BIS HETEROCYCLIC AZO DYES
Field of Invention
The present invention concerns laundry shading dye compositions.
Background of the Invention
WO2006/045375 (Unilever), disclose the use of uncharged blue or violet monoazo
dyes in detergent formulations. Azothiophenes, azobenzothiazoles and
azopyridones are disclosed.
US7208459 (Procter and Gamble) and WO2008/087497 (Procter and Gamble)
disclose the use of uncharged blue or violet thiopene dyes in detergent
formulations. These dyes have one heterocyclic component and show high
lightfastness on nylon-elastane fabrics and result in overblueing of fabrics.
Summary of the Invention
We have found that overblueing of nylon-elastane fabrics after multiple washes
is reduced by selecting heterocyclic mono-azo dyes of lower lightfastness.
In one aspect the present invention provides a laundry treatment composition
comprising:
(i) from 2 to 70 wt% of a surfactant; and,
from 0.00001 to 0.5 wt% of an uncharged blue or violet mono-azo dye,
wherein the uncharged blue or violet mono-azo dyes are selected from
Di-N=N-D 2
wherein D is a heterocyclic aromatic group; and,
D2 is a heteroaromatic aromatic group.
In another aspect the present invention provides a method of treating a laundry
textile, the method comprising the steps of:
treating a textile with an aqueous solution of the uncharged blue or violet
mono-azo dye, the aqueous solution comprising from 0.1 ppb to 500 ppm,
most preferably 20ppb to 1ppm of the dye and, from 0.0 g/L to 3 g/L,
preferably 0.3 to 2 g/L, of a surfactant;
(ii) optionally rinsing; and,
(iii) drying the textile.
Detailed Description of the Invention
The uncharged blue or violet mono-azo dye is an organic molecule which when
dissolved in an organic solvent has a molar absorption extinction coefficient of at
least 5000 mol 1 L cm 1, preferably greater than 20000 mol 1 L cm 1 at a
wavelength in the range 400 to 700nm, preferably 500 to 650nm, most
preferably 540 to 600nm.
Molar absorption coefficients are preferably measured in an organic solvent,
preferably propan-2-ol, using a 1, 5 or 10 cm cell.
By uncharged it should be taken that the dye is uncharged in an aqueous
medium at a pH of 7 .
The shading dyes used in the present invention are blue or violet. In this regard
the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to
345, more preferably 260 to 320, most preferably 270 to 300. The white cloth
used is bleached non-mercerised woven cotton sheeting.
The uncharged blue or violet mono-azo dye may be a mixture of dyes falling
under the generic structure.
Heteroaromatic groups have at least one ring containing one of more elements
other than carbon. Preferably the heteroatom is selected from N, O and S, most
preferably N and S. Preferably the heteroatom(s) of the heteroaromatic groups
is part of a five or six membered ring. Preferably the Heteroaromatic is a
monocyclic six or five membered heterocyclic aromatic group.
D and D2 are directly bound to the nitrogen atoms of the azo group. Preferably,
the azo group is directly bound to the carbon atoms of the heterocyclic aromatic
groups of D and D and not directly bound to the heteroatoms of the
heterocyclic aromatic groups of D and D .
Preferably the D2 has an amine covalently bound to a carbon atom adjacent (one
bond removed therefrom) to the heteroatom on the heteroaromatic ring.
Preferably the amine is a secondary or tertiary amine, most preferably a tertiary
amine. Preferably D does not contain an amine.
Preferably D and D2 are selected from: thiophene; thiazole; isothiazole;
thiadiazole; and, pyridinyl. Most preferably D is a thiophene.
Preferred dyes are of the form:
wherein:
Ri and R2 are independently selected from: H; C 1-C8-alkyl; benzyl; phenyl; and,
polyoxyalkylene, and wherein only one of Ri and R2 may be H. Preferably, one
of Ri and R2 is a polyoxyalkylene.
R3 is selected from: acid amide; C1-C8-alkyl; heteroaromatic; and, aryl. Most
preferably R3 is selected from: NHCOCH3; phenyl; and, thienyl, more preferably
phenyl; and, thienyl.
R4 is selected from: CN; NO2; alkoxy; carboxylic acid ester; alkylsulfonyl; and,
arylsulfonyl. Preferably R4 is CN.
R5 is selected from: F; CI; Br; CN; NO2; alkoxy; phenyl; benzyl; amine; alkyl; and,
carboxylic acid ester. Preferably R5 is selected from: CH3; and, C2H5.
R 6 selected from: H; CN; NO2; alkoxy; carboxylic acid ester alkylsulfonyl; and,
arylsulfonyl. Preferably Re is CN.
