity of from 0 4 to 4 m/s, either under positive or negative pressure Inlet air temperatures generally range from -10 or 5°C up to 250°C However inlet air temperatures are generally below 200°C, or even below 150°C Suitable processes for forming detergent matrix components by extrusion are described for example in W091/02047

The detergent matrix may comprise only one pre-formed component as described or it may comprise a mixture of components, for example mixtures of different spray dried powders or of different agglomerates etc or mixtures of combinations of agglomerates, spray dried powders and/or extrudates etc as described above In order to obtain a detergent matrix having such a low eRH, the detergent matrix component or mixture thereof, will have undergone drying to provide the required low moisture content. Such drying may be provided in any conventional drying step, or may be the result of more thorough drying than is conventional using the usual processing route. Alternatively, an extra drying step may be provided in which the agglomerates/spray dried powders/extrudates etc are dried by any convenient means Suitable examples include drying ovens and fluidised bed dryers. For example, in a drying oven, the detergent matrix powder may be passed through such a drying oven on a conveyor or other convenient means. Preferably the free moisture in the detergent matrix component will be dried to below 1 wt%, more preferably below 0.5 wt%, or even below 0.1 or 0.05 wt% of the detergent matrix component There is not necessarily a direct correlation between the free moisture content of the detergent matrix component and the eRH, so the eRH for a particular detergent matrix must be measured in order to ensure the appropriate eRH is achieved. In a particularly preferred aspect of the invention, the detergent matrix component is over-dried (i.e. at least some of the bound water which is naturally associated with one or more of the chemical constituents of the component is at least partially removed).

Particularly preferred detergent matrix components are spray dried powders Additional Detergent Ingredients

As described above, the detergent matrix may comprise one or more additional detergent ingredients These may comprise detergent raw materials or may be pre-formed particulates made by processing at least one detergent ingredient with other ingredients which may be active or inactive in the detergent to form a solid particulate Where the particulate components are detergent raw materials, any particulate detergent ingredient is suitable These may be solid surfactants or soaps, or water soluble or dispersible polymeric materials, enzymes, bleaching components such as bleach activators or bleach salts such as peroxy salts These ingredients are discussed in more detail below

Any of the ingredients listed below may be added either as individual solid particulates or as preformed particulates. These additional detergent ingredients must be incorporated into the detergent matrix if needed, having undergone a drying step Whether a drying step is needed depends upon the form and level of incorporation of the individual additional ingredient materials and the eRH which they and the detergent matrix component and other ingredients provide in the overall detergent matrix The final detergent matrix must have an eRH below 30% Detergent Ingredients Surfactant Suitable surfactants for use in the invention are anionic, nomonic, ampholytic, and zwitteπonic classes of these surfactants, is given m U S P 3,929,678 issued to Laughhn and Heuπng on December 30, 1975 Further examples are given in "Surface Active Agents and Detergents" (Vol I and II by Schwartz, Perry and Berch) A list of suitable catiomc surfactants is given in U S P 4,259,217 issued to Murphy on March 31 , 1981

Preferably, the detergent compositions of the present invention and compositions comprising such particles comprises an additional anionic surfactant Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and tπethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants Anionic sulfate and sulfonate surfactants are preferred

The anionic surfactants may be present in the detergent matrix component in amounts below 25 wt % or even below 20 wt % but in a final detergent composition comprising the particle, is preferably present at a level of from 0 1% to 60%, more preferably from 1 to 40%, most preferably from 5% to 30% by weight

Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyls") such as water- soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l - undecanoic acid, 2-ethyl-l-decanoιc acid, 2-propyl-l-nonanoιc acid, 2-butyl-l-octanoιc acid and 2-pentyl-l -heptanoιc acid Certain soaps may also be included as suds suppressors Other suitable anionic surfactants are the alkali metal sarcosinates of foπnula R-CON (R^ ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R' is a C1 -C4 alkyl group and

