BRPI0612701A2 - granule, laundry detergent composition, and granulation methods, and for treating a new or dirty textile article - Google Patents

Abstract

GRANULES, DETERGENT COMPOSITION FOR WASHING CLOTHES, AND GRANULATION METHODS, AND FOR TREATING A NEW OR DIRTY TEXTILE The present invention provides a granule comprising one or more variations of solubilized dyes in a solvent. The bead, used in laundry compositions, has reduced staining properties.

Description

"GRANULY, DETERGENT COMPOSITION FOR DEROUP WASH, AND GRANULATION METHODS, AND TO TREAT A NEW OR DIRTY TEXTILE"

TECHNICAL FIELD

The present invention relates to laundry treatment compositions comprising a dye.

BACKGROUND OF THE INVENTION

Many synthetic garments lose their whiteness after repeated use. Whiteness can be maintained through the use of graded decorating hues.

SUMMARY OF THE INVENTION

Dyes are difficult to dissolve / disperse in water. Therefore methods for granulating dyes are required so that they can be released from washing powder detergents. The present invention provides such granules.

The method involves dissolving the dye in a non-aqueous but water-miscible solvent to provide a solution. This solution is then mixed with a carrier material and possibly a binder to create suitable dosage granules within a detergent powder.

In one aspect the present invention provides a granule comprising: (i) from 5 to 40% by weight of a water-miscible non-volatile solvent having been dissolved from 0.0001 to 4% by weight of a dye, wherein the dye has a solubility in the water. solvent of at least 0.01 wt.%, preferably at least 0.5 wt.%, the water miscible non-volatile solvent other than a nonionic surfactant;

(ii) from 20 to 90% by weight of a solid carrier;

(iii) from 0 to 50% by weight of a binder (preferably from 0 to 20% by weight); and

(iv) from 0 to 1% by weight of a photo bleach. In another aspect the present invention provides a degranulation method comprising the steps of:

(i) dissolving from 0.0001 to 4 wt% of a dye in 5 to 40 wt% of a water miscible nonvolatile solvent, the dye has a solubility in the water miscible nonvolatile solvent of at least 0.1 wt% to form a solution of the dye in the water-miscible non-volatile solvent;

(ii) taking the dye solution from step (i) and mixing with from 20 to 90% by weight of a solid carrier, the nonvolatile water-miscible solvent other than a nonionic surfactant; and,

(iii) granulating the resulting mixture from step (ii) to form a post-dose granule for a base powder.

The granule is then used to form a commercial product by taking from 0.1 to 5% by weight of granule and mixing as a post-dose with a 100% laundry wash base.

In another aspect the present invention provides a method for treating a new or dirty textile article comprising the steps of:

(i) adding the granule to a stirred aqueous medium;

(ii) treating the textile article with the aqueous medium; and,

(iii) rinse the treated textile article; and dry the textile article.

A unit dose as used herein is a particular amount of the composition used for a type of wash. The unit dose may be in the form of a defined volume of powder, granules or tablet or a unit dose detergent liquid.

DETAILED DESCRIPTION OF THE INVENTION

NON-VOLTABLE WATER MISCIBLE SOLVENT

The solvent may be a solid or liquid at ambient temperature, and compatible with inclusion in a detergent formulation. It should not be volatile, so that when included in a detergent powder it will keep the dye in a dissolved state. Non-volatile for the purpose of this application is defined as having a volatility less than or equal to water. More preferably, nonvolatile means having a saturated vapor pressure at 25 ° C and atmospheric pressure (101325 Pa) below 3000 Pa, and more preferably below 100 Pa.

The solvent should be readily miscible with water so that at least 1% by weight of the solvent water solution can be created.

Suitable solvents include surfactants, fatty acids, soaps and polymers. The surfactants may be isotropic or contain a dispersed water phase, for example, anionic surfactants and aqueous anionic surfactant pastes, fatty acids, polyethylene glycol polymers. Preferably they should be able to function as granule binders. So that when in contact with fine solid particles they promote particle growth through agglomeration, or expansion and solidification on the surface of larger particles to create a resistant coating. However, additional binding materials such as aqueous polymer solutions may also be added to create resistant granules. Preferred solvents for dissolving the dye are charged species. The most preferred solvents for dissolving dyes are charged surfactants.

