Title of Invention	PERSONAL WASH BAR COMPOSITION
Abstract	A personal wash bar composition comprising : (a) 20 to 85% by wt. first anionic surfactant which is fatty acid soap or synthetic anionic; (b) 0 to 25% by wt. second surfactant; (c) 0 to 15% by wt. free fatty acid; (d) 0 to 20% by wt. of a water soluble structurant which is neither soap nor non-soap detergent and has MP ( melting point) in the range 40 to 100°C and (e) 0.1 to 10% of a sunscreen and/or salt thereof wherein sunscreen and/or salt thereof has SPF greater than 2 to 25, wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H2O at neutral pH; and wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds.

Title of Invention

PERSONAL WASH BAR COMPOSITION

Abstract

A personal wash bar composition comprising : (a) 20 to 85% by wt. first anionic surfactant which is fatty acid soap or synthetic anionic; (b) 0 to 25% by wt. second surfactant; (c) 0 to 15% by wt. free fatty acid; (d) 0 to 20% by wt. of a water soluble structurant which is neither soap nor non-soap detergent and has MP ( melting point) in the range 40 to 100°C and (e) 0.1 to 10% of a sunscreen and/or salt thereof wherein sunscreen and/or salt thereof has SPF greater than 2 to 25, wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H2O at neutral pH; and wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds.

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See section 10; rule 13) 1. Title of the invention. PERSONAL WASH BAR COMPOSITION 2 Applicant (a) Hindustan Lever Limited, (b) 165/166, Backbay Reclamation, Mumbai 400 020 Maharashtra, India. (c) an Indian Company incorporated under the Indian Companies Act, 1933. The following specification (particularly) describes the nature of this invention (and the manner in which it is to be performed) PERSONAL WASH SUNSCREEN COMPOSITIONS WHICH DEPOSIT AND LATHER WELL The invention relates to personal wash compositions which deposit high levels of sunscreen (SPF >2) while maintaining good lather (i.e., suffer minimal lather degradation over time relative to composicions with more "oily" sunscreens). Enhanced deposition is found from both bar and liquid compositions and is based on the solubility or 'non-solubility of the sunscreen used. It is a difficult task to deposit significant levels of sunscreen from skin cleansers. Moreover, most sunscreens severely defoam the cleanser composition. Therefore, previous attempts to deliver sunscreen from cleansers resulted in cleanser having low levels of protection (i.e., SPF One reason deposition has been so difficult to achieve is that most of sunscreens used are either water insoluble oils or insoluble fine solid particles (e.g., ZnO, Ti02). Such sunscreens are generally dispersed into dilute suspensions by surfactants present in the cleanser. As a 'result, and without wishing to be bound by theory, it is believed that most of the sunscreen.will remain suspended, the suspended sunscreen will be removed when skin is rinsed, and little will be left to deposit or. the skin. Further, dispersions of the sunscreens into the wash liquid cends to defoarn the liquor. In addition, incorporation of oily sunscreen in bars also generally increases softness, stickiness and mush. Unexpectedly, applicants have found a novel class of sunscreens which can be delivered and provide superior sun protection. These sunscreens can be deposited even in presence of anionic surfactants. Unlike most sunscreens, these are much more soluble in water than the usual "oily" suras'creen and- provide .measurable sun protection even at low levels of addition (e.g., 0.1-15%, preferably 0.5 to 12%, more preferably 1.0 to 10% by wt.). Moreover, since they are more soluble in water, they do not defoarn cleanser during wash process. More specifically, applicants have found specific sunscreen agents which are organic molecules absorbing light in the UV range. These sunscreens are water-soluble UV absorbers (greater than or equal to 0.1% preferably greater than 0.5% water solubility on a weight to weight basis at neutral pH). The sunscreens include a functional group that is anionic or at least part of the sunscreen becomes anionic (e.g., anionic functional group incorporated at sufficiently high pK) at suitable pH (e.g., pH J: 3, preferably greater than -., preferably 4 to 10) and the sunscreens are water soluble or become soluble at