WO2000027980A1

WO2000027980A1 - Speckle particles and compositions containing the speckle particles

Info

Publication number: WO2000027980A1
Application number: PCT/US1999/025259
Authority: WO
Inventors: Christopher Andrew Morrison; Steven Patterson; Judit Ester Jansen
Original assignee: The Procter & Gamble Company
Priority date: 1998-11-06
Filing date: 1999-11-03
Publication date: 2000-05-18
Also published as: GB2343456A; CA2348603A1; AU1238900A; CN1325438A; GB9824225D0; JP2002529583A; EP1124930A1; BR9915124A

Abstract

The present invention provides a cleaning composition speckle particles having a specific sparkle index and transparency index, the particle comprising solid material, preferably specific crystalline material, which is coloured by addition of a dye pigment and/or a brightener. The invention also relates to cleaning compositions comprising the speckle particles of the invention, in particular laundry and dish washing compositions.

Description

Speckle Particles and Compositions Containing the Speckle Particles

Technical Field The invention relates to improved speckle particles and compositions comprising the speckle particles, in particular cleaning compositions.

Background to the Invention

In recent years, detergent manufacturers have introduced in their products small amounts of dyed particles or speckles. It has been found that the detergent users associate products having dyed particles with improved cleaning that the consumer acceptance of product comprising coloured particles is normally higher than product not comprising such coloured particles. Furthermore, the speckles can mask de-coloration in the product and/ or allows the incorporation in the products of small amounts of ingredients which do not have the colour of the bulk of the product by masking this colour difference.

These speckles are often obtained by spraying-on an aqueous solution of a specific dye onto hygroscopic material and addition of these materials to the other ingredients, or directly onto the final detergent base particles and subsequently drying the thus dyed materials or particles. A problem associated with this method is that the hygroscopic material absorbs large amount of water which may result in caking of the product. This is particularly a problem when higher amounts of aqueous dye-solution need to be used, for example, when very diluted dye solutions are to be used, or strongly dyed particles are needed or the dye is absorbed by the material or particles which are to be dyed. Another problem associated with detergents comprising large amounts of dye per particle can be that the dye can 'bleed' in the presence of water. This may be the case when the detergent is made by spraying on large amounts of aqueous dye solutions, or when the detergent comprises large amount of hygroscopic material or of course, when the detergents are introduced to the washing or cleaning liquid. This 'bleeding' may cause colour changes of the product and the packing material. Moreover, under certain conditions, the dye or the dye particles which may deposit on the fabrics, can 'bleed' on the fabrics and cause colour changes on the washed fabric.

Also, it has now been found to be essential that the dye in the product is evenly applied at the surface of the particles and throughout the product, to avoid localised high concentrations of dye, which may amount to any of the above problems.

However, despite these problems, it may be desirable to have speckles particles present in the product to provide the required contrast in the product and/ or masking of certain ingredients in the product.

The inventors have now found improved speckle particles, namely the inventors have found that particle which have a certain light reflection resulting in a specific sparkle, and which have a certain transparency, provide a better contrast with the other ingredients of the products, or can mask the undesired colour of other ingredients of the product. In particular, they have found that speckle particles comprising crystalline material can provide the required contrasting and/ or masking. Hereby, the speckle particles are preferably coloured, although in certain applications even the uncoloured crystalline material may provide a contrast or the masking.

Thus, due to the reflection/ transparency potential of these speckles, the amount of colorant required to provide the required contrast or masking can be reduced.

Moreover, the inventors have also found that speckle particle herein which comprise crystalline material, only require limited amounts of dye, because the crystalline material is less porous and/ or hygroscopic and thus absorbs less colorant. Thus, the speckle particles of the invention can be coloured more effectively and efficiently.

Thus, an optimum colour appearance of the product can be obtained with a minimum amount of dye, when the speckle materials of the invention are used.

An additional benefit is that less colorant is introduced in the speckle particles and thus in the compositions comprising the particles. Hereby, the risk of bleeding of the colorant is reduced and the problems associated therewith.

