LAUNDRY TREATMENT COMPOSITIONS

Description

TECHNICAL FIELD

[0001] The present invention relates to laundry treatment compositions that comprise a dye.

BACKGROUND OF THE INVENTION

[0002] WO02/10327, to Unilever, discloses the use of sodium chloride to reduce staining of fabrics.

[0003] US 6,696,400, to Unilever, discloses a speckle composition for use in particulate laundry detergent compositions comprising a porous granular carrier, and at least 0.01 wt % photobleach based on the active ingredient the composition being layered with a finely divided high carrying capacity particulate material and/or a water-soluble material.

[0004] US 3 748 093 discloses a spray dried granule compostion for increasing the apparent whiteness of laundry to a human eye.

[0005] Dyes are used in detergent powders in order to provide colouring of the powder or shading benefits to white fabrics. One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.

SUMMARY OF THE INVENTION

[0006] We have found that the use of non-ionic surfactants may be applied to non-ionic surfactant soluble dyes in order to reduce and/or prevent undesired spotting of fabrics by the dye under wash conditions. In particular, the present invention is applicable to dyes that are substantive to fabrics.

[0007] In one aspect the present invention provides a granule comprising:

(i) between 5 to 40 wt% of a non-ionic surfactant having dissolved therein between 0.0001 to 5% wt % of a dye, wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt%;

(ii) between 20 to 90 wt% of a solid carrier;

(iii) between 0 to 20 wt% of a binder; and,

(iv) between 0 to 1 wt% of a photo-bleach,
wherein the dye is selected from: a hydrophobic dye; a hydrolysed reactive dye; an acid dye; and a direct dye, and wherein the acid dye is selected from:

blue and violet acid dyes of structure

where at least one of X and Y must be an aromatic group, preferably both, the aromatic groups may be a substituted phenyl 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 phenyl group and Y is a phenyl group;

red acid dyes of structure:

where B is a napthyl 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;
groups the following structures:

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;
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; groups of the following structures:

wherein:

X is selected from the group consisting of -OH and -H2;

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;
wherein the direct dye is selected from:

tris-azo direct blue dyes of the formula:

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 phenyl 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;
and,
bis-azo direct violet dyes of the formula:

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 sulphonate group and may be mono or disubstituted by methyl groups.

[0008] Preferably the granule comprises between 10 to 2.5 wt% of a non-ionic surfactant

[0009] Preferably the binder is present in the range 2 to 10 wt%.

[0010] Preferably the amount of dye dissolved in the non-ionic surfactant is in the range between 0.1 to 2 wt%. Preferably the dye has a solubility in the non-ionic surfactant of at least 0.1 wt%, more preferably 1 wt %, and even more preferably at least 5 wt%.

[0011] The solubility of the dye referred to herein is that to be measured at 25 °C.

[0012] It is preferred that the dye has a visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm. The most preferred is a dye or a mixture thereof that have the visual appearance as blue or violet. Preferably the dyes are those substantive to a fabric, in particular cotton and polyester.

[0013] In another aspect the present invention provides a laundry composition comprising a granule as defined herein and a method of treating a textile.

[0014] In a further aspect the present invention provides a method of granulation comprising the steps of:

(i) dissolving between 0.0001 to 5 wt %, preferably 1 wt %, of a dye in 5 to 40 wt% of a non-ionic surfactant, the dye having a solubility in the non-ionic surfactant of at least 0.1 wt%;

(ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,

(iii) granulating the resultant mixture from step (ii).

[0015] In step (ii) and/or step (iii) it is preferred that a binding agent, other than the non-ionic surfactant, is used.

[0016] A "unit dose" as used herein is a particular amount of the laundry treatment composition used for a type of wash, conditioning or requisite treatment step. The unit dose may be in the form of a defined volume of powder, granules or tablet or unit dose detergent liquid.

DETAILED DESCRIPTION OF THE INVENTION

Non-Ionic Surfactant Soluble Dye

[0017] The dye or mixture of dyes used in the granule of the present invention need to have a solubility % in the non-ionic surfactant, or mixture thereof, of at least 0.1 wt%.

[0018] The dye individually or as a mixture of dyes preferably have the visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm, most preferably from 570nm to 630nm. This visual effect provides the aesthetic appearance of blue to violet-blue which in turn the consumer perceives as whiteness. Preferred dyes for shading polyester are hydrophobic dyes and preferred dyes for shading cotton are: hydrolysed reactive dyes; acid dyes; and direct dyes.

