Indian Patents. 253723:LAUNDRY TREATMENT COMPOSITION

Title of Invention	LAUNDRY TREATMENT COMPOSITION
Abstract	A laundry treatment composition which comprises a surfactant and from 0.0001 to 0.1 wt% of a combination of dyes which together have a visual effect on the human eye as a single dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, preferably from 570 mn to 630 mn, the combination comprising a photostable dye which is substantive to cotton.

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. Title of the invention. - LAUNDRY TREATMENT COMPOSITION 2. Applicant (a)NAME : HINDUSTAN UNILEVER LIMITED (b) NATIONALITY : An Indian Company (c) ADDRESS : Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai - 400 020, Maharashtra, India. .? . 3. PREAMBLE TO THE DESCRIPTION I The following specification particularly describes the nature of the invention and the manner in which it is to be performed. This application is divided out of Application No. 1399/MUMNP/2005 LAUNDRY TREATMENT COMPOSITIONS TECHNICAL FIELD The present invention relates to laundry treatment compositions which comprise dye which is substantive to cotton. BACKGROUND AND PRIOR ART Dyes have been included in laundry treatment products for many years. Perhaps the oldest use of dyes is to add a substantive coloured dye to coloured clothes which require rejuvenation of colour for example a substantive blue dye. . for rejuvenation of denim. These compositions usually contain a relatively high concentration of substantive dye. More recently non-substantive dyes have also been used to colour otherwise white laundry detergent compositions. In-the case of particulate detergents this has been in. the form of so-called-speckles to add colour to an otherwise white powder, however laundry detergent powders which are completely blue are also known.: When dyes have been -included in laundry treatment products in this way it was regarded as essential that non-substantive ciyes were used to prevent undesired staining of washed fabrics. It is also known that a small amount of blue or violet dye impregnated into an otherwise white' fabric can appear to have enhanced whiteness as described in Industrial Dyes {K.Hunger ed Wiley-VCH 2003). Modern white fabrics are sold with some dye in their material in order to enhance the whiteness at the point of sale of the garment. This dye is often blue or violet though other colours ere used. However-once these garments are worn and subsequent washed with a detergent composition the dye is rapidly removed from the fabric often cue to dissolution by a surfactant solution. Dye is also lost by reaction with bleach in the wash and fading cue to light. This results in £ gradual less of whiteness in addition to any other negative whiteness effects such as soiling. In many cases this leads to the appearance of a yellow colour on the cloth. Accordingly, the present invention provides a laundry treatment composition according to claim 1. DETAILED DESCRIPTION OF INVENTION Unless otherwise stated, ail percentages or parts are en a weight basis. Laundry" treatment- compositions The present invention relates to compositions which are used to treat laundry items such as clothes. Such compositions are preferably la'undry detergent compositions used for washing (especially particulate detergents, liquid detergents, laundry bars, pastes, gels or tablets), laundry fabric conditioners used for softening fabrics, pre-treatment products, post-treatment products, tumble dryer products, ironing products etc. Preferably treatment products which are applied in an aqueous environment. he eyes may be incorporated into the treatment conducts in wide variety of ways. For exar.pl e dves which are net e spray dried when the treatment product is a particulate ietergent composition. Another way cf incorcoretino dyes into particulate detergent products is to add them to :ranules which are post-added to the main detercent oovcer. in this case there nay be a concentration of eve in the granules which could present the dancer cf spcttinc and eve iamage on the clothes to be treated. This can be avoidsd ii the concentration of eye in the' granules is less than 0.1%. for liquid products the dyes are simply added to the lieuid and blended in substantially homogeneously. secsuse" the dyes are substantive, only a 'small' amount required to provide the enhanced whiteness' effect hence preferably the treatment competition comprises from O.00.1 ;o 0.1 vt%, preferably from 0.0.CC5 to 0.05 wt% of the dye, nore preferably froia 0.001 to 0.01wt%, most preferably from 3.002 to 0.003 wt%- fhe dyes : The photostable dyes of the present invention"are unusual in that they are substantive to cotton. It is preferred that the eye has a substactivity to cttton in a standard test rf greater tnan 7%, p-referbly. from 8to 80% ,more prete raly from 10 to 60%, most preferably from 15 to 40% wherein the standard test is with a dye concentration such that the solution has an optical density cf approximately 1 (5 cm pathlength} at the maximum absorption cf the dye in the . visible wavelengths (400-700nm) a surfactant concentration ot 0.3 c/L and under wash condition? of a liquour to cloth minutes, agitation time of 10 minutes- Higher substantivities are preferred as this means less eye must be added to the formulation to achieve the effect. This is creferred for reasons cf cost and also because excess levels-of dye in the formulation can lead to an unacceptable level of dye colour in the wash liquor and also in the powcer. A photostable five is a eye vnith does not quickly photodegrade in the presence of natural summer sunlight. A photostable dye in the current context may be defined as a dye which, when on cotton, does not degrade by more than 10% when subjected to 1 hour of irradiation by simulated Florida 2 2 sunlight (42 W/m in UV and 343 W/m in visible). It is preferable that the dyes have a blue and/or violet ghade. This can mean that the peak absorption frequency cf the dyes absorbed oh the cloth lies within the ranee cf from 540nm to 650nm, preferably from 570nm to 630ns. This effect can advantageously be achieved by 2 combination or dyes, each of which not necessarily having a peak absorption within these preferred ranees but together procuce an effect on the human eye which is equivalent to a single eye witn a peak absorption within one cf the orererred range;. Organic dyes are described in Industrial Dyes Iviley-VCH 2003) . A compilation of avaiarle eyes is the Colour Index published by Society of Dyer and Colourists and American Association of Textile Chemists and Colorists 2002 (see http: //www, colour-index, org' Suitable eves for the current application may be taken from any cf the chromophone quinophthaicre, azine, oxatine thiamine. It is preferbly that the dye does not contain a reactive crcuo -such as fcuni in procion and rematci dyes. Due to the wider ranee available azo, anthracutnone and triarvlmethane dves are preferred, Azo dves are especially preferbly Dyes are conventionally defined as being reactive, disoerse, direct, vat, sulphur, cationic, acid cr solvent* dyes. For Che purposes of the present invention, acid and/or direct dyes are preferred. ?or use in products which contain predominately anicnic surfactants, dyes containing acid groups are preferred. For use in products which contain predominantly catior.ic Surfactants, dyes containing basic croups are preferred. This is to prevent precipitation between the dye and - surfactant. Suitable dyes for use in products containing predominately anionic-surfactants include those listed in the Colour Index as Direct Violet Dyes (e.g. Direct Violet 1-103), Direct Blue dyes, Acid Blue and Acid Violet dyes. Suitable dyes for use in products containing predominately cationic surfactants include these listed in the Color Index as Basic Blue and Basic Violet Dyes. To avoid shade changes caused by pick or loss of a proton i-is preferred that the dye does not have 3 pKs or rKb at or near the pH of the product. Most preferably no cl-'.a :r pKs in the pH ranee of from 7 to 11. It is preferred that the dye has a high extinction coefficient, so that: a small amount of dye gives a large amount of colour. Preferably the extinction coefficient at the maximum absorption of the dye is greater than 1000 mcl~ L cm"1, preferably greater than 10,000 mol-1 L cm"1, more preferably greater than 50,000 mcl-1 L cm"1. Suitable dyes can be obtained from any major supplier such as Clariant, Ciba Speciality Chemicals, Dystar, Avecia or Bayer. Laundrv deteroent comocsitions Detergent-active compounds (surfactants) may be chosen from scap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active-' compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The preferred detergent-active compounds that can be used are soaps and synthetic non-soap- anionic and nonionic compounds. The range of from 5 to 60 wt%, preferably from 5 to 40 wt% Anionic surfactants are we11-known to t hose skilled in the art. Examples include alkyibenzene suiphonates, particularly linear aikylbenzene suiphonates having ar. =1 chain length of C5-C25; primary and secondary alkylsulphates, particularly C8-C20 primary alkyl sulphates; alkyl ether sulphates; olefin suiphonates; alkyl xylene suiphonates; dialkyl sulphosuccinates; and fatty acid ester suiphonates. Sodium salts are generally preferred. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C5-C20 aliphatic alcohols ethoxylated; with an' average of from 1 to 20 moles of ethylene oxide.perVmole of alcohol, and more especially the C10-C15 primary iand secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 mcles of ethylene oxide per mole of alcohol. Non-ethoxyiated nonionic surfactants include alkanoiamides, aikylpolygiycosides, glycerol monoethers, and polyhydroxyamides (glucamide). Cationic surfactants that may be used include quaternary ,ammonium salts of the general formula R1R2R3R4N+ X wherein the R groups are long or short hydrocarbyi chains, typically alkyl, hydroxyaikyl cr ethoxylated alkyl groups, and X is a solubilising anion {for example, compounds in which ?.i is a C3-C22 alkyl group, preferably a C8-C10 cr C12-C24 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl cr hydroxyethyi groups); and cationic esters (for example, chorine esters). Amphoteric and zwertericnic surfactents that may be used include alkyl amine oxides, betaines and sulohcbetsines. sulphonate or sulrhone :e surfactant oPtionally dmixture with one cr surfacants selected from ethoxyiated nonionic SUFICANTS non-ethrxvlated contains surfcants -. — / surfactants, oxides, alkanclamibes and combinationthereof. Surfactants are preferably present in a total amount of from 5 to €0 wt%, more preferably from 10to 40wt% Laundry detergent compositions :f the precent invention preferably contain a detergerzy building, although it is conceivable that formuletins without any butliar are possible. Laundry deterrent compositions cf the invention suitably contain from preferably from 15 to 70w % by weight, of deterg.enry outlier. Preferably, the quantity of builder is in the rente of from 15 to 50% by weight. Preferably the builder is selected from zeolite, sodium The tecle used as a builder may be the commercially available zeolite A {zeolite 4A) now widely used in laundry detergent powders. Alternatively, the zeolite may be maximum aluminium zeolite ? (zeolite KA?) as described and claimed in. I? 184 0703 (Unilever)., and commercially available as Do-zil (Trace Mark] A24 from UK Zeolite KAP is defined as an alkali metal aluminosilicate of zeolite ? type having a silicon to aluminium ratio not exceeding 1 . 32, preferably within the range of from 0.90 to 1.33, preferbly within the range of from 0.S0 to 1.20. Especially referred is zeolite MA? having a silicon to aluminium ritio not exceeding 1.07, more preferably about 1.00. The particle size of the zeolite is not critical. Zeolite A cr zeolite MAP of any suitable particle size may be used. Also preferred according to the present invention are phosphate builders, especially sodium tripolyphosphate. This may be used in combination with sodium orthophosphate,. and/or sodium pyrophosphate. Other inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate/ amorphous aiuminosilicates. Organic builders that may be present include poiycarboxyiate polymers such as pciyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric poiycarboxyiates such as citrates, gluconates, cxydisuccinates, glycer:1 men:-di-and trisuccinates, carboxymethyioxysuccinates, carboxy- methyloxymalonates, dipicolinates, hydrcxyethyl- iminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites. Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form. As well as the surfactants and builders discussed above, the compositions may optionally contain bleaching components and other active ingredients to enhance performance and properties. These optional ingredients may include, but are not limited to, any one or more of the following': soap, peroxyacid and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, proteases, lipases, cellulases, amylases, other detergent enzymes, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles and perfume. Detergent compositions according to the invention may suitably contain a bleach system. The bleach system is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution. Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred, inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating i comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao). The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%. The peroxy bleach compound may be used in conjunction with a ■ bleach activator, (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED). Also of interest are peroxybenzoic acid precursors, in particular, N,N,N-trimetnylarrcnonium toluoyloxy benzene sulphonate. A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethyleneciatine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP. Although, as previously indicated, in one preferred embodiment of the invention enzymes are preferably absent, in other embodiments detergent enzymes may be present. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. In particulate detergent compositions; detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount. Antiredeposition agents, for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present. The compositions may also contain soil release polymers, for example sulphonated and unsulphonateci PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22. Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie). Powder detergent composition of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosinc (dry-mixing) further ingredients. "Concentrated" or "compact" powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes. Tablets may be prepared by compacting powders, especially "concentrated" powders. Fabric conditioners Cationic softening material is preferably a quaternary ammonium fabric softening material. The quaternary ammonium fabric softening material compound has two C12-28 alkyl or alkenyl groups connected to the nitrogen head group, preferably via at least one ester link. It is more preferred if the quaternary ammonium material' has two ester links present. Preferably, the average chain length of the alkyl or alkenyl-group is at least C14, more preferably at least C15. Most preferably at least half of the chains have a length of C16 It is generally preferred if the alkyl or alkenyl chains are predominantly linear. The first group of cationic fabric softening compounds for use in the invention is represented by formula (I): wherein each R is independently selected from a C5-35 alkyl cr alkenyl group, R1 represents a C1-4 alkyl, C2-4 alkenyi or a C1-4 hydroxyalkyl croup, T is n is 0 or a number selected from 1 to 4, m is 1, 2 cr 3 and denotes the number of moieties to which it relates that pend directly from the N atom, and X is an anionic group, such as halides or alkyl sulphates, e.g. chloride, methyl sulphate or ethyl sulphate. Especially preferred materials within this formula are di¬al kenyl esters of trietnanol ammonium methyl sulphate. Commercial examples" include Tetrar.yl AH7-1 (di-hardened oleic ester of trietnanol ammonium methyl sulphate =0% active), AT-1 (di-cleic ester of triethanc-1 ammonium methyl sulphate 901 active), L5/90 {palm ester of trietnanol ammonium methyl sulphate 90% active), ail ex Kao. Other unsaturated quaternar" ammonium materials include Rewoquat WE_15 (C10-C20 AND C16-C18 unsaturated fatty acid reaction products with triet hand amine dimethyl sulphate quaternis 90 % activel, ex Witco Ccrcoration. The second group of cationic fabric softening compounds use in the invention is represented by formula {II}: wherein each R group is independently selected from C2-4 alkyi, hydroxyalkyl or C2-4 alkenyl groups; and wherein each R2 croup is independently selected from C8-28 alkyi or alkenyl groups; n is 0 or an integer from 1 to 5 and T and X are as defined above. Preferred materials of this class such as 1,2 his[tallowoyloxy]-3- trimethylammonium propane chloride and 1, 2-bis [oleylcxyj -3-trimethyIammonium propane chloride and their method of preparation are, for example, described in US 4137180 (Lever Brothers), the contents of which are incorporated herein. Preferably these materials also comprise small amounts of the corresponding monoester, as described in US 4137180. independently selected from C1-_22 alkyl cr alkenyl group and X is as defined above - tte iodine value of the parent fattv asyl compound acid 0 to 140, preferably from 0 to 100, more preferably from 0 to 60. It is especially preferred that the iodine value of the parent compound is from 0 to 20, e.g. 0 to 4. Where the loding value is 4 or less, the softening materials provide When unsaturated hydrocarbyl chains are present, it is preferred that the cis:trans weight ratio of the material is 50:50 or more, more preferably 60:40 or more, most preferably 70:30 or more, e.g. B5:15 or more. The iodine value of the parent fatty acid or acyl compound is measured according to the method set out in respect of parent fatty acids in WO-A1-01/46513. The softening material is preferably present in an amount of from 1 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. Typical silicones for use in the compositions of the present invention are siloxanes which have the ceneral formula RsSiO(4-a)/2 wherein each R is the same cr different and is selected from hydrocarbon and hvdroxvl a groups a be in a from 0 to 3. In the bulk material, 'a' typically has an average value of from 1.85-2-2. The silicone can have a linear or cyclic structure. It is particularly preferred that the silicone is cyclic as it is believed that cyclic silicones deliver excellent faster crying characteristics to fabrics. Preferably, the silicone is a pclydi-Ci-salkyl siloxane. Particularly preferred is polydimethyl siloxane. The siloxane is preferably end-terminated, if linear, either by a tri-Ci-g alkvlsilvl croup (e.g. trimethylsiiyl) or a hydroxy-ci-Ci-6 alkvlsilvl croup (e.g. hydroxy-dimethylsiiyl) croups, or by both. More preferably the silicone is a cyclic polymdimethyl siloxane. Suitable commercially available silicones include DC2 4 5 (pclydimethylcyclopentasiio:-:ane also known as D5), DC245 (polydimethyicyciohexasiloxane also known as D6), DC113 4 {a pre-emuIsified polycime thy 1 pentasilane also known as 15} and DC347 (a pre-emulsifled 100cSt ?DM5 fluid) ail ex Dow Corning. The silicone may be received and incorporated into the composition either directly as an oil or ore-emulsified. pre-emulsiiication is tyoicaily recuired when the silicone is of a more visecus nature. Suitable emulsifiers include cationic emulsifiers, nonionic emulsifiers or mixtures thereof. The reference to the viscosity of the silicone denotes either the viscosity before emulsification vhen the silicone i is provided as an emulsion for linccrpcration into the fabric conditioning composition cr the viscosity of the silicone itself vhen provided as an oil for incorporation into the fabric conditioning composition. The silicone preferably has a viscosity (as measured on a Brookfield RV4 viscometer at 25°C using spindle No. 4 at 100 rpni) of from icSt to less than :10,000 centi-Stokes (cSt), -preferably from 10cSt to 5,000cSt, more preferably from 2cSt to l,000cSt andmost preferably 2cSt to lOOcSt. It has been found that drying time can be reduced using silicones having a viscosity of from 1 to 500,000 cSt. However, it is most preferred that the viscosity is from 1 to less than 10,000oSt. The silicone active ingredient is preferably present at a level of from 0.5 to 20%, more preferably from 1 to 12%, most preferably from 2 to 8% by weight, based on the total weight of the composition. Optionally and advantageously, one or more un-alkoxvlated fatty alcohols are present in fabric conditioners of the present invention. Preferred alcohols have a hydrocarbyl chain length of from 10 to 22 carbon atoms, more preferably 11 to 20 carbon atoms, most preferably 15 to 19 carbon atoms. The fatty alcohol may be saturated or unsaturated, though saturated fatty alcohols are preferred as these have been found to deliver greater benefits in terms of stability, especially low temperature stability. Suitable commercially available fatty alcohols include tallow alcohol {available as.Hydrenol S3, ex Sidobre Sinnova, and Laurex CS, ex Clariant). The fatty alcohol content in the compositions is from 0 to ' 10% by weight, more preferably from 0.005 to 5% by weight, most preferably from 0.01 to 3% by weight, based on the . total weight of the composition. It is particularly preferred that a fatty alcohol is present if the composition is concentrated, that is if more than 8% by weight of the cstionic softening agent is present in the composition. It is preferred that the compositions further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. Suitable nonionic surfactants include a edit ion products- of ethylene Oxide and/or propylene oxide with fatty alcohols, Any of the alkoxylated materials of the particular type described naiter can be used as the nonionic surfactant. Suitable rurfactants are substantially water soluble surfactant;of the general formula: where R. is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyi groups; primary, secondary and branched chain alkenyl hydrocarbyi groups; and primary:, secondary and branched chain alkenyl-substituted phenolic hydrocarbyi groups; the hydrocarbyi croups having a chain length of from -8 to about 25, preferably 10 to 20, e.g. 14 to 13 carbon, atoms. - in the general formula for the alkoxylated nonionic surfactant, Y is typically: in which R has the meaning given above or can be hydrocer.; and Z is preferably from S to 40, more preferably from 10 30, most preferably from 11 to 24, e.g. 12 to 22. The level " of alloxylation, 2 denotes the average number of alkoxy groups per molecule. Preferably the nonmonic surfactant has an HIE of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16. Examples of nonionic surfactants follow. In the examples, the integer defines the nunmber of ethoxy (EG) groups in the ~olecule. The deca-, undeca-, codecs-, tetradeca-, and pentadecaethoxylates cf n-hexacecanol, and n-cctadecanol having an KL3 within the range recited herein are useful viscosity/cispersibility modifiers in the context of this invention. Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers cf the compositions are C18 EO{10}; and C18 E0{11). The ethcxylates of mixed natural or synthetic alcohols in the "tallow" chain-length range are also useful herein specific examples of such materials include tallow. alcohol-E0(11), tallow aicohol-EO(18), and tallow alcohol-EO (25), coco aicohol-EO(IC), coco alcohol-EO(lS), coco alcohol-EO{20} and coco alcohol-EO(25). The decaa-, uDdeca dodeca-, tetradeca-, pentabeca-, cctaceca-, and nonadeca-ethoxylates of 3~hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicoseriCl having an HL3 within the range recited herein are useful viscosity and/or disoersibilicy modifiers in the context of this invention. Exemplary ethoxylated secondary alcohols useful herein as the viscosity -and/or cispersibility modifiers of the compositions are: C16 10(11); C2o SO(ll); and C16 E0(14)- As in the case of the alcohol alkcxylates, the hexa- to octaceca-ethoxylates of alkylated phenols, particularly nonchydric alkylphencls, having an HLB within the rance recited herein are useful as the viscosity and/cr ! dispersibility modifiers of the instant compositions. The hex:a- to octadeca-ethoxylates of p-tri-decyloherci, m- pentadecyiphencl, and the like, are useful herein. Exemplary ethoxyiated alkyiphenols useful as the viscositv and/or dispersibility modifiers of the mixtures herein are: p-tridecyiphenol EO(ll) and s-pentaciecyiohenoi EO(IS). As used herein and as generally recognized in the art, a phenylene group in the nonionic formula is the ecuivalent o: an alkylene group containing from 2 to 4 carbon atoms. Per present purposes, nonionics containing a phenylene croup are considered to contain an equivalent number of carbonatoms " calculated as the sum of the carbon atoms in the alkyl grou; plus about 3.3 carbon atoms for each phenylene croup. The alkenyl alcohols, both primary and secondary, and alker.yi phenols corresponding to those disclrsed immediate 1 hereinabove can be ethoxyiated to an HLB within the ranee recited herein and used as the viscosity and/or dispersibility modifiers of the instant compositions. Branched chain primary and secondary alcohols which are available from the well-known "0X0" process can be ethoxylated and employed as the viscosity and/or dispers bility modifiers of compositions herein. Suitable p o i y o 1 based surfactants include sucrose esters such sucrose cnoeleates, alkyl polyclucosides such as stearyl 1 uses ices and stearyl tricluccside and alkyl