Summary of the Invention

The invention provides a cleaning composition particle which comprises a solid material which is coloured with a colorant, the particle has a sparkle index of at least 5% and a transparency index of at least 5%. Preferably the particle has a colour saturation of at least 10, preferably at least 30, a sparkle index of at least 10% and a transparency index of at least 15%.

The invention also provides a cleaning composition speckle particle comprising a crystalline material preferably selected from the group comprising crystalline hydrated salts, crystalline acids, crystalline acid salts, crystalline surfactants, saccharides, or mixtures thereof.

The speckle particle is in particular for incorporation in solid laundry or dish washing or hard-surface cleaning compositions.

The invention also relates to a process for making the compositions and the speckle particle and the use thereof.

Detailed Description of the Invention Speckle Particles The speckle particle of the invention have a sparkle index of at least 5%, preferably at least 10% or even at least 15% or even at least 20%.

The speckle particle has a transparency index of at least 1%, preferably at least 5%, or even at least 15% or even at least 30% or even at least 60%.

The sparkle index and transparency index can be determined as follows, using a spectrophotometer capable of light transmission and reflectance measurements, such as the UltraScan XE unit from Hunter Labs Inc which is connected to a suitable personal computer, such as an IBM ThinkPad type 2640, being installed with Universal analysis software provided by Hunter Labs Inc:

25g of a speckle particle is poured into a glass cuvette with 4mm path length and 50mm length. Suitable cuvettes may be obtained via Hunter Labs Inc. The spectrophotometer is calibrated using a light trap and a white tile, according to the operating manual provided with the spectrophotometer and the sample placed in the sample holder. Light reflectance and transmission is then measured: the light reflectance measurements is taken such that it include the specular reflected component (Spec in) and also such that it exclude the specular reflected component (Spec ex). The spectrophotomer generates spectral emission plots which are viewed on the personal computer.

The sparkle index, when used herein, is then: % reflectance (spec in) - % reflectance (spec ex), where both % reflectance are measured at the peak reflectance wavelength, determined by the computer: this is seen by the maxima on the spectral reflectance emission curve. This typically will differ depending on the colour of the particles. For example, for blue particles using Monastral blue dye the peak wavelength is 460nm; for green particles with Pigmasol green dye, the peak wavelength is 500nm.

The transparency index, when used herein is then: % light transparency at peak wavelength. This is read from the personal computer after measuring transmission analysis on the spectrophotometer. Preferably the speckle particle has a colour saturation, given as a delta saturation of at least 10, preferably at least 30, or even more preferably at least 50 or even at least 100.

The delta colour saturation or saturation can be determined by any standard measurement used in the art. For example, it can be calculated by the UltraScan XE and Universal software using the standard L,a,b values which are generally used in the art, comparing the colour saturation of a coloured material after colouring, with the colour saturation of the same material prior to colouring.

The colour saturation of the sparkle particle herein is the delta colour saturation which equals the colour saturation of the coloured particle minus the colour saturation of an equivalent uncoloured particle.

The speckled particles of the invention may have any colour. When present in cleaning compositions the speckle may preferably be of another colour than the majority of the other ingredients or particles of the compositions. When used herein, 'colour' includes any shade of white and black. The words colorant, coloured and colouring are to be interpreted accordingly.

In a preferred embodiment, the speckle particle is preferably coloured with a dye, pigment or brightener, or mixtures thereof as described hereinafter.

The speckle particle of the invention has a specific light reflection and/or light transparency. Thereto, the speckle particle comprises preferably a crystalline hydrated inorganic salt, a crystalline organic acid salt, a crystalline organic salt, a crystalline surfactant, saccharide or mixtures thereof. Preferably the crystalline material of the speckle particle has preferably at least a transparancey and/ or reflection equal to coarse trisodium citrate dihydrate as available from ADM.

Highly preferred crystalline organic salts include carboxylate salts. Also preferred are crystalline polymeric polycarboxylic acids and salts thereof, preferably poly acrylic and/ or maleic acid polymers and salts thereof.

Particular preferred is that the crystalline material comprises trisodium citrate dihydrate, most preferably coloured with a dye.

