(19)
(11) EP 2 521 764 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
26.11.2014 Bulletin 2014/48

(21) Application number: 10767957.3

(22) Date of filing: 27.09.2010
(51) International Patent Classification (IPC): 
C11D 3/02(2006.01)
C11D 3/37(2006.01)
C11D 3/42(2006.01)
C11D 17/06(2006.01)
C11D 3/22(2006.01)
C11D 3/40(2006.01)
C11D 11/02(2006.01)
C11D 3/04(2006.01)
(86) International application number:
PCT/EP2010/064246
(87) International publication number:
WO 2011/082842 (14.07.2011 Gazette 2011/28)

(54)

DETERGENT FORMULATION CONTAINING SPRAY DRIED GRANULE

Waschmittelformulierung, die sprühgetrocknetes Granulat enthält

Formulation de détergent contenant des granules séchées par atomisation


(84) Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

(30) Priority: 07.01.2010 EP 10150207

(43) Date of publication of application:
14.11.2012 Bulletin 2012/46

(73) Proprietors:
  • Unilever PLC
    London Greater London EC4Y 0DY (GB)
    Designated Contracting States:
    CY GB IE MT 
  • Unilever N.V.
    3013 AL Rotterdam (NL)
    Designated Contracting States:
    AL AT BE BG CH CZ DE DK EE ES FI FR GR HR HU IS IT LI LT LU LV MC MK NL NO PL PT RO SE SI SK SM TR 

(72) Inventors:
  • BARCHINI, Raquel, Beatriz
    NL-3133 AT Vlaardingen (NL)
  • BATCHELOR, Stephen, Norman
    Wirral Merseyside CH63 3JW (GB)
  • HERMANT, Roelant, Mathijs
    NL-3133 AT Vlaardingen (NL)
  • WIERINGA, Jan, Alders
    NL-3133 AT Vlaardingen (NL)

(74) Representative: Avila, David Victor 
Unilever Patent Group Colworth House
Sharnbrook Bedford MK44 1LQ
Sharnbrook Bedford MK44 1LQ (GB)


(56) References cited: : 
WO-A1-2006/053598
WO-A1-2007/039042
WO-A1-2007/006357
WO-A1-2009/141173
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF INVENTION



    [0001] The present invention concerns laundry shading dye compositions.

    BACKGROUND



    [0002] WO2005/014769 (Ciba) discloses granule containing 2-70wt% of an azo, triphenyl methane and phthalocyanine dyestuff, for inclusion in granular detergent compositions. The granules were preferably made by fluid bed processes or spray drying.

    [0003] WO2008/017570 (Unilever) discloses acid azine dyes for inclusion in laundry detergent formulations.

    [0004] WO/2009/141173 (Unilever) discloses preferably spray dried cationic phenazine or acid azine dye powder which contain 20 to 100 wt% of the dye. Preferably, the dye powder has an average particle size, APS, from 0.1 to 300 microns, preferably 10 to 100 microns. The spray dried dye powder is mixed with a Na2SO4 or NaCl or pre-prepared granular base or full detergent formulation to give a 0.1 to 5 dye wt% mixture. This dry mix is then mixed into the granular formulation.

    [0005] WO2007/039042 (Unilever) discloses the stabilization of a dye in granular for but combining with a carboxylic acid containing polymer and sodium sulphate.

    [0006] For inclusion in granular laundry detergent formulations, spray dried dye granules lack the strength to prevent fragmentation of the granule on mixing with the powder or Na2SO4 or NaCl. Fragmentation of the granule can lead to discoloration of the powder.

    SUMMARY OF THE INVENTION



    [0007] The present invention provides a granule that has required robustness for laundry detergent compositions and provides reduced dye dust in handling.

    [0008] In one aspect the invention provides a granular laundry detergent composition comprising:
    1. (a) from 0.00005 to 0.2 wt% of a spray dried dye granule, wherein the dye granule comprises:
      1. (i) 20 to 90 wt% of a blue or violet shading dye;
      2. (ii) 1 to 20 wt% of carboxylic acid containing polymer polymer, preferably sodium carboxymethyl cellulose;
      3. (iii) 0 to 60 wt% of a alkali metal salt selected from: sodium sulphate and sodium chloride;
    2. (b) from 2 to 70 wt% of a surfactant;
    3. (c) from 5 to 50 wt% builder selected from: calcium sequestrant materials; precipitating materials; and, calcium ion-exchange materials; and,
    4. (d) 0.05 to 50 wt% a water soluble carrier salt; and,
    5. (e) 0 to 20 wt% other ingredients.