polygiycercl s . The above ncnicnic surfactants are useful in the present compositions alone or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surface active agents. The nonicnic surfactant is present in"an amount from 0.01 to 10%, more preferably 0.1 to 5%, most preferably 0.35 to 3.5%, e.g. 0.5 to 2% by weight, based on the total weight of the composition. The fabric conditioner compositions of the invention preferably comprise one or more perfumes. It is well known that perfume is provided as a mixture of various components. Suitable components for use in the perfume include those described in "Perfume and Flavor Chemicals (Aroma Chemicals} by Steffen Arctander, pusiisned by the author 1S6- Hcntciait, N.J. (US), reprinted Is' April 19:2 library of Congress Catalog Number 75-91293. The perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.5 to 4.0% by weight, based on. the total we-irrt of the composition. The liquid carrier employed in the instant compositions is = t least partly water due to its low cost, relative availability, safety, and environments compatibility. The level of water in the liquid carrier is more than about 50-% preferably more than about 80%, more preferably mere than about 85%, by weight of the carrier. The level of liquid carrier is greater than about 50%, preferably greater than about 65%, more preferably greater th£n about 70%. Mixtures of water and a low molecular weight, e.a. solvent, e.g. a lower alcohol,such as ethanol, orcpanoi, i isopropanol or butanol are useful as the carrier liquid. Low molecular weight alcohols]including monohycric, dihvdric (glycol, etc.) trihydric (glycerol, etc.), and polyhydric (polyols) alcohols are also suitable carriers for use in the compositions of the present invention.. ■Co-active softeners for the cationic surfactant may also be incorporated in an amount from 0.01 to 2C% by weight, more preferably 0.05 to 10%, based on the total weight of the composition. Preferred co-active softeners include fattv esters, and fatty N - oxides . Preferred fatty esters include fatty monoesters, such as glycerol monostearate (hereinafter referred to as "GKS"). If GMS is present, then it is preferred that the level of GMS in the composition is iron 0.01 to 10% by weight, based on the total weioht cf the composition. The co-active softener may also comprise en oily sugar derivative. Suitable oily sugar derivatives, their methods oi manufacture and their oreferred amounts are described in WO-A1-01/4636I an page S line 16 to page 11 line 20, the disclosure of which is incorporated herein. in is useful, though not essential, if the compositions comprise one or more polymeric viscosity control aqents. Suitable polymeric viscosity control agents include nonionic and cationic polymers, such as hydrophcbicaliy modified cellulose ethers (e.g."Natrosol Plus, ex Hercules), cationicaliy modified starches (e.g- Softgel 5DA and Softgei SD, both ex Ave.be) . A particularly preferred viscosity control agent is a copolymer of methacrylate and cationic acrylamide available under the tradename Flosoft 2.00 (ex SN? Floerger). Nonionic and/or cationic polymers are preferably present in en amount of 0.01 to 5wt%, more preferably 0.02 to 4wt%, based on the total weight of the composition. Cther optional nonionic softeners, bactericides, soil-releases agents may also be incorporated in fabric concitioners of the invention. The compositions may also contain one or more optional ingredients conventionally included in fabric conditioning comocsit i ons such as cH buffering a cent s, oer fume carrier: fiuorescers, colourants, hydrotrcpes, antifoaming acent3, antireceoosition agents, poiyelectrolytes, enzymes, optical brightening agents, pearlescers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, antioxidants, sunscreens, anti-corrosion agents, crape imparting agents, preservatives, anti-static agents, ironing aids and other dyes . The product may be a liquid or solid. Preferably the product is a liquid which, in ,its undiluted state at ambient temperature, comprises an aqueous liquid, preferably an aqueous dispersion of the cationic softening material. When the product is an aqueous liquid, it preferably has a pH of greater than 1.5 and less than 5, more preferably greater.than 2 and less than 4.5 . The fabric conditioner composition is preferably used in the rinse cycle of a home textile laundering operation, where," it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation. EXAMPLES To determine the substantivity of a ranee- of dyes the following experiment was performed. A stock soluticn: of I.5g/L of a base washing powder in water was created. The washing powder contained 18% NaLAS, 73% salts {silicate, sodium tri-pciy-phosphate, sulphate, carbonate), 3% minors including perborate, flucrescer and enzymes, remainder impurities and water. The solution was divided into 60ml aiiquots and dye added to this to give a solution of optical density of approximately 1 (5 cm pathlength) at the maximum absorption of the dye in the visible lengths, 4OO-7O0nm. The optical density was measured using a "OV-visibie spectrometer. 1 piece of bleached, non-mercerised, hon-fiuorescent woven cotton cloth (ex Phoenic Calico} weighing 1. 3g was placed in the solution at room temperature {20DC) .-This clcth represents a slightly yellow cotton. The cloth was left to soak for 45 minutes then the solution agitated for 10 mins, rinsed and dried. Following this the optical density of the solution was re-measured and the amount of dye absorbed by the cloth calculated. This experiment was repeated for each eye and 4 replicates were done per eye. The dyes used and the % deposition is given in table 1. Table 2 gives the maximum extinction coefficient, fmax/ -in the wash solution and the peak absorption wavelength in solution and en cotton. All values are reported to 2 significant figures. Table 1 Dye % Deposition Acid Slack 1 23 food Black 1 0.50 Direct B1ue 1 48 Direct Violet 51 69 Direct Blue "71 34 Acid Violet 9 2.1 Acid Blue 80 i 6.8 Acid Violet 17 18 Acid Red 88 47 Acid Red 150 33 Table 2 Dye Type ■ [mol-1L cnf:) Amax [nm] in solution, on cotton Acid Black 1 Food Black 1 Direct 31ue 1 Direct Violet 51 Direct 31ue "71 Acid Violet 9 Acid Blue 80 Acid Violet 17 acid Red 88 Acid Red 150 Azo Azo Azo A20 Azo Triaryl Anthraquinone Triaryl Azo Azo j ■ 5.1000 41000 130000 65000 12.0000 4 6000 27000 53000 . 14400 23600 620, 630 570, 590 600, 640 550, 570 S90, 600 540 630, 630 520, 590 510, 520 520, 530 ELxamnle 2 The experiment, of example 1 was repeated except the dye level in the wash solution was decrease to 1/10th, so that the optical density was 0.1 (5 cm clath length). following the washes the Ganz whiteness of the cloth was measured (see "assessment of whiteness and Tint of Fluorescent Substrates with Good Interinstrument Correlation" Colour F.asearch and Application 19, 15S4} . The results are displayed in table 3, t-he ganz whiteness values are accurate to T/-5 units. "Large increase in the measured Ganz whiteness are iourid lor the substantive blue and violet dyes with Amax on cotton in the range 570 to 64 0. Table 3 152 17 0 Dye G&nz whiteness Control 150 Acid Black 1 171 Food Black 1 155 Direct Blue 1 25O. Direct Violet 51 203 Direct Blue 71 205 Acid Violet 9 153 Acid Blue 80 Acid Violet 17 Acid black i, direct blue 1, direct violet 51, direct blue 71 and acid violet 17 cave the greatest increase m Ganz whiteness. 71 cave a higher Gahz ;irect violet 51 and direct blu withiteness value than direct blue 1 and they nave tne ther advantage over direct blue 1 that they are not metabolised in the body to give carcinogenic amine, unlike the huge number of direct blue and violet eyes (e.g. direct blue 1} which contain moieties which breakdown to give the carcinogenic benzidine, 3,3' dimethoxyberizicir.e cr 3,3'-dimethyibenzidir.e. These dyes also have an advantage over -any direct violet dyes which contain transition metals that are hazardous to the environment and to humans. Preferred direct dyes fail into two croups: The first group ccmt>rises tris-azo direct blue dves based on the structure: where at least two of the A, 3 and C napthyl rings, are subsituted by a sulphonate group. The C ring may be substituted at the 5 position by an NK2 or NHPh" group, X is a benzyl or napthyl ring substituted with upto 2 sulphonate croups and may be substituted at 2 position with a OH croup and may also be substituted with an NH2 or HHPh group. Non-limiting examples of these dyes are direct blue 34, -'0, 71, 72, 75, 78, 82, 120. The second group comprises bis-azo direct violet dyes basec on the structure 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 ngphthyl ring, which is substituted by sulphate group and may be mono or disubstituted by methyl croups. Non-limiting examples of these dyes are direct violet 5, 7, 11, 31, 51. The invention also comprises compositions including a single dye of the structure of the first or second group, or mixtures thereof, the dye or mixture having the defined peak absorption wavelength. 'Example 3 The experiment of example 1 was repeated except using dyes at lower concentrations, such that the optical density (5cm) was approximately 0.05 and 0.025 giving faintly coloured wash liquors (i.e. using dye levels 1/20 and l/40th of experiment 1). Following washing and drying the increase in whiteness was measured by a reflectometer and expressed in Garze units. The Genz values are accurate to +/- 5 units. The results are shown in the Table 3 below. Table 4 Direct blue 71 cave the best results. Example A Example 3 was repeated but [using the blue dye Acid Black i, i the red dyes Acid Red 88 and Acid Red 150, and mixtures thereof. The results are shown in the tables below. Table 5 Table 5 The results show that mixtures of red and blue dyes gives a greater increase in whiteness than either alone. This is because the mixture produces a violet shade. 1. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01. wt% of a combination of dyes which together have a visual effect on the human eye as a single dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, the combination comprising a photostable dye which is substantive to cotton, wherein the photostable dye is selected from bis-azo direct violet dyes of the formula: where Z is H or phenyl, the A ring may be substituted by a' methyl and methoxy group at the positions indicated by arrowsf the A ring may also be a naphthyl ring, the y group is a phenyl or naphthyl ringr which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein dye is not sensitive to heat and is included in a slurry which is spray dried. 2. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01 wt% of a combination of dyes which together have a visual effect on the human eye as a single dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, the combination comprising a photostable dye which is substantive to cotton, wherein the photostable dye is selected from the group comprising a bis-azo direct violet dye of the formula: where Z is H or phenyl, the A ring may be substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a. naphthyl ring, the Y grou] is a phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the laundry treatment composition comprise; from 5 to 35 wt% sodium percarbonate having a protective coating against destabilisation, by moisture. 3. A particulate laundry detergent treatment composition which comprises a surfactant and from'0.0001 to 0.01 wt%. of a photostable dye which is substantive to cotton, the dye having a peak absorption wavelength on cotton of from 540 n to 650 nm, and wherein the photostable dye is selected from the group comprising bis-azo direct violet dyes of the formula: where 2 is H or phenyl, the A ring may be 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 phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the dye is not sensitive to heat and is included in a slurry which is spray dried. 4. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01 wt% of a photostable dye which is substantive to cotton, the dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, and wherein the photostable dye is selected from the group comprising bis-azo direct violet dyes of the formula: where Z is H or phenyl, the A ring may be 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 phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the laundry treatment composition comprises from 5 to 35 wt% sodium percarbonate having a protective coating against destabilisation by moisture. 5. A composition as claimed in any one of claims 1 to 4, which is a laundry detergent composition, preferably a particulate laundry detergent composition. 6. A composition as claimed in any of claims 1 to 4, which is a laundry fabric conditioner. 7. A composition as claimed in any preceding claim, which comprises from 5 to 60% of surfactant. Dated this 29th day of September 2008 Dr. Sanchita Ganguli Of S. Majumdar&Co. (Applicant's Agent)

