WO2009087032A1

WO2009087032A1 - Shading composition

Info

Publication number: WO2009087032A1
Application number: PCT/EP2008/067790
Authority: WO
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird
Original assignee: UNILEVER PLC, a company registered in England and Wales under company no. 41424 of; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2008-01-10
Filing date: 2008-12-17
Publication date: 2009-07-16
Also published as: EP2227534A1; CN101910394A; CN101910394B; ES2368976T3; BRPI0821869A2; EP2227534B1; ZA201003970B; ATE515558T1

Abstract

The present invention concerns the use of specific mono-azo dyes in laundry- detergent composition.

Description

SHADING COMPOSITION

FIELD OF INVENTION

The present invention relates to the delivery of dyes to fabrics .

BACKGROUND OF THE INVENTION

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. A number of problems arise during use, that are dependent on the structure 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 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 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. GB 1 562 421 discloses industrial dying of substrates with Acid blue 117 using glacial acetic acid and perchloroethylene .

EP 0 355 575 discloses an aqueous composition comprising a combination of dyes including Acid Violet 11 and Solvent Yellow 2; the composition is intended for preventing polymer scale formation.

WO 2005/003275 discloses a treatment composition for laundry shading comprising a surfactant and dye which has a substantively to non-mercerised cotton of at least 8% but has a substantively to nylon of less than 5%.

SUMMARY OF INVENTION

We have found that some specific acid violet mono-azo dyes formed from aminonaptholsulfonic acid coupling components (DANSA dyes) whilst depositing well on cotton substrates deposit poorly on nylon and are capable of providing a true blue/violet shade to the cotton substrate.

In one aspect the present invention provides a laundry treatment composition comprising:

(a) from 2 to 70 wt% of a surfactant;

(b) from 0.005 to 2 wt % of a fluorescent agent;

(c) from 0.00001 to 0.1 wt% of a DANSA dye selected from:

wherein R is selected from: H; a branched or linear Cl to C7-alkyl chain; CORi wherein Ri is a branched or linear Cl to C7-alkyl chain; and, a -SO₂Ar group, wherein Ar is phenyl or methyl substituted phenyl group;

Y is selected from: NO₂; CN; I; Br; Cl; F; H; OCOR₂; NHCOR₃; R₄; R5O; and, NR₆R7, wherein R₂, R₃, R₄, and R₅ are independently selected from a branched or linear Cl to Cl- alkyl chain and Re and R₇ are independently selected from: H; a branched or linear Cl to C7-alkyl chain that is unsubstituted or is substituted by groups independently selected from: OH; Cl; F; OCOCH_3; COOCH₃; OCOC₂H₅; and, COOC₂H₅; and, X is selected from: H; SO₂N(R₈)COCH₃; SO₂N (R₈) -Ar; and SO₂-Ar, wherein Ar is an aromatic group and R₈ is H, CH₃ or C₂H₅, with the proviso that the Y ring does not carry a negatively charged group or salt thereof.

In another aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of a DANSA dye, the aqueous solution comprising from 1 ppb to 1 ppm of the dye, and from 0 ppb to 1 ppm of another dye or - A -

pigment selected from: pigments, hydrophobic dyes and direct dyes; and, from 0.1 g/L to 3 g/L of a surfactant; and, (ii) Rinsing and drying the textile.

Preferably the method is conducted where the aqueous solution is 10 to 30 ⁰C. This aids deposition of the DANSA dye .

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 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 DANSA dye is present from 10 ppb to 200 ppb of the dye.

If present, the hydrophobic dye is preferably present in the range 10 ppb to 200 ppb.

If present, the direct dye is preferably present in the range from 2 ppb to 40 ppb.

If present, the pigment is preferably present in the range from 10 ppb to 200 ppb.

Preferably, the aqueous solution has an ionic strength of greater than 0.01 and more preferably greater than 0.05. The invention may also be used to enhance black and blue garments on washing. The present invention also extends to a commercial package comprising the laundry treatment composition together with instructions for its use.

Photobleaches may be used in the present invention.

Singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Zl where Zl is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1-4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba) .

DETAILED DESCRIPTION OF THE INVENTION

DYES and PIGMENTS

Dyes and pigments are listed in the Color Index

International published by Society of Dyers and Colourists and the American Association of Textile Chemists and

Colorists .