R7 is selected from: CN; SCN; F; CI; Br. Preferably R7 is CN.
Rs is selected from: C 1-C8-alkyl; heteroaromatic; and, aryl. R8 is preferably
selected from: thienyl; and, phenyl.
R9 is selected from CN; NH2C(O); NO2; and, acetyl. Preferably R9 is CN.
R10 is a C 1-C8-alkyl group and is preferably CH3or C2H5.
R11 is an acid amide and is preferably NHCOCH3.
More preferably the dye is selected from structures (I) and (II), most preferably
dyes selected from structure (I).
Preferably the polyoxyalkylene chain is of the form:
[(CH2CRi2HO)x(CH 2CRi4HO)yRi 3), wherein x+y < 5, y > 1 and z = 0 to 5, and
Ri2 is selected from: H; CH3; CH2O(CH2CH 2O)zH and mixtures thereof; and,
Ri3 is selected from: CH3; C2H5; H; CH2O(CH 2CH2O)zH and mixtures thereof;
and,
R is selected from: H; and, CH3.
C 1-C8-alkyl includes linear, branched or cyclic C 1-C8-alkyl. It is preferred that
C 1-C8-alkyl is linear and of this group methyl and ethyl are preferred. Aryl is
preferably selected from phenyl and naphthyl, most preferably phenyl.
The dye may be further substituted by uncharged organic groups. It is preferred
that the uncharged organic groups should have a total molecular weight of less
than 400, preferably less than 150. Preferred uncharged organic groups are
selected from NHCOCH3, CH3, C2H5, CH3O, C2H5O, amine, OH, COOCH3,
COOC2H5, OCOCH3, OCOC2H5, CI, F, Br, I, NO2, CH3SO2, and CN.
The above uncharged organic groups are preferably found as substituents on
the alkyl, aryl and the heteroaromatic groups.
Preferred examples of these compounds are:
Suitable uncharged blue or violet mono-azo dyes for use in the present invention
have been disclosed in EP 0201 896 (BASF), EP 0362637 (BASF) and
US51 3241 2 (BASF).
Other Dyes
In a preferred embodiment of the invention, other shading colourants may be
present. They are preferably selected from blue and violet pigment such as
pigment violet 23, solvent and disperse dyes such as solvent violet 13, disperse
violet 28, bis-azo direct dyes such as direct violet 9, 35, 5 1 and 99, and
triphenodioxazine direct dyes such as direct violet 54.
Even more preferred is the presence of acid azine dyes as described in
WO 2008/01 7570; the level of the acid azine dyes should be in the range from
0.0001 to 0.1 wt%. Preferred acid azine dyes are acid violet 50, acid blue 59
and acid blue 98. Blue and Violet cationic phenazine dyes may also be present.
Photobleaches such as sulphonated Zn/AI phthalocyanins may be present.
Surfactant
The laundry composition comprises between 2 to 70 wt percent 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.
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 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 C s to
C18 primary or secondary linear or branched alcohols with ethylene oxide,
generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are usually watersoluble
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 s to Cis alcohols,
produced for example from tallow or coconut oil, sodium and potassium alkyl
C 9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl
Cio to C i 5 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 Cn to C15 alkyl benzene sulphonates and sodium
Ci2 to C i 8 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 Ci6 to Cis primary
alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.
The nonionic detergent is preferably present in amounts less than 50wt%, most
preferably less than 20wt% of the surfactant system. Anionic surfactants can be
present for example in amounts in the range from about 50% to 100 wt % of the
surfactant system.
In another aspect which is also preferred the surfactant may be a cationic such
that the formulation is a fabric conditioner.
Cationic Compound
When the present invention is used as a fabric conditioner it needs to contain a
cationic compound.
Most preferred are quaternary ammonium compounds.
It is advantageous if the quaternary amnnoniunn compound is a quaternary
ammonium compound having at least one C12 to C22 alkyl chain.
It is preferred if the quaternary ammonium compound has the following formula:
R2
R 1-N-R3 X
IR
4
in which R1 is a C12 to C22 alkyl or alkenyl chain; R2, R3 and R4 are independently
selected from C i to C4 alkyl chains and X is a compatible anion. A preferred
compound of this type is the quaternary ammonium compound cetyl trimethyl
quaternary ammonium bromide.
A second class of materials for use with the present invention are the quaternary
ammonium of the above structure in which R1 and R2 are independently selected
from C12 to C22 alkyl or alkenyl chain; R3 and R4 are independently selected from
Ci to C4 alkyl chains and X is a compatible anion.
