LAUNDRY PARTICLE MADE BY EXTRUSION COMPRISING A HUEING DYE AND FATTY ACID SOAP

FIELD OF THE INVENTION

5 The present invention relates to a particle comprising a soap and hueing dye as well as compositions comprising such particles.

BACKGROUND OF THE INVENTION

Attempts have been made to incorporate particles comprising a dye into cleaning

10 compositions, either to provide particular product aesthetics, blueing of the wash water, or even to increase perceived cleaning of white fabrics. When the dye is a hueing dye, the choice of the hueing dye and the way to incorporate it in a composition should be carefully monitored to avoid spotting or staining of the fabrics being laundered and/or to avoid the migration or the bleeding of the hueing dye across the composition which may lead to a rather unattractive composition.

15 WO 2005/003274 relates to laundry treatment compositions which comprise dye which is substantive to cotton. The dye may for example be included in a slurry which is sprayed dried or may be added to granules which are post-added to the main detergent powder. To avoid spotting, WO 2005/003274 teaches to have a concentration of dye in the granules of less than 0.1%.

The present inventors have found that spotting or staining of the fabrics being laundered

20 and migration or bleeding of the hueing dye across a composition could be reduced when the hueing dye is in particles comprising a soap. The particles of the invention can incorporate relatively high levels of hueing dye and enable use of such particles in compositions at relatively high levels without causing substantial staining or spotting and without substantially bleeding or migrating in the composition.

25

SUMMARY OF THE INVENTION

In one embodiment of the present invention, the invention concerns a particle comprising a hueing dye and C8-C ₂ 0 fatty acid soap(s). At least 27.5wt% of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle may be C ₁₆ fatty acid soap(s).

30 The invention also concerns a composition comprising the particles.

The invention also concerns the use of particles according to the invention in a composition to improve the aesthetic appearance of the composition and/or to hue fabrics to be washed without causing spotting of items to be washed and/or without causing bleeding in the composition. The invention also concerns a process to prepare the particle of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The particle of the invention comprises a hueing dye and C ₈ -C ₂₀ fatty acid soap(s). The Particle

The particle of the invention may be part of a composition comprising a plurality of particles according to the invention.

The particles may comprises 50 or 80 or 95% by weight of particles having a particle size distribution (PSD) between 10 μm and 10 000 μm or 5 000 μm, typically between 50 μm and 4000 μm, or between 200 μm and 2000 μm or even from 500 to 1500 μm. Typically, the particles of the present invention have a Mean Particle Size (MPS) between 200 μm and 2000 μm, or of a least 400, 500 or 600 μm and/or of less than 1000 μm or less than 700 μm. The Particle Size Distribution (PSD) and Mean Particle Size (MPS) of the particles of the present invention are measured as indicated below in the test method 1. The particles may have a size distribution span of from about 1.0 to about 10.0, from about 1.05 to about 3, from about 1.1 to about 2, or even from about 1.1 to about 1.5.

The particles may have a bulk density of from about 350 g/1 to about 2000 g/1, from about 500 g/1 to about 1200 g/1, from about 600 g/1 to about 1100 g/1, or even from about 700 g/1 to about 1000 g/1. The bulk density may be measured as indicated in test method 2. The particles may have a median particle aspect ratio of from about 1.0 to about 10.0, from about 1.05 to about 5.0 or 2.0 or 1.5 or even from about 1.1 to about 1.25. The median particle aspect ratio may be measured as indicated in test method 3.

The particles may be coloured or white. By coloured, it should be understood that the particles are not white. The hueing dye

The particle comprises a hueing dye. The particle may comprise at least 0.1 wt%, typically at least 0.2 wt% or 0.5, or 1, or even 2 wt% or 5wt% of hueing dye based on the total weight of the particle. The particle may contain up to 30 wt%, or up to 20 wt%, or up to 10 wt% per weight of a hueing dye. A hueing dye of the present invention may be a water soluble or water dispersible compound.

The particle comprising the hueing dye may be such that the hueing dye present in the particle of the invention is soluble at 25 ⁰ C in a mixture of 1 litre of deionised water and 1 mg, 10 mg, 100 mg, or 1 g of particles of the invention. If the particles are in a detergent or fabric treatment composition, said composition and said particles may be such that the hueing dye present in said composition is soluble at 25 ⁰ C in a mixture of 1 litre of deionised water and 10 mg, 100 mg, 1 g, or 10 g of said composition.

A hueing dye is defined as a dye which upon washing provides white fabrics with a light off-white tint, modifying whiteness appearance and acceptance (e.g. providing aqua, or blue, or violet, or pink hue). The hueing dye may have a substantially intense color as a raw material and may color a fabric by selectively absorbing certain wavelengths of light. Preferred hueing dyes include dyes that are such that the fabrics treated with said hueing dye according to the fabric substantive component test below (test method 4) show an average difference in hue of greater than 0.1, in particular greater than 0.2 or 0.5 units on either the a axis or b axis.

Preferred hueing dye exhibits a hueing efficiency of at least 1, or of at least 2, preferably of at least 5, 10 for example of at least 15. The hueing efficiency of a dye is measured as indicated in test method 5 below and is measured by comparing a fabric sample washed in a solution containing no dye with a fabric sample washed in a solution containing the dye, and indicates if a hueing dye is effective for providing the desired tinting, for example, whitening. Suitable hueing dyes may be hueing dyes described in US 7,208,459.

The principle feature of dyes may be a conjugated system, allowing them to absorb energy in the visible part of the spectra. The most commonly encountered conjugated systems include phthalocyanine, anthraquinone, azo, phenyl groups, referred to as chromophore. Dyes can be, but are not required to be, chosen from the following categories: reactive dyes, direct dyes, sulphur and azoic dyes, acid dyes, and disperse dyes.

The hueing dye may be a photobleach. Photobleaches are molecules which absorb the energy from sunlight and transfer it by reacting with another molecule (typically oxygen) to produce bleaching species (singlet oxygen). Photobleaches generally comprise conjugated rings, and therefore usually present a strong visible color. Typical photobleaches comprises phthalocyanines based on zinc, copper, silicon, or aluminium.

The hueing dye may have the following structure of formula I:

wherein each R ¹ and R ² are independently selected from the group consisting of R, -

[(CH ₂ CR'HO) _x (CH2CR"HO) _y H], and mixtures thereof, wherein R is independently selected from H, Ci -C ₄ linear or branched alkyl, benzyl and mixtures thereof; each R' is independently selected from the group consisting of H, CH ₂ θ(CH ₂ CH ₂ θ) _z H, and mixtures thereof, and each R" is selected from the group consisting of H, CH ₃ , CH ₂ O(CH ₂ CH ₂ O) _Z H, and mixtures thereof; wherein x + y < 5; wherein y > 1; and wherein z = 0 to 5.

The compounds of formula I may be synthesized according to the procedure disclosed in US Patent No. 4,912,203 to Kluger et al.

In particular, the hueing dye of formula I may be one of the following compounds 1-5:

Compound 1

Compound 3

Compound 4

Compound 5

The hueing dye may be a small molecule dye or a polymeric dye. Suitable small molecule dyes include, but are not limited to, small molecule dyes selected from the group consisting of dyes falling into the Colour Index (CI.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof, for example: (1) Tris-azo Direct blue dyes of the formula

where at least two of the A, B and C naphthyl rings are substituted by a sulfonate group, the C ring may be substituted at the 5 position by an NH ₂ or NHPh group, X is a benzyl or naphthyl ring substituted with up to 2 sulfonate groups and may be substituted at the 2 position with an OH group and may also be substituted with an NH ₂ or NHPh group. (2) bis-azo Direct violet dyes of the formula:

where Z is H or phenyl, the A ring is typically 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 may be substituted with one or more sulphonate group(s) and may be mono or disubstituted by methyl groups.