[0019] The dyes found below may be used individually or in mixture with the present invention and are provided, as example, but are preferred dyes.

HYDROPHOBIC DYE

[0020] 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.

[0021] Many examples of hydrophobic dyes are found in the classes of solvent and disperse dyes.

[0022] 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.

[0023] 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.

[0024] Preferred azo 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-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.

[0025] Preferred anthraquinone hydrophobic 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, 33, 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.

[0026] Other preferred (non-azo) (non-anthraquinone) hydrophobic 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.

HYDROLYSED REACTIVE DYE

[0027] 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.

[0028] A marked advantage of reactive dyes over direct dyes is that their chemical structure is much simpler, their absorption 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.

[0029] 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.

[0030] 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.

[0031] 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-.

[0032] 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 heteroatom, having at least one -OH substituent covalently bound to the heteroaromatic ring, and

[0033] It is preferred that the anchor group is of the form:





wherein:

n takes a value between 1 and 3;

X is selected from the group consisting of: -Cl, -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:

[0034] Preferably, the chromophore is selected from the group consisting of: azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine.

[0035] Preferably, the chromophore is linked to the hydrolysed anchor by a bridge selected from the group consisting of: - NA-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, and -N=N-.

[0036] 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

[0037] 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 DYES

[0038] Examples of these dyes are direct violet 5, 9, 11, 31, and 51. Further examples of these dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and 120. Preferably the dye is direct violet 9.

Mixed Fibre Dye Mixtures

[0039] When a garment is of mixed fibre, e.g., polyester cotton, dyes that are substantive to each respective fibre are preferred because otherwise even whiteness across the fibre threads is not maintained. In this regard, the granules may comprise different dyes or a mixture of dyes such that a laundry composition comprising the granules of the present invention comprise between 0.001 to 0.01 wt % of a hydrophobic dye for shading polyester and/or between 0.001 to 0.01 wt % of one or more other dyes selected from cotton substantive shading dyes of the group consisting of: hydrolysed reactive dye; acid dye; and direct dye. The level of dye found in the laundry composition is provided by the dye in the granule as defined herein. With respect to the above, the total dye in the laundry composition is most preferably in the range between 0.001 to 0.01 wt %.

[0040] It is preferred that the dye(s) has a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 nm. Tuning of levels of the respective dyes in the composition will be such that dye deposition to the polyester and cotton will be aesthetically matched. It is preferred that the dyes have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm. A combination of dyes may be used which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester or cotton of from 550nm to 650nm, preferably from 570nm to 630nm. This may be provided, for example by mixing a red and green-blue dye to yield a blue or violet shade. A specific example for the acid dyes is a mixture of acid red 17, acid red 88, acid red 51, and/or acid red 73 with acid black 1 and/or acid blue 25. The same spectral quantities are required for both the cotton and polyester substantive dyes.

The Non-Ionic Surfactant

[0041] Preferred non-ionic surfactants are, for example, polyethoxylated alcohols, ethoxylated alkyl phenols, anhydrosorbitols, and alkoxylated anhydrosorbitol esters. An example of a preferred nonionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol". Examples of preferred Neodols are Neodol 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with about 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide, and Neodol 45-7, a C14-15 mixture with about seven moles of ethylene oxide. Other nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those, manufactured and marketed by Union Carbide Corporation under the Trademark Tergitol, octyl phenoxy polyethoxy ethanols sold by Rohm and Haas under the Trademark Triton, and polyoxyethylene alcohols, such as Brij 76 and Brij 97, trademarked products of Atlas Chemical Co. The hydrophilic lipophilic balance (HLB), is preferably below about 13, and more preferably below 10.

[0042] Where an agglomeration process is used, and preferably where zeolite and/or clay is the carrier, it is preferred that a ratio of carrier to surfactant falls within the range of about 1:1 to 10:1, more preferably about 2:1 to 5:1. It is within the scope of the invention to use mixtures of non-ionic surfactants. Most preferably the non-ionic surfactant is an ethoxylated surfactant.

THE CARRIER

[0043] 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), clay and minerals; most preferably clay. The preferred clay is bentonite.

THE GRANULE

[0044] The granule is preferably 180 to 1000 microns in maximum width. This is deflected by the ability of the granule to pass through a graded sieve.

