Title of Invention

STABILIZATION WITH SUBSTITUTED UREAS AGAINST COLOR DEGRADATION OF PERSONAL CARE PRODUCTS

Abstract

A personal care product is provided which includes an unsaturated organic material with at least one olefinic double bond susceptible to degradation into a color bearing substance, the unsaturated material being selected from C10-C50 terpenoids and C12-C48 unsaturated fatty compounds selected from the group consisting of fatty alcohols, fatty acids, fatty acid glycerides, fatty acid salts, fatty acid esters and combinations thereof, a substituted urea as a stabilization agent to prevent color body formation, and a cosmetically acceptable carrier. Particularly useful as a stabilizing agent is hydroxyethyl urea.

Full Text

FORM - 2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2006 COMPLETE SPECIFICATION (See Section 10 and Rule 13) STABILIZATION WITH SUBSTITUTED UREAS AGAINST COLOR DEGRADATION OF PERSONAL CARE PRODUCTS 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 Dated 04/01/2006 DESCPAMD EP04801214 J6886(C) PCT 1- STABILZATION WFTH SUBSTITUTED UREAS AGAINST COLOR DEGRADATION OF PERSONAL CARE PRODUCTS 5 The invention concerns personal care products having labile ingredients which are prevented from generating aesthetically displeasing color bodies. Color stability is an important aesthetic of personal care products. Some commonly formulated ingredients are susceptible to photo and/or oxidative degradation. Common 10 among many of these ingredients is the presence of one or more unsaturated bonds. Structures with conjugated double and triple bonds (pi systems) are particularly vulnerable to generation of chromophoric color bodies. The present invention seeks to provide a system which insures color stability in personal care products. 15 SUMMARY OF THE INVENTION 20 2S A personal care composition is provided which Includes: (i) an unsaturated organic material with at least two olefinic double bonds in a conjugated relationship susceptible to degradation into a color bearing substance, the unsaturated material being selected from C10-C50 terpenoids and C12–C48 unsaturated fatty compounds, the C12-C48compounds being selected from the group consisting of fatty alcohols, fatty acids, fatty acid glycerides, fatty acid salts, fatty add esters and combinations thereof; (ii) a substituted urea of general structure (1) O RiR2NCNR5R4 30 I wherein R1, R2 and R3 are selected from the group consisting of hydrogen, C1-C6 alkyl, (R5)nOH, and mixtures thereof; R5 is methylene, ethylene, propylene or combinations thereof, and n ranges from 1 to 6; and R4 is (R5)nOH; and (iii) a cosmetically acceptable carrier. FmPf.7eit:06/07/2005 13:37 AMENDED SHEET : 167 P.004 06707/200 WO 2005/079740 PCT/EP2004/013959 -2- DETAILED DESCRIPTION OF THE INVENTION Now it has been found that certain types of unsaturated organic materials in personal care compositions can be preserved against degradation into visible color species. Materials requiring stabilization are those with at least one olefinic double bond such as 5 the C10-C50 terpenoids and the C12 -C48 unsaturated fatty compounds. The latter include fatty alcohols, fatty acids, fatty acid salts, fatty acid glycerides, fatty acid esters and combinations thereof. Color inhibition is achieved through use of substituted ureas. By the term personal care composition is meant any product applied to a human body for improving appearance, cleansing, odor control or general aesthetics. Non-limiting 10 examples of personal care compositions include leave-on skin lotions and creams, shampoos, conditioners, shower gels, toilet bars, antiperspirants, deodorants, dental products, shave creams, depilatories, lipsticks, foundations, mascara, sunless tanners and sunscreen lotions. An important element of the present invention is the color stabilization agent. This is a 15 substituted urea having general structure (I) O R1R2NCNR3R4 20 I wherein R1,R2 and R3 are selected from the group consisting of hydrogen, C1-C6 alkyl, (R5)nOH, and mixtures thereof; R5 is methylene, ethylene, propylene or combinations thereof, and n ranges from 1 to 6; and R4 is (R5)nOH. Illustrative species of the substituted urea are hydroxymethyl urea, hydroxyethyl urea, 25 hydroxypropyl urea; bis(hydroxymethyl) urea; bis(hydroxyethyl) urea; bis(hydroxypropyl) urea; N,N'-di-hydroxymethyl urea; N.N'-di-hydroxyethyl urea; N.N'-di-hydroxypropyl urea; N.N.N'-tri-hydroxyethyl urea; tetra(hydroxymethyl) urea; tetra(hydroxyethyl) urea; tetra(hydroxypropyl) urea; N-methyl-N'- hydroxyethyl urea; N-ethyl-N'-hydroxyethyl urea; N-hydroxypropyl-N'- hydroxyethyl urea and N,N'-dimethyl-N-hydroxyethyl urea. Where 30 the term hydroxypropyl appears, the meaning is generic for either 3-hydroxy-n-propyl, 2- WO 2005/079740 PCT/EP2004/013959 -3- hydroxy-n-propyl, 3-hydroxy-i-propyl or 2-hydroxy-i-propyl radicals. Most preferred is hydroxyethyl urea. The latter is available as a 50% aqueous liquid from the National Starch & Chemical Division of ICI under the trademark Hydrovance. Amounts of the substituted urea may range from 0.01 to 20%, preferably from 0.1 to 10%, 5 more