Title of Invention	IMPROVED COSMETIC COMPOSITION COMPRISING TITANIUM OXIDE
Abstract	The present invention relates to facial wash compositions delivering enhanced whitening using sub-micron titanium dioxide, optional modifier and specific deposition systems.

Full Text

J6896 FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10 and Rule 13) BEAUTY WASH PRODUCT COMPOSITIONS COMPRISING TITANIUM OXIDE 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 2005/094779 PCT/EP2005/002703 BEAUTY WASH COMPOSITIONS COMPRISING TITANIUM OXIDE 5 The present invention relates to rinse-off cleanser compositions delivering an immediate skin whitening effect. This is accomplished by using sub-micron titanium dioxide, preferably together with an optical modifier (e.g., micron size mica or talc or emollient oil) from a facial cleanser 10 base. Generally, the enhancement is obtained by use of a specific deposition system (e.g.,cationic polymer/anionic surfactant precipitates) and/or by ensuring dispersion of particles (e.g., little or no agglomeration) onto skin or deposited substrate. 15 It is extremely difficult to deliver enhanced whitening, especially rapid whitening, from a rinse-off composition. The optical modifiers delivering these properties are not readily deposited, are readily rinsed off and, because they readily 20 agglomerate, are not in a sufficiently dispersed state to be efficiently delivered to a substrate (which is another way to say that they rinse off too easily). The applicants' co-pending U.S.Serial No. 10/241,401 to 25 Zhang et al., filed September 11, 2002 discloses personal care formulations comprising particles of defined refractive index, thickness, geometry and size. While this disclosure relates to how size, shape, etc. of the particles themselves help deposition (and thus shine), it fails to disclose 30 specific deposition enhancement systems (e.g. based on a type of surfactant and/or polymers) , and the use of WO 2005/094779 PCT/EP2005/002703 - 2 - dispersed, sub-micron Ti02 (preferably with other optical modifiers) to deliver enhanced whiteness. It also does not disclose how particles must be adequately dispersed on substrate (e.g., skin) to deliver defined change values 5 needed to perceive measure optical traits. U.S. Serial No. 10/443,396 to Zhang et al., filed May 23, 2003 discloses structured benefit agent for enhanced delivery of optical modifier, but again does not disclose 10 combination of sub-micron titanium dioxide, cationic deposition polymers (forming precipitates as deposition aid) and adequate dispersal to deliver enhanced whiteness. Unexpectedly, the applicants have now found both compositions 15 and ways to manipulate such compositions to provide enhanced whitening from rinse-off systems. That is, using deposition enhancement systems (e.g., characterised for example by precipitates formed through interaction of polymers and surfactants),modifiers associated with specified optical 20 properties (e.g., sub-micron titanium dioxide for whiteness), can be dispersed and delivered to provide desired optical whiteness (i.e., by providing sufficient change in absolute or percentage values of the whitening component to result in perceived whitening changes). Changes in optical attributes 25 previously unobtainable from wash-off/rinse-off systems are provided by selecting the specified components. More particularly, in one aspect the invention comprises as follows: 30 WO 2005/094779 PCT/EP2005/002703 - 3 - Beauty wash product compositions for delivery of enhanced (changed) whitening or brightening to the skin comprising: a) from about 0.5 % to about 90 %, preferably 5 % to 5 75 %, more preferably 10 % to 75 %, most preferably 20 % to 70 % by weight surfactant selected from anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof; b) from 0 to 35 %, preferably 0.2 % to 25 % by weight 10 of solid particulate optical modifier which exhibits a specific set of optical properties (e.g., defining radiance or shine (∆ gloss), whiteness (∆ L), degree of red or greenness (∆a*), degree of yellow or blueness (∆b*), change in 15 opacity) and which, in combination with a deposition enhancement system, provides at least 5 % improvement (i.e., 5 % change) in at least one visual attribute being targeted (e.g., shine, color), wherein values reflecting various optical 2 0 properties are measured before or after conducting tests according to a defined protocol, when said composition is applied to the skin; c) from 0.01 % to 30 %, preferably 0.1 % to 25 % by wt. of titanium dioxide particles having size of 2 5 about 100 nm to 300 nm d) from 0.1 % to 25 % by wt. of a deposition enhancement system, wherein, the deposition enhancement system enhances delivery to the skin of a target or defined visual attribute (i.e., t 3 0 whitening) by the optical modifier relative to a composition that has the same surfactant and WO 2005/094779 PCT/EP2005/002703 - 4 - optical modifier used at the same concentration but does not have the deposition enhancement system; and e) from about 0.1% to 45% of a hydrophilic 5 structural dispersant (e.g., polyalkylene glycol). The enhanced whiteness may be measured by a change in L value (measure of whiteness) of at least 5 % in absolute or per cent terms. 