FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
DYE DELIVERY GRANULES
HINDUSTAN UNILEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed

WO 2007/006357 PCT/EP2006/004318
DYE DELIVERY GRANULES
TECHNICAL FIELD
The present invention relates to laundry treatment
compositions that comprise a dye.
BACKGROUND OF INVENTION
Many synthetic garments lose their whiteness after repeated
wearing. Whiteness can be maintained via the use of shading
dyes.
SUMMARY OF INVENTION
Dyes are difficult to dissolve/disperse in water. Thus methods are required to granulate the dyes, such that they may be delivered from detergent washing powders. The current invention provides such granules.
The method encompasses dissolving the dye in a non-aqueous but water miscible solvent to provide a solution. This solution is then mixed with a carrier material and possibly a binder to create granules suitable for dosing into a detergent powder.
In one aspect the present invention provides a granule comprising: (i) between 5 to 40 wt% of non-volatile water miscible solvent having dissolved therein between 0.0001 to 4 wt% of a dye, wherein the dye has a solubility in the solvent of at least 0.01 wt%, preferably at least 0.5 wt%, the non-volatile water miscible solvent other than a non-ionic surfactant; (ii) between 20 to 90 wt% of a solid carrier;

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(iii) between 0 to 50 wt% of a binder, (preferably 0 to 20
wt%); and,
(iv) between 0 to 1 wt% of a photo-bleach.
In another aspect the present invention provides a method of granulation comprising the steps of:
(i) dissolving between 0.0001 to 4% wt % of a dye in 5 to 40 wt% of a non-volatile water miscible solvent, that dye having a solubility in the non-volatile water miscible solvent of at least 0.1 wt % to form a solution of the dye in the non-volatile water miscible solvent;
(ii) taking the dye solution of step (i) and mixing with from 20 to 90 wt% of a solid carrier, the non-volatile water miscible solvent other than a non-ionic surfactant; and, (iii) granulating the resultant mixture from step (ii) to form a granule for post dosing to a base powder.
The granule is then used to form a commercial product by taking the 0.1 to 5 wt % of the granule and mixing as a post dose with a base laundry powder to 100 wt %.
In a further aspect the present invention provides a method of treating a new or soiled textile comprising the steps of: (i) adding the granule to an agitated aqueous medium;
(ii) treating a textile with the aqueous medium; and, (iii)rinsing the treated textile; and drying the textile.
A unit dose as used herein is a particular amount of the composition used for a type of wash. The unit dose may be in the form of a defined volume of powder, granules or tablet or unit dose detergent liquid.

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DETAILED DESCRIPTION OF INVENTION
NON-VOLATILE WATER MISCIBLE SOLVENT
The solvent may be a solid or liquid at room temperature, and compatible with inclusion in a detergent formulation. It should not be volatile, so that when included in a detergent powder it remains to maintain the dye in a dissolved state. Non-volatile for the purposes of this application is defined as having a volatility less than or equal to water. Most preferably, non-volatile means having a saturated vapour pressure at 25 °C and atmospheric pressure (101325Pa) below 3000Pa, and more preferably below lOOPa.
The solvent should be readily miscible with water, such that at least 1% weight solution in water of the solvent may be created.
Suitable solvents include surfactants, fatty acids, soaps and polymers. The surfactants may be isotropic or contain a dispersed water phase, for example, anionic surfactants and aqueous anionic surfactant pastes, fatty acids, polyethylene glycol polymers. Preferably they should be capable of functioning as binders or coatings in granules. So that when contacted with fine particle solids they promote particle growth by agglomeration, or spread over the surface of larger particles and solidify to create a robust coating. However, additional binder materials such as aqueous polymer solutions may also be added to create robust granules. Preferred solvents for dissolving the dye are charged species. Most preferred solvents for dissolving the dye are charged surfactants.