preferably from 1 to 8%, and optimally from 3 to 6% wAv of the composition. Components of the personal care compositions susceptible to color degradation are materials which have at least one olefinic bond, and particularly those with at least 2, 3 or 4 olefinic bonds. Especially susceptible to color producing bodies are those compounds where the olefin bond is conjugated with other olefin, alkyne or aromatic pi bonded systems. Unsaturated fatty acid or alcohol derivatives may be susceptible to color body formation. By the term fatty is meant an alkyl chain length from C12 to C48, most often from C12 to C24. Typical fatty acids of this category are oleic acid, linoleic acid, linolenic acid, ricinoleic acid, elaidic acid, petroselenic acid, erucic acid, palmitoleic acid, myristoleic acid and 12-hydroxyoleic acid. Most common of the aforementioned fatty acids are oleic acid, linoleic acid, linolenic acid and ricinoleic acid. Exemplative unsaturated fatty alcohols include oleyl alcohol, linoleyl alcohol, linolenyl alcohol and mixtures thereof. Among the salts are the sodium, ammonium, potassium and triethanolammonium fatty acid salts. Illustrative but not limiting are salts such as sodium oleate, potassium oleate, ammonium oleate, triethanolammonium oleate, sodium linolenate, potassium linolenate, ammonium linolenate and triethanolammonium linolenate. Longer chain unsaturated fatty acids are illustrated by a group generically known as conjugated linoleic acids. Conjugated linoleic acids (referred to as CLA) are illustrative of polyunsaturated compounds of the present invention susceptible to color body formation. These comprise a group of positional and geometric isomers of linoleic acid in which various configurations of cis and trans double bonds at positions (6,8), (7,9), (8,10), (9,11), (10, 12) or (11, 13) are possible. Thus, twenty-four different isomers of CLA exist. Conjugated is a term meaning adjacent pairs of double bonds forming an extended pi orbital system. WO 2005/079740 PCT/EP2004/013959 -4 Gfycerides are a further category of the unsaturated fatty compounds. These may be mono- di- or tri- glycerides. One, two or three of the fatty acid chains esterified to the glycerol are unsaturated. Nonlimiting examples of glycerides include sunflower seed oil, soybean oil, olive oil, cotton seed oil, groundnut oil, shea nut oil, palm oil, cocoa butter, illipe, borage and borage seed oil, coriander seed oil, linseed oil, safflower oil, triglycerides with conjugated linoleic acid residues and mixtures thereof. 10 Terpenoids are another category of unsaturated organic materials according to the present invention. Terpenoids may be further divided into classes such as alcohols, ethers, aldehydes, acetals, acids, ketones, ester and terpene compounds that contain hetero atoms such as nitrogen or sulphur. The tables which follow describe illustrative but not limiting examples. TABLE 1. Acyclic Terpenoids HYDROCARBONS 15 Myrcene Ocimene beta-Farnesene ALCOHOLS 2 0 Dihydromyrcenol Geraniol Nerol Linalool Myrcenol 25 Lavandulol Citronellol Trans-trans-Famesol Trans-Nerolidol (2,6-dimethyl-7-octen-2-ol) (3,7-dimethyl-frans-2,6-octadien-1 -ol) (3,7-dimethyl-cfe-2,6-octadien-1-ol) (3,7-dimethyJ-1,6-octadien-3-ol) (2-methyl-6-methylene-7-octen-2-ol) (3,7-dimethyl-6-octen-1 -ol) (3,7,11-trimeth yt-2,6,10-dodecatrien-1-ol) (3,7,11-trimethyM ,6,10-dodecatrien-3-ol) 3 0 ALDEHYDES AND ACETALS Citral Citral diethyl acetal Citronelial (3,7-dimethyl-2,6-octadien-1-al) (3,7-dimethyl-2,6-octadien-1-al diethyl acetal) (3,7-dimethyl-6-octen-1 -al) WO 2005/079740 PCTYEP2004/013959 -5- Citronellyloxyacetaldehyde 2,6,10-Trimethyl-9-undecenal KETONES 5 Tagetone Solanone Geranylacetone (6,10-dimethyl-5,9-undecadien-2-one) ACIDS AND ESTERS 10 Cis-Geranic acid Citronellic acid Geranyl esters, including geranyl formate, geranyl acetate, geranyl propionate, geranyl isobutyrate, geranyl isovalerate Neryl esters, including neryl acetate 15 Linalyl esters, including linalyl formate, linalyl acetate, linalyl propionate, linalyl butyrate, linalyl isobutyrate, Lavandulyl esters, including lavendulyl acetate Citronellyl esters, including citronellyl formate, citronellyl acetate, citronellyl propionate, citronellyl isobutyrate, citronellyl isovalerate, citronellyl tiglate 20 NITROGEN CONTAINING UNSATURATED TERPENE DERIVATIVES Cis -geranic acid nitrile Citronellic acid nitrile 25 TABLE 2. Cyclic Terpenoids HYDROCARBONS Limonene Alpha-Terpinene 30 Gamma-Terpinene Terpinolene Alpha-Phellandrene Beta-Phellandrene Alpha-Pinene 35 Beta-Pinene (1,8-p-menthadiene) (1,4-p-menthadiene) (1,5-p-menthadiene) (2-pinene) (2(10)-pinene) WO 2005/079740 PCT/EP2004/013959 Camphene 3-Carene Caryophyllene (+)-Valencene 5 Thujopsene Alpha-Cedrene Beta-Cedrene Longifolene 10 ALCOHOLS AND ETHERS (+)-Neoiso-isopulegol Isopulegol Afpha-Terplneol Beta-Terpineol 15 Gamma-Terpineol Delta-Terpineol 1-Terpinen-4-ol ALDEHYDES AND KETONES 20 Carvone Alpha-lonone Beta-lonone Gamma-lonone Irone, alpha-, beta-, gamma- 25 n-Methylionone. alpha-, beta-, gamma- Isomethylionone, alpha-, beta-, gamma- Allylionone Pseudoionone n-Methylpseudoionone 