10 These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one 15 aspect of the present invention may be utilized in any other aspect of the invention. It is noted that the examples given in the description below are intended to clarify the invention, and are not intended 20 to limit the invention to those examples per se. Other than in the experimental examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about". Similarly, all 25 percentages are weight/weight percentages of the total composition unless otherwise indicated. Numerical ranges expressed the format "from x to y" are understood to include x and y. When for a specific feature 30 multiple preferred ranges are described in -the format ""from x to y", it is understood that all ranges combining the WO 2005/094779 PCT/EP2005/002703 - 5 - different endpoints are also contemplated. Where the term "comprising" is used in the specification or claims, it is not intended to exclude any terms, steps or features not specifically, recited. All temperatures are in degrees 5 Celsius (°C) unless specified otherwise. All measurements are in SI units unless specified otherwise. All documents cited are — in the relevant part - incorporated herein by reference. 10 The present invention relates to composition and to methods of delivering enhancement in delivery of whiteness from rinse-off compositions. Specifically, by using sub-micron titanium dioxide, preferably together with other optical modifiers, and specific deposition enhancement systems, a 15 targeted value can be manipulated to deliver desired whiteness. Specifically, in one embodiment the rinse-off compositions of the invention comprise: 20 a) 0.5 % to 90 %, preferably 5 % to 75 %, more preferably 10 % to 75 % by wt. of a lathering surfactant. (By lathering is meant the composition will have foam of at least 30 cc in a lather wash test); 25 b) O to 35 %, preferably 0.2 % to 25 % by wt. of a solid particulate optical modifier enhancing a specific set of properties (e.g. whiteness) and which, in combination with deposition enhancement system for the modifier (e.g. precipitate formed 30 from interaction of polymer and surfactant) provides at least 5 % change in at least one EPD571601 J-689 6(C)CT - 6 targeted visual attribute., wherein said change is defined by increase or decrease in absolute or percentage value characterizing a specific trait . (i.e., ∆ gloss is associated with radiance or ∆L 5 with.whiteness) and evaluation is made after using a defined in vitro skin protocol test; c) from 0.01 % to 30 % by wt. titanium dioxide particles having size of 100 to 300 nm; d) from 0.1 % to 25 % by wt. of said deposition 10 enhancement system, wherein said system (c) is defined by its ability to enhance delivery of said targeted visual attribute, by, the modifier relative to composition with some surfactant and modifier at same 15 concentration, but which does not have the deposition enhancement system, and e) from 0.1 % to 45 % by wt. of a hydrophilic structural dispersant. 20 Surfactant is present at a level of 0.5 I to 90 %, preferably 5 % to 75 %, more preferably 10 % to 75 %, even more preferably 20 %. to 75 % most preferably 20%to70%-by wt. of the composition, depending on product form. 25 In general, as noted, the surfactant may be selected from the group consisting of soap (including pure soap systems), anionic surfactant, nonionic surfactant, amphoteric/ zwitterionic surfactant, cationic surfactant and mixtures thereof. 30 t*> AMENDED SHEET 31/01/2005 WO 2005/094779 PCT/EP2005/002703 - 7 - "Soap" is used as in the popular sense i.e., alkali metal or alkanol ammonium salts of aliphatic, alkane or alkene monocarboxylic acids. Other surfactants which may be used are described in "Surface Active Agents and Detergents" (Vol. I & II) by Schwartz, Perry & Berch, a copy of which is incorporated by reference into the subject application. As indicated, the particulate optical modifier (titanium dioxide plus optional other modifier) should provide, in combination with deposition enhancement system, at least a 5 % change in L value associated with lightening. Specifically, improvement is measured by taking a value for a particular measured component (e.g., L value for whitening) and measuring (e.g., using in-vitro pig assay) values of the components before and after application of particle deposition enhancement system. The optical benefit carried by the deposition of optical 20 modifier can be targeted to either plateaus on the skin surface or to skin crevices. In one embodiment, the formulation deposition of TiO2 and optional modifier creates skin lightening, whitening, 25 and/or color or similar attributes, and the composition deposits sub-micron Ti02 and optional particulate optical modifier to exhibit AL value in the range of ± 10 L units, wherein said L units are defined by Hunter Lab Color Meter as described in the protocol. ∆a* values may be in the range from about 0 to about ± 10, ∆b* value may be in range from about 0 to about ± WO 2005/094779 PCT/EP2005/002703 - 8 - 10, and a change in opacity may be in the range from about 0 to about ± 50 %. The reflectance should be within normal skin reflectancy range. In this case, this means change in reflectance is ≤ 10 %. Reflectance is measured by a change in 5 gloss measured from a gloss meter. Although there may be a focus on ∆a* and' ∆b*values (since there is a focus on general color attributes), it is important L value (associated with whitening) be changed at least 5 %. 