EP2268784A1 - Reduced spotting granules - Google Patents

Reduced spotting granules

Info

Publication number
EP2268784A1
EP2268784A1 EP20090737914 EP09737914A EP2268784A1 EP 2268784 A1 EP2268784 A1 EP 2268784A1 EP 20090737914 EP20090737914 EP 20090737914 EP 09737914 A EP09737914 A EP 09737914A EP 2268784 A1 EP2268784 A1 EP 2268784A1
Authority
EP
European Patent Office
Prior art keywords
dyes
dye
granule
sokalan
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20090737914
Other languages
German (de)
French (fr)
Other versions
EP2268784B1 (en
EP2268784B2 (en
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP09737914.3A priority Critical patent/EP2268784B2/en
Publication of EP2268784A1 publication Critical patent/EP2268784A1/en
Publication of EP2268784B1 publication Critical patent/EP2268784B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers

Definitions

  • the present invention relates to the delivery of shading dyes to fabrics.
  • WO 2005/003274 discloses that shading dyes are added to laundry detergents to increase whiteness.
  • One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
  • a shading dye granule present in a laundry detergent formulation is susceptible to providing unwanted spotting of fabrics .
  • the present invention provides a shading dye granule comprising:
  • a shading dye (i) from 0.001 to 95 wt% of a shading dye; (ii) from 0.1 to 99.999 wt% of a dye transfer polymer selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles ;
  • the present invention provides a granular laundry detergent composition
  • a granular laundry detergent composition comprising:
  • the surfactant that comes from the base powder may be a mixture of different types of surfactants but the total concentration of anionic surfactant in the granulate laundry detergent is in the range from 10 to 50 wt %.
  • the surfactant that comes from the base powder is preferably greater than 70% anionic surfactant.
  • the shading dye granule is visually distinct (VD) from a granular background powder in order to provide a visual cue.
  • the shading dye granule is for adding to a base powder (main detergent powder) .
  • the shading dye granule does not contain an anionic surfactant.
  • the shading dye granule is admixed with the base powder, which must contain an anionic surfactant, there may be some migration of anionic surfactant to the shading dye granule.
  • the ratio of the dye transfer polymer: the charged surfactant prevents spotting whilst permitting dye deposition of substantive dyes from the wash liquors.
  • the shading dye is blue or violet. It is preferred that the shading dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm.
  • Dyes are coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes are described in 'Industrial Dyes', Wiley VCH 2002, K. Hunger (editor) .
  • Dyes are listed in the Color Index International published by Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Dyes are preferably selected from the classes of basic, acid and direct dyes.
  • Direct violet and direct blue dyes are preferred.
  • the dyes are bis-azo or tris-azo dyes.
  • the carcinogenic benzidene based dyes are not preferred.
  • Bis-azo copper containing dyes such as direct violet 66 may be used.
  • the direct dye is a direct violet of the following structures:
  • ring D and E may be independently naphthyl or phenyl as shown;
  • Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
  • R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
  • R3 and R4 are independently selected from: hydrogen and Cl- C4-alkyl, preferably hydrogen or methyl;
  • Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet
  • Cotton substantive acid dyes give benefits to cotton containing garments.
  • Preferred dyes and mixes of dyes are blue or violet.
  • Preferred acid dyes are:
  • R a , R b , R c and R d are selected from: H, an branched or linear Cl to C7-alkyl chain, benzyl a phenyl, and a naphthyl ; the dye is substituted with at least one SC>3 ⁇ or -COO ⁇ group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO 2 .
  • Preferred azine dyes are: acid violet 50 and acid blue 9 ⁇
  • R is selected from: H; a branched or linear Cl to
  • Y is selected from: NO 2 ; CN; I; Br; Cl; F; H; OCOR 2 ; NHCOR 3 ; R4; R5O; and, NR6R7, wherein R 2 , R3, R 4 , and R5 are independently selected from a branched or linear Cl to Cl- alkyl chain and Re and R7 are independently selected from: H; a branched or linear Cl to C7-alkyl chain that is unsubstituted or is substituted by groups independently selected from: OH; Cl; F; OCOCH 3 ; COOCH 3 ; OCOC 2 H 5 ; and, COOC 2 H 5 ; and,
  • X is selected from: H; SO 2 N(R 8 )COCH 3 ; SO 2 N(Rg)-Ar; SO 2 N(Rg)-Ar; and SO 2 -Ar, wherein Ar is an aromatic group and Rg is H, CH 3 or C 2 H 5 , with the proviso that the Y ring does not carry a negatively charged group or salt thereof.
  • X is selected from -OH, CH 3 O-, CH 3 CH 2 O-, and -NR 1 R 2 , wherein R 1 and R 2 are independently selected from: H, a branched or linear -Cl-C7-alkyl chain, -COR 3 , wherein R 3 is a branched or linear -Cl-C7-alkyl chain, and a -SO 2 Ar group, wherein Ar is a phenyl or methyl substituted phenyl group;
  • Y is an aromatic group selected from: phenyl and napthyl, and Y may be substituted by R 4 O-, R 4 CONH-, R 4 -, Cl, Br, I, F, NO 2 , and -NR 4 R 5 , wherein R 4 and R 4 are independently selected from: H, a branched or linear -Cl-C7-alkyl chain or a phenyl group .