30 Isomethylpseudoionone Damascones Beta-Damascenone Nootkatone 35 Cedryl methyl ketone (8-p-menten-3-ol) (1-p-menten-8-ol) (1-p-menten-4-ol) (1,8-p-mentadien-6-one) (C13H20O) (C13H20O) (C13H20O) {C14H20O) (C14H22O) (C14H22O) (C16H24O) 1 -(2,6,6-trimethylcyclohexenyl)-2-buten-1 -ones 1 -(2,6,6-trimethyM,3-cyclohexadienyl)-2-buten-1-one 5,6-dimethyl-8-isopropenylbicyclo[4.4.0)-1-decen-3-one (C17H26O) WO 2005/079740 PCT/EP2004/013959 ESTERS Alpha-Terpinyl acetate (1-p-menthen-8-yl acetate) Nopyl acetate (-)-2-(6.6-dimethylbicyclo[3.1.1]hept-2-en-2-yl) ethyl acetate 5 Khusymil acetate TABLE 3. Cycloaliphatic Compounds Structurally Related to Terpenes 10 ALCOHOLS 5-(2,2,3-Trimethyl-3-cyclopenten-1-yl)-3-methylpentan-2-ol ALDEHYDES 15 2,4-Dimethyl-3-cyclohexene carboxaldehyde 4-(4-Methyl-3-penten-1-yl)-3-cyclohexene carboxaldehyde 4-(4-Hydroxy-4-methypentyl)-3-cyclohexene carboxaldehyde KETONES 20 Civetone Dihydrojasmone (3-methyl-2-pentyl-2-cyclopenten-1 -one) Cis-Jasmone 3-methyl-2-(2-c/s-penten-1-yl)-2-cyclopenten-1-one 5-Cyclohexadecen-1-one 2,3,8,8-Tetramethyl-1,2,3,4,5,6,7,8,-octahydro-2-napthalenyl methyl ketone 2 5 3-Methyl-2-cyclopenten-2-ol-1 -one ESTERS 4.7-Methano-3a,4,5,6,7,7a-hexahydro-5-(or 6)-indenyl acetate Allyl 3-cyclohexylpropionate 30 Methyl dihydrojasmonate methyl (3-oxo-2-pentylcyclopentyl) acetate. Another subclass of the terpenoids category are the sterols. Examples are betulin (betulinic acid and alcohol), cholesterol, sitosterol, ergosterol. stigmasterol, and linosterol. Amounts of the unsaturated material which may lead to color formation may range from 35 0.0001 to 20%. usually from 0.001 to 10%, more usually from 0.1 to 5% w/w. WO 2005/079740 PCT/EP2004/013959 -8- Advantageously but not necessarily the amount of the substituted urea relative to the unsaturated material ranges in weight from 10,000:1 to 1:100, preferably from 1,000:1 to 1:10, more preferably from 500:1 to 1:5, optimally from 100:1 to 10:1. 5 Certain types of unsaturated material of the present invention can be characterized by an Iodine Value ranging from 20 to 300, preferably from 30 to 200, optimally from 50 to 150. Iodine Values are often associated with fatty compounds such as the fatty acids, fatty alcohols, fatty acid salts and fatty acid glycerides. 10 Compositions of this invention will also include a cosmetically acceptable carrier. Amounts of the carrier may range from 1 to 99.9%, preferably from 70 to 95%, optimally from 80 to 90% by weight of the composition. Among the useful carriers are water, saturated emollients, saturated fatty acids, saturated fatty alcohols, humectants, thickeners and combinations thereof. The carrier may be aqueous, anhydrous or an 15 emulsion. Preferably the compositions are aqueous, especially water and oil emulsions of the W/O or O/W or triplex W/O/W variety. Water when present may be in amounts ranging from 5 to 95%, preferably from 20 to 70%, optimally from 35 to 60% w/w. Emollient materials may serve as cosmetically acceptable carriers. These may be in the form of silicone oils, synthetic esters and hydrocarbons. Amounts of the emollients may 20 range anywhere from 0.1 to 95%, preferably between 1 and 50% by weight of the composition. Silicone oils may be divided into the volatile and non-volatile variety. The term "volatile" as used herein refers to those materials which have a measurable vapor pressure at ambient temperature. Volatile silicone oils are preferably chosen from cyclic 25 (cyclomethicone) or linear polydlmethylsiloxanes containing from 3 to 9, preferably from 4 to 5, silicon atoms. Non-volatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. The essentially non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with 30 viscosities of from 5 x 10-6 to 0.1 m2/s at 25°C. Among the preferred non-volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from 1 x 10-5 to 4 x 10-4 m2/s at 25°C. WO 2005/079740 PCT/EP2004/013959 Another class of non-volatile silicones are emulsifying and non-emulsifying silicone elastomers. Representative of this category is dimethicone/vinyl dimethicone crosspolymer available as Dow Coming 9040, General Electric SFE 839, and Shin-Etsu KSG-18. Silicone waxes such as Silwax WS-L (dimethicone copolyol laurate) may also 5 be useful. Among the ester emollients are: 1) Alkyl esters of saturated fatty acids having 10 to 24 carbon atoms. Examples thereof include behenyl neopentanoate, isononyl isonanonoate, isopropyl myristate and octyl stearate. 10 2) Ether-esters such as fatty acid esters of ethoxylated saturated fatty alcohols. 3) Polyhydric alcohol esters. Ethylene glycol mono and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol 15 monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty esters, ethoxylated glyceryl mono-stearate, 1,3-butyiene glycol monostearate, 1,3- butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters. Particularly useful are pentaerythritol, 20 trimethylolpropane and neopentyl glycol esters of C1-C30 alcohols. 