M is an alkali metal ion Other anionic surfactants include lsethionates such as the acyl lsethionates, N-acyl taurates, fatty acid amides of methyl tauπde, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C. --C. - monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C,-C. . diesters), N- acyl sarcosinates Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι -C4 alkyl) and -N-(C] -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nomonic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary Ci Q-C I g alkyl sulfates, more preferably the Ci 1 -Ci 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Ci Q-C I g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C\ )-Cι g, most preferably Ci 1 -C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants optionally with catiomc surfactant Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C -C22 primary or secondary alkane sulfonates, -C24 olefin sulfonates, sulfonated polycarboxyhc acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof

Essentially any alkoxylated nomonic surfactant or mixture is suitable herein The ethoxylated and propoxylated nomonic surfactants are preferred

Preferred alkoxylated surfactants can be selected from the classes of the nomonic condensates of alkyl phenols, nomonic ethoxylated alcohols, no onic ethoxylated/propoxylated fatty alcohols, no onic ethoxylate/propoxylate condensates with propylene glycol, and the nomonic ethoxylate condensation products with propylene oxide/ethylene diamine adducts

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are particularly suitable for use herein Particularly preferred are the condensation products of straight or branched, primary or secondary alcohols having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONR^Z wherein : Rl is H, Ci -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C_j -C4 alkyl, and R2 is a C5-C3 ] hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof Z preferably will be derived from a reducing sugar in a reductive animation reaction, more preferably Z is a glycityl

Suitable alkylpolysaccharides for use herein are disclosed in U S Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysacchaπde, e g , a polyglycoside, hydrophihc group containing from 1 3 to 10 sacchaπde units Preferred alkylpolyglycosides have the formula

R2θ(C_nH_2nO)t(glycosyl)_x wherein R^ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms, n is 2 or 3, t is from 0 to 10, and x is from 1 3 to 8 The glycosyl is preferably derived from glucose

Suitable amphoteπc surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids Suitable amme oxides include those compounds having the formula R (OR )_xNθ(R )2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to

5, preferably from 0 to 3, and each R~> is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups Preferred are C J Q-

C] g alkyl dimethylamine oxide, and C] Q-18 acylamido alkyl dimethylamine oxide

Zwitteπomc surfactants can also be incorporated into the detergent compositions in accord with the invention These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocychc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds Betaines such as C i2-i g dimethyl-ammomo hexanoate and the C_{j Q}.i acylamidopropane (or ethane) dimethyl

(or diethyl) betaines and sultaine surfactants are exemplary zwitteπonic surfactants for use herein

Suitable catiomc surfactants to be used herein include the quaternary ammonium surfactants Preferably the quaternary ammonium surfactant is a mono Cg-Cj g, preferably Cg-

C J O N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants

Catiomc ester surfactants such as chohne ester surfactants, have for example been disclosed in US Patents No s 4228042, 4239660 and 4260529 are also suitable as are catiomc mono-alkoxylated amme surfactants

The levels of the catiomc mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0 1% to 20%, preferably from 0 2% to 7%, most preferably from 0 3% to 3 0% by weight

Catiomc bis-alkoxylated amine surfactant such as

are also useful, wherein R is Ci -C_j hydrocarbyl and mixtures thereof, preferably C J Q, C_j2,

Cj4 alkyl and mixtures thereof X is any convenient a on to provide charge balance, preferably chloride

Bleach Activator

The detergent compositions of the invention preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophihc peroxy acid bleach precursor, as defined herein The production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach Preferably, the bleach activator is present as a separate, admixed particle

Preferably, any bleach activator is present in a particulate component having an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1 100 microns It may be preferred that at least 80%, preferably at least 90% or even at least 95 % or even substantially 100% of the component or components comprising the bleach activator have a particle size of from 300 microns to 1700 microns, preferably from 425 microns to 1400 microns Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS Preferred hydrophihc peroxy acid bleach precursors preferably comprises TAED Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid Generally peroxyacid bleach precursors may be represented as X-C(0)-L where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

O

X - C - OOH

For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophihc peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e g , a wash cycle) However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition Suitable and preferred L groups are discussed in greater detail in the copending application of Hall et al , entitled "Detergent Compositions", having Serial No 09/230,877 and being filed on February 1 , 1999, which is hereby incorporated by reference