  • acid dyes are acid violet 17, acid black 1, acid red 17 and acid blue 29.
  • the acid dye is present at 0.001 wt% to 0.006 wt% of the formulation.
  • the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores .
  • Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
  • Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
  • the hydrophobic dye is present at 0.0005 wt% to 0.004 wt% of the formulation.
  • Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
  • Preferred examples include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes.
  • Reactive dyes include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes.
  • Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
  • the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
  • Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
  • Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
  • the shading dye granule according to the present invention comprising from 0.1 to 99.999 wt%, preferably from 0.5 to 18 wt%, more preferably from 0.5 to 2 wt% by weight of an anti- dye transfer polymer (ADTP) selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles .
  • ADTP anti- dye transfer polymer
  • ADTPs anti-dye transfer polymers
  • the preferred anti-dye transfer polymer is PVP.
  • CARRIERS are preferred anti-dye transfer polymer.
  • the shading dye granule preferably contains a carrier preferred examples of carrier are bentonite, sodium chloride, zeolite, and sodium sulphate.
  • carrier is present in the range from 80 to 99.8 wt%.
  • a binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion.
  • the binder is other than a non- ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
  • the binder has a melting point above 30 0 C.
  • the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
  • Suitable polymers for use herein are water-soluble.
  • water-soluble it is meant herein that the polymers have a solubility greater than 5 g/1 at 20 0 C in demineralised water .
  • the binder is preferably an acidic polymer.
  • an acidic polymer it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150, 000.
  • Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I
  • the proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
  • Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-I, 597, 756.
  • Preferred polycarboxylate polymers fall into several categories.
  • a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
  • preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or Cl-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
  • Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form) .
  • Binder materials are commercially readily available.
  • the water soluble polymers of the Sokalan® type sold by BASF® are preferred.
  • the granules are preferably of the size from 50 to 1800 microns.
  • the granule size is as determined by passing through a mesh sieve.
  • Preferably the size is in the range 100 to 800 microns.
  • Example 1 The dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution. To this was added the [nitrolotris (2, 1-ethanediyloxy) ] tris [propanol] salt of direct violet 9, DV9, (Ex Ciba Speciality Chemicals) . The non-ionic was added to the carrier in a high shear mixer. Following this the binder, Sokalam CP5 (ex BASF) was added. Where appropriate polyvinylpyrrolidone, PVP, was added to the starting non-ionic solution.
  • 7EO non-ionic surfactant
  • PVP polyvinylpyrrolidone
  • the resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1400 microns .
  • the granules had the following composition. All percentages refer to dry weight%.
  • the granules of example 1 were separately added to a detergent powder (20% linear alkyl benzene sulphonate, 30% sodium carbonate, 40% sodium chloride, remainder minors including fluorescer and moisture), at 2 wt%. 10 g of the powder was sprinkled onto a 25 by 25 cm piece of white cotton sheeting, immersed in 1 cm of demineralised water. The cloth was soaked for 90 minutes, then thoroughly rinsed and dried. Each experiment was repeated four times. Cloths soaked with Granule 1 and 2 were compared, and Granule 3 and 4 were compared, as they had equivalent levels of DV9. The eight clothes from each comparison were ranked in terms of the degree of dye staining/spotting. The cloth with the least staining/spotting received a score of 1, that with the second lowest level of staining a score of 2, and so on, so that the most stained/spotted cloth had a score of 8.
  • the granules containing the dye transfer inhibition polymer show reduced levels of spotting/staining.
  • the granules of example 1 were added to the base washing powder of example 2, such that when the washing powder was dissolved at 2g/L the wash liquor contained 200ppb of SV13.
  • To the wash liquor was added pieces of woven cotton and knitted nylon-elastane fabric such the liquoricloth was 100:1.
  • the liquor was agitated for 60 minutes at 293K, the clothes rinsed twice and the colour change measured by reflectometry and expressed as CIE L*a*b* values. The results are given below expressed as the ⁇ E values relative to the control washed without dye
  • Granule 2 and granule 3 were individually added to exemplary powder formulations A, B, C and D at 1 wt % to generate final formulations for use in washing and shading textiles.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Coloring (AREA)