Colour coordinates and colour differences are expressed using the internationally standardized CIELAB tristimulus values : a* = red-green (+,-) b* = yellow-blue (+,-)

L* = lightness (light = 100)

C* = chroma H* = hue (angle of 0° = red, 90° = yellow, 180° = green, 270° = blue), and the colour differences DeltaE*, DeltaH*, DeltaC*, DeltaL*, Deltaa*, and Deltab*, together with an identification number of the sample.

The hue angle is measured when the dye or pigment is deposited on white cloth. It is preferred that the hue angle is between 260 and 340°, preferably 270 to 315 °. This hue angles reflects the blue/violet colour that is provided to the cloth thereby imparting a perception of whiteness.

The hue angle measurements are taken with UV-excluded.

This internationally accepted system has been developed by CIE ("Commission Internationale de 1 ' Eclairage") . It is for example part of DIN 6174: 1979-01 as well as DIN 5033-3: 1992-07.

It is within the scope of the invention to have a mixture of a direct dye, other acid dyes, hydrophobic dyes, pigments and a DANSA dye. This does not preclude the presence of other classes of dye.

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 it is preferred that the shading dyes are co-granulated. When the dyes are used in a granular format, to reduce spotting, it is preferred that the shading dyes granules contain a non-ionic surfactant or a polyvinylalcohol polymer, a polyethylene glycol or glycerol. AIl dye levels refer to pure dye.

DANSA DYE The laundry treatment composition may comprise a single DANSA dye or a mixture thereof.

With respect to the DANSA dyes described above, preferred DANSA dyes have the following subsituents.

Preferably, R is selected from the group consisting of: H; CH₃ and C2H5, most preferably R is H.

Preferably, Y is para substituted to the azo bond. Y is preferably selected from NO₂, CN, I, Br, Cl, F, H, OCOR₂, NHCOR₃, most preferably Y is NO₂.

Preferably, R₂, R3, R₄, and R₅ are independently selected from CH₃ or C₂H₅.

Preferably, X is selected from SO₂N (C₂H₅) -Ar, SO₂N (CH₃) -Ar, SO₂-Ar, wherein Ar is phenyl or methyl substituted phenyl group .

Preferred DANSA dyes are acid violet 14, acid violet 11 and acid blue 117.

Most preferably the DANSA dye is acid blue 117.

The DANSA dye is present in the formulation at levels of 0.00001 to 0.1 wt%, preferably 0.0005 to 0.05 wt%, most preferably 0.001 to 0.006 wt%. In a preferred embodiment of the invention, the main wash formulation contains further shading dyes selected from hydrophobic dyes, most preferably disperse violet 26, disperse violet 28, disperse violet 77, solvent violet 13 or disperse violet 27. These dyes give benefits to synthetic fibres such as elastane and polyester. The hydrophobic dyes are preferably blue or violet.

The hydrophobic dyes when present are preferably present at a level of 0.0001 to 0.1% and most preferably at a level of 0.0005 to 0.005 wt%.

In a preferred embodiment of the invention, the main wash formulation contains further shading dyes selected from direct violet and direct blue dyes.

In this embodiment the acid dye 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 be provided to the consumer.

DANSA dyes have advantage over triphenylmethane dyes in that they are more stable to high pH. 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 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; anthraquinone; phthalocyanine; benzodifuranes ; quinophthalones; azothiophenes; azobenzothioazoles 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.

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, 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 example as listed by the European Union in directive 76/768/EEC Annex 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, 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 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.

Preferred 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 Blue 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 35, 36, 40, 41, 45, 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, 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.

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 570.

Solvent violet 13 is most preferred.

PIGMENTS

Organic pigments are described in industrial Organic Pigments', Wiley VCH 2004 by W.Herbst and K. Hunger. Dyes are organic chemicals that are soluble in their application medium. Pigments are inorganic or organic particles that are insoluble in their application medium.

When pigments are present they are preferably present at levels of 0.0001 to 0.1%, preferably 0.0005 to 0.005 wt%.

Inorganic pigments such as pigment blue 29 or pigment pigment violet 15 may be used, however organic pigments are preferred.