4) Wax esters such as beeswax, spermaceti wax and tribehenin wax. 5) Sugar esters of fatty acids such as sucrose polybehenate and sucrose polycottonseedate. Hydrocarbons which are suitable cosmetically acceptable carriers include petrolatum, 25 mineral oil, C11-C13 isoparaffins, and especially isohexadecane, available commercially as Permethyl 101A from Presperse Inc. WO 2005/079740 PCT/EP2004/013959 -10- Saturated fatty acids having from 10 to 30 carbon atoms may also be suitable as cosmetically acceptable carriers. Illustrative of this category are pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic and behenic acids. Fatty alcohols having from 10 to 30 carbon atoms are another useful category of 5 cosmetically acceptable carrier. Illustrative of this category are stearyl alcohol, auryl alcohol, myristyl alcohol and cetyl alcohol. Humectants of the polyhydric alcohol-type can be employed as cosmetically acceptable carriers. Typical polyhydric alcohols include glycerol, polyalkylene glycols and more preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene 10 glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, isoprene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of humectant may range anywhere from 0.5 to 50%, preferably between 1 and 15% by weight of the composition. 15 Thickeners can be utilized as part of the cosmetically acceptable carrier of compositions according to the present invention. Typical thickeners include crosslinked acrylates (e.g. Carbopol 982®), hydrophobically-modified acrylates (e.g. Carbopol 1382®), cellulosic derivatives and natural gums. Among useful cellulosic derivatives are sodium carboxymethylcellulose, hydroxypropyl methocellulose, hydroxypropyl cellulose, 20 hydroxyethyl cellulose, ethyl cellulose and hydroxymethyl cellulose. Natural gums suitable for the present invention include guar, xanthan, scterotium, carrageenan, pectin and combinations of these gums. Inorganics may also be utilized as thickeners, particularly days such as bentonites and hectorites, fumed silicas, and silicates such as magnesium aluminum silicate (Veegum®). Amounts of the thickener may range from 25 0.0001 to 10%, usually from 0.001 to 1%, optimally from 0.01 to 0.5% by weight of the composition. Personal care compositions of the present invention may be in any form. These forms may include lotions, creams, roll-on formulations, sticks, mousses, aerosol and non-aerosol sprays and fabric (e.g. nonwoven textile)-applied formulations. WO 2005/079740 PCT/EP2004/013959 -11 - Surfactants may also be present in compositions of the present invention. Total concentration of the surfactant when present may range from 0.1 to 40%, preferably from 1 to 20%, optimally from 1 to 5% by weight of the composition. The surfactant may be selected from the group consisting of anionic, nonionic, cationic and amphoteric actives. Particularly preferred nonionic surfactants are those with a C10-C20 fatty alcohol or fatty acid hydrophobe condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C2-C10 alkyl phenols condensed with from 2 to 20 moles of alkylene oxide; mono- and di-fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di- C8-C20 fatty acids; and polyoxyethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and saccharide fatty amides (e.g. methyl gluconamides) are also suitable nonionic surfactants. Preferred anionic surfactants include soap; alkyl ether sulfates and sulfonates; alkyl sulfates and sulfonates; alkylbenzene sulfonates; alkyl and dialkyl sulfosuccinates; C8-C20 acyl isethionate; C8-C20 alkyl ether phosphates; C8-C20 sarcosinates; and combinations thereof. Sunscreen actives may also be included in compositions of the present invention. Particularly preferred are such materials as ethylhexyl p-methoxycinnamate, available as Parsol MCX®; Avobenzene, available as Parsol 1789®; and benzophenone-3, also known as Oxybenzone. Inorganic sunscreen actives may be employed such as microfine titanium dioxide; zinc oxide; polyethylene; and various other polymers. Amounts of the sunscreen agents when present may generally range from 0.1 to 30%, preferably from 2 to 20%, optimally from 4 to 10% by weight of the composition. Preservatives can desirably be incorporated into the cosmetic compositions of this invention to protect against the growth of potentially harmful microorganisms. Suitable traditional preservatives for compositions of this invention are alkyl esters of para-hydroxybenzoic acid. Other preservatives which have more recently come into use include hydantoin derivatives, propionate salts, and a variety of quaternary ammonium compounds. Cosmetic chemists are familiar with appropriate preservatives and routinely choose them to satisfy the preservative challenge test and to provide product stability. Particularly preferred preservatives are phenoxyethanol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate and benzyl alcohol. The preservatives should be selected having regard for the use of the composition and possible WO 2005/079740 PCT/EP2004/013959 -12- incompatibilities between the preservatives and other ingredients in the emulsion. Preservatives are preferably employed in amounts ranging from 0.01% to 2% by weight of the composition. Compositions of the present invention may include vitamins. Illustrative vitamins are 5 Vitamin A (retinol), Vitamin B2, Vitamin B3 (niacinamide), Vitamin B6, Vitamin C, Vitamin E and Biotin. Derivatives of the vitamins may also be employed. For instance, Vitamin C derivatives include ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glycoside. Derivatives of Vitamin E include tocopheryl acetate, tocopheryl palmitate and tocopheryl linoleate. DL-panthenol and derivatives may also be employed. 