The dye is soluble in the solvent so that a solution of from 0.01 to 10 wt% can be created, preferably from 0.05 to 1 wt%.

The solvent does not include nonionic surfactants. Those skilled in the art will be aware of what a nonionic surfactant is and references are made in "Surface Activer Agents" Vol. 1, by Schwartz & Perry, Interscience1949, Vol. 2 by Schwartz, Perry & Berch, Intercience 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.

In addition to the above references, the following are provided with respect to nonionic solvents. Nonionic surfactants are, for example, polyethylene glycol fatty alcohol ether or fatty alcohol ethoxylates, alkylphenol ethoxylates, ethylene oxide and depropylene oxide copolymers, amine oxides, alkylamines, alkanolamines, polyglycerol alkyl esters, polyglycosides , and N-alkylglucosamides fatty acid. A typical class of nonionic surfactant is the formula H (CH2) mO [CH2CH2O] nH, where mél2al5ené3a9; of the alkyl chain in the ClOa C18 range.

Typical dye suppliers can be found in the color index, and include Clariant, Dystar, Ciba & BASF.

Preferred dyes are those which deposit on the textile articles and provide a hue to the textile article so that the hue angle h in the CIELAB system of the hue of the textile article is between 220 ° and 320 °, more preferably between 250 ° and 290 °. A detailed description of the hue angle can be found on pg. 57 of Color Chemistry 3rd edition by H. Zollinger published by Wiley-VCH. Preferred dyes are violet blue.

Preferred dyes are hydrophobic dyes, those which are based on polyester.

Hydrophobic dyes are defined as organic compounds with a maximum extinction coefficient greater than 1000L / mol / cm in the wavelength range 400 to 750 ran and which are discharged into an aqueous solution with a pH in the range of 7 to 11. Hydrophobic dyes are devoid of solubilizing polar groups. In particular the hydrophobic dye does not contain any sulfonic acid, carboxylic acid, or quaternary ammonium groups. The dye chromophore is preferably selected from a group comprising: chromophores azo, methine, pyrazol, naptoquinone, anthraquinone, phthalocyanine; and triphenylmethane. Most preferred are azo and anthraquinone dye chromophores.

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

The nuance of white garments can be done with any color depending on consumer preference. Blue and Violet are particularly preferred and consequently preferred dyes or dye mixtures are some which have a blue or violet shade on white polyester.

A wide range of suitable solvent and dispersed dyes is available. However detailed toxicological studies have shown that a number of such dyes are possible carcinogens, such dyes are not preferred.

Preferred mono azo dyes are of the formula:

<formula> formula see original document page 6 </formula>

Wherein R 3 and R 4 are optionally substituted by C 2 to C 12 alkyl chains optionally having ether (-O-) or deester bonds thereto, the chain being optionally substituted with -Cl, -Br, -CN, -NO 2, and -SO 2 CH 3; and, D denotes an aromatic or heteroaromatic group. Preferably D is selected from a group consisting of: azothiophenes, azobenzothiazoles and azopyridones.

It is preferred that R3 is -CH2CH2R5 and R4 is -CH2CH2R6 and R5 and R6 are independently selected from a group consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl . Preferred aryls are -C6H5 and C10H7. The following is an example of a class of mono-azoprefered dyes:

<formula> formula see original document page 7 </formula>

wherein XeY are independently selected from a group consisting of: -H5 -Cl, -Br, -CN, -NO2, and -SO2CH3;

A is selected from -H, CH 3, -Cl and -NHCOR;

B is selected from -H, -OCH 3, -OC 2 H 5, and -Cl;

R1 and R2 are independently selected from a group consisting of: -H, -CN, -OH, -OCOR, -COOR, -aryl; and

R is C1-C8 alkyl

The following are preferred azo dyes: Dispersed blue 10, 11.12, 21, 30, 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, Scattered 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, Dianixviolet cc, and colorants m CAS-No's and 42783-06-2, 210758-04-L6, 104366-25-8, 122063-39-2, 167940-11-6, 52239-04-0, 105076-77-5, 84425-43 -4, e87606-56-2. The following are preferred azo dyes: Dispersed blue 250, 354, 364, 366, Violet solvent 8, solvent blue 43, solvent blue 57, Lumogen F Blau Blue 650, and Lumogen F Violet 570.