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention. - LAUNDRY TREATMENT COMPOSITION
2. Applicant
(a)NAME : HINDUSTAN UNILEVER LIMITED
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Hindustan Lever House, 165/166, Backbay Reclamation,
Mumbai - 400 020, Maharashtra, India. .? .
3. PREAMBLE TO THE DESCRIPTION
I The following specification particularly describes the nature of the invention and the manner in which it is to be performed.

This application is divided out of Application No. 1399/MUMNP/2005
LAUNDRY TREATMENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to laundry treatment compositions which comprise dye which is substantive to
cotton.
BACKGROUND AND PRIOR ART
Dyes have been included in laundry treatment products for many years. Perhaps the oldest use of dyes is to add a substantive coloured dye to coloured clothes which require rejuvenation of colour for example a substantive blue dye. . for rejuvenation of denim. These compositions usually contain a relatively high concentration of substantive dye. More recently non-substantive dyes have also been used to colour otherwise white laundry detergent compositions. In-the case of particulate detergents this has been in. the form of so-called-speckles to add colour to an otherwise white powder, however laundry detergent powders which are completely blue are also known.: When dyes have been -included in laundry treatment products in this way it was regarded as essential that non-substantive ciyes were used to prevent undesired staining of washed fabrics.
It is also known that a small amount of blue or violet dye impregnated into an otherwise white' fabric can appear to have enhanced whiteness as described in Industrial Dyes {K.Hunger ed Wiley-VCH 2003). Modern white fabrics are sold with some dye in their material in order to enhance the

whiteness at the point of sale of the garment. This dye is often blue or violet though other colours ere used. However-once these garments are worn and subsequent washed with a detergent composition the dye is rapidly removed from the fabric often cue to dissolution by a surfactant solution. Dye is also lost by reaction with bleach in the wash and fading cue to light. This results in £ gradual less of whiteness in addition to any other negative whiteness effects such as soiling. In many cases this leads to the

appearance of a yellow colour on the cloth.
Accordingly, the present invention provides a laundry treatment composition according to claim 1.
DETAILED DESCRIPTION OF INVENTION
Unless otherwise stated, ail percentages or parts are en a weight basis.
*Laundry" treatment- compositions
The present invention relates to compositions which are used to treat laundry items such as clothes. Such compositions are preferably la'undry detergent compositions used for washing (especially particulate detergents, liquid detergents, laundry bars, pastes, gels or tablets), laundry fabric conditioners used for softening fabrics, pre-treatment products, post-treatment products, tumble dryer products, ironing products etc. Preferably treatment products which are applied in an aqueous environment.

he eyes may be incorporated into the treatment conducts in wide variety of ways. For exar.pl e dves which are net
e spray dried when the treatment product is a particulate
ietergent composition. Another way cf incorcoretino dyes
into particulate detergent products is to add them to
:ranules which are post-added to the main detercent oovcer.
in this case there nay be a concentration of eve in the
granules which could present the dancer cf spcttinc and eve
iamage on the clothes to be treated. This can be avoidsd i*i
the concentration of eye in the' granules is less than 0.1%.
for liquid products the dyes are simply added to the lieuid
and blended in substantially homogeneously.

