FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2006
PROVISIONAL SPECIFICATION
(See Section 10 and Rule 13)
SHADING DYE NON-SOAP BAR
HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification describes the invention

04538(C)

TECHNICAL FIELD
The present invention relates to detergent bars for laundry treatment that comprise a hydrophobic dye.
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BACKGROUND OF INVENTION
Garments containing the synthetic fibres, polyester, nylon
10 and elastane fibres are ubiquitous. Many garments are white but over the lifetime of these garments the whiteness is dulled, reducing the aesthetic value of the garment. Hydrophobic shading dyes have been used in particulate and liquid detergent formulation to maintain and rejuvenate the
15 whiteness of garments containing synthetic fibers as disclosed in WO2005/045375 and WO2006/032397.
Hydrophobic dyes do not contain water solubilising groups and have extremely low water solubilities at room
20 temperature. For example disperse blue 79:1 has a water solubility of only 0.0052 mg/L at 25°C, Baughman G.L., Perenich T.A. Textile Chem. Color 1989, 21, 33-37. To obtain shading benefits from hydrophobic dyes they must be properly dispersed in water. For powders the large surface area of
25 the granules aids the dispersion, particularly when combined with dispersion aids as disclosed in WO2006/053598 and WO2007/006357.
A problem with use of many hydrophobic dyes from laundry
30 powder and liquids is that adsorption is greatest to nylon
containing fabrics. It would be preferred if greatest
adsorption was to polyester as it is a much more widely used
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fabric. It would also be preferred if good adsorption to cotton also occurred.
5 SUMMARY OF THE INVENTION
To effectively include hydrophobic shading dyes in non-soap laundry detergent bars used for laundry presents problems as the low surface area makes effective dispersion difficult.
10 Due to the direct contact between garment and bar, poor dispersion of the dye can lead to the dye staining the garments in unwanted streaks. There is a need to provide non-soap laundry detergent bars that enhance the appearance of garments containing synthetic fibers without unwanted
15 staining or streaking.
Non-soap laundry detergent bars containing hydrophobic dyes give good shading benefits to garments. Surprising benefits are greatest on polyester garments and good benefits are
20 also seen on cotton garments. Preferably the hydrophobic dye is included into the bar from a solution in a water miscible organic solvent.
In one aspect the present invention provides a non-soap
25 detergent bar comprising:
(i) 5 to 60% of a non-soap detergent;
(ii) 0 to 30% of a builder; (iii) 0.5 to 50 % of a silicate; (iv) 0 to 70 % of an inorganic particulate;
30 (v) 0 to 10 % of a non-volatile water miscible solvent; and, (vi) 0.00001 to 0.1% of a hydrophobic dye.
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DETAILED DESCRIPTION OF THE INVENTION
Whilst the invention concerns non-soap bars it is within the scope of the invention for the non-soap bar to tolerate a
5 content of up to 10 % soap in the total surfactant composition. Soap may be incorporated as a minor to aid processing. However it is most preferred that the level of soap is minimized so that any effect there from is de minimis and the level of soap is preferably zero. Soap is
10 preferably minimal in order to minimize co-precipitation of calcium soaps with the dye leading to dye spotting of the garment being washed.
All percentages expressed herein are weight present unless 15 otherwise specified.
HYDROPHOBIC DYES
Typical dye suppliers may be found in the colour index, and 20 include Clariant, Dystar, Ciba & BASF.
Preferred dyes are those which deposit on textile and provide a shade to the textile such that the hue angle, h, in the CIELAB system of the shade on the textile is between
25 230° and 340° most preferably between 260° and 290°. A
detailed description of hue angle may be found on p57 of Color Chemistry 3rd edition by H. Zollinger published by Wiley-VCH. The preferred dyes are blue or violet.
30 Preferred dyes are hydrophobic dyes those which deposit on polyester.
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Hydrophobic dyes are defined as organic compounds with a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 nm and that are uncharged in aqueous solution at a pH in the range from 7 to 11. The
5 hydrophobic dyes are devoid of polar solubilizing groups. In particular the hydrophobic dye does not contain any sulphonic acid, carboxylic acid, or quaternary ammonium groups. The dye chromophore is preferably selected from the group comprising: benzodifuranes, methine,
10 triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores Most preferred are mono-azo and anthraquinone dye chromophores.
Many examples of hydrophobic dyes are found in the classes 15 of solvent and disperse dyes.
Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred
20 dyes or mixtures of dyes are ones that give a blue or violet shade on white polyester.
A wide range of suitable solvent and disperse dyes are available. However detailed toxicological studies have shown
25 that a number of such dyes are possible carcinogens, such
dyes are not preferred.
Preferred mono-azo dyes are of the form:


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wherein R3 and R4 are optionally substituted C2 to C12 alkyl chains having optionally therein ether (-0-) or ester links, the chain being optionally substituted with -CI, -Br, -CN, -NO2, and -SO2CH3; and, D denotes an aromatic or hetroaromatic
5 group. Preferably D is selected from the group consisting of: azothiophenes, azobenzothiazoles and azopyridones.
It is preferred that R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group
10 consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl. Preferred aryl are -C6H5 and C10H7.
The following is an example of a preferred class of mono-azo 15 dyes:

where X and Y are independently selected from the group
20 consisting of: -H, -CI, -Br, -CN, -N02, and -S02CH3;
A is selected -H, -CH3, -CI, and -NHCOR;
B is selected -H, -OCH3, -OC2H5, and -CI;
R1 and R2 are independently selected from the group consisting
of: -H, -CN, -OH, -OCOR, -COOR, -aryl; and
25 R is Cl-C8-alkyl.
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The following are preferred dyes: Disperse blue 10, 11, 12, 21, 30, 33, 36, 38, 42, 43, 44, 47, 79, 79:1, 79:2, 79:3, 82, 85, 88, 90, 94, 96, 100, 101, 102, 106, 106:1, 121, 122, 124, 125, 128, 130, 133, 137, 138, 139, 142, 146, 148, 149,
5 165, 165:1, 165:2, 165:3, 171, 173, 174, 175, 177, 183, 187, 189, 193, 194, 200, 201, 202, 205, 206, 207, 209, 210, 211, 212, 219, 220, 222, 224, 225, 248, 252, 253, 254, 255, 256, 257, 258, 259, 260, 264, 265, 266, 267, 268, 269, 278,
279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 10 303, 304, 305, 313, 315, 316, 317, 319, 321, 322, 324, 328,
330, 333, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 351, 352, 353, 355, 356, 358, 360, 366, 367, 368,
369, 371, 373, 374, 375, 376 and 378, Disperse Violet 2, 3, 5, 6, 7, 9, 10, 12, 13, 16, 24, 25, 33, 39, 42, 43, 45, 48,
15 49, 50, 53, 54, 55, 58, 60, 63, 66, 69, 75, 76, 77, 82, 86, 88, 91, 92, 93, 93:1, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 106 or 107, Dianix violet cc, and dyes with CAS-No's 42783-06-2, 210758-04-6, 104366-25-8, 122063-39-2, 167940-11-6, 52239-04-0, 105076-77-5, 84425-43-4, and 87606-56-2.
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The following are preferred dyes: Disperse Blue 250, 354, 364, 366, Solvent Violet 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570.
25 The dye may be fluorescent.
Preferred anthraquinone are of the following structure (I):
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wherein Rl, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH2, -NHR9, and -NO2, such
5 that a maximum of only one -N02 group and a maximum of two -H are present as Rl, R4, R5, and R8 substituents; where R9 is an branched or linear Cl-C7-alkyl chain or an aryl group or substituted aryl groups, or a branched or linear C1-C7-alkyl chain optionally substituted by an -OH group; R2, R3,
10 R6, and R7 may be selected from -H, -F, -Br, -CI, S03aryl or -N02, and -OR10, wherein RIO is selected from the group consisting of branched or linear Cl-C7-alkyl or aryl; and, R2 and R3 may together be joined to form a five membered non-aromatic ring of the form -C(=0)N(HR11)C(=X)-, wherein X
15 is 0 or NH and Rll is selected from the group consisting of Cl-C6-alkyl optionally substituted with alkoxy groups.
It is preferred that the branched or linear alkyl chain of R9 and RIO have less than six carbon atoms. It is preferred
20 that Rl, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH2, and -N02, and R2, R3, R6, and R7 is selected from -H, F, Br, CI or -N02, and -Oaryl. It is also preferred that the aryl is an optionally substituted phenyl. Of the Rl, R4, R5 and R8 it is most
25 preferred that is -OH and one is selected from -NH2 and -NHR9.
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It is preferred that R2, R3, R5, R6, R7, and R8 are -H, Rl -OH, R4 = -NHR9 or -NH2.
It is preferred that R5, R6, R7, and R8 = -H, Rl = R4 =
5 NH2, R2 = R3 = -Oaryl, or -CI.
It is most preferred that Rll is -CH2CH2CH20Me.