10 For the purposes of this invention, vitamins where present are not considered as unsaturated materials. The total amount of vitamins, when present, in compositions according to the present invention may range from 0.001 to 10%, preferably from 0.01% to 1%, optimally from 0.1 to 0.5% by weight of the composition. Another type of useful substance can be that of an enzyme such as oxidases, proteases, 15 lipases and combinations. Particularly preferred is superoxide dismutase, commercially available as Biocell SOD from the Brooks Company, USA. Skin lightening compounds may be included in the compositions of the invention. Illustrative substances are placental extract, lactic acid, niacinamide, arbutin, kojic acid, ferulic acid, resorcinol and derivatives including 4-substituted resorcinols and 20 combinations thereof. Amounts of these agents may range from 0.1 to 10%, preferably from 0.5 to 2% by weight of the composition. Desquamation promoters may be present. Illustrative are the alpha-hydroxycarboxylic acids and oeta-hydroxycarboxylic acids. The term "acid" is meant to include not only the free acid but also salts and C1-C30 alkyl or aryl esters thereof and lactones generated 25 from removal of water to form cyclic or linear lactone structures. Representative alpha-hydroxy acids are glycolic, lactic and malic acids. Salicylic acid is representative of the beta-hydroxycarboxylic acids. Amounts of these materials when present may range from 0.01 to 15% by weight of the composition. A variety of herbal extracts may optionally be included in compositions of this invention. 30 The extracts may either be water-soluble or water-insoluble carried in a solvent which WO 2005/079740 PCT/EP2004/013959 - 13- respectively is hydrophilic or hydrophobic. Water and ethanol are the preferred extract solvents. Also included may be such materials as lipoic acid, retinoxytrimethylsilane (available from Clariant Corp. under the Silcare 1M-75 trademark), dehydroepiandrosterone (DHEA) and 5 combinations thereof. Ceramides (including Ceramide 1, Ceramide 3, Ceramide 3B and Ceramide 6) as well as pseudoceramides may also be utilized for many compositions of the present invention but may also be excluded. For purposes of this invention, materials of this paragraph are not considered as unsaturated materials. Amounts of these materials may range from 0.000001 to 10%, preferably from 0.0001 to 1% by weight of 10 the composition. Colorants, opacifiers and abrasives may also be included in compositions of the present invention. Each of these substances may range from 0.05 to 5%, preferably between 0.1 and 3% by weight of the composition. The compositions of the present invention can also be, optionally, incorporated into an 15 insoluble substrate for application to the skin such as in the form of a treated wipe. The term "comprising" is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words "including" or "having" are used, these terms are meant to be equivalent to 20 "comprising" as defined above. All documents referred to herein, including all patents, patent applications, and printed publications, are hereby incorporated by reference in their entirety in this disclosure. The following examples will more fully Illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by 25 weight unless otherwise illustrated. WO 2005/079740 PCT/EP2004/013959 - 14-EXAMPLE 1 A representative personal care composition of the present invention in the form of a cosmetic lotion is outlined under Table I. TABLE I 5 INGREDIENT WEIGHT % PHASE A Water Balance Disodium EDTA 0.05 Methyl paraben 0.15 Magnesium aluminum silicate 0.60 Triethanolamine 1.20 Hydroxyethyl urea 1.00 PHASEB Xanthan gum 0.20 Natrosol® 250HHR (ethyl cellulose) 0.50 Butylene glycol 3.00 Glycerin 2.00 PHASE C Sodium stearoyl lactylate 0.10 Glycerol monostearate 1.50 Stearyl alcohol 1.50 Isostearyl palmitate 3.00 Silicone fluid 1.00 Cholesterol 0.25 Sorbitan stearate 1.00 Butylated hydroxy toluene 0.05 Vitamin E acetate 0.01 PEG-100 stearate 2.00 Stearic acid 3.00 Propyl paraben 0.10 Parsol MCX® 2.00 Caprylic/Capric triglyceride 0.50 Hydroxycaprylic acid 0.01 C12-15Alkyloctanoate 3.00 PHASE D Vitamin A palmitate 0.10 Bisabolol 0.01 Vitamin A acetate 0.01 Fragrance 0.03 Retinol 50C 0.02 Conjugated linoleic acid 0.50 WO 2005/079740 PCT/EP2004/013959 -15- EXAMPLE 2 A water-in-oil topical liquid make-up foundation according to invention is described in Table II below. 