(3) Blue or red Acid dyes of the formula

where at least one of X and Y must be an aromatic group. In one aspect, both the aromatic groups may be a substituted phenyl or naphthyl 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 sulfonates or carboxylates. In another aspect, X is a nitro substituted phenyl group and Y is a phenyl group (4) Red acid dyes of the structure

where B is a naphthyl or phenyl 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 sulfonates or carboxylates. (5) Dis-azo dyes of the structure

OH

x SO ₃ H a or wherein X and Y, independently of one another, are each hydrogen, Ci-C ₄ alkyl or Ci-C ₄ -alkoxy, Ra is hydrogen or aryl, Z is C ₁ -C ₄ alkyl; Ci-C ₄ -alkoxy; halogen; hydroxyl or carboxyl, n is 1 or 2 and m is 0, 1 or 2, as well as corresponding salts thereof and mixtures thereof (6) Triphenylmethane dyes of the following structures

N(CHXH ₈ )-

and mixtures thereof.

The hueing dye may be a small molecule dye selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof.

Suitable small molecule dyes may include small molecule dyes selected from 1,4- Naphthalenedione, 1 - [2- [2- [4- [ [4-(acetyloxy)butyl]ethylamino] -2-methylphenyl]diazenyl] -5 - nitro-3-thienyl]-Ethanone, l-hydroxy-2-(l-naphthalenylazo)-Naphthalenedisulfonic acid, ion(2-), l-hydroxy-2-[[4-(phenylazo)phenyl]azo]-Naphthalenedisulfonic acid, ion(2-), 2-[(lE)-[4-[bis(3- methoxy-3-oxopropyl)amino]-2-methylphenyl]azo]-5-nitro-3-Thi ophenecarboxylic acid, ethyl ester, 2-[[4-[(2-cyanoethyl)ethylamino]phenyl]azo]-5-(phenylazo)-3- Thiophenecarbonitrile, 2-[2-[4-[(2-cyanoethyl)ethylamino]phenyl]diazenyl]-5-[2-(4-n itrophenyl)diazenyl]-3- Thiophenecarbonitrile, 2-hydroxy-l-(l-naphthalenylazo)-Naphthalenedisulfonic acid, ion(2-), 2- hydroxy- l-[[4-(phenylazo)phenyl]azo]-Naphthalenedisulfonic acid, ion(2-), 4,4'-[[4- (dimethylamino)-2,5-cyclohexadien-l-ylidene]methylene]bis[N, N-dimethyl-Benzenamine, 6- hydroxy-5-[(4-methoxyphenyl)azo]-2-Naphthalenesulfonic acid, monosodium salt, 6-hydroxy-5- [(4-methylphenyl)azo]-2-Naphthalenesulfonic acid, monosodium salt, 7-hydroxy-8-[[4- (phenylazo)phenyl]azo]-l,3-Naphthalenedisulfonic acid, ion(2-), 7-hydroxy-8-[2-(l- naphthalenyl)diazenyl]-l,3-Naphthalenedisulfonic acid, ion(2-), 8-hydroxy-7-[2-(l- naphthalenyl)diazenyl]-l,3-Naphthalenedisulfonic acid, ion(2-), 8-hydroxy-7-[2-[4-(2- phenyldiazenyl)phenyl]diazenyl]-l,3-Naphthalenedisulfonic acid, ion(2-), Acid Black 1, Acid black 24, Acid Blue 113, Acid Blue 25, Acid blue 29, Acid blue 3, Acid blue 40, Acid blue 45, Acid blue 62, Acid blue 7, Acid Blue 80, Acid blue 9, Acid green 27, Acid orange 12, Acid orange 7, Acid red 14, Acid red 151, Acid red 17, Acid red 18, Acid red 266, Acid red 27, Acid red 4, Acid red 51, Acid red 73, Acid red 87, Acid red 88, Acid red 92, Acid red 94, Acid red 97, Acid Violet 17, Acid violet 43, Basic blue 9, Basic violet 2, C.I. Acid black 1, C.I. Acid Blue 10, C.I. Acid Blue 290, C.I. Acid Red 103, C.I. Acid red 91, C.I. Direct Blue 120, C.I. Direct Blue 34, C.I. Direct Blue 70, C.I. Direct Blue 72, C.I. Direct Blue 82, C.I. Disperse Blue 10, C.I. Disperse Blue 100, C.I. Disperse Blue 101, C.I. Disperse Blue 102, C.I. Disperse Blue 106: 1, C.I. Disperse Blue 11, C.I. Disperse Blue 12, C.I. Disperse Blue 121, C.I. Disperse Blue 122, C.I. Disperse Blue 124, C.I. Disperse Blue 125, C.I. Disperse Blue 128, C.I. Disperse Blue 130, C.I. Disperse Blue 133, C.I. Disperse Blue 137, C.I. Disperse Blue 138, C.I. Disperse Blue 139, C.I. Disperse Blue 142, C.I. Disperse Blue 146, C.I. Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, I. Disperse Blue 165:1, C.I. Disperse Blue 165:2, C.I. Disperse Blue 165:3, C.I. Disperse Blue 171, C.I. Disperse Blue 173, C.I. Disperse Blue 174, C.I. Disperse Blue 175, C.I. Disperse Blue 177, C.I. Disperse Blue 183, C.I. Disperse Blue 187, C.I. Disperse Blue 189, C.I. Disperse Blue 193, C.I. Disperse Blue 194, C.I. Disperse Blue 200, C.I. Disperse Blue 201, C.I. Disperse Blue 202, C.I. Disperse Blue 205, C.I. Disperse Blue 206, C.I. Disperse Blue 207, C.I. Disperse Blue 209, C.I. Disperse Blue 21, C.I. Disperse Blue 210, C.I. Disperse Blue 211, C.I. Disperse Blue 212, C.I. Disperse Blue 219, C.I. Disperse Blue 220, C.I. Disperse Blue 222, C.I. Disperse Blue 224, C.I. Disperse Blue 225, C.I. Disperse Blue 248, C.I. Disperse Blue 252, C.I. Disperse Blue 253, C.I. Disperse Blue 254, C.I. Disperse Blue 255, C.I. Disperse Blue 256, C.I. Disperse Blue 257, C.I. Disperse Blue 258, C.I. Disperse Blue 259, C.I. Disperse Blue 260, C.I. Disperse Blue 264, C.I. Disperse Blue 265, C.I. Disperse Blue 266, C.I. Disperse Blue 267, C.I. Disperse Blue 268, C.I. Disperse Blue 269, C.I. Disperse Blue 270, C.I. Disperse Blue 278, C.I. Disperse Blue 279, C.I. Disperse Blue 281, C.I. Disperse Blue 283, C.I. Disperse Blue 284, C.I. Disperse Blue 285, C.I. Disperse Blue 286, C.I. Disperse Blue 287, C.I. Disperse Blue 290, C.I. Disperse Blue 291, C.I. Disperse Blue 294, C.I. Disperse Blue 295, C.I. Disperse Blue 30, C.I. Disperse Blue 301, C.I. Disperse Blue 303, C.I. Disperse Blue 304, C.I. Disperse Blue 305, C.I. Disperse Blue 313, C.I. Disperse Blue 315, C.I. Disperse Blue 316, C.I. Disperse Blue 317, C.I. Disperse Blue 321, C.I. Disperse Blue 322, C.I. Disperse Blue 324, C.I. Disperse Blue 328, C.I. Disperse Blue 33, C.I. Disperse Blue 330, C.I. Disperse Blue 333, C.I. Disperse Blue 335, C.I. Disperse Blue 336, C.I. Disperse Blue 337, C.I. Disperse Blue 338, C.I. Disperse Blue 339, C.I. Disperse Blue 340, C.I. Disperse Blue 341, C.I. Disperse Blue 342, C.I. Disperse Blue 343, C.I. Disperse Blue 344, C.I. Disperse Blue 345, C.I. Disperse Blue 346, C.I. Disperse Blue 351, C.I. Disperse Blue 352, C.I. Disperse Blue 353, C.I. Disperse Blue 355, C.I. Disperse Blue 356, C.I. Disperse Blue 357, C.I. Disperse Blue 358, C.I. Disperse Blue 36, C.I. Disperse Blue 360, C.I. Disperse Blue 366, C.I. Disperse Blue 368, C.I. Disperse Blue 369, C.I. Disperse Blue 371, C.I. Disperse Blue 373, C.I. Disperse Blue 374, C.I. Disperse Blue 375, C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 38, C.I. Disperse Blue 42, C.I. Disperse Blue 43, C.I. Disperse Blue 44, C.I. Disperse Blue 47, C.I. Disperse Blue 79, C.I. Disperse Blue 79:1, C.I. Disperse Blue 79:2, C.I. Disperse Blue 79:3, C.I. Disperse Blue 82, C.I. Disperse Blue 85, C.I. Disperse Blue 88, C.I. Disperse Blue 90, C.I. Disperse Blue 94, C.I. Disperse Blue 96, C.I. Disperse Violet 10, C.I. Disperse Violet 100, C.I. Disperse Violet 102, C.I. Disperse Violet 103, C.I. Disperse Violet 104, C.I. Disperse Violet 106, C.I. Disperse Violet 107, C.I. Disperse Violet 12, C.I. Disperse Violet 13, C.I. Disperse Violet 16, C.I. Disperse Violet 2, C.I. Disperse Violet 24, C.I. Disperse Violet 25, C.I. Disperse Violet 3, C.I. Disperse Violet 33, C.I. Disperse Violet 39, C.I. Disperse Violet 42, C.I. Disperse Violet 43, C.I. Disperse Violet 45, C.I. Disperse Violet 48, C.I. Disperse Violet 49, C.I. Disperse Violet 5, C.I. Disperse Violet 50, C.I. Disperse Violet 53, C.I. Disperse Violet 54, C.I. Disperse Violet 55, C.I. Disperse Violet 58, C.I. Disperse Violet 6, C.I. Disperse Violet 60, C.I. Disperse Violet 63, C.I. Disperse Violet 66, C.I. Disperse Violet 69, C.I. Disperse Violet 7, C.I. Disperse Violet 75, C.I. Disperse Violet 76, C.I. Disperse Violet 77, C.I. Disperse Violet 82, C.I. Disperse Violet 86, C.I. Disperse Violet 88, C.I. Disperse Violet 9, C.I. Disperse Violet 91, C.I. Disperse Violet 92, C.I. Disperse Violet 93, C.I. Disperse Violet 93:1, C.I. Disperse Violet 94, C.I. Disperse Violet 95, C.I. Disperse Violet 96, C.I. Disperse Violet 97, C.I. Disperse Violet 98, C.I. Disperse Violet 99, C.I. Reactive Black 5, C.I. Reactive Blue 19, C.I. Reactive Blue 4, C.I. Reactive Red 2, C.I. Solvent Blue 43, C.I. Solvent Blue 43, C.I. Solvent Red 14, C.I.Acid black 24, C.I. Acid blue 113, C.I.Acid Blue 29, C.I.Direct violet 7, C.I.Food Red 14, Dianix Violet CC, Direct Blue 71, Direct blue 75, Direct blue 78, Direct violet 11, Direct violet 31, Direct violet 5, Direct Violet 51, Direct violet 9, Disperse Blue 106, Disperse blue 148, Disperse blue 165, Disperse Blue 3, Disperse Blue 354, Disperse Blue 364, Disperse blue 367, Disperse Blue 56, Disperse Blue 77, Disperse Blue 79, Disperse blue 79:1, Disperse Red 1, Disperse Red 15, Disperse Violet 26, Disperse Violet 27, Disperse Violet 28, Disperse violet 63, Disperse violet 77, Eosin Y, Ethanol 2,2'-[[4-[(3,5-dinitro-2- thienyl)azo]phenyl]imino]bis-, diacetate (ester), Lumogen F Blue 650, Lumogen F Violet 570, N-[2-[2-(3-acetyl-5-nitro-2-thienyl)diazenyl]-5-(diethylamin o)phenyl]-Acetamide, N-[2-[2-(4- chloro-3-cyano-5-formyl-2-thienyl)diazenyl]-5-(diethylamino) phenyl]-Acetamide, N-[5-[bis(2- methoxyethyl)amino] -2- [2-(5 -nitro-2, 1 -benzisothiazol-3 -yl)diazenyl]phenyl] - Acetamide, N- [5 - [bis[2-(acetyloxy)ethyl]amino]-2-[(2-bromo-4,6-dinitrophenyl )azo]phenyl]-Acetamide, Naphthalimide and derivatives thereof, Oil Black 860, Phloxine B, Pyrazole, Rose Bengal, Sodium 6-hydroxy-5-(4-isopropylphenylazo)-2-naphthalenesulfonate, Solvent Black 3, Solvent Blue 14, Solvent Blue 35, Solvent Blue 58, Solvent Blue 59, Solvent Red 24, Solvent Violet 13, Solvent Violet 8, Sudan Red 380, Triphenylmethane, Triphenylmethane and derivatives thereof, or mixtures thereof.

Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof.

In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of fabric-substantive hueing dyes of formula I above available from Milliken (Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of carboxymethyl cellulose (CMC) conjugated with a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM- CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, alkoxylated thiazolium polymeric colourants, and mixtures thereof.

The hueing dye may be part of a dye clay conjugate. Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic

Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 C.I. 42595 conjugate,

Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green Gl C.I. 42040 conjugate, Montmorillonite Basic

Red Rl C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic

Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic

Violet V3 C.I. 42555 conjugate, Hectorite Basic Green Gl C.I. 42040 conjugate, Hectorite Basic

Red Rl C.I. 45160 conjugate, Hectorite C.I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3

C.I. 42555 conjugate, Saponite Basic Green Gl C.I. 42040 conjugate, Saponite Basic Red Rl

C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate and mixtures thereof.

The soap

The particle comprises a soap. Soap is understood to have its ordinary meaning in the art. The particles may comprise from 10 to 99.9% for example from 20 to 95%, or from 50 to 90% or at least 65 or 80% by weight of soap.

The particle comprises C ₈ -C ₂₀ fatty acid soap(s). At least 27.5wt% of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle may be Q ₆ fatty acid soap(s).

The particle may comprise at least 15 or 30 wt%, typically at least 50 wt% or 70, or 80, or 90wt% of C ₈ -C ₂₀ fatty acid soap(s) based on the total weight of the particle. The particle may contain up to 99 wt%, or up to 95 wt%, or up to 90 or 70 wt% per weight of a C8-C ₂ 0 fatty acid soap(s).

The particle may comprise at least 10 wt%, in particular at least 20 wt%, or 25, or 30, or 35, or even 45wt% or 50wt%, of C ₁₆ fatty acid soap(s) based on the total weight of the particle. The particle may contain up to 50 wt%, or up to 40 wt%, or up to 30 or 20 wt% per weight of a C ₁ 6 fatty acid soap(s).