suitable pH (again about 3 to 10). Examples cf such molecules include: pher.yibenzimidazole suiphonic acid, anionic salts cf said acid which form at pH of 7 and above and mixtures thereof (forming at pH between 4 and 7); ferulic 'acid, its anionic salts and mixtures thereof; benzophenone-4, its anionic salts and mixtures thereof; and benzophenone-9, 'its anionic salts and mixtures thereof. Preferably, the sunscreen agents are used.in the form of their salts generally at pH 7 and above. While not wishing to be bound by theory, these anionic organic sunscreen molecules are believed to bind to positively charged sites on proteins within the skin thereby accounting for enhanced deposition.- Because molecules deposited through binding from solution cover the surface uniformly, the UV protection is also believed to be more effective than protection obtained from oily or particulate sunscreens where the deposition may be localized to small areas of skin and leave some areas unprotected. Moreover, because the agents are more soluble in water than oily components, they cause less defoaming than the oily or particulate sunscreen agents. As noted above, oily, particulate sunscreens are believed to suspend in surfactants and more readily wash off when rinsed, thereby leading to lower deposition. Oily agents also lead to mushier bars. The specific sunscreen agents of the invention avoid these problems. Some of the organic sunscreen materials of the invention are not new. For example, WO 14053 to Cussons Int. Ltd. teaches personal wash compositions containing sunscreen agents including phenylbenzimidazole sulphonic acid (which is recited among a list of sunscreen agents which may be used (page 7). The reference does net recognize that the sulphonic acid sunscreen agent or salts thereof provide superior sun protection relative to other sunscreens including even those used in the reference itself (see Examples 1-3 of reference). The higher water solubility also makes the sunscreens less dsfoaming and more soluble for personal wash products where foaming.is considered a desirable attribute. U.S. Patent Nos. 4,933,174 and U.S. 4,701,321 by J. Bernstein (assigned to Amethyst Investment Group, Inc.) teaches a liquid PW composition, which comprises nonionic and amphoteric surfactants, and sunscreen materials including aminobenzoic acid, the esters of an aminobenzoic acid, homosalate, 2-hydroxy-4-methoxylbenzophenone (oxybenzone) or 2-ethoxyethyl p-methoxycinnamate (cinoxate). Nonionic and amphoteric surfactants instead of anionic surfactants are used to enhance the deposition of sunscreen agents. Repeated washing and bathing with the compositions leaves a long-lasting layer of sunscreens in the stratum corneum of the skin. The reference fails to recognize that specific anionic sunscreens (e.g., anionic salts) of the invention, particularly when used in systems comprising anionic surfactants, deposit better than other sunscreens. "The noted U.S. patents also do not specifically include phenyibenzimidazole sulphonic acid, benzophenone-4 or any of the other materials suitable for our invention as candidates for the sunscreen agents claimed. These patents further require that formulations contain only nonionic or amphoteric surfactant and further requires that the compositions be used repeatedly over many weeks to achieve the claimed effects. Unexpectedly, applicants have found that when specific sunscreen and'/or their salts are used in personal wash compositions, they are more water soluble than many oily particulate sunscreens normally useci (e.g., "normal" oils having solubility of less than 0.1% wt. by wt. water compared to more soluble -"salts" of subject invention) ; they provide enhanced sun protection factor or SPF (e.g. SPF greater than 2, to about 25, preferably greater than 3 to 20, more preferably from about 4 to "i5); and the sunscreen does not depress foaming (e.g., foaming does not depress over time compared with more oily components whose lather does depress more quickly over time), Generally, using the sunscreens of invention, foaming does not depress more than about 50%, preferably more than 30%, preferably more than about 25% over 30 minutes time using test as defined in examples. More specifically, the present invention provides a pergonal wash composition, particularly personal wash compositions which may be in bar or