Peroxyacid bleach precursor compounds are preferably incorporated in final detergent compositions at a level of from 0 5% to 30% by weight, more preferably from 1% to 15% by weight, most preferably from 1 5% to 10% by weight The ratio of hydrophihc to hydrophobic bleach precursors, when present, is preferably from 10 1 to 1 10, more preferably from 5,1 to 1 5 or even from 3 1 to 1 3 Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes Examples of useful materials within these classes are disclosed in GB-A-1586789 Suitable esters are disclosed in GB-A-836988, 864798, 1 147871 , 2143231 and EP-A-0170386 Alkyl percarboxyhc acid bleach precursors form percarboxyhc acids on perhydrolysis Preferred precursors of this type provide peracetic acid on perhydrolysis Preferred alkyl percarboxyhc precursor compounds of the lmide type include the N-,N,N'N ' tetra acetylated 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 Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophihc peroxy acid bleach precursor Other preferred alkyl percarboxyhc acid precursors include sodium 3,5,5-tπ-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae R¹ C N — R² C L R¹ N — C R² C L

O R⁵ O or R⁵ O O wherein R* is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group R! preferably contains from about 6 to 12 carbon atoms R^ preferably contains from about 4 to 8 carbon atoms R may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat Analogous structural variations are permissible for R^ R2 can include alkyl, aryl, wherein said R^ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds R-> is preferably H or methyl R* and R-> should not contain more than 18 carbon atoms total Amide substituted bleach activator compounds of this type are described in EP-A-0170386 It can be preferred that

R! and R^ forms together with the nitrogen and carbon atom a ring structure

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamιdo-caproyl)oxybenzenesulfonate, (6-decanamιdo- caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamιdocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386 Other preferred bleach precursoi compounds include perbenzoic acid precursors and catio c peroxyacid precursors which are described in greater detail in the copending application of Hall et al , entitled "Detergent Compositions", having Serial No 09/230,877, incorporated above

Peroxide Source

Inorganic perhydrate salts are a preferred source of peroxide Preferably these salts are present at a level of from 0 01% to 50% by weight, more preferably of from 0 5% to 30% by weight of the composition

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persihcate salts Generally these materials are prepared by crystallisation or fluidised bed processes The inorganic perhydrate salts are normally the alkali metal salts The inorganic perhydrate salt may be included as the crystalline solid without additional protection For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2 3H2O Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3 3H2O2, and is available commercially as a crystalline solid Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein

Chelants

As used herein, chelants refers to detergent ingredients which act to sequester (chelate) heavy metal ions These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper Chelants are generally present in the detergent matrix component and/or as dry added additional detergent ingredients so that they are present in the final detergent composition at total levels of from 0 005% to 10%, preferably from 0 1% to 5%, more preferably from 0 25% to 7 5% and most preferably from 0 3% to 2% by weight of the compositions or component

Suitable chelants include organic phosphonates, such as the am o alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitπlo tπmethylene phosphonates, preferably, diethylene tπamine penta (methylene phosphonate), ethylene diamine tπ (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxv - ethylene 1 ,1 diphosphonate, 1 ,1 hydroxyethane diphosphonic acid and 1 , 1 hydroxyethane dimethylene phosphomc acid

Other suitable chelants for use herein include nitπlotπacetic acid and polyaminocarboxyhc acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaπc acid, 2-hydroxypropylenedιamιne disuccinic acid or any salts thereof, and lminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133 The lminodiacetic acιd-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonιc acid sequestrants described in EP-A-516,102 are also suitable herein The β-alanine-N.N'-diacetic acid, aspartic acιd-N,N'-dιacetιc acid, aspartic acid-N-monoacetic acid and lminodisuccimc acid sequestrants 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 lminodiacetic acid sequestrant Dipicohnic acid and 2-phosphonobutane-l ,2,4-tπcarboxyhc acid are alos suitable Glycιnamιde-N,N'- disuccinic acid (GADS), ethylenediamme-N-N'-diglutaπc acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable Especially preferred are diethylenetπamine pentacetic acid, ethylenedιamιne-N,N'-dιsuccιnιc acid (EDDS) and 1 ,1 hydroxyethane diphospho c acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof In particular the chelating agents comprising a amino or amme group can be bleach-sensitive and are suitable in the compositions of the invention Water-Soluble Builder Compound