    [0009] Preferably the spray dried dye granule has an average particle size, APS, from 0.1 to 300 microns. The APS is as measured by a laser diffraction particle size analyser, preferably a Malvern HP with 100mm lens.

    DETAILED DESCRIPTION OF THE INVENTION



    [0010] The dye in the spray dried dye granule is preferably selected from cationic dyes, anionic dyes and uncharged alkoxylated dyes. These dyes are particularly effective in shading when delivered from the granule to the wash.

    [0011] The dye is preferably selected from:
    1. (1) acid azine dyes, wherein the acid azine dye is of the following core structure:

      wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
      the dye is substituted with at least one SO3- 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;
    2. (2) a cationic azine dye;
    3. (3) a cationic monoazo dye preferably selected from thiazloium dyes, isothiazolium dye, pyridine/pyridazine dye;
    4. (4) cationic naptholactam dye;
    5. (5) Direct Violet and Direct Blue dyes, for example direct violet 9, direct violet 99, direct violet 51, direct violet 35;
    6. (6) uncharged alkoxylated dyes, preferably mono-azo preferably of the following formula:

      wherein D denotes an aromatic or hetroaromatic group and R1 and R2 are independently selected from polyoxyalkylene chains having 2 or more repeating units.


    [0012] Preferably the polyoxyalkylene chains has from 4 to 20 repeating units. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

    [0013] A preferred polyoxyalkylene chain is [(CH2CR3HO)x(CH2CR4HO)yR5) in which x+y ≤ 5 wherein y ≥ 1 and z = 0 to 5, R3 is selected from: H; CH3; CH2O(CH2CH2O)zH and mixtures thereof; R4 is selected from: H; CH2O(CH2CH2O)zH and mixtures thereof; and, R5 is selected from: H; and, CH3

    [0014] It is most preferred that the dye is selected from: acid blue 59; acid blue 98; and, acid violet 50.

    CARBOXYLIC ACID CONTAINING POLYMER



    [0015] The polymer should have a weight average molecular weight greater than 2000 Daltons. The polymer must contain carboxylic acid groups. Preferred polymers are selected from sodium carboxymethyl cellulose's and polymers containing acrylic acid. More preferably are selected from acrylic acid / maleic acid co-polymer and sodium carboxymethyl cellulose's. Most preferably the polymer is sodium carboxymethyl cellulose.

    [0016] The Sodium carboxymethyl cellulose (SCMC) preferably has: a weight average molecular weight up to 1,000, 00 Daltons, more preferably 25,000 Daltons to 500,000 Daltons, even more preferably 30,000 Daltons to 120,000 Daltons.

    SURFACTANT



    [0017] The composition comprises between 2 to 70 wt% of a surfactant, most preferably 10 to 30 wt %. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.

    [0018] Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C8 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

    [0019] Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

    [0020] Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.

    [0021] The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.

    BUILDER



    [0022] Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.

    [0023] Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetraacetic acid.

    [0024] Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate. Preferably, the laundry treatment composition comprises sodium carbonate in the range from 5 to 50 wt%, most preferably 10 to 35 wt%. In the method, when used with granular laundry treatment composition, the aqueous wash solution preferably comprises 0.1 to 4 g/L of sodium carbonate.

    [0025] Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.

    [0026] The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.

    [0027] Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders.

    [0028] The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:

            0.8-1.5 M2O. Al2O3. 0.8-6 SiO2

    where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.

    [0029] Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).

    [0030] Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.

    ENZYMES



    [0031] The composition may comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.

    [0032] Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectases, lyases, and mannanases, or mixtures thereof.

    [0033] Most suitable lipases are disclosed in WO 2007/087257.

    FLUORESCENT AGENT



    [0034] The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

    PERFUME



    [0035] Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

    [0036] In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

    [0037] Perfume and top note may be used to cue the whiteness benefit of the invention.