10 The optional optical modifier which may be used for the subject invention may be chosen from non-colored and colored, organic and inorganic materials. Among the materials which may be used are included organic 15 pigments, inorganic pigments, polymers and fillers such as titanium oxide, zinc oxide, colored iron oxide, chromium oxide/hydroxide/hydrate, alumina, silica, zirconia, barium sulfate, silicates, natural/alkaloid (including derivatives) polymers, polyethylene, polypropylene, nylon, ultramarine, 20 and alkaline earth carbonates. The materials can be platy materials such as talc, sericite, mica, synthetic mica, or platy substrates coated with organic and inorganic molecules, such as bismuth oxychloride or barium sulfate. 25 Particles can be composed of several materials (like dyes, lakes, toners). Lakes are, for example, dyes with aluminum hydroxide to help them bind to solid. Color can be generated through fluorescence, absorption or iridescence. That is, color of modifier materials is generated through 30 optical means rather than, for example, chemical means. WO 2005/094779 PCT/EP2005/002703 - 9 - The optical modifier may also be a UV screen material with a D50 5 The optical modifiers may also be defined by their physical properties. For example, the optical modifier may be broadly defined as follows: i) an exterior surface having a refractive index of 10 1.3 to 4.0 ii) a geometry which is spheroidal, platy or cylindrical iii) dimensions: spheroidal - 0.1 to 200 µm, platy - 1 to 200 µm, cylindrical - 1 to 200 µm in length and 15 0.5 to 5.0 µm in diameter iv) a D50 of ≤ 200 microns in particle size, v) may have fluorescence color, absorption color and/or interference color (color through optics) 20 More specifically, particles providing change in shine/glow/radiance may be defined as follows: i) an exterior surface having a refractive index of 1.8 to 4.0, 25 ii) a geometry which is platy or cylindrical, iii)dimensions: spheroidal - 0.1 to 200 µm (microns), platy - 10 to 200 µm, cylindrical - 10 to 200 µm in length and 0.5 to 5.0 µm in diameter, and iv) a D50 of 30 WO 2005/094779 PCT/EP2005/002703 10 - Particles providing skin lightening/color may be defined as follows: i) an exterior surface having a refractive index of 5 1.3 to 4.0, ii) a geometry which is spheroidal or platy, iii) dimensions: spheroidal - 0.1 to 1 µm microns, platy - 1 to 30 µm , iv) a D50 of 10 v) may have fluorescence color, absorption color and/or interference color (color through optics). Particles producing evenness or soft focus may toe defined as follows: 15 i) an exterior surface having a refractive index of 1.3 to 2.0, ii) a geometry which is spheroidal, platy or cylindrical, 20 iii) dimensions: spheroidal - 0.1 to 200 µm , platy - 1 to 10 µm , cylindrical - 1 to 10 µm in length and 0.5 to 5.0 µm in diameter, and iv) a D50 of 25 Of course, the formulation can contain a mixture of particles, each containing characteristics of a specific visual benefit, to create a combination of visual effects. It is also to be understood that for visual effects/ 30 attributes to have maximum effect, the particles have to be WO 2005/094779 PCI7EP2005/002703 - 11 - well dispersed on the skin, and should also give minimal to no sensory negatives. By being "well dispersed1" is meant that the particles should 5 not agglomerate, and that they should be spread easily through the skin surface. In a preferred embodiment, less than 30 % of particles TiO2 and other optical modifiers are agglomerates having a size 10 of ten times or more than the particle size. This can be measured using optical or electron microscopy. The particle is used at about 0 to 35 % by weight, preferably 0.2 % to 25 % by wt., of the composition. 15 Compositions of the invention require use of titanium dioxide wherein the particle size is sub-micron. Specifically, particle must be in the range 100 to 300 nanometers, preferably 120 to 300 nanometers. 20 The key aspect of the particle size requirement is to combine and balance out two optical effects. For particles with a size larger than 200 nm, one gets Mie light scattering. This light scattering mechanism scatters all 25 the wavelengths in the visible spectrum creating a white, opaque effect. Such particle sizes are good for generating effective concealing hiding power and white color. Particles that are less than 200 nm in size create Rayleigh 30 light scattering. This form of light scattering only scatters back blue light. The rest of the visible spectrum WO 2005/094779 PCT/EP2005/002703 - 12 - wavelengths are transmitted through. Such characteristics would create a bluish translucent effect, which would counteract the yellow color in the skin tone to produce a lighter, fairer visual effect. By combining the two light 5 scattering mechanisms (and requiring the particle sizes used be in the range 100 to 300 nanometers), a balance between opacity and translucency, as well as whiteness and blueness, can be obtained to produce the desired visual appearance/ effect sought. 10 The Ti02 should be used at level of from about 0.01 % to 30 %, preferably to 0.1 % to 25 % by wt. Deposition enhancement is key to the delivery of titanium 5 dioxide and optical particles providing enhanced visual benefit (e.g., as defined in changes in ∆L, ∆a*, etc. and in methods to manipulate the values to provide the desired benefit, e.g. radiance, color, etc.). 20 In one embodiment, the deposition is provided by a deposition system comprising as follows: a) from about 0.1 % to about 10 % by wt., preferably 0.1 % to 8 % by wt. of a cationic polymer having 25 change density ≥lMeq/gram, and b) about 0.1 % to 30 % by wt., preferably 0.5 % to 25 % by wt. of an anionic surfactant which forms a precipitate with cationic polymer upon dilution. WO 2005/094779 PCT/EP2005/002703 - 13 - The precipitate formed can be a floe which can be broken up upon shear or rubbing to form a uniform and dispersed film on the surface of the skin. 5 Examples of such surfactants include C10 - C24 fatty acid soaps (e.g., laurates), alkyl taurate (e.g., cocoyl methyl taurate or other alkyl taurates), sulfosuccinates , alkyl sulfates, glycinates, sarcosinates and mixtures thereof. 