WO2012049053A1

WO2012049053A1 - Package comprising a laundry composition, dispenser for said package and method for washing using said dispenser and said package

Info

Publication number: WO2012049053A1
Application number: PCT/EP2011/067387
Authority: WO
Inventors: Judith Maria Bonsall; Andrew Paul Chapple; Stephen Thomas Keningley; Alyn James Parry
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2010-10-14
Filing date: 2011-10-05
Publication date: 2012-04-19
Also published as: EP2627577A1; EP2627577B1; BR112013008991A2; CN103153813A; BR112013008991B1; ES2591003T3; ZA201302294B; CN103153813B

Abstract

A dispenser (1) for dispensing a blister pack (3) of predetermined doses (5) of concentrated laundry composition into a washing machine, the dispenser comprising a rigid support frame (7) on which is mounted said blister pack whereby manual force on a selected dose ejects that dose from the blister pack.

Description

PACKAGE COMPRISING A LAUNDRY COMPOSITION, DISPENSER FOR SAID PACKAGE AND METHOD FOR WASHING USING SAID DISPENSER AND SAID PACKAGE

The present invention relates to a dispensing device for dispensing concentrated particulate detergent compositions in e.g. a washing machine.

5

Particulate detergent compositions with improved environmental profiles could, in theory, be designed by eliminating all components from the composition that provide limited, or no, cleaning action. Such compact products would also reduce packaging requirements. One problem with compact or concentrated

0 compositions is that consumers must dose accurately however they tend to use more of the composition than is recommended, probably due to their familiarity with the previous less concentrated variants. Studies have shown that consumers tend to overdose concentrated compositions and this is bad for their pocket and bad for the environment. Dosing measures are frequently provided, and ignored. 5

It is an object of the present invention to provide a packaged particulate

concentrated detergent composition wherein the dosage is more controllable by the consumer. 0 Accordingly, in a first aspect, the present invention provides a packaged product comprising a package comprising a plurality of individual reservoirs, each of the reservoirs containing a predetermined dose of a concentrated particulate laundry wherein at least 70 % by number of the particles of the composition comprising a high-surfactant hard core and a coating and wherein all the particles are non 5 spherical and at least 0.2 mm in diameter.

With this arrangement, the consumer has pre-measured doses so there is no need to measure and the tendency to overdose is eliminated or at least reduced. At the same time, coated particulate concentrated detergent compositions of the 0 invention, with large non-spherical similarly shaped and sized particles provide a slow, steady and predictable flow from the small reservoirs and eliminates or at least minimises product residue in the reservoirs. With conventional powders, the inner surfaces of the reservoir become coated with a fine dusting, which would affect the transparency. For this reason, traditionally powders are mostly sold in opaque cartons or pouches. However, the large hard-coated particles of the invention do not form a film over the reservoir surface. The coating reduces the stickiness of the hygroscopic surfactant core to a point where the particles are free flowing across a surface. This together with the particle size means that any composition left in the package after tipping/pouring etc. are present in minor and localised amounts. A gentle tap releases them from the surface. Even liquid formulations do not provide this advantage - liquids coat then inner surfaces of reservoirs and so leave residue.

The package is preferably sufficiently rigid in material and/or construction such that a portion e.g. the base or a side wall, can be tapped to move the particles from the reservoir/s. Preferably such tapping creates audible feedback to the user to guide them as to the movement of the particles.

The large format of the particles reduces the impact of stickiness as the number of potential bridging points is reduced and the force exerted by each particle when it attempts to move is much greater than a conventional powder due to the mass of each particle being about 25 times greater. Thus even under slightly damp conditions, as may be experienced in a laundry room, the particles remain more reliably slow flowing.

The package may comprise a tray of individual recesses, each recess providing an individual reservoir covered by a lid. There may be a common lid for two or more recesses. Preferably the package comprises a blister pack. The blister pack preferably comprises a planar sheet of plastic provided with "blisters" or concave protrusions configured in various patterns, e.g. rows and columns. Each of the blisters or concave protrusions is sized to receive a predetermined dose of the composition. Preferably, the blister pack further comprises at least one backing layer is fastened to the solid receiving side of the blister pack. This layer is a low strength retaining layer. This low strength retaining layer stretches across the backs of the blisters and retains the doses individually sealed within each of the blisters. Preferably the blister pack is mounted with the low strength retaining layer facing down.

In a second aspect the invention provides a dispenser for dispensing from the package of the first aspect, the dispenser comprising a rigid support frame on which is mounted said pack, whereby manual force on a selected reservoir ejects that dose from the package.

With this arrangement, the precise doses of the composition can be dispensed highly efficiently. The dispenser may be installed in a machine e.g. washing machine drawer so manual force on a selected dose ejects this dose from the blister pack directly into the drawer or drawer compartment if compartments are provided. The blister pack and dispenser are preferably water insoluble.

The rigid support frame preferably comprises at least one wall with one or more apertures therein such that water flow is minimally restricted. Alternatively or additionally the frame may comprise a mesh structure and/or support pillars optionally with cross ties or the like. The structure should also have smooth contours and generally convex rather than concave surface configuration/ patterning such that water and/or laundry composition cannot become trapped.

