FIELD OF INVENTION
[0001] The present invention concerns laundry shading dye compositions.
BACKGROUND
[0002] W02005/014769 (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] W02008/017570 (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 Na
2SO
4 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] 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 Na
2SO
4 or NaCl. Fragmentation of the granule can lead to discoloration of the powder.
SUMMARY OF THE INVENTION
[0006] The present invention provides a granule that has required robustness for laundry
detergent compositions and provides reduced dye dust in handling.
[0007] In one aspect the invention provides 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, preferably sodium
carboxymethyl cellulose;
(iii) 0 to 60 wt% of a alkali metal salt selected from: sodium sulphate and sodium
chloride, wherein;
- (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.
[0008] 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
[0009] 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.
[0010] The dye is preferably 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, for example direct violet 9, direct violet
99, direct violet 51, direct violet 35;
- (6) uncharged alkoxylated dyes, preferably mono-azo preferably of the following formula:

wherein D denotes an aromatic or hetroaromatic group and R
1 and R
2 are independently selected from polyoxyalkylene chains having 2 or more repeating
units.
[0011] 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.
[0012] A preferred polyoxyalkylene chain is [(CH
2CR
3HO)
X(CH
2CR
4HO)
yR
5) in which x+y ≤ 5 wherein y ≥ 1 and z = 0 to 5, R
3 is selected from: H; CH
3; CH
2O(CH
2CH
2O)
zH and mixtures thereof; R
4 is selected from: H; CH
2O(CH
2CH
2O)
zH and mixtures thereof; and, R
5 is selected from: H; and, CH
3
[0013] It is most preferred that the dye is selected from: acid blue 59; acid blue 98; and,
acid violet 50.
CARBOXYLIC ACID CONTAINING POLYMER
[0014] 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.
[0015] The Sodium carboxymethyl cellulose (SCMC) preferably has: a weight average molecular
weight up to 1,000,000 Daltons, more preferably 25,000 Daltons to 500,000 Daltons,
even more preferably 30,000 Daltons to 120,000 Daltons.
SURFACTANT
[0016] 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.
[0017] 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 C
6 to C
22 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 C
8 to C
18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5
to 40 EO.
[0018] 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 C
8 to C
18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl
C
9 to C
20 benzene sulphonates, particularly sodium linear secondary alkyl C
10 to C
15 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 C
11 to C
15 alkyl benzene sulphonates and sodium C
12 to C
18 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. 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 C
16 to C
18 primary alcohol sulphate together with a C
12 to C
15 primary alcohol 3 to 7 EO ethoxylate.
[0019] 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
[0020] Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating
materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
[0021] Examples of calcium sequestrant builder materials include alkali metal polyphosphates,
such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine
tetraacetic acid.
[0022] 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.
[0023] 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.
[0024] 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.
[0025] Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are
preferred builders.
[0026] 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 M
2O. Al
2O
3. 0.8-6 SiO
2
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 SiO
2 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.
[0027] 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).
[0028] Preferably the laundry detergent formulation is a non-phosphate built laundry detergent
formulation, i.e., contains less than 1 wt% of phosphate.
ENZYMES
[0029] The composition may comprise one or more enzymes, which provide cleaning performance,
fabric care and/or sanitation benefits.
[0030] Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases,
peroxidases/oxidases, pectases, lyases, and mannanases, or mixtures thereof.
FLUORESCENT AGENT
[0032] 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
[0034] 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] Perfume and top note may be used to cue the whiteness benefit of the invention.
Experimental
Example 1
[0037] 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
60% Acid Violet 50
40% Na2SO4
Granule 2
55% Acid Violet 50
35% Na2SO4
10% Sokalan™ CP5 ex BASF, the sodium saly of an Acrylic acid / Maleic acid co-polymer.
Granule 3
55% Acid Violet 50
35% Na2SO4
10% Sodium carboxymethyl cellulose (SCMC)
Example 2
[0038] 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 it the table below.
|
ΔE |
Granule 1 |
38 |
Granule 2 |
28 |
Granule 3 |
14 |
[0039] 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.
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, wherein;
(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)]aminolstilbene-2-2' disulfonate,
disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]aminol stilbene-2-2'
disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.