Typically, at least 30wt%, or 32.5, or 35, or 37.5, or 40, or 50wt% of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are C ₁ 6 fatty acid soap(s). Typically, from 0.5% to 4%, in particular from 1 % to 2% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are Cs fatty acid soap(s).

Typically, from 0.5% to 4%, in particular from 1 % to 2% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are Ci ₀ fatty acid soap(s). Typically, from 4% to 16%, in particular from 8 % to 12% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are Ci ₂ fatty acid soap(s).

Typically, from 2% to 8%, in particular from 3.5 % to 5.5% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are C ₁₄ fatty acid soap(s).

Typically, from 0% to 1% by weight of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle is/are C ₁₅ fatty acid soap(s).

Typically, from 27.5% to 50%, in particular from 32.5 % to 40% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are C ₁ 6 fatty acid soap(s).

Typically, from 0% to 2%, in particular from 0 % to 1% by weight of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle is/are C ₁₆ fatty acid soap(s) with the C ₁₆ alkyl chain comprising at least one, in particular one, double bond.

Typically, from 27.5% to 50%, in particular from 32.5 % to 40% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are C ₁ 6 fatty acid soap(s) with the C ₁ 6 alkyl chain comprising no double bond.

Typically, from 0% to 1% by weight of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle is/are Cn fatty acid soap(s).

Typically, from 25% to 53%, in particular from 35% to 50%, typically from 40% to 47% by weight of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle is/are Ci ₈ fatty acid soap(s).

Typically, from 1% to 15%, in particular from 2 % to 10%, typically from 3% to 5% by weight of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are Ci 8 fatty acid soap(s) with the Ci ₈ alkyl chain comprising no double bond.

Typically from 25 % to 40%, or even from 30% to 35.5% by weight, of the total amount of C8-C ₂ 0 fatty acid soap(s) in the particle is/are Ci ₈ fatty acid soap(s) with the Ci ₈ alkyl chain comprising one and only one double bond. Typically, from 3% to 15%, in particular from 5 % to 12%, typically from 7% to 9.5% by weight of the total amount of C ₈ -C ₂₀ fatty acid soap(s) in the particle is/are Ci ₈ fatty acid soap(s) with the Ci ₈ alkyl chain comprising at least two, in particular two, double bonds. The chain length distribution of the fatty acid can be measured by gas chromatography, mass spectrometry, or dynamic mechanical analysis. The level of unsaturation may be measured by the iodine value.

The soap may comprise non-animal soap such as vegetable soap. The soap may comprise fatty acids derived from nut oils, such as coconut, palm kernel, or babassu or may be derived from tallow class fats which may be partly hardened or mixture thereof. In particular, due to their fatty acid chain length distribution, the soap may comprise fatty acids derived from nut oils, such as coconut, palm kernel, or mixture thereof.

The soap may comprise animal soap, for example may comprise a mixture of animal and vegetable soap.

The weight ratio of hueing dye to C ₈ -C _2O fatty acid soap(s) in the particle may be from 0.0005 to 0.1 in particular from 0.002 to 0.04.

The weight ratio of hueing dye to Ci ₆ fatty acid soap(s) in the particle may be from 0.002 to 0.4 in particular from 0.008 to 0.15. Adjunct ingredients

In addition to the hueing dye and the soap, the particle may comprise adjunct ingredients. The particle may comprise at least one adjunct ingredient suitable for use in a detergent composition, for example a laundry detergent composition. The skilled person would preferably chose the nature and the quantity of the adjunct ingredient(s) which provide satisfactory physical properties to the particles, for example providing an excellent balance between low deformability during cutting, good dissolution and frangibility.

The particle may comprise water. The particle may comprise from 0.1 to 20% for example from 1 to 15% or from 2 to 10% or 3 to 8% by weight of water. The particle may comprise more than 4% or more than 5% by weight of water. The particle may comprise less than 5% by weight of water.

The particle may also comprise an inorganic salt, for example from 0.05% to 90%, or even from 0.1% to 75%, or even from 0.5% to 50% and or even from 0.65% to 20% or from 1 to 10% or 5% by weight of an inorganic salt, such as sodium chloride.

The particle may also comprise glycerine, typically from 0.01 % to 10%, or even from 1% to 5% and or even from 2% to 4% by weight of glycerine. The colouring of the particles may be improved with the presence of glycerine.

The particle may comprise a surfactant for example from 0.01% to 90%, or from 1 to 20% or from 2 to 12% or from 5 to 9%, by weight of surfactant. The surfactant may be an anionic surfactant such as an alkyl sulphate or an alkyl sulphonate. Suitable surfactants may be chosen from the one disclosed in the list of adjunct ingredient of the composition comprising the particle.

The particle may comprise a film-forming material. A film-forming material may be a material that is able to form a film when cooling or drying. The film forming material may be a film-forming polymer or a film-forming inorganic salt. The film-forming polymer may be selected from synthetic organic polymers such as polyvinyl alcohol, polyethylene glycols, polyvinylpyrrolidones, polyacetates, polymeric polycarboxylates such as water-soluble acrylate (co)polymers, cationic polymers such as ethoxylated hexamethylene diamine quaternary compounds, starch, carboxymethylcellulose, glucose, sugars and sugar alcohol such as sorbitol, manitol, xylitol and mixtures thereof. The film-forming inorganic salt may be a silicate salt such as sodium silicate.

According to one aspect of the invention, the particle may comprise less than 5% or even less than 1 % and or even 0 % by weight of free fatty acids. The particle may also comprise from 2 to 15% by weight of free fatty acids. While not essential for the purposes of the present invention, the particle may also comprise any of the following adjunct ingredients which may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance cleaning performance or ease of processing to form the particle, for treatment of the substrate to be cleaned, or to modify the aesthetics of the particle as in the case with perfumes, additional colorants or the like. The precise nature of these additional adjunct components, and levels of incorporation thereof, will depend on the physical form of the particle or the nature of the cleaning operation for which they are to be used or for which the composition comprising the extruded particles is to be used. Suitable adjunct materials include, but are not limited to, surfactants such as non-soap surfactant, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, bleach catalysts, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. Suitable examples of such other adjuncts and levels of use may be found in the disclosure below in the part concerning the adjunct ingredients in the composition comprising the particles, as well as in U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl that are incorporated by reference. Process to prepare the particle

The particles of the present invention may be made by any suitable process known in the art. In particular, the particles may be prepared according to a process as follows. The particles may be obtained by a process comprising an attrition step. For example, one or more raw materials, such as the fatty acids, may be heated prior to their mixing with other raw material.

The particles may be obtained by a process comprising a mixing step, in particular a step of mixing the fatty acids with the hueing dye and optionally other ingredients in a mixer, for example a drum mixer or a paddle mixer or a ploughshare mixer.