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The dye is soluble in the solvent such that solution of between 0.01 and 10 wt% may be created, preferably 0.05 to 1 wt%.
The solvent does not include non-ionic surfactants. One skilled in the art will be aware as to what is a non-ionic surfactants and reference in made to "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
Further to the above reference, the following is provided concerning non-ionic solvents. Non-ionic surfactant are, for example, fatty alcohol polyethylene glycol ether or fatty alcohol ethoxylates, alkylphenol ethoxylates, ethylene oxide and propylene oxide co-polymers, amine oxides, alkylamines, alkanolamines, polyglycerol esters, alkyl polyglucosides, and fatty acid N-alkylglucosamides. A typical class of non-ionic surfactant is of the form H(CH2)mO[CH2CH20]nH, where m is 12 to 15 and n is 3 to 9; the an alkyl chain in the range CIO to C18.
Dyes
Typical dye suppliers may be found in the colour index, and
include Clariant, Dystar, Ciba & BASF.
Preferred dyes are those which deposit on textile and provide a shade to the textile such that the hue angle, h,

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in the CIELAB system of the shade on the textile is between 220° and 320° most preferably between 250° and 290°. A detailed description of hue angle may be found on p57 of Color Chemistry 3rd edition by H. Zollinger published by Wiley-VCH. The preferred dyes are blue or violet.
Preferred dyes are hydrophobic dyes those which deposit on polyester.
Hydrophobic dyes are defined as organic compounds with a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 nm and that are uncharged in aqueous solution at a pH in the range from 7 to 11. The hydrophobic dyes are devoid of polar solubilizing groups. In particular the hydrophobic dye does not contain any sulphonic acid, carboxylic acid, or quaternary ammonium groups. The dye chromophore is preferably selected from the group comprising: azo; methine, pyrazole, napthoquinone, anthraquinone, phthalocyanine; and, triphenylmethane chromophores. Most preferred are azo and anthraquinone dye chromophores.
Many examples of hydrophobic dyes are found in the classes of solvent and disperse dyes.
Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white polyester.

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A wide range of suitable solvent and disperse dyes are available. However detailed toxicological studies have shown that a number of such dyes are possible carcinogens, such dyes are not preferred.
Preferred mono-azo dyes are of the form:

wherein R3 and R4 are optionally substituted C2 to C12 alkyl chains having optionally therein ether (-0-) or ester links, the chain being optionally substituted with -CI, -Br, -CN, -N02, and -SO2CH3; and, D denotes an aromatic or hetroaromatic group. Preferably D is selected from the group consisting of: azothiophenes, azobenzothiazoles and azopyridones.
It is preferred that R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl. Preferred aryl are -C6H5 and C10H7.
The following is an example of a preferred class of mono-azo dyes:

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where X and Y are independently selected from the group
consisting of: -H, -CI, -Br, -CN, -N02, and -SO2CH3;
A is selected -H, -CH3, -CI, and -NHCOR;
B is selected -H, -OCH3, -OC2H5, and -CI;
R1 and R2 are independently selected from the group consisting
of: -H, -CN, -OH, -OCOR, -COOR, -aryl; and
R is Cl-C8-alkyl.
The following are preferred azo dyes: Disperse blue 10, 11, 12, 21, 30, 33, 36, 38, 42, 43, 44, 47,79, 79:1, 79:2, 79:3, 82, 85, 88, 90, 94, 96, 100, 101, 102, 106, 106:1, 121, 122, 124, 125, 128, 130, 133, 137, 138, 139, 142, 146, 148, 149, 165, 165:1, 165:2, 165:3, 171, 173, 174, 175, 177, 183, 187, 189, 193, 194, 200, 201, 202, 205, 206, 207, 209, 210, 211, 212, 219, 220, 222, 224, 225, 248, 252, 253, 254, 255, 256, 257, 258, 259, 260, 264, 265, 266, 267, 268, 269, 270, 278, 279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 303, 304, 305, 313, 315, 316, 317, 319, 321, 322, 324, 328, 330, 333, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 351, 352, 353, 355, 356, 358, 360, 366, 367, 368, 369, 371, 373, 374, 375, 376 and 378, Disperse Violet 2, 3, 5, 6, 7, 9, 10, 12, 13, 16, 24, 25, 33, 39, 42, 43, 45, 48, 49, 50, 53, 54, 55, 58, 60, 63, 66, 69, 75, 76, 77, 82, 86, 88, 91, 92, 93, 93:1, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 106 or 107, Dianix violet cc, and dyes with CAS-No's

