C4519/C FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) SHADING COMPOSITION 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 2008/017570 PCT7EP2007/057264 - 1 -SHADING COMPOSITION FIELD OF INVENTION 5 The present invention relates to the delivery of dyes to fabrics. BACKGROUND OF THE INVENTION 10 Many garments yellow over multiple wash wear cycles, reducing the aesthetic value of the garment. In order to maintain the white appearance shading dyes may be used. For main wash applications these are preferably blue or violet dyes of the acid, direct or hydrolysed reactive dye classes. 15 A number of problems arise during use that are dependent on the class of dye. Direct dyes build up over multiple washes, and this can lead to a strong blue or violet colour on the garment. To make 20 this overshading acceptable lower level of dye must be used reducing the benefit. Acid dyes have the advantage that they do not build up over multiple washes. However no single acid dye has been found 25 that shows high deposition to cotton and gives a true blue or violet shade to the cloth. Many are too green in colour for optimum shading effects. Additionally many acid dyes that deposit to cotton also deposit on nylon and this leads to overshading of nylon after multiple washes. 30 WO 2008/017570 PCT/EP2007/057264 ■ - 2 - SUMMARY OF INVENTION We have found that some acid azine dyes whilst depositing well on cotton substrates deposit poorly on nylon and. are 5 capable of providing a true blue shade to the cotton substrate. In one aspect the present invention provides a laundry treatment composition comprising: 10 (i) from 2 to 70 wt% of a surfactant, and from 0.0001 to 0.1 wt% of an azine dye, wherein the dye is of the following core structure: 20 wherein Ra, Rb, Rc and Rd are selected from: H, a branched or linear CI to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO3" or -COO" group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methxy ethoxy, phenoxy, C1, Br, I, F, and N02. WO 2008/017570 PCT/EP2007/057264 - 3 - In another aspect the present invention provides a doraestic method of treating a textile, the method comprising the steps of: (i) treating a textile with an aqueous solution of an 5 acid azine dye as defined in any one of claims 1 to 7, the aqueous solution comprising from 1 ppb to 1 ppm of the dye, and from 0 ppb to 1 ppm of another dye selected from: hydrophobic dyes and direct dyes; and, from 0.0 g/L to 3 g/L of a surfactant; and, 10 (ii) rinsing and drying the textile. Preferably the method is conducted where the aqueous solution is 10 to 30 °C. This aids deposition of the azine dye. 15 Preferably the aqueous solution contains from 0.3 to 2.5g/L surfactant. The pH of the aqueous solution, provided by a unit dose of 20 the laundry treatment composition is in the range from 2 to 12. Preferably the pH of the aqueous solution is in the range from 7 to 11. Preferably the azine dye is present from 10 ppb to 200 ppb 25 of the dye. Preferably the hydrophobic dye is present in the range 10 ppb to 200 ppb. 30 Preferably the direct dye is present in the range from 2 ppb to 4 0 ppb. WO 2008/017570 PCT/EP2007/057264 - 4 - Preferably the aqueous solution has an ionic strength of greater than 0.01, more preferably greater than 0.05. The invention may also be used to enhance black and blue 5 garments on washing. The present invention also extends to a commercial package comprising the laundry treatment composition together with instructions for its use. 10 Photobleach.es may be sued in the present invention but preferably a photobleaoh is not present. DETAILED DESCRIPTION OF THE INVENTION 15 DYES It is within the scope of the invention to have a mixture of a direct dye, hydrophobic dyes and asine dye. This does not preclude the presence of other classes of dye. 20 The dyes are preferably added to granular products via the surfactant slurry or via post-dosed granules. If more than one dye is used then for a powder formulation 25 it is preferred that the shading dyes are co-granulated. All dye levels refer to pure dye. AZINE DYE 30 With respect to the asins dye of core structure (I) it is preferred that the A ring is further substituted to form a naphthyl. The dye is preferably substituted by two SO3" group WO 2008/017570 PCT7EP2007/057264 10 15 and no other charged substituents. One skilled in the art will appreciate that the .metal cation that is exemplified as sodium may be easily varied and such is within the scope of the invention, for example, such as alkali earth metals and alkaline earth metals and these are preferred, in particular potassium and calcium. One skilled in the art will appreciate that apart from the requirement that the azine dye is substituted with at least one SO3" or -COO" group and that the B ring does not carry a negatively charged group or salt thereof the latitude to vary substituents is large without effecting the efficacy of the dye to deposit on cotton as required. The groups Ra, Rb, Rc and Rd as specified above may carry other substituents. With respect to the E ring not carrying a negatively charged group B this in particular a S03- or COO-. Preferably the dye has the following structure: 20 wherein R1, P2, P3 and R4 is selected from the group consisting of: H, Me, Et, n-Pr and i- Pr; and the dye is 25 optionally substituted by a methoxy group. WO 2008/017570 PCT/EP2007/057264 - 6 A preferred dye is of the following structure: 5 Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98. 10 Most preferably the azine dye is acid blue 98. The azine dye is present in the formulation at levels of 0.00001 to 0.1%, preferably 0.0001 to 0.01%, most preferably 0.0005 to 0.005%. 15 In a preferred embodiment of the invention, the main wash formulation contains further shading dyes selected from hydrophobic dyes, most preferably solvent violet 13 or disperse violet 27. These dyes give benefits to synthetic fibres such as elastane and polyester. The hydrophobic dyes 20 are preferably blue or violet. The hydrophobic dyes are preferably present at levels of 0.0001 to 0.1% preferably 0.0005 to 0.005 wt%. WO 2008/017570 PCT/EP2007/057264 - 7 - In a preferred embodiment of the invention, the main wash formulation contains further shading dyes selected from direct violet and direct blue dyes. 5 In this embodiment the acid clye provides a shading in the first few washes that is visual and pleasing. The effect of the direct dye only becomes visible after multiple washes and serves to counteract the long term yellowing. In this way, both rejuvenation and whiteness maintenance may 10 be provided to the consumer. Azine dyes have advantage over triphenylmethane dyes in that they are more stable to high pH. 15 HYDROPHOBIC DYE 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 20 in aqueous solution at a pli 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 25 group comprising: azo; anthraquinone; phthalocyanine; benzodifuranes; quinophthalones/ azothiophenes; azobenzothioazoles and, triphenylmethane chromophores. Most preferred are azo and anthraquinone dye chromophores. 30 Many examples of hydrophobic dyes are found in the classes of solvent and disperse dyes. WO 2008/017570 PCT/EP2007/057264 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. 10 15 20 25 A wide range of suitable solvent and disperse dyes are available. However detailed toxicological studies hsive shown that a number of such dyes are possible carcinogens, for example disperse blue 1. Such dyes are not preferred. More suitable dyes may be selected from those solvent and disperse dyes used in cosmetics. For examp'le as listed by the European Union in directive 7 6/7 68/EEC Anne:-: IV part 1. For example disperse violet 27 and solvent violet 13. Preferred azo hydrophobic dykes for use in the present invention are: 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, 260, 264, 265, 266, 267, 268, 269, 270, 273, 279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 303, 304, 305, 30 313 315, 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, 32, 86, 83, 91, 92, 93, WO 2008/017570 PCT/EP2007/057264 93:1, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 106 or 107, Diani:: violet cc, and dyes with CAS-No's 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. Freierred anthraquinone hydrophobic dykes for use in the present invention are: 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 Elue 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 35, 36, 40, 41, 45, 59, 59:1, 63, 65, 63, 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 Elue 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, 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, 215, 217, 218, 223, 226, 227, 228, 229 , 230 ,231, 232, 234, 235, 236, 237, 238, 239, 240, 241 242, 243, 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. WO 2008/017570 PCT/EP2007/057264 10 - Other preferred (non-azo) (non-anthraquinone) hydrophobic dykes for use in the present invention are: Disperse Blue 250, 354, 364, 366, Solvent Violet 8, solvent blue 43,solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 5 570. Solvent violet 13 is most preferred. DIRECT DYE 10 The direct violet or direct blue dye is preferably present at levels of 0.00001 to 0.001% preferably 0.0001 to 0.0005%. The following are preferred direct dyes that may be used with the present invention. 15 Preferred direct dyes are selected from the group comprising tris-azo direct blue dyes of the formula: 20 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 25 phenyl or napthyl ring substituted "with upto 2 sulphonate WO 2008/017570 PCT/EP2007/057264 - 11 - 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 5 comprising his-azo direct violet dyes of the formula: ,OCH3 10 15 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 phenyl or naphthyl ring, which is substituted by 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. 20 25 SURFACTANT The composition comprises between 2 to 70 wt % of a surfactant, most preferably 10 to 30 wt %. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. WO 2008/017570 PCT/EP2007/057264 - 12 - 2 by Schwartz, Perry & Berch, Interscience 1953, 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 5 Verlag, 1981. Preferably the surfactants used are saturated. Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for 10 example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene o:-:ides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of 15 ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cis p 3) is given by acid black 1, acid blue 29, acid blue 59 and acid blue 98. Acid blue 59 and 10 acid blue 98 are less green than acid black 1 and acid blue 2 9 as shown by the a* and b* values. Acid blue 98 gives the best colour changes, with the predominate change in the blue direction (large decrease in b*, little change in a* relative to control). 15 The results for nylon are shown below WO 2008/017570 PCT7EP2007/057264 - 19 - Dye Chromophore AE Control (no dye) - - Acid black 1 Azo 0.3 Acid Violet 17 Tripheny1methane 0.1 Acid blue 2 5 Anthraquinone 1.2 Acid blue 29 Azo 0.1 Acid blue 62 Anthraquinone 0.6 Acid blue 18 Azine 0.1 Acid blue 59 Azine 0.5 Acid blue 98 Azine 0.1 The azine dyes show low deposition onto nylon. 5 Example 2 A wash load was created containing 80% white cotton sheeting and 20% of 65:35 polyester-cotton sheeting. This was washed in 2g/L of the base washing powder described in example 1, rinsed and dried. The liquor to cloth ratio was 16:1. The 10 experiment was repeated but with addition of shading dyes to the base washing powder, Two shading formulation "was created, containing: (a) 0.005 wt% acid blue 98 (b) 0.005 wt% acid blue 93, 0.001 wt% direct violet 9 and 15 0.004 wt% solvent vio let 13. The solvent violet 13 was added via a zeolite/non-ionic granule which contained 0.2% dye. The wash experiment was repeated with these formulations. 20 Following drying the reflectance spectrum of the cloth were recorded (UV-exclucled to remove the effect of the WO 2008/017570 PCT/EP2007/057264 - 20 fluorescer) From the reflectance values the K/S values were calculated via the Kubelka-Munk equation K/S = (1-R)2/2R where R = %reflectance/100 K/S is proportional to the dye loading on the cloth. 10 As the dyes have maximum optical absorption in the range 550-600nm the K/S values were summed over this range. The washes were then repeated and further measurement taken The cotton sheeting results are given below: AK/S compared to control Wash 1 Wash 2 Wash 3 Wash 4 (a) 0.0166 0.0184 0.0251 0.0259 (b) 0.0161 0.0231 0.0331 0.0363 15 AK/S is the difference between control and shading formulation washed cloth. The results for (a) show that Acid blue 98 does not build up linearly over multiple washes. After the 3rd wash the dye 20 loading becomes constant. In analogous experiment with direct dyes, such as direct violet 51 and direct violet 9, AK/S constantly increases with wash nubmer indicating a linear build up of dye. In (b) the effect of a small addition of direct violet 9 to the formulation is seen, with 25 AK/S gradually increasing over multiple washes. The acid WO 2008/017570 PCT/EP2007/057264 - 21 - blue 98 provides a large shading benefit in the first washes and the direct violet 9 counteracts long terra yellowing. For polycotton only small benefits were seen with (a), 5 however with (b) due to the addition of solvent violet 13 good shading benefits were observed. This was indicated by a ΔK/S of 0.0202 after the 4th wash. A 12.5ppm solution of the acid blue 93 used in these 10 experiments had an optical density (1cm) at its absorption maximum in the visible region of 0.67. The solvent violet 13 and direct violet 9 used were of high purity (95% + ) . WO 2008/017570 PCT/EP2007/057264 - 22 - Claims 1. A laundry treatment composition comprising: (i) from 2 to 70 wt% of a surfactant, and from 0.0001 to 5 0.1 wt% of an azine dye, wherein the dye is of the following core structure: 0 wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear CI to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO3" or -COO" group; 5 the E ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected 0 from: amine, methyl, ethyl, hydro::yl, metho::y, ethoxy, phenoxy, Cl, Br, I, F, and NO2. 2. A laundry treatment composition according to claim 1, wherein the A ring is further substituted to form a 5 naphthyl. WO 2008/017570 PCT/EP2007/057264 - 23 - 3. A laundry treatment composition according to claim 1 or 2, wherein the dye is substituted by two SO3" group and no other charged substituents. 5 4. A laundry treatment composition according to claim 1 or 3, wherein dye has the following core structure: o wherein R1, R2, R3 and R4 is selected from the group consisting of: H, Me, Et, n-Pr and i- Pr; and the dye i optionally substituted by a methoxy group. 5. A laundry treatment composition according to claim 4, wherein dye has the following structure: WO 2008/017570 PCT/EP2007/057264 - 24 - 6. A laundry treatment composition according to claim 1, wherein the azine dye is selected from the group: acid blue 98, acid violet 50, and acid blue 59. 5 7. A laundry treatment composition according to claim 6, wherein the azine dye is acid, blue 98 8. A laundry treatment composition according to any preceding claim, wherein the composition comp.romised a 0 further shading dye selected from the group consisting of: direct dye and hydrophobic dye. 9. A laundry treatment composition according to claim 8, wherein the hydrophobic dyes is selected from: solvent 5 violet 13 and disperse violet 27. 10. A laundry treatment composition according to claim 8, wherein the direct dye is selected from: direct violet 9, 51 and 35. o. 11. A laundry treatment composition according to claim 8, wherein the direct dye is present at a level from 0.00001 to 0.001 wt%. 5 12. A laundry treatment composition according to claim 8, wherein the hydrophobic dye is present at a level from 0.00001 to 0.01 wt%. 13. A domestic method of treating a textile, the method 0 comprising the steps of: "/O 2008/017570 PCT/EP2007/057264 - 25 - (i) treating a textile with an aqueous solution of an acid azine dye as defined in any one of claims 1 to 7, the aqueous solution comprising from 1 ppb to 1 ppm of the dye, and from 0 ppb to 1 ppm of another dye selected 5 from: hydrophobic dyes and direct dyes; and, from 0.2 g/L to 3 g/L of a surfactant; and, (ii) rinsing and drying the textile. 14. A method according to claim 13, wherein the azine dye is 10 present from 10 ppb to 2 00 ppb. 15. A method according to claim 13 or 14, wherein a hydrophobic dye is present in the range 10 ppb to 200 ppb. 15 16. A method according to any one of claim 13 to 15, wherein a direct dye is present in the range from 2 ppb to 4 0 Ppb. 20 Dated this 28th day of May 2008 HINDUSTAN UNILEVER LIMITED (S. Venkatramani) Senior Patents Manager