10 It is important that the cationic have the noted charge in order to form the precipitate which is a key to the deposition of optical modifiers delivering the desired optical attributes. The polymers may be modified polysaccharides including cationic guar gums, synthetic 15 cationic polymers, cationic starches, etc. Specific cationic polymers which are to be used include Merquat® polymers such as polyquaternium 6 (e.g., Merquat® 100 or Salcare® SC30) and polyquatrnium 7 (e.g. Merquat® 20 2200 or Salcare® SC10); guar gums and/or derivatives (e.g. Jaguar CI7) ; quaternized vinylpyrrolidone/methacrylate copolymers (e.g., Gafquat® 775); and polyquaternium-16 (e.g.; Luviquat® FC550). WO 2005/094779 PCT/EP2005/002703 - 14 - Type of Polymer TradeName Company Charge Density (meg/g) Guar Guar hydroxypropyltrimonium chloride Jaguar C17 Rhodia >JaguarC13S Hydroxypropyl guar hydroxypropyltrimonium chloride Jaguar 162 Rhodia -Jaguar C13S Guar hydroxypropyltrimonium chloride Jaguar C13S Rhodia 0.8 Guar hydroxypropyltrimonium chloride Jaguar C14S Rhodia -JaguarC13S Guar hydroxypropyltrimonium chloride Jaguar Excel Rhodia -JaguarC13S Guar hydroxypropyltrimonium chloride N-Hance 3000 Hercules 0.41 Guar hydroxypropyltrimonium chloride N-Hance3196 Hercules 0.72 Guar hydroxypropyltrimonium chloride N-Hance 3215 Hercules 1.05 Synthetics Polyquaternium-6 Merquat 100 Ondeo Nalco 6.2 Polyquaternium-7 Merquat 2200 Ondeo Nalco 3.1 Polyquaternium-7 Merquat 550 Ondeo Nalco 3.1 Polyquaternium-7 Merquat S Ondeo Nalco 3.1 Polyquaternium-7. Salcare Super 7 Ciba 1.5 Polyquaternium-7 SalcareSCIO Ciba 4.3 Polyquaternium-7 Salcare SC11 Ciba 3.1 Polyquaternium-6 Salcare SC30 Ciba 6.2 Polyquaterniumj-16 Luviquat FC370 BASF 2 Polyquaterniumj-16 Luviquat FC550 BASF 3.3 Polyquaterniumj-16 Luviquat FC552 BASF 3 Polyquaterniumj-16 Luviquat FC905 BASF 6.1 Polyquatemium-44 Luviquat MS370 BASF 1.4 Cationic Cellulose Derivatives Polyquaternium-4 Celquat H-100 National Starch 0.71 Polyquaternium-4 Celquat L-200 National Starch 1.43 Polyquatemium-4 Celquat SC230M National Starch 1.36 Polyquaternium-4 Celquat SC240C National Starch 1.29 Polyquaternium-4 UCARE Polymer JR Dow Amerchol 1.3 Polyquaternium-4 UCARE Polymer JR Dow Amerchol 0.7 Dextran Derivatives Dextran hydroxypropylammonium chloride CDC Meito Sangyo 1.6 In general, other deposition aids (e.g., for the Ti02 and optional optical modifier particles) may include granular 5 anionic polymers (e.g. alkaloid polymer such as starch, WO 2005/094779 PCT/EP2005/002703 - 15 - cellulose or their derivatives) . That is, if the deposition system additionally comprises such deposition aid, the results are further enhanced. 5 Yet another way to enhance deposition may b>e through modification (e.g. surface modification) of" particles. In another embodiment, the deposition enhancement system may comprise: 10 1) from 0.1 % to 10 % by wt. of an anionic polymer having charge density of at least ≥ 1.0 Meg/gram; and 2) from about 0.1 % to 30 % cationic surfactant which 15 forms a precipitate with the anionic polymer upon dilution. This system is the inverse of cationic polymer anionic surfactant system. The precipitate can also be a floe which 20 can be broken up on shear or rubbing and form a uniform and dispersed film on the skin surface. Suitable cationic surfactant may be a quaternary amino surfactant or an amphoteric such as betaine(e.g., 25 cocoamidopropyl betaine). The anionic polymer may be a polyacrylate, cross-linked polyacrylate, polyurethane and/or alkaloid derived polymer (e.g., starch, cellulose and derivatives), polysaccharide i 30 (e.g. xanthan gum), agar and/or mixtures thereof. WO 2005/094779 PCT/EP2005/002703 - 16 - This system may also additionally comprise 0.1 % to 30 % granular anionic polymer which is a natural alkaloid polymer (starch, cellulose and derivatives) as deposition aid. 5 EXAMPLES All amounts in the examples are % by weight unless specified otherwise. 10 Protocol In Vitro Porcine/Pig Skin Assay A piece of black porcine skin is used (L = 40 +3), where 15 skin has dimensions of 5.0 cm by 10 cm, and the skin is mounted on black background paper card. Initial measurements of untreated skin are made. The mounted skin is then washed and rinsed with 0.2 g of liquid wash-off formulation or soap bar. After two (2) hours of drying, 20 final measurements are made. Color Measurements Initial and final color measurements were made of porcine or 25 in-vivo human skin using a Hunter Lab spectra colormeter using a 0° light source and 4 5° detector geometry. The spectra colormeter was calibrated with the appropriately black and white standards. Measurements were made before and after wash treatment. Three measurements were made each t 30 time and averaged. Values of L, a*, and b*, which came from the L a* b* color space representation, were obtained in WO 2005/094779 PCT/EP2005/002703 - 17 - this manner. L measures units of "Lightness", a* measures values from red to green and b* measures values from yellow to blue. 5 Reflectance (Gloss) Determination Initial and final reflectance/radiance measurements of porcine or in-vivo human skin were made with a cylossmeter which measures units of gloss. The glossmeter was first set 10 with both detector and light source at 85° from normal. The glossmeter was calibrated with appropriate reflection standard. Measurements of gloss were taken before and after application of formulation, and A gloss was calculated to obtain percent difference. 15 Opacity Determination Opacity of washable deposition was calculated from Hunter Lab color measurements. Opacity contrast was calculated from ∆ 20 L (change in whiteness after deposition compared to prior to deposition) divided by 60 (which is the difference in L value of skin and a pure white color). EXAMPLES 1-5 25 The following compositions show changes in value (i.e. ∆ gloss (%), ∆L, ∆a*, ∆b*, as seen at bottom of chart) when surfactant and deposition systems are used relative to compositions either without same ingredients and/or with 30 different or no deposition systems. - 18 - Pigment-Containing Compositions Component Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Lauric/Myristic/Paimitic/ Stearic acid (fatty acids) 3.27/5.37/7.1 2/6.24/3.91 KOH Sodium N-cocoyl N-methyl taurate (30%) (surfactant) 6.0 20Eocetylethe r/di pro pyleneg lycol/glyceri n/maltitiol solution(75%) (sensory) 4/8.8/12/4 Dibutylhydroxytoluene/EDTA 0.05/0.05 Jaguar C13S (Cationic Polymer) 0.4 0.4 0.4 0.4 0.4 Titanium Dioxide(Kronos 2071-U, 0.3 to 0.5 urn) 20 10 10 10 10 Metal soap treated Talc (J68MT, Mica (T102 coated mica, Mica22 (22 pm, Cardre Inc.) - - - - 5 Petrolatum - - - - - Neosil CP10 (Crossfield, silica gel 50 to 200 pm as exfoliate) - - - - - Perfume 0.25 0.25 0.25 0.25 0.25 Deionized water To 100 To 100 To 100 To 100 To 100 Pig Skin in vivo A gloss (%) 39.8 20.8 0 16.6 34.3 ∆L 19.3 7.6 7.9 7.8 14.5 ∆a* -0.7 -0.5 -0.3 -0.1 -1.5 ∆b* -8.3 -5.7 -6.7*• -7.5 -6.7 For the top 4 rows, the same ratios were used for all 5 5 examples. As seen from the Table above, systems of the invention create optical attributes (∆L, ∆a*, etc.) which vary in change of the value (and accordingly with the attribute which is 10 highlighted) depending on the exact particle size of particle, and deposition system used. Thus, the applicants WO 2005/094779 PCT/EP2005/002703 - 19 - are able to manipulate values from a wash-off system; and to provide values and the ability to manipulate previously unknown. 5 A more detailed discussion of observations which can be made from the many examples is set forth below. Examples 1 to 5, are Jaguar C13S-based formulations , which show some deposition. 10 Examples 1 and 2 have 20 % Ti02 and 10 % Ti02, respectively, with the 20 % TiO2 formulation showing higher deposition and larger AL change. There is also a large (and negative) change in the b* value (becoming bluer). The deposition also 15 has a matting visual effect, as can be seen from the negative A gloss (which indicates a lowering of shine). Examples 3 to 5 use Example 2 formulation with an addition of a reflective particle material. 20 Example 3 has talc (D50 of l0µm) included into the formulation. The slight reflectivity of talc counteracts the matting effect of the deposited Ti02, as can be seen by the zero change in ∆gloss. This combination gives a whiter, 25 lighter appearance while still maintaining the skin ' s normal shine. The addition of the talc did not alter the ∆L or ∆b*seen from Example 2. Example 5 is the same as Example 3 except that natural mica 30 (D50 of 22 µm) is used. The higher reflectivity of the WO 2005/094779 PCT/EP2005/002703 - 20 - larger sized mica counteracts the matting effect of the deposited Ti02 and increases the visual shine, as can be seen by the increase in ∆gloss. The addition of the natural mica did not alter the ∆L or ∆b* seen from Example 2. 5 Example 4 is the same as Example 3 except that a titan coated mica (D50 of 6µm) is used. The greater reflectivity of the titan-coated mica counteracts the matting effect of the deposited TiO2 and increases the visual shine, as can be 10 seen by the increase in ∆gloss. The addition of the coated mica does increase the ∆L or ∆b*as compared to Example 2. The control is for comparison purposes. It has the same formulation as Example 2 except there is no cationic polymer 15 (Jaguar C13S). From the L, a*, b*, and gloss values, no deposition is observed. From Examples 1 to 5, changes in visual attributes can be seen, but they are not large enough. The particle 20 deposition needs to be larger. For this to occur, a cationic polymer with a larger charge density must be used (in this case Merquat 100) . Example 6 is the same as Example 2, except the cationic 25 polymer used is Merquat 100 instead of Jaguar. As can be seen from the ∆L and ∆gloss, the deposition of the TiO2 is much greater (by a factor of 5). The visual effect is a much greater whiteness, but also a larger increase in WO 2005/094779 PCT7EP2005/002703 - 21 - mattness. To counteract the mattness, natural mica or talc can be added to the formulations. Examples 7 and 8 are Merguat 100 formulations with natural 5 mica or talc. Both examples show an attenuation in the matting effect of the large Ti02 deposition as can be seen by the lower negative or even positive ∆gloss relative to, for .example, Example 6. Example 9 is a Merquat 100 formulation with Timiron super blue, an iridescent titania coated mica 10 pigment. The example shows attenuation in the matting effect of the large TiO2 deposition, as can be seen by the positive ∆gloss. It also crates a blue hue from the iridescent color. 