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42783-06-2, 210758-04-6, 104366-25-8, 122063-39-2, 167940-11-6, 52239-04-0, 105076-77-5, 84425-43-4, and 87606-56-2.
The following are preferred non-azo dyes: Disperse Blue 250, 354, 364, 366, Solvent Violet 8, solvent blue 43,solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570.
The dye may be fluorescent.
Preferred anthraquinone are of the following structure (I):

wherein Rl, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH2, -NHR9, and -N02, such that a maximum of only one -N02 group and a maximum of two -H are present as Rl, R4, R5, and R8 substituents; where R9 is an branched or linear Cl-C7-alkyl chain or an aryl group or substituted aryl groups, or a branched or linear C1-C7-alkyl chain optionally substituted by an -OH group; R2, R3, R6, and R7 may be selected from -H, -F, -Br, -CI, SO3aryl or -NO2, and -OR10, wherein R10 is selected from the group consisting of branched or linear Cl-C7-alkyl or aryl; and, R2 and R3 may together be joined to form a five membered non-aromatic ring of the form -C(=0)N(HR11)C(=X)-, wherein X

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is 0 or NH and R11 is selected from the group consisting of Cl-C6-alkyl optionally substituted with alkoxy groups.
It is preferred that the branched or linear alkyl chain of R9 and RIO have less than six carbon atoms. It is preferred that Rl, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH2, and -NO2/ and R2, R3, R6, and R7 is selected from -H, F, Br, CI or -NO2, and -Oaryl. It is also preferred that the aryl is an optionally substituted phenyl. Of the Rl, R4, R5 and R8 it is most preferred that is -OH and one is selected from -NH2 and -NHR9.
It is preferred that R2, R3, R5, R6, R7, and R8 are -H, Rl = -OH, R4 = -NHR9 or -NH2.
It is preferred that R5, R6, R7, and R8 = -H, Rl = R4 = -NH2, R2 = R3 = -Oaryl, or -CI.
It is most preferred that R11 is -CH2CH2CH2OMe.
The following are examples of preferred dyes: Solvent Violet
11, 13, 14, 15, 15, 26, 28, 29, 30, 31, 32, 33, 34, 26, 37,
38, 40, 41, 42, 45, 48, 59; Solvent Blue 11, 12, 13, 14, 15,
17, 18, 19, 20, 21, 22, 35, 36, 40, 41, 45, 58, 59, 59:1,
63, 65, 68, 69, 78, 90; Disperse Violet 1, 4, 8, 11, 11:1,
14, 15, 17, 22, 26, 27, 28, 29, 34, 35, 36, 38, 41, 44, 46,
47, 51, 56, 57,, 59, 60, 61, 62, 64, 65, 67, 68, 70, 71, 72,
78, 79, 81, 83, 84, 85, 87, 89, 105; Disperse Blue 2, 3,
3:2, 8, 9, 13, 13:1, 14, 16, 17, 18, 19, 22, 23, 24, 26, 27.
28, 31, 32, 34, 35, 40, 45, 52, 53, 54, 55,, 56, 60, 61, 62,

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64, 65, 68, 70, 72,73, 76, 77, 80, 81, 83, 84, 86, 87, 89, 91, 93, 95, 97, 98, 103, 104,105, 107, 108, 109, 11, 112, 113, 114, 115, 116, 117, 118, 119, 123, 126, 127, 131, 132,134, 136, 140, 141, 144, 145, 147, 150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 168, 169, 170, 176, 179, 180, 180:1,181, 182, 184, 185, 190, 191, 192, 196, 197, 198, 199, 203, 204, 213,214, 215,216, 217, 218, 223, 226, 227, 228, 229, 230, 231, 232, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 249, 252, 261, 262, 263, 271, 272, 273, 274, 275, 276, 277, 289, 282, 288, 289, 292, 293, 296, 297, 298, 299, 300, 302, 306, 307, 308, 309, 310, 311, 312, 314, 318, 320, 323, 325, 326, 327, 331, 332, 334, 347, 350, 359, 361, 363, 372, 377 and
379.
The composition may also comprise between 0.0001 to 0.1 wt % of one or more other dyes having same or differing substantively to a fabric substrate. These include dyes selected from cotton substantive shading dyes of the group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
Hydrolysed Reactive Dye
The reactive dyes may be considered to be made up of a chromophore which is linked to an anchoring moiety, The chromophore may be linked directly to the anchor or via a bridging group. The chromophore serves to provide a colour and the anchor to bind to a textile substrate.
A marked advantage of reactive dyes over direct dyes is that their chemical structure is much simpler, their absorption

