ES2368976T3 - DARK COMPOSITION. - Google Patents

Abstract

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

Description

Darkening composition

Field of the Invention

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

Background of the Invention

Many garments turn yellow after multiple washing cycles, reducing the aesthetic value of the garment. In order to maintain the white appearance, darkening dyes can be used. For applications in the main wash, these are preferably blue or violet dyes of the classes of acid reactive dyes, direct or hydrolyzed. During its use a certain number of problems arise, which depend on the structure of the dye.

Direct dyes accumulate after multiple washes, and this can lead to a strong blue or violet color on the garment. To make this over-darkening acceptable, a lower level of dye must be used, which reduces the advantage.

Acid dyes have the advantage that they do not accumulate after multiple washes. However, no single acid dye has been found that shows a high deposit in cotton and provides true blue or violet darkening of the clothing. Many are too green in color for optimal darkening effects. Additionally, many acid dyes that are deposited in cotton are also deposited in nylon and this leads to an over-darkening of the nylon after multiple washes.

GB 1,562,421 describes the industrial dyeing of substrates with Acid blue 117 using glacial acetic acid and perchlorethylene.

EP 0,355,575 describes an aqueous composition comprising a combination of dyes that includes Acid violet 11 and Solvent yellow 2; The composition is intended to prevent the formation of polymer inlays.

WO 2005/003275 describes a treatment composition for a darkening of laundry comprising a surfactant and a dye that has a substantivity for non-mercerized cotton of at least 8%, but has a substantivity for nylon of less than 5%.

Summary of the invention

It has been found that some specific acidic violet mono-azo dyes, formed from components that couple aminonaphtosulfonic acid (DANSA dyes), although deposited well on cotton substrates, are sparsely deposited on nylon and are capable of providing true blue dimming / violet to the cotton substrate.

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

(to)

from 2 to 70% p of a surfactant;

(b)

from 0.005 to 2% p of a fluorescent agent;

35 (c) from 0.00001 to 0.1% p of a DANSA dye selected from: in which R is selected from: H; a linear or branched C1 to C7 alkyl chain; COR1 in which R1 is a linear or branched C1 to C7 alkyl chain and a -SO2Ar group, in which Ar is a methyl substituted phenyl or phenyl group;

And it is selected from: NO2; CN; I; Br; Cl; F; H; OCOR2; NHCOR3; R4; R5O; and NR6R7, in which R2, R3, R4 and R5 are

5 independently selected from a linear or branched C1 to C7 alkyl chain and R6 and R7 are independently selected from H; a linear or branched C1 to C7 alkyl chain that is unsubstituted or substituted with groups independently selected from: OH; Cl; F; OCOCH3; COOCH3; OCOC2H5 and COOC2H5; Y

X is selected from: H; SO2N (R8) COCH3; SO2N (R8) -Ar and SO2-Ar, in which Ar is an aromatic group and R8 is H; CH3 10 or C2H5, provided that the Y ring does not carry a group with a negative charge or a salt thereof.

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

(i) treating a textile material with an aqueous solution of a DANSA dye, comprising the aqueous solution of 1

ppb at 1 ppm of the dye and 0 ppb at 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; Y

(ii) rinse and dry the textile.

Preferably, the method is performed when the aqueous solution is between 10 and 30 ° C. This helps deposit the DANSA coloring. Preferably, the aqueous solution contains from 0.3 to 2.5 g / l of surfactant.

The pH of the organic solution, provided by a unit dose of the laundry treatment composition, is in the range of 2 to 12. Preferably, the pH of the aqueous solution is in the range of 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 in the range of 10 ppb to 200 ppb. If present, the direct dye is preferably present in the range of 2 ppb to 40 ppb.

25 If present, the pigment is preferably present in the range of 10 ppb to 200 ppb. Preferably, the aqueous solution has a resistance of more than 0.01 and, more preferably, more than 0.05. The invention can also be used to improve black and blue garments when washed.