Abstract

The present invention provides a granular laundry detergent composition comprising a shading dye granule, comprising a shading dye, a dye transfer polymer and optional ingredients. Said granular laundry detergent composition further comprises 10 to 50 wt % of an anionic surfactant.

Description

REDUCED SPOTTING GRANULES
FIELD OF INVENTION
The present invention relates to the delivery of shading dyes to fabrics.
BACKGROUND OF THE INVENTION
WO 2005/003274, to Unilever, discloses that shading dyes are added to laundry detergents to increase whiteness. One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
SUMMARY OF THE INVENTION A shading dye granule present in a laundry detergent formulation is susceptible to providing unwanted spotting of fabrics .
This problem is ameliorated by having an anti-dye transfer agent present in the shading dye granule.
In one aspect the present invention provides a shading dye granule comprising:
(i) from 0.001 to 95 wt% of a shading dye; (ii) from 0.1 to 99.999 wt% of a dye transfer polymer selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles ;
(iii) from 0 to 80 wt% of a non-ionic surfactant;
(iv) from 0 to 20 wt % of an anionic or cationic surfactant;
(v) from 0 to 99.5 wt% of a carrier; and,
(vi) from 0 to 50 wt% of a binder, wherein the weight ratio of the dye transfer polymer: the charged surfactant is from 1:0 to 1:1.
In another aspect the present invention provides a granular laundry detergent composition comprising:
(a) from 0.00005 to 10 wt% of visually distinct laundry detergent granule as defined in any one of claims 1 to 4; (b) from 99.99995 % to 90 wt % of a granular base powder, wherein the granular laundry detergent composition comprises 10 to 50 wt % of an anionic surfactant.
The surfactant that comes from the base powder may be a mixture of different types of surfactants but the total concentration of anionic surfactant in the granulate laundry detergent is in the range from 10 to 50 wt %. The surfactant that comes from the base powder is preferably greater than 70% anionic surfactant. DETAILED DESCRIPTION OF THE INVENTION
Preferably, the shading dye granule is visually distinct (VD) from a granular background powder in order to provide a visual cue.
The shading dye granule is for adding to a base powder (main detergent powder) .
Preferably the shading dye granule does not contain an anionic surfactant. When the shading dye granule is admixed with the base powder, which must contain an anionic surfactant, there may be some migration of anionic surfactant to the shading dye granule.
The ratio of the dye transfer polymer: the charged surfactant prevents spotting whilst permitting dye deposition of substantive dyes from the wash liquors.
Shading Dye Preferably the shading dye is blue or violet. It is preferred that the shading dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm. A combination of dyes which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester of from 550nm to 650nm, preferably from 570nm to 630nm. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. - A -
Dyes are coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes are described in 'Industrial Dyes', Wiley VCH 2002, K. Hunger (editor) .
Dyes are listed in the Color Index International published by Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Dyes are preferably selected from the classes of basic, acid and direct dyes.
Direct dyes
Direct violet and direct blue dyes are preferred. Preferably the dyes are bis-azo or tris-azo dyes. The carcinogenic benzidene based dyes are not preferred.
Bis-azo copper containing dyes such as direct violet 66 may be used.
Most preferably the direct dye is a direct violet of the following structures:
or R^2
wherein : ring D and E may be independently naphthyl or phenyl as shown;
Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
R3 and R4 are independently selected from: hydrogen and Cl- C4-alkyl, preferably hydrogen or methyl;
X and Y are independently selected from: hydrogen, C1-C4- alkyl and Cl-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet
35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. Acid dyes
Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
(i) azine dyes, wherein the dye is of the following core structure :
wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear Cl to C7-alkyl chain, benzyl a phenyl, and a naphthyl ; the dye is substituted with at least one SC>3~ or -COO~ group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.