liquid form. In one embodiment the compositions are bars comprising: (1) .20% to 85% by wt of first Anionic surfactant which may be fatty acid"soap or a synthetic anionic; (2) 0-25% preferably 1-20% second surfactant selected c„ \| n—- -\| ■■- .. from the group consisting of second anionic surfactant (different from first), nonionic, amphoteric, cationic and mixture thereof; (3) 0-15% free fatty acid; (4) 0-20% water soluble structiarant (e.g., polyalkylene glycol, EO-PO copolymers); (5) 0 to 40%, preferably .0-35% alkanoate (e.g., glycerol monostearate) having chain length of C12 to C24; and (6) 0.1 to 10% of a sunscreen agent, anionic salt (e.g., functional group attached to sunscreen agent which, in solution, yields negative charge such as, for example, sulfates, sulfonates, carboxylates, phosphates, phosphonates, etc.), or mixtures thereof (at least some portion of the : sunscreen-.must be ,in ,i-t,s ..salt, form; .however, this is inherently accomplished by specifying minimum pH values) ; wherein sunscreen agent (by which is meant overall equilibrium of the acid form of the sunscreen, its salt and mixtures) has a water solubility of greater than or equal to 0.1%, preferably greater than 0.5% on.weight to weight basis as measured at pH 7; wherein said sunscreen has SPF of greater than 2 to 25; and wherein composition does not degrade more than 50% lather, preferably no more than 35%, more preferably no more than 25% over 30 minutes as defined in -examples. Bars generally will have 1-15%, preferably 2-12% water. In a second embodiment, composition may be liquid composition comprising: (I! 10-301 anionic surfactant; (2) 0-25% of second surfactant selected from group consisting of anionic different from first, nonionic, amphoteric/zwitterionic, caiionic and mixtures thereof; and (3) 0.1 to 10% of a sunscreen agent, salt thereof or mixtures as defined above; wherein sunscreen agent has a water solubility of greater than or equal to 0.1%, preferably greater than 0.5% on weight to weight basis as measured at pH 7; wherein said sunscreen has SPF of greater than 2 to 25; and wherein composition does not degrade more than 50% lather, preferably no more than 35%, more preferably no more than 25% over 30 minutes as defined in examples. The present invention is based on applicants unexpected finding that certain sunscreen agents and/or salts thereof are anionic, water-soluble compounds which provide enhanced SPF while simultaneously not depressing foam relative to more oily, less water soluble sunscreen compounds (e.g., those which are generally less soluble and have solubility of less than 0.5% wt. for wt. water) . These "more" water-soluble sunscreen agents and/or anionic salts thereof (counterions may exist to anionic group as well) provide unexpectedly enhanced effect whether used in bar or liquid cleanser compositions. In one embodiment, the invention comprises bar compositions comprising: (1) 20 to 85% by wt. of a first anionic surfactant which is fatty acid soap or synthetic anionic; (2) 0 to 25% by wt. of a second surfactant selected from the group consisting of a second anionic (differing from the first), nonionic surfactant, amphcteric/zwitterionic surfactant, "cationic surfactant and mixtures thereof; (3) 0 to 15% by wt. free fatty acid (particularly where bar is a predominantly fatty acid soap bar) ; (4) 0 to 20% of a water-soluble structurant which is neither soap nor non-soap detergent and has MW in the range 40 to 100°C (e.g., polyalkylene glycol EO-PO copolymers); (5) 0 to 40% glycerol monoalkanoate of C12-C24 chain length; and (6) 0.1 to 10% of a sunscreen agent and/or salt thereof (providing anionic charge) wherein sunscreen and/or salt thereof has SPF greater than 2 to 25, preferably greater than 3 to 20, more preferably greater than about 4 to 15; wherein sunscreen agent and/or salt has solubility of greater than or equal to 0.1%, preferably greater than 0.5% on weight to weight basis as measured neutral pH; and wherein sunscreen agent and/or salt has lather which does not substantially degrade over time relative to more oily components. In second embodiment of the invention, compositions may >e liquid cleanser comprising: (1) 10-80% first anionic surfactant; and (2) 0 to 25% second surfactant selected from the croup consisting of anionic different from first, nonionic, amphoteric/zwitterionic, cationic