Title of Invention

GRANULAR LAUNDRY TREATMENT COMPOSITIONS

Abstract The present invention provides a granule comprising one or more shading dyes solubilized in a non-ionic surfactant. The granule, for use in laundry compositions, has reduced spotting properties.
Full Text C4408/C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
LAUNDRY TREATMENT COMPOSITIONS
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 particularly describes the invention and the manner in which it is to be performed

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LAUNDRY TREATMENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to laundry treatment 5 compositions that comprise a dye.
BACKGROUND OF THE INVENTION
WO02/10327, to Unilever, discloses the use of sodium
chloride to reduce staining of fabrics.
10
US 6,696,400, to Unilever, discloses a speckle composition
for use in particulate laundry detergent compositions
comprising a porous granular carrier, and at least 0.01 wt %
photobleach based on the active ingredient the composition
15 being layered with a finely divided high carrying capacity
particulate material and/or a water-soluble material.
Dyes are used in detergent powders in order to provide colouring of the powder or shading benefits to white
20 fabrics. One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
SUMMARY OF THE INVENTION
25 We have found that the use of non-ionic surfactants may be applied to non-ionic surfactant soluble dyes in order to reduce and/or prevent undesired spotting of fabrics by the dye under wash conditions. In particular, the present invention is applicable to dyes that are substantive to
30 fabrics.

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In one aspect the present invention provides a granule comprising:
(i)between 5 to 40 wt% of a non-ionic surfactant having dissolved therein between 0.0001 to 5% wt % of a dye,
5 wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt %;
(ii) between 20 to 90 wt% of a solid carrier; (iii) between 0 to 20 wt% of a binder; and, (iv) between 0 to 1 wt% of a photo-bleach.
10
Preferably the amount of dye dissolved in the non-ionic surfactant is in the range between 0.1 to 2 wt%. Preferably the dye has a solubility in the non-ionic surfactant of at least 0.1 wt%, more preferably 1 wt %, and even more
15 preferably at least 5 wt%.
The solubility of the dye referred to herein is that to be measured at 25 °C.
20 It is preferred that the dye has a visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm. The most preferred is a dye or a mixture thereof that have the visual appearance as blue or violet. Preferably the dyes are those
25 substantive to a fabric, in particular cotton and polyester.
In another aspect the present invention provides a laundry composition comprising a granule as defined herein and a method of treating a textile.
30

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In a further aspect the present invention provides a method of granulation comprising the steps of:
(i)dissolving between 0.0001 to 5 wt %, preferably 1 wt %, of a dye in 5 to 40 wt% of a non-ionic surfactant, the dye
5 having a solubility in the non-ionic surfactant of at least 0.1 wt%;
(ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,
(iii) granulating the resultant mixture from step (ii) .
10
In step (ii) and/or step (iii) it is preferred that a binding agent, other than the non-ionic surfactant, is used.
A "unit dose" as used herein is a particular amount of the
15 laundry treatment composition used for a type of wash,
conditioning or requisite treatment step. The unit dose may be in the form of a defined volume of powder, granules or tablet or unit dose detergent liquid.
20 DETAILED DESCRIPTION OF THE INVENTION
Non-Ionic Surfactant Soluble Dye
The dye or mixture of dyes used in the granule of the present invention need to have a solubility % in the non-
6
25 ionic surfactant, or mixture thereof, of at least 0.1 wt%.
The dye individually or as a mixture of dyes preferably have the visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to
30 650nm, most preferably from 570nm to 630nm. This visual
effect provides the aesthetic appearance of blue to violet-

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blue which in turn the consumer perceives as whiteness. Preferred dyes for shading polyester are hydrophobic dyes and preferred dyes for shading cotton are: hydrolysed reactive dyes; acid dyes; and direct dyes.
5
The dyes found below may be used individually or in mixture with the present invention and are provided, as example, but are preferred dyes.
10 HYDROPHOBIC DYE
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 ran and that are uncharged in aqueous solution at a pH in the range from 7 to 11. The
15 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: azo; anthraquinone; phthalocyanine;
20 benzodifuranes; quinophthalones; azothiophenes;
azobenzothioazoles and, triphenylmethane chromophores. Most preferred are azo and anthraquinone dye chromophores.
Many examples of hydrophobic dyes are found in the classes
25 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
30 dyes or mixtures of dyes are ones that give a blue or violet shade on white.