    Experimental


    Example 1



    [0038] Granules of 100 micron average particle size where prepared by spray drying aqueous slurries containing the ingredients. The granules had the following compositions:

    Granule 1

    57% Acid Violet 50

    43% Na2SO4

    Granule 2

    57% Acid Violet 50

    33% Na2SO4

    10% Sokalan™ CP5 ex BASF, the sodium salt of an Acrylic acid / Maleic acid co-polymer.

    Granule 3

    62% Acid Violet 50

    28% Na2SO4

    10% Sodium carboxymethyl cellulose (SCMC)


    Example 2



    [0039] 0.3 wt% of the granules of example 1 were mixed with sodium sulphate for 5 minutes. The sodium sulphate was sieved to give the 250 to 500 micron size fraction. After mixing the colour of the blend was measured using are reflectometer and expressed as the ΔE value relative to sodium sulphate which did not contain the dye. The results are given in the table below.
      ΔE
    Granule 1 37
    Granule 2 28
    Granule 3 15


    [0040] Granule 2 contains the same level of Acid Violet 50 as granule 1. Granule 3 contains slightly more Acid Violet 50 than Granule 1.

    [0041] Fragmentation of the granules in the mixing process leads to discolouration of the sodium sulphate. The granules containing the polymers give lower ΔE value, indicating they are stronger.

    [0042] Granule 2 has a lower ΔE value than granule 1, indicating it is stronger.

    [0043] Granule 3 has a lower ΔE value than granule 1, indicating it is stronger.

    Example 3



    [0044] The spray dried granules of examples 1 were added to a white granular detergent powder consisting of 20% surfactant, 30% Na2CO3 remainder Na2SO4 and minors so that the powder contained 0.0018wt% Acid Violet 50. The powder was vigorously mixed and placed in open plastic cartons and stored at room temperature and humidity. The samples were examined after storage for 1 day the colour of the powders were examined
    Granule 1: light purple powder
    Granule 2: white powder
    Granule 3: white powder



    Claims

    1. A granular laundry detergent composition comprising:

    (a) from 0.00005 to 0.2 wt% of a spray dried dye granule, wherein the dye granule comprises:

    (i) 20 to 90 wt% of a blue or violet shading dye;

    (ii) 1 to 20 wt% of carboxylic acid containing polymer polymer;

    (iii) 0 to 60 wt% of a alkali metal salt selected from: sodium sulphate and sodium chloride;

    (b) from 2 to 70 wt% of a surfactant;

    (c) from 5 to 50 wt% builder selected from: calcium sequestrant materials; precipitating materials; and, calcium ion-exchange materials; and,

    (d) 0.05 to 50 wt% a water soluble carrier salt; and,

    (e) 0 to 20 wt% other ingredients.


     
    2. A granular laundry detergent composition according to claim 1, wherein the carboxylic acid containing polymer is sodium carboxymethyl cellulose.
     
    3. A granular laundry detergent composition according to claim 1 or 2, wherein the spray dried dye granule has an average particle size, APS, from 0.1 to 300 microns.
     
    4. A granular laundry detergent composition according to any one of the preceding claims, wherein the dye is selected from cationic dyes, anionic dyes and uncharged alkoxylated dyes.
     
    5. A granular laundry detergent composition according to claim 4, wherein the dye is selected from:

    (1) acid azine dyes, wherein the acid azine dye is of the following core structure:

    wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
    the dye is substituted with at least one SO3- 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;

    (2) a cationic azine dye;

    (3) a cationic monoazo dye preferably selected from thiazloium dyes, isothiazolium dye, pyridine/pyridazine dye;

    (4) cationic naptholactam dye;

    (5) Direct Violet and Direct Blue dyes;

    (6) uncharged alkoxylated dyes, preferably mono-azo preferably of the following formula:

    wherein D denotes an aromatic or hetroaromatic group and R1 and R2 are independently selected from polyoxyalkylene chains having 2 or more repeating units.


     
    6. A granular laundry detergent composition according to claim 5, wherein the dye is selected from: acid blue 59; acid blue 98; and, acid violet 50.
     