The dispensing device is preferably water insoluble so it can be left in the machine. Alternatively, the device may be installed for use e.g. on the upper edges of the drawer, so that the dose can be dosed directly into the drawer, and then removed prior to the washing operation.

By "rigid" is meant here that the frame has sufficient rigidity to withstand the manual force required to break the blister pack. Some elasticity may be allowed, at higher forces than that required to break the blister open, and indeed may even be desirable. For example the walls may be flexible (or flexibly attached to the rest of the frame), so that the will flex against the drawer sides. With this feature, during fitting these can be forced to flex inward and then once in place, and they are released so as to urge against the sides of the drawer, thereby preventing movement of the dispensing device whilst in place in the drawer.

Preferably the blister pack is mounted removably. This way it may be replaced when required, e.g. all the doses have been used, or for an alternative blister pack with different composition. To negate the need for frequent changes, the blister pack may contain unit doses with different compositions. Preferably the rigid frame and blister pack comprise an engaging mechanism for secure mounting. Advantageously, this mechanism comprises mutually interengaging projections and recesses on the frame and pack. The rigid support frame may comprise recesses corresponding with the shape of the blisters. For example, if the blisters are circular, there may be annular or semi-circular recesses along the support frame. These can engage with the blisters and provide support and/or secure positioning of the blister pack. Preferably the rigid frame comprises a wall or walls having supporting upper edges which correspond to an outer perimeter of the blister pack so that it is supported along its perimeter. Further walls can be provided to provide further support between the unit doses, these further walls preferably corresponding with areas of the blister pack between the unit doses. The support frame may comprise an upper supporting edge which is inclined with respect to the base, whereby the mounted blister pack is also inclined. With this arrangement, the blister pack may be better viewed by the user. ln a third aspect the invention provides a method of washing fabrics within a washing machine, with the package of the first aspect of the invention, the method comprising the step of manually pressing on a dose in one of the reservoirs to eject the dose from the blister pack.

The above method preferably comprises the earlier step of mounting the package e.g. blister pack onto the rigid support frame. The method may comprise the step of installing the rigid support frame, before or after installing the package thereon, into the drawer of a washing machine, whereby the step of manually pressing externally of a reservoir in the package, ejects the dose from the reservoir into the drawer. The method may optionally comprise the step of removing the rigid support frame from the drawer before washing or it may comprise the step of beginning the wash process with the rigid support frame installed in the drawer, with or without the package. Where the blister pack is to remain in place mounted on the rigid support frame during a wash it should comprise water soluble materials or at least an outer water soluble barrier.

In a fourth aspect the present invention provides a packaged concentrated laundry composition further comprising a dispenser of the second aspect. The package preferably contains instructions for use according to the method of the invention.

In a fifth aspect the present invention provides a washing machine having a drawer for receiving and supplying laundry compositions, including concentrated laundry compositions, said drawer containing a dispenser according to the second aspect of the invention.

Preferably the or each reservoir comprises a transparent portion. This allows the consumer to see when all the dose has been preferably the or each transparent portion comprises at least a part of the base of the reservoir, such that the composition contained within is visible when viewed looking at the base. This is advantageous for e.g. blister packs which tend to be used base upwards.

Preferably the or each transparent portion comprises more than 50%, more preferably more than 60%, and most preferably more than 75% of the surface area of the reservoir.

In so far as the packaging is concerned, "transparent" means that its light transmittance is greater than 25% at wavelength of about 410-800 nm. The or each transparent portion according to the invention preferably has a transmittance of more than 25%, more preferably more than 30%, more preferably more than 40%, more preferably more than 50% in the visible part of the spectrum (approx. 410-800 nm). Alternatively, absorbency of transparent layer may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals:

1 x 100%

10 ^a'^5Sor'^5ency

Conversely, absorbency of the opaque layer may be measured as more than 0.6.

For purposes of the invention, as long as one wavelength in the visible light range has greater than 25% transmittance, the container is considered to be

transparent. Alternatively, absorbency of bottle may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals: 1 10^absorbency x 100% and corresponding absorbency levels for the remaining preferred levels above. Suitable materials for the package include, but are not limited to: polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamides (PA) and/or

polyethylene terephthalate (PETE), polyvinylchloride (PVC); and polystyrene (PS). The reservoirs may formed by moulding e.g. blow moulding from a preform or by thermoforming or by injection moulding.

Preferably the packaged particles are substantially the same shape and size as one another. Preferably the composition comprises greater than 40 wt% detergent surfactant. Preferably, at least 70% by number of the particles comprise a core, comprising mainly surfactant, and around the core a water soluble coating comprising 15 to 45 wt% of the coated particle. Preferably each coated particle has perpendicular dimensions x, y and z, wherein x is from 0.2 to 2 mm, y is from 2.5 to 8mm (preferably 3 to 8 mm), and z is from 2.5 to 8 mm (preferably 3 to 8 mm) and preferably the packaged particles are substantially the same shape and size as one another. Preferably the coating comprises at least 10 wt% of a water soluble salt. More preferably the water soluble salt comprises an inorganic salt. Most preferably it comprises sodium carbonate. The coating may further comprise a minor amount of sodium carboxy methyl cellulose (SCMC), sodium silicate, water soluble fluorescer, water soluble or dispersible shading dye, pigment, coloured dye and mixtures thereof.