secsuse" the dyes are substantive, only a 'small' amount required to provide the enhanced whiteness' effect hence preferably the treatment competition comprises from O.00.1 ;o 0.1 vt%, preferably from 0.0.CC5 to 0.05 wt% of the dye, nore preferably froia 0.001 to 0.01wt%, most preferably from 3.002 to 0.003 wt%-
fhe dyes :
The photostable dyes of the present invention"are unusual in that they are substantive to cotton. It is preferred that the eye has a substactivity to cttton in a standard test rf greater tnan 7%, p-referbly. from 8to 80% ,more prete raly from 10 to 60%, most preferably from 15 to 40% wherein the standard test is with a dye concentration such that the solution has an optical density cf approximately 1 (5 cm pathlength} at the maximum absorption cf the dye in the .

visible wavelengths (400-700nm) a surfactant concentration ot 0.3 c/L and under wash condition? of a liquour to cloth
minutes, agitation time of 10 minutes- Higher substantivities are preferred as this means less eye must be added to the formulation to achieve the effect. This is creferred for reasons cf cost and also because excess levels-of dye in the formulation can lead to an unacceptable level of dye colour in the wash liquor and also in the powcer.
A photostable five is a eye vnith does not quickly photodegrade in the presence of natural summer sunlight. A photostable dye in the current context may be defined as a dye which, when on cotton, does not degrade by more than 10% when subjected to 1 hour of irradiation by simulated Florida
2 2
sunlight (42 W/m in UV and 343 W/m in visible).
It is preferable that the dyes have a blue and/or violet ghade. This can mean that the peak absorption frequency cf the dyes absorbed oh the cloth lies within the ranee cf from 540nm to 650nm, preferably from 570nm to 630ns. This effect can advantageously be achieved by 2 combination or dyes, each of which not necessarily having a peak absorption within these preferred ranees but together procuce an effect on the human eye which is equivalent to a single eye witn a peak absorption within one cf the orererred range;.
Organic dyes are described in Industrial Dyes Iviley-VCH 2003) . A compilation of avaiarle eyes is the Colour Index published by Society of Dyer and Colourists and American Association of Textile Chemists and Colorists 2002

(see http: //www, colour-index, org' Suitable eves for the current application may be taken from any cf the chromophone
quinophthaicre, azine, oxatine thiamine. It is preferbly
that the dye does not contain a reactive crcuo -such as fcuni
in procion and rematci dyes. Due to the wider ranee
available azo, anthracutnone and triarvlmethane dves are
preferred, Azo dves are especially preferbly

Dyes are conventionally defined as being reactive, disoerse,
direct, vat, sulphur, cationic, acid cr solvent* dyes. For
Che purposes of the present invention, acid and/or direct
dyes are preferred.

?or use in products which contain predominately anicnic
surfactants, dyes containing acid groups are preferred. For
use in products which contain predominantly catior.ic
Surfactants, dyes containing basic croups are preferred.
This is to prevent precipitation between the dye and -
surfactant.
Suitable dyes for use in products containing predominately anionic-surfactants include those listed in the Colour Index as Direct Violet Dyes (e.g. Direct Violet 1-103), Direct Blue dyes, Acid Blue and Acid Violet dyes.
Suitable dyes for use in products containing predominately cationic surfactants include these listed in the Color Index as Basic Blue and Basic Violet Dyes.

To avoid shade changes caused by pick or loss of a proton i-is preferred that the dye does not have 3 pKs or rKb at or near the pH of the product. Most preferably no cl-'.a :r pKs in the pH ranee of from 7 to 11.
It is preferred that the dye has a high extinction coefficient, so that: a small amount of dye gives a large amount of colour. Preferably the extinction coefficient at the maximum absorption of the dye is greater than 1000 mcl~ L cm"1, preferably greater than 10,000 mol-1 L cm"1, more preferably greater than 50,000 mcl-1 L cm"1.
Suitable dyes can be obtained from any major supplier such as Clariant, Ciba Speciality Chemicals, Dystar, Avecia or Bayer.
Laundrv deteroent comocsitions
Detergent-active compounds (surfactants) may be chosen from scap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active-' compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The preferred detergent-active compounds that can be used are soaps and synthetic non-soap- anionic and nonionic compounds. The

range of from 5 to 60 wt%, preferably from 5 to 40 wt%

Anionic surfactants are we11-known to t hose skilled in the art. Examples include alkyibenzene suiphonates, particularly linear aikylbenzene suiphonates having ar. =1
chain length of C5-C25; primary and secondary
alkylsulphates, particularly C8-C20 primary alkyl sulphates;
alkyl ether sulphates; olefin suiphonates; alkyl xylene suiphonates; dialkyl sulphosuccinates; and fatty acid ester suiphonates. Sodium salts are generally preferred. Nonionic surfactants that may be used include the primary
and secondary alcohol ethoxylates, especially the C5-C20
aliphatic alcohols ethoxylated; with an' average of from 1 to 20 moles of ethylene oxide.perVmole of alcohol, and more
especially the C10-C15 primary iand secondary aliphatic
alcohols ethoxylated with an average of from 1 to 10 mcles of ethylene oxide per mole of alcohol. Non-ethoxyiated nonionic surfactants include alkanoiamides, aikylpolygiycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
Cationic surfactants that may be used include quaternary
,ammonium salts of the general formula R1R2R3R4N+ X wherein
the R groups are long or short hydrocarbyi chains, typically alkyl, hydroxyaikyl cr ethoxylated alkyl groups, and X is a
solubilising anion {for example, compounds in which ?.i is a C3-C22 alkyl group, preferably a C8-C10 cr C12-C24 alkyl group, R2 is a methyl group, and R3 and R4, which may be the
same or different, are methyl cr hydroxyethyi groups); and cationic esters (for example, chorine esters).

Amphoteric and zwertericnic surfactents that may be used include alkyl amine oxides, betaines and sulohcbetsines.
sulphonate or sulrhone :e surfactant oPtionally dmixture
with one cr surfacants selected from ethoxyiated
nonionic SUFICANTS non-ethrxvlated contains surfcants
-. — /
surfactants, oxides, alkanclamibes and combinationthereof.
Surfactants are preferably present in a total amount of from 5 to €0 wt%, more preferably from 10to 40wt%
Laundry detergent compositions :f the precent invention preferably contain a detergerzy building, although it is conceivable that formuletins without any butliar are possible.
Laundry deterrent compositions cf the invention suitably contain from preferably from 15 to 70w % by weight, of deterg.enry outlier. Preferably, the quantity of builder is in the rente of from 15 to 50% by weight.
Preferably the builder is selected from zeolite, sodium
The tecle used as a builder may be the commercially available zeolite A {zeolite 4A) now widely used in laundry detergent powders. Alternatively, the zeolite may be

maximum aluminium zeolite ? (zeolite KA?) as described and claimed in. I? 184 0703 (Unilever)., and commercially available as Do-zil (Trace Mark] A24 from UK
Zeolite KAP is defined as an alkali metal aluminosilicate of
zeolite ? type having a silicon to aluminium ratio not
exceeding 1 . 32, preferably within the range of from 0.90 to
1.33, preferbly within the range of from 0.S0 to 1.20.
Especially referred is zeolite MA? having a silicon to
aluminium ritio not exceeding 1.07, more preferably about
1.00. The particle size of the zeolite is not critical.
Zeolite A cr zeolite MAP of any suitable particle size may
be used.
Also preferred according to the present invention are phosphate builders, especially sodium tripolyphosphate. This may be used in combination with sodium orthophosphate,. and/or sodium pyrophosphate.
Other inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate/ amorphous aiuminosilicates.
Organic builders that may be present include poiycarboxyiate polymers such as pciyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric poiycarboxyiates such as citrates, gluconates, cxydisuccinates, glycer:1 men:-di-and trisuccinates, carboxymethyioxysuccinates, carboxy- methyloxymalonates, dipicolinates, hydrcxyethyl-

iminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites. Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
As well as the surfactants and builders discussed above, the compositions may optionally contain bleaching components and other active ingredients to enhance performance and properties.
These optional ingredients may include, but are not limited to, any one or more of the following': soap, peroxyacid and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, proteases, lipases, cellulases, amylases, other detergent enzymes, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles and perfume.

Detergent compositions according to the invention may
suitably contain a bleach system. The bleach system is
preferably based on peroxy bleach compounds, for example,
inorganic persalts or organic peroxyacids, capable of
yielding hydrogen peroxide in aqueous solution. Suitable
peroxy bleach compounds include organic peroxides such as
urea peroxide, and inorganic persalts such as the alkali
metal perborates, percarbonates, perphosphates, persilicates
and persulphates. Preferred, inorganic persalts are sodium
perborate monohydrate and tetrahydrate, and sodium
percarbonate. Especially preferred is sodium percarbonate
having a protective coating against destabilisation by
moisture. Sodium percarbonate having a protective coating
i
comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
The peroxy bleach compound may be used in conjunction with a ■ bleach activator, (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED). Also of interest are

peroxybenzoic acid precursors, in particular, N,N,N-trimetnylarrcnonium toluoyloxy benzene sulphonate.
A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethyleneciatine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
Although, as previously indicated, in one preferred embodiment of the invention enzymes are preferably absent, in other embodiments detergent enzymes may be present. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
In particulate detergent compositions; detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
Antiredeposition agents, for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present.
The compositions may also contain soil release polymers, for example sulphonated and unsulphonateci PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22. Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie).