5 TABLE II INGREDIENT WEIGHT % PHASE A Cyclomethicone 9.25 Oleyl oleate 2.00 Dimethicone copolyol 20.00 PHASE B Talc 3.38 Pigment (iron oxides) 10.51 Spheron L-1500 (silica) 0.50 PHASE C Synthetic wax durachem 0602 0.10 Arachidyl behenate 0.30 PHASE D Cyclomethicone 1.00 Trihydroxystearin 0.30 PHASE E Laureth-7 0.50 Propyl paraben 0.25 PHASE F Fragrance 0.05 PHASE G Water Balance Hydroxymethyl urea 3.00 Methyl paraben 0.12 Propylene glycol 8.00 Niacinamide 4.00 Glycerin 3.00 Sodium chloride 2.00 Sodium dehydroacetate 0.30 WO 2005/079740 PCT/EP2004/013959 - 16-EXAMPLE 3 illustrated herein is a skin cream with unsaturated material(linseed oil) incorporating a substituted urea of the present invention. TABLE III INGREDIENT WEIGHT % Glycerin 6.93 Niacinamide 5.00 Hydroxyethyl urea 5.00 Permethyl 101A1 3.00 Sepigel 305z 2.50 Q2-14033 2.00 Linseed oil 1.33 Arlatone 21214 1.00 Cetyl alcohol CO-1695 0.72 SEFA cottonate5 0.67 Tocopherol acetate 0.50 Panthenol 0.50 Stearyl alcohol 0.48 Titanium dioxide 0.40 Disodium EDTA 0.10 Glydant plus6 0.10 PEG-100 stearate 0.10 Stearic acid 0.10 Purified water Balance 10 1 Isohexadecane (Presperse Inc., South Plainfield, NJ) 2 Polyacrylamide (and) C13-14 isoparaffin (and) Laureth-7 (Seppic Corporation, Fairfield, NJ) 3 dimethicone (and) dimethiconol (Dow Coming Corp. Midland, Ml) 4 Sorbitan monostearate and sucrococoate (ICI Americas Inc., Wilmington, DE) 15 5 Sucrose ester of fatty acid 6 DMDM Hydantoin (and) iodopropynyl butylcarbamate (Lonza Inc., Fairlawn, NJ) WO 2005/079740 PCT/EP2004/013959 -17- EXAMPLE4 Illustrative of another cosmetic composition with unsaturated material (sunflower seed oil) 5 incorporating a substituted urea according to the present invention is the formula of Table IV. TABLE IV INGREDIENT WEIGHT % Polysilicone-11 22 Cyclomethicone 54 Petrolatum 11 Hydroxyethy! urea (50% in water) 7 Dimethicone copolyol 0.5 Sunflower seed oil 0.5 EXAMPLE 5 15 A relatively anhydrous composition with unsaturated material (borage seed oil) and a substituted urea according to the present invention is reported in Table V. TABLE V INGREDIENT WEIGHT % Cyclomethicone 80.65 Dimethicone 9.60 Squalane 6.00 Isostearic acid 1.90 Borage seed oil 0.90 Hydroxyethyl urea (50% in water) 0.50 Retinyi palmitate 0.25 Ceramide 6 0.10 Tocopherol 0.10 WO 2005/079740 PCT/EP2004/013959 -18- EXAMPLE 6 An aerosol packaged foaming cleanser with unsaturated material (sunflower seed oil and polyglycero-4-oleate) protected with a substituted urea suitable for the present invention 5 is outlined in Table VI. TABLE VI INGREDIENT WEIGHT % Sunflower seed oil 20.00 Maleated soybean oil 5.00 Silicone urethane 1.00 Polyglycero-4 oleate 1.00 Sodium C14-16 olefin sulfonate 15.00 Sodium lauryl ether sulphate (25% active) 15.00 Cocoamidopropylbetaine 15.00 DC 1784® (silicone emulsion 50%) 5.00 Polyquatemium-11 1.00 Hydroxyethyl urea (50% in Water) 1.00 WATER Balance EXAMPLE 7 10 A disposable, single use personal care towelette product is described according to the present invention. A 70/30 polyester/rayon non-woven towelette is prepared with a weight of 1.8 grams and dimensions of 15 cm by 20 cm. Onto this towelette is impregnated a composition with an unsaturated material (terpenoid fragrance) protected 15 against discoloration by a substituted urea as outlined in Table VII below. TABLE VII INGREDIENT WEIGHT % Hydroxyethyl urea (50% in water) 7.50 Glycerin 2.00 Hexylene glycol 2.00 Disodium capryl amphodiacetate 1.00 Gluconolactone 0.90 Silicone microemulsion 0.85 Witch hazel 0.50 PEG-40 hydrogenated castor oil 0.50 Fragrance (terpenoid mixture) 0.20 vitamin E acetate 0.001 water Balance WO 2005/079740 PCT/EP2004/013959 - 19-EXAMPLE 8 Experiments were conducted to evaluate the color stabilizing activity of a typical substituted urea. A series of skin creams containing a relatively substantial amount of conjugated linoleic acid (color former) were prepared with the components listed in Table VIII. TABLE VIII INGREDIENTS SAM PLE (WEIGHT %) A B C D E Glycerin 20.00 10.00 15.00 10.00 10.00 Hydroxyethyl urea (50% active in water) — 10.00 — 5.00 — Silicone/clay 5.50 5.50 5.50 5.50 5.50 Conjugated linoleic acid 1.00 1.00 1.00 1.00 1.00 Cholesterol 0.20 0.20 0.20 0.20 0.20 Linoleic acid 0.10 0.10 0.10 0.10 0.10 Stearic acid 0.25 0.25 0.25 0.25 0.25 Dermoblock OS® 1.00 1.00 1.00 1.00 1.00 Cyclopentasiloxane 13.00 13.00 13.00 13.00 13.00 Silicone elastomer (DC 9045®) 13.00 13.00 13.00 13.00 13.00 Dimethicone 1.00 1.00 1.00 1.00 1.00 Glycolic acid (70% active) 5.70 5.70 5.70 5.70 5.70 Ammonium hydroxide 1.60 1.60 1.60 1.60 1.60 Titanium dioxide 2.00 2.00 2.00 2.00 2.00 Nutrient components 1.60 1.60 1.60 1.60 1.60 Fragrance 0.35 0.35 0.35 0.35 0.35 Sodium chloride 0.20 0.20 0.20 0.20 0.20 Disodium EDTA 0.05 0.05 0.05 0.05 0.05 Methyl paraben 0.20 0.20 0.20 0.20 0.20 Propyl paraben 0.10 0.10 0.10 0.10 0.10 Water Balance Balance Balance Balance Balance All of the samples were stored in beakers under normal indoor conditions. They were exposed at room temperature to mixed lighting of natural and fluorescent light. Discoloration or the development of color bodies in the creams were noted after 2 months storage. A standard color chart for stability tests was used to evaluate the amount of color generated. Ratings ran from 1 to 20. On the color rating chart, 1 is white; continuous color increases to