The amount of coating on each coated particle is preferably 20 to 35 % by weight of the particle. The number percentage of the packaged composition of particles comprising the core and coating is preferably at least 85%.

The coated particles preferably comprise from 0.001 to 3 wt% perfume.

The core of the coated particles preferably comprises less than 5 wt%, even more preferably less than 2.5 wt% inorganic materials.

The particles are desirably oblate spheroids with diameter (y and z) of 3 to 6 mm and thickness (x) of 1 to 2 mm.

At least some, and preferably a major portion by number of the particles may be coloured other than white, as this makes it easier to see them to determine that the required dose level has been reached. Multicoloured, e.g. some blue and some white, particles have been found to provide even higher visual definition for the optimum control of dose. Colour may be imparted by dye, pigment or mixtures thereof.

MANUFACTURE OF THE PARTICLES

A preferred manufacturing process is set forth in PCT/EP2010/055256. It comprises blending surfactants together and then drying them to a low moisture content of less than 1 %. Scraped film devices may be used. A preferred form of scraped film device is a wiped film evaporator. One such suitable wiped film evaporator is the "Dryex system" based on a wiped film evaporator available from Ballestra S.p.A.. Alternative drying equipment includes tube-type driers, such as a Chemithon Turbo Tube® drier, and soap driers. The hot material exiting the scraped film drier is subsequently cooled and broken up into suitable sized pieces to feed to the extruder. Simultaneous cooling and breaking into flakes may conveniently be carried out using a chill roll. If the flakes from the chill roll are not suitable for direct feed to the extruder then they can be milled in a milling apparatus and /or they can be blended with other liquid or solid ingredients in a blending and milling apparatus, such as a ribbon mill. Such milled or blended material is desirably of particle size 1 mm or less for feeding to the extruder.

It is particularly advantageous to add a milling aid at this point in the process. Particulate material with a mean particle size of 10 nm to 10 pm is preferred for use as a milling aid. Among such materials, there may be mentioned, by way of example: aerosil®, alusil®, and microsil®.

Extruding and Cutting

The dried surfactant blend is then extruded. The extruder provides further opportunities to blend in ingredients other than surfactants, or even to add further surfactants. However, it is generally preferred that all of the anionic surfactant, or other surfactant supplied in admixture with water; i.e. as paste or as solution, is added into the drier to ensure that the water content can then be reduced and the material fed to and through the extruder is sufficiently dry. Additional materials that can be blended into the extruder are thus mainly those that are used at very low levels in a detergent composition: such as fluorescer, shading dye, enzymes, perfume, silicone antifoams, polymeric additives and preservatives. The limit on such additional materials blended in the extruder has been found to be about 10 wt%, but it is preferred for product quality to be ideal to keep it to a maximum of 5 wt%. Solid additives are generally preferred. Liquids, such as perfume may be added at levels up to 2.5 wt%, preferably up to 1 .5 wt%. Solid particulate structuring (liquid absorbing) materials or builders, such as zeolite, carbonate, silicate are preferably not added to the blend being extruded. These materials are not needed due to the self structuring properties of the very dry LAS-based feed material. If any is used the total amount should be less than 5 wt%, preferably less than 4 wt%, most preferably less than 3 wt%. At such levels no significant structuring occurs and the inorganic particulate material is added for a different purpose, for instance as a flow aid to improve the feed of particles to the extruder.

The output from the extruder is shaped by the die plate used. The extruded material has a tendency to swell up in the centre relative to the periphery. We have found that if a cylindrical extrudate is regularly sliced as it exits the extruder the resulting shapes are short cylinders with two convex ends. These particles are herein described as oblate spheroids, or lentils. This shape is pleasing visually.

Coating

The sliced extruded particles are then coated. Coating allows the particles to be coloured easily. Coating makes the particles more suitable for use in detergent compositions that may be exposed to high humidity for long periods.

The extruded particles can be considered as oblate spheroids with a major radius "a" and minor radius "b". Hence, the surface area(S) to volume (V) ratio can be calculated as:

When <≡ is the eccentricity of the particle.

Although the skilled person might assume that any known coating may be used, for instance organic, including polymer, it has been found to be particularly advantageous to use an inorganic coating deposited by crystallisation from an aqueous solution as this appears to give positive dissolution benefits and the coating gives a good colour to the detergent particle, even at lower coating levels. An aqueous spray-on of coating solution in a fluidised bed may also generate a further slight rounding of the detergent particles during the fluidisation process.