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A wide range of suitable solvent and disperse dyes are available. However detailed toxicological studies have shown that a number of such dyes are possible carcinogens, for example disperse blue 1. Such dyes are not preferred. More
5 suitable dyes may be selected from those solvent and
disperse dyes used in cosmetics. For example as listed by the European Union in directive 76/768/EEC Annex IV part 1. For example disperse violet 27 and solvent violet 13.
10 Preferred azo hydrophobic dykes for use in the present
invention are: 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-, 165, 165:1, 165:2,
15 165:3, 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, 270, 278, 279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 303, 304, 305,
20 313, 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, 49, 50, 53, 54,
25 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.
30
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bridging group. The chromophore serves to provide a colour and the anchor to bind to a textile substrate.
A marked advantage of reactive dyes over direct dyes is that
5 their chemical structure is much simpler, their absorption bands are narrower and the dyeing/shading are brighter; industrial Dyes, K. Hunger ed. Wiley-VCH 2003 ISBN 3-527-30426-6. However, mammalian contact with reactive dyes results in irritation and/or sensitisation of the
10 respiratory tract and/or skin. In addition, wash conditions are not ideal for deposition of dyes because the efficiency of deposition is low.
With regard to reducing irritation and/or sensitisation, it
15 is preferred that each individual anchor group of each reactive dyes is hydrolysed such that the most reactive group(s) of anchor groups of the dye is/are hydrolysed. In this regard, the term hydrolysed reactive dye encompasses both fully and partially hydrolysed reactive dyes.
20
The reactive dye may have more than one anchor. If the dye has more than one anchor, then each and every anchor, that contributes to irritation and/or sensitisation, needs to be hydrolysed to the extent discussed above.
25
The hydrolysed dyes comprise a chromophore and an anchor - that are covalently bound and may be represented in the following manner: Chromophore-anchor. The linking between the chromophore and an anchor are preferably provided by -
30 NH-CO-, -NH-, NHCO-CH2CH2-, -NH-C0-, or -N=N-.

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Preferably the hydrolysed reactive dye comprises a .
chromophore moiety covalently bound to an anchoring group,
the anchoring group for binding to cotton, the anchoring
group selected from the group consisting of: a
5 heteroaromatic ring, preferably comprising a nitrogen
heteroatom, having at least one -OH substituent covalently
SO2-C—C—OH
H2 H2
bound to the heteroaromatic ring, and
It is preferred that the anchor group is of the form:

wherein:
n takes a value between 1 and 3;
15 X is selected from the group consisting of: -CI, -F, NHR, a
quaternary ammonium group, -OR and -OH;
R is. selected from: an aromatic group, benzyl, a C1-C6-
alkyl; and, wherein at least one X is -OH. It is preferred
that R is selected from napthyl, phenyl, and -CH3. Most
20 preferably the anchor group is selected from the group
consisting of:

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N CI
SO^-C—C—OH
DH H, H,
UM , and 2 2
Preferably, the chromophore is selected from the group consisting of: azo, anthraquinone, phthalocyanine, formazan
5 and triphendioaxazine.
Preferably, the chromophore is linked to the hydrolysed anchor by a bridge selected from the group consisting of: -NH-CO-, -NH-, NHC0-CH2CH2-, -NH-CO-, and -N=N-.
10
Most preferred hydrolysed reactive dyes are hydrolysed Reactive Red 2, hydrolysed Reactive Blue 4, hydrolysed Reactive Black 5, and hydrolysed Reactive Blue 19.
15 ACID DYE
The following are preferred classes of acid dyes.
The group comprising blue and violet acid dyes of structure

20

NH2 O HN

where at least one of X and Y must be an aromatic group, preferably both, the aromatic groups may be a substituted
25 benzyl or napthyl group, which may be substituted with non

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water solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulphonates or carboxylates, most preferred is where X is a nitro substituted benzyl
5 group and Y is a benzyl group.
The group comprising red acid dyes of structure



-0,S
-03S
or

10

15

where B is a napthyl or benzyl group that may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, B may not be substituted with water solubilising groups such as sulphonates or carboxylates.