The dye may be fluorescent.

Preferred anthraquinones are those of the following structure (I):

<formula> formula see original document page 8 </formula>

wherein R1, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH2, -NHR9, and NO2, so that the maximum of a single group -N02 and the maximum of two -H are present as substituents of R1, R4, R5, and R8; wherein R9 is a branched or straight C1-C7 alkyl chain or a substituted aryl group or aryl groups, or a branched or straight C1-C7 alkyl chain optionally substituted by an -OH group; R2, R3, R6, and R7 may be selected from -H, -F, -Br, -Cl, SO3 aryl or NO2, and -OR10, where R10 is selected from a group consisting of branched or linear C1-C7 alkyl or aryl ; and, R2 and R3 may be linked together to form a non-aromatic five-membered ring of the form -C (= O) N (HR11) C (= X) -, wherein X is O or NH and R11 is selected from one. group consisting of C1-C6 alkyl optionally substituted with alkoxy groups.

It is preferred that the branched or straight alkyl chain of R 9 and R 10 have less than six carbon atoms. It is preferred that R1, R4, R5, and R8 are independently selected from groups consisting of -H, -OH, -NH2, and NO2, and R2, R3, R6, and R7 are selected from -H, F, Br, Cl. or - NO2, and -Oaryl. It is also preferred that aryl is an optionally substituted phenyl. From R1, R4, R5 and R8 it is more preferred that they are -OH and one is selected from -NH2 and -NHR9. It is preferred that R2, R3, R5, R6 and R7, and R8 are -H5 R1 = -OH, R4 = -NHR9 or -NH2.

It is preferred that R5, R6, R7, and R8 = -H, R1 = R4 = -NH2, R2 = -Oryl, or -Cl.

It is more preferred that R 11 is -CH 2 CH 2 CH 20 Me.

The following are examples of preferred dyes: Violet solvent 11, 13, 14, 15, 15, 26, 28, 29, 30, 31, 32, 33, 34, 26, 37, 38, 40, 41.42, 45, 48 , 59; Solvent blue 11.12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 35, 36.40, 41, 45, 58, 59, 59: 1, 63, 65, 68, 69, 78, 90; Scattered 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; 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.

The composition may also comprise from 0.0001 to 0.1% by weight of one or more other dyes having the same or differentially from a tissue substrate. These include dyes selected from substantial cotton-group dyes of the group consisting of: hydrolyzed reactive dye; acid dye; and direct dye. Hydrolyzed Reactive Dye Reactive dyes may be considered to be made of a chromophore that is attached to an anchor portion. The chromophore may be attached directly to the anchor or via a bridging group. The chromophore serves to provide a color and the anchor to bond with a textile substrate.

A striking advantage of reactive dyes over direct dyes is that their chemical structure is much simpler, their absorption bands are narrower and the dye / nuance is lighter Industrial dyes, K. Hunger ed. Wiley-VCH 2003 ISBN 3-527-30426-6.However, mammal contact with reactive dyes results in irritation and / or sensitization of the respiratory tract and / or skin. In addition, washing conditions are not ideal for dye deposition because the deposition efficiency is low.

With reference to reducing irritation and / or sensitization, it is preferred that each individual anchor group of each reactive dye is hydrolyzed so that the most reactive group (s) of the docent anchor groups are hydrolyzed. In this respect, the term hydrolyzed reactive dye cools both partially and completely hydrolyzed reactive dyes.

The reactive dye may have more than one anchor. If the anchor has more than one anchor, then each and every anchor that contributes to irritation and / or sensitization needs to be hydrolyzed to the extent discussed above.

Hydrolysed dyes comprise a chromophore and an anchor which are co-valent bonds and can be represented as follows: Chromophore-anchor. The bond between the chromophore and an anchor is preferably provided by -NH-CO-, -NH-, NHCO-CH 2 CH 2 -, -NH-CO-, or -N = N-.