Suitable inorganic coating solutions include sodium carbonate, possibly in admixture with sodium sulphate, and sodium chloride. Food dyes, shading dyes, fluorescer and other optical modifiers can be added to the coating by dissolving them in the spray-on solution or dispersion. Use of a builder salt such as sodium carbonate is particularly advantageous because it allows the detergent particle to have an even better performance by buffering the system in use at an ideal pH for maximum detergency of the anionic surfactant system. It also increases ionic strength, which is known to improve cleaning in hard water, and it is compatible with other detergent ingredients that may be admixed with the coated extruded detergent particles. If a fluid bed is used to apply the coating solution, the skilled worker will know how to adjust the spray conditions in terms of Stokes number and possibly Akkermans number (FNm) so that the particles are coated and not significantly agglomerated. Suitable teaching to assist in this may be found in EP1 187903, EP993505 and Powder technology 65 (1991 ) 257-272 (Ennis).

It will be appreciated by those skilled in the art that multiple layered coatings, of the same or different coating materials, could be applied, but a single coating layer is preferred, for simplicity of operation, and to maximise the thickness of the coating. The amount of coating should lie in the range 3 to 50 wt% of the particle, preferably 20 to 40 wt% for the best results in terms of anti-caking properties of the detergent particles.

The Extruded Particulate Detergent Composition

The coated particles dissolve easily in water and leave very low or no residues on dissolution, due to the absence of insoluble structurant materials such as zeolite. The coated particles have an exceptional visual appearance, due to the smoothness of the coating coupled with the smoothness of the underlying particles, which is also believed to be a result of the lack of particulate structuring material in the extruded particles. Compositions with up to 100 wt% of the particles are possible when basic additives are incorporated into the extruded particles, or into their coating. The composition may also comprise, for example, an antifoam granule.

SHAPE AND SIZE

The coated detergent particle is preferably curved. The coated detergent particle is most preferably lenticular (shaped like a whole dried lentil), an oblate ellipsoid, where z and y are the equatorial diameters and x is the polar diameter; preferably y = z. The size is such that y and z are at least 3 mm, preferably at least 4 mm, most preferably at least 5 mm and x lies in the range 0.2 to 2 mm, preferably 1 to 2 mm.

The coated laundry detergent particle may be shaped as a disc. CORE COMPOSITION

The core is primarily surfactant. It may also include detergency additives, such as perfume, shading dye, enzymes, cleaning polymers and soil release polymers. SURFACTANT

The coated laundry detergent particle comprises between 50 to 90 wt% of a surfactant, most preferably 70 to 90 wt %. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing

Confectioners Company or in "Tenside Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 . Preferably the surfactants used are saturated.

1 ) Anionic Surfactants

Suitable anionic detergent compounds that may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Most preferred anionic surfactants are sodium lauryl ether sulphate (SLES), particularly preferred with 1 to 3 ethoxy groups, sodium C10 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. Also applicable are surfactants such as those described in

EP-A-328 177 (Unilever), which show resistance to salting out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides. The chains of the surfactants may be branched or linear.

Soaps may also be present. The fatty acid soap used preferably contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. The anionic contribution from soap may be from 0 to 30 wt% of the total anionic. Use of more than 10 wt% soap is not preferred. Preferably, at least 50 wt% of the anionic surfactant is selected from: sodium C1 1 to C15 alkyl benzene sulphonates; and, sodium C12 to C18 alkyl sulphates.

Preferably, the anionic surfactant is present in the coated laundry detergent particle at levels between 15 to 85 wt%, more preferably 50 to 80wt%.

2) Non-Ionic Surfactants

Suitable non-ionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Preferred nonionic detergent compounds are C6 to C22 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C8 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO. Preferably, the non-ionic is 10 to 50 EO, more preferably 20 to 35 EO. Alkyl ethoxylates are particularly preferred. Preferably the non-ionic surfactant is present in the coated laundry detergent particle at levels between 5 to 75 wt%, more preferably 10 to 40 wt%.

Cationic surfactant may be present as minor ingredients at levels preferably between 0 to 5 wt%.

Preferably all the surfactants are mixed together before being dried. Conventional mixing equipment may be used. The surfactant core of the laundry detergent particle may be formed by roller compaction and subsequently coated with an inorganic salt. Calcium Tolerant Surfactant System

In another aspect the core is calcium tolerant and this is a preferred aspect because this reduces the need for a builder.

Surfactant blends that do not require builders to be present for effective

detergency in hard water are preferred. Such blends are called calcium tolerant surfactant blends if they pass the test set out hereinafter. However, the invention may also be of use for washing with soft water, either naturally occurring or made using a water softener. In this case, calcium tolerance is no longer important and blends other than calcium tolerant ones may be used.