15 The facial wash-off formulation can also use a different hydrophilic structural dispersent, such as starch. Similar correlations and trends can be seen with the starch formulation system as with the previous examples. 20 Example 12 and Example 13 compare the deposition of TiO2/~talc from formulations using Merquat 100 and Jaguar C13S respectively. As before, the higher charge density Merqaat shows greater deposition than Jaguar, with similar visual attributes. 25 Example 10 is a control formulation, with no cationic polymer. From the L, a*, b*, and gloss measurements, ther-e is little to no deposition. WO 2005/094779 PCT/EP2005/002703 - 22 - Example 11 shows the importance of compatibility of surfactant systems to deposition efficiency. Example 11 uses a mixture of CAP Betaine and lauryl ether sulfate. In comparison with Example 12, the deposition is less efficient as seen from the lower AL values. This is an indication that the CAP Betaine/lauryl ether sulfate surfactant system is not as effective precipitating cationic polymer upon dilution. Example 6 The chart below provides additional examples. Pigment-Containing Compositions WO 2005/094779 PCT/EP2005/002703 - 23 - Component Ex.6 Laurie acid 3.27 Myristic acid 5.37 Palmitic acid 7.12 Stearic acid 6.24 Potassium hydroxide 3.91 Sodium N-cocoyl N-methyl taurate (30%) 6.0 Polyoxyethylene cetylether(20 E.O.) 4 Dipropylene glycol 8.8 Glycerin, concentrated 12 Sorbitol - Maltitol solution (75%) 4 Dibutylhydroxytoluene 0.05 EDTA tetrasodium tetrahydrate 0.05 Jaguar C13S (Cationic Polymer) - Merquat 100 (Cationic Polymer) 0.4 Titanium Dioxide (0.3 to 0.5 urn) 10 UVT102 (Treated) - UV Ti02 (M212, Presperse) - Petrolatum Perfume 0.25 Deionized water To 100 WO 2005/094779 PCT/EP2005/002703 - 24 - Pig skin in-vitro A gloss (%) -50.0 AL 34.6 ∆a* -2.4 Ab* -8.6 Again, it can be seen from the above chart how deposition system and particles of invention provide compositions with 5 desired values providing desired optical attributes (e.g., radiance, color, shine). WO 2005/094779 PCT7EP2005/002703 - 25 - Control The chart below provides an additional example. Component Control Laurie acid 3.27 Myristic acid 5.37 Palmitic acid 7.12 Stearic acid 6.24 Potassium hydroxide 3.91 Sodium N-cocoyl N-methyl taurate (30%) 6.0 Polyoxyethylene cetylether(20E.O.) 4 Dipropylene glycol 8.8 Glycerin, concentrated 12 Maltitol solution (75%) 4 Dibutylhydroxytoluene 0.05 EDTA tetrasodium tetrahydrate 0.05 Jaguar C13S 0 Polymer J R Merquat 100 - Titanium Dioxide (0.3 to 0.5 urn) 10 Timiron Super blue - Petrolatum - Perfume 0.25 Deionized water To 100 Pig skin in-vitro A gloss (%) -3.9 ∆L 0.1 ∆a* 0.1 ∆b* 0.1 WO 2005/094779 PCT/EP2005/002703 - 26 - Again it can be seen from the above control that when there is no cationic, there is little or no deposition. Example 7 5 The chart below again shows different variations. WO 2005/094779 PCT/EP2005/002703 - 27 - Pigment-Containing Compositions Component Ex.7 Ex.9 Laurie acid 3.27 3.27 Myristic acid 5.37 5.37 Palmitic acid 7.12 7.12 Stearic acid 6.24 6.24 Potassium hydroxide 3.91 3.91 Sodium N-cocoyl N-methyl taurate (30 %) 6.0 6.0 Polyoxyethylene cetylether(20 E.O.) 4 4 Dipropylene glycol 8.8 8.8 Glycerin, concentrated 12 12 Maltitol solution (75 %) 4 4 Dibutylhydroxytoluene 0.05 0.05 EDTA tetrasodium tetrahydrate 0.05 0.05 Jaguar C13S - 0.4 Merquat 100 0.8 - Titanium Dioxide(PW liquid Ti02, 0.3 µm ) 10 - UVTi02(M212) - - Mica (T102 coated mica, Mica22 (22 urn, Cardre Inc.) 5 - Petrolatum - - Perfume 0.25 0.25 Deionized Water To 100 To 100 Pig skin in-vitro A gloss (%) 20.0 +4.96 L 33.03 +8.35 A* -3.8 =0.39 B* -9.55 -7.35 WO 2005/094779 PCT7EP2005/002703 - 28 - Examples 8 The chart below shows one more example. 5 Component Ex.8 Laurie acid 3.27 Myristic acid 5.37 Palmitic acid 7.12 Stearic acid 6.24 Potassium hydroxide 3.91 Sodium N-cocoyl N-methyl taurate (30 %) 6.0 Polyoxyethylene cetylether(20 E.O.) 4 Dipropylene glycol 8.8 Glycerin, concentrated 12 Maltitol solution (75 %) 4 Dibutylhydroxytoluene 0.05 EDTA tetrasodium tetrahydrate 0.05 Merquat 100 0.4 Titanium Dioxide 10 Soft Talc 5 Dl Water To 100 Petrolatum 10 Perfume 0.25 Dl water To 100 Pig skin in-vitro A gloss (%) -5.6 L 31.3 A* -3.6 B* -8.0 The -5.6 shows a somewhat neutral gloss counteracts the matting effect of the titanium dioxide. 5 WO 2005/094779 PCT/EP2005/002703 - 29 - Examples 10-13 The chart below shows examples with starch structured liquids. Component Ex. 10 Ex. 11 Ex.12 Ex. 13 v K La urate 6 - 6 6 Na cocoyl methyl taurate 3 - 3 3 Lauryl ether sulfate 0 6 0 0 Cocoamidoprogyl Betaine - 3 - - Corn starch 10 10 10 10 Structure XLCo-water soluble cross-linked starch 1.5 1.5 1.5 1.5 Glycerin 6 6 6 6 Jaguar C13S - - - 0.4 Merquat l00 - 0.4 0.4 - TiO2 15 15 15 15 Soft Talc 5 5 5 5 Petrolatum 5 5 0 0 Sunflower seed oil - - - - Dl Water to 100 to 100 to 100 to 100 Pig skin in-vitro A gloss (%) -21.4 -24.6 -26.4 0.0 L 4.7 21.3 44.3 15.7 A* -0.5 -5.2 -5.8 -4.23 B* 4.0 10.9 -10.6 -11.0 CLAIMS 1. A foeauty ■vaah product! composition for delivery of enhanced visual benefits to the skin with specific 5 optical attributes comprising: (a) from about 0.5. % to about 90 % of by wt. surfactant; Q (b) from 0 % to 35 % by wt. of solid, particulate optical modifier which exhibits a specific set of 10 optical properties, defined by ∆L, ∆a*, ∆b*, change in reflectivity and/or change in opacity* fc.id Ti?hlsj in combination with a deposition enjjaiaeeiffent system, provides at least 5%ch>aji^""'inat least one of the opticalprj3peT"c7res being targeted when the 15 ff (c) from 0.01 % to 30 % by wt. of a titanium dioxide particle having size of about to 100 run to 300 run; (d) from 2 % to 25 % by wt. of a deposition enhancement system, wherein the deposition enhancement system 20 ■ ^nhancca delivery-to the 3kin 'of a target "ii attribute by the optical modifi^r^e^ri^ftive to a composition that hasjtise-^ame surfactant and optical modifierai-"-ttTesame concentration and that does not :vc the»dopooition enhancement systorafl; and 25 (e) from about 0.1 % to 45 % of a hydrophilic structural dispersant] 2. A composition according to claim 1 wherein the optical attribute affected by change of at least 5 % in at least " 30 one of said optical properties is chosen from skin shine, skin lightness, skin color, skin glow, skin- AMENDED SHEET.. WO 2005/094779 PCT/EP2005/002703 - 31 - radiance, skin optical uniformity, skin evenness and mixtures thereof. 3. A composition according to claim 1 or claim 2, comprising 20 % to 75 % by wt. surfactant. 4. A composition according to any one of the preceding claims, wherein the skin site where the delivery of optical benefits is targeted is skin plateaus and/or crevices in skin. 5. A composition according to any one of the preceding claims, comprising 0.2 % to 25 % by wt. optical modifier. 6. A composition according to any one of the preceding claims providing change in lightening or whitening, wherein delivery of modifier provides change in defined values as noted below: ∆ L of from 0 to ±10 L units, wherein L units are defined by Hunter Lab Color Meter; ∆a* of from 0 to ±10 a* units, wherein a* units are defined by Hunter Lab Color Meter; ∆b*of from 0 to ±10 b* units, wherein b* units are defined by Hunter Lab Color Meter; change in opacity of 0 to ±50 % measured by opacity contrast, wherein the contrast is defined by AL divided by 60; J6896(C)CT - 32 - wherein ∆ reflectance is ≤10 %, A reflectance being measured as change in gloss where gloss is measured in a gloss meter; wherein at least L has a change of at least 5 % from' 5 initial-value prior to delivery of modifier. 7. A composition according to any one of the preceding claims, wherein the optical modifier is a non-colored or colored organic or inorganic material selected from 10 organic pigments; inorganic pigments; polymers and fillers in turn selected from ttitanium diown do;j zinc oxide, colored iron oxide, chromium oxi.de/ hydroxide or hydrate; alumina; silica; zirconia; barium sulfate; silicates; alkaloid polymers and derivatives thereof; 15 polyalkylene; nylon; ultramarine; alkaline earth carbonate; talc; sericite; natural and synthetic mica; platy substrate coated with organic and inorganic materials; bismuth oxychloride; and mixtures thereof. 20 8. A composition according to any one Of the preceding claims, wherein the optical modifier is a UV sunscreen material with a D50 9. A composition according to any one of the preceding 25 claims, the optical modifier being defined as follows: (a)Exterior surface with refractive index of 1.3 to 4.0; (b)geometry which is spheriodal, platy or cylindrical; (c)D50 of ≤200 microns particle size.; 30 (d)color which is obtained fluorescence color, absorption and/or interference color. AMENDED SHEET SiySi/200&: J6896(C)CT - 33 - 10. A composition according to claim 8 wherein the particulate optical modifier is further defined by: 5 (a) an exterior surface of refractive index 1.3 to 4.0; (b) geometry which are platy or spheroidal; (c) diversions of spheroidal particles of 0.1 to 1 urn; and diversion of platty particles 1 to.30 µm; (d) D50 of ≤30 microns in particle size; and 10 (e) color by florescence, absorption and/or interference. 11. A composition according to any one of the preceding claims, wherein the deposition system comprises: 15 0.I-to-l0 (a) fco-lj % by wt. cat ionic polymer or polymers having an average charge density >1 Meq/gram; and (b)/to 30 % by wt. anionic surfactant which forms precipitate with cationic polymer upon dilution.. 20 25 12. A composition according to claim 11, wherein the precipitate is a floe which can be broken upon shear or rubbing to form a uniform and dispersed film on surface of skin. 13. A composition according to claim 11 or claim 12, wherein the anionic is C10 to C24 fatty acid soap, alkyl taurate, sulfosuccinate, alkyl sulfate, glycinate, sarcosinate or mixture thereof. 30 AMENDED SHEET 31701/2005 WO 2005/094779 PCT/EP2005/002703 - 34 - 14. A composition according to any one of claims 11 to 13, wherein" the cationic polymer is selected from polyquaternium 6, polyquaternium 7, polyquaternium'16, quartenized vinyl pyrrolidone/methacrylate copolymers, 5 hydroxypropylguar gums and mixtures thereof. 15. A composition according to any one of claims 11 to 14, additionally comprising about 0.1 % to 30 % by wt. of a 10 granular anionic polymer which is a natural alkaloid polymer. 16. A composition according to claim 15, wherein the polymer is starch and derivatives, cellulose and derivatives and 15 mixtures thereof. 17. A composition according to claim 7, wherein optical particles of interest contain a surface modification selected from amino acids, proteins, fatty acids, 20 lipids, phospholipids, anionic and/or cationic oligemers/polymers and mixtures thereof. 18. A composition according to any one of the preceding claims, wherein the particles are dispersed on the skin 25 in that less than 30 % of the particles have a size of 10 times or more than the D50 particle size as measured by optical microscopy. Dated this 27th day of September 2006

Documents:

1151-MUMMP-2006-FORM 3(15-2-2011).pdf

1151-MUMNP-2006-ABSTRACT(19-1-2009).pdf

1151-mumnp-2006-abstract(granted)-(21-1-2010).pdf

1151-MUMNP-2006-ASSIGNMENT(18-5-2009).pdf

1151-MUMNP-2006-CANCELLED PAGES(18-5-2009).pdf

1151-MUMNP-2006-CLAIMS 7-7-2008.pdf

1151-MUMNP-2006-CLAIMS(18-5-2009).pdf

1151-MUMNP-2006-CLAIMS(19-1-2009).pdf

1151-MUMNP-2006-CLAIMS(GRANTED)-(21-1-2010).pdf

1151-mumnp-2006-claims.doc

1151-mumnp-2006-claims.pdf

1151-MUMNP-2006-CORRESPONDENCE 1(18-5-2009).pdf

1151-mumnp-2006-correspondence 1(23-1-2007).pdf

1151-mumnp-2006-correspondence 2(1-2-2008).pdf

1151-MUMNP-2006-CORRESPONDENCE 7-7-2008.pdf

1151-MUMNP-2006-CORRESPONDENCE(18-5-2009).pdf

1151-MUMNP-2006-CORRESPONDENCE(19-1-2009).pdf

1151-MUMNP-2006-CORRESPONDENCE(4-12-2009).pdf

1151-MUMNP-2006-CORRESPONDENCE(8-2-2012).pdf

1151-mumnp-2006-correspondence(ipo)-(16-2-2010).pdf

1151-mumnp-2006-correspondence-received.pdf

1151-mumnp-2006-description (complete).pdf

1151-MUMNP-2006-DESCRIPTION(COMPLETE)-(18-5-2009).pdf

1151-MUMNP-2006-DESCRIPTION(COMPLETE)-(19-1-2009).pdf

1151-MUMNP-2006-DESCRIPTION(GRANTED)-(21-1-2010).pdf

1151-MUMNP-2006-FORM 1(19-1-2009).pdf

1151-MUMNP-2006-FORM 1(27-9-2006).pdf

1151-mumnp-2006-form 13(4-10-2007).pdf

1151-MUMNP-2006-FORM 18(23-01-2007).pdf

1151-mumnp-2006-form 2(18-5-2009).pdf

1151-mumnp-2006-form 2(19-1-2009).pdf

1151-mumnp-2006-form 2(granted)-(21-1-2010).pdf

1151-MUMNP-2006-FORM 2(TITLE PAGE)-(18-5-2009).pdf

1151-MUMNP-2006-FORM 2(TITLE PAGE)-(19-1-2009).pdf

1151-mumnp-2006-form 2(title page)-(granted)-(21-1-2010).pdf

1151-MUMNP-2006-FORM 3(12-8-2011).pdf

1151-MUMNP-2006-FORM 3(19-1-2009).pdf

1151-MUMNP-2006-FORM 3(24-2-2010).pdf

1151-MUMNP-2006-FORM 3(4-8-2010).pdf

1151-MUMNP-2006-FORM 5(19-1-2009).pdf

1151-mumnp-2006-form-1.pdf

1151-mumnp-2006-form-2.doc

1151-mumnp-2006-form-2.pdf

1151-mumnp-2006-form-3.pdf

1151-mumnp-2006-form-5.pdf

1151-mumnp-2006-form-pct-ipea-409.pdf

1151-mumnp-2006-form-pct-ipea-416.pdf

1151-mumnp-2006-general power of attorney(7-7-2008).pdf

1151-MUMNP-2006-INVENTION SEARCH RESULTS(19-1-2009).pdf

1151-MUMNP-2006-OTHER DOCUMENT 7-7-2008.pdf

1151-MUMNP-2006-OTHER DOCUMENT(18-5-2009).pdf

1151-mumnp-2006-pct-search report.pdf

1151-MUMNP-2006-WO INTERNATION PUBLICATION REPORT(27-9-2006).pdf