Title of Invention	RED BLEACHING COMPOSITIONS
Abstract	The present invention concerns photo-bleaching with Food red 14 (colours Index 45430) and in particular the bleaching of laundry items.

Full Text

C4334/C FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) RED BLEACHING 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. WO 2005/047441 PCIYEP2004/010942 - 1 - RED BLEACHING COMPOSITIONS FIELD OF INVENTION The present invention relates to the photo-bleaching of products, in particular laundry bleaching. BACKGROUND OF INVENTION In a conventional bleaching treatment, a substrate such as a laundry fabric or other textile is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides. A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with 15 organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetra acetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United 20 States laundry bleach products are typically based on sodium nonanoyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. Alternatively, or additionally, hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron 25 and the ligand N4Py (i.e. N, N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) disclosed in W095/34628. Another approach to bleaching is that of using radical photo-initiators, which are generally organic chemicals which on absorption of light, particularly UV light, form reactive radicals. They are widely used to initiate the WO 2005/047441 PCT/EP2004/010942 - 2 - polymerisation of alkenes and thereby cure coatings. They may also be used as photobleach agents as discussed in GB 9917451. Radical photoinitiators, in general, are discussed by H.F. Gruber in Prog. Polym. Sci. Vol 11. 953-1044. 5 SUMMARY OF INVENTION We have found that Food red 14 is surprisingly active in photo-bleaching catechol-type stains, polyphenolics-type stains and polycyclic hydroxylated aromatic-type stains. 10 The Food red 14 may be used on its own as the bleaching species or in conjunction with other bleaching species. It is preferred that those other bleaching species, if used, possess different bleaching profiles. The stain bleaching profile of known photo-bleaches is generally that of 15 ceretenoid type stains, for example tomato stains which is similar to the bleaching profile of "air" bleaching catalysts. These catechol-type stains, polyphenolics-type stains and polycyclic hydroxylated aromatic-type stains are as a result of the chromophores found in tea, coffee, blackberry, blueberry, blackcurrant, red wine, banana and the like. These stains are characteristic and distinct from oily food type stains such as tomato oil stain, curry oil stain, mango stain, annatto derived stain, colorau derived stain, and sebum derived stain etc. The economic factors in cleaning products are a dominant in many decisions to launch a product. By substituting or reducing the amounts of more expensive bleaching components with Food red 14 an efficacious product may be produced with WO 2005/047441 PCT/EP2004/010942 - 3 - at less cost. This exemplified by the following, Food red 14 exhibits similar bleaching efficacy to that of perborate/percarbonate when used in conjunction with TAED on certain stains. Another benefit is that Food red 14 may be used in washes of lower temperature than that of the peroxyl systems. In addition, the level of Food Red 14 exhibits bleaching effects at surprisingly low levels. Of the red dyes Food Red 14 deposited effectively on the textile. 10 The present invention provides a bleaching composition comprising: a) from 0.0001 wt/wt% to 0.1 wt/wt% of Food red 14 dye; b) from 0 to 40% other bleaching species; and, c) the balance carriers and adjunct ingredients to 15 100 wt/wt % of the total bleaching composit-ion, wherein upon addition of a unit dose of the bleaching composition to an aqueous environment a wash liquor having a pH in the range 8 to 11 is provided, wherein the bleaching composition comprises less than 1 % of a peroxyl species. 20 The fact that Food Red 14 is brightly red makes its application in textile bleaching unusual because one would expect their use to result in discoloured rather than whitened textiles. When Food red 14 is used solely as the 25 bleaching species the consumer is reassured in the laundry context that the bleach used is mild because of that fact that it is an acceptable a food additive. Food dy.es are used to enhance the visual appearance of many foods. As humans consume them, they undergo rigorous testing and examination 30 to ensure they represent no risk to health. In addition, a solution of Food Red 14 under indoor lighting is much paler WO 2005/047441 PCT/EP2004/010942 - 4 - to the eye than that of Rose Bengal, which has an intense colour in solution, despite having a lower optical density than Food red 14. This permits higher dosages of Food red 1 to be used than, for example, Rose Bengal without overly colouring the liquor. The present invention also extends to a method of photo-bleaching a textile stain. 