Calcium-tolerance of the surfactant blend is tested as follows: The surfactant blend in question is prepared at a concentration of 0.7 g surfactant solids per litre of water containing sufficient calcium ions to give a French hardness of 40 (4 x 10-3 Molar Ca2+). Other hardness ion free electrolytes such as sodium chloride, sodium sulphate, and sodium hydroxide are added to the solution to adjust the ionic strength to 0.05M and the pH to 10. The adsorption of light of wavelength 540 nm through 4 mm of sample is measured 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. Samples that give an absorption value of less than 0.08 are deemed to be calcium tolerant. Examples of surfactant blends that satisfy the above test for calcium tolerance include those having a major part of LAS surfactant (which is not of itself calcium tolerant) blended with one or more other surfactants (co-surfactants) that are calcium tolerant to give a blend that is sufficiently calcium tolerant to be usable with little or no builder and to pass the given test. Suitable calcium tolerant co- surfactants include SLES 1 -7EO, and alkyl ethoxylate non-ionic surfactants, particularly those with melting points less than 40°C.

A LAS/SLES surfactant blend has a superior foam profile to a LAS Nonionic surfactant blend and is therefore preferred for hand washing formulations requiring high levels of foam. SLES may be used at levels of up to 30%. A preferred calcium tolerant coated laundry detergent particle comprises 15 to 100 wt% anionic surfactant of which 20 to 30 wt % is sodium lauryl ether sulphate. A LAS/NI surfactant blend provides a harder particle and its lower foam profile makes it more suited for automatic washing machine use.

THE COATING The coating may comprise a water soluble inorganic salt. Other water compatible ingredients may be included in the coating. For example fluorescer, SCMC, shading dye, silicate, pigments and dyes.

Water Soluble Inorganic Salts

The water soluble inorganic salts are preferably selected from sodium carbonate, sodium chloride, sodium silicate and sodium sulphate, or mixtures thereof, most preferably 70 to 100 wt % sodium carbonate. The water soluble inorganic salt is present as a coating on the particle. The water soluble inorganic salt is preferably present at a level that reduces the stickiness of the laundry detergent particle to a point where the particles are free flowing.

It will be appreciated by those skilled in the art that multiple layered coatings, of the same or different coating materials, could be applied, but a single coating layer is preferred, for simplicity of operation, and to maximise the thickness of the coating. The amount of coating should lay in the range 15 to 45 wt % of the particle, preferably 20 to 40 wt %, even more preferably 25 to 35 wt % for the best results in terms of anti-caking properties of the detergent particles and control of the flow from the package.

The coating is applied to the surface of the surfactant core, by crystallisation from an aqueous solution of the water soluble inorganic salt. The aqueous solution preferably contains greater than 50g/L, more preferably 200 g/L of the salt. An aqueous spray-on of the coating solution in a fluidised bed has been found to give good results and may also generate a slight rounding of the detergent particles during the fluidisation process. Drying and/or cooling may be needed to finish the process.

By coating the large detergent particles of the current invention the thickness of coating obtainable by use of a coating level of say 5 wt% is much greater than would be achieved on typically sized detergent granules (0.5-2 mm diameter sphere).

For optimum dissolution properties, this surface area to volume ratio must be greater than 3 mm^"1. However, the coating thickness is inversely proportional to this coefficient and hence for the coating the ratio "Surface area of coated particle" divided by "Volume of coated particle" should be less than 15 mm^"1.

The Coated Detergent Particle

Preferably, the coated detergent particle comprises from 70 to 100 wt %, more preferably 85 to 90 wt %, of a detergent composition in a package.

Preferably, the coated detergent particles are substantially the same shape and size by this is meant that at least 90 to 100 % of the coated laundry detergent particles in the in the x, y and z dimensions are within a 20%, preferably 10%, variable from the largest to the smallest coated laundry detergent particle in the corresponding dimension. Water Content

The coated particles preferably comprise from 0 to 15 wt % water, more preferably 0 to 10 wt %, most preferably from 1 to 5 wt % water, at 293K and 50% relative humidity. This facilitates the storage stability of the particle and its mechanical properties.

Other Ingredients

The ingredients described below may be present in the coating or the core.

Dye

Dye may advantageously be added to the coating; it may also or alternatively be added to the core. In that case preferably the dye is dissolved in the surfactant before the core is formed.

Dyes are described in Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6. Dyes are selected from anionic and non-ionic dyes Anionic dyes are negatively charged in an aqueous medium at pH 7. Examples of anionic dyes are found in the classes of acid and direct dyes in the Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). Anionic dyes preferably contain at least one sulphonate or carboxylate groups. Non-ionic dyes are uncharged in an aqueous medium at pH 7, examples are found in the class of disperse dyes in the Color Index.

The dyes may be alkoxylated. Alkoxylated dyes are preferably of the following generic form: Dye-NR1 R2. The NR1 R2 group is attached to an aromatic ring of the dye. R1 and R2 are independently selected from polyoxyalkylene chains having 2 or more repeating units and preferably having 2 to 20 repeating units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

A preferred polyoxyalkylene chain is [(CH2CR3HO)x(CH2CR4HO)yR5) in which x+y < 5 wherein y > 1 and z = 0 to 5, R3 is selected from: H; CH3;

CH20(CH2CH20)zH and mixtures thereof; R4 is selected from: H;

CH20(CH2CH20)zH and mixtures thereof; and, R5 is selected from: H; and, CH3

A preferred alkoxylated dye for use in the invention is:

Preferably the dye is selected from acid dyes; disperse dyes and alkoxylated dyes.