Preferred pigments are pigment blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 4, 5, 7, 9, 10, 10:1, 11, 12, 13, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 20, 21, 22, 23, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 56, 57, 58, 59, 60, 61, 61:1, 62, 63, 64, 65, 66, 67, 69, 71, 72, 73, 74, 75, 79, 80, 83 and pigment violet 1, 1:1, 1:2, 2, 3, 3:1, 3:3, 3:4, 5, 5:1, 7:1, 8, 9, 11, 12, 13, 14, 15, 16, 18, 19, 23, 25, 27, 28, 29, 31, 32, 35, 37, 39, 41, 42, 43, 44, 45, 47, 48, 50, 54, 55 and 56.

More Preferred organic pigments are pigment violet 1, 1:1,

1:2, 2, 3, 5:1, 13, 23, 25, 27, 31, 37, 39, 42, 44, 50 and

Pigment blue 1, 2, 9, 10, 14, 18, 19, 24:1, 25, 56, 60, 61, 62, 66, 75, 79 and 80.

More preferred pigments are pigment violet 3, 13, 23, 27, 37, 39, pigment blue 14, 25, 66 and 75.

The most preferred is pigment violet 23.

DIRECT DYE

When a direct violet or direct blue dye is present it is preferably present at levels of 0.00001 to 0.001%, preferably 0.0005 to 0.0003%.

Direct violet and direct blue dyes are preferred. Preferably the dye are bis-azo or tris-azo dyes. The carcinogenic benzidene based dyes are not preferred.

Bis-azo copper containing dyes such as direct violet 66 may be used.

Most preferably the direct dye is a direct violet of the following structures: R^2

or

R₂

wherein : ring D and E may be independently naphthyl or phenyl as shown;

Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;

R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R3 and R4 are independently selected from: hydrogen and Cl-

C4-alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, C1-C4- alkyl and Cl-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.

SURFACTANT The composition comprises from 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. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.

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 example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are Ce to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl Cio to Ci₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cu to Ci₅ alkyl benzene sulphonates and sodium C12 to Cis alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .

Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16 to Cis primary alcohol sulphate together with a C12 to Ci₅ primary alcohol 3 to 7 EO ethoxylate.

The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system. In another aspect which is also preferred the surfactant may be a cationic such that the formulation is a fabric conditioner .

CATIONIC COMPOUND

When the present invention is used as a fabric conditioner it needs to contain a cationic compound.

Most preferred are quaternary ammonium compounds.

It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain.

It is preferred if the quaternary ammonium compound has the following formula:

R2

I ₊

R1-N-R3 X I R4 in which R¹ is a C12 to C22 alkyl or alkenyl chain; R², R³ and R⁴ are independently selected from Ci to C₄ alkyl chains and X^~ is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.

A second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R¹ and R² are independently selected from C12 to C22 alkyl or alkenyl chain; R³ and R⁴ are independently selected from Ci to C₄ alkyl chains and X^~ is a compatible anion. A detergent composition according to claim 1 in which the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2:1.

Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble) .

It is preferred if the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.

The cationic compound may be present from 1.5 wt % to 50 wt % of the total weight of the composition. Preferably the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.

The softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more preferably from 2 to 40%, most preferably from 3 to 30% by weight.

The composition optionally comprises a silicone.

FLUORESCENT AGENT The composition preferably comprises a fluorescent agent

(optical brightener) . Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3- sulfophenyl) -2H-napthol [ 1 , 2-d] triazole, disodium 4,4'- bis { [ (4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1,3,5- triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium 4, 4 ' -bis { [ (4-anilino-6-morpholino-l, 3,5-triazin-2-yl) ] amino } stilbene-2-2' disulfonate, and disodium 4, 4 '-bis (2- sulfostyryl) biphenyl .

PERFUME

Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

EXPERIMENTAL

The acid dyes used have the following structures

Example 1 Acid dyes were tested for shading benefit by separately washing cotton cloth at room temperature, in 1.8g/L of a base washing powder which contained: 18% NaLAS, 73% salts

(silicate, sodium tri-poly-phosphate, sulphate, carbonate) , 3% minors including perborate, fluorescer and enzymes, remainder impurities and water. A liquor to cloth of with a 100:1 was used, the washes lasted for 30 mins, and were conducted with and without the addition of 200 part per billion of the shading dye. All dyes were used as received. Following the wash, the cloths were rinsed then dried. The colour of the cloth was then assessed using a reflectometer

(UV excluded for all measurements) and expressed as the ΔE value relative to cloth washed without dye. The colour of the cloth was expressed in CIELAB colour space as the a*

(red-green axis) and b* (blue-yellow axis) values.