A detergent composition according to claim 1 in which the ratio of (ii) cationic
material to (iv) anionic surfactant is at least 2:1 .
Other suitable quaternary ammonium compounds are disclosed in EP 0 239 9 10
(Proctor and Gamble).
It is preferred if the ratio of cationic to nonionic surfactant is from 1:100 to 50:50,
more preferably 1:50 to 20:50.
The cationic compound may be present from 1.5 wt % to 50 wt % of the total
weight of the composition. Preferably the cationic compound may be present
from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20
wt %.
The softening material is preferably present in an amount of from 2 to 60% by
weight of the total composition, more preferably from 2 to 40%, most preferably
from 3 to 30% by weight.
The composition optionally comprises a silicone.
Builders or Complexing Agents
Builder materials may be selected from 1) calcium sequestrant materials,
2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures
thereof.
Examples of calcium sequestrant builder materials include alkali metal
polyphosphates, such as sodium tripolyphosphate and organic sequestrants,
such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and
sodium carbonate.
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.
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.
Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)
are preferred builders.
Preferably the heterocyclic dyes are post-dosed into granular detergent
formulation in the form of spray dried granules with a size of less than 200
microns, or in coloured cues with a size of greater than 0.4mm.
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 M20 . AI2O3. 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
S1O2 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 .
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).
Preferably the laundry detergent formulation is a non-phosphate built laundry
detergent formulation, i.e., contains less than 1 wt% of phosphate. Preferably
the laundry detergent formulation is carbonate built.
Fluorescent Agent
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.
It is preferred that the aqueous solution used in the method has a fluorescer
present. When a fluorescer is present in the aqueous solution used in the
method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to
0.02 g/l.
Perfume
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.
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
[ 1 955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate,
lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
Perfume and top note may be used to cue the whiteness benefit of the invention.
It is preferred that the laundry treatment composition does not contain a
peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
Polymers
The composition may comprise one or more further polymers. Examples are
carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol),
polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and
lauryl methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition, for example poly(vinylpyrrolidone),
poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from
the formulation.
Enzymes
One or more enzymes are preferred present in a composition of the invention
and when practicing a method of the invention.
Preferably the level of each enzyme is from 0.0001 wt% to 0.1 wt% protein.
Especially contemplated enzymes include proteases, alpha-amylases,
cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or
mixtures thereof.
Suitable lipases include those of bacterial or fungal origin. Chemically modified
or protein engineered mutants are included. Examples of useful lipases include
lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa
(T. lanuginosus) as described in EP 258 068 and EP 305 2 16 or from H. insolens
as described in WO 96/1 3580, a Pseudomonas lipase, e.g. from P. alcaligenes
or P. pseudoalcaligenes (EP 2 18 272), P. cepacia (EP 331 376), P. stutzeri
(GB 1,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720
and WO 96/27002), P. wisconsinensis (WO 96/1 201 2), a Bacillus lipase, e.g.
from B. subtilis (Dartois et al. ( 1993), Biochemica et Biophysica Acta, 1131 , 253-
360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/1 6422).
Other examples are lipase variants such as those described in WO 92/05249,
WO 94/01 541 , EP 407 225, EP 260 105, WO 95/35381 ,WO 96/00292,
WO 95/30744, WO 94/25578, WO 95/14783, WO 95/2261 5, WO 97/04079 and
WO 97/07202, WO 00/60063, WO 09/1 07091 and WO09/1 11258.
Preferred commercially available lipase enzymes include Lipolase™ and
Lipolase Ultra™, Lipex™ (Novozymes A/S).
The method of the invention may be carried out in the presence of
phospholipase classified as EC 3.1 .1 .4 and/or EC 3.1 .1 .32. As used herein, the
term phospholipase is an enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol
esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions
and esterified with phosphoric acid in the third position; the phosphoric acid, in
turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which
participate in the hydrolysis of phospholipids. Several types of phospholipase
activity can be distinguished, including phospholipases A and A2 which
hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to
form lysophospholipid; and lysophospholipase (or phospholipase B) which can
hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C
and phospholipase D (phosphodiesterases) release diacyl glycerol or
phosphatidic acid respectively.
The enzyme and the shading dye may show some interaction and should be
chosen such that this interaction is not negative. Some negative interactions
may be avoided by encapsulation of one or other of enzyme or shading dye
and/or other segregation within the product.
Suitable proteases include those of animal, vegetable or microbial origin.
Microbial origin is preferred. Chemically modified or protein engineered mutants
are included. The protease may be a serine protease or a metallo protease,
preferably an alkaline microbial protease or a trypsin-like protease. Preferred
commercially available protease enzymes include Alcalase™, Savinase™,
Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and
Kannase™, (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™,
Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor
International Inc.).