Most preferably the dye is a non-ionic dye.

Preferably the dye is selected from those having: anthraquinone; mono-azo; bis- azo; xanthene; phthalocyanine; and, phenazine chromophores. More preferably the dye is selected from those having: anthraquinone and, mono-azo

chromophores.

In a preferred process, the dye is added to the coating slurry and agitated before applying to the core of the particle. Application may be by any suitable method, preferably spraying on to the core particle as detailed above.

The dye may be any colour, preferable the dye is blue, violet, green or red. Most preferably the dye is blue or violet.

Preferably the dye is selected from: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid blue 59, acid blue 98, direct violet 9, direct violet 99, direct violet 35, direct violet 51 , acid violet 50, acid yellow 3, acid red 94, acid red 51 , acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, acid violet 9, acid red 52, food black 1 , food black 2, acid red 163, acid black 1 , acid orange 24, acid yellow 23, acid yellow 40, acid yellow 1 1 , acid red 180, acid red 155, acid red 1 , acid red 33, acid red 41 , acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, sulphonated Al and Zn

phthalocyanines, solvent violet 13, disperse violet 26, disperse violet 28, solvent green 3, solvent blue 63, disperse blue 56, disperse violet 27, solvent yellow 33, disperse blue 79: 1 .

The dye is preferably a shading dye for imparting a perception of whiteness to a laundry textile.

The dye may be covalently bound to polymeric species. A combination of dyes may be used. Fluorescent Agent

The coated laundry detergent particle preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such

fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Suitable Fluorescers for use in the invention are described in chapter 7 of

Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527-30426-6.

Preferred fluorescers are selected from the classes distyrylbiphenyls,

triazinylaminostilbenes, bis(1 ,2,3-triazol-2-yl)stilbenes, bis(benzo[b]furan-2- yl)biphenyls, 1 ,3-diphenyl-2-pyrazolines and courmarins. The fluorescer is preferably sulphonated.

Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)- 2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2

hydroxyethyl) amino 1 ,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

Tinopal® DMS is the disodium salt of disodium 4,4'-bis{[(4-anilino-6-morpholino- 1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate. Tinopal® CBS is the disodium salt of disodium 4,4'-bis(2-sulfostyryl)biphenyl. Perfume

Preferably, the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and

Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components. In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).

Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. The perfume may be added into the core either as a liquid or as encapsulated perfume particles. The perfume may be mixed with a nonionic material and applied as a coating the extruded particles, for example by spraying it mixed with molten nonionic surfactant. Perfume may also be introduced into the composition by means of a separate perfume granule and then the detergent particle does not need to comprise any perfume.

It is preferred that the coated detergent particles do not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, peracid. Polymers

The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol), polyethylene imines, ethoxylated polyethylene imines, water soluble polyester polymers polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

Enzymes

One or more enzymes are preferably present in the composition.

Preferably the level of each enzyme is from 0.0001 wt% to 0.5 wt% protein. Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.

Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB

1 ,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720 and

WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). Other examples are lipase variants such as those described in WO 92/05249, WO 94/01541 , EP 407 225, EP 260 105, WO 95/35381 , WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063, WO 09/107091 and WO09/1 1 1258.

Preferred lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™

(Novozymes A/S) and Lipoclean™.

The method of the invention may be carried out in the presence of phospholipase classified as EC 3.1 .1 .4 and/or EC 3.1 .1.32. As used herein, the term

phospholipase is an enzyme that has activity towards phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or

phosphatidic acid respectively. Suitable proteases include those of animal, vegetable or microbial origin.

Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Suitable protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).

The method of the invention may be carried out in the presence of cutinase.

classified in EC 3.1 .1 .74. The cutinase used according to the invention may be of any origin. Preferably, cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.

Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060. Suitable amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™,

Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia,

Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 , 178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307. Cellulases include Celluzyme™, Carezyme™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao

Corporation).

Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Peroxidases include Guardzyme™ and Novozym™ 51004

(Novozymes A/S).

Further suitable enzymes are disclosed in WO2009/087524, WO2009/090576, WO2009/148983 and WO2008/007318.

Enzyme Stabilizers

Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.

Sequestrants may be present in the detergent particles. The invention will be further described with reference to the following non-limiting examples.

EXAMPLES In example 1 coated large detergent particles are manufactured, following the process in PCT/EP2010/055256. EXAMPLE 1 - Preparation of the coated particles

Surfactant raw materials were mixed together to give a 67 wt% active paste comprising 85 parts LAS (linear alkyl benzene sulphonate), 15 parts Nonionic Surfactant. The raw materials used were:

LAS: Unger Ufasan 65

Nonionic: BASF Lutensol AO30 The paste was pre-heated to the feed temperature and fed to the top of a wiped film evaporator to reduce the moisture content and produce a solid intimate surfactant blend, which passed the calcium tolerance test. The conditions used to produce this LAS/NI blend are given in Table 1 .