10 One method of the present invention comprises the steps of: (i) treating a textile with a solution of Food red 14 dye, (ii) irradiating the treated textile. The light used for photo-bleaching may be sunlight, 15 florescent light or that from an ordinary light bulb. Photo-bleaching is still effective where the concentration of Food red 14 on the textile/cloth is so low as to be barely perceptible to the human eye. The Food red 14 if perceptible rapidly photo-fades. The present invention may be applied locally, suitable pre-treatment means for application include sprays, pens, roller-ball devices, bars, soft solid applicator sticks. A unit dose as used herein is a particular amount of the bleaching composition used for a type of wash. The unit dose may be in the form of a defined volume of powder, granules or tablet. WO 2005/047441 PCTYEP2004/010942 - 5 - DETAILED DESCRIPTION OF THE INVENTION Food red 14 (Erythrosine B) (E 127; CI number 45430) (CAS 16423-68-0) is a widely used red food colouring, see Hunger K. Industrial Dyes: Chemistry Properties And Applications. 5 Wiley-VCH, Heidelberg 2003. The concentration of Food red 14 in a wash liquor is from 5ppb to l000 ppm, preferably l0ppb to l00ppm, more preferably 50ppb to 5ppm, and most preferably l00ppb to lppm. A same 10 concentration may also be used for a spot treatment of a stain or of a commercial liquid formulation. A suitable concentration in a powder detergent would be 0.0001 wt/wt% to 0.1 wt/wt%, most preferred is 0.001 wt/wt% to 0.01 wt/wt%. 15 Other Bleaching Species The bleaching composition may also contain other bleaching components, for example other photo-bleaches, a transition metal catalyst which is present in a bleaching composition 20 that is substantially devoid of peroxyl species, and peroxyl bleaching systems. An example of a preferred additional photo-bleach is vitamin K3. The use of bleaching catalysts for stain removal has been 25 developed over recent years and may be used in the present invention. Examples of transition metal catalysts that may be used are found, for example, in: WO0060045, WO0248310, WO0029537 and WO0012667. The catalysts may be used for catalysing peroxyl or "air" bleaching as described in 30 WO0248301. The catalyst may alternatively be provided as the free ligand that forms a complex in situ. WO 2005/047441 PCT/EP2004/010942 - 6 - The bleaching composition when use as an "air" bleaching composition is substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system. It is believed that adventitious hydroperoxides within an oily 5 stain serve to bleach the stain together with the catalyst. The term "substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system" should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species 10 present as possible. It is preferred that the bleaching formulation (with or without an "air" bleaching catalyst) contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt/wt total 15 concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof. The method of bleaching a textile stain may have peroxyl 20 species present. If peroxyl species are present the method, it is preferred that sodium percarbonate or perborate is used in the method. Balance Carriers and Adjunct Ingredients 25 The following provides examples of suitable balance carriers and adjunct ingredients. These are generally surfactants, builders, foam agents, anti-foam agents, solvents, and enzymes. The use and 30 amounts of these components are such that the bleaching composition performs depending upon economics, environmental WO 2005/047441 PCT/EP2004/010942 - 7 - factors and use of the bleaching composition. It is preferred that the bleaching composition comprises from 5 to 40 wt/wt % of a surfactant having an HLB greater than 15. 5 To that extent, the composition comprises a surfactant and optionally other conventional detergent ingredients. The invention in its second aspect provides an enzymatic detergent composition which comprises from 0.1 - 50 % by weight, based on the total detergent composition, of one or 10 more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in 15 not normally desired owing to their relatively high cost. The enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%. 