The method of the invention may be carried out in the presence of cutinase.
classified in EC 3.1 .1 .74. The cutinase used according to the invention may be
of any origin. Preferably cutinases are of microbial origin, in particular of
bacterial, of fungal or of yeast origin.
Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin.
Chemically modified or protein engineered mutants are included. Amylases
include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain
of B. licheniformis, described in more detail in GB 1,296,839, or the Bacillus sp.
strains disclosed in WO 95/026397 or WO 00/060060. Commercially available
amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™,
Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and
Purastar™ (from Genencor International Inc.).
Suitable cellulases include those of bacterial or fungal origin. Chemically
modified or protein engineered mutants are included. Suitable cellulases include
cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium,
Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola
insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium
oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,1 78, US
5,776,757,
WO 89/09259, WO 96/029397, and WO 98/01 2307. Commercially available
cellulases include Celluzyme™, Carezyme™, Endolase™, Renozyme™
(Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.),
and KAC-500(B)™ (Kao Corporation).
Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin.
Chemically modified or protein engineered mutants are included. Examples of
useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus,
and variants thereof as those described in WO 93/2461 8, WO 95/1 0602, and
WO 98/1 5257. Commercially available peroxidases include Guardzyme™ and
Novozym™ 51004 (Novozymes A/S).
Further enzymes suitable for use are disclosed in WO2009/087524,
WO2009/090576, WO2009/1 48983 and WO2008/00731 8.
Enzyme Stabilizers
Any enzyme present in the composition may be stabilized using conventional
stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or
sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic
borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic
acid, and the composition may be formulated as described in e.g. WO 92/1 9709
and WO 92/1 9708.
Where alkyl groups are sufficiently long to form branched or cyclic chains, the
alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl
groups are preferably linear or branched, most preferably linear.
The indefinite article "a" or "an" and its corresponding definite article "the" as
used herein means at least one, or one or more, unless specified otherwise.
Examples
Example 1
Individual detergents liquids containing 0.01 wt% of the dyes below were
prepared. The liquids contained 10% Non-ionic surfactant (R-(OCH 2CH2)nOH,
where R is an alkyl chain of C 12 to C 15, and n is 7), 5% linear alkyl benzene
sulphonate, and 5% Sodium lauryl ether sulphate with a mean of 3, ether (-
CH2CH2O-) groups. The remainder of the formulation was water.
Example 2
A mixture of cotton, polyester and nylon-elastane (80:20) fabric was washed 4
times in demineralised water with 5g/L of the detergents of examples 1, at a
liquor:cloth of 30:1 and a temperature of 293K. Following the washes the cloth
were dried and the reflectance spectrum recorded on a reflectometer (UV
excluded). The cloths were then placed in a weatherometer and exposed to
standard Florida sunlight (0.35 W/m2 at 340nm, with 20% relative humidity) for
12 hours. The reflectance spectrum was then recorded again.
The %Reflectance values were then converted to the remission function K/S
(Kulbelka Munk) using the equation:
K/S = (1-R)2/(2R)
Where R is %Reflectance/100. These values were then used to calculate the %
of dye that had been photobleached by the light, using the equation:
%bleached = 100 x [ 1 - {K/S(1)-K/S(2)}/{K/S(3)-K/S(4)}
where
K/S(1 ) = K/S value at 570nm of sample washed with dye after irradiation
K/S(2) = K/S value at 570nm of sample washed without dye after irradiation
K/S(3) = K/S value at 570nm of sample washed with dye before irradiation
K/S(4) = K/S value at 570nm of sample washed without dye before irradiation.
The results are given in the table below:
The dyes with two heterocyclic components are photobleached more then the
reference samples with one.
Example 3
Compound E 1 was sand milled in an aqueous slurry containing lignin
sulphonate. After milling the average particle size of the E 1 particles was 0.35
microns. The aqueous slurry was then spray dried to produce granules
containing 20wt% of the dye and 80wt% ligninsulfonate, with a mean diameter of
70 microns. These granules were named GE1 .
The experiment was repeated but with the addition of sodium carboxymethyl
cellulose (SCMS) to the slurry, such that the spray dried granules contained
22wt% E 1, 10wt% SCMC and 68wt% ligninsulfonate. These granules were
named GE2.
These granules provide a convenient route to dose the dye into granular
detergents.
Comparable granules were made containing a 1:1 mix of Disperse Violet 28 and
acid violet 50.