FLUORESCENT AGENT

[0045] The granule 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 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-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.

PHOTOBLEACH

[0046] The granule may also comprise a photo-bleach which is a compounds that absorbs light in the range 290 to 750nm. On absorption of light the photobleach produces reactive species such as singlet oxygen or radicals, with high quantum yields (>0.05), that can bleach stains. Examples of photobleaches are radical photoinitiators, such as vitamin K3 and singlet oxygen producing dyes
such as metallated phthalocyanines (marketed by CIBA under the TINOLUX tradename).

THE LAUNDRY DETERGENT COMPOSITION

[0047] The granule of the present invention may be the laundry detergent composition per se. Conversely and preferably, the granule of the present invention may be mixed with other adjuncts and carriers to make up the laundry detergent composition. These other adjuncts and carriers may include, as will as components listed above, non-ionic, cationic and anionic surfactants, builders, enzymes, antifoam agents, soil release polymers, sodium percarbonate, activators, transition metal catalysts, chelants, dye transfer inhibition polymers and brighteners. It is preferred that a laundry detergent composition comprising the dye containing granule is such that the dye level contribution from the granule in the total detergent composition is between 0.00005 to 0.01 wt%, preferably 0.001 to 0.01 wt%.

Experimental

Example 1

[0048] Acid Black 1 was dissolved in COCO 7EO nonionic surfactant to give a 1 wt%. The dye/NI solution (2.5 g) was added to 10g bentonite clay powder and mixed thoroughly. At this level the mixture is still a free-flowing powder. The resultant powder was then granulated with 3 g of a 40% solution of Sokalan CP5 polymer solution. The resultant granules were then dried in an oven at 80 C, and finally sieved to give granules in the range 180 to 1000 microns.

[0049] The dry composition of these granules, granules A, was:

Component	wt (g)	% by weight
Dye	0.025g	0.18
NI	2.475	18.1
Bentonite	10g	73.0
CP5	1.2 g	8.8

[0050] Comparable granules without non-ionic were created by mixing 0.025 g of dye with 10 g bentonite and then granulating the mixture with 4 g of CP5 solution. The resulting granules were again dried at 80 C and finally sieved to 180 to 1000 microns.

[0051] The dry composition of the granules, granules B, are therefore:

Component	wt (g)	% by weight
Dye	0.025	0.215
Bentonite	10g	86.0
CP5	1.6g	13.8

Example 2

[0052] The granules of Example 1 were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 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.

[0053] A 20 x 20cm piece of white bleached woven non-mercerised cotton was placed in a solution of water, such that the cloth was flat and the liquor to cloth ration was 3:1. 10g of the powder was spread on the cloth and left for 30 minutes. Then the cloth was thoroughly rinsed, dried and the number of visible dye spots counted. The results are shown below.

[0054] Powder with Granule A had 62 spots.

[0055] Powder with Granule B had 385 spots.

[0056] The dye granule with non-ionic showed substantially less spotting.

Example 3

[0057] The experiment of Example 1 and 2 were repeated except using direct violet 51 as the dye.

[0058] The results are shown below.

[0059] Powder with Granule A type had 2 spots.

[0060] Powder with Granule B type had 78 spots.

[0061] The dye granule with non-ionic (A type), showed substantially less spotting.

Example 4

[0062] The granules C and D, described below, were made in an analogous manner to Example 1, except with different levels of components. In all cases acid black 1 was the dye used. For granule E, the bentonite was replaced by zeolite (4A).

Granule C

Component	wt (g)	% by weight
Acid Black 1	0.025	0.16
Nonionic	4.975	31.4
Bentonite	10	63.1
CP5	0.84	5.3

Granule D

Component	wt (g)	% by weight
Acid Black 1	0.05g	0.32
Nonionic	4.95g	31.3
Bentonite	10g	63.1
CP5	0.84g	5.3

Granule E

Component	wt (g)	% by weight
Acid Black 1	0.069	0.22
Nonionic	6.83	22.1
Zeolite 4A	24	77.7

Example 5

[0063] The experiment of Example 2 was repeated using the granules created in Example 5.
Powder with Granule C type had 54 spots.
powder with Granule D type had 62 spots
Powder with Granule E type had 123 spots.

[0064] Granule C and D contain approximately twice the level of non-ionic as granule A (Example 1), but the spotting is similar. Granule D has double the concentration of dye compared to Granule C, (and hence is preferably be dosed in a laundry detergent composition at half the weight) but has similar loading. Granule E on zeolite shows less spotting than granule B, without non-ionic but more than the clay granules.