Powder detergent composition of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosinc (dry-mixing) further ingredients.
"Concentrated" or "compact" powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.

Tablets may be prepared by compacting powders, especially "concentrated" powders.

Fabric conditioners

Cationic softening material is preferably a quaternary ammonium fabric softening material.
The quaternary ammonium fabric softening material compound has two C12-28 alkyl or alkenyl groups connected to the nitrogen head group, preferably via at least one ester link. It is more preferred if the quaternary ammonium material' has two ester links present.
Preferably, the average chain length of the alkyl or alkenyl-group is at least C14, more preferably at least C15. Most
preferably at least half of the chains have a length of C16
It is generally preferred if the alkyl or alkenyl chains are predominantly linear.
The first group of cationic fabric softening compounds for use in the invention is represented by formula (I):

wherein each R is independently selected from a C5-35 alkyl cr alkenyl group, R1 represents a C1-4 alkyl, C2-4 alkenyi or a C1-4 hydroxyalkyl croup,
T is
n is 0 or a number selected from 1 to 4, m is 1, 2 cr 3 and denotes the number of moieties to which it relates that pend
directly from the N atom, and X is an anionic group, such
as halides or alkyl sulphates, e.g. chloride, methyl sulphate or ethyl sulphate.
Especially preferred materials within this formula are di¬al kenyl esters of trietnanol ammonium methyl sulphate. Commercial examples" include Tetrar.yl AH7-1 (di-hardened oleic ester of trietnanol ammonium methyl sulphate =0% active), AT-1 (di-cleic ester of triethanc-1 ammonium methyl sulphate 901 active), L5/90 {palm ester of trietnanol ammonium methyl sulphate 90% active), ail ex Kao. Other unsaturated quaternar" ammonium materials include Rewoquat

WE_15 (C10-C20 AND C16-C18 unsaturated fatty acid reaction products with triet hand amine dimethyl sulphate quaternis 90 % activel, ex Witco Ccrcoration.
The second group of cationic fabric softening compounds use in the invention is represented by formula {II}:

wherein each R group is independently selected from C2-4
alkyi, hydroxyalkyl or C2-4 alkenyl groups; and wherein each
R2 croup is independently selected from C8-28 alkyi or alkenyl groups; n is 0 or an integer from 1 to 5 and T and X are as defined above.
Preferred materials of this class such as 1,2 his[tallowoyloxy]-3- trimethylammonium propane chloride and 1, 2-bis [oleylcxyj -3-trimethyIammonium propane chloride and their method of preparation are, for example, described in US 4137180 (Lever Brothers), the contents of which are incorporated herein. Preferably these materials also comprise small amounts of the corresponding monoester, as described in US 4137180.

independently selected from C1-_22 alkyl cr alkenyl group and X is as defined above -
tte iodine value of the parent fattv asyl compound acid
0 to 140, preferably from 0 to 100, more preferably from 0 to 60.
It is especially preferred that the iodine value of the parent compound is from 0 to 20, e.g. 0 to 4. Where the loding value is 4 or less, the softening materials provide
When unsaturated hydrocarbyl chains are present, it is preferred that the cis:trans weight ratio of the material is 50:50 or more, more preferably 60:40 or more, most preferably 70:30 or more, e.g. B5:15 or more.
The iodine value of the parent fatty acid or acyl compound is measured according to the method set out in respect of parent fatty acids in WO-A1-01/46513.
The softening material is preferably present in an amount of from 1 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. Typical silicones for use in the compositions of the present

invention are siloxanes which have the ceneral formula RsSiO(4-a)/2 wherein each R is the same cr different and is selected from hydrocarbon and hvdroxvl a groups a be in a from 0 to 3. In the bulk material, 'a' typically has an average value of from 1.85-2-2.
The silicone can have a linear or cyclic structure. It is particularly preferred that the silicone is cyclic as it is believed that cyclic silicones deliver excellent faster crying characteristics to fabrics.
Preferably, the silicone is a pclydi-Ci-salkyl siloxane.
Particularly preferred is polydimethyl siloxane. The siloxane is preferably end-terminated, if linear, either by
a tri-Ci-g alkvlsilvl croup (e.g. trimethylsiiyl) or a
hydroxy-ci-Ci-6 alkvlsilvl croup (e.g. hydroxy-dimethylsiiyl) croups, or by both.
More preferably the silicone is a cyclic polymdimethyl siloxane.
Suitable commercially available silicones include DC2 4 5 (pclydimethylcyclopentasiio:-:ane also known as D5), DC245 (polydimethyicyciohexasiloxane also known as D6), DC113 4 {a pre-emuIsified polycime thy 1 pentasilane also known as 15} and DC347 (a pre-emulsifled 100cSt ?DM5 fluid) ail ex Dow Corning.

The silicone may be received and incorporated into the composition either directly as an oil or ore-emulsified.
pre-emulsiiication is tyoicaily recuired when the silicone is of a more visecus nature.
Suitable emulsifiers include cationic emulsifiers, nonionic emulsifiers or mixtures thereof.
The reference to the viscosity of the silicone denotes
either the viscosity before emulsification vhen the silicone
i
is provided as an emulsion for linccrpcration into the fabric
conditioning composition cr the viscosity of the silicone
itself vhen provided as an oil for incorporation into the
fabric conditioning composition.
The silicone preferably has a viscosity (as measured on a Brookfield RV4 viscometer at 25°C using spindle No. 4 at 100 rpni) of from icSt to less than :10,000 centi-Stokes (cSt), -preferably from 10cSt to 5,000cSt, more preferably from 2cSt to l,000cSt andmost preferably 2cSt to lOOcSt.
It has been found that drying time can be reduced using silicones having a viscosity of from 1 to 500,000 cSt. However, it is most preferred that the viscosity is from 1 to less than 10,000oSt.
The silicone active ingredient is preferably present at a level of from 0.5 to 20%, more preferably from 1 to 12%, most preferably from 2 to 8% by weight, based on the total weight of the composition.

Optionally and advantageously, one or more un-alkoxvlated fatty alcohols are present in fabric conditioners of the present invention.
Preferred alcohols have a hydrocarbyl chain length of from 10 to 22 carbon atoms, more preferably 11 to 20 carbon atoms, most preferably 15 to 19 carbon atoms.
The fatty alcohol may be saturated or unsaturated, though saturated fatty alcohols are preferred as these have been found to deliver greater benefits in terms of stability, especially low temperature stability.
Suitable commercially available fatty alcohols include tallow alcohol {available as.Hydrenol S3, ex Sidobre Sinnova, and Laurex CS, ex Clariant).
The fatty alcohol content in the compositions is from 0 to ' 10% by weight, more preferably from 0.005 to 5% by weight, most preferably from 0.01 to 3% by weight, based on the .
total weight of the composition.
It is particularly preferred that a fatty alcohol is present if the composition is concentrated, that is if more than 8% by weight of the cstionic softening agent is present in the composition.
It is preferred that the compositions further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions.

Suitable nonionic surfactants include a edit ion products- of ethylene Oxide and/or propylene oxide with fatty alcohols,
Any of the alkoxylated materials of the particular type described naiter can be used as the nonionic surfactant.
Suitable rurfactants are substantially water soluble surfactant;of the general formula:

where R. is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyi groups; primary, secondary and branched chain alkenyl hydrocarbyi groups; and primary:, secondary and branched chain alkenyl-substituted phenolic hydrocarbyi groups; the hydrocarbyi croups having a chain length of from -8 to about 25, preferably 10 to 20, e.g. 14 to 13 carbon, atoms. -
in the general formula for the alkoxylated nonionic surfactant, Y is typically:

in which R has the meaning given above or can be hydrocer.; and Z is preferably from S to 40, more preferably from 10 30, most preferably from 11 to 24, e.g. 12 to 22.