The present invention also extends to a commercial package comprising the laundry treatment composition together with instructions for its use. Photobleaching agents can be used in the present invention. The singlet oxygen photobleach can be

selected from water and water-soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds in which the metal is Zn or Al-Z1 in which Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably, the phthalocyanine has 1-4 SO3X groups covalently bonded thereto in which X is an alkali metal or ammonium ion. These compounds are described in WO 2005/014769 (Ciba).

Detailed description of the invention

Dyes and pigments

The dyes and pigments are included in the “Color Index International” index published by the Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Color coordinates and color differences are expressed using triple stimulus values

CIELAB internationally standardized: a * = red-green (+, -) b * = yellow-blue (+, -) L * = luminosity (light = 100) C * = chrominance H * = tone (angle of 0º = red, 90º = yellow, 180º = green, 270º = blue) and DeltaE * color differences,

DeltaH *, DeltaC *, DeltaL *, Deltaa *, and Deltab *, along with a sample identification number. The pitch angle is measured when the dye or pigment is deposited on white cotton. It is preferred that the

pitch angle is between 260 and 340º, preferably 270 to 315º. This pitch angle reflects the blue / violet color which is proportionate to clothing, thus conferring a perception of whiteness. Tone angle measurements are taken excluding UV. This internationally accepted system has been developed by the CIE entity (“Commission Internationale de l

'Éclairage ”). For example, it is 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, dyes hydrophobes, pigments and a DANSA dye. This does not exclude the presence of other kinds of dyes. The dyes are preferably added to granular products through the suspension of surfactants or to

through subsequently dosed granules. If more than one dye is used for a powder formulation, it is preferred that the darkening dyes be co-granules. When dyes are used in a granular form, to reduce staining, it is preferred

that the dye granules contain a non-ionic surfactant or poly (alcohol polymer) vinyl), a polyethylene glycol or glycerol. All dye levels refer to pure dye. DANSA coloring The laundry treatment composition may comprise a single DANSA dye or a mixture of the

same.

With respect to the DANSA dyes described above, the preferred DANSA dyes have the following substituents. Preferably, R is selected from the group consisting of: H; CH3 and C2H5, most preferably R is H. Preferably, Y is substituted in respect to the azo bond. And it 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 a methyl substituted phenyl or phenyl group.

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% p, preferably 0.0005 to 0.05% p, most preferably 0.001 to 0.006% p.

In a preferred embodiment of the invention, the main wash formulation contains additional darkening 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 provide advantages to Synthetic fibers such as elastane and polyester. The hydrophobic dyes are preferably blue or violet.

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% p.

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

In this embodiment, the acid dye provides a darkening in the first few washes that is visible and pleasant. The direct dye effect is visible only after multiple washes and serves to counteract long-term yellowing. In this way, rejuvenation and maintenance of whiteness can be provided to the consumer.

DANSA dyes have the advantage over triphenylmethane dyes that are more stable at a high pH.

Hydrophobic dye

Hydrophobic dyes are defined as organic compounds with a maximum extinction coefficient of more than 1,000 l / mol / cm in the wavelength range of 400 to 750 nm and because they have no charge in aqueous solution at a pH in the range of 7 to 11. Hydrophobic dyes are devoid of polar solubilizing groups. In particular, the hydrophobic dye does not contain any sulfonic acid, carboxylic acid or quaternary ammonium groups. The chromophore of the dye is preferably selected from the group comprising: azo chromophores, anthraquinone, phthalocyanine; benzodifurans, quinoftalones, azothiophenes; azobenzothiazoles and triphenylmethane. Most preferred are chromophores of azo dyes and anthraquinone.

Many examples of hydrophobic dyes are found in solvent and dispersed dye classes.

The darkening of white garments can be done with any color, depending on the consumer's preference. Blue and violet are particularly preferred obscurators and, consequently, the preferred dyes or mixtures of dyes are those that provide a blue or violet darkening over the white.