20 In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's 25 Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Suitable nonionic detergent compounds which may be used ■ 30 include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for WO 2005/047441 PCT/EP2004/010942 - 8 - example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6-C22 alkyl phenol-ethylene oxide condensates, 5 generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C8-Ci8 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO. 10 Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. 15 Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs-Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9-C20 benzene sulphonates, particularly sodium linear 20 secondary alkyl C10-C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cn-Cis alkyl benzene 25 sulphonates and sodium C12-C18 alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides. 30 WO 2005/047441 PCT/EP2004/010942 - 9 - Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred 5 is surfactant system that is a mixture of an alkali metal salt of a Ci6-Ci8 primary alcohol sulphate together with a C12-C15 primary alcohol 3-7 EO ethoxylate. The nonionic detergent is preferably present in amounts 10 greater than 10%, e.g. 25-90% by weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight- of the surfactant system. 15 The composition may contain additional enzymes as found in WO 01/00768 Al page 15, line 25 to page 19, line 29, the contents of which are herein incorporated by reference. Builders, polymers and other enzymes as optional ingredients 20 may also be present as found in WO0060045. Suitable detergency builders as optional ingredients may also be present as found in WO0034427. 25 The composition of the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed in waste-water 30 treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food WO 2005/047441 PCT/EP2004/010942 - 10 - processing, starch bleaching, sterilisation", whitening in oral hygiene preparations and/or contact lens disinfection. In the context of the present invention, bleaching should be 5 understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of 10 malodours or other undesirable components attached to or otherwise associated with a substrate. Examples 15 Example 1 A 1.5g/L stock solution of a base washing powder was created. The washing powder contained 18% NaLAS, 73% salts (silicate, sodium tripolyphosphate, sulphate, carbonate), 3% 20 minors including perborate, fluoreser and enzymes, remainder impurities and water. The solution was divided into 4, 200ml aliquots. To each was added various amounts of the food red 14, and then 2 BCl test clothes and 4 white cotton clothes. All clothes were the same size and weight, the total weight 25 of cloth added was 5g. BCl is a standard stained test cloth used in laundry evaluation and is a model tea stain monitor. BCl clothes may be purchased from e.g., the center for test materials, Vlaardingen, NL. 30 The clothes were then agitated in solution for 20 mins, removed rinsed and the 2 BCl clothes and 2 of the white WO 2005/047441 PCT/EP2004/010942 - 11 - clothes irradiated in a weatherometer (WOM) for 30 minutes. A WOM produces artificial sunlight and was set up to give 385 W/m2 in the UV-visible range. The remaining 2 white clothes were dried in the dark in a tumble drier. 5 Following these procedures the colour of the clothes were measured using a reflectance spectrometer and expressed as the DeltaE relative to washed clean white cloth. The results are presented in the table below [Acid red 51] g/L BCl White -irradiated White -dark 0 19.1 1.9 - 0.001 17.5 1.2 2.1 0.002 16.4 0.9 4.2 Clear photo-bleaching of the BCl stain is observed. A small amount of red colouration is transferred to the white cloth. This red colouration is removed by exposure to sunlight. Example 2 A lg/L SDS surfactant stock solution in water was created. The solution was divided in two and the two halves, and buffered to pH 10 and pH 8 respectively using standard salts (Hydrion ™ buffer, purchased from Sigma-Aldrich). The solution was used to wash BCl stains as follows. A 3.7g piece of BCl stained cotton cloth plus a 0.7g piece of clean white woven cotton cloth were agitated in 100ml of wash solution for 20 mins, rinsed twice, then the BCl cloth irradiated in a WOM for thirty minutes. The DeltaE of the WO 2005/047441 PCT/EP2004/010942 - 12 - clothes relative to a clean standard was then measured. The clothes were then irradiated for a further 30 minutes and remeasured. 