The particles may be obtained by a process comprising a spraying step, for example, the hueing dye and optionally other ingredients may be sprayed on the fatty acids. Typically the spraying takes place in a fluid bed. Typically, extrusion is understood to mean any process by which a body of material (the feed material) is forced through a die or orifice so as to form a length of extruded material (the first article). The length of the extruded material or of the first article refers to the length of the first article in the direction normal to the cutting plane. The feed material may have substantially the same chemical composition than the extruded material (the first article) and than the extruded particles. In the case of the present invention the extrusion will normally be performed using a commercially available extruder, such as a screw extruder. Commercially available screw extruders typically comprise one or more feeders or hoppers, for storing the feed material prior to extrusion; a barrel which houses one or more screws; and a die through which the material is extruded. The screws are rotated and the material is typically heated and/or kneaded and/or compacted as it is drawn through the barrel. The particle may be extruded at a rotating speed, (the rotating speed of the screw(s)) of from 100 rpm to 500 rpm, for example of from 200 to 300 rpm. Typically, the material is forced through the one or more dies, which are usually situated at the end of the barrel furthest from the one or more feeders. It is preferable to use more than one die as this increases the number of first articles, and thus particles, which can be produced at any one time. In a preferred embodiment of the present invention the extruder die comprises greater than or equal to 50 orifices, preferably greater than or equal to 100 orifices and even more preferably greater than or equal to 200 orifices. The shape of the one or more dies' orifices will determine the cross-section and/or shape of articles extruded therefrom. "Cross-section" refers to the shape of the face of either the particle or first articles (as referred to) which is parallel to the cutting plane. The screw configuration is typically chosen depending on how deformable the material is and at what temperature the material is mobile enough to be properly compacted and extruded. In certain embodiments of the present invention the temperature of the extrudate may typically be from 20 ⁰ C to 130 ⁰ C, or from 30 ⁰ C to 120 ⁰ C or even from 40 ⁰ C to 110 ⁰ C. During the extrusion process, the extrudate may be heated at temperature above 45, for example above 50 or 55 or 60 ⁰ C. Screw configurations can be chosen with varying amounts of back-flow, sheer, compaction, heat and combinations thereof. Commercially available screw extruders suitable for use in the present invention include but are not limited to the TX- 85 Twin Screw Extruder manufactured by Wenger. The particles may be cut from the first article as it is extruded. This is understood to mean that as the material leaves the die it is cut immediately to form the particles, as opposed to lengths of material being formed which are then stored and cut at a later time. Typically, the first article (the extrudate) will be cut when the length of extrudate equal to the desired length of the particle has been extruded. Typically the particles will be cut from the first article by running the blade flush to the die. Preferably the blade will be tension mounted against the die's surface so as to ensure it runs as closely over the face of the die as possible. It is of course understood that in other embodiments of the invention, the material may be formed into extended lengths of material and cut at a later time. The particles may further be coated. The coating may be applied by spraying. The coating material may be a film-forming material. The film-forming material may be as defined above.

The particles may be obtained by a process comprising a drying step. Typically, after the mixing step, the particles may be dried for example in a fluid bed dryer. Composition comprising the particles The invention also concerns a composition comprising the particles of the invention. The composition may be a detergent composition or a laundry treatment or fabric care composition.

In addition to the particles of the invention, the composition may further comprise an adjunct ingredient such as a laundry adjunct ingredient.

The composition may comprise from 0.01 to 99% of the particles of the invention, for example from 0.1 to 10% or from 0.2 to 5% or from 0.5 to 2% or from 1 to 1.5% of particles according to the invention.

While not essential for the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention. The precise nature of these additional adjunct components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants such as non-soap surfactant, builders, flocculating aid, chelating agents, dye transfer inhibitors, enzymes and enzyme stabilizers, catalytic materials, bleach activators, bleach catalysts, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti- redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl that are incorporated by reference. When one or more adjuncts are present, such one or more adjuncts may be present as detailed below:

SURFACTANT - The compositions according to the present invention may comprise a surfactant or surfactant system. The compositions may comprise from 0.01% to 90%, or from 1 to 20% or from 2 to 12% or from 5 to 9%, by weight of a surfactant system. The surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof. Anionic surfactants

Typically, the composition comprises from 1 to 50 wt% anionic surfactant, more typically from 2 to 40 wt%. Suitable anionic surfactants typically comprise one or more moieties selected from the group consisting of carbonate, phosphate, phosphonate, sulphate, sulphonate, carboxylate and mixtures thereof. The anionic surfactant may be one or mixtures of more than one of C$-n alkyl sulphates and C _8-I8 alkyl sulphonates, linear or branched, optionally condensed with from 1 to 9 moles of Ci_ ₄ alkylene oxide per mole of C _8-I8 alkyl sulphate and/or C _8-I8 alkyl sulphonate. Preferred anionic detersive surfactants are selected from the group consisting of: linear or branched, substituted or unsubstituted, Ci _2-I8 alkyl sulphates; linear or branched, substituted or unsubstituted, Cio- ₁ 3 alkylbenzene sulphonates, preferably linear Cio- ₁ 3 alkylbenzene sulphonates; and mixtures thereof. Highly preferred are linear Cio- ₁₃ alkylbenzene sulphonates. Highly preferred are linear Cio- ₁₃ alkylbenzene sulphonates that are obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzenes (LAB); suitable LAB include low 2- phenyl LAB, such as those supplied by Sasol under the tradename Isochem ^® or those supplied by Petresa under the tradename Petrelab ^® , other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene ^® . Alkoxylated anionic surfactants The composition may comprise an alkoxylated anionic surfactant. When present alkoxylated anionic surfactant will generally be present in amounts form 0.1 wt% to 40 wt%, for example from lwt% to 3wt% based on the composition as a whole. Preferably, the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted Ci ₂ - _I8 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 1 to 30, preferably from 3 to 7.

Suitable alkoxylated anionic detersive surfactants are: Texapan LESTTM by Cognis; Cosmacol AESTM by Sasol; BES 15 ITM by Stephan; Empicol ESC70/UTM; and mixtures thereof.

Non-ionic detersive surfactant

The compositions of the invention may comprise non-ionic surfactant. Where present the non-ionic detersive surfactant(s) is generally present in amounts of from 0.5 to 20wt%, or from 2wt% to 4wt%.

The non-ionic detersive surfactant can be selected from the group consisting of: alkyl polyglucoside and/or an alkyl alkoxylated alcohol; Ci ₂ -Ci ₈ alkyl ethoxylates, such as, NEODOL ^® non-ionic surfactants from Shell; C ₆ -Ci ₂ alkyl phenol alkoxylates wherein the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; Ci ₂ -Ci ₈ alcohol and C ₆ -Ci ₂ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic from BASF; C ₁₄ -C ₂₂ mid-chain branched alcohols, BA, as described in more detail in US 6,150,322; C ₁₄ -C ₂₂ mid-chain branched alkyl alkoxylates, BAEx, wherein x = from 1 to 30, as described in more detail in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as described in more detail in US 4,565,647, specifically alkylpolyglycosides as described in more detail in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as described in more detail in US 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; ether capped poly(oxyalkylated) alcohol surfactants as described in more detail in US 6,482,994 and WO 01/42408; and mixtures thereof.

Cationic detersive surfactant In one aspect of the invention, the compositions are free of cationic surfactant. However, the composition optionally may comprise a cationic detersive surfactant. When present, preferably the composition comprises from 0.1 wt% to 10 wt%, or from lwt% to 2wt% cationic detersive surfactant.

Suitable cationic detersive surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, and alkyl ternary sulphonium compounds. The cationic detersive surfactant can be selected from the group consisting of: alkoxylate quaternary ammonium (AQA) surfactants as described in more detail in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium surfactants as described in more detail in US 6,004,922; polyamine cationic surfactants as described in more detail in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as described in more detail in US 4,228,042, US 4,239,660, US 4,260,529 and US 6,022,844; amino surfactants as described in more detail in US 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine; and mixtures thereof. Highly preferred cationic detersive surfactants are mono-Cg-io alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-Cio- ₁₂ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride. Cationic surfactants such as Praepagen HY (tradename Clariant) may be useful and may also be useful as a suds booster. FLOCCULATING AID - The composition may further comprise a flocculating aid.

Typically, the flocculating aid is polymeric. Preferably the flocculating aid is a polymer comprising monomer units selected from the group consisting of ethylene oxide, acrylamide, acrylic acid and mixtures thereof. Preferably the flocculating aid is a polyethyleneoxide. Typically the flocculating aid has a molecular weight of at least 100,000 Da, preferably from 150,000 Da to 5,000,000 Da and most preferably from 200,000 Da to 700,000 Da. Preferably the composition comprises at least 0.3% by weight of the composition of a flocculating aid.