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

One preferred detergent composition of the invention comprises phosphate-containing builder material, preferably present at a level of from 0 5% to 60%, more prefeiably from 5% to 50%, more preferably from 8% to 40% by weight Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tπpolyphosphate

Suitable water-soluble builder compounds include the water soluble monomeπc polycarboxylates, or their acid forms, homo or copolymeπc polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing Furthei examples of suitable water-soluble builders are discussed in greater detail in the copending application of the copending application of Hall et al , entitled "Detergent Compositions", having Serial No 09/230,877, incorporated above

Partially Soluble or Insoluble Builder Compound

The compositions of the invention may contain a partially soluble or insoluble builder compound present in the detergent matrix component and/or the optional additional ingredients Where present, typically they will be present in the detergent compositions in a total amount of from 0 5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight Examples of largely water insoluble builders include the sodium aluminosihcates As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present Suitable partially soluble or insoluble builders are disclosed in greater detail in the copending application of Hall et al , entitled "Detergent Compositions", having Serial No 09/230,877, incorporated above Dyes, Perfumes. Enzymes, Optical Bπghteners

A preferred ingredient of the compositions herein are dyes and dyed particles or speckles, which can be bleach-sensitive The dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle, or more preferably up to 0 5% by weight, as described above The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nomonic surfactants Optionally, the dye also comprising other ingredients such as organic binder materials, which may also be a non-aqueous liquid The dyestuff can be any suitable dyestuff Specific examples of suitable dyestuffs include El 04 - food yellow 13 (qumohne yellow), El 10 - food yellow 3 (sunset yellow FCF), El 31 - food blue 5 (patent blue V), Ultra Marine blue (trade name), El 33 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphylhns), E141 and Pigment green 7 (chlorinated Cu phthalocyanine) Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name)

Another preferred ingredient of the compositions of the invention is a perfume or perfume composition Any perfume composition can be used herein The perfumes may also be encapsulated Preferred perfumes containing at least one component with a low molecular weight volatile component , e g having a molecular weight of from 150 to 450 or preferably 350 Preferably, the perfume component comprises an oxygen-containing functional group Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof

Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139. Further discussion of suitable and preferred enzyme species can be found in the copending application of Hall et al., entitled "Detergent Compositions", having Serial No. 09/230,877, incorporated above. Organic Polymeric Ingredients

Organic polymeric compounds are preferred additional herein and are preferably present as components of any particulate component such as the detergent matrix component where they may act as binders. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention. Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions or component. Further examples of suitable organic polymeric ingredients can be found in the copending application of Hall et al., entitled "Detergent Compositions", having Serial No. 09/230,877, incorporated above.

In addition to those discussed in the incorporated reference, another organic compound, which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:

X -f- OCH₂CH₂)_n CH₂CH₂0 )_ή X

(CH₂CH₂0-)-X (CH₂CH₂0 )_n X wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42. Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Polymeric dye transfer inhibiting agents when present are generally in amounts from 0.01% to 10 %, preferably from 0.05% to 0.5% and are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrohdone and N-vinyhmidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross- linked polymers

Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present components or compositions If utilized, SRAs will generally be used in amounts from 0 01% to 10 0%, typically from 0 1% to 5%, preferably from 0 2% to 3 0% by weight Preferred SRA's typically have hydrophihc segments to hydrophihze the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchoi for the hydrophihc segments This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesteπfication/oligomeπzation, often with a metal catalyst such as a tιtanιum(IV) alkoxide Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosshnked overall structure

