WO2003066793A1

WO2003066793A1 - Granule and composition containing same

Info

Publication number: WO2003066793A1
Application number: PCT/EP2003/000695
Authority: WO
Inventors: Stephen Norman Batchelor; Andrew Paul Chapple; Peter Leslie Gratton
Original assignee: Hindustan Lever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2002-02-06
Filing date: 2003-01-23
Publication date: 2003-08-14
Anticipated expiration: 2004-08-06
Also published as: AR038352A1; GB0202783D0; AU2003208340A1

Abstract

The invention subsists in a water-soluble or water dispersible granule comprising at least 0.05%wt of a macrocyclic (tetra) amido N-donor catalyst and at least 50%wt of a water-dispersible material which is not a catalyst. In typical formulations the water-soluble or water dispersible granule comprises: a) 0.05-10 %wt of a macrocyclic (tetra) amido N-donor catalyst, b) 50-99.85 %wt of a water dispersible material such as a sulphate salt c) 0.1-49.95 %wt of a binder.The present invention has particular application in detergent bleaching, especially for laundry cleaning. Accordingly, the granules are preferably present in a detergent composition which contains a surface-active material, optionally together with detergency builder. The amount of catalyst in the detergent composition is typically sufficient to provide a concentration in the wash liquor of generally 0.005 μm to 100 μm, preferably from 0.025 μM to 50 μM, more preferably from 0.05 μM to 10 μM.

Description

GRANULE AND COMPOSITION CONTAINING SAME

Technical Field

The present invention relates to a macrocyclic tetra amido N-donor metal-ligand complexes in granular form for use as a bleaching catalyst .

Background of the Invention

Oxidation catalysts comprising metal-complexes are well known. One class being macrocyclic ligands which co- ordinate with a transition metal ion. Such catalysts have been proposed for use in laundry compositions as components of a bleaching system. These catalysts activate H₂O₂ or other peroxygen sources and are effective at neutral to basic pH.

One proposed purpose of these catalysts has been to assist in the bleaching of dyestuffs released from articles being laundered. If these dyestuffs are not removed from the wash liquor then they will re-deposit onto articles and cause a loss of colour definition or even catastrophic damage to

'white' articles.

A particular catalyst is disclosed in WO 98/03263, filed 21 July 1997, (Collins) , which comprises a macrocyclic (tetra) amido N-donor. The macrocycle is capable of complexing with a metal ion, for example an iron III or IV. The complex also comprises axial ligands, for example as chloride or water, and one or more counter ions, for example tetraphenylphosphonium and tetraethylammonium. United States Patent 5,853,428, filed 24 Peb 1997, (Collins) discloses use of similar catalysts in laundry detergent compositions. Many other metal-based bleach catalysts are known.

Other bleaching agents are generally present in laundry detergents. These typically include percarbonates and/or perborates, which act as sources of hydrogen peroxide and/or other peroxyl species.

Amongst preferred macrocyclic N-donors are the Fe complexes of tetrahydro-hexamethyl-benzo-tetraazocyclotridecane tetrones. These molecule are believed to be relatively stable against self-oxidation in the presence of hydrogen peroxide. Consequently, should quantities of this catalyst come into contact with a peroxide source in a laundry detergent composition it will not be decomposed and will remain present to decompose the peroxide source.

Other methods of prevent dye-transfer are known. In particular it is known to use the so-called DTI (dye transfer inhibition) polymers to hold dyes in the wash liquor and prevent re-deposition. Brief Description of the Invention

We have determined that the macrocyclic (tetra) amido N- donor catalyst is particularly efficacious and storage stable when prepared in a granular form.

It is the aim of this invention to provide a granule that is easy to make, use and store for bleach applications, particularly in domestic and industrial laundry applications.

Accordingly, a first aspect of the present invention subsists in a water-soluble or water dispersible granule comprising at least 0.05%wt of a macrocyclic (tetra) amido N-donor catalyst and at least 50%wt of a water-dispersible material which is not a catalyst.