The level " of alloxylation, 2 denotes the average number of alkoxy groups per molecule.
Preferably the nonmonic surfactant has an HIE of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16.
Examples of nonionic surfactants follow. In the examples, the integer defines the nunmber of ethoxy (EG) groups in the ~olecule.
The deca-, undeca-, codecs-, tetradeca-, and pentadecaethoxylates cf n-hexacecanol, and n-cctadecanol having an KL3 within the range recited herein are useful viscosity/cispersibility modifiers in the context of this invention. Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers cf the compositions are C18 EO{10}; and C18 E0{11). The ethcxylates
of mixed natural or synthetic alcohols in the "tallow" chain-length range are also useful herein specific examples of such materials include tallow. alcohol-E0(11), tallow aicohol-EO(18), and tallow alcohol-EO (25), coco aicohol-EO(IC), coco alcohol-EO(lS), coco alcohol-EO{20} and coco alcohol-EO(25).
The decaa-, uDdeca dodeca-, tetradeca-, pentabeca-, cctaceca-, and nonadeca-ethoxylates of 3~hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicoseriCl having an HL3 within the range recited herein are useful viscosity and/or disoersibilicy modifiers in the context of this invention. Exemplary ethoxylated secondary alcohols useful herein as

the viscosity -and/or cispersibility modifiers of the compositions are: C16 10(11); C2o SO(ll); and C16 E0(14)-
As in the case of the alcohol alkcxylates, the hexa- to
octaceca-ethoxylates of alkylated phenols, particularly
nonchydric alkylphencls, having an HLB within the rance
recited herein are useful as the viscosity and/cr
! dispersibility modifiers of the instant compositions. The
hex:a- to octadeca-ethoxylates of p-tri-decyloherci, m-
pentadecyiphencl, and the like, are useful herein.
Exemplary ethoxyiated alkyiphenols useful as the viscositv
and/or dispersibility modifiers of the mixtures herein are:
p-tridecyiphenol EO(ll) and s-pentaciecyiohenoi EO(IS).
As used herein and as generally recognized in the art, a phenylene group in the nonionic formula is the ecuivalent o:

an alkylene group containing from 2 to 4 carbon atoms. Per present purposes, nonionics containing a phenylene croup are considered to contain an equivalent number of carbonatoms " calculated as the sum of the carbon atoms in the alkyl grou; plus about 3.3 carbon atoms for each phenylene croup.
The alkenyl alcohols, both primary and secondary, and alker.yi phenols corresponding to those disclrsed immediate 1 hereinabove can be ethoxyiated to an HLB within the ranee recited herein and used as the viscosity and/or dispersibility modifiers of the instant compositions.
Branched chain primary and secondary alcohols which are available from the well-known "0X0" process can be

ethoxylated and employed as the viscosity and/or dispers bility modifiers of compositions herein.
Suitable p o i y o 1 based surfactants include sucrose esters such sucrose cnoeleates, alkyl polyclucosides such as stearyl 1 uses ices and stearyl tricluccside and alkyl polygiycercl s .
The above ncnicnic surfactants are useful in the present compositions alone or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surface active agents.
The nonicnic surfactant is present in"an amount from 0.01 to 10%, more preferably 0.1 to 5%, most preferably 0.35 to 3.5%, e.g. 0.5 to 2% by weight, based on the total weight of the composition.
The fabric conditioner compositions of the invention preferably comprise one or more perfumes.
It is well known that perfume is provided as a mixture of various components. Suitable components for use in the perfume include those described in "Perfume and Flavor Chemicals (Aroma Chemicals} by Steffen Arctander, pusiisned by the author 1S6- Hcntciait, N.J. (US), reprinted Is' April 19:2 library of Congress Catalog Number 75-91293.

The perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.5 to 4.0% by weight, based on. the total we-irrt of the composition.
The liquid carrier employed in the instant compositions is
= t least partly water due to its low cost, relative
availability, safety, and environments compatibility. The
level of water in the liquid carrier is more than about 50-%
preferably more than about 80%, more preferably mere than
about 85%, by weight of the carrier. The level of liquid
carrier is greater than about 50%, preferably greater than
about 65%, more preferably greater th£n about 70%. Mixtures
of water and a low molecular weight, e.a. solvent, e.g. a lower alcohol,such as ethanol, orcpanoi,
i isopropanol or butanol are useful as the carrier liquid.
Low molecular weight alcohols]including monohycric, dihvdric
(glycol, etc.) trihydric (glycerol, etc.), and polyhydric
(polyols) alcohols are also suitable carriers for use in the
compositions of the present invention..
■Co-active softeners for the cationic surfactant may also be incorporated in an amount from 0.01 to 2C% by weight, more preferably 0.05 to 10%, based on the total weight of the composition. Preferred co-active softeners include fattv esters, and fatty N - oxides .
Preferred fatty esters include fatty monoesters, such as glycerol monostearate (hereinafter referred to as "GKS"). If GMS is present, then it is preferred that the level of

GMS in the composition is iron 0.01 to 10% by weight, based on the total weioht cf the composition.
The co-active softener may also comprise en oily sugar derivative. Suitable oily sugar derivatives, their methods oi manufacture and their oreferred amounts are described in WO-A1-01/4636I an page S line 16 to page 11 line 20, the disclosure of which is incorporated herein.
in is useful, though not essential, if the compositions comprise one or more polymeric viscosity control aqents. Suitable polymeric viscosity control agents include nonionic and cationic polymers, such as hydrophcbicaliy modified cellulose ethers (e.g."Natrosol Plus, ex Hercules), cationicaliy modified starches (e.g- Softgel 5DA and Softgei SD, both ex Ave.be) . A particularly preferred viscosity control agent is a copolymer of methacrylate and cationic acrylamide available under the tradename Flosoft 2.00 (ex SN? Floerger).
Nonionic and/or cationic polymers are preferably present in en amount of 0.01 to 5wt%, more preferably 0.02 to 4wt%, based on the total weight of the composition.
Cther optional nonionic softeners, bactericides, soil-releases agents may also be incorporated in fabric concitioners of the invention.

The compositions may also contain one or more optional ingredients conventionally included in fabric conditioning comocsit i ons such as cH buffering a cent s, oer fume carrier: fiuorescers, colourants, hydrotrcpes, antifoaming acent3, antireceoosition agents, poiyelectrolytes, enzymes, optical brightening agents, pearlescers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, antioxidants, sunscreens, anti-corrosion agents, crape imparting agents, preservatives, anti-static agents, ironing aids and other dyes .
The product may be a liquid or solid. Preferably the product is a liquid which, in ,its undiluted state at ambient temperature, comprises an aqueous liquid, preferably an aqueous dispersion of the cationic softening material.
When the product is an aqueous liquid, it preferably has a pH of greater than 1.5 and less than 5, more preferably greater.than 2 and less than 4.5 .
The fabric conditioner composition is preferably used in the rinse cycle of a home textile laundering operation, where," it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation.

EXAMPLES
To determine the substantivity of a ranee- of dyes the following experiment was performed. A stock soluticn: of I.5g/L of a base washing powder in water was created. The washing powder contained 18% NaLAS, 73% salts {silicate, sodium tri-pciy-phosphate, sulphate, carbonate), 3% minors including perborate, flucrescer and enzymes, remainder impurities and water. The solution was divided into 60ml aiiquots and dye added to this to give a solution of optical density of approximately 1 (5 cm pathlength) at the maximum absorption of the dye in the visible lengths, 4OO-7O0nm. The optical density was measured using a "OV-visibie spectrometer. 1 piece of bleached, non-mercerised, hon-fiuorescent woven cotton cloth (ex Phoenic Calico} weighing 1. 3g was placed in the solution at room temperature {20DC) .-This clcth represents a slightly yellow cotton. The cloth was left to soak for 45 minutes then the solution agitated for 10 mins, rinsed and dried. Following this the optical density of the solution was re-measured and the amount of dye absorbed by the cloth calculated. This experiment was repeated for each eye and 4 replicates were done per eye.
The dyes used and the % deposition is given in table 1. Table 2 gives the maximum extinction coefficient, fmax/ -in the wash solution and the peak absorption wavelength in solution and en cotton. All values are reported to 2 significant figures.

Table 1

Dye % Deposition
Acid Slack 1 23
food Black 1 0.50
Direct B1ue 1 48
Direct Violet 51 69
Direct Blue "71 34
Acid Violet 9 2.1
Acid Blue 80 i 6.8
Acid Violet 17 18
Acid Red 88 47
Acid Red 150
33

Table 2

Dye Type ■ [mol-1L cnf:) Amax [nm]
in solution,
on cotton
Acid Black 1 Food Black 1 Direct 31ue 1 Direct Violet 51 Direct 31ue "71 Acid Violet 9 Acid Blue 80 Acid Violet 17 acid Red 88 Acid Red 150 Azo
Azo
Azo
A20
Azo
Triaryl
Anthraquinone
Triaryl
Azo
Azo j ■
5.1000
41000
130000
65000
12.0000
4 6000 27000 53000 . 14400 23600 620, 630 570, 590 600, 640 550, 570
S90, 600
540 630, 630 520, 590 510, 520 520, 530

ELxamnle 2
The experiment, of example 1 was repeated except the dye level in the wash solution was decrease to 1/10th, so that the optical density was 0.1 (5 cm clath length). following the washes the Ganz whiteness of the cloth was measured (see "assessment of whiteness and Tint of Fluorescent Substrates with Good Interinstrument Correlation" Colour F.asearch and Application 19, 15S4} . The results are displayed in table 3, t-he ganz whiteness values are accurate to T/-5 units. "Large increase in the measured Ganz whiteness are iourid lor
the substantive blue and violet dyes with Amax on cotton in the range 570 to 64 0.
Table 3

152 17 0

Dye G&nz whiteness
Control 150
Acid Black 1 171
Food Black 1 155
Direct Blue 1 25O.
Direct Violet 51 203
Direct Blue 71 205
Acid Violet 9 153
Acid Blue 80 Acid Violet 17

Acid black i, direct blue 1, direct violet 51, direct blue 71 and acid violet 17 cave the greatest increase m Ganz whiteness.