The group the following structures:





20 wherein:

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the naphthyl is substituted by the two S03- groups in one of the following selected orientations about ring: 7,8; 6,8; 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3, and 4,3;
5
B is an aryl group selected from phenyl and naphthyl, the aryl group substituted with a group independently selected from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one
N=N-C10H7 group; one or more -OMe; and, one or more -Me.
10
The group of the following structures:


15 wherein:
X. is selected from the group consisting of -OH and -NH2;
R is selected from the group consisting of -CH3 and -OCH3;
n is an integer selected from 0, 1 2,and 3; and
one of the rings A, B and C is substituted by one sulphonate
20 group.
The following are examples of preferred acid dyes that may be used with the present invention: acid black 24, acid blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17,

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acid red 51, acid red 73, acid red 88, and acid red 87, acid red 91, acid red 92, acid red 94, and acid violet 17.
DIRECT DYE
5 The following are examples of direct dyes that may be used with the present invention.
Preferred direct dyes are selected from the group comprising tris-azo direct blue dyes of the formula:
10

where at least two of the A, B and C napthyl rings are 15 subsituted by a sulphonate group, the C ring may be
substituted at the 5- position by an NH2 or NHPh group, X is a benzyl or napthyl ring substituted with upto 2 sulphonate groups and may be substituted- at 2 position with a OH group and may also be. substituted with an NH2 or NHPh group,
20
Other preferred direct dyes are selected from the group comprising bis-azo direct violet dyes of the formula:

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-ChS
where Z is H or phenyl, the A ring is preferably substituted by a methyl and methoxy group at the positions indicated by
5 arrows, the A ring may also be a naphthyl ring, the Y group is a benzyl or naphthyl ring, which is substituted by sulphate group and may be mono or disubstituted by methyl groups.
10 Non-limiting examples of these dyes are direct violet 5, 7, 9, 11, 31, and 51. Further non-limiting examples of these dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and 120. Preferably the dye is direct violet 9.
15 Mixed Fibre Dye Mixtures
When a garment is of mixed fibre, e.g., polyester cotton, dyes that are substantive to each respective fibre are preferred because otherwise even whiteness across the fibre threads is not maintained. In this regard, the granules may
20 comprise different dyes or a mixture of dyes such that a
laundry composition comprising the granules of the present invention comprise between 0.001 to 0.01 wt % of a hydrophobic dye for shading polyester and/or between 0.001 to 0.01 wt % of one or more other dyes selected from cotton
25 substantive shading dyes of the group consisting of:
hydrolysed reactive dye; acid dye; and direct dye. The level of dye found in the laundry composition is provided by the

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dye in the granule as defined herein. With respect to the above, the total dye in the laundry composition is most preferably in the range between 0.001 to 0.01 wt %.
5 It is preferred that the dye(s) has a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 run. Tuning of levels of the respective dyes in the composition will be such that dye deposition to the polyester and cotton will be aesthetically matched. It
10 is preferred that the dyes have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm. A combination of dyes may be used which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester or cotton of from 550nm
15 to 650nm, preferably from 570nm to 630nm. This may be
provided, for example by mixing a red and green-blue dye to yield a blue or violet shade. A specific example for the acid dyes is a mixture of acid red 17, acid red 88, acid red 51, and/or acid red 73 with acid black 1 and/or acid blue
20 25. The same spectral quantities are required for both the cotton and polyester substantive dyes.
The Non-Ionic Surfactant
Preferred non-ionic surfactants are, for example,
25 polyethoxylated alcohols, ethoxylated alkyl phenols,
anhydrosorbitols, and alkoxylated anhydrosorbitol esters. An example of a preferred nonionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol".
30 Examples of preferred Neodols are Neodol 25-7 which is a
mixture of 12 to 15 carbon chain length alcohols with about