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The composition may also comprise between 0.0001 to 0.1 wt % of one or more other dyes having same or differing substantively to a fabric substrate. These include dyes
5 selected from cotton substantive shading dyes of the group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
Most Preferably the dyes are selected from solvent violet
10 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
NON-VOLATILE WATER MISCIBLE SOLVENT
It is preferred that during the preparation of the bar that 15 the hydrophobic dye is added via a solution of the dye in a
non-volatile water miscible solvent.
The solvent may be a solid or liquid at room temperature, and compatible with inclusion in a detergent formulation.
20 Non-volatile for the purposes of this application is defined as having a volatility less than or equal to water. Most preferably, non-volatile means having a saturated vapour pressure at 25 °C and atmospheric pressure (101325Pa) below 3000Pa, and more preferably below l00Pa.
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The solvent should be readily miscible with water, such that at least 1% weight solution in water of the solvent may be created.
30 Suitable solvents include surfactants, fatty acids, soaps and polymers. The surfactants may be isotropic or contain a dispersed water phase, for example, anionic surfactants and
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aqueous anionic surfactant pastes, fatty acids, polyethylene glycol polymers. Preferred solvents for dissolving the dye are neutral species. Most preferred solvents for dissolving the dye are non-ionic surfactants and alcoholic solvents
5 such as glycol and glycerol.
The dye is soluble in the solvent such that solution of between 0.01 and 10 wt% may be created, preferably 0.05 to 1 wt%.
10
Preferably non-ionic surfactant are, for example, fatty alcohol polyethylene glycol ether or fatty alcohol ethoxylates, alkylphenol ethoxylates, ethylene oxide and propylene oxide co-polymers, amine oxides, alkylamines,
15 alkanolamines, polyglycerol esters, alkyl polyglucosides, and fatty acid N-alkylglucosamides. A typical class of non-ionic surfactant is of the form H (CH2) mO [CH2CH20] nH, where m is 12 to 15 and n is 3 to 9; the an alkyl chain in the range C10 to C18.
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THE DETERGENT ACTIVE
The detergent active is selected from non-soap actives and
is anionic and specific detergent actives used in detergent
bar technology are described in the literature, for example 25 in Surface Active Agents and Detergents, Volume II by
Schwartz, Perry and Berch (Interscience Publishers, N.Y. 1958) .
Specific examples of suitable anionic actives useful in this 30 invention are selected from linear and branched alkyl
benzene sulphonates, alkane sulphonates, secondary alcohol sulphates, primary alcohol sulphates, alpha olefin
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sulphonates, alkyl ether sulphates, fatty acyl ester sulphonates, and mixtures of these.
The other detergent active compounds may be anionic,
5 nonionic, cationic, zwitterionic or amphoteric surfactants, or mixtures thereof as are well known to those skilled in the art can also be incorporated in the formulation. Especially preferred are compositions in which the anionic detergent active comprises linear alkyl benzene sulphonate
10 (LAS). The detergent active is present in quantities normal for detergent bars, e. g., 5 to 60 % by weight, preferably 10 to 50, more preferably about 12 to 45% by weight of the total bar composition. The in situ generation of the structuring system is done using silicate which is
15 preferably sodium silicate of the type having a molar ratio of Si02:H20 of less than 4, more preferably less than 3, most preferably between 3 and 1.
BUILDERS
20 The detergency builders used in the formulation are
preferably inorganic and suitable builders include, for example, alkali metal aluminosilicates (zeolites), alkali metal carbonate, sodium tripolyphosphate (STPP), tetrasodium pyrophosphate (TSPP), citrates, sodium nitrilotriacetate
25 (NTA) and: combinations of these. Builders are used in an amount: ranging from 0 to 30%, preferably 5 to 15%.
INORGANIC PARTICULATES
Inorganic particulate is not an essential ingredient of the 30 formulation but may be incorporated especially for hard
surface cleaning compositions. Preferably, the particulate phase comprises a particulate structurant and/or abrasive
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which is insoluble in water. Suitable inorganic particulates can be selected from, particulate zeolites, calcites, dolomites, feldspars, silicas, silicates, other carbonates, bicarbonates, borates, sulphates and polymeric materials
5 such as polyethylene.
The most preferred inorganic particulates are calcium carbonate (as Calcite), mixtures of calcium and magnesium carbonates (as dolomite), sodium hydrogen carbonate, borax,
10 sodium/potassium sulphate, zeolite, feldspars, talc, koalin
and silica.
Calcite, talc, kaolin, feldspar and dolomite and mixtures thereof are particularly preferred due to their low cost and
15 colour.
Other conventional inorganic particulate structurants such as alumina silicate may be generated in situ or readily available forms can be incorporated.
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The Inorganic particulate may include the silicate which is essential for structuring the bar.
OTHER ADDITIVES
25 Other additives such as one or more water insoluble
particulate materials such as polysaccharides such as starch or modified starches and celluloses may be incorporated.
MINOR ADDITIVES
30 Minor and conventional ingredients preferably selected from
enzymes, anti-redeposition agents, colour, and preservatives, also bleaches, bleach precursors, bleach
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stabilizers, sequestrants, soil release agents (usually 15 polymers) and other polymers may optionally be incorporated up to 10 %.
5 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
10 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
15 (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'-
20 bis{f(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-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl. Most preferred are disodium 4,4'-
25 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-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
30
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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
5 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.
10 All compositions are defined with respect to weight percentage unless otherwise specified.
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EXAMPLES
Example 1
Non-soap laundry detergent bars of the following composition
were made.