Exemplary Base Powder Formulations A, B, C and D
Formulations were made using Lipex as the lipase, Savinase and Polarzyme as
the protease, Carezyme as the cellulose and Stainzyme as the amylase.
Disperse violet 28 is included as a post dosed 50 micron spray dried granule
containing 20% dye and 80% lignin sulfonate.
Acid Violet 50 is added via a post dosed 75 micron spray dried granule contain
50wt% dye, 45wt% Na2SO4 and 5 wt% sodium carboxymethylcellulose.
E 1 was added via GE2 of example 3 .
Exemplary Base Liquid Formulations A, B, C and D
For both powder and liquids formulations, enzyme levels are given as percent
pure enzyme. NI(7EO) refers to R-(OCH2CH2)nOH, where R is an alkyl chain of
C 2 to C 5, and n is 7 . NaLAS is linear alkyl benzene sulphonate (LAS) and
(SLES(3EO)) is C12-C18 alkyl polyethoxylate (3.0) sulphate, SDS is sodium
dodecyl sulfate.
CLAIMS
A laundry treatment composition comprising
(i) from 2 to 70 wt% of a surfactant; and
from 0.00001 to 0.5 wt% of an uncharged blue or violet mono-azo
dye, wherein the uncharged blue or violet mono-azo dyes are
selected from:
wherein D is a heterocyclic aromatic group; and,
D2 is a heteroaromatic group.
A laundry treatment composition according to claim 1, wherein D and D2
are independently selected from: thiophenes; thiazole; isothiazole;
thiadiazole; and, pyridinyl.
A laundry treatment composition according to claim 2, wherein the dye is
selected from:
wherein:
Ri and R2 are independently selected from: H; C 1-C8-alkyl; benzyl;
phenyl; and, polyoxyalkylene, and wherein only one of Ri and R2 may be
H;
R 3 is selected from: acid amide; C1-C8-alkyl; heteroaromatic; and, aryl;
R4 is selected from: CN; NO2; alkoxy; carboxylic acid ester; alkylsulfonyl;
and, arylsulfonyl;
R5 is selected from: F; CI; Br; CN; NO2; alkoxy; phenyl; benzyl; amine;
alkyl; and, carboxylic acid ester;
R 6 selected from: H; CN; NO2; alkoxy; carboxylic acid ester alkylsulfonyl;
arylsulfonyl;
R7 is selected from: CN; SCN; F; CI; and, Br;
Rs is selected from: C 1-C8-alkyl; heteroaromatic; and, aryl.
R9 is selected from CN; NH2C(O); NO2; and, acetyl;
R10 is a C 1-C8-alkyl; and,
R11 is an acid amide.
4 . A laundry treatment composition according to claim 3, wherein R and R2
are independently selected from: H; and, polyoxyalkylene.
5 . A laundry treatment composition according to claim 3, wherein R3 is
selected from: NHCOCH3; phenyl; and, thienyl.
6 . A laundry treatment composition according to claim 3, wherein R is CN.
7 . A laundry treatment composition according to claim 3, wherein R5 is
selected from: CH3; and, C2H5.
8 . A laundry treatment composition according to claim 3, wherein R7 is CN.
9 . A laundry treatment composition according to claim 3, wherein R8 is
selected from: thienyl; and, phenyl.
10 . A laundry treatment composition according to claim 3, wherein R9 is CN.
11. A laundry treatment composition according to claim 3, wherein Rio is
selected from: CH3; and, C2H5.
12 . A laundry treatment composition according to claim 3, wherein R is
NHCOCH3.
13 . A laundry treatment composition according to claim 3, wherein the
polyoxyalkylene is of the form: [(CH2CRi2HO)x (CH2CRi4HO)yRi 3),
wherein x+y < 5, y > 1, and
R12 is selected from: H; CH3; CH2O(CH2CH2O)zH, wherein z = 0 to 5, and
mixtures thereof; and,
Ri3 is selected from: CH3; C2H5; H; CH2O(CH2CH2O)zH, wherein z = 0 to
5, and mixtures thereof; and, Ri4 is selected from: H; and, CH3.
14. A laundry treatment composition according to any one of the preceding
claim, wherein the dye is further substituted by uncharged organic groups.
15 . A laundry treatment composition according to any one of the preceding
claim, wherein composition comprises perfume in the range from 0.001 to
3 wt %.
16 . A method of treating a laundry textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of the uncharged blue or
violet mono-azo dye as defined in any one of the preceding claims,
the aqueous solution comprising from 0.1 ppb to 500 ppm of the
dye and, from 0.0 g/L to 3 g/L, preferably 0.3 to 2 g/L, of a
surfactant;optionally rinsing; anddrying the textile.