Suitable SRAs are for example as described in U S 4,968,451 , November 6, 1990 to J J Scheibel and E P Gosselink Other SRAs include the nomonic end-capped 1 ,2- propylene/polyoxyethylene terephthalate polyesters of U S 4,71 1 ,730, December 8, 1987 to Gosselink et al Other examples of SRA's include the partly- and fully- amonic-end-capped oligomeric esters of U S 4,721 ,580, January 26, 1988 to Gosselink, the nonionic-capped block polyester oligomeric compounds of U S 4,702,857, October 27, 1987 to Gosselink, and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U S 4,877,896, October 31 , 1989 to Maldonado, Gosselink et al SRAs also include simple copolymeπc blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U S 3,959,230 to Hays, May 25, 1976 and U S 3,893,929 to Basadur, July 8 1975, cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow, the C1 -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U S

4,000,093, December 28, 1976 to Nicol, et al , and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1 6 to about 2 3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shm-etsu Kagaku Kogyo KK Additional classes of SRAs include those described in U S 4,201,824, Violland et al and U S 4,240,918 Lagasse et al , U S 4,525,524 Tung et al , and U S 4,201 ,824, Violland et al Suds Suppressing System

The detergent compositions herein, in particular when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0 01% to 15%, preferably from 0 02% to 10%, most preferably from 0 05% to 3% by weight of the composition or component Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example sihcone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution copending application of Hall et al , entitled "Detergent Compositions", having Serial No 09/230,877, incorporated above

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid Also, preferably combined with a carbonate salt, minor amounts (e g , less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti- oxidants, bacteπcides and dyes, such as those described in US Patent 4,285,841 to Barrat et al , issued August 25, 1981 (herein incorporated by reference), can be present

The detergent compositions can include as an additional component a chlorine-based bleach However, since the detergent compositions of the invention are solid, most liquid chloπne-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable Alternatively, a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process The chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution The hypochlorite ion is chemically represented by the formula OCI Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochloπtes, hypochlorite addition products, chloramines, chloπmines, chloramides, and chlorimides Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated tπsodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, tπchlorocyanuπc acid, l,3-dιchloro-5,5-dιmethylhydantoιn, N- chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).

Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions. Laundry Washing Method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Preferred washing machines may be the so-called low-fill machines.

In a preferred use aspect the composition is formulated such that it is suitable for hard- surface cleaning or hand washing. In another preferred aspect the detergent composition is a pretreatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.

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

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS : Sodium linear C 1 1 - 13 alkyl benzene sulfonate

TAS : Sodium tallow alkyl sulfate

CxyAS : Sodium Clx - Cly alkyl sulfate

Branched AS :branched sodium alkyl sulfate as described in W099/19454 C46SAS :Sodium C14 - C16 secondary (2,3) alkyl sulfate

CxyEzS -.Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide

CxyEz :C 1 x-C 1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+(CH3)2(C2H40H) with R2 = C 12 - C 14

QAS 1 :R2.N+(CH3)2(C2H40H) with R2 = C8 - C 1 1

APA :C8 - CIO amido propyl dimethyl amine Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids

STS Sodium toluene sulphonate

CFAA C12-C14 (coco) alkyl N-methyl glucamide

TFAA C16-C18 alkyl N-methyl glucamide

TPKFA C12-C14 topped whole cut fatty acids

STPP Anhydrous sodium tripolyphosphate

TSPP Tetrasodium pyrophosphate

Zeolite A Hydrated sodium aluminosilicate of formula Nal2(A102Si02)12.27H20 having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)

NaSKS-6 :Crystalline layered silicate of formula d- Na2Si205 Citric acid Anhydrous citric acid Borate : Sodium borate Carbonate Anydrous sodium carbonate: particle size 200μm to 900μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amorphous sodium silicate (Si02:Na20 = 2.0: 1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate :Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850μm

MA/AA :Copolymer of 1 :4 maleic/acrylic acid, average m. wt. about 70,000 MA/AA (1 ) :Copolymer of 4:6 maleic/acrylic acid, average m. wt. about 10,000 AA :Sodium polyacrylate polymer of average molecular weight 4,500 CMC :Sodium carboxymethyl cellulose Cellulose ether :Methyl cellulose ether with a degree of polymerization of 650 available from

Shin Etsu Chemicals

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

Industries A/S under the tradename Savinase

Protease I :Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO

95/10591 , sold by Genencor Int. Inc.