Preferred hydrated crystalline materials herein are hydrated inorganic salts including hydrated sulphate salt; hydrated carbonate salt; hydrated phosphate salt; hydrated magnesium salt; hydrated carboxylic acids and/ or salts thereof. Highly preferred are sodium sulphate deca hydrate or hepta hydrate; sodium carbonate monohydrate, hepta hydrate or decahydrate; sodium tripolyphosphate, ortho phosphate, meta phosphate and/ or pyrophosphate with the applicable hydration numbers, in particular mono, di, tri hexa or deca hydrate; magnesium sulphate mono or hepta hydrate, sodium citrate di hydrate or penta hydrate; glucose, maltose, galactose or fructose or mixtures thereof, in particular sugar.

Also useful can be other ingredients commonly employed in detergent compositions which are crystalline materials, such as crystalline silicate, including crystalline layered silicate.

Preferably, the speckle particle comprises at least 20% by weight of the particle of the crystalline hydrated material, preferably at least 50% or even at least 75%, whereby it may be preferred that the particle is substantially free of amorphous material. The speckle particle may comprise other ingredients. In one embodiment it is preferred that the speckle particle comprises a binder, to bind the crystalline hydrated material and/ or the colorant.

Preferred hereby may be that the speckle particle is made by agglomerating the binder and the crystalline hydrated material and/ or the colorant.

Any binder material can be used herein. Preferred binders include water, or mixtures of water with other ingredients, such as surfactant pastes. Also useful are liquid or viscous surfactants, polyalkylene glycols, preferably polyethylene glycol, wax and oils.

In one preferred embodiment, the speckle particle a weight average particle size of 400 microns to 2000 microns, preferably from 500 microns to 1400 microns or even from 600 microns to 1180 microns or even 710 microns to 1000 microns.

When the weight average particle size is from 500 to 1400, it may be preferred hereby that at least 70% or even at least 80% or even at least 90% or even substantially all of the particles has a particle size of from 600 microns to 1180 microns. When the weight average particle size is from 600 to 1180, it may be preferred hereby that at least 70% or even at least 80% or even at least 90% or even substantially all of the particles has a particle size of from 710 microns to 1000 microns.

Namely, it has been found that when the speckle particles have an average particle size within these ranges, a smaller amount of speckle particles can be used to obtain the required result. Also, it been found that the use of speckle particles of a specific particle size ensures a more efficient and controlled dyeing of the particles, which enables the effective use of small amounts of dye per particle whilst obtaining a homogeneously dyed particle.

The speckle particles of this particle size may preferably be obtained by binding smaller particles with a binder, for example by agglomeration, as described herein. They may also be obtained from larger particle size material, for example by grinding this material. Also, the speckle particle of this particle size may alternatively or additionally be obtained by sieving the particles and selecting the required particle size material.

Other methods for controlling the particle size of crystalline material are known to the skilled person and may also be used to obtain the particles of the required size.

The speckle particle may be coloured by any method known in the art. Preferably colorant is mixed with the crystalline material, preferably in the presence of a binder. Preferably, the speckle particle herein may be coloured with a colorant, preferably a dye and/ or a brightener by spraying the colorant into a mixing-container or mix drum, containing the speckle particles and optionally drying the coloured speckle particles, preferably in a fiuidised-bed.

Dye

The speckle particles of the invention are preferably dyed particles. The dye used for dyeing the particles as used herein can be a dye stuff or an aqueous solution of a dye stuff or an non-aqueous solution of or mixture with a dye stuff, for example using a carrier material such as a nonionic surfactant or other organic binder material. The use of an non- aqueous solution may have as an advantage herein that no subsequent drying step is needed when the solution is applied to the speckle particles.

It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight, as described above. Optionally, the dye also comprising other ingredients such as organic binder materials.

The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E104 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), E131 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), El 40 - natural green 3 (chlorophyll and chlorphyllins), El 41 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BN paste (trade name) and/ or Pigmasol Green (trade name).

The speckle particle preferably comprise such a^" dyestuff or even at low levels, preferably only up to 2% or more preferably up to 1% or even up to 0.7% and it may be preferred that the dye is present a t a level of below 0.5% or even 0.2% or even 0.1 % by weight of the speckle particle.

Brightener

The speckle particle herein may be coloured with a brightener, preferably certain types of hydrophilic optical brighteners.

The speckle particle preferably comprise such a brightener at levels of up to 20% or more preferably up to 10% or even up to 5% by weight of the speckle particle.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R\ is selected from anilino, Ν-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R_2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, Rj is anilino, R > is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, Ri is anilino, R-2 is N-2-hydroxyethyl-N-2-methylamino and

M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R^ is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.

Pigment

The speckle particle may also comprise as a colorant a pigment. Any pigement suitable for cleaning compositions may be used herein.

Compositions

The speckle particle is preferably present in cleaning compositions, preferably granular cleaning compositions. The precise level of speckle particles present in the composition depends in particular on the colour of the degree of light reflection or transparency of the speckle particle, the colour of the speckle particle and the other ingredients of the composition, the particle size of the speckled particles and the other ingredients of the composition, and the application of the composition. The compositions may comprise the speckle particles at a level any level, but preferably from 0.05%) to 50%, more preferably from 0.1 % to 30%, more preferably from 0.3% to 10%) by weight of the composition.

The cleaning compositions of the invention are preferably solid laundry, dishwashing or hard-surface cleaning compositions, preferably in the form of granules, extrudates, flakes or tablets.

The cleaning composition may additionalcomprise any conventional ingredient, not being the coloured speckle particles herein, commonly employed in cleaning compositions, preferred ingredeints described herein after.

The speckle particle of the invention is particularly useful in compositions comprising ingredients which do not have the desired product colour, or in compositions comprising hygroscopic ingredients which may absorb moisture and may cause any dye present, to bleed.

The compositions herein thus preferably comprising ingredients such as particles comprising surfactant, enzymes, bleach activators, cellulose derivative or mixtures thereof, which tend to have an undesired colour.

The surfactant containing particles are preferably agglomerates with anionic and/ or nonionic surfactants, preferably with LAS and/ or ethoxylated alcohol surfactants.

Also preferred are particles containing peroxy acid bleach precursors, such as TAED, NAC-OBS, and other OBS- variants, or mixtures thereof.

When a composition herein, containing the speckle particles contains other ingredients in particulate form, it may be preferred that these other particles or part thereof, also have the hereinafter specified weight average particle size, so that a homogeneously distribution of the dye throughout the product can be obtained by reduction of segregation of the particles and thus a reduction of the formation of localised high concentrations of dye. This will also amount to a reduction of the chance of colour changes in the products, packaging material and moreover of the fabrics in the washing or cleaning process.

Then, in one embodiment, it may be preferred that composition preferably comprises granules whereof at least 60%, more preferably at least 80% of have an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns or even 750 to 1000 microns. It may be preferred that the compositions comprises less than 20% or even less than 10% or 5% by weight of particulate components of a particle size of less than 300 microns, or even 450 microns or even 600 microns, and/ or less than 20% or even 10% or even 5% by weight of particulate components of a particle size of more than 1600 microns, or even more than 1400 microns or even 1200 microns.

The composition can be made by any method known in the art, including by agglomeration and/ or spray-drying, whereby certain ingredients may be admixed or sprayed-on as described herein. It may be preferred that the composition is made by mixing all or part of the granules, including those made by agglomeration or spray-drying and even the speckle particle of the invention, and subsequently adding a binder and agglomerating the mixture and binder to form agglomerated detergent granules, which may be of the required particle size or which may be sieved to obtain particles of the required size.

The compositions are preferably solid detergents which preferably have a density of at least 350g/litre, more preferably at least 500 g/ litre or even 580 g/ litre.

It may be preferred that the detergent composition herein comprise one or more anionic surfactants and an aluminosilicate builder, whereby it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant are in an intimate mixture, i.e. less than 50% or even less than 30% of the total amount of the anionic surfactant and less than 50% or even less than 30% of the total amount of alumnisilicate; it may even be preferred that substantially no anionic surfactant and aluminosilicate builder are in an intimate mixture. Thus, it may be preferred that the composition comprises at least two separate particles which comprise either anionic surfactant or aluminosilicate. 'Intimate mixture' means for the purpose of the invention that the two or more ingredients the component are substantially homogeneously divided in the component or particle. Namely, it has been found that the solubility and/ or dispensing of the composition is thereby improved.

It may also be preferred that the composition only comprises low levels of aluminosilicate builder, for example less than 10% or even less than 5% by weight of the composition, whereby it is preferred that the composition comprises highly soluble builders, for example sodium citrate or citric acid, carbonate, and/ or crystalline layered silicate.

It may also be preferred that the composition comprises as builder system or as part of the builder system, an agglomerate comprising from 0.5% to 80% by weight a crystalline layered silicate, from 10% to 70% by weight of a surfactant, preferably an anionic surfactant and preferably less than 10% by weight of the agglomerate of free moisture, more preferably 30%o to 60% by weight a crystalline layered silicate and 20% to 50% by weight of an anionic surfactant.

Effervescence Component

It may be highly preferred that the detergent composition comprises an effervescence component, preferably comprising an acid source and an alkali source capable of reacting together to form a gas upon contact with water, in particular a carbon dioxide gas, formed by reaction of an organic carboxylic acid and a carbonate source. For the puφose of the invention, the ingredients of the effervescence components may be present in an intimate mixture with one another, preferably in the form of a granule or the may be present in separate particles. It may be preferred that the effervescence component is a particulate component having an average particle size, by weight, of from 700 microns to 1400 microns, preferably from 750 microns to 1100 microns, preferably comprising an acid source and an alkali source.

It may be preferred that the effervescence component is substantially free of water, preferably such that no water has been intimately mixed with the effervescence component or part thereof, or that no water is present other than the moisture of the raw materials themselves. Typically, the level of water in intimate mixture with the effervescence component is below 5% by weight of the total granule, preferably below 3% and more preferably below 1.5%, preferably obtainable by dry-powder compaction or pressure agglomeration.

These preferred dry effervescent particles result in a very fast carbon dioxide production and therefore in accelerated dispersibility and dissolution rate of the granular composition. The granular compositions of the present invention, as described herein, comprising the dry effervescent granules allow dispensing and dissolution in water of the granular compositions in a shorter period of time and at lower total level of effervescent particles/materials and ensure a faster and more effective delivery of detergent ingredients to the wash.

Suitable acids to be used herein include solid organic, mineral or inorganic acids, salts or derivatives thereof or a mixture thereof. It may be preferred that the acids are mono-, bi- or tri-protonic acids. Such acids include mono- or polycarboxylic acids preferably citric acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acidic forms, and it may be preferred that their anhydrous forms are used, or mixtures thereof. Derivatives also include ester of the acids.

The effervescence component or source preferably comprises a carbonate source, including carbonate, bicarbonate and percarbonate salts, in particular bicarbonate and/or carbonate. Suitable carbonates to be used herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium carbonate are 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-weigh effective, i.e., at parity weigh bicarbonate is a larger CO2 "reservoir" than carbonate. However, the choice of carbonate or bicarbonate or mixtures thereof in the dry effervescent granules may be made depending on the pH desired in the aqueous medium wherein the dry effervescent granules are dissolved. For example where a relative 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.

Such an effervescence granule may also comprise a binder, including surfactants, such as anionic and nonionic surfactants..

The effervescence component is preferably present in the composition according to the present invention at a level of from 0.5% to 60%) by weight, preferably from 2% to 50%, more preferably from 5% to 45 % and preferably such that the acid component is present at a level of from 0.3% to 40%, more preferably from 1.0% to 35%, or even 2% to 25% or even to 15% by weight of the composition.

Surfactant The compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring 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 cationic surfactants is given in U.S.P. 4,259,217 issued to Muφhy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic Surfactant

The compositions in accord with the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive puφoses 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 triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, 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 Surfactant

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-(Cι-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary lO" i 8 ^alkyl sulfates, more preferably the C1 1-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C\ 0-C18 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_j \-

C\$, ^most preferably C\ \-C\ 5 alkyl sulfate which has been ethoxylated with from 0.5 to

7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant

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

Anionic Carboxylate Surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x

CH2C00^"M⁺ wherein R is a Cg to Ci g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRτ -CHR2-O)-R3 wherein R is a Cg to Ci g alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON

(R!) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R^ is a C\ -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

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

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONR^Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C\ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula: R^CON(R^)2 wherein R^ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, Ci -C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4O)_xH, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

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 polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide 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.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(OR4)_XNO(R-*)2 wherein R^ 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 o-C^g alkyl dimethylamine oxide, and C^o-18 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants can also be incoφorated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N⁺R2C00^" wherein R is a C6-Ci g hydrocarbyl group, each R* is typically C1-C3 alkyl, and R^ is a C1-C5 hydrocarbyl group. Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the Cιo-18 acylamidopropane (or ethane) dimethyl (or di ethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C -

C , preferably Cg-Cjo 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. Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic mono-alkoxylated amine surfactants

Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:

wherein Rl is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R^ and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R^ and R-* are methyl groups; R^ is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR^ group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR^ groups are — CH₂CH₂OH, — CH₂CH₂CH₂OH, — CH₂CH(CH₃)OH and —

CH(CH3)CH₂OH, with — CH2CH2OH being particularly preferred. Preferred R¹ groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula

wherein Rl is CJ O- I S hydrocarbyl and mixtures thereof, especially C\ 0-C14 alkyl, preferably CI Q and Ci 2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1 % to 20%, more preferably from

0.2%) to 1%, most preferably from 0.3% to 3.0%ι by weight of the composition.

Cationic Bis-alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the general formula It:

wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C\ -C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula

wherein Rl is Ci Q-CJS hydrocarbyl and mixtures thereof, preferably Ci Q, Cj2_. C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound Rl is derived from (coconut) C12- 14 alkyl fraction fatty acids, R^ is methyl and ApR- and A'qR^ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:

wherein R^ is C\ 0-C1 hydrocarbyl, preferably C\ 0-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R^ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and

[CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Perhydrate Bleaches

An preferred additional components of the compositions is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. The perhydrate bleach may be coated, for example with sulphate salts or carbonate salts or silicate or mixtures thereof.

Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.

Bleach Activator The composition preferably comprises 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 hydrophilic peroxy acid bleach precursor, as defined herein.

The bleach activator may also comprise a preformed peroxy acid bleach.

The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.

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

O

I!

X-C-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 puφose 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 hydrophilic peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms.

Peroxyacid bleach precursor compounds are preferably incoφorated at a level of from 0.5%) to 20% by weight, more preferably from 1% to 15%> by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

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, 1147871, 2143231 and EP-A-0170386.

Leaving Groups

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. Preferred L groups are selected from the group consisting of:

O

-N— C— R N A O N II

— N-C-CH— R⁴ I

R³ R³ Y

I Y

R³ Y I I -O-CH=C-CH=CH₂ -O-CH=C-CH=CH₂

R³ O Y

-0-C i =CHR⁴ , and — N— S ιι— C i H— R⁴

R³ O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to

14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.

The preferred solubilizing groups are -SO-. M , -CO ^~M , -SO M , -N (R )₄X^" and

3 - + - + 3 O<~N(R )., and most preferably -SO,, M and -CO₂ M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-

,N,N1N* 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 hydrophilic peroxy acid bleach precursor.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide Substituted Plkyl Peroxyacid Precursors Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

R >1¹

wherein Rl 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 R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from about 6 to 12 carbon atoms. R^ preferably contains from about 4 to 8 carbon atoms. Rl 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. Rl and

R5 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

Rl 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-octanamido-caproyl)oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6- nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A- 0170386.

Perbenzoic Acid Precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrohdone, dibenzoyl taurine and benzoyl pyroglutamic acid. Preformed Organic Peroxyacid

The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15%> by weight, more preferably from 1% to 10%> by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R N — R² OOH R N R OOH

O R >5° O or R 5° O O

wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.

Heavy metal ion sequestrant

The compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant or chelant or chelating agent. By heavy metal ion sequestrant it is meant herein components 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.

Heavy metal ion sequestrants are generally present at a level 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 heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic 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 iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic 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 iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide-

N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

In particular the chelating agents comprising a amino or amine group can be bleach- sensitive and are suitable in the compositions of the invention.

Enzyme

Another highly preferred ingredient useful in the 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 incoφorated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incoφorated into the compositions in accordance with the invention at a level of from 0.0001%> to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.

Amylase enzyme may be incoφorated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%ι to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Optical Brightener

The compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.

Photo-bleaching agent

Photo-bleaching agents are preferred ingredients of the compositions herein. Preferred photo-bleaching agent herein comprise a compounds having a poφhin or poφhyrin structure.

Poφhin and poφhyrin, in the literature, are used as synonyms, but conventionally poφhin stands for the simplest poφhyrin without any substituents; wherein poφhyrin is a subclass of poφhin. The references to poφhin in this application will include poφhyrin.

The poφhin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al , most preferably Zn. It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

The photo-bleaching compound or component can have solubilizing groups as substituents. Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PNNP, PNI or co-polymers thereof or mixtures thereof.

Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above.

Metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and/or Figure 2, wherein the atom positions of the phthalocyanine structure are numbered conventionally.

The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atom positions.

Water-Soluble Builder Compound

The compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1%> to 80%) by weight, preferably from 10%> to 60%> by weight, most preferably from 15% to 40%) by weight of the composition.

The detergent compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymefhyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1 % to 15%, more preferably from 0.5% to 8%> by weight of the composition.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

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.

Partially Soluble or Insoluble Builder Compound

The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50%> by weight, most preferably from 8% to 40% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates. As mentioned above, it may be preferred in one mbodiment of the inevntion, that only small amounts of alumino silicate builder are present. Suitable aluminosilicate zeolites have the unit cell formula Na_z[(AlO2)_z(SiO2)y]- XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18%> to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof Zeolite A has the formula:

Na 12 [AlO₂) 12 (SiO₂)i2]- *H₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(AlO₂)86(SiO2)i06]- 276 H₂O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. The zeolite MAP can be present at a level of from 1% to 80%>, more preferably from 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070 A.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of the compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. 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 incoφorated in the detergent compositions of the invention at a level of from 0.01%ι to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Teφolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incoφoration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.

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:

wherein X is a nonionic group selected from the group consisting of H, Ci -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.

Suds Suppressing System

The detergent compositions of the invention, 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.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

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.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci g-C4Q ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises:

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%>, preferably 75% to 95%> by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incoφorated at a level of from

5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10%> by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544; (c) an inert carrier fluid compound, most preferably comprising a C \ -C \ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.

Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5%) by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.

Polymeric Soil Release Agent Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%>, preferably from 0.2%> to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize 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 anchor for the hydrophilic 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 transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end- capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric 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 Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al. Other classes include: (ID) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20%o by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides can be present.

Form of the Compositions

The composition of the invention can be made via a variety of methods, including dry- mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.

The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.

The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

Example I The following speckle particle is a preferred speckle particle of the invention. coarse sodium citrate dihydrate ex ADM are mixed with Monastral blue BV paste solution in a mixing drum, by spraying the dye paste solution into the drum containing the sodium citrate particles. The coloured particles are subsequently dried, obtaining speckle particles comprising lOOOppm of dye.

Measurements:

Sodium citrate dihydrate crystals with Monastral blue dye was found to have, as measured with the method set out herein: sparkle index = 10.4% transparency value = 22% delta colour saturation = 120

Sodium citrate dihydrate crystals with Pigmasol green dye was found to have, as measured with the method set out herein: sparkle index = 10.1% transparency value = 22% delta colour saturation = 63

Abbreviations used in the Granular Detergent Composition Examples In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear CI 1-13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz : Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14

QAS 1 : R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11 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(AlO2SiO2)12.27H2O 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 δ- Na2Si2O5 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous sodium silicate (SiO2:Na2O = 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 molecular weight about 70,000

MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight 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 : Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2 O, the particles having a weight average particle size of 950 microns, 85% particles having a particle size of from 850 microns to 950 microns

PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202, the particles having a weight average particle size of 800 microns, 85% particles having a particle size of from 750 microns to 950 microns

Percarbonate Particle containing sodium percarbonate of nominal formula

2Na2CO3.3H2O2, the particles having a weight average particle size of 850 microns, 95% particles having a particle size of from

750 microns to 950 microns NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns

NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns

TAED I : Particle containing tetraacetylethylenediamine, the particles having a weight average particle size of from 700 microns to 1000 microns

TAED II : Tetraacetylethylenediamine of a particle size from 150 microns to

600 microns

DTPA : Diethylene triamine pentaacetic acid

DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by

Monsanto under the Tradename Dequest 2060

Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer

Photoactivated : 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-moφholino-l.3.5-triazin-2- yl)amino) stilbene-2 :2'-disulfonate

EDDS Ethylenediamine-N-N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

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 molecular weight of

60,000

PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000

QEA bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H5O)-(C2H4 O))n, wherein n = from 20 to 30

SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen

Silicone 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 Speckle as made in example 1

In the following examples all levels are quoted as % by weight of the composition:

TABLE I

The following compositions are in accordance with the invention.

TABLE II

The following compositions are in accordance with the invention.

Claims

WHAT IS CLAIMED IS :

1. A cleaning composition speckle particle which comprises a solid material which is coloured with a colorant, the particle has a sparkle index of at least 5% and a transparency index of at least 5%.

2. A cleaning composition speckle-particle according to claim 1, having a colour saturation of at least 10, preferably at least 30, a sparkle index of at least 15% and a transparency index of at least 15%.

3. A cleaning composition speckle-particle according to claim 1 or 2 comprising a coloured crystalline material, preferably selected from the group comprising crystalline hydrated salts, crystalline acids, crystalline acid salts, crystalline surfactants, saccharides, or mixtures thereof.

4. A speckle particle according to any preceding claim which is coloured with a dye, pigment and/ or brightener.

5. A speckle particle according to claim 1, 2, 3 or 4 wherein the crystalline material comprises: a hydrated sulphate salt; hydrated carbonate salt; a hydrated phosphate salt; a hydrated magnesium salt; a crystalline carboxylic acid or salt thereof; crystalline silicate; a crystalline polymeric polycarboxylic acid or salts thereof; a crystalline surfactant; a saccheride, preferably sugar; or mixtures thereof.

6. A speckle particle according to claim 1, 2, 3 or 4 wherein the crystalline material comprises sodium citrate dihydrate.

7. A speckle particle according to any preceding claim comprising a binder.

8. A speckle particle according to any preceding claim having a weight average particle size of 300 microns to 2000 microns, preferably from 500 microns to 1400 microns, more preferably from 600 microns to 1180 microns.

9. A process for making coloured cleaning composition speckle particles by spraying a colorant into a mixing container, containing the solid material, preferably being a crystalline material, and mixing the colorant and the speckle particle, and optionally drying the coloured speckle particles.

10. A process according to claim 9 wherein the speckle particle comprises crystalline material and a binder, whereby the speckle particle preferably is in the form of an agglomerate.

11. A cleaning composition comprising the speckle particle according to any preceding claim at a level of from 0.05% to 30% by weight.

12. A composition according to claim 11 comprising a coloured speckle particle and other ingredients, the composition obtainable by a process comprising the steps of a) colouring the solid material with a colorant to obtain coloured speckle particles, preferably by spraying a colorant into a mix drum containing the speckle particles; b) optionally drying the coloured speckle particles obtained in step b); c) mixing of the coloured speckle particles of step a) or b) with the other ingredients of the cleaning composition.

13. A composition according to claim 11 or 12, being a solid laundry or dishwashing detergent composition, preferably a granular composition, extruded composition or a tablet composition, preferably comprising a particle comprising surfactant, an enzyme, a bleach activator, a cellulose derivative or mixtures thereof.

14. Use in a cleaning composition of a speckle as in any of claims 1 to 8, to provide a contrasting appearance with the other ingredients of the composition.

15. Use in a cleaning composition of a speckle particle as in any of claims 1 to 8, to mask undesired colours of other detergent ingredients.