BLEACHING AGENTS - The compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include, but are not limited to, photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject composition. Examples of suitable bleaching agents include, but are not limited to:

(1) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxone ^® , and mixtures thereof. Suitable percarboxylic acids include, but are not limited to, hydrophobic and hydrophilic peracids having the formula R-(C=O)O-O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen;

(2) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate, percarbonate and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, but are not limited to, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and

(3) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof - especially benzene sulphonate. Suitable bleach activators include, but are not limited to, dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect of the invention the subject composition may comprise NOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally present in the composition in an amount of from about 0.1 to about 60 wt%, from about 0.5 to about 40 wt % or even from about 0.6 to about 10 wt% based on the composition. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracid or precursor thereof.

The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

BLEACH CATALYST- the composition may comprise a bleach catalyst. The bleach catalyst is capable of accepting an oxygen atom from a peroxyacid and/or salt thereof, and transferring the oxygen atom to an oxidizeable substrate. Suitable bleach catalysts include, but are not limited to: iminium cations and polyions; iminium zwitterions; modified amines; modified amine oxides; N- sulphonyl imines; N-phosphonyl imines; N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclic sugar ketones and mixtures thereof.

Suitable iminium cations and polyions include, but are not limited to, N-methyl-3,4- dihydroisoquinolinium tetrafluoroborate, prepared as described in Tetrahedron (1992), 49(2), 423-38 (see, for example, compound 4, p. 433); N-methyl-3,4-dihydroisoquinolinium p-toluene sulphonate, prepared as described in U.S. Pat. 5,360,569 (see, for example, Column 11, Example 1); and N-octyl-3,4-dihydroisoquinolinium p-toluene sulphonate, prepared as described in U.S. Pat. 5,360,568 (see, for example, Column 10, Example 3). Suitable iminium zwitterions include, but are not limited to, N-(3-sulfopropyl)-3,4- dihydroisoquinolinium, inner salt, prepared as described in U.S. Pat. 5,576,282 (see, for example, Column 31, Example II); N-[2-(sulphooxy)dodecyl]-3,4-dihydroisoquinolinium, inner salt, prepared as described in U.S. Pat. 5,817,614 (see, for example, Column 32, Example V); 2-[3- [(2-ethylhexyl)oxy]-2-(sulphooxy)propyl]-3,4-dihydroisoquino linium, inner salt, prepared as described in WO05/047264 (see, for example, page 18, Example 8), and 2- [3- [(2- butyloctyl)oxy]-2-(sulphooxy)propyl]-3,4-dihydroisoquinolini um, inner salt.

Suitable modified amine oxygen transfer catalysts include, but are not limited to, 1,2,3,4- tetrahydro-2-methyl-l-isoquinolinol, which can be made according to the procedures described in Tetrahedron Letters (1987), 28(48), 6061-6064. Suitable modified amine oxide oxygen transfer catalysts include, but are not limited to, sodium l-hydroxy-N-oxy-N-[2- (sulphooxy)decyl]-l,2,3,4-tetrahydroisoquinoline.

Suitable N-sulphonyl imine oxygen transfer catalysts include, but are not limited to, 3- methyl-l,2-benzisothiazole 1,1 -dioxide, prepared according to the procedure described in the Journal of Organic Chemistry (1990), 55(4), 1254-61. Suitable N-phosphonyl imine oxygen transfer catalysts include, but are not limited to, [R-

(E)]-N-[(2-chloro-5-nitrophenyl)methylene]-P-phenyl-P-(2, 4,6-trimethylphenyl)- phosphinic amide, which can be made according to the procedures described in the Journal of the Chemical Society, Chemical Communications (1994), (22), 2569-70.

Suitable N-acyl imine oxygen transfer catalysts include, but are not limited to, [N(E)J-N- (phenylmethylene)acetamide, which can be made according to the procedures described in Polish Journal of Chemistry (2003), 77(5), 577-590.

Suitable thiadiazole dioxide oxygen transfer catalysts include but are not limited to, 3- methyl-4-phenyl-l,2,5-thiadiazole 1,1 -dioxide, which can be made according to the procedures described in U.S. Pat. 5,753,599 (Column 9, Example 2). Suitable perfluoroimine oxygen transfer catalysts include, but are not limited to, (Z)-

2,2,3, 3,4,4,4-heptafluoro-N-(nonafluorobutyl)butanimidoyl fluoride, which can be made according to the procedures described in Tetrahedron Letters (1994), 35(34), 6329-30. Suitable cyclic sugar ketone oxygen transfer catalysts include, but are not limited to, l,2:4,5-di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyra nose as prepared in U.S. Pat. 6,649,085 (Column 12, Example 1).

Preferably, the bleach catalyst comprises an iminium and/or carbonyl functional group and is typically capable of forming an oxaziridinium and/or dioxirane functional group upon acceptance of an oxygen atom, especially upon acceptance of an oxygen atom from a peroxyacid and/or salt thereof. Preferably, the bleach catalyst comprises an oxaziridinium functional group and/or is capable of forming an oxaziridinium functional group upon acceptance of an oxygen atom, especially upon acceptance of an oxygen atom from a peroxyacid and/or salt thereof. Preferably, the bleach catalyst comprises a cyclic iminium functional group, preferably wherein the cyclic moiety has a ring size of from five to eight atoms (including the nitrogen atom), preferably six atoms. Preferably, the bleach catalyst comprises an aryliminium functional group, preferably a bi-cyclic aryliminium functional group, preferably a 3,4-dihydroisoquinolinium functional group. Typically, the imine functional group is a quaternary imine functional group and is typically capable of forming a quaternary oxaziridinium functional group upon acceptance of an oxygen atom, especially upon acceptance of an oxygen atom from a peroxyacid and/or salt thereof.

Preferably, the bleach catalyst has a chemical structure corresponding to the following chemical formula

wherein: n and m are independently from 0 to 4, preferably n and m are both 0; each R ¹ is independently selected from a substituted or unsubstituted radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulphonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; and any two vicinal R ¹ substituents may combine to form a fused aryl, fused carbocyclic or fused heterocyclic ring; each R ² is independently selected from a substituted or unsubstituted radical independently selected from the group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any R ² may be joined together with any other of R ² to form part of a common ring; any geminal R ² may combine to form a carbonyl; and any two R ² may combine to form a substituted or unsubstituted fused unsaturated moiety; R ³ is a Ci to C ₂₀ substituted or unsubstituted alkyl; R ⁴ is hydrogen or the moiety Q _t -A, wherein: Q is a branched or unbranched alkylene, t = 0 or 1 and A is an anionic group selected from the group consisting of OS(V, SO ₃ ^" , CO ₂ ^" , OCO ₂ ^" , OPO ₃ ^2" , OPO ₃ H ^" and OPO ₂ ^" ; R ⁵ is hydrogen or the moiety [(CR ⁹ R ¹⁰ ) _y -O] _k -R ⁸ , wherein: each Y is independently selected from the group consisting of O, S,

N-H, or N-R ; and each R is independently selected from the group consisting of alkyl, aryl and heteroaryl, said moieties being substituted or unsubstituted, and whether substituted or unsubsituted said moieties having less than 21 carbons; each G is independently selected from the group consisting of CO, SO ₂ , SO, PO and PO ₂ ; R ⁹ and R ¹⁰ are independently selected from the group consisting of H and Ci-C ₄ alkyl; R ¹¹ and R ¹² are independently selected from the group consisting of H and alkyl, or when taken together may join to form a carbonyl; b = 0 or 1 ; c can = 0 or 1, but c must = 0 if b = 0; y is an integer from 1 to 6; k is an integer from 0 to 20; R ⁶ is H, or an alkyl, aryl or heteroaryl moiety; said moieties being substituted or unsubstituted; and X, if present, is a suitable charge balancing counterion, preferably X is present when R ⁴ is hydrogen, suitable X, include but are not limited to: chloride, bromide, sulphate, methosulphate, sulphonate, p-toluenesulphonate, borontetraflouride and phosphate.