Alcalase :Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO

Industries A/S Cellulase :Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO

Industries A/S under the tradename Carezyme

Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO

Industries A/S under the tradename Termamyl 120T

Lipase :Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO

Industries A/S under the tradename Lipolase

Lipase (1) :Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO

Industries A/S under the tradename Lipolase Ultra

Endolase :Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by

NOVO Industries A/S

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

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

Percarbonate :Sodium percarbonate of nominal formula 2Na2C03.3H202

NOBS :Nonanoyloxybenzene sulfonate in the form of the sodium salt

NAC-OBS :(6-nonamidocaproyl) oxybenzene sulfonate

TAED : Tetraacety 1 ethy lenedi amine

DTPA :Diethylene triamine pentaacetic acid

DTPMP :Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060

EDDS :Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer sodium salt.

Photoactivated bleach :Sulfonated zinc phthlocyanine encapsulated in bleach ( 1 ) dextrin- sol.pol.

Photoactivated bleach :Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer

Brightener 1 :Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 :Disodium 4,4'-bis(4-anilino-6-mo holino-1.3.5-triazin-2-yl)amino) stilbene-

2:2'-disulfonate

HEDP : 1 , 1 -hydroxyethane diphosphonic acid

PEGx :Polyethylene glycol, with a molecular weight of x (typically 4,000)

PEO :Polyethylene oxide, with an average molecular weight of 50,000

TEPAE :Tetraethylenepentaamine ethoxylate

PVI :Polyvinyl imidosole, with an average molecular weight of 20,000

PVP :Polyvinylpyrolidone polymer, with an average m. wt. of 60,000 PVNO Polyvinylpyπdme N-oxide polymer, with an av m wt of 50,000

PVPVI Copol of polyvinylpyrohdone and vinyhmidazole (av m wt of 20,000)

QEA bιs((C2H50)(C2H40)n)(CH3) -N+-C6H 12-N+-(CH3) bιs((C2H50)-(C2H4

0))n, wherein n = from 20 to 30 SRP 1 Amonically end capped poly esters

SRP 2 Diethoxylated poly (1 , 2 propylene terephthalate) short block polymer

PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Si cone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10 1 to 100 1 Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax Paraffin wax

HMEO Hexamethylenediamine tetra( ethylene oxιde)24

EXAMPLE I A 2 kg batch of citric acid and sodium carbonate having a composition of 64wt% citric acid/36 wt% sodium carbonate was prepared by mixing in a Hosokawa Mikron 'Nautamix' DBY- 5R rotating screw mixer for five minutes at a speed setting of 9(maxιmum) 1280 g anhydrous citric acid ex Citπque Beige (Fine Granular Grade 16/40) having a particle size of from 200- 400μm and 720g anhydrous Sodium Carbonate(Lιght Soda Ash ex Brunner Mond) pre-nnlled using a Hosokawa Mikron Air-Classifying Mιll(ACM 15) to a median particle size of 5μm The mixture was then compacted in a Bepex Compaction Unit (Roll 200mm Diameter, 50mm Width) the pre-mixed powders were poured into the feed-hopper above the compacting rolls The feed- hopper has a vertical screw which feeds the powder into the rolls The force applied to push these two rolls together known as compaction force was adjusted to 80kN by adjusting the feed-screw speed The compacted material was collected in the form of broken and unbroken corrugated sheets which were then milled in a Hosokawa Bepex F200 Flake Breaker at speed setting 1 This equipment consists of a Rolling Cage with a l OOOμm Screen

The material produced by the Flake breaker was then placed on a Vibrating Sieving devιce( Retsch model AST200) with sieve size of 355μm The material retained on the screen was the desired finished particle (effervescence particle A in the table below) with median particle size 620μm, and the fines were removed for recycle Detergent compositions as produced above and having the following compositions are examples of the present invention.

This composition was then used in the following manner The garments are placed in a conventional, top-loading automatic washing machine. Care should be taken to insure that the load is balanced

Step 1 A sufficient number of garments to form a medium load are selected Stains on a garment from sources such as ink, lipstick, salad dressing, collar soil and other similar sources are then identified and selected for pretreatment For pretreatment, localized stained areas of the garment are situated over a paper towel and are treated by directly applying about 0.1 to 5 ml (depending on the size of the stain) of a mixture of water and the granular product of Example I, which is gently worked into the garment. Optionally, excess liquid product may be rinsed off the stain with running cold tap water.