    7. A granular laundry detergent composition according to any one of the preceding claims, wherein the composition comprises a fluorescer selected from the group consisting of: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
     


    Ansprüche

    1. Körnige Waschmittelzusammensetzung,
    die Folgendes aufweist:

    (a) 0,00005 bis 0,2 Gew.-% sprühgetrocknetes Farbstoffgranulat,
    wobei das Farbstoffgranulat Folgendes aufweist:

    (i) 20 bis 90 Gew.-% eines blauen oder violetten Nuancierfarbstoffs;

    (ii) 1 bis 20 Gew.-% eines Carbonsäure enthaltenden Polymers;

    (iii) 0 bis 60 Gew.-% eines Alkalimetallsalzes, das aus Natriumsulfat und Natriumchlorid ausgewählt ist;

    (b) 2 bis 70 Gew.-% eines Tensids;

    (c) 5 bis 50 Gew.-% Komplexbildner, der ausgewählt ist aus: Calcium im Komplex bildenden Materialien, fällenden Materialien und Calciumionen-Austauschmaterialien; und

    (d) 0,05 bis 50 Gew.-% eines wasserlöslichen Trägersalzes; und

    (e) 0 bis 20 Gew.-% weitere Bestandteile.


     
    2. Körnige Waschmittelzusammensetzung nach Anspruch 1,
    wobei das Carbonsäure enthaltende Polymer Natriumcarboxymethylcellulose ist.
     
    3. Körnige Waschmittelzusammensetzung nach Anspruch 1 oder 2,
    wobei das sprühgetrocknete Farbstoffgranulat eine mittlere Teilchengröße APS von 0,1 bis 300 µm aufweist.
     
    4. Körnige Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche,
    wobei der Farbstoff aus kationischen Farbstoffen, anionischen Farbstoffen und ungeladenen alkyoxylierten Farbstoffen ausgewählt ist.
     
    5. Körnige Waschmittelzusammensetzung nach Anspruch 4,
    wobei der Farbstoff ausgewählt ist aus:

    (1) sauren Azinfarbstoffen, wobei der saure Azinfarbstoff die folgende Kernstruktur aufweist:

    worin Ra, Rb, Rc und Rd ausgewählt sind aus: H, einer verzweigten oder linearen C1-C7-Alkylkette, Benzyl, einem Phenyl und einem Naphthyl; wobei der Farbstoff mit einer SO3- und/oder -COO--Gruppe substituiert ist; der Ring B keine negative geladene Gruppe oder ein Salz davon aufweist; und der Ring A ferner substituiert sein kann, um ein Naphthyl zu bilden; wobei der Farbstoff gegebenenfalls mit Gruppen substituiert ist, die aus Amin, Methyl, Ethyl, Hydroxyl, Methoxy, Ethoxy, Phenoxy, Cl, Br, I, F und NO2 ausgewählt sind;

    (2) einem kationischen Azinfarbstoff;

    (3) einem kationischen Monoazofarbstoff, der vorzugsweise aus Thiazoliumfarbstoffen, Isothiazoliumfarbstoff, Pyridin/Pyridazin-Farbstoff ausgewählt ist;

    (4) kationischem Naphtholactamfarbstoff;

    (5) den Farbstoffen Direct Violet und Direct Blue;

    (6) ungeladenen alkoxylierten Farbstoffen, vorzugsweise Monoazo, vorzugsweise mit der folgenden Formel:

    wobei D für einen aromatischen oder heteroaromatischen Rest steht und R1 und R2 unabhängig voneinander aus Polyoxyalkylenketten mit zwei oder mehr Struktureinheiten ausgewählt sind.


     
    6. Körnige Waschmittelzusammensetzung nach Anspruch 5,
    wobei der Farbstoff ausgewählt ist aus: Acid Blue 59, Acid Blue 98 und Acid Violet 50.
     
    7. Körnige Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche,
    wobei die Zusammensetzung einen Aufheller aufweist, der aus der Gruppe ausgewählt ist, die aus Folgendem besteht: Natrium-2-(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazol, Dinatrium-4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino 1,3,5-Triazin-2-yl)]amino}stilben-2-2'-disulfonat, Dinatrium-4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilben-2-2'-disulfonat und Dinatrium-4,4'-bis(2-sulfostyryl)biphenyl.
     