The dyes tested and results are given in the table below for cotton .

As can be seen from the results all dyes show some deposition to the cotton reflected by the change in a* and b* values. Acid violet 14, acid violet 128 give a true blue/violet shade. Acid black 1 and acid blue 116 give a green blue colour (i.e., a large positive change in Δa* = a* (control) - a* (dye) )

Example 2 The experiment of example 1 was repeated using nylon fabric The results are shown below.

Acid black 1, and acid violet 14 show very low deposition to nylon. Acid Violet 128 and acid blue 116 shows strong deposition to nylon.

Example 3

Exemplary Granular Laundry Formulations A, B, C, D

Enzyme levels are given as percent pure enzyme. Levels of direct violet 9, solvent violet 13 and Sulfonated Zn Pthalocyanine photobleach are given as pure dye. NI (7EO) refers to R- (OCH₂CH₂) _nOH, where R is an alkyl chain of C12 to C15, and n is 7. The formulations are prepared by adding direct violet 9, acid violet 7 and the Sulfonated Zn Pthalocyanine photobleach into the slurry which is then spray dried. Alternatively, the dyes and photobleach may be added via post-dosed MgSO₄ granules.

The solvent violet 13 was dissolved in non-ionic surfactant (7EO) and granulated onto bentonite clay, to give a granule containing 0.2wt% dye. This was post-dosed to the formulation.

Claims

We Claim :

1. A laundry treatment composition comprising:

(a) from 2 to 70 wt% of a surfactant;

(b) from 0.005 to 2 wt % of a fluorescent agent;

(c) from 0.00001 to 0.1 wt% of a DANSA dye selected from:

Y is selected from: NO₂; CN; I; Br; Cl; F; H; OCOR₂; NHCOR₃; R₄; R5O; and, NR₆R7, wherein R₂, R₃, R₄, and R₅ are independently selected from a branched or linear Cl to C7- alkyl chain and Re and R₇ are independently selected from: H; a branched or linear Cl to C7-alkyl chain that is unsubstituted or is substituted by groups independently selected from: OH; Cl; F; OCOCH_3; COOCH₃; OCOC₂H₅; and, COOC₂H₅; and, X is selected from: H; SO₂N(R₈)COCH₃; SO₂N (R₈) -Ar; and SO₂-Ar, wherein Ar is an aromatic group and R₈ is H, CH₃ or C₂H₅, with the proviso that the Y ring does not carry a negatively charged group or salt thereof.

2. A laundry treatment composition according to claim 1, wherein R is selected from the group consisting of: H; CH₃, and C₂H₅.

3. A laundry treatment composition according to claim 2, wherein R is H.

4. A laundry treatment composition according to any preceding claim, wherein Y is para substituted to the azo bond

5. A laundry treatment composition according to any preceding claim, wherein Y is selected from NO2, CN, I, Br, Cl, F, H, OCOR₂, NHCOR₃.

6. A laundry treatment composition according to claim 5, wherein Y is NO₂.

7. A laundry treatment composition according to any preceding claim, wherein R₂, R₃, R₄, and R₅ are independently selected from CH₃ or C₂H₅.

8. A laundry treatment composition according to any preceding claim, wherein X is selected from SO₂N (C₂H₅) -Ar, SO₂N (CH₃) -Ar, SO₂-Ar, wherein Ar is phenyl or methyl substituted phenyl group.

9. A laundry treatment composition according to any preceding claim, wherein the DANSA dyes is selected from the group consisting of: acid violet 14, acid violet 11 and acid blue 117.

10. A domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of a DANSA dye as defined in any one of claims 1 to 9, the aqueous solution comprising from 1 ppb to 1 ppm of the dye, and from 0 ppb to 1 ppm of another dye or pigment selected from: pigments, hydrophobic dyes and direct dyes; and, from 0.1 g/L to 3 g/L of a surfactant; and,

(ii) rinsing and drying the textile.