Step 2. A conventional, top-loading washing machine is used and the washing machine settings are set on: medium water level (approximately 17 gallons), and a water temperature and agitation setting appropriate to the type and color of garments and their degree of soiling. The washing machine is started so that the drum inside the washing machine begins to fill with water.

Step 3. When the washing machine has filled with a sufficient amount of water to raise the water level in the drum to a height of 2 inches, an amount of the granular detergent is added to the water to from a wash liquor. When the detergent composition is added the wash liquor will reach a temporary maximum concentration of about 10,000 ppm. After the washing machine has completed filling with water, the steady-state concentration of the detergent is about 1100 ppm.

Step 4. The garments are added to the detergent/water solution (wash liquor).

Step 5. When the washing machine has completed all of its cycles, the garments are removed from the washing machine

Claims

What is claimed is

1 A method of laundering soiled textile articles in a washing apparatus characterized by the steps of

(a) adding a granular detergent composition characterized by of an effervescence granule and a detergent matrix to water to form an aqueous wash liquor characterized by from 400 ppm to 600000 ppm of the granular detergent composition, wherein the effervescence granule is characterized by an alkali- source and an acid-source and upon contact of the granular detergent composition with water a reaction occurs between the alkali-source and the acid-source occurs to produce an effervescent gas, and

(b) distributing substantially evenly and completely onto the textile articles in their substantially dry state a cleaning-effective amount of the wash liquor, wherein step (b) is performed simultaneously with or subsequently to step (a)

2 A method according to claim 1 wherein the method further is characterized by the steps of

(c) rinsing the textile articles with a quantity of water sufficient to produce enough free water on the surface of the textile to form a rinse liquor characterized by suspended soil, suspended wash liquor and suspended undissolved detergent composition, and

(d) separating the rinse liquor from the textile articles

3 A method according to any of claims 1 -2 wherein the cleanmg-effective amount of the wash liquor is at least just enough to distribute the wash liquor substantially evenly and completely onto said textiles

4 A method according to any of claims 1-3 wherein before step (a), the process further is characterized by the steps of

(I) applying a pretreatment solution directly to a stain covering a localized area of one of the textile articles, (π) concurrently with step (1), applying mechanical action to the stain, and (in) optionally, rinsing the pretreatment solution off the localized area of one of the textile articles

5. A method according to any of claims 1-4 wherein the detergent matrix is characterized by surfactant, builder and enzyme detergent ingredients.

6. A method according to any of claims 1-5 wherein the acid-source is selected from the group consisting of organic, mineral or inorganic acids, salts of the acids, derivatives of the acids and the salts, and mixtures thereof; and wherein the alkali-source is selected from the group consisting of carbonates, bicarbonates, sesquicarbonates, percarbonates and mixtures thereof.

7. A method according to any of claims 1-6 wherein the cleaning-effective amount of the wash liquor is from 45 liters to 100 liters.

8. A method according to any of claims 1-7 wherein: a drum is disposed within the washing apparatus and the water of step (a) is introduced into the drum; and step (b) is commenced after the water level in the drum has reached a height of 0.5 cm, preferably 5 cm, more preferably 30 cm, as measured from the base of the drum.

9. An article of manufacture characterized by a granular detergent composition packaged in association with instructions for use in a method of laundering soiled textile articles, wherein the instructions comprise the steps of:

(a) mixing water and a granular detergent composition characterized by of an effervescence granule and a detergent matrix to form an aqueous wash liquor characterized by from 400 ppm to 600000 ppm of the granular detergent composition; and

(b) subsequent to step (a), distributing substantially evenly and completely onto the textile articles in their substantially dry state a cleaning-effective amount of the wash liquor.

10. An article of manufacture according to any of claims 1-9 wherein the effervescence granule is characterized by an alkali-source and an acid-source and upon contact of the granular detergent composition with water a reaction occurs between the alkali-source and the acid-source occurs to produce an effervescent gas.