    Revendications

    1. Composition granulaire de détergent pour le linge comprenant :

    (a) de 0,00005 à 0,2 % en poids d'un granulé de colorant séché par pulvérisation,
    dans laquelle le granulé de colorant comprend :

    (i) de 20 à 90 % en poids d'un colorant nuanceur bleu ou violet ;

    (ii) de 1 à 20 % en poids d'un polymère contenant un acide carboxylique ;

    (iii) de 0 à 60 % en poids d'un sel de métal alcalin choisi parmi : le sulfate de sodium et le chlorure de sodium ;

    (b) de 2 à 70 % en poids d'un tensioactif ;

    (c) de 5 à 50 % en poids d'un adjuvant choisi parmi : des matériaux séquestrant le calcium ; des matériaux de précipitation ; et, des matériaux d'échange d'ions calcium ; et,

    (d) de 0,05 à 50 % en poids d'un sel de support soluble dans l'eau ; et,

    (e) de 0 à 20 % en poids d'autres ingrédients.


     
    2. Composition granulaire de détergent pour le linge selon la revendication 1, dans laquelle le polymère contenant un acide carboxylique est le sodium carboxyméthylcellulose.
     
    3. Composition granulaire de détergent pour le linge selon la revendication 1 ou 2, dans laquelle le granulé de colorant séché par pulvérisation présente une taille moyenne de particule, APS, de 0,1 à 300 microns.
     
    4. Composition granulaire de détergent pour le linge selon l'une quelconque des revendications précédentes, dans laquelle le colorant est choisi parmi des colorants cationiques, des colorants anioniques et des colorants alcoxylés non chargés.
     
    5. Composition granulaire de détergent pour le linge selon la revendication 4, dans laquelle le colorant est choisi parmi :

    (1) des colorants d'azines acides, dans lesquels le colorant d'azine acide est un de la structure de noyau suivante :

    où Ra, Rb, Rc et Rd sont choisis parmi : H, une chaîne alkyle en C1 à C7 linéaire ou ramifiée, un groupe benzyle, un groupe phényle, et un groupe naphtyle ;
    le colorant est substitué avec au moins un groupe SO3- ou -COO-;
    le cycle B ne porte pas un groupe négativement chargé ou un sel de celui-ci ;
    et le cycle A peut de plus être substitué pour former un groupe naphtyle ;
    le colorant est éventuellement substitué par des groupes choisis parmi : une amine, un groupe méthyle, éthyle, hydroxyle, méthoxy, éthoxy, phénoxy, Cl, Br, I, F et NO2 ;

    (2) un colorant d'azine cationique ;

    (3) un colorant monoazo cationique de préférence choisi parmi des colorants de thiazolium, des colorants d'isothiazolium, un colorant de pyridine/pyridazine ;

    (4) un colorant de naphtolactame cationique ;

    (5) des colorants violet direct et bleu direct ;

    (6) des colorants alcoxylés non chargés, de préférence mono-azo de préférence de la formule suivante :

    où D indique un groupe aromatique ou hétéroaromatique et R1 et R2 sont indépendamment choisis parmi des chaînes polyoxyalkylène ayant 2 unités répétitives ou plus.


     
    6. Composition granulaire de détergent pour le linge selon la revendication 5, dans laquelle le colorant est choisi parmi : le bleu acide 59 ; le bleu acide 98 ; et, le violet acide 50.
     
    7. Composition granulaire de détergent pour le linge selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend un fluorescent choisi dans le groupe constitué de : sodium 2 (4-styryl-3-sulfophényl)-2H-naphtol[1,2-d]triazole, 4,4'-bis{[(4-anilino-6-(N-méthyl-N-2-hydroxyéthyl)amino-1,3,5-triazin-2-yl)]amino}stilbène-2,2'-disulfonate de disodium, 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbène-2,2'-disulfonate de disodium, et disodium 4,4'-bis(2-sulfostyryl)biphényle.
     






    Cited references

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    Non-patent literature cited in the description