very slightly yellow (natural to light beige rated at 2-5); slightly yellow (light beige to beige rated at 6-10); yellow (rated at 11-15); and bright WO 2005/079740 PCT/EP2004/013959 -20- yellow (rated at 16-20). Color rating results after the 2 month storage are reported in the Table below. TABLE IX INGREDIENT SAMPLE (WEIGHT %) A B C D E Color rating chart score 16 J 8 16 9 15 Overall visual effect Bright yellow Beige Bright yellow Beige Yellow 5 Based on results reported in Table IX, it appears that samples B and D were the least damaged by light. These formulas differed from samples A, C and E by having hydroxyethyl urea present. It is evident that the hydroxyethyl urea performed a color stabilizing function. Dated 04/01/2006 FROM CLMSPAMD TO 993493923994465 EP 04801; J6886(C) PCT 30 june 2003 -21- 10 CLAIMS: 1. A personal care composition comprising: (i) an unsaturated organic material with at least two lope olefinic double bonds in a conjugated relation ship susceptible to degradation into a color bearing substance, the unsaturated material being selected from C10-C50 terpenoids and C12-C48 unsaturated tatty compounds, the C12-C48 compounds being selected from the group consisting of fatty alcohols, fatty acids, fatty acid glycerides, fatty acid salts, fatty acid esters and combinations thereof; (ii) a substituted urea of genera/ structure (I) R1R2NCNR3R4 15 20 wherein R1, R2 and R3 are selected from the group consisting of hydrogen, C1 –C6 alkyl, (R5)nOH, and mixtures thereof; R5 is methylene, ethylene, propylene or combinations thereof, and n ranges from 1 to 8; and R4. is (R5)nOH; and (iii) a cosmetically acceptable earner. 2. The composition according to claim 1 wherein the substituted urea is hydroxyethyl urea. 25 3. The composition according to claims 1 or 2 wherein the unsaturated material is a glyceride selected from the group consisting of sunflower seed oil, safflower oil, linseed oil, borage oil, borage seed oil, coriander seed oil, triglycerides with conjugated linoleic acid residues and mixtures thereof. 30 4. The composition according to any of the preceding claims wherein the unsaturated material is present in an amount from 0.0001 to 20% by weight FmPf.zeit:C6/07/2005 13:37 AMENDED SHEET. 167 P.005 06/07/200 Dated 04/01/2006 CLMSEAMK EP 0480121 FROM TO 900498923994465 , J6886(C) PCT -22- 5. The composition according to any of the preceding claims wherein the substituted urea Is present in an amount from 0.01 to 20% by weight 6. The composition according to any of the preceding claims wherein the substituted urea 5 relative to the unsaturated material is present in a weight ratio from 10,000:1 to 1:100. f*—Tho composition according to any of thc-precoding -claims whoroin tho unsaturateU-fflaterial has at tot two olefinic double bond&r^ 10 3 the-mmprreftiriH ?rrnrrfing tn rlaim 7 wharatn n pair nf fha at loa^t fwn ntefinir- rtrmhlo_ bends 6 The composition according to any of the preceding claims wherein the unsaturated material is a conjugated linoleic acid. 15 8.The composition according to any of the preceding claims wherein the unsaturated material has an Iodine Value ranging from 20 to 300. 9.Use of a substituted urea for reducing color degradation of a pergonal care 2 0 composition, wherein the substituted urea has general structure (I) 25 30 I ■ wherein R1, R2 and R3 are selected from the group consisting of hydrogen, C1-C6 alkyl, (R5)nOH, and mixtures thereof, R5 is methylene, ethylene, propylene or ambulations thereof, and n ranges from 1 to 6; and R4 is (R5)nOH; and wherein the personal care composition contains an unsaturated organic material with at least one olefinic double bond susceptible to degradation into a color bearing absfance, the unsaturated material being selected from C10-C50 terpenoids and C12-C48unsaturated fatly compounds, the C12-C48 compounds being selected from EnPf .zeit:06/2005 13:37 AMENDED SHEET 167 p 006 06/07/200 Dated 04/01/2006;:40 FRQf1 CLMSPAMD TQ B9004998923994465 EP801214 J$886(C) PCT Amened 30 june 2005 -23- the group consisting of fatty alcohols, fatty acids, fatty add glycerides, fatty acid salts, fatty acid esters and combinations thereof. 10 A method of reducing color degradation of a personal care composition containing an unsaturated organic material with at least one olefinic double bond susceptible to degradation into a color bearing substance, the unsaturated material being selected from C10-C50 terpenoids and C12-C48 unsaturated fatty compounds, the C12-C48 compounds being selected from the group consisting of fatty alcohols, fatty adds, fatty acid glycerides, fatty acid salts, fatty acid esters and combinations thereof, 10 said method comprising adding to said personal care composition a substituted urea of general structure (I) O I RiR2NCNR3Ri I wherein R1, R2 and R3 are selected from the group consisting of hydrogen, C1-C6 20 alkyl. (R5)nOH, and mixtures thereof; R5 is methylene, ethylene, propylene or combinations thereof, and n ranges from 1 to 6; and R4 is (R5)nOH. DATED 4 AUG2006 HINDUSTAN LEVER LIMITED (S. Venkatramani) Senior Patents Manager 06/07/2005 AMENDED SHEET >167 P 007