A wide range of colorants in suitable solvents and disperses is available. However, detailed toxicological studies have shown that a certain number of these dyes are possible carcinogens, for example, the dispersion blue 1. These dyes are not preferred. The most suitable dyes can be selected from the dyes in solvents and disperses used in cosmetic products. For example, as cited by the European Union in Directive 76/768 / EN Annex IV, part 1. For example, the disperse violet 27 and the solvent violet 13.

The preferred azoic hydrophobic dyes 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 numbers 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 hydrophobic anthraquinone dyes 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-anthraquinone hydrophobic (non-azoic) dyes, 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.

The most preferred is solvent violet 13.

Pigments

Organic pigments are described in the publication "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 at levels of 0.0001 to 0.1%, preferably 0.0005 to 0.005% p.

Inorganic pigments such as pigment blue 29 or 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.

The most preferred organic pigments are pigment blue 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.

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

The most preferred pigment 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 is a bis-azoic or tris-azoic dye. Benzidene-based carcinogen dyes are not preferred.

Dyes containing bis-azoic copper such as direct violet 66 can be used.

Most preferably, the direct dye is a direct blue of the following structures: in which:

rings D and E can independently be naphthyl or phenyl, as shown;

R1 is selected from: hydrogen and C1-C4 alkyl, preferably hydrogen;

R3 and R4 are independently selected from: hydrogen and C1-C4 alkyl, preferably hydrogen or methyl;

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

10 Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 29, direct violet 35, direct violet 40, direct violet 41, direct violet 51 and direct violet 99.

Surfactant

The composition comprises 2 to 70% p of a surfactant, most preferably 10 to 30% p. In general, the nonionic or anionic surfactants of the surfactant system can be chosen from the surfactants described in

15 publication " Surface Active Agents " Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 of Schwartz, Perry & Berch, Interscience 1958, in the current edition of " McCutcheon's Emulsifiers and Detergents " published by the Manufacturing Confectioners Company or in the publication "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably, the surfactants used are saturated.

Non-ionic detergent compounds that can be used include, in particular, the reaction products of

20 compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially alkylene oxide alone or with propylene oxide. Specific non-ionic detergent compounds are condensates of C6 to C22 alkyl-phenol / oxide

ethylene, generally with 5 to 25 EO (ethylene oxide units), that is, 5 to 25 units of ethylene oxide per molecule and the condensation products of linear or branched, primary or secondary alcohols of C8 to C18 aliphatic with oxide of ethylene, generally 5 to 40 EO.

Suitable anionic detergent compounds that can be used are usually water-soluble alkali metal salts of sulfates and organic sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl part of radicals upper acyls

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfating higher C8 to C18 alcohols, produced, for example from tallow or coconut oil, C9 to C20 alkyl-sodium benzene sulphonates and potassium, particularly C10 to C15 alkyl benzenesulfonates of secondary linear sodium and sodium alkyl glyceryl ether sulfates, especially ethers of alcohols derived from tallow or coconut oil and petroleum derived synthetic alcohols. Preferred anionic detergent compounds are C11 to C15 alkyl sodium benzene sulphonates and C12 alkyl to C18 sodium sulfates. Also applicable are surfactants such as those described in EP-A-328,177 (Unilever), which show desalination resistance and alkyl polyglycolide surfactants described in EP-A 070.074 and alkyl monoglycosides.

Preferred surfactant systems are mixtures of active materials such as anionic and non-ionic detergents, in particular the groups and examples of anionic and non-ionic surfactants indicated in EP-A-346,995 (Unilever). A surfactant system which is a mixture of an alkali metal salt of a C16 to C18 primary sulfate alcohol together with a C12 to C15 primary alcohol ethoxylate of 3 to 7 EO is especially preferred.

The non-ionic detergent is preferably present in amounts of more than 10%, for example, 25 to 90% p of the surfactant system. Anionic surfactants may be present, for example in amounts in the range of about 5% to about 40% p of the surfactant system.