Example 6

[0065] To check relative performance of the dye granules, in terms of even colour delivery to cotton, a 60 ml solution of 1 g/L base powder with 0.5 g/L of the respective granules was created. In this 2 g of woven cotton cloth was washed, rinsed, dried and compared to cotton washed with out addition of the dye granules using a reflectance spectrometer and expressing the difference in colour as delta E.

[0066] The results are given in the Table below.

Granule	Delta E
A	5.2
B	5.0
C	3.5
D	6.9
E	5.4

[0067] It should be noted that in the experiment for Granule D, there is twice as much dye added as for the others.

[0068] The granules with the lower level of non-ionic, A and E function as well in terms of even colour delivery to the cloth as that for the granule without non-ionic (B). The higher level of non-ionic granules, C and D deliver less colour per weight dye.

Example 7

[0069] Solvent Violet 13 was dissolved in COCO 7EO nonionic surfactant to give a 1%wt solution. The dye/NI solution (2.5 g) was added to 10g bentonite clay powder and mixed thoroughly. At this level the mixture is still a free-flowing powder. The resultant powder was then granulated with 3 g of a 40% solution of Sokalan CP5 polymer solution as binder. The resultant granules were then dried in an oven at 80 C, and finally sieved to give granules in the range 180 to 1000 microns.

[0070] The dry composition of these granules was:

Component	wt (g)	% by weight
Dye	0.025g	0.18
NI	2.475	18.1
Bentonite	10g	73.0
CP5	1.2 g	8.8

Example 8

[0071] The experiment of example 7 was repeated, except Solvent Violet 13 was initially dissolved in COCO 3EO nonionic surfactant to give a 1 wt% solution.

Example 9

[0072] Mixtures of solid Solvent violet 13 and coco 7EO non-ionic surfactant was prepared to give 1 %wt dye. This mixture was heated in glass vessels to 80 C in a laboratory oven. This mixtures melted to form dye solutions which were then poured onto zeolite A24 carrier solid in a Sirman high 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.

Component	wt (g)	% by weight
SV13 Dye	0.4	0.29
NI7EO	39.6	28.9
Zeolite A24	100	71.4

[0073] The resultant granules were sieved to remove oversized materials (>1000um) and stored in sealed containers.

Example 10

[0074] Analogous experiments to example 9 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 granule created had the following composition accordingly.

Component	wt (g)	% by weight
DB79:1 Dye	0.2	0.14
NI7EO	39.8	28.9
Zeolite A24	100	71.4

[0075] The granules of examples 6 to 10 show low spotting and good delivery of dye to polyester.

[0076] Additional granules similar to those of examples 7 and 8 were prepared except sodium carbonate was used instead of zeolite. Granules similar to example 9 were created except a mixture (1:2) of zeolite/light soda ash was used as a carrier material.

[0077] The granules of examples 7 to 10 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.

[0078] The granules of examples 7 to 10 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% zeolile 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.

Claims

1. A granule comprising:

(i) between 5 to 40 wt% of a non-ionic surfactant having dissolved therein between 0.0001 to 5% wt % of a dye, wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt%;

(ii) between 20 to 90 wt% of a solid carrier;

(iii) between 0 to 20 wt% of a binder; and,

(iv) between 0 to 1 wt% of a photo-bleach,
wherein the dye is selected from: a hydrophobic dye; a hydrolysed reactive dye; an acid dye; and a direct dye, and wherein the acid dye is selected from:

blue and violet acid dyes of structure

where at least one of X and Y must be an aromatic group,
preferably both, the aromatic groups may be a substituted phenyl 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 phenyl group and Y is a phenyl group;

red acid dyes of structure:

where B is a naphthyl 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;
groups the following structures:

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;
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; groups of the following structures:

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;
wherein the direct dye is selected from:

tris-azo direct blue dyes of the formula:

where at least two of the A, B and C naphthyl 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 phenyl 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;
and,
bis-azo direct violet dyes of the formula:

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 sulphonate group and may be mono or disubstituted by methyl groups.

2. A granule according to claim 1, wherein the granule comprises between 10 to 25 wt% of a non-ionic surfactant.

3. A granule according to claim 1 or 2, wherein the solid carrier is insoluble in water and surfactants.

4. A granule according to any preceding claim, wherein the dye is substantive to a fabric and has a visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm.