5 The experiment was repeated using wash solution containing different amounts of Food red 14. The optical density (5cm) of the wash solutions were measured at the lambda (max) of the dye (527nm) 10 All the white clothes were tumbled dried in the dark and the pick up of red dye measured by measuring the DeltaE of the clothes relative to a clean undyed standard. The results are reported in the table below: 15 ppm dye in solution PH Optical density DeltaE(BCD130 mins DeltaE(BCD16"0 mins DeltaE(whitecloth)2 0 8 0 17.3 16.9 0.5 0.1 8 0.08 16.0 15.7 1.1 0.3 8 0.16 14.8 14.4 2.3 0.8 8 0.36 14.2 13.7 4.7 3.8 8 1.78 10.6 9.9 14.6 0 10 0.0 17.2 16.8 0.5 0.1 10 0.09 15.8 15.4 0.9 0.3 10 0.14 15.0 14.6 1.9 0.8 10 0.36 12.1 11.7 4.1 3.8 10 1.71 9.4 8.8 13.8 Table WO 2005/047441 PCT7EP2004/010942 - 13 - 1average of 4 independent measurements 2average of 2 independent measurements 5 Photobleaching of the BC1 stain was observed from all solution containing food red 14. Notably this occurs even at extremely low levels of the dye, O.lppm, at this level the dye is barely visible in solution and no red colour could be discerned by eye on the white cloth. However the BC1 cloth 10 was visibly bleached. The red colour on the white cloth was removed simply by leaving in natural light. Example 3 15 Stains were created on white woven cotton by: placing 1 drop of (a) a saturated solution of turmeric in soya oil or (b) placing 2 drop of Brazilian palm oil. Three of each type of stains (a), (b) , BC1 stains and four 20 clean white ballast pieces (total weight =11.4g) were wash at 40°C for 20 minutes in 200 ml of water containing 7g/L of Persil Colour™ washing powder. Persil Colour™ contains less than 5% soap. Polycarboxylate and phosphonate, 5 to 15% anionic and non-ionic surfactants, 15-30% zeolite and also 25 contains enzymes. Following the wash the cloths were rinsed once in water, once in an acidic solution, and finally once more in water. They were then all irradiated in a WOM for 36 minutes. The residual staining and relative to clean white cloth measured using a reflectometer and expressed as the AE 30 value. The discoloration of the white ballast due to WO 2005/047441 PCT/EP2004/010942 - 14 - transfer of coloured stain matter in the wash was measured in an analogous manner. The experiment was repeated but with the following, added to 5 the wash solution: (a) 1 ppm food red 14 (b) 10 ppm vitamin K3 (a radical photo-initiator which bleaches carotenoid stains) (c) 1 ppm food red 14 plus 10 ppm vitamin K3 10 The results are displayed in the table below DeltaE BCl Turmeric Palm oil White cotton Control 16.8 22.5 23.9 2.9 (a) 15.5 22.4 22.8 2.2 (b) 16.6 20.7 8.0 2.5 (c) 15.0 19.3 7.6 1.5 Table 15 The combination of the Food red 14 with the vitamin K3 gives good overall bleach effects. Example 4 20 A 3.7g piece of BCl stained cotton cloth was washed in 80ml of a pH=10 buffered solution of 0.2g/L SDS. The wash consisted in a 15 minute agitation followed by rinsing. The cloth was then irradiated in a WOM for 30 minutes and the WO 2005/047441 PCT/EP2004/010942 - 15 - residual staining measured as the DeltaE relative to clean white cotton. The experiment was also performed with wash liquors containing various xanthene type dyes. The % deposition of the dyes onto the cloth was obtained by 5 measuring the UV-VI spectrum of the wash liquors before and after washing. The results are shown in the table below. Dye Amount of dye BC1 DeltaE1 Q. Odeposition Control - 17.7 - Eosin B 2.2ppm 18.1 35 Eosin Y 2.2ppm 12.9 52 Phloxine B 2.lppm 14.0 9 Rose Bengal 2.2ppm 10.8 19 Food Red 14 2.2ppm 10.9 44 Table 1average of 4 independent measurements From the results Food red 14 and Rose Bengal provide superior bleaching. WO 2005/047441 - 16 - Name Eosin B Eosin Y Phloxine B Rose Bengal Food Red 14 PCT7EP2004/010942 Dye Anion Structure Br Br WO 2005/047441 PCT7EP2004/010942 - 17 - Example 5 A stock solution of 1.5g/L of a base washing powder in water was created. The washing powder contained 18% NaLAS, 73% 5 salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water. The solution was divided into 60ml aliquots and various combination of food red 14 dye with acid blue 29 added to this in amount as 10 indicated in the results table. 