Preferred azine dyes are: acid violet 50 and acid blue 9ϊ
(ii) DANSA dyes of the following core structure:-
(i: wherein R is selected from: H; a branched or linear Cl to
C7-alkyl chain; CORi wherein Ri is a branched or linear Cl to
C7-alkyl chain; and, a -SO2Ar group, wherein Ar is phenyl or methyl substituted phenyl group;
Y is selected from: NO2; CN; I; Br; Cl; F; H; OCOR2; NHCOR3; R4; R5O; and, NR6R7, wherein R2, R3, R4, and R5 are independently selected from a branched or linear Cl to Cl- alkyl chain and Re and R7 are independently selected from: H; a branched or linear Cl to C7-alkyl chain that is unsubstituted or is substituted by groups independently selected from: OH; Cl; F; OCOCH3; COOCH3; OCOC2H5; and, COOC2H5; and,
X is selected from: H; SO2N(R8)COCH3; SO2N(Rg)-Ar; SO2N(Rg)-Ar; and SO2-Ar, wherein Ar is an aromatic group and Rg is H, CH3 or C2H5, with the proviso that the Y ring does not carry a negatively charged group or salt thereof.
(iii) MAAD dyes the following core structure:
wherein :
X is selected from -OH, CH3O-, CH3CH2O-, and -NR1R2, wherein R1 and R2 are independently selected from: H, a branched or linear -Cl-C7-alkyl chain, -COR3, wherein R3 is a branched or linear -Cl-C7-alkyl chain, and a -SO2Ar group, wherein Ar is a phenyl or methyl substituted phenyl group;
Y is an aromatic group selected from: phenyl and napthyl, and Y may be substituted by R4O-, R4CONH-, R4-, Cl, Br, I, F, NO2, and -NR4R5, wherein R4 and R4 are independently selected from: H, a branched or linear -Cl-C7-alkyl chain or a phenyl group .
Other preferred acid dyes are acid violet 17, acid black 1, acid red 17 and acid blue 29.
Preferably the acid dye is present at 0.001 wt% to 0.006 wt% of the formulation.
Hydrophobic dyes
The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores . Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
Preferably the hydrophobic dye is present at 0.0005 wt% to 0.004 wt% of the formulation.
Basic dyes Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
Preferred examples include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes. Reactive dyes
Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton. Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
ANTI -DYE TRANSFER POLYMER The shading dye granule according to the present invention comprising from 0.1 to 99.999 wt%, preferably from 0.5 to 18 wt%, more preferably from 0.5 to 2 wt% by weight of an anti- dye transfer polymer (ADTP) selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles .
The anti-dye transfer polymers (ADTPs) discussed above are well known in the art and commercially available, reference in made to US6833336 and references found therein.
The preferred anti-dye transfer polymer is PVP. CARRIERS
The shading dye granule preferably contains a carrier preferred examples of carrier are bentonite, sodium chloride, zeolite, and sodium sulphate. Preferably the carrier is present in the range from 80 to 99.8 wt%.
BINDER
A binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion. The binder is other than a non- ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
Preferably, the binder has a melting point above 30 0C.
Preferably the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
Suitable polymers for use herein are water-soluble. By water-soluble, it is meant herein that the polymers have a solubility greater than 5 g/1 at 20 0C in demineralised water . The binder is preferably an acidic polymer. By an acidic polymer, it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5
Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150, 000.
Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I
wherein X is 0 or CH2 ; Y is a comonomer or comonomer mixture; Rl and R2 are bleach-stable polymer-end groups; R3 is H, OH or Cl-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof. The proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-I, 597, 756. Preferred polycarboxylate polymers fall into several categories. A first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer. Referring to formula I, therefore, preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or Cl-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
H H
CO2M CO2M
Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form) .