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7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with about 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide; and Neodol 45-7, a C14-15 mixture with about seven moles of
5 ethylene oxide. Other nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those, manufactured and marketed by Union Carbide Corporation under the Trademark Tergitol, octyl phenoxy polyethoxy ethanols sold by Rohm and Haas
10 under the Trademark Triton, and polyoxyethylene alcohols, such as Brij 7 6 and Brij 97, trademarked products of Atlas Chemical Co. The hydrophilic lipophilic balance (HLB), is preferably below about 13, and more preferably below 10.
15 Where an agglomeration process is used, and preferably where zeolite and/or clay is the carrier, it is preferred that a ratio of carrier to surfactant falls within the range of about 1:1 to 10:1, more preferably about 2:1 to 5:1. It is within the scope of the invention to use mixtures of non-
20 ionic surfactants. Most preferably the non-ionic-surfactant is an ethoxylated surfactant.
THE CARRIER
The carrier may be water/surfactant soluble carrier or
25 water/surfactant insoluble. Preferred examples of
water/surfactant soluble carriers are sodium carbonate, sodium sulphate, sodium chloride, and sodium citrate. It is however preferred that the carrier is water/surfactant insoluble and in this regard preferred carriers are zeolite (e.g., zeolite
30 4A and zeolite MAP), clay and minerals; most preferably clay. The preferred clay is bentonite.

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THE GRANULE
The granule is preferably 180 to 1000 microns in maximum width. This is reflected by the ability of the granule to pass through a graded sieve.
5
FLUORESCENT AGENT
The granule most preferably comprises a fluorescent
agent(optical brightener). Fluorescent agents are well known
and many such fluorescent agents are available commercially.
10 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 laundry treatment composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
15 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:
20 sodium 2 (4-styryl-3~sulfophenyl)-2H-napthol[1,2-d]trazole, 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-l,3,5-triazin~2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-
25 bis(2-sulfoslyryl)biphenyl.
PHOTOBLEACH
The granule may also comprise a photo-bleach which is a compounds that absorbs light in the range 290 to 750nm. On
30 absorption of light the photobleach produces reactive species such as singlet oxygen or radicals, with high

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quantum yields (>0.05), that can bleach stains. Examples of photobleaches are radical photoinitiators, such as vitamin K3 and singlet oxygen producing dyes
such as metallated phthalocyanines (marketed by CIBA under
5 the TINOLUX tradename).
THE LAUNDRY DETERGENT COMPOSITION
The granule of the present invention may be the laundry
detergent composition per se. Conversely and preferably,
10 the granule of the present invention may be mixed with other adjuncts and carriers to make up the laundry detergent composition. These other adjuncts and carriers may include, as will as components listed above, non-ionic, cationic and anionic surfactants, builders, enzymes, antifoam agents,
15 soil release polymers, sodium percarbonate, activators, transition metal catalysts, chelants, dye transfer inhibition polymers and brighteners. It is preferred that a laundry detergent composition comprising the dye containing granule is such that the dye level contribution from the
20 granule in the total detergent composition is between 0.00005 to 0.01 wt%, preferably 0.001 to 0.01 wt%.
Experimental
25 Example 1
Acid Black 1 was dissolved in COCO 7EO nonionic surfactant to give a 1 wt%. The dye/NI solution (2.5 g) was added to lOg bentonite clay powder and mixed thoroughly. At this level the mixture is still a free-flowing powder. The
30 resultant powder was then granulated with 3 g of a 4 0% solution of Sokalan CP5 polymer solution. The resultant

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granules were then dried in an oven at 80 C, and finally-sieved to give granules in the range 180 to 1000 microns.
The dry composition of these granules, granules A, was:
5