Preferably the hydrolyzed reactive dye comprises a covalent bond with the chromophore moiety to an anchor group, the anchor group for agglutinating the anchor group selected from a group consisting of: a heteroaromatic ring, preferably comprising a nitrogen heteroatom having at least one -OH substituent covalently bonded to the heteroaromatic ring, and

<formula> formula see original document page 11 </formula>

It is preferred that the anchor group be of the form:

<formula> formula see original document page 11 </formula>

on what:

η has a value between 1 and 3;

X is selected from a 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 be selected from naphthyl, phenyl, and -CH 3. More preferably the anchor group is selected from a group consisting of:

<formula> formula see original document page 11 </formula>

Preferably, the chromophore is selected from a group consisting of: azo, anthraquinone, phthalocyanine, formazan and tripendioaxazine.

Preferably, the chromophore is attached to the anchor by a bridging selected from a group consisting of: -NH-CO-, -NH-, NHCO-CH 2 CH 2 -, -NH-CO-, and -N = N-.

The most preferred hydrolyzed reactive dyes are Hydrolyzed Reactive 2 Red, Hydrolyzed Reactive Blue 4, Hydrolyzed Reactive Black 5, and Hydrolyzed Reactive Blue 19.

Acid Dye

The following are the preferred classes of acid dyes. The group comprising acid violet and blue dyes

<formula> formula see original document page 12 </formula>

wherein at least one of X and Y must be an aromatic group, preferably both, the aromatic groups may be a substituted benzyl or naphthyl group which may be substituted by water-non-solubilizing groups such as alkyl or alkyloxy or aryloxy groups, XeY may not be Substituted with water-solubilizing groups such as sulfonates or carboxylates, most preferred is where X is a nitro substituted by a groupobenzyl and Y is a benzyl group.

The group comprising red acid structure dyes

<formula> formula see original document page 12 </formula>

where B is a naphthyl or benzyl group that may be substituted by non-water-solubilizing groups such as alkyl or alkyloxy or aryloxy groups, B may not be substituted by water-solubilizing groups such as sulfonates or carboxylates.

The group with the following structures: <formula> formula see original document page 13 </formula>

on what:

naphthyl is substituted by the two SO3- groups in one of the following selected ring orientations: 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 by a group independently selected from: an -NH2 group; a -NH-Ph group; -N = N-C 6 H 5; a group -N = N-C 10 H 7; one or more -OMe; and one or more Me.

The group with the following structures:

<formula> formula see original document page 13 </formula>

on what:

X is selected from a group consisting of -OH and -NH2; R is selected from a group consisting of -CH3 and -OCH3;

N is an integer selected from 0, 1, 2 and 3; One of the rings A, B and C is replaced by a sulfonate group.

The following are examples of preferred acid dyes that may be used with the present invention: acid black 24, acid blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17, acid red 51, acid red 73, acid red 88 , and acid red 87, acid red 91, acid red 92, acid red 94, and acid violet 17.Direct Dye

The following are examples of preferred direct dyes that may be used with the present invention:

Preferred direct dyes are selected from a group comprising trisazo direct blue dyes of the formula: where at least two of naphthyl rings A, B and C are substituted by a sulfonate group, ring C may be substituted at position 5 by a group NH 2 or NHPh X is a naphthyl or benzyl ring substituted with up to 2 groupsulfonate and may be substituted at position 2 with an OH group and may also be substituted with an NH 2 or NHPh group.

Other preferred direct dyes are selected from a group comprising bis-azo direct violet dyes of the formula:

<formula> formula see original document page 14 </formula>

where Z is H or phenyl, ring A is preferably substituted by a group methyl and methoxy at the positions indicated by the arrows, ring A may also be a naphthyl ring, group Y is a benzyl or naphthyl ring which is substituted by a sulfate group and may be mono or disubstituted by methyl groups.

Non-limiting examples of these dyes are direct violet 5,7, 9, 11, 31, and 51. Other non-limiting examples of these dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and 120. Preferably the colorant is direct violet 9.THE CARRIER

The carrier may be a water-soluble / surfactant or water-insoluble carrier. Preferred examples of water-soluble carriers / surfactant are sodium carbonate, sodium sulfate, sodium chloride, and sodium citrate. It is preferred however that the carrier be insoluble in water / surfactant and in this respect preferred carriers are zeolite [e.g. zeolite 4A and zeolite MAP (A24)], clay and minerals; most preferably clay. The preferred clay is bentonite or kaolin.

The bead

The granule is preferably 180 to 1000 microns in maximum width. This is reflected by the ability of the bead to pass through a graduated sieve.