71 cave a higher Gahz
;irect violet 51 and direct blu
withiteness value than direct blue 1 and they nave tne

ther

advantage over direct blue 1 that they are not metabolised in the body to give carcinogenic amine, unlike the huge number of direct blue and violet eyes (e.g. direct blue 1} which contain moieties which breakdown to give the carcinogenic benzidine, 3,3' dimethoxyberizicir.e cr 3,3'-dimethyibenzidir.e. These dyes also have an advantage over -any direct violet dyes which contain transition metals that are hazardous to the environment and to humans.
Preferred direct dyes fail into two croups: The first group ccmt>rises tris-azo direct blue dves based on the structure:

where at least two of the A, 3 and C napthyl rings, are subsituted by a sulphonate group. The C ring may be substituted at the 5 position by an NK2 or NHPh" group, X is a benzyl or napthyl ring substituted with upto 2 sulphonate croups and may be substituted at 2 position with a OH croup and may also be substituted with an NH2 or HHPh group.
Non-limiting examples of these dyes are direct blue 34, -'0, 71, 72, 75, 78, 82, 120.
The second group comprises bis-azo direct violet dyes basec on the structure

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 ngphthyl ring, which is substituted by sulphate group and may be mono or disubstituted by methyl croups.
Non-limiting examples of these dyes are direct violet 5, 7, 11, 31, 51. The invention also comprises compositions including a single dye of the structure of the first or second group, or mixtures thereof, the dye or mixture having the defined peak absorption wavelength.
'Example 3
The experiment of example 1 was repeated except using dyes at lower concentrations, such that the optical density (5cm) was approximately 0.05 and 0.025 giving faintly coloured wash liquors (i.e. using dye levels 1/20 and l/40th of experiment 1). Following washing and drying the increase in whiteness was measured by a reflectometer and expressed in Garze units. The Genz values are accurate to +/- 5 units. The results are shown in the Table 3 below.

Table 4

Direct blue 71 cave the best results.
Example A
Example 3 was repeated but [using the blue dye Acid Black i,
i
the red dyes Acid Red 88 and Acid Red 150, and mixtures thereof. The results are shown in the tables below.

Table 5

Table 5

The results show that mixtures of red and blue dyes gives a greater increase in whiteness than either alone. This is because the mixture produces a violet shade.

1. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01. wt% of
a combination of dyes which together have a visual effect on
the human eye as a single dye having a peak absorption
wavelength on cotton of from 540 nm to 650 nm, the
combination comprising a photostable dye which is
substantive to cotton, wherein the photostable dye is selected from bis-azo direct violet dyes of the formula:

where Z is H or phenyl, the A ring may be substituted by a' methyl and methoxy group at the positions indicated by arrowsf the A ring may also be a naphthyl ring, the y group is a phenyl or naphthyl ringr which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein dye is not sensitive to heat and is included in a slurry which is spray dried.
2. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01 wt% of
a combination of dyes which together have a visual effect on
the human eye as a single dye having a peak absorption
wavelength on cotton of from 540 nm to 650 nm, the
combination comprising a photostable dye which is
substantive to cotton, wherein the photostable dye is
selected from the group comprising a bis-azo direct violet
dye of the formula:

where Z is H or phenyl, the A ring may be substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a. naphthyl ring, the Y grou] is a phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the laundry treatment composition comprise; from 5 to 35 wt% sodium percarbonate having a protective coating against destabilisation, by moisture.
3. A particulate laundry detergent treatment composition which comprises a surfactant and from'0.0001 to 0.01 wt%. of
a photostable dye which is substantive to cotton, the dye
having a peak absorption wavelength on cotton of from 540 n
to 650 nm, and wherein the photostable dye is selected from
the group comprising bis-azo direct violet dyes of the

formula:

where 2 is H or phenyl, the A ring may be 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 phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the dye is not sensitive to heat and is included in a slurry which is spray dried.
4. A particulate laundry detergent treatment composition which comprises a surfactant and from 0.0001 to 0.01 wt% of
a photostable dye which is substantive to cotton, the dye
having a peak absorption wavelength on cotton of from 540 nm
to 650 nm, and wherein the photostable dye is selected from
the group comprising bis-azo direct violet dyes of the
formula:

where Z is H or phenyl, the A ring may be 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 phenyl or naphthyl ring, which is substituted by a sulphonate group and may be mono or disubstituted by methyl groups, wherein the laundry treatment composition comprises from 5 to 35 wt% sodium percarbonate having a protective coating against destabilisation by moisture.
5. A composition as claimed in any one of claims 1 to 4, which is a laundry detergent composition, preferably a particulate laundry detergent composition.

6. A composition as claimed in any of claims 1 to 4, which is a laundry fabric conditioner.
7. A composition as claimed in any preceding claim, which comprises from 5 to 60% of surfactant.
Dated this 29th day of September 2008
Dr. Sanchita Ganguli
Of S. Majumdar&Co.
(Applicant's Agent)

Documents:

2106-mumnp-2008-abstract.doc

2106-mumnp-2008-abstract.pdf

2106-MUMNP-2008-CLAIMS(AMENDED)-(1-6-2012).pdf

2106-MUMNP-2008-CLAIMS(AMENDED)-(12-5-2011).pdf

2106-MUMNP-2008-CLAIMS(MARKED COPY)-(1-6-2012).pdf

2106-mumnp-2008-claims.doc

2106-mumnp-2008-claims.pdf

2106-MUMNP-2008-CORRESPONDENCE(13-5-2009).pdf

2106-MUMNP-2008-CORRESPONDENCE(16-12-2009).pdf

2106-MUMNP-2008-CORRESPONDENCE(16-7-2010).pdf

2106-MUMNP-2008-CORRESPONDENCE(17-9-2009)pdf.pdf

2106-MUMNP-2008-CORRESPONDENCE(19-12-2011).pdf

2106-mumnp-2008-correspondence(26-8-2009).tif

2106-MUMNP-2008-CORRESPONDENCE(6-11-2008).pdf

2106-mumnp-2008-correspondence.pdf

2106-mumnp-2008-description(complete).doc

2106-mumnp-2008-description(complete).pdf

2106-mumnp-2008-form 1.pdf

2106-MUMNP-2008-FORM 13(7-2-2012).pdf

2106-MUMNP-2008-FORM 18(6-11-2008).pdf

2106-mumnp-2008-form 2(title page).pdf

2106-mumnp-2008-form 2.doc

2106-mumnp-2008-form 2.pdf

2106-MUMNP-2008-FORM 3(12-8-2011).pdf

2106-MUMNP-2008-FORM 3(15-2-2011).pdf

2106-MUMNP-2008-FORM 3(15-2-2012).pdf

2106-MUMNP-2008-FORM 3(24-2-2010).pdf

2106-MUMNP-2008-FORM 3(4-8-2010).pdf

2106-MUMNP-2008-FORM 3(8-8-2012).pdf

2106-mumnp-2008-form 3.pdf

2106-mumnp-2008-form 5.pdf

2106-MUMNP-2008-GENERAL POWER OF ATTORNEY(1-6-2012).pdf

2106-MUMNP-2008-OTHER DOCUMENT(1-6-2012).pdf

2106-MUMNP-2008-OTHER DOCUMENT(4-6-2012).pdf

2106-mumnp-2008-pct-ipea-237.pdf

2106-mumnp-2008-pct-ipea-409.pdf

2106-mumnp-2008-pct-isa-210.pdf

2106-mumnp-2008-pct-isa-237.pdf

2106-MUMNP-2008-PETITION UNDER RULE 137(1-6-2012).pdf

2106-MUMNP-2008-REPLY TO EXAMINATION REPORT(12-5-2011).pdf

2106-MUMNP-2008-REPLY TO HEARING(1-6-2012).pdf

2106-MUMNP-2008-REPLY TO HEARING(4-6-2012).pdf

2106-MUMNP-2008-SPECIFICATION(AMENDED)-(12-5-2011).pdf

2106-mumnp-2008-wo international publication report a1.pdf

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Patent Number

253723

Indian Patent Application Number

2106/MUMNP/2008

PG Journal Number

34/2012

Publication Date

24-Aug-2012

Grant Date

17-Aug-2012

Date of Filing

01-Oct-2008

Name of Patentee

HINDUSTAN UNILEVER LIMITED

Applicant Address

HINDUSTAN UNILEVER LIMITED, UNILEVER HOUSE, B.D. SAWANT MARG, CHAKALA, ANDHERI EAST, MUMBAI -400 099

Inventors:

#	Inventor's Name	Inventor's Address
1	BARBIZAN, DANIELLE, SANTINHO	UNILEVER BRAZIL-HPC LA HEAD OFFICE ANASTACIO, AV. MANOEL DOMINGOS PINTO 481, 052120-000 SAO PAULO.
2	BATCHELOR, STEPHEN, NORMAN	UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON, WIRRAL MERSEYSIDE CH63 3JW.
3	GRIGOLON, LISANNE, BEATRIZ	UNILEVER BRAZIL-HPC LA HEAD OFFICE ANASTACIO, AV. MANOEL DOMINGOS PINTO 481, 052120-000 SAO PAULO.
4	SORZE, ANDREA, DIAS	UNILEVER BRAZIL-HPC LA HEAD OFFICE ANASTACIO, AV. MANOEL DOMINGOS PINTO 481, 052120-000 SAO PAULO.
5	STEEL, ANDREW, THOMAS	UNILEVER R & D PORT SUNLIGHT, QUARRY ROAD EAST, BEBINGTON, WIRRAL MERSEYSIDE CH63 3JW.

PCT International Classification Number

C11D3/00

PCT International Application Number

PCT/EP2004/006085

PCT International Filing date

2004-06-04

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0314210.6	2003-06-18	U.K.