Component wt (g) % by weight
Dye 0.025g 0.18
NI 2.475 18.1
Bentonite lOg 73.0
CP5 1.2 g 8.8
Comparable granules without non-ionic were created by mixing 0.025 g of dye with 10 g bentonite and then granulating the mixture with 4 g of CP5 solution. The resulting granules
10 were again dried at 80 C and finally sieved to 180 to 1000 microns.
The dry composition of the granules, granules B, are therefore:
15

component wt (g) =5 cy weight
Dye 0.025- 0.215
Bentonite lOg 86.0
CP5 1.6g 13.8
Example 2
The granules of Example 1 were separately added to a base
20 washing powder and thoroughly mixed to give a powder with a final dye level of 0.004% by weight. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-

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phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water.
5 A 20 x 20cm piece of white bleached woven non-mercerised cotton was placed in a solution of water, such that the cloth was flat and the liquor to cloth ration was 3:1. lOg of the powder was spread on the cloth and left for 30 minutes. Then the cloth was thoroughly rinsed, dried and the
10 number of visible dye spots counted. The results are shown below.
Powder with Granule A had 62 spots. Powder with Granule B had 385 spots.
15
The dye granule with non-ionic showed substantially less spotting.
Example 3
20 The experiment of Example 1 and 2 were repeated except using direct violet 51 as the dye.
The results are shown below.
25 Powder with Granule A type had 2 spots. Powder with Granule B type had 78 spots.
The dye granule with non-ionic (A type), showed substantially less spotting.
30

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Example 4
The granules C and D, described below, were made in an analogous manner to Example 1, except with different levels of components. In all cases acid black 1 was the dye used.
5 For granule E, the bentonite was replaced by zeolite (4A).
Granule C

Component wt (g) % by weight
Acid Black 1 0.025 0.16
Nonionic 4.975 31.4
Bentonite 10 63.1
CP5 0.84 5.3
Component wt (g) % by weight
Acid Black 1 0.05g 0.32
Nonionic 4.95g 31.3
Bentonite lOg 63.1
CP5 0.84g 5.3
Granule D

10


Granule E

Component wt (g) % by weight
Acid Black 1 0.069 0.22
Nonionic 6.83 22.1
Zeolite 4A 24 77.7 .
Example 5
15 The experiment of Example 2 was repeated using the granules created in Example 5.

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Powder with Granule C type had 54 spots. Powder with Granule D type had 62 spots Powder with Granule E type had 123 spots.
5
Granule C and D contain approximately twice the level of non-ionic as granule A (Example 1), but the spotting is similar. Granule D has double the concentration of dye compared to Granule C, (and hence is preferably be dosed in
10 a laundry detergent composition at half the weight) but has similar loading. Granule E on zeolite shows less spotting than granule B, without non-ionic but more than the clay granules.
15 Example 6
To check relative performance of the dye granules, in terms of even colour delivery to cotton, a 60 ml solution of 1 g/L base powder with 0.5 g/L of the respective granules was created. In this 2 g of woven cotton cloth was washed,
20 rinsed, dried and compared to cotton washed with out addition of the dye granules using a reflectance spectrometer and expressing the difference in colour as delta E.
25 The results are given in the Table below.

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Granule Delta E
A 5.2
B 5.0
C 3.5
D 6.9
E 5.4
It should be noted that in the experiment for Granule D, there is twice as much dye added as for the others.
5 The granules with the lower level of non-ionic, A and E function as well in terms of even colour delivery to the cloth as that for the granule without non-ionic (B). The higher level of non-ionic granules, C and D deliver less colour per weight dye.
10
Example 7
Solvent Violet 13 was dissolved in COCO 7EO nonionic surfactant to give a l%wt solution. The dye/NI solution (2.5 g) was added to lOg bentonite clay powder and mixed.
15 thoroughly. At this level the mixture is still a free-flowing powder. The resultant powder was then granulated with 3 g of a 40% solution of Sokalan CP5 polymer solution as binder. The resultant granules were then dried in an oven at 80 C, and finally sieved to give granules in the range
20 180 to 1000 microns.
The dry composition of these granules was:

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Component wt (g) % by weight
Dye 0.025g 0.18
NI 2.475 18.1
Bentonite lOg 73.0
CP5 1.2 g 8.8