In another aspect that is also preferred, the surfactant may be cationic, so that the formulation is a fabric conditioner.

Cationic compound

When the present invention is used as a fabric conditioner, it is necessary that it contain a cationic compound.

Most preferred are quaternary ammonium compounds.

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

It is preferred that the quaternary ammonium compound have the following formula:

wherein R1 is a C12 to C22 alkyl or alkenyl chain; R2 R3 and R4 are independently selected from C1 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 moride.

A second class of materials for use with the present invention are those of quaternary ammonium of the above structure in which R1 and R2 are independently selected from a C12 to C22 alkyl or alkenyl chain;

R3 and R4 are independently selected from C1 to C4 alkyl chains and X- is a compatible anion.

A detergent composition according to claim 1 wherein the ratio of cationic material (ii) to anionic surfactant (iv) is at least 2: 1.

Other suitable quaternary ammonium compounds are described in EP 0.239.910 (Procter and Gamble).

It is preferred that the ratio of cationic to non-ionic surfactant is 1: 100 to 50:50, more preferably 1:50 to

20:50

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

The softening material is preferably present in an amount of 2 to 60% by weight of the total composition, more preferably 2 to 40%, most preferably 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 commercially available. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, sodium salts. The total amount of fluorescent agent or agents used in the composition is generally 0.005 to 2% p, more preferably 0.01 to 0.1% p. Preferred classes of fluorescents are: diestyryl biphenyl compounds, for example, Tinopal (registered trademark) CBS-X, di-amino-stilbene di-sulfonic acid, for example, pure Tinopal DMS Xtra and Blankophor (registered trademark (HRH and pyrazoline compound, for example, Blankophor SN Preferred fluorescents are: (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] sodium triazole, 4,4'-bis {[(4 -anilino-6- (Nmethyl-N-2-hydroxyethyl) -amino-1,3,5-triazin-2-yl)] amino} -stilbene-2,2'-disulfonate disodium, 4,4'-bis {[(4-Anilino-6morpholino-1,3,5-triazin-2-yl)] amino} -stilbene-2,2'-disulfonate disodium and 4,4'-bis (2-sulfoestyryl) diphenyl disodium .

Fragrance

Preferably, the composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3% p, most preferably 0.1 to 1% p. Many suitable examples of perfumes are provided in the entity 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 part

The acid dyes used have the following structures: Example 1

Acid dyes were tested for the benefit of dimming separately by washing cotton clothes at room temperature in 1.8 g / l of a base washing powder containing: 18% NaLAS, 73% salts (silicate, tri-polyphosphate of sodium, sulfate, carbonate), 3% of minor components that include perborate, contrast agent and enzymes and other impurities and water. A liquid to clothing ratio of 100: 1 was used, the washings lasted 30 minutes and were performed with and without the addition of 200 parts per 1 billion of the darkening dye. All dyes were used as received. After washing, the clothes were rinsed and then dried. Next, the color of the clothes was assessed using a reflectometer (UV excluded for all measurements and expressed as the ΔE value relative to the washed clothes without dye. The color of the clothes was expressed in CIELAB color space as the values of a * (red-green axis) and b * (blue-yellow axis).

The dyes tested and the results are provided in the following Table for cotton.

Colorant

to* b *

Witness (without dye)

-0.3 1.25

Acid Black 1

-3.58 -2.06

Acid violet 128

-0.31 -0.70

Acid blue 116

1.52 -3.36

Acid violet 14

0.38 0.39

5 As can be seen from the results, all dyes show some deposit in the cotton reflected by the change in the values of a * and b *. The acid violet 14, acid violet 128 provide a true blue / violet darkening. Acid black 1 and acid blue 116 provide a green-blue color (i.e. a large positive change in Δa * = a * (control) -a * (dye))

Example 2

The experiment of Example 1 was repeated using a nylon cloth. The results are shown below.