5. A granule according to any preceding claim, wherein the binder is present in the range 2 to 10 wt%.

6. A granule according to any preceding claim, wherein the carrier is selected from zeolite, clay and minerals.

7. A granule according to claim 6, wherein the carrier is selected from bentonite, zeolite 4A and zeolite MAP.

8. 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.

9. A granule according to any preceding claim, wherein the ratio of carrier to surfactant from about 1:1 to 10:1.

10. A granule according to claim 9, wherein the ratio of carrier to surfactant from about 2:1 to 5:1.

11. A granule according to any one of claims 1 to 10,
wherein the dye is a mixture of a hydrophobic dye and a dye selected from the group consisting of: a hydrolysed reactive dye; an acid dye; and a direct dye.

12. A granule according to any preceding claim, wherein the hydrophobic dye is a solvent or disperse dye.

13. A granule according to any one of claims 1 to 10,
wherein the hydrophobic dye is selected from: disperse blue 79:1, solvent black 3, solvent violet 13, solvent blue 59, solvent blue 35, solvent red 24, disperse red 1, disperse blue 3, and disperse blue 106.

14. A granule according to any one of claims 1 to 10,
wherein the dye is selected from: acid black 24, and 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, direct violet 9 and acid violet 17.

15. A granule according to claim 14, wherein the dye is direct violet 9.

16. 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 0.00005 to 0.01 wt%.

17. A laundry detergent composition comprising the granule according to claim 16, wherein the dye level contribution from the granule in the total detergent composition is between 0.001 to 0.01 wt%.

18. A method of granulation comprising the steps of:

(i) dissolving between 0.0001 to 1% wt % of a dye in 5 to 40 wt% of a non-ionic surfactant, that dye having a solubility in the non-ionic surfactant of at least 0.1 wt %;

(ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,

(iii) granulating the resultant mixture from step (ii).

Ansprüche

1. Granulat, umfassend:

(i) zwischen 5 und 40 Gewichts-% eines nicht-ionischen Tensids, das darin zwischen 0,0001 und 5 Gewichts-% eines Farbstoffs gelöst hat, wobei der Farbstoff eine Löslichkeit in dem nicht-ionischen Tensid von wenigstens 0,01 Gewichts-% hat;

(ii) zwischen 20 und 90 Gewichts-% eines festen Trägers;

(iii) zwischen 0 und 20 Gewichts-% eines Bindemittels und

(iv) zwischen 0 und 1 Gewichts-% eines Fotobleichmittels, wobei der Farbstoff ausgewählt ist aus: einem hydrophoben Farbstoff; einem hydrolysierten Reaktivfarbstoff; einem Säurefarbstoff und einem Direktfarbstoff, und wobei der Säurefarbstoff ausgewählt ist aus:

blauen und violetten Säurefarbstoffen der Struktur

worin wenigstens eines von X und Y, vorzugsweise beide, eine aromatische Gruppe sein muss, wobei die aromatischen Gruppen eine substituierte Phenyl- oder Naphthyl-Gruppe sein können, die mit nicht-wassersolubilisierenden Gruppen, zum Beispiel Alkyl- oder Alkyloxy- oder Aryloxy-Gruppen, substituiert sein kann, X und Y nicht mit wassersolubilisierenden Gruppen, zum Beispiel Sulfonaten oder Carboxylaten, substituiert sein dürfen, wobei am bevorzugtesten ist, wenn X eine Nitrosubstituierte Phenyl-Gruppe ist und Y eine Phenyl-Gruppe ist;
roten Säurefarbstoffen der Struktur:

wobei B eine Naphthyl-Gruppe ist, die mit nicht-wassersolubilisierenden Gruppen, zum Beispiel Alkyl- oder Alkyloxy- oder Aryloxy-Gruppen, substituiert sein kann, B nicht mit wassersolubilisierenden Gruppen, zum Beispiel Sulfonaten oder Carboxylaten, substituiert sein darf;
Gruppen der folgenden Strukturen:

worin:
das Naphthyl mit zwei SO₃-Gruppen in einer der folgenden ausgewählten Orientierungen am Ring substituiert ist: 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, und 4,3;
B eine Aryl-Gruppe, ausgewählt aus Phenyl und Naphthyl, ist, wobei die Aryl-Gruppe mit einer Gruppe substituiert ist, die unabhängig ausgewählt ist aus: einer -NH₂-Gruppe; einer -NH-Ph-Gruppe; einer -N=N-C6H5-Gruppe; einer -N=N-C10H7-Gruppe; einem oder mehreren -OMe und einem oder mehreren -Me;
Gruppen der folgenden Strukturen:

worin:

X ausgewählt ist aus der Gruppe, bestehend aus -OH und -NH2;

R ausgewählt ist aus der Gruppe, bestehend aus -CH3 und -OCH3;

n eine ganze Zahl ist, ausgewählt aus 0, 1, 2 und 3; und

einer der Ringe A, B und C mit einer Sulfonat-Gruppe substituiert ist;
wobei der Direktfarbstoff ausgewählt ist aus:
blauen Triazo-Direktfarbstoffen der Formel:

worin wenigstens zwei der Naphthyl-Ringe A, B und C mit einer Sulfonat-Gruppe substituiert sind, der Ring C an der Position 5 mit einer NH₂ oder NHPh-Gruppe substituiert sein kann, X ein Phenyl- oder Naphthyl-Ring ist, der mit bis zu 2 Sulfonat-Gruppen substituiert ist und an Position 2 mit einer OH-Gruppe substituiert sein kann und auch mit einer NH₂ oder NHPh-Gruppe substituiert sein kann; und violetten Bisazo-Direktfarbstoffen der Formel:

worin Z H oder Phenyl ist, der Ring A vorzugsweise mit einer Methyl- und Methoxy-Gruppe an den durch Pfeile gekennzeichneten Positionen substituiert ist, der Ring A auch ein Naphthyl-Ring sein kann, die Gruppe Y ein Phenyl- oder Naphthyl-Ring ist, der mit einer Sulfonat-Gruppe substituiert ist und mit Methyl-Gruppen mono- oder di-substituiert sein kann.

2. Granulat nach Anspruch 1, wobei das Granulat zwischen 10 und 25 Gewichts-% eines nicht-ionischen Tensids umfasst.

3. Granulat nach Anspruch 1 oder 2, wobei der feste Träger in Wasser und Tensiden unlöslich ist.

4. Granulat nach einem vorangehenden Anspruch, wobei der Farbstoff substantiv für ein Gewebe ist und einen visuellen Effekt auf das menschliche Auge als ein Einzelfarbstoff hat, der eine Peak-Absorptionswellenlänge an einer Textilie von 550 nm bis 650 hat.

5. Granulat nach einem vorangehenden Anspruch, wobei das Bindemittel im Bereich von 2 bis 10 Gewichts-% vorliegt.

6. Granulat nach einem vorangehenden Anspruch, wobei der Träger aus Zeolith, Ton und Mineralien ausgewählt ist.

7. Granulat nach Anspruch 6, wobei der Träger aus Bentonit, Zeolith 4A und Zeolith MAP ausgewählt ist.

8. Granulat nach einem vorangehenden Anspruch, wobei das Bindemittel ausgewählt ist aus der Gruppe, bestehend aus einem Polyacrylat, Polyethylenglykol und Polyacrylat/Maleat-Copolymer.

9. Granulat nach einem vorangehenden Anspruch, wobei das Verhältnis von Träger zu Tensid von etwa 1:1 bis 10:1 ist.

10. Granulat nach Anspruch 9, wobei das Verhältnis von Träger zu Tensid von etwa 2:1 bis 5:1 ist.

11. Granulat nach einem der Ansprüche 1 bis 10, wobei der Farbstoff ein Gemisch aus einem hydrophoben Farbstoff und einem Farbstoff ist, der ausgewählt ist aus der Gruppe, bestehend aus: einem hydrolysierten Reaktivfarbstoff; einem Säurefarbstoff und einem Direktfarbstoff.

12. Granulat nach einem vorangehenden Anspruch, wobei der hydrophobe Farbstoff ein Lösungsmittel- oder Dispersionsfarbstoff ist.

13. Granulat nach einem der Ansprüche 1 bis 10, wobei der hydrophobe Farbstoff ausgewählt ist aus: Dispersionsblau 79:1, Lösungsmittelschwarz 3; Lösungsmittelviolett 13, Lösungsmittelblau 59, Lösungsmittelblau 35, Lösungsmittelrot 24, Dispersionsrot 1, Dispersionsblau 3 und Dispersionsblau 106.

14. Granulat nach einem der Ansprüche 1 bis 10, wobei der Farbstoff ausgewählt ist aus: Säureschwarz 24, Säureblau 25, Säureblau 29, Säureschwarz 1, Säureblau 113, Säurerot 17, Säurerot 51, Säurerot 73, Säurerot 88 und Säurerot 87, Säurerot 91, Säurerot 92, Säurerot 94, Direktviolett 9 und Säureviolett 17.

15. Granulat nach Anspruch 14, wobei der Farbstoff Direktviolett 9 ist.

16. Waschmittel, umfassend das Granulat, wie es in einem vorangehenden Anspruch definiert ist, wobei der Farbstoff-Konzentrationsbeitrag aus dem Granulat in dem gesamten Waschmittel zwischen 0,00005 und 0,01 Gewichts-% liegt.

17. Waschmittel, umfassend das Granulat nach Anspruch 16, wobei der Farbstoff-Konzentrationsbeitrag aus dem Granulat in dem gesamten Waschmittel zwischen 0,001 und 0,01 Gewichts-% liegt.

18. Granulierungsverfahren, umfassend die Schritte:

(i) Lösen von zwischen 0,0001 und 1 Gewichts-% eines Farbstoffs in 5 bis 40 Gewichts-% eines nicht-ionixhen Tensids, wobei der Farbstoff in dem nicht-ionischen Tensid eine Löslichkeit von wenigstens 0,1 Gewichts-% hat;

(ii) Mischen der Lösung von Farbstoff und nicht-ionischem Tensid mit zwischen 20 und 90 Gewichts-% eines festen Trägers und

(iii) Granulieren des resultierenden Gemisches aus Schritt (ii).

Revendications

1. Granule comprenant :

(i) entre 5 et 40 % en poids d'un agent tensioactif non ionique dans lequel sont dissous entre 0,0001 et 5 % en poids d'un colorant, où le colorant a une solubilité dans l'agent tensioactif non ionique d'au moins 0,01 % en poids ;

(ii) entre 20 et 90 % en poids d'un support solide ;

(iii) entre 0 et 20 % en poids d'un liant ; et

(iv) entre 0 et 1 % en poids d'un agent de photo-blanchiment,
où le colorant est choisi parmi : un colorant hydrophobe ; un colorant réactif hydrolysé ; un colorant acide ; et un colorant direct, et où le colorant acide est choisi parmi :

les colorants acides bleus et violets de structure

où au moins l'un de X et Y doit être un groupe aromatique, de préférence, les deux, les groupes aromatiques peuvent être un groupe phényle ou
naphtyle substitué, qui peut être substitué par des groupes non solubilisants dans l'eau tels que des groupes alkyle ou alkyloxy ou aryloxy, X et Y peuvent ne pas être substitués par des groupes solubilisants dans l'eau tels que des groupes sulfonate ou carboxylate, de manière préférée entre toutes, X est un groupe phényle substitué par nitro et Y est un groupe phényle ; les colorants acides rouges de structures :

où B est un groupe naphtyle qui peut être substitué par des groupes non solubilisants dans l'eau tels que des groupes alkyle ou alkyloxy ou aryloxy, B peut ne pas être substitué par des groupes solubilisants dans l'eau tels que des groupes sulfonate ou carboxylate ;
des groupes des structures suivantes :

dans lesquels :
le naphtyle est substitué par les deux groupes SO₃^- dans l'une des orientations sélectionnées suivantes autour du cycle : 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, et 4,3 ;
B est un groupe aryle choisi parmi les groupes phényle et naphtyle, le groupe aryle étant substitué par un groupe indépendamment choisi parmi : un groupe -NH₂ ; un groupe -NH-Ph ; un groupe -N=N-C₆H₅ ; un groupe -N=N-C₁₀H₇ ; un ou plusieurs -OMe ; et un ou plusieurs -Me ;
les groupes des structures suivantes :

dans lesquels :
X est choisi dans le groupe consistant en -OH et -NH₂ ;
R est choisi dans le groupe consistant en -CH₃ et -OCH₃ ;

n est un nombre entier choisi parmi 0, 1, 2 et 3 ; et
l'un des cycles A, B et C est substitué par un groupe sulfonate ;
où le colorant direct est choisi parmi :

les colorants bleus directs tris-azo de formule :

où au moins deux des cycles naphtyle A, B et C sont substitués par un groupe sulfonate, le cycle C peut être substitué en position 5 par un groupe NH₂ ou NHPh, X est un cycle phényle ou naphtyle substitué par jusqu'à 2 groupes sulfonate et peut être substitué en position 2 par un groupe OH et peut également être substitué par un groupe NH₂ ou NHPh ; et
les colorants violets directs bis-azo de formule :

où Z est H ou un groupe phényle, le cycle A est de préférence substitué par un groupe méthyle et méthoxy aux positions indiquées par les flèches, le cycle A peut également être un cycle naphtyle, le groupe Y est un cycle phényle ou naphtyle, qui est substitué par un groupe sulfonate et peut être mono- ou di-substitué par des groupes méthyle.

2. Granule selon la revendication 1, dans lequel le granule comprend entre 10 et 25 % en poids d'un agent tensioactif non ionique.

3. Granule selon la revendication 1 ou 2, dans lequel le support solide est insoluble dans l'eau et les agents tensioactifs.

4. Granule selon l'une quelconque des revendications précédentes, dans lequel le colorant est direct pour un tissu et provoque sur l'oeil humain l'effet visuel d'un seul colorant ayant une longueur d'onde d'absorption pic sur un textile de 550 nm à 650 nm.

5. Granule selon l'une quelconque des revendications précédentes, dans lequel le liant est présent dans la gamme de 2 à 10 % en poids.

6. Granule selon l'une quelconque des revendications précédentes, dans lequel le support est choisi parmi une zéolite, une argile et les minéraux.

7. Granule selon la revendication 6, dans lequel le support est choisi parmi la bentonite, la zéolite 4A et la zéolite MAP.

8. Granule selon l'une quelconque des revendications précédentes, dans lequel le liant est choisi dans le groupe consistant en poly(acrylate), poly(éthylène glycol) et copolymère de poly(acrylate/maléate).

9. Granule selon l'une quelconque des revendications précédentes, dans lequel le rapport entre support et agent tensioactif vaut d'environ 1:1 à 10:1.

10. Granule selon la revendication 9, dans lequel le rapport entre support et agent tensioactif vaut d'environ 2:1 à 5:1.

11. Granule selon l'une quelconque des revendications 1 à 10, dans lequel le colorant est un mélange d'un colorant hydrophobe et d'un colorant choisi dans le groupe consistant en : un colorant réactif hydrolysé ; un colorant acide ; et un colorant direct.

12. Granule selon l'une quelconque des revendications précédentes, dans lequel le colorant hydrophobe est un colorant solvant ou de dispersion.

13. Granule selon l'une quelconque des revendications 1 à 10, dans lequel le colorant hydrophobe est choisi parmi : bleu de dispersion 79:1, noir solvant 3, violet solvant 13, bleu solvant 59, bleu solvant 35, rouge solvant 24, rouge de dispersion 1, bleu de dispersion 3 et bleu de dispersion 106.

14. Granule selon l'une quelconque des revendications 1 à 10, dans lequel le colorant est choisi parmi : noir acide 24, bleu acide 25, bleu acide 29, noir acide 1, bleu acide 113, rouge acide 17, rouge acide 51, rouge acide 73, rouge acide 88 et rouge acide 87, rouge acide 91, rouge acide 92, rouge acide 94, violet direct 9 et violet acide 17.

15. Granule selon la revendication 14, dans lequel le colorant est le violet direct 9.

16. Composition détergente pour le linge comprenant le granule tel que défini dans l'une quelconque des revendications précédentes, dans laquelle la contribution au taux de colorant du granule dans la composition détergente totale est comprise entre 0,00005 et 0,01 % en poids.

17. Composition détergente pour le linge comprenant le granule selon la revendication 16, dans laquelle la contribution au taux de colorant du granule dans la composition détergente totale est comprise entre 0,001 et 0,01 % en poids.

18. Procédé de granulation comprenant les étapes consistant à :

(i) dissoudre entre 0,0001 et 1 % en poids d'un colorant dans 5 à 40 % en poids d'un agent tensioactif non ionique, le colorant ayant une solubilité dans l'agent tensioactif non ionique d'au moins 0,1 % en poids ;

(ii) mélanger le colorant et la solution d'agent tensioactif non ionique avec entre 20 et 90 % en poids d'un support solide ; et,

(iii) granuler le mélange résultant de l'étape (ii).