In one embodiment of the present invention, the bleach catalyst has a structure corresponding to general formula below:

wherein R ¹³ is a branched alkyl group containing from three to 24 carbon atoms (including the branching carbon atoms) or a linear alkyl group containing from one to 24 carbon atoms; preferably R ¹³ is a branched alkyl group containing from eight to 18 carbon atoms or linear alkyl group containing from eight to eighteen carbon atoms; preferably R ¹³ is selected from the group consisting of 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; preferably R ¹³ is selected from the group consisting of 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, iso-tridecyl and iso-pentadecyl. BUILDERS - The composition of the present invention may comprise one or more detergent builders or builder systems. When a builder is used, the subject composition will typically comprise at least about 1%, from about 5% to about 60% or even from about 10% to about 40% builder by weight of the subject composition. The composition may comprise less than 15, or less than 10 or less than 5% of builder.

Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

CHELATING AGENTS - The compositions herein may contain a chelating agent. Suitable chelating agents include, but are not limited to, copper, iron and/or manganese chelating agents and mixtures thereof. When a chelating agent is used, the subject composition may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the subject composition.

DYE TRANSFER INHIBITING AGENTS - The compositions of the present invention may also include, but are not limited to, one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in a subject composition, the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the composition. BRIGHTENERS - The compositions of the present invention can also contain additional components that may tint articles being cleaned, such as fluorescent brighteners. Suitable fluorescent brightener levels include lower levels of from about 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.

DISPERSANTS - The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials include, but are not limited to, the homo- or co- polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.

ENZYMES - The compositions can comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a composition, the aforementioned enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% enzyme protein by weight of the composition. ENZYME STABILIZERS - Enzymes for use in detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, can be added to further improve stability. CATALYTIC METAL COMPLEXES - Applicants' compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water- soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243.

If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, but are not limited to, for example, the manganese-based catalysts disclosed in U.S. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. 5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. 5,597,936, and U.S. 5,595,967.

Compositions herein may also suitably include a transition metal complex of ligands such as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands - abbreviated as "MRLs". As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous washing medium, and will typically provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.

Suitable transition-metals in the instant transition-metal bleach catalyst include, but are not limited to, for example, manganese, iron and chromium. Suitable MRLs include, but are not limited to, 5,12-diethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. 6,225,464.

The composition may be a cleaning or a detergent composition. The composition may be a fabric-care composition.

The compositions disclosed herein are typically formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 12, or between about 7.5 and 10.5. Particulate dishwashing product formulations that may be used for hand dish washing may be formulated to provide wash liquor having a pH between about 6.8 and about 9.0. Cleaning products are typically formulated to have a pH of from about 7 to about

12. Techniques for controlling pH at recommended usage levels include, but are not limited to, the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. The composition is for example in particulate form, preferably in free-flowing particulate form, although the composition may be in any solid form. The composition in solid form can be in the form of an agglomerate, granule, flake, extrudate, bar, tablet or any combination thereof.

The solid composition can be made by methods such as dry-mixing, agglomerating, compaction, spray drying, pan-granulation, spheronization or any combination thereof. The solid composition preferably has a bulk density of from 300 g/1 to 1,500 g/1, preferably from 500 g/1 to 1,000 g/1.

The composition may be in unit dose form, including not only tablets, but also unit dose pouches wherein the composition is at least partially enclosed, preferably completely enclosed, by a film such as a polyvinyl alcohol film.

The composition may also be in the form of an insoluble substrate, for example a non- woven sheet, impregnated with detergent actives.

The composition may be capable of cleaning and/or softening fabric during a laundering process. Typically, the laundry treatment composition is formulated for use in an automatic washing machine, although it can also be formulated for hand-washing use.

It is to be understood that in the present specification, the percentage and ratio are in weight if not otherwise indicated.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the invention.

EXAMPLES

In the following examples, violet hueing dye refers to any of compounds 1-5 of formula I above (about 20% active in a solvent system). The violet hueing dye could be replaced by any other suitable hueing dye.

Example 1 : process to make the extruded particle of the invention

In a Kenwood food mixer a feed material is prepared by introducing successively 372.99 g of vegetable (coco/palm) soap supplied by Kay's limited, 2.63 g of violet hueing dye, and 124.33 g of tallow soap supplied by Kay's limited and then pre-mixing the ingredients to ensure that the hueing dye is present in all parts of the feed material.

The feed material is then introduced via a feeder into a twin screw extruder form APV

Baker, then the feed material is conveyed and further mixed by the forward twin screws of the extruder at a speed of 250 rpm. The screws comprise a 1 forward kneading section. The feeder plate is not heated and has a temperature of 25 ⁰ C. The die plate has multiple holes of 0.5 mm diameter.

The extruded material is in form of strands which can easily be broken to form particles having an average length of about 2.5 to 5 mm and an average diameter of about 0.5 mm. Example 2: process to make the extruded particle of the invention

In a Kenwood food mixer a feed material is prepared by introducing successively 497.44 g of the vegetable soap of example 1, 2.63 g of violet hueing dye, and then pre-mixing the ingredients to ensure that the hueing dye is present in all parts of the feed material.

The feed material is then introduced via a feeder into the extruder of example 1, then the feed material is conveyed and further mixed by the forward twin screws of the extruder at a speed of 250 rpm. The screws comprise a 1 forward kneading section. The feeder plate is heated and has a temperature of about 30 ⁰ C. The die plate has multiple holes of 0.5 mm diameter.

The extruded material is in form of strands which can easily be broken to form particles having an average length of about 2.5 to 5 mm and an average diameter of about 0.5 mm. Example 3: process to make the extruded particle of the invention In a Kenwood food mixer a feed material is prepared by introducing successively 497.44 g of the vegetable soap of example 1, 2.63 g of violet hueing dye, and then pre-mixing the ingredients to ensure that the hueing dye is present in all parts of the feed material.

The feed material is then introduced via a feeder into the extruder of example 1 , then the feed material is conveyed and further mixed by the forward twin screws of the extruder at a speed of 250 rpm. The screws comprise a 1 forward kneading section. The feeder plate is heated and has a temperature of about 35°C. The die plate has multiple holes of 0.5 mm diameter.

The extruded material is in form of strands which can easily be broken to form particles having an average length of about 2.5 to 5 mm and an average diameter of about 0.5 mm. The particles are then agitated in a drum mixer and a solution of 6.45 g of polyvinyl alcohol in 8.5 g of water is sprayed on the particles while the particles are agitated. The particles are then dried in an oven at 60 ⁰ C.

Example 4: process to make the extruded particle of the invention

In a Kenwood food mixer a feed material is prepared by introducing successively 123.67 g of the vegetable soap of example 1, 2.63 g of violet hueing dye, and 123.67 g of fine carbonate

(supplied by Brunner Mond and which has been sieved on a 63 μm sieve to select the smaller particles), and then pre-mixing the ingredients to ensure that the hueing dye is present in all parts of the feed material.