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bands are narrower and the dyeing/shading are brighter; industrial Dyes, K. Hunger ed. Wiley-VCH 2003 ISBN 3-527-30426-6. However, mammalian contact with reactive dyes results in irritation and/or sensitisation of the respiratory tract and/or skin. In addition, wash conditions are not ideal for deposition of dyes because the efficiency of deposition is low.
With regard to reducing irritation and/or sensitisation, it is preferred that each individual anchor group of each reactive dyes is hydrolysed such that the most reactive group(s) of anchor groups of the dye is/are hydrolysed. In this regard, the term hydrolysed reactive dye encompasses both fully and partially hydrolysed reactive dyes.
The reactive dye may have more than one anchor. If the dye has more than one anchor, then each and every anchor, that contributes to irritation and/or sensitisation, needs to be hydrolysed to the extent discussed above.
The hydrolysed dyes comprise a chromophore and an anchor that are covalently bound and may be represented in the following manner: Chromophore-anchor. The linking between the chromophore and an anchor are preferably provided by -NH-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, or -N=N-.
Preferably the hydrolysed reactive dye comprises a chromophore moiety covalently bound to an anchoring group, the anchoring group for binding to cotton, the anchoring group selected from the group consisting of: a heteroaromatic ring, preferably comprising a nitrogen

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heteroatom, having at least one -OH substituent covalently
SO2C—C—OH
H5 H,
bound to the heteroaromatic ring, and *
It is preferred that the anchor group is of the form:
Wxn Wxn Y>n Y\X"
N^N N^^N ^N^ ^N^
i i t i
1 JXn JL 1 JJ Xn I II -+"Xn
/ I I
XrrC J J —sorc—c-x
V^ , and H> H2
wherein:
n takes a value between 1 and 3;
X is selected from the group consisting of: -CI,-F, NHR, a
quaternary ammonium group, -OR and -OH;
R is selected from: an aromatic group, benzyl, a C1-C6-
alkyl; and, wherein at least one X is -OH. It is preferred
that R is selected from napthyl, phenyl, and -CH3. Most
preferably the anchor group is selected from the group
consisting of:
W
J SOrC—C—OH
0H , and H* H* .

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Preferably, the chromophore is selected from the group consisting of: azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine.
Preferably, the chromophore is linked to the hydrolysed anchor by a bridge selected from the group consisting of: -NH-C0-, -NH-, NHCO-CH2CH2-, -NH-CO-, and -N=N-.
Most preferred hydrolysed reactive dyes are hydrolysed Reactive Red 2, hydrolysed Reactive Blue 4, hydrolysed Reactive Black 5, and hydrolysed Reactive Blue 19.
Acid Dye
The following are preferred classes of acid dyes.
The group comprising blue and violet acid dyes of structure NH2 0 HN
II I T
where at least one of X and Y must be an aromatic group, preferably both, the aromatic groups may be a substituted benzyl or napthyl group, which may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulphonates or carboxylates, most preferred is where X is a nitro substituted benzyl group and Y is a benzyl group.

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The group comprising red acid dyes of structure
B
I
„B ^NH
0 HN N
where B is a napthyl or benzyl group that may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, B may not be substituted with water solubilising groups such as sulphonates or carboxylates.
The group the following structures:
B
I
^NH ^B
N O HN
so I so SQ ——S03-
6 ^^\^ 6 ^^^^
4 and 4 ' ,
wherein:
the naphthyl is substituted by the two SO3- groups in one of the following selected orientations about ring: 7,8; 6,8; 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3, and 4,3;

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B is an aryl group selected from phenyl and naphthyl, the aryl group substituted with a group independently selected from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one -N=N-C10H7 group; one or more -OMe; and, one or more -Me.
The group of the following structures:
O X
I A I B I
O HN.^-.
I C H-Rn
wherein:
X is selected from the group consisting of -OH and -NH2;
R is selected from the group consisting of -CH3 and -OCH3;
n is an integer selected from 0, 1 2 and 3; and
one of the rings A, B and C is substituted by one sulphonate
group.
The following are examples of preferred acid dyes that may be used with the present invention: acid black 24, acid blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17, acid red 51, acid red 73, acid red 88, and acid red 87, acid red 91, acid red 92, acid red 94, and acid violet 17.
Direct Dye
The following are examples of direct dyes that may be used
with the present invention.

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Preferred direct dyes are selected from the group comprising tris-azo direct blue dyes of the formula:
^—,J N=^ C f—v
where at least two of the A, B and C napthyl rings are subsituted by a sulphonate group, the C ring may be substituted at the 5 position by an NH2 or NHPh group, X is a benzyl or napthyl ring substituted with upto 2 sulphonate groups and may be substituted at 2 position with a OH group and may also be substituted with an NH2 or NHPh group,
Other preferred direct dyes are selected from the group comprising bis-azo direct violet dyes of the formula:
OCH3
CH3 y=^
'03S
where Z is H or phenyl, the A ring is preferably substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a naphthyl ring, the Y group is a benzyl or naphthyl ring, which is substituted by

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sulphate group and may be mono or disubstituted by methyl groups.
Non-limiting examples of these dyes are direct violet 5, 7, 9, 11, 31, and 51. Further non-limiting examples of these dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and 120. Preferably the dye is direct violet 9.
THE CARRIER
The carrier may be water/surfactant soluble carrier or water/surfactant insoluble. Preferred examples of water/surfactant soluble carriers are sodium carbonate, sodium sulphate, sodium chloride, and sodium citrate. It is however preferred that the carrier is water/surfactant insoluble and in this regard preferred carriers are zeolite [e.g., zeolite 4A and zeolite MAP (A24)], clay and minerals; most preferably clay. The preferred clay is bentonite or kaolin.
THE GRANULE
The granule is preferably 180 to 1000 microns in maximum width. This is reflected by the ability of the granule to pass through a graded sieve.
BALANCE CARRIERS AND ADJUNCT INGREDIENTS (Base Powder) The granule of the present invention preferably forms part of a laundry detergent composition. In this regard, there may be other ingredients present in the dye containing granule and/or other granules or powders present. These include amongst others, for example enzymes, bleaching species, sequestrants, builders, anti-re-deposition agents,

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anti-dye transfer agents, perfumes, transition metal catalysts, soil release agents and fluorescent agents. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
Bleaching Species
The laundry treatment composition may comprise bleaching species. The bleaching species, for example, may selected from perborate and percarbonate. These peroxyl species may be further enhanced by the use of an activator, for example, TAED or SNOBS. Alternatively or in addition to, a transition metal catalyst may used with the peroxyl species. A transition metal catalyst may also be used in the absence of peroxyl species where the bleaching is termed to be via atmospheric oxygen, see, for example WO02/48301. Photobleaches, including singlet oxygen photobleaches, may be used with the laundry treatment composition. A preferred photobleach is vitamin K3.
Fluorescent Agent
The laundry treatment composition most preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in laundry treatment

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composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis{[(4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino)stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
PERFUME
Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
Experimental Example 1
Mixtures of solid Solvent violet 13 and the following materials were prepared to give 1 %wt dye. These mixtures were heated in glass vessels to 80 °C in a laboratory oven: PEG6000 and Laurie acid. These mixtures melted to form dye solutions which were then poured onto, either zeolite A24, sodium sulphate or soda ash carrier solids in a Sirman high

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shear mixer and mixed thoroughly in proportions that maximise agglomeration. As is well known in the art, the addition of too little liquid binder results in agglomeration of only part of the solids present whilst excess binder causes the creation of a wet-mass or dough.

Granule Component wt (g) % by weight
(a) SV13 Dye 0.4 0.14
PEG6K 39.6 13.7
Na sulphate 250 86.2
(b) SV13 Dye 0.7 0.22
Laurie Acid 69.3 21.7
Light Soda Ash 250 78.1
(c) SV13 Dye 0.5 0.2
Laurie Acid 4 9.5 19.8
Dense Soda Ash 200 80.0
The resultant granules were sieved to remove oversize materials (>1000um) and stored in sealed containers.
Example 2
Analogous experiments to example 3 were repeated except the dye disperse blue 79:1 was used. The mixtures of dye and solvent were generally of lower concentration, between 0.4 and 0.6 %wt. The granules created had the following composition accordingly.

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Granule Component wt (g) % by weight
(a) DB79:1 Dye 0.2 0.07
PEG6K 39.8 13.7
Na sulphate 250 86.2
(b) DB79:1 Dye 0.4 0.13
Laurie Acid 69.6 21.7
Light Soda Ash 250 78.1
(c) DB79:1 Dye 0.2 0.08
Laurie Acid 49.8 19.8
Dense Soda Ash 200 80.0
Example 3
To compare performance of the granules of examples 1 to 2 the following experiment was carried out. Washing powder, 1.8g/L, was dissolved in water. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water. To this was added a piece of knitted polyester such that the liquor to cloth ratio was 100:1. The solution was agitated and the granules added to give 0.2 ppm of dye in solution. The wash solution was then left agitating for 30 minutes, the polyester removed, rinsed and dried.
Following this the colour of the polyester was measured using a reflectometer and expresses as the DE value relative to a piece of unwashed polyester. The results are given in the table below

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Granule DE
SV13/PEG6000/sulphate 0.5
SV13/lauric acid/Light soda ash 1.1
DB79:l/PEG6000/sulphate 0.8
DB79:l/lauric acid/ Light soda ash 1.8
Control experiments in the absence of dye gave DE values of 0.2, thus all granules gave delivery of dye to the polyester fabric.
The exemplified granules of the present invention show low spotting and good delivery of dye to polyester.
The granules of the examples were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 0.001 and 0.004% by weight. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water.
The granules of examples were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 0.0005 and 0.002% by weight. The washing powder contained 10% NaLAS, 5% 7EO non-ionic, 1% soap, 17% zeolite A24, 12% percarbonate, 4% TAED, 40% salts (sodium sulphate, sodium carbonate), remainder, fluorescer, enzymes, anti-redep agents, moisture, perfume, sequesterants, anti-ashing agents, antifoam and dispersants.

We Claim:
1. A granule comprising:
(i) between 5 to 4 0 wt% of non-volatile water miscible solvent having dissolved therein between 0.0001 to 4 wt% of a dye, the non-volatile water miscible solvent other than a non-ionic surfactant;
(ii) between 20 to 90 wt% -of a solid carrier; (iii) between 0 to SO wt% of a binder; and, (iv) between 0 to 1 wt% of a -photo-bleach,
wherein the dye is a hydrophobic dye.
2. A granule according to claim 1, wherein solvent is selected from anionic surfactants and aqueous anionic surfactant pastes, fatty acids or polyethyl-ene -glycol polymers.
3. A granule according to any preceding claim, wherein the solid carrier is insoluble in water and surfactants.
4. A granule according to any preceding claim, wherein the solid carrier is selected from: zeolite, clay and minerals.
5. A granule according to claim 4, wherein the carrier is selected from bentonite, zeolite 4A and zeolite A24.
6. A granule according to any preceding claim, wherein the dye is substantive to a fabric and colours the fabric to give a colour with hue angle between 220 and 320

degrees.
7. A granule according to any preceding claim, wherein the
binder is selected from the group consisting of a
polyacrylate, polyethylene glycol, and
polyacrylate/maleate copolymer.
8. A granule according to any preceding claim, wherein the
binder is present in the range 2 to 10 wt%.
9. A granule according to any preceding claim, wherein the
ratio of carrier solid to solvent from about 1:1 to
10:1.
10. A granule according to claim 10, wherein the ratio of carrier solid to solvent from about 2:1 to 5:1.
11. A granule according to any preceding claim, wherein the hydrophobic dye is a solvent or disperse dye.
12. A granule according to claim 11, wherein the hydrophobic dye is selected from the group of: disperse arid solvent blue and violet dyes.
13. A granule according to any one of claims 12, wherein the hydrophobic dye is selected from: solvent violet 13, disperse violet 27, disperse blue 79:1.
14. A laundry detergent composition comprising the granule as defined in any preceding claim, wherein the dye level

contribution from the granule in the total detergent composition is between 0.0005 to 0.01 wt%.
15. A method of granulation comprising the steps of:
(i) dissolving between 0.0001 to 4% wt % of a dye in 5 to 40 wt% of a non-volatile water miscible solvent to form a solution of the dye in the non-volatile water miscible solvent;
(ii) taking the dye solution of step (i) and mixing with from 2 0 to 90 wt% of a solid carrier, the nonvolatile water miscible solvent other than a non-ionic surfactant;
(iii) granulating the resultant mixture from step (ii) to form a granule for post dosing to a base powder, and (iv) taking the 0.1 to 5 wt % of the product of claim 17
and mixing as a post dose with a base laundry powder to 100
wt %.
16. Method of treating a new or soiled textile comprising
the steps of:
(i) adding the granule as define in any one of claims 1
to 14 to an agitated aqueous medium;
(ii) treating a textile with the aqueous medium; and,
(iii)rinsing the treated textile; and drying the
textile.