Example 8
The experiment of example 7 was repeated, except Solvent
5 Violet 13 was initially dissolved in COCO 3EO nonionic surfactant to give a 1 wt% solution.
Example 9
Mixtures of solid Solvent violet 13 and coco 7EO non-ionic
10 surfactant was prepared to give 1 %wt dye. This mixture was heated in glass vessels to 80 C in a laboratory oven. This mixtures melted to form dye solutions which were then poured onto zeolite A24 carrier solid in a Sirman high shear mixer and mixed thoroughly in proportions that maximise
15 agglomeration. As is well known in the art, the addition of too little liquid binder results in agglomeration of only part of the solids present whilst excess binder causes the creation of a wet-mass or dough.

Component wt (g) % by weight
SV13 Dye 0.4 0.29
NI7EO 39.6 28.9
Zeolite A24 100 71.4
20
The resultant granules were sieved to remove oversized materials (>1000um) and stored in sealed containers.

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Example 10
Analogous experiments to example 9 were repeated except the dye disperse blue 79:1 was used. The mixtures of dye and solvent were generally of lower concentration, between 0.4
5 and 0.6 %wt. The granule created had the following composition accordingly.



The granules of examples 6 to 10 show low spotting and good 10 delivery of dye to polyester.
Additional granules similar to those of examples 7 and 8 were prepared except sodium carbonate was used instead of zeolite. Granules similar to example 9 were created except a
15 mixture (1:2) of zeolite/light soda ash was used as a carrier material.
The granules of examples 7 to 10 were separately added to' a base washing powder and thoroughly mixed to give a powder
20 with a final dye level of 0.001 and 0.004% by weight. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water.
25
The granules of examples 7 to 10 were separately added to a base washing powder and thoroughly mixed to give a powder

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with a final dye level of 0.0005 and 0.002% by weight. The washing powder contained 10% NaLAS, 5% 7EO non-ionic, 1% soap, 17% zeolite A24, 12% percarbonate, 4% TAED, 40% salts (sodium sulphate, sodium carbonate) , remainder, fluorescer,
5 enzymes, anti-redep agents, moisture, perfume,
sequesterants, anti-ashing agents, antifoam and dispersants.

08-03-2006 \ EP0509518
C4408 (C) COM-Art 19
Amended 21 February 2006
- 26 -
What is claimed is:
1. A granule comprising:
(i) between 5 to 40 wt% of a non-ionic surfactant having
5 dissolved therein between' 0.0001 to 5% wt % of adye, wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt%;
(ii) between 20 to 90 wt% of a solid carrier;
(iii) between 0 to 20 wt% of a binder; and,
10 (iv) between 0 to 1 wt% of a photo-bleach,
wherein the dye is selected from: a hydrophobic dye; a hydrolysed reactive dye; an acid dye; and a direct dye, and wherein the acid dye is selected from: blue and violet acid dyes of structure
15


NH2 O

where at least one of X and Y must be an- aromatic group, preferably both, -he aromatic groups may be a substituted
20 benzyl or napthyl group, which may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulphonates or carboxylates, most preferred is where X is a nitro substituted benzyl
25 group and Y is a benzyl group;
red acid dyes of structure:
AMENDED SHEET

08-03-2006
C4408 (C) COM-Art 19
Amended 21 February 2006

EP0509518

- 27



and

where B is a napthyl or benzyl group that may be substituted with non water solubilising groups such as alkyl or alkyloxy or
5 aryloxy groups, B may not be substituted with water solubilising groups such as sulphonates or carboxylates;
groups the following structures:



10

and

SO,

wherein:
the naphthyl is substituted by the two S03- groups in one of the following selected orientations about ring: 7,8; 6,8;
15 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3, and 4,3;
B is an aryl group selected from phenyl and naphthyl, the aryl group substituted with a group independently selected from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one -
20 N=N-C10H7 group; one or more -OMe; and, one or more -Me; groups of the following structures:

AMENDED SHEET

08^03-2006
C4408 (C) COM-Art 19
Amended 21 February 2 006

EP0509518

- 28



wherein:
X is selected from the group consisting of -OH and -NH2;
5 R is selected from the group consisting of -CH3 and -OCH3; n is an integer selected from 0, 12 and 3; and one of the rings A, B and C is substituted by one sulphonate group;
10 wherein the direct dye is selected from: tris-azo direct blue dyes of the formula:


n*U7\ /
X—N


15

20

where at least two of the A, B and C napthyl rings are subsituted by a sulphonate group, the C ring may be substituted at the 5 position by an NH2 or NHPh group, X is a benzyl or napthyl ring substituted with upto 2 sulphonate groups and may be substituted, at 2 position with a OH group and may also be substituted with an NH2 or NHPh group;

AMENDED SHEET

08-03-2006 EP0509518
C4408 (C) COM-Art 19 X
Amended 21 February 2 006
- 29 -
and,
bis-azo direct violet dyes of the formula:

■o3s
5 where Z is H or phenyl, the A ring is preferably substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a naphthyl ring, the Y group is a benzyl or naphthyl ring, which is substituted by sulphate group and may be mono or disubstituted by methyl
10 groups.
2. A granule according to claim 1, wherein the granule comprises between 10 to 25 wt% of a non-ionic surfactant.
15 3. A granule according to claim 1 or 2, wherein the solid carrier is insoluble in water and surfactants.
4. A granule according to any preceding claim, wherein the
dye is substantive to a fabric and has a visual effect on
20 the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm.
5. A granule according to any preceding claim, wherein the
binder is present in the range 2 to 10 wt%.

25

6. A granule according to any preceding claim, wherein the carrier is selected from zeolite, clay and minerals.

AMENDED SHEET

'08-03-2006
C4408 (C) COM-Aft 19

EP0509518

Amended 21 February 2006
- 30 -
7. A granule according to claim 6, wherein the carrier is
selected from bentonite, zeolite 4A and zeolite MAP.
8. A granule according to any preceding claim, wherein the
5 binder is selected from the group consisting of a
polyacrylate, Polyethylene glycol, and polyacrylate/maleate copolymer.
9. A granule according to any preceding claim, wherein the
10 ratio of carrier to surfactant from about 1:1 to 10:1.
10. A granule according to claim 9, wherein the ratio of
carrier to surfactant from about 2:1 to 5:1.
15 11. A granule according to any one of claims 1 to 10,
wherein the dye is a mixture of a hydrophobic dye and a dye selected from the group consisting of: a hydrolysed reactive dye; an acid dye; and a direct dye.
20 12. A granule according to any preceding claim, wherein the hydrophobic dye is a solvent or disperse dye.
13. A granule according to any one of claims 1 to 10,
wherein the hydrophobic dye is selected from: disperse blue
25 79:1, solvent black 3, solvent violet 13, solvent blue 59, solvent blue 35, solvent red 24, disperse red 1, disperse blue 3, and disperse blue 106.
14. A granule according to any one of claims 1 to 10,
30 wherein the dye is selected from: acid black 24, acid blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17,
AMENDED SHEET

08-03-2006 EP0509518
C4408 (C) COM-Aft 19
Amended 21 February 2 006
- 31 -
acid red 51, acid red 73, acid red 88, and acid red 87, acid red 91, acid red 92, acid red 94, direct violet 9 and acid violet 17.
5 15. A granule according to claim 14, wherein the dye is direct violet 9.
16. A laundry detergent composition comprising the granule
as defined in any preceding claim, wherein the dye level
10 contribution from the granule in the total detergent composition is between 0.00005 to 0.01 wt%.
17. A laundry detergent composition comprising the granule
according to claim 16, wherein the dye level contribution
15 from the granule in the total detergent composition is between 0.001 to 0.01 wt%.
18. A method of granulation comprising the steps of:
(i) dissolving between 0.0001 to 1% wt % of a dye in 5 to
20 40 wt% of a non-ionic surfactant, that dye having a
solubility in the non-ionic surfactant of at least 0.1 wt %;
(ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,
25 (iii) granulating the resultant mixture from step (ii).
Dated this 15th day of May 2007

Documents:

713-MUMNP-2007-CANCELLED PAGES(29-1-2009).pdf

713-MUMNP-2007-CLAIMS(29-1-2009).pdf

713-mumnp-2007-claims(amended)-(29-1-2009).pdf

713-mumnp-2007-claims(complete)-(15-5-2007).pdf

713-mumnp-2007-claims(granted)-(9-9-2005).pdf

713-mumnp-2007-claims.doc

713-mumnp-2007-claims.pdf

713-mumnp-2007-correspondence(12-9-2007).pdf

713-MUMNP-2007-CORRESPONDENCE(13-5-2009).pdf

713-mumnp-2007-correspondence(22-7-2007).pdf

713-MUMNP-2007-CORRESPONDENCE(29-1-2009).pdf

713-MUMNP-2007-CORRESPONDENCE(8-2-2012).pdf

713-mumnp-2007-correspondence(ipo)-(16-9-2009).pdf

713-mumnp-2007-correspondence-received.pdf

713-mumnp-2007-description (complete).pdf

713-mumnp-2007-description(complete)-(15-5-2007).pdf

713-MUMNP-2007-DESCRIPTION(COMPLETE)-(29-1-2009).pdf

713-mumnp-2007-description(granted)-(9-9-2005).pdf

713-mumnp-2007-diagrame.doc

713-MUMNP-2007-FORM 1(15-5-2007).pdf

713-mumnp-2007-form 13(3-10-2007).pdf

713-mumnp-2007-form 18(12-9-2007).pdf

713-mumnp-2007-form 2(29-1-2009).pdf

713-mumnp-2007-form 2(complete)-(15-5-2007).pdf

713-mumnp-2007-form 2(granted)-(9-9-2005).pdf

713-MUMNP-2007-FORM 2(TITLE PAGE)-(29-1-2009).pdf

713-mumnp-2007-form 2(title page)-(complete)-(15-5-2007).pdf

713-mumnp-2007-form 2(title page)-(granted)-(9-9-2005).pdf

713-mumnp-2007-form 3(15-5-2007).pdf

713-MUMNP-2007-FORM 3(29-1-2009).pdf

713-mumnp-2007-form 5(15-5-2007).pdf

713-MUMNP-2007-FORM 5(29-1-2009).pdf

713-mumnp-2007-form-1.pdf

713-mumnp-2007-form-2.doc

713-mumnp-2007-form-2.pdf

713-mumnp-2007-form-3.pdf

713-mumnp-2007-form-pct-ipea-409.pdf

713-mumnp-2007-form-pct-ipea-416.pdf

713-mumnp-2007-form-pct-separate sheet-409.pdf

713-MUMNP-2007-GENERAL POWER OF ATTORNEY(29-1-2009).pdf

713-MUMNP-2007-OTHER DOCUMENT(29-1-2009).pdf

713-mumnp-2007-wo international publication report(15-5-2007).pdf


Patent Number 235933
Indian Patent Application Number 713/MUMNP/2007
PG Journal Number 38/2009
Publication Date 18-Sep-2009
Grant Date 09-Sep-2009
Date of Filing 15-May-2007
Name of Patentee HINDUSTAN UNILEVER LIMITED
Applicant Address HINDUSTAN LEVER HOUSE, 165-166 BACKBAY RECLAMATION MUMBAI 400 020,
Inventors:
# Inventor's Name Inventor's Address
1 BATCHELOR STEPHEN NORMAN UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON WIRRAL, MERSEYSIDE CH63 3JW,
2 BIRD JAYNE MICHELLE UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON WIRRAL, MERSEYSIDE CH63 3JW,
3 CHAPPLE ANDREW PAUL UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON WIRRAL, MERSEYSIDE CH63 3JW,
4 GRAHAM PETER UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON WIRRAL, MERSEYSIDE CH63 3JW,
5 QUADIR ANGELA 70,WILFRID ROAD, HOVE, EAST SUSSEX, BN3 7FL,
PCT International Classification Number C11D3/40
PCT International Application Number PCT/EP2005/009518
PCT International Filing date 2005-09-05
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0425580.8 2004-11-22 U.K.