The feed material is then introduced via a feeder into the extruder of example 1 , then the feed material is conveyed and further mixed by the forward twin screws of the extruder at a speed of 250 rpm. The screws comprise a 1 forward kneading section. The feeder plate is heated and has a temperature of about 35 ⁰ C. The die plate has multiple holes of 0.8 mm diameter.

The extruded material is in form of strands which can easily be broken to form particles having an average length of about 2.5 to 5 mm and an average diameter of about 0.8 mm. Example 5 : process to make particle

247.34 g of the vegetable soap of example 1 and 2.63 g of violet hueing dye are mixed in a Kenwood food mixer until ensuring that the hueing dye is present in all parts of the soap.

The particles are then classified by sieving into 500 μm and 710 μm sieves (example 5a) or between 710 μm and 850 μm sieves (example 5b) or 850 μm and 1 mm sieves (example 5c). Example 6: process to make particle

247.34 g of the vegetable soap of example 1 and 2.63 g of violet hueing dye are mixed in a Kenwood food mixer until ensuring that the hueing dye is present in all parts of the soap. The particles are macerated in a coffee grounder. Example 7: preparation of laundry compositions comprising the particles of examples 1-6.

Those compositions are showing no significant bleeding of the dye. No significant spotting is observed on the fabric when washed with these compositions.

Example 8: preparation of laundry compositions comprising the particles of examples 1-6.

TEST METHODS

The test methods that are disclosed below can be used to determine the respective values of the parameters as described and claimed herein.

Test method 1: measurement of a particle size distribution and a mean particle size.

The particle size distribution of granular detergent products, intermediates and raw materials are measured by sieving the granules/powders through a succession of sieves with gradually smaller dimensions. The weight of material retained on each sieve is then used to calculate a particle size distribution and median or mean particle size.

Equipment: RoTap Testing Sieve Shaker Model B (as supplied by: W. S. Tyler Company, Cleveland, Ohio), supplied with cast iron sieve stack lid with centrally mounted cork. The RoTap should be bolted directly to a flat solid inflexible base, typically the floor. The tapping speed used should be 6 taps/minute with a 12 rpm elliptical motion. Samples used should weight 100 g, and total sieving time should be set at 5 mins.

Particle Size Distribution: The fraction on each sieve is calculated from the following equation: Mass on sieve (g) x 100

Fraction on sieve (%) =

Original sample weight (g) If this calculation is done for each sieve size used then a particle size distribution is obtained. However a cumulative particle size distribution is of more use. The cumulative distribution is calculated by adding the fractions on a particular sieve to the fractions on sieves above it (i.e. of higher mesh size).

Calculation of Mean particle size: Mean Particle Size is the geometric mean particle size on a mass basis calculated as the X intercept of the weighted regression line on the sigma versus log (size) plot.

Test method 2: Bulk Density Test The core material bulk density is determined in accordance with Test Method B, Loose- fill Density of Granular Materials, contained in ASTM Standard E727-02, "Standard Test Methods for Determining Bulk Density of Granular Carriers and Granular Pesticides," approved October 10, 2002.

Test method 3: Particle Aspect Ratio Test The particle aspect ratio is defined as the ratio of the particle's major axis diameter

(d _m a _j o _r ) relative to the particle's minor axis diameter (d _minor ), where the major and minor axis diameters are the long and short sides of a rectangle that circumscribes a 2-dimensional image of the particle at the point of rotation where the short side of the rectangle is minimized. The 2- dimensional image is obtained using a suitable microscopy technique. For the purpose of this method, the particle area is defined to be the area of the 2-dimensional particle image.

In order to determine the aspect ratio distribution and the median particle aspect ratio, a suitable number of representative 2-dimensional particle images must be acquired and analyzed. For the purpose of this test, a minimum of 5000 particle images is required. In order to facilitate collection and image analysis of this number of particles, an automated imaging and analysis system is recommended. Such systems can be obtained from Malvern Instruments Ltd., Malvern, Worcestershire, United Kingdom; Beckman Coulter, Inc., Fullerton, California, USA; JM Canty, Inc., Buffalo, New York, USA; Retsch Technology GmbH, Haan, Germany; and Sympatec GmbH, Clausthal-Zellerfeld, Germany.

A suitable sample of particles is obtained by riffling. The sample is then processed and analyzed by the image analysis system, to provide a list of particles containing major and minor axis attributes. The aspect ratio (AR) of each particle is calculated according to the ratio of the particle's major and minor axis, AK = Clma _j or ' 1 _mlnor .

The list of data are then sorted in ascending order of particle aspect ratio and the cumulative particle area is calculated as the running sum of particle areas in the sorted list. The particle aspect ratio is plotted against the abscissa and the cumulative particle area against the ordinate. The median particle aspect ratio is the abscissa value at the point where the cumulative particle area is equal to 50% of the total particle area of the distribution.

Test method 4: fabric substantive component test 1.) Fill two tergotometer pots with 800 ml of water having a water hardness of 14.4 English

Clark Degrees Hardness with a 3:1 Calcium to Magnesium molar ratio. 2) Insert pots into tergotometer, with water temperature controlled at 30 ⁰ C and agitation set at 40 rpm for the duration of the experiment.

3) Add 4.8g of IEC-B detergent (IEC 60456 Washing Machine Reference Base Detergent Type B), supplied by wfk, Bruggen-Bracht, Germany, to each pot.

4) After two minutes, add 2.0 mg of the component to be tested to the first pot. 5) After one minute, add 50 g of flat cotton vest (supplied by Warwick Equest, Consett, County Durham, UK), cut into 5cm x 5cm swatches, to each pot.

6) After 10 minutes, drain the pots and re-fill with cold Water (16°C) having a water hardness of 14.4 English Clark Degrees Hardness with a 3:1 Calcium to Magnesium molar ratio.

7) After 2 minutes rinsing, remove fabrics. 8) Repeat steps 3-7 for a further three cycles using the same treatments.

9) Collect and line dry the fabrics indoors, in the dark, for 12 hours.

10) Analyse the swatches using a Hunter Miniscan spectrometer fitted with D65 illuminant, 10° observer, and UVA cutting filter, to obtain Hunter a (red-green axis) and Hunter b (yellow- blue axis) values. 11) Average the Hunter a and Hunter b values for each set of fabrics to deduce the average difference in hue on the a and b axis between the two sets of fabrics. Test method 5: hueing efficiency

A 25 cmx25 cm fabric piece of 16 oz cotton interlock knit fabric (270 g/square meter, brightened with Uvitex BNB fluorescent whitening agent, obtained from Test Fabrics. P.O. Box 26, Weston, Pa., 18643), is employed. The samples are washed in one litre of distilled water containing 1.55 g of AATCC standard heavy duty liquid (HDL) test detergent as set forth in Table 1 of patent US 7,208,459, for 45 minutes at room temperature and rinsed by allowing to stand undisturbed with 500 mL of distilled water at 25°C for 5 minutes, then filtering off the rinse water. Respective samples are prepared using a detergent containing no dye (control) and using a detergent containing a 30 ppm wash concentration of a dye to be tested. After rinsing and then air drying during 24 hours at 25 ⁰ C in the dark each fabric sample, the hueing efficiency, DE* _ef τ, in the wash is assessed by the following equation: DE* _ett =((L* _c -L* _s ) ² +(a* _c -a* _s ) ² +(b* _c -b* _s ) ² ) ^m wherein the subscripts c and s respectively refer to the L*, a*, and b* values measured for the control, i.e., the fabric sample washed in detergent with no dye, and the fabric sample washed in detergent containing the dye to be screened. The L*, a*, and b* value measurements are carried out using a Hunter Colorquest reflectance spectrophotometer with D65 illumination, 10° observer and UV filter excluded.