BALANCING CARRIERS AND ADJUSTED INGREDIENTS

The granule of the present invention preferably forms from the laundry detergent composition. In this regard, other ingredients may be present in the granule-containing dye and / or other granules or powders present. These include, but are not limited to, enzymes, bleach species, builders, anti-redeposition agents, anti-dye transfer agents, perfumes, transition metal catalysts, dirt release agents and fluorescent agents. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinylpyrrolidone, polyacrylates, citric acid and mixtures thereof.

Bleach Species

The laundry treatment composition may comprise bleach species. Bleach species, for example, may be selected from perborate and percarbonate. These peroxyl species may be further enhanced by the use of an activator, eg TAED orSNOBS. Alternatively or in addition to this, a metal transitioning catalyst may be used with the peroxyl species. The metal-transfer catalyst may also be used in the absence of peroxyl species where bleaching is designed to be via atmospheric oxygen, see for example W002 / 48301.

Photo bleaches, including T-shirt oxygen photo bleaches, can be used with the laundry wash composition. A preferred photo bleach is vitamin K3.

Fluorescent agent

The laundry treatment composition most preferably comprises a fluorescent (optical brightening) agent. Fluorescent agents are well known and a number of such fluorescent agents are commercially available. Commonly, these fluorescent agents are provided and used in the form of their alkali metal salts, for example sodium salts. The total amount of fluorescent agent or agents used in laundry treatment compositions is generally from 0.005 to 2% by weight, more preferably from 0.01 to 0.1% by weight. Preferred classes of fluorescent are: Di-styryl biphenyl compounds, for example Tinopal (Trade Mark) CBS-X, Di-sulfonic acid Di-amine stilbene compounds, for example Tinopal DMS pure Xtra eBlankophor (Trade Mark) HRH, and Pyrazoline compounds e.g. Blankophor SN. Preferred fluorescent materials are: 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] bringsol sodium, 4,4'bis {[(- anilino-6- (N-methyl -N-2 hydroxyethyl) amino 1,4,5-triazin-2-yl)] amino} stilbene-2,2'-disulfonate, 4,4'-bis {[(4-aniline-6-morpholine-1,2,5- triazin-2-yl)] amino} stilbene-2-2'-disodium disulfonate, and 4,4'-bis (2-sulfosyryl) biphenyl-disisodium.

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

Experimental

Example 1

Mixtures of solid Violet solvent 13 and the following materials were prepared to provide 1% by weight of dye. These mixtures were heated in glass vessels to 80 ° C in a laboratory oven: PEG6000 and lauric acid. These mixtures fused to form decorating solutions which were then poured into either zeolite A24 sodium sulfate or solid barrel carriers in a Sirman high shear mixer, and mixed thoroughly in proportions that maximize agglomeration. As is well known in the art, the addition of very little liquid binder results in agglomeration of only part of the present solids, while excess binder causes the creation of a wet mass or paste.

<table> table see original document page 17 </column> </row> <table>

The resulting granules were sieved to remove oversized materials (> 1000 µm) and stored in sealed containers. Example 2

Experiments analogous to example 3 were repeated except that the scattered blue dye 79: 1 was used. The dye and solvent mixtures were generally at lower concentrations of 0.4 to 0.6% by weight.

Consequently the created granules had the following composition.

<table> table see original document page 18 </column> </row> <table>

Example 3

To compare the performance of the granules from example 1 to 2 the following experiment was performed. 1.8g / L washing powder was dissolved in water. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tripolyphosphate, sulfate, carbonate), the remaining 3% including perborate, fluorescent and enzymes, remaining impurities and water. To this was added a piece of interwoven polyester so that the cloth-scorching liquor was 100: 1. The solution was stirred and the granules added to give 0.2 ppm dye in the solution. The wash solution was then allowed to stir for 30 minutes, the polyester removed, rinsed and dried.

Following this, the color of the polyester was measured using a reflectometer and expressed as the ΔE value relative to a piece of washed polyester. Results are presented in the table below.

<table> table see original document page 18 </column> </row> <table>

Control experiments in the absence of dye presented DE values of 0.2, therefore all granules presented dye release to the polyester fabric.

The exemplified granules of the present invention showed low stain removal properties and good parapolyester dye release.