5

% Incorporation by weight
Ingredient Control Barl Bar2
Sodium carbonate 7.8 7.8 7.8
LAS (Acid 96% pure) 17.5 17.5 17.5
Non-ionic (3E0) 0 1 1
Solvent Violet 13 0 0.01 0.002
Aluminum Sulphate (50% pure) 3 3 3
STPP 8 8 8
Calcite-300 49.75 48.74 48.75
Alkaline Silicate (42% pure) 3 3 3
HA20 2.5 2.5 2.5
Tinopal CBSX 0.0045 0.045 0.045
Perfume 0.15 0.15 0.15
Water remainder Remainder Remainder
Solvent Violet 13 was dissolved in the non-ionic surfactant to give a 1 wt % solution for bar 1 and a 0.2 wt % solution for bar 2, prior to inclusion.

10 Non-ionic (3EO) is an alcohol ethoxylate of formula R-(OCH2CH2)nOH, where R is an alkyl chain with a C12 to C15 chain length and n is 3
Tinopal CBSX (ex Ciba Speciality Chemicals) is disodium 15 4,4'-bis(2-sulfostyryl)biphenyl.
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STPP is sodium tripolyphosphate.
HA20 is Calcium Hydroxide
5 Mixing of the formulation ingredients was done in a z-blade
sigma mixer. The mixer has a jacket to circulate hot water
at 80°C. The sequence of addition for the control batch and
bar 1 and bar 2 was as follows.

10 Control Bar 1 and Bar2
Sodium carbonate Sodium carbonate
LAS acid LAS acid
Aluminium sulphate Svl3/nonionic solution E03
STPP Aluminium sulphate
15 Calcite 300 STPP
Alkaline silicate Calcite 300
Calcite 300 Alkaline silicate
HA-2 0 Calcite 300
Tinopal CBSX HA-20
20 Perfume Tinopal CBSX Perfume
Mixing of all the formulation ingredients was done at 80°C in z-blade mixer. The batch mixing time was from 20 to 23
25 minutes. The mixed formulation was then extruded in a duplex twin screw plodder with chilled water provided in the barrel.
Example 2
30 The bars of Example 1 were used to wash 10cm x 20cm pieces
of knitted polyester, knitted nylon and woven cotton
fabrics. The fabrics were washed together in 500ml of cold
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demineralised water (20°C) . Each side of each fabric was scrubbed ten times with the bar. Following the scrubbing the fabrics were left together in the water for several minutes, rinsed then dried.
5
Following drying the reflectance spectra (UV excluded from 420nm) of the cloths were recorded. Each measurement was through 4 thicknesses of cloth, and 4 measurements were made from different parts of each cloth. The average %
10 reflectance at 570nm, R570, (where solvent violet 23 adsorbs) are given in the table below.

R570
Control 0.002% dye 0.01% dye
Cotton 88.6 88.3 87.5
Nylon 89.9 89.9 88.6
Polyester 88.2 87.4 83.6
15 Adsorbed of the dye to the cloths may be observed by a decrease in R570. Dye adsorption is greatest for polyester, then cotton then nylon.
20
25
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In separate Top Loading Automatic washing machine experiments were cloths are washed with 2g/L of a sodium tripolyphosphate built, LAS based detergent powder containing 0.01 wt% solvent violet 13, most adsorption is 5 seen on nylon, then polyester, then cotton. The drops in reflectance were 3.5 for nylon, 2.1 for polyester and 1.3 for cotton.
Dated this 8th day of March 2007 10

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