For practical application it is extremely useful to have the catalyst in granular form, as this allows the catalyst to be dosed easily and accurately. To create a similar powder from the neat catalyst would require very small quantities of catalyst to be weighed out and evenly distributed: a much harder task.

Gruanulation also gives a much easier material to work with, as the pure catalyst is a dark red, powdery and hygroscopic solid, that with storage easily becomes sticky and not free flowing.

Use of a granule improves safety for workers as it reduces the risk of fine dust from the catalyst being inhaled. This is especially important when the catalyst is used in large scale industrial applications where relatively large quantities of the catalyst are applied.

Moreover, use of a granulation route to a product allows the catalyst to be introduced and stored sufficiently separately from the peroxy bleaching agents present in the composition to prevent significant decomposition of the peroxides.

Detailed Description of the Invention

In preferred embodiments of the invention the granule further comprises a binder. The relative amount of materials can be simply changed to give a more/less concentrated granule .

In typical formulations the water-soluble or water dispersible granule comprises :

a) 0.05-10 %wt of a macrocyclic (tetra) amido N-donor catalyst,

b) 50-99.85 %wt of a water dispersible material which is not a catalyst, and,

c) 0.1-49.95 %wt of a binder.

The present invention has particular application in detergent bleaching, especially for laundry cleaning. Accordingly, the granules are preferably present in a detergent composition which contains a surface-active material, optionally together with detergency builder.

The amount of catalyst in the detergent composition is typically sufficient to provide a concentration in the wash liquor of generally 0.005 μm to 100 μm, preferably from 0.025 μM to 50 μM, more preferably from 0.05 μM to 10 μM.

These and other aspects of the invention are described in further detail below

Macrocyclic catalysts:

Preferred metal-complexed ligands are those having the structure as shown in general formula 1 :

General formula 1 :

wherein : B , B₃ and B₄ each represent a bridging group having zero, one two or three carbon containing nodes for substitution, and B₂ represents a bridging group having at least one carbon containing node for substitution, each said node containing a C (R) , C(Rχ) (R₂) or C (R) ₂ ,

each R substituent is the same is the same or different from the remaining R substituents, and

(i) is selected from the group consisting of alkyl , alkenyl , cycloalkyl , cycloalkenyl , aryl , alkynyl , alkylaryl, halogen, alkoxy, phenoxy and combinations thereof, or

(ii) form a substituted or unsubstituted benzene ring of which two carbons on the ring form nodes in the B-unit ;

M is a transition metal ion;

L is an axial ligand; and,

Q is an alkali metal or tetra-alkyl ammonium or tetra- phenyl phosphonium counter-ion.

Preferably, the axial ligand is selected from the group consisting of water and halide. Particularly preferred axial ligands are water and chloride. It is within the scope of the present invention to have a bleach activator, wherein M is selected from the group consisting of Fe, Mn, Cr, Cu, Co, Ni, Mo, V, Zn and W.

The most preferred catalyst is that in which the ligand is 5, β-benzo-3 , 8, 11, 13-tetraoxo-2 , 2, 9, 9, 12 , 12-hexamethyl- 1,4 , 7, 10- tetraaza-cyclo-tridecane.

The axial ligand ^λL' is water or preferably chloride. The counter-ion ^ΛQ' is preferably lithium. The ligand is also known as 3 , 4 , 8 , 9-tetrahydro-3 , 3 , 6 , 6 , 9 , 9-hexa-methyl-lH- 1,4,8, ll-benzotetraazocyclotridecane-2,5, 7, 10 (6H, 11H) tetrone .

Water Dispersible Material:

The water dispersible material acts as a filler and carrier in the granule, but may also have a function in the overall composition. It is therefore convenient to make use of materials which would otherwise be present in a laundry detergent composition as the water dispersible material. In its broadest context, water dispersible materials include both water soluble and insoluble materials .