The granules of the examples were separately added to a wash base powder and thoroughly mixed to give a powder with a final dye level of 0.001 and 0.004 wt%. The ground dust contained 18% NaLAS, 73% salts (silicate, sodium tripolyphosphate, sulfate, carbonate), the remaining 3% including perborate, fluorescent enzymes, remaining impurities and water.

The granules of the examples were separately added to a wash base powder and thoroughly mixed to give a powder with a final dye level of 0.0005 and 0.002 wt%. The ground dust contained 10% NaLAS, 5% nonionic 7EO, 1% soap, 17% A24 zeolite, 12% percarbonate, 4% TAED, 40% salts (disodium sulfate, sodium carbonate), remaining, fluorescent, enzymes, anti-redeposition agents, moisture, perfume, sequestrants, anti-formation, anti-foaming agents and dispersants.

Claims (19)

1.Granule, characterized in that it comprises: (i) from 5 to 40% by weight of a water miscible non-volatile solvent having been dissolved from 0.0001 to 4% by weight of a dye, wherein the dye has a solubility in the solvent of at least 0.01% by weight, the water-miscible non-volatile solvent other than a nonionic surfactant, (ii) from 20 to 90% by weight of a solid carrier, (iii) from 0 to 50% by weight of a binder; and (iv) from 0 to 1% by weight of a photo bleach. Granule according to Claim 1, characterized in that the dye has a solvent solubility of at least 0.5% by weight. Granule according to Claim 1 or 2, characterized in that the solvent is selected from anionic surfactants and aqueous anionic surfactant pastes, fatty acids or polyethylene glycol polymers. Granule according to any preceding claim, characterized in that the solid carrier is insoluble in water and is active. Granule according to any preceding claim, characterized in that the solid carrier is selected from: zeolite, clay and minerals. Granule according to Claim 5, characterized in that the solid carrier is selected from bentonite, zeolite 4A and azeolite A24. A bead according to any preceding claim, characterized in that the dye is essential for a fabric and colors until it has a color with a tint angle of 220 to 320 degrees. Granule according to any preceding claim, characterized in that the binder is selected from a group consisting of a polyacrylate, polyethylene glycol, and a copolymer polyacrylate / maleate. Granule according to any preceding claim, characterized in that the binder is present in a range of 2 to 10% by weight. Granule according to any preceding claim, characterized in that the ratio of solid carrier to solvent is about 1: 1 to 10: 1. Granule according to Claim 10, characterized in that the solid carrier to solvent ratio is about 2: 1 to -5: 1. Granule according to any preceding claim, characterized in that the dye is a hydrophobic dye. Granule according to any preceding claim, characterized in that the hydrophobic dye is a solvent or dispersed dye. Granule according to Claim 12, characterized in that the hydrophobic dye is selected from a group consisting of: dispersed dyes and solvent of blue and violet dyes. Granule according to any one of claims 12 to 12, characterized in that the hydrophobic solvent is selected from: solvent violet 13, scattered violet 27, scattered blue 79: 1. Laundry detergent composition, characterized in that it comprises the granule as defined in any preceding claim, wherein the level of dye contribution from the granule in the total detergent composition is between 0.0005 to 0.1% by weight. 17. Granulation method, characterized in that it comprises the steps of: (i) dissolving from 0.0001 to 4% by weight of a dye to 5 to 40% by weight of a water-miscible non-volatile solvent, the dye tended to have a water-miscible non-volatile solvent solubility of at least -0.1% by weight to form a dye solution in the water-miscible non-volatile solvent, (ii) take the dye solution from step (i) and mix with between 20 to 90% by weight of a solid carrier, the nonvolatile water-miscible solvent other than a nonionic surfactant; and (iii) granulating the resulting mixture from step (ii) to form a post-dose granule for a base powder. A method for producing a laundry detergent powder containing a colorant comprising the steps of: (i) taking from 0.1 to 5% by weight of the product as defined in claim 17 and mixing as a post-dose with 100% laundry washing powder. A method for treating a new or soiled textile article, comprising the steps of: (i) adding the granule as defined in any one of claims 1 to 15 to an agitated aqueous medium; (ii) treating the article textile with the aqueous medium; and (iii) rinsing the treated textile article; and dry the textile article.