Table 1

^*analysed by Karl Fischer method On exit from the base of the wiped film evaporator, the dried surfactant blend dropped onto a chill roll, where it was cooled to less than 30°C.

After leaving the chill roll, the cooled dried surfactant blend particles were milled using a hammer mill, 2% Alusil® was also added to the hammer mill as a mill aid. The resulting milled material is hygroscopic and so it was stored in sealed containers.

The cooled dried milled composition was fed to a twin-screw co-rotating extruder fitted with a shaped orifice plate and cutter blade. A number of other components were also dosed into the extruder as shown in Table 2.

Table 2

The average particle diameter and thickness of samples of the extruded particles were found to be 4.46 mm and 1.13 mm respectively. The standard deviation was acceptably low. The particles were then coated using a Strea 1 fluid bed. The coating was added as an aqueous solution and coating completed under conditions given in Table 3. Coating wt% is based on weight of the coated particle.

Table 3

Coated particles composition is given in Table 4.

Table 4

The coated extruded particles have an excellent appearance due to their high surface smoothness. Without wishing to be bound by theory it is thought that this is because the uncoated particles are larger and more flattened than usual detergent particles and that their core has a much lower solids content than usual (indeed it is free of solid structuring materials, unlike prior art coated extruded particles).

Example 2

We measured the ratio of Tapped BD to Poured BD for the coated particles from example 1 (oblate spheroids) and two conventional laundry detergent powders. The results are given in table 5. Poured BD - The bulk density of the whole detergent composition in the

uncompacted (untapped) aerated form, determined by measuring the increase in weight due to pouring the composition to fill a 1 litre container. In fact the container is overfilled and then excess powder removed by moving a straight edge over the brim to leave the contents level to the maximum height of the container.

Tapped BD - The BD container was fitted with a removable collar to extend the height of the container. This extended container was then filled via the poured BD technique. The extended container was then placed on a Retsch Sieve Shaker and allowed to vibrate/tap for 5 min using the 0.2mm/"g" setting on the instrument. The collar was then removed and the excess powder levelled as per the standard BD measurement, the mass of the container measured and the Tapped BD calculated in the usual way.

Table 5

^*extruded 5mm diameter and cut to 1 mm thick before spray coating with sodium carbonate solution to give a particle having a 30 wt% sodium carbonate coating which is an oblate spheroid with slightly flattened sides resulting from the extrusion.

As can be seen from table 1 the larger coated particles of the invention settle down in much the same way as the prior art powders. The small difference in the ratios of Poured BD to tapped BD is not significant.

Example 3 We measured settling volume after tapping for 1 min using the Retsch sieve shaker at a setting of 0.2 mm/"g". The results are given in table 6.

Table 6

Only the crystals flowed freely out of the measuring cylinder after this experiment. In contrast, both of the prior art powders were compacted and the cylinder needed tapping to get them to flow.

Example 4 Standard DFR (Dynamic Flow Rate) is measured in ml/sec using a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped with its longitudinal axis vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15 DEG and a lower outlet orifice of diameter 22.5 mm. A beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.

To determine the dynamic flow rate of a detergent composition sample, the outlet orifice is temporarily closed, for example, by covering with a piece of card, and detergent composition is poured into the top of the cylinder until the detergent composition level is about 100 mm above the upper sensor. The outlet is then opened and the time t (seconds) taken for the detergent composition level to fall from the upper sensor to the lower sensor is measured electronically. The DFR is the tube volume between the sensors, divided by the time measured. We mounted this equipment onto the sieve shaker set at 0.2mm/"g" for 1 min. The shaking or vibration being done after filling the cylinder and before the outlet is opened. Each sample was given one "prod" after vibration to initiate flow as the outlet was narrow and tended to block with all powders. If one prod was insufficient to start flow then zero flow rate was recorded. Results are given in table 7.

Table 7

It can be seen from table 7 that the crystals have much improved retention of their flow properties under these conditions - it remained to be determined whether this better retention of flow for the crystals was due to their greater size, their non- spherical shape, or their coating (it being assumed that the spherical powders were not coated). Example 5

The DFR of the uncoated crystals was worse than the smaller spherical coated particles under both tests (tapped and untapped). Uncoated crystals do however, flow much better than the uncoated prior art powders. It is thus feasible to use a small proportion of uncoated crystals in the composition, say up to 30% of the total particles, preferably up to 15% by number.

Surprisingly, from table 8, the coated crystals, despite their superior appearance to the uncoated crystals have a lower DFR then the uncoated ones, hence the coating is improving appearance but not the flow. However, the coated crystals do have a very consistent DFR. They seem to flow the same way reliably no matter what their history.

Various non-limiting embodiments of the invention will now be more particularly described with reference to the following figures in which: Figure 1 shows a dispenser according to one aspect of the invention, with rigid support rack and blister pack separate;

Figure 2 shows the dispenser of figure 1 in use with manual force being applied to eject a dose from the blister pack; and Figure 3 shows an exploded view of the dispenser of figure 1 being installed in a washing machine drawer.