Documents:

0932-MUMNP-2006-CORRESPONDENCE(18-8-2008).pdf

932-mumnp-2006-abstract(07-12-2006).doc

932-mumnp-2006-abstract(07-12-2007).pdf

932-MUMNP-2006-ASSIGNMENT 9-3-2008.pdf

932-mumnp-2006-cancelled pages(07-12-2007).pdf

932-mumnp-2006-claims(granted)-(07-12-2006).doc

932-mumnp-2006-claims(granted)-(07-12-2007).pdf

932-mumnp-2006-claims.doc

932-mumnp-2006-claims.pdf

932-mumnp-2006-correspondance-received.pdf

932-mumnp-2006-correspondence 1(09-03-2008).pdf

932-mumnp-2006-correspondence 2(18-12-2006).pdf

932-MUMNP-2006-CORRESPONDENCE 9-3-2008.pdf

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

932-mumnp-2006-correspondence(ipo)-(27-10-2008).pdf

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

932-MUMNP-2006-FORM 1 4-8-2006.pdf

932-mumnp-2006-form 1(04-08-2006).pdf

932-mumnp-2006-form 13(04-10-2007).pdf

932-mumnp-2006-form 18(18-12-2006).pdf

932-mumnp-2006-form 2(granted)-(07-12-2006).doc

932-mumnp-2006-form 2(granted)-(07-12-2007).pdf

932-MUMNP-2006-FORM 3 9-3-2008.pdf

932-mumnp-2006-form 3(09-03-2008).pdf

932-mumnp-2006-form 5(04-08-2006).pdf

932-mumnp-2006-form-1.pdf

932-mumnp-2006-form-2.doc

932-mumnp-2006-form-2.pdf

932-mumnp-2006-form-3.pdf

932-mumnp-2006-form-5.pdf

932-mumnp-2006-form-pct-isa-210(07-12-2007).pdf

932-MUMNP-2006-INVENTION SEARCH REPORT(CANCELLED) 9-3-2008.pdf

932-mumnp-2006-pct-ipea-409.pdf

932-mumnp-2006-pct-ipea-416.pdf

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

932-mumnp-2006-power of attorney(07-12-2007).pdf

932-mumnp-2006-power of attorney(11-11-2005).pdf