Colorant

to* b *

Witness (without dye)

-0.77 1.43

Acid Black 1

-0.71 1.34

Acid violet 128

1.34 -0.23

Acid blue 116

-2.3 -1.99

Acid violet 14

-0.71 1.25

Acid black 1 and acid violet 14 show very little deposit in nylon. Acid violet 128 and acid blue 116 show a strong deposit in nylon. Example 3 Examples of granular casting formulations A, B, C, D

Formulation

TO B C D

Nalas

fifteen twenty 10 14

NI (7EO)

- - - 10

Na tripolyphosphate

7 fifteen - -

Soap

- - - 2

Zeolite A24

- - - 17

Sodium silicate

5 4 5 one

Sodium carbonate

25 twenty 30 twenty

Sodium sulfate

40 33 40 22

Carboxymethyl cellulose

0.2 0.3 - 0.5

Sodium chloride

- - - 5

Lipase

0.005 0.01 - 0.005

Protease

0.005 0.01 - 0.005

Amylase

0.001 0.003 - -

Cellulase

- 0.003 - -

Contrast agent

0.1 0.15 0.05 0.3

Direct viloet 9

0.0002 0.00015 - 0.0001

Solvent violet 13

- 0.002 - 0.001

Acid violet 14

0.002 0.002 - -

Acid blue 117

- - 0.004 0.006

Sulphonated Zn Phthalocyanine Photobleach

0.002 0.004 - -

Water / impurity / minor components

rest rest rest rest

Enzyme levels are provided as a percentage of pure enzyme. The levels of direct violet 9, solvent violet 13 and sulfonated Zn phthalocyanine photobleach are provided as pure dye. NI (7EO) refers to R- (OCH2CH2) nOH, in which R is a C12 to C15 alkyl chain and n is 7.

The formulations are prepared by adding direct violet 9, acid violet 7 and the Zn phthalocyanine photobleach

5 sulfonated to the suspension which is then spray dried. Alternatively, the dyes and the photobleach can be added through granules of MgSO4 subsequently dosed.

Solvent violet 13 was dissolved in non-ionic surfactant (7EO) and granulated in bentonite clay, to provide a granule containing 0.2% p dye. This was subsequently dosed to the formulation.

Claims (10)

1. A laundry treatment composition comprising:

(to)

from 2 to 70% p of a surfactant;

(b)

from 0.005 to 2% p of a fluorescent agent;

(C)

0.00001 to 0.1% p of a DANSA dye selected from:

in which R is selected from: H; a linear or branched C1 to C7 alkyl chain; COR1 in which R1 is a linear or branched C1 to C7 alkyl chain and a -SO2Ar group, in which Ar is a methyl substituted phenyl or phenyl group; And it is selected from: NO2; CN; I; Br; Cl; F; H; OCOR2; NHCOR3; R4; R5O; and NR6R7, in which R2, R3, R4 and R5 are 10 independently selected from a linear or branched C1 to C7 alkyl chain and R6 and R7 are independently selected from H; a linear or branched C1 to C7 alkyl chain that is unsubstituted or substituted with groups independently selected from: OH; Cl; F; OCOCH3; COOCH3; OCOC2H5 and COOC2H5; Y X is selected from: H; SO2N (R8) COCH3; SO2N (R8) -Ar and SO2-Ar, in which Ar is an aromatic group and R8 is H; CH3 15 or C2H5, provided that the Y ring does not carry a group with a negative charge or a 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.

Four.

A laundry treatment composition according to any one of the preceding claims, wherein Y is substituted in respect to the azo bond.

5.

A laundry treatment composition according to any one of the preceding claims, wherein Y is selected from NO2, CN, I, Br, Cl, F, H, OCOR2 or NHCOR3.

6.

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

7.

A laundry treatment composition according to any one of the preceding claims, wherein R2, R3, R4, and R5 are independently selected from CH3 or C2H5.

8.

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

9.

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

10.

A domestic method for treating a textile material, the method comprising the steps of:

(i)

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

(ii)

rinse and dry the textile.