Binder materials are commercially readily available. The water soluble polymers of the Sokalan® type sold by BASF® are preferred. The following is a list of such suitable products: Sokalan CP 10; Sokalan CP 10 S; Sokalan CP 12 S; Sokalan CP 13 S; Sokalan CP 45; Sokalan CP 5; Sokalan CP 7; Sokalan CP 9; Sokalan DCS; Sokalan HP 165; Sokalan HP 22 G; Sokalan HP 25; Sokalan HP 50; Sokalan HP 53; Sokalan HP 53 K; Sokalan HP 56; Sokalan HP 59; Sokalan HP 60; Sokalan HP 66; Sokalan PA 110 S; Sokalan PA 15; Sokalan PA 15 CL; Sokalan PA 20; Sokalan PA 20 PN; Sokalan PA 25 CL; Sokalan PA 30; Sokalan PA 40; Sokalan PM 70; and, Sokalan SR 100.
Granules
The granules are preferably of the size from 50 to 1800 microns. The granule size is as determined by passing through a mesh sieve. Preferably the size is in the range 100 to 800 microns.
EXAMPLES Example 1 The dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution. To this was added the [nitrolotris (2, 1-ethanediyloxy) ] tris [propanol] salt of direct violet 9, DV9, (Ex Ciba Speciality Chemicals) . The non-ionic was added to the carrier in a high shear mixer. Following this the binder, Sokalam CP5 (ex BASF) was added. Where appropriate polyvinylpyrrolidone, PVP, was added to the starting non-ionic solution.
The resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1400 microns .
The granules had the following composition. All percentages refer to dry weight%.
Example 2
The granules of example 1 were separately added to a detergent powder (20% linear alkyl benzene sulphonate, 30% sodium carbonate, 40% sodium chloride, remainder minors including fluorescer and moisture), at 2 wt%. 10 g of the powder was sprinkled onto a 25 by 25 cm piece of white cotton sheeting, immersed in 1 cm of demineralised water. The cloth was soaked for 90 minutes, then thoroughly rinsed and dried. Each experiment was repeated four times. Cloths soaked with Granule 1 and 2 were compared, and Granule 3 and 4 were compared, as they had equivalent levels of DV9. The eight clothes from each comparison were ranked in terms of the degree of dye staining/spotting. The cloth with the least staining/spotting received a score of 1, that with the second lowest level of staining a score of 2, and so on, so that the most stained/spotted cloth had a score of 8.
The total score across the 4 cloths for each granule were then compared: Granules containing 0.20 wt% DV9 Granule 1 (no PVP) total score = 24 Granule 2 (PVP) total score = 12
Granules containing 0.08 wt% DV9
Granule 3 (PVP) total score = 11 Granule 4 (no PVP) total score = 25
The granules containing the dye transfer inhibition polymer show reduced levels of spotting/staining.
Example 3
The granules of example 1 were added to the base washing powder of example 2, such that when the washing powder was dissolved at 2g/L the wash liquor contained 200ppb of SV13. To the wash liquor was added pieces of woven cotton and knitted nylon-elastane fabric such the liquoricloth was 100:1. The liquor was agitated for 60 minutes at 293K, the clothes rinsed twice and the colour change measured by reflectometry and expressed as CIE L*a*b* values. The results are given below expressed as the ΔE values relative to the control washed without dye
All granules gave good deposition of the dyes to the fabrics evidenced by the ΔE values.
Example 4
Exemplary Base Powder Formulations A, B, C and D
Granule 2 and granule 3 were individually added to exemplary powder formulations A, B, C and D at 1 wt % to generate final formulations for use in washing and shading textiles.

Claims

What is claimed is :
1. A shading dye granule comprising:
(i) from 0.001 to 95 wt% of a shading dye;
(ii) from 0.1 to 99.999 wt% of a dye transfer polymer selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and poIyvinylimidazoles;;
(iii) from 0 to 80 wt% of a non-ionic surfactant; (iv) from 0 to 20 wt % of an anionic or cationic surfactant; (v) from 0 to 99.5 wt% of a carrier; and,
(vi) from 0 to 50 wt% of a binder, wherein the weight ratio of the dye transfer polymer: the charged surfactant is from 1:0 to 1:1.
2. A shading dye granule as defined in claim 1, wherein the charged surfactant is an anionic surfactant.
3. A shading dye granule as defined in claim 1, wherein the carrier is present from 80 to 99.8 wt%.
4. A shading dye granule according to any preceding claim, wherein the shading dye is selected from: acid dyes, basic dyes and direct dyes.
5. A granular laundry detergent composition comprising: (a) from 0.00005 to 10 wt% of visually distinct laundry detergent granule as defined in any one of claims 1 to 4 ;
(b) from 99.99995 % to 90 wt % of a granular base powder, wherein the granular laundry detergent composition comprises 10 to 50 wt % of an anionic surfactant.
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