Referring to figures 1 and 2, a dispenser 1 is shown, the dispenser 1 for dispensing a blister pack 3 of predetermined doses 5 of concentrated laundry composition according to any of the examples above, into a washing machine (not shown). The dispenser 1 comprises a rigid support frame 7 on which is mounted the blister pack 3 whereby manual force on a selected dose ejects that dose 5 from the blister pack 3. The blister pack comprises a planar sheet of plastic provided with individual reservoirs comprising "blisters" 5 which are concave protrusions configured in rows and columns. The blister pack 3 further comprises at least one backing layer (not shown) which is fastened to the solid receiving side of the blister pack. This layer is a low strength retaining layer. This low strength retaining layer stretches across the backs of the blisters 5 and retains the individually sealed within each of the blisters 5. Preferably the blister pack 3 is mounted with the low strength retaining layer facing down. The package is sufficiently rigid in material and/or construction such that a portion e.g. the base or a side wall, can be tapped to move the particles from the reservoir/s and preferably such tapping creates audible feedback to the user to guide them as to the movement of the particles. Suitable materials for the package include, but are not limited to: polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyamides (PA) and/or polyethylene terephthalate (PETE), polyvinylchloride (PVC); and polystyrene (PS). The reservoirs may formed by moulding e.g. blow moulding from a preform or by thermoforming or by injection moulding.

Figure 3 shows an exploded view of the dispenser being installed into the drawer 1 1 of an automatic washing machine (machine not shown). The drawer 1 1 is provided with a plurality of separate compartments and the dispenser is being installed into the middle compartment 1 1 , for containing main wash products to be flushed by an incoming water flow (not shown) into the machine drum. The dispenser 1 is installed in a machine drawer so manual force on a selected dose ejects this dose from the blister pack directly into the drawer compartment 13. The rigid support frame 7 comprises apertures 15 in each wall. The frame 7 also has smooth contours 17 and generally convex rather than concave surfaces configuration/patterning such that water and/or laundry composition cannot become trapped. The dispensing device is an injection moulded plastic, water insoluble and of robust construction so that removal during the washing process is not required. The dispenser may be constructed of any suitable material such as a water insoluble material such as a polyolefin e.g. polypropylene (PP),

polyethylene (PE), polyethylene terephthalate (PET). The frame has sufficient rigidity to withstand the manual force required to break the blister pack but has elasticity at higher manual forces in that the walls 7a can be flexed against the sides 13a of the drawer compartment during fitting. Once in place, manual pressure is released so as to urge the walls 7a against the sides 13a of the drawer compartment 13, thereby preventing movement of the dispensing device 1 whilst in place in the drawer 1 1 . The frame 7 comprises a wall or walls having supporting upper edges 17 which correspond to an outer perimeter of the blisters 5 so that the pack is supported further. The support frame has an upper supporting edge 19 which is inclined with respect to the base 21 , whereby the mounted blister pack 3 is also inclined. With this arrangement, the blister pack 3 may be better viewed by the user. The device is removable, however, it may contain temporary means of retaining the device in place for a single or multiple washes such as flexible walls as referred to above but also adhesive . It is of course to be understood that the invention is not intended to be restricted to the details of the above embodiment which are described by way of example only.

Claims

A packaged product comprising a package comprising a plurality of individual reservoirs, each of the reservoirs containing a predetermined dose of a concentrated particulate laundry wherein at least 70 % by number of the particles of the composition comprising a high-surfactant hard core and a coating and wherein all the particles are non spherical and at least 0.2 mm in diameter.

A packaged product according to claim 1 wherein the package is rigid in material and/or construction such that a portion e.g. the base or a side wall, can be tapped to move the particles from the reservoir/s.

A packaged product according to claim 2 wherein the tapping creates audible feedback to the user to guide them as to the movement of the particles.

A packaged product according to any preceding claim wherein the package comprises a tray of individual recesses, each recess providing an individual reservoir covered by a lid.

A packaged product according to any preceding claim wherein the packaged product comprises a planar sheet with blisters or concave protrusions and a retaining layer fastened to the planar sheet, said retaining layer being of low strength.

A packaged product according to any preceding claim wherein the or each reservoir comprises a transparent portion. A packaged product according to any preceding claim wherein the or each transparent portion comprises at least a part of the base of the reservoir, such that the composition contained within is visible when viewed looking at the base.

A dispenser for dispensing from the packaged product of any preceding claim, the dispenser comprising a rigid support frame on which is mounted said packaged product, whereby manual force on a selected reservoir ejects that dose from the reservoir.

A washing machine comprising a drawer-mounted dispenser according to any preceding claim, whereby manual force on a selected dose ejects this dose from the blister pack directly into the drawer or drawer compartment.

A packaged concentrated laundry composition comprising a dispenser of preceding claim.

A method of washing fabrics within a washing machine, with package of claims 1 -6 and/or the dispenser of claim 7, the method comprising the step of manually pressing on a dose in a reservoir to eject the dose from the reservoir.

A packaged product and/or dispenser substantially as hereinbefore described with reference to and/or as illustrated in the accompanying drawings.