1 piece of bleached, non-mercerised, non-fluorscent woven cotton cloth (ex Phoenic Calico) weighing 1.3g was placed in the solution at room temperature (20°C). This cloth represents a slightly yellow cotton. The cloth was left to soak for 45 minutes then the 15 solution agitated for 10 mins, rinsed and dried in the dark. After the washes the Ganz whiteness of the cloth was measured (see "assessment of Whiteness and Tint of Fluorescent Substrates with Good Interinstrument Correlation" Colour Research and Application 19, 1994). A 20 higher value of Ganz is associated with whiter cloth. The results are the average of 2 experiments. WO 2005/047441 PCT/EP2004/010942 - 18 - Food Red 14/ ppm Acid Blue 29/ ppm Ganz 0 0 147 0.18 0 150 0.135 0.058 150 0.09 0.117 158 0.045 0.175 162 0 0.233 170 0.09 0 146 0.067 0.029 152 0.045 0.058 156 0.022 0.087 160 0 0.117 163 Table 5 Mixture of food red 14 with the blue dyes gives an increase in the whiteness of the cloth. The dye acid black 1 gave similar results. 10 Example 6 The experiment of example 5 was repeated. Except here one 3.7g piece of BC1 stained cotton cloth was washed in 60 ml of solution containing various amounts of food red 14 and 15 acid blue 29. The wash consisted of 30 minutes of agitation. Following the rinses the clothes were irradiated in a WOM for 30 minutes and the residual stain measured as WO 2005/047441 PCT/EP2004/010942 4 - 19 - the AE relative to clean white cloth. The results are shown in the table below. Food red 14/ppm Acid blue 29/ppm 3C1 DeltaE1 0 0 16.9 0.18 0 16.2 0.135 0.058 16.1 0.09 0.117 16.4 0.045 0.175 16.7 5 Table 1average of 4 independent measurements. Hence the mixture of dyes gives photo-bleach effects and 10 shading benefit (example 5). Example 7 A solution of 0.2g/L SDS surfactant was created in pH=10 15 buffer (Hydrion ™) . The solution was divided in 2 and RoseBengal added to one half such that its Optical density at the maximum absorption of the dye in the visible was 0.81 (5cm). A similar solution was created for Food Red 14 but with a higher optical density of 0.93. The Solution of Food 20 Red 14 under indoor lighting was much .paler to the eye than that of Rose Bengal. This was confirmed by 12 independent adults aged in the range 25-60 years. All stated the Rose Bengal solution to have a more intense colour, despite the fact it had a lower optical density. This clearly shows the WO 2005/047441 PCT/EP2004/010942 - 20 - advantage in being able to dose Food red 14 at a higher level without over colouring the liquor. WO 2005/047441 PCT/EP2004/010942 - 21 -We claim: 1. A bleaching composition comprising: c) from 0.0001 wt/wt% to 0.1 wt/wt% of Food red 14 dye; 5 d) from 0 to 40% other bleaching species; and, c) the balance carriers and adjunct ingredients to 100 wt/wt % of the total bleaching composition, wherein upon addition of a unit dose of the bleaching composition to an aqueous environment a wash liquor having a pH in the 10 range 8 to 11 is provided, wherein the bleaching composition comprises less than 1 % of a peroxyl species. 2. A bleaching composition according to claim 1, wherein 15 the Food red 14 bleaching composition is present in the range of 0.001 to 0.01 wt/wt%. 3. A bleaching composition according to claim 1 or 2, wherein the bleaching composition comprises other photo- 20 bleaches. 4. A bleaching composition according to claim 3, wherein the bleaching composition comprises vitamin K3. 25 5. A bleaching composition according to any preceding claim, wherein the bleaching composition comprises an air bleach catalyst or ligand thereof. 6. A bleaching composition according to any preceding 30 claim, wherein the bleaching composition is a liquid bleaching composition. WO 2005/047441 PCT/EP2004/010942 - 22 - 7. A bleaching composition according to any preceding claim, wherein the bleaching composition comprises from 5 to 40 wt/wt % of a surfactant having an HLB greater than 15. 5 8. A bleaching composition according to any preceding claim, wherein the bleaching composition is devoid of a peroxygen species. 10 9. A method of bleaching a textile stain, the method comprising the steps of: (i) treating a textile with a solution of Food red 14 dye, (ii) irradiating the treated textile. 15 10. A method according to claim 9, wherein the solution comprises from l00ppb to 1 ppm of Food red 14 dye. 11. A method according to claim 9 or 10, wherein the method further comprises a step of drying the textile. 20 Dated this 3rd day of May 2006 HINDUSTAN LEVER LIMITED (S. Venkatramani) Sr Patents Manager

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