Suitable dispersible insoluble materials include insoluble silicates or alumino-silicates and whitening agents. Suitable alumino silicates include the zeolite builders as described in further detail below. Suitable whitening agents include titanium dioxide. Suitable water soluble materials include salts selected from sulphates, citrates, phosphates, and silicates.

Particularly preferred salts include carbonates. These have the advantage that they can adsorb hydrogen peroxide in the vapour phase and form percarbonates .

Binders :

Binders are sticky, non-toxic, dispersible material suitable for forming granules

Preferred binders include acrylate/maleate co-polymers such as Sokolan™ CP5 and/or CP45. Alternative binders include polyalkylene glycols, polyvinylacetate and soluble nonionic surfactants .

Granulation:

Preferred granule size is 250-1000 microns, preferably 250- 700 microns.

Granulation may be achieved in an Eirich Mixer, for example an Eirich RV02 Granulator. Other equipment suitable for use in the present invention include the Fukae mixer, produced by Fukae Powtech Co. of Japan, the Diosna V Series supplied by Dierks & Sohne Germany, the Pharma Matrix ex TK Fielder Ltd England, the Fuji V-C Series produced by Fuji Sangyo Company Japan and the Roto produced by Zanchetta & Company Sri, Italy. Other suitable equipment can include the Lδdige

Series CB for continuous high shear granulation available from Morton Machine Company Scotland, the Drais T160 Series manufactured by Drais Werke GmbH, Mannheim Germany.

High shear mixing can be achieved by the skilled person in a manner well known in the art. For example, where a Lδdige Mixer is used, a rotation speed of 500-3000 rpm may be used.

End-Product Form:

As noted above, the granules of the invention may be present in a detergent composition.

Preferably, the overall character of the detergent composition will be such that it comprises a population of catalyst-containing granules according to the invention and one of more populations of other granules containing one or more of surface-active agents, builders, bleaches and/or other components. Detergent compositions are described in further detail below.

Surface-active Agents

The detergent composition may contain a surface-active material in an amount, for example, of from 10 to 50% by weight.

The surface-active material may comprise materials which are naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surface-actives are usually water- soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl groups.

Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C₈-Cιg) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C₉-C₂0) benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀-C ₅) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (Cg-Ciβ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha- olefins (C₈-C₂₀) with sodium bisulphite and those derived by reacting paraffins with SO₂ and CI₂ and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium (C₇-C₁₂) dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, particularly (C₁0-C₂₀) alpha-olefins, with

SO₃ and then neutralising and hydrolysing the reaction product .

The preferred anionic detergent compounds are sodium

(C₁₀-C₁₅) alkylbenzene sulphonates (C10-C15 LAS) , and sodium (C₁₆-C₁₈) alkyl ether sulphates (C16-C18 LES) .

Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic surface- active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C₆-C₂₂) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (Cβ-Cis) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO . Other so- called nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides .

Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives . It is believed that the catalysts become less effective as the level of nonionic surfactant approaches 100% on surfactant. Conversely, where nitrogen-containing, dye binding, DTI polymers are used, the effectiveness of these polymers is reduced at high levels of anionic surfactant.

Embodiments of the present invention which comprise a DTI (dye transfer inhibiting) polymer preferably comprise a mixed active system which comprises both anionic and nonionic surfactants. These compositions will preferably comprise from 1 to 15 %wt/product of anionic surfactant and from 10 to 40 %wt/product of nonionic surfactant. In such compositions it is preferable that the level of anionic surfactant ranges from 10-90%wt/surfactant and that the level of nonionic ranges from 90-10%wt/surfactant . It is especially preferred to use 30-60%wt/surfactant of anionic surfactant selected from: LAS, PAS, soap and mixtures thereof, together with 70 -40%wt/surfactant of ethoxylated alcohol nonionic surfactant .

In absence of DTI polymers the formulations preferably contain at least 80%wt/surfactant of anionic surfactant. Preferably the anionic surfactant will be LAS although small amounts (0.5-2%wt on product) of soap can be present. Nonionic surfactant levels should in this case be less than 2%wt on product.

Most preferably, the formulation is free of DTI polymers and the surfactant system includes 20-25%wt/product of LAS and 0.2-2.0%wt/product of a cationic surfactant. Preferably, not more than 1.5%wt/product of nonionic is present in the compositions .

Preferably the anionic surfactant is present in granules .

The anionic surfactant granules may be manufactured by any suitable process. Preferably, such granules are manufactured by mixing the components in a high speed mixer to agglomerate the components. Suitable mixers will be discussed further below.

Processes for producing granules containing high quantities of anionic surfactant are set out in WO 96/06916A and WO 96/06917A (Unilever) .

The method of WO 97/32002A (Unilever) is particularly preferred. In this method, a paste material comprising water and an anionic surfactant, or a mixture of acid surfactant precursor and alkaline neutralising agent, is fed into a drying zone, the paste material being heated in the drying zone to reduce the water content thereof and the paste material being subsequently cooled in a cooling zone to form detergent particles, a layering agent being introduced into the cooling zone during the cooling step.

Alternatively, a paste material comprising water and an anionic surfactant, or a mixture of acid surfactant precursor and alkaline neutralising agent fed into a drying zone, the material being heated in the drying zone to reduce the water content thereof and the material being subsequently cooled in a cooling zone to form detergent particles, the material being treated in the cooling zone with a stream of cooling gas. This process can provide detergent particles comprising at least 60% by weight of the particle of an anionic surfactant and not more than 5% by weight of the particle of water. The particles are preferably coated with layering agent .

Builders :

The composition may also contain a detergency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight.

Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) • calcium ion-exchange materials and 4) mixtures thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4, 144,226 and US-A-4 , 146 , 495.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate .

Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0 , 384 , 070.

In particular, the composition may contain any one of the organic and inorganic builder materials.

Typical builders usable in the present invention are, for example^', sodium tripolyphosphate (STP) , sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.

Preferred builder systems comprise 10-30%wt/product STP and 10 -20%wt/product sodium carbonate.

Other Additives

Apart from the components already mentioned, the composition can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions.

Examples of these additives include carbonates as bufferes, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e. Dequest^® types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants .

Of the additives, transition metal sequestrants such as EDTA and the phosphonic acid derivatives, e.g. ethylene diamine tetra- (methylene phosphonate) -EDTMP- are of special importance, as not only do they improve the stability of the catalyst/H₂0₂ system and sensitive ingredients, such as enzymes, fluorescent agents, perfumes and the like, but also improve the bleach performance, especially at the higher pH region of above 10, particularly at pH 10.5 and above.

Other suitable transition metal sequestrants are known and can be chosen by those skilled in the art, for example aminocarboxylates, aminophosphonates, and polyfunctionally substituted aromatic chelating agents, as disclosed further in WO-A-98/39406.

If present, the sequestrants are generally present in amounts of 0.001 to 15%, more preferably 0.01 to 3.0%, by weight of the overall composition.

The present invention may be conveniently embodied in both a powder or tablet form of product. If the product is a powder then the bulk density will typically fall in the range 400- 600 g/1.

Bleach Components:

It is preferable that the detergent composition also contains a peroxygen bleach or a peroxy-based or -generating system. The peroxygen bleach is preferably a compound which is capable of yielding hydrogen peroxide in aqueous solution although it is possible to use more complex systems which involve peracids and/or peracid precursors.

Hydrogen peroxide sources are well known in the art . They include the inorganic peroxides, for example alkali metal peroxides, organic peroxides for example as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates . Mixtures of two or more such compounds may also be suitable.

Typical levels of peroxygen source in fully formulated composition will range from 0.05-55 wt . % with 1-40 wt . % being particularly preferred and 1-25 wt . % being most particularly preferred.

Typical levels of peroxygen source (as hydrogen peroxide equivalents) in fully formulated composition will be such that the in-use concentration will range from 0.005mM to lOOmM with 0.025mM to 50mM being particularly preferred and 0.05mM to lOmM being most particularly preferred. Preferred peroxygen sources include percarbonate and perborate .

Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its high active oxygen content. Typical levels of perborate in compositions according to the invention range from 1- 15%wt/product . Sodium percarbonate may also be preferred for environmental reasons.

Peroxyacid bleach precursors are also known and amply described in literature, such as in GB-A-836988; GB-A-864,798; GB-A-907 , 356 ; GB-A-1 , 003 , 310 and GB-A-1, 519, 351; DE-A-3 , 337 , 921 ; EP-A-0 , 185 , 522 ;

EP-A-0,174,132; EP-A-0 , 120 , 591 ; and US-A-1, 246 , 339 ; US-A-3,332,882; US-A-4 , 128 , 494 ; US-A-4 , 412 , 934 and US-A-4, 675, 393.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US-A-4, 751, 015 and US-A-4, 397, 757, in EP-A-0 , 284, 292 and EP-A-331, 229. Examples of peroxyacid bleach precursors of this class are: 2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride - (SPCC) ;

N-octyl,N,N-dimethyl-Nio-carbophenoxy decyl ammonium chloride - (ODC) ; 3- (N,N,N-trimethyl ammonium) propyl sodium-4 -sulphophenyl carboxylate; and

N,N,N-trimethyl ammonium toluyloxy benzene sulphonate. A . further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303 , 520 ; EP-A-458,396 and EP-A-464, 880.

Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.

Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS) ; N,N,N'N' -tetraacetyl ethylene diamine (TAED); sodium-1 -methyl-2 -benzoyloxy benzene-4 -sulphonate; sodium-4- methyl-3 -benzoloxy benzoate; 2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride (SPCC) ; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5- trimethyl hexanoyl-oxybenzene sulphonate (STHOBS) ; and the substituted cationic nitriles.

Of the peracid precursors, TAED and SNOBS are preferred. Hydrogen peroxide based bleaching systems according to the present invention are markedly preferred to peroxyacid based systems. Where present the precursors are typically used in an amount of up to 12%, more preferably from 0.5 - 5% by weight of the composition.

When using a hydrogen peroxide source, such as sodium perborate or sodium percarbonate, as the bleaching compound, it is preferred that the overall detergent composition contains not more than 5 % by weight of a carbonate buffer, expressed as sodium carbonate, more preferable not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.

Preferred compositions according to the invention are granular LAS-based powders comprising on wt/product:

20-30% LAS 0.2-2% cationic surfactant

0-2% nonionic surfactant

0-2% soap

10-30% sodium sulphate

10-30% sodium carbonate 10-20% sodium tripolyphosphate

1-15% perborate monohydrate

1-5% TEAD

0-2% soil release polymer low levels of enzymes, silicone antifoams, sequestering agents and fluorescer.

Examples

In order that the invention may be further and better understood it will be described in detail with reference to following non-limiting examples.

The catalyst referred to in the examples is the Fe complex of 3,4,8,9-tetrahydro-3,3,6,6,9,9-hexamethyl-lH-l,4, 8,11- benzo-tetraazocyclotri-decane -2,5,7,10 (6H,11H) tetrone, with lithium as the counter-ion and water as the axial ligand. This was synthesised in accordance with the method set out in our co-pending patent application GB 0020846.2.

For model laundry washes, the detergent used in the examples was such that the wash liquor contained 1.8g/L of a LAS and phosphate based washing powder (OMO MA , ex Gessy-Lever,

Brazil) .

Washes were simulated in a Rotawash Linitester at 40°C, using 30 minutes agitation in 200ml of wash liquor. Washes contained one 10 by 10 cm square of white woven cotton fabric and one 10 by 10 cm of woven cotton fabric dyed with direct green 26 and fixed with Croscolor F3. The green cloth looses dye into solution during the wash which re- deposits onto the white cloth causing a green discoloration.

All fabrics were measured after washing on an ICS Texicon

Spectraflash 500 which was calibrated using the following settings:

UV Excluded - (420nm cut-off) Specular included Large aperture

Each monitor was measured through one thickness of cloth with bleached, non-fluorescent mercerised white cotton sheeting as the reference standard. Each monitor was measured four times and the average of these four measurements was taken to be the value of that monitor. All experiments were repeated three times. Reflectance values were taken and converted into delta E values by a computer software package which reported average delta E values according to the following equation:

Example 1 - preparation of a granule:

The pure catalyst, a red powdery solid, was mixed with sodium sulphate in a mortar and pestle and the organic builder Sokalan CP5 (ex BASF) , a maleic Anhydride and acrylic acid copolymer, was then added till a good granule was created. The resulting granules were sieved to give pale orange granules in the range 250-710 μm.

The composition of the granule was

1% catalyst

93% sodium sulphate

6% Sokala CP5

Example 2 - Use of granule in a washing powder;

5g of the granules of example 1 were added to 170g of OMO TM

MA washing powder and to this 5g of perborate monohydrate was added as a source of hydrogen peroxide. The powder was then gently agitated to evenly distribute the granules around the powder.

The so-formed powder was then used in the model wash described above and the colour of the white cloth after the wash compared to that of a control wash conducted with a powder not containing the catalyst .

The results are:

OMO MA ΔE = 7.4

OMO MA plus granule and perborate ΔE = 2.4

The standard deviation in the experiments was approximately 0.5 ΔE units. Lower numbers indicate better results as there has been less change in the colour due to dye transfer.

From these results it can be seen that the use of the granulated catalyst in the washing powder successfully reduced the amount of dye transferred in the presence of a hydrogen peroxide source (perborate) .

Example 3 - Storage of granule in a washing powder:

The washing powder of example 2 was stored in the dark for 4 weeks in a sealed polythene contained at room temperature and humidity. The experiments of example 2 were then repeated. The results are:

OMO MA ΔE = 8.9

OMO MA plus granule and perborate ΔE = 2.9

These results show (when compared with example 2) that the catalyst in the granule successfully survives storage with a hydrogen peroxide source present in the same overall composition.

Claims

1. A water-soluble or water dispersible granule comprising at least 0.05%wt of a macrocyclic (tetra) amido N-donor catalyst and at least 50%wt of a water-dispersible material which is not a catalyst .

2. A granule according to claim 1 further comprising a binder.

3. A granule according to claim 2 which comprises:

a) 0.05-10 %wt of a macrocyclic (tetra) amido N-donor catalyst,

b) 50-99.85 %wt of a water dispersible material which is not a catalyst, and,

c) 0.1-49.95 %wt of a binder.

4. A granule according to claim 3 present in a detergent composition which detergent composition contains a surface-active material and detergency builder. A granule according to claim 1 wherein the macrocyclic (tetra) amido N-donor catalyst has the structure:

wherein :

B_, B₃ and B₄ each represent a bridging group having zero, one two or three carbon containing nodes for substitution, and B₂ represents a bridging group having at least one carbon containing node for substitution, each said node containing a C (R) ,

C(Rι) (R₂) or C(R)₂,

(i) is selected from the group consisting of alkyl, alkenyl , cycloalkyl, cycloalkenyl , aryl , alkynyl , alkylaryl, halogen, alkoxy, phenoxy and combinations thereof, or (ii) form a substituted or unsubstituted benzene ring of which two carbons on the ring form nodes in the B-unit;

-M is a transition metal ion;

-L is an axial ligand; and,

-Q is an alkali metal or tetra-alkyl ammonium or tetra-phenyl phosphonium counter-ion.

6. A granule according to claim 1 wherein the water dispersible material is a salt selected from sulphates, citrates, phosphates, and silicates.

7. A granule according to claim 2 wherein the binder is an acrylate/maleate co-polymer.

8. A granule according to claim 4 wherein the detergent composition contains at least 80%wt/surfactant of anionic surfactant .