and mixtures thereof; (3) O.1 to 10% of sunscreen and/or salt thereof as defined with bar compositions thereof; and (4) balance water, wherein compositions has SPF values, solubility and lather parameters as defined for bar compositions above. Each of these embodiments is described in more detail below. BAR COMPOSITIONS First Anionic The first anionic surfactant may be a synthetic surfactant or fatty acid soap. Although not preferred, the bar compositions may comprise a "pure" soap composition. Such bars are generally not mild (although they do foam well and have sensory properties preferred by some consumers) and so it is generally preferred to use bars which are predominantly synthetic or which are combinations of synthetic and soap. The term "soap" is used here in its popular sense, i.e., the alkali metal or alkanol ammonium salts of aliphatic alkane- or alkene monocarboxylic acids. Sodium, potassium, mono-, di and tri-ethanol ammonium cations, or combinations thereof, are suitable for purposes of this invention. In general, sodium soaps are used in the compositions of this invention, but from about 1% to about 25% of the soap may be potassium soaps. The soaps useful herein are the well known alkali metal salts of natural or synthetic aliphatic {alkanoic or alkanoic) acids' having about 12.to.22,carbon atoms, preferably about 12 to about 18 carbon atoms. They may be described as alkali metal carboxylates of acrylic hydrocarbons having about 12 to about 22 carbqn atoms. Soaps having the fatty acid distribution of coconut oil may provide the lower end of the broad molecular weight range. Those soaps having the fatty acid distribution of peanut or rapeseed oil, or their hydrogenated derivatives may provide the upper end of the broad molecular weight range. It is preferred to use soaps having the fatty acid distribution of coconut oil or tallow, or mixtures thereof, since these are among the more readily available fats. The proportion of fatty acids having at least 12 carbon atoms in coconut oil soap is about 85%. The proportion will be greater when mixtures of coconut oil and fats such as tallow, palm oil or non-tropical nut oils or fats are used, wherein the principle chain lengths are C16 and higher. Preferred soap for use in the compositions of this invention has at least about 85% fatty acids having about 12-18 carbon atoms. Coconut oil employed for the soap may be substituted in whole or in part by other "high-lauric" oils, that is, oils or fats wherein at least 50% of the total fatty acids are composed of lauric or myristic acids and mixtures thereof. These oils are general exemplified by the tropical nut oils of the coconut oil class. For instance, they include: palm kernel oil, babassu oil, ouricuri oil, tucum oil, cohune nut oil, muru-muru oil, jaboty kernel oil, khakan kernel oil, dika nut oil,and ucuhuba butter. A preferred soap is a mixture of about 15% to about 20% coconut oil and about 80% to about 85% tallow. These mixtures contain about 95% fatty acids haying about 12 to about 18 carbon atoms. The soap may be prepared from coconut oil in which case the fatty acid content is about 85% of C12-C18 chain length. The soaps may contain unsaturation in accordance with commercially acceptable standards. Excessive unsaturation is normally avoided. Soaps may be made by the classic kettle boiling process or modern continuous soap manufacturing processes wherein natural fats and oils such as tallow or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art. Alternatively, the soaps may be made by neutralizing fatty acids, such as lauric (C12), myristic (C14), palmitic (C16) or staric (C18) acid's with an alkali metal hydroxide or -carbonate. The first anionic detergent active which may be usec may be aliphatic sulfonates., such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disuifonate, C8-C22 alkene sulfonate, C8-C22 hydroxy alkane sulfonate or alky'i. glycerol ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate. The first anionic may also be an alkyl sulfate (e.g., C12-C18 alkylsulfate) or alkyl ether sulfate (including alkyl glycerol ether sulfates). Among the alkyl ether sulfates are those having the formula: RO(CH2(CK2-0)nS03M wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons; n has an average value of greater than 1.0, preferably greater than 3: and M is a solubilizing cation such as sodium, potassium ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred. The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e\|.g., C&-C22 sulfosuccinates); alkyl and acyl taurates, alkyl \|and acyl sarcosinates, sulfoacetates, Cg-C22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates,. sulphoacetates, alkyl glycosides and acyl isethionates. Sulfosuccinates may be monoalkyl sulfosuccinates having the formula: R"'02CCH2CH (SO3M) CO2M; and amide-MEA sulfosuccinates of the formula R4CONHCK2CH202CCH2CK(SO3M)CO2M 4 wherein R ranges from C8-C22 alkyl and M is a solubilizing cation. Sarcosinates are generally indicated by the formula RCON(CK3)CK2C02M, wherein R ranges from C8-C20 alkyl and M is a solubilizing cation. Taurates are generally identified by formula: R2CONR3CH2CH2S03M 2 3 wherein R ranges from C8-C20 alkyl, R ranges from C1- C4 alkyl and H is a solubilizing cation. Particularly preferred are the Cs-Cig acyl isethionates. These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to IB carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms. Acyl isethionates, when present, will generally range from about 10% to about 70% by weight of the total composition. Preferably, this component is present from about 30% to about 60%. The acyl isethionate may be an alkoxylated isethionate such as'is'-de-scribed'-in I lardi et ai., U.S. Serial No. 796,748, hereby incorporated by reference. This compound has the general formula: wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are hydrogen or an alkyl .L. group having 1 to 4 carbons and M' is a monovelent cation such as, for example, sodium, potassium or ammonium. In general the anionic component will comprise from about 10 to 70% of the composition, preferably 20-50% by wt. of the composition. Second Surfactant The second surfactant may be any of the anionics defined above except-, that it differs from the first anionic. The second component may also be any of the amphoteric or nonionics discussed below as well as a mixture of the anionic, amphoteric and/or nonionic. .Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylio. or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula: wherein R is alkyl or alkenyl of 7 to 18 carbon atoms: 2 3 R and R are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms; m is 2 to 4; n is 0 to 1 X is alkylene of to 3 carbon atoms optionally substituted with hydroxyl, and Y is —CO2— or —SO3— Suitable amphoteric detergents within the above general formula include simple betaines of formula: where m is 2 or 3; In both formulae R1,R2 and R3 are as defined previously. R may in particular be a mixture of C12 and C14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R have 10 2 3 to 14 carbon atoms. R and R are preferably methyl. A further possibility is that the amphoteric detergent is a sulphobetaine of formula: where m is 2 or 3 ,or variants of these in which (CH2)3S03— is replaced by : In these formula R1, R2 and R3 are as discussed previously. The nonionic which may be used as the second component of the invention include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for 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 alkyl (C6-C22) phenols- ethylene oxide condensates, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides. The nonionic may also be a sugar amice, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Serial No. 816,419 to Au et al. which is hereby incorporated by-reference or it may be one of the sugar amices described in U.S. Patent No. 5,009,814 to Kelkenberc, hereby incorporated into the subject application by reference. Other surfactants which may be used are described in U.S. Patent No. 3,723,325 to Parran Jr., which is also incorporated into the subject application by reference. In general the second component (i.e., second anionic nonionic and/or amphoteric compound or mixture) is incorporated into the composition as less than 20% by weight, preferably 1 to 15% by weight of the composition. Structurant- In general, bars of the invention may comprise 0 to 75% structurant (e.g., free fatty acid, water soluble structurant, glycerol monoalkanoate noted below). Preferably, the bar will contain 5% to 65% structurant though none is required. Free Fatty Acid Free fatty acids of 8-22 carbon atoms may also be desirably incorporated within the compositions of the present invention. Some of these fatty acids are present to operate as superfatting agent's and others- as skin .feel and creaminess enhancers. Superfatting agents enhance lathering properties and may be selected from fatty acids of carbon atoms numbering 8-18, preferably 10-16, generally in an amount up to 15% by weight (although higher amounts may be used) of the composition. Skin feel and creaminess enhancers, the mosr important of which is stearic acid, are also desirabiv present in these cor.posirions. Water Soluble Structurant Another compound which may be used in the bar is water soluble structurant (e.g., polyalkylene glycol). This component should comprise 0% by wt. to 60%, preferably greater than 5% to 40% by wt. of the bar composition. The structurant (e-. g., po1yalkylene glycol) has a melting point of 400C to 100°C, preferably 45°C to 100°C, more preferably 50°C to 90°C. Materials which are envisaged as the water soluble structurant (b) are moderately high molecular weight polyalkylene oxides cf appropriate melting point and in particular polyethylene glycols or mixtures thereof. Polyethylene glycols (PEG's) which may be used may have a molecular weight in the range 1,500-20,000. It should be understood that each product (e.g., Union Carbide's Carbowax® PEG 8,000) represents a distribution of molecular weights. Thus PEG 8,000, for example, has an average MW range of 7,000-9,000, while PEG 300 has an average MW range fro- 285 to 315. The average MW of the product can be anywhere between the low and high value, and there may still be a good portion of the material with MW below, the low., value and above the high value. In some embodiments of this invention it is preferred to include a fairly small quantity of polyalkylene glycol (e.g., polyethylene glycol) with a molecular weight in the range from-50,000 to 50,000, especially molecular weights of around 100,000. Such polyethylene glycols have been found to improve the wear rate of the bars. It is believed that this is because their long polymer chains remain entangled even when the bar composition is wetted during use. If such high molecular weight polyethylene glycols (or any other water soluble high molecular weight polyalkylene oxides) -are used, the quantity is preferably .from- l%-to-5-% more preferably from 1% or 1.5% to 4% or 4.5% by weight of the composition. These materials will generally be used jointly with a larger quantity of other water soluble structurant (b) such as the above mentioned polyethylene glycol of molecular weight 1,500 to 10,000. Some polyethylene oxide polypropylene oxide block copolymers melt at temperatures in the required range of 40°C to 100°C, and may be used as part or all of the water soluble structurant (b). Preferred ere are block- copolymers in which polyethylene oxide provides at least 40% by weight of the block copolymer. Such block copolymers may be used in mixtures with polyethylene glycol or other polyethylene glycol water soluble structurant. Glycerol Monoalkanoate Another optional structurant which may be used is glycerol monoalkanoate wherein alkanoate group may be C12-C24 alkyl (e.g., glycerol monostearate) . This may comprise C-60% by wt.,of bar, preferably 5% to 50% by wt. Sunscreen The sunscreens of the invention are defined by the fact that they are sunscreens which form salts (at sufficient pH) sc that the salts or an equilibrium of salt and the acid form of the sunscreen have a solubility of greater than 0.1% wt/wt., preferably greater than 0.5% as measured at neutral pH. As noted, in general the pH of the composition has to be high enough to have at least some portion of the anionic salt. The anionic salts are formed by functional anionic groups well known to those skilled in the art such as sulphates, sulfonates, carboxylates, phosphates, phospnonates and other groups which are well known to provide anionic charges in solution. Unexpectedly, applicants have found that use of these sunscreens and/or salts which have the defined solubility will provide enhanced S?F (e.g., 2 to 25) relative to other sunscreens while at the same time not depressing the lather function of the final composition. Examples of such sunscreen compounds include phenylbenzimidazole sulphonic acid and salts thereof; ferulic acid and salts thereof; benzophenone and its salts thereof. Other examples include variants of benzophenone and salts thereof. Other Compounds Skin mildness improvers also preferably used in the composition of the invention are salts of isethionate. Effective salts cations may be selected from the group consisting of alkali metal, alkaline earth metal, ammonium, alkyl ammonium and mono-, di or tri-alkanolammonium ions. Specifically preferred cations include sodium potassium, lithium, calcium, magnesium, ammonium, triethylammonium, monoe.thanolammonium,, diethanaLammonium or triethanolammonium ions. Particularly preferred as a mildness improver is simple unsubstituted sodium isethionate. The skin mildness improver will be present from about 0.5% to about 50%. Preferably, the mildness improver is present from about 1% to about 25%, more preferably from about 2% to about 15, optimally from 3% to 10% by weight of the total composition. Other performance chemicals and adjuncts may be needed with these compositions. The amount of these chemicals and adjuncts may range from about 1% to about 40% by weight of the total composition. For instance, from 2 to 10% of a suds-busing detergent salt may be incorporated. Illustrative of this type additive are salts selected from the group consisting of alkali metal and organic amine higher aliphatic fatty alcohol sulfates, alkyl aryl sulfonates and the hiaher aliphatic fattv acid taurinates. Adjunct materials including germicides, perfumes, colorants pigments such as titanium dioxide and water may also be present. The bar compositions of the invention have SPF of greater than 2 to 25, preferably greater than about 3 to 20 and more preferably greater than about 4 to 15. SPF is defined as per the protocol in the example section. In addition compositions have lather of which does not degrade more than 50%, preferably more than 35%, preferably more than 25% over 30 minute period. In a second embodiment, the compositions of the invention may also be liquid compositions as noted above. LIQUID First Anionic In the liquid compositions, the first anionic surfactant may be any of the surfactants as for the bars above except that it will not be "soap" as defined therein. Second surfactant The second surfactant may also be one of the above as defined for bars. Optional The liquids of this invention may be isotropic single phase liquids or they may be structured as defined and using structurants as defined in U.S. Patent No. 5,952,286 to Puvvada et al. hereby incorporated by reference into the subject invention. The compositions may contain oils or emollients as noted below. Vegetable oils: Arachis oil, castor oil, cocoa butter, coconut oil, corn .oil, cotton seed oil, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, sesame seed oil and soybean oil. Esters: Butyl myristate, cetyl palmitate, decyloleate, glyceryl laurate, glyceryl ricinoleate, glyceryl stearate, glyceryl isostearate, hexyl laurate, isobutyl palmitate, isocetyl stearate, isopropyi isostearate, isopropyi laurate, isopropyi linoleate, isopropyi myristate, isopropyi palmitate, isopropyi stearate, propylene glycol monolaurate, propylene glycol ricinoleate, propylene glycol stearate, and propylene glycol isostearate. Animal Fats: Acytylatelte lanolin alcohols, lanolin, lard, mink oil and tallow. Fatty acids and alcohols: Behenic acid, palmitic acid, stearic acid, behenyl alcohol, cetyl alcohol, eicosanyi alcohol and isocetvl alcohol. Other examples of oil/emollients include mineral oil, petrolatum, silicone oil such as dimethyl polysiloxane, lauryl and myristyl lactate. It should be understood that where the emollient may also function as a structurant, it should .not be doubly included such that, for example, if the structurant is 15% oleyl alcohol, no more than 5% oleyl alcohol as "emollient" would be added since the emollient (whether functioning as emollient or -structurantl- never comprises more than. 20%, preferably no more than 15% of the composition. The emollient/oil is generally used in an amount from about 1 to 20%, preferably 1 to 15% by wt. of the composition. Generally, it should comprise no more than 20% of the composition. In addition, the compositions of the invention may include optional ingredients as follows: Organic solvents, such as ethanol; auxiliary thickeners, such as carboxymeuhyicellulose, magnesium aluminum silicate, hydroxyethylcellulose, methylcellulose, (R) carbopols, glucamides, or Antil from Rhone Poulenc; perfumes; sequestering agents, such as tetrasodium ethylenediaminetetraacetare (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and peariizers such as zinc stearate, magnesium stearate, TiO2, EGMS (ethylene glycol monostearate) or Lytror. 621 (Styrene/Acrylate copolymer) ; all of which are useful in enhancing the appearance or cosmetic properties of the product. The compositions may further comprise antimicrobials such as 2-hydroxy-4, 2 ' 4 ' trich-lorodiphenylether (DP300) ; preservatives such as dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid etc. The compositions may also comprise coconut acyl mono-or diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may also be used to advantage. Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate. Cationic conditioners which may be used include .. Quatrisoft LM-200 Polyquaternium-24, Merquat Plus 3330 - (R) Polyquaternium 39; and Jaguar type conditioners. Polyethylene glycols which may be used include: Polyox WSR-205 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750 PEG 7M. Thickeners which may be used include Amerchol Polymer HM 1500 (Nonoxynyl Hydroethyl Cellulose); Glucam DOE 120 (R) (PEG 120 Methyl Glucose Dioleate); Rewoderm (PEG modified glyceryl cocoate, palmate or tallowate) from Rewo Chemicals; (R) Antil 141 (from Gcldschmidt). Another optional ingredient which may be added are the defloculating polymers such as are taught in U.S. Patent Nc. 5,147,576 to Montague, hereby incorporated by reference. Another ingredient which may be included are exfoliants such as polyoxyethylene beads, walnut sheets and apricot seeds. The liquid compositions, like the bar compositions will have SPF values and lather volume as defined for the bars. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Where used in the specification, the term "comprising" is intended to include the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more features, integers, steps / "components' or- "groups thereof. The following examples are intended to further illustrate the invention and are not intended to limit the invention in any way. Unless indicated otherwise, ail percentages are intended to be percentages by weight. Protocol In-Vitro SPF Measurement for Evaluating Skin Cleansing Compositions Containing Sunscreens This method involves the measurement of the transmission of light across the UV spectrum through a treated substrate. From the transmittance data an estimate of SPF can be obtained. In-vitro SPF measurements were made on an Optometries SPF 2 90 instrument (Optometries Corp., Ayre MA, USA). The instrument measures diffuse transmittance through a treated substrate at 5 nm increments covering wavelengths from 290 to 400 nm and reports a calculated SPF. Measurements were taken at 6 sites over a 6.5 cm by 6.5 cm piece of each treated substrate. The substrate used was Vitro-skin™ (IMS Testing Group, Milford, CT,- USA). The Vitro-Skin substrate was pre-hydrated in a desiccator at 80% relative humidity as recommended by the supplier. The vitro-skin substrate was treated by rubbing a wet bar across it. 10. times, then rubbing the Vitro-skin substrate for 15 seconds. After this the substrate was rinsed under tap water for 15 seconds and blotted dry with a paper towel. Lather Measurements Lather was measured using stoppered, graduated 100 ml. cylinders. The cylinders were shaken 10 seconds and foam height observed. Example 1-4 and Comparative 1-3 The following formulations were made where Table 1 represents formulae containing anionic (water-soluble) UV sunscreens and Table 2 represents formulae containing hydrophobic UV absorbers Table 1 Formulations Containing Anionic (Water-Soluble) UV Absorbers Components Function Example 1 Example 2 Example 3 Example 4 Polyethylene glvcoi -8000 Structurant 10 10 10 10 Glycerol monostearate Structurar.t 27.6 27.6 27.6 27.5 Palmitic-stearic acid Structurar.t 8.4 8.4 8.4 8.4 Sodium cocoyl isethionate Surfactant 27 27 27 2" Cocamidgprqpyl betaine Surfactant 5 5 5 - Sunflower seed oil Emollient - - - 7.5 Petrolatum Emollient 16 " S - Polyquaiternium-S Skin feel - = - 2.5 Sodiur; ferulate Sunscreen - - - 10 2-phenlylben:imidazole-5-suifonic acid Sunscreen 4 4 4 - Octocrylene Sunscreen 1 - - ; - Water 1 2 2 2 - Table 2 Formulations Containing Only Hydrophobic UV Absorbers Consonants Function Comparative 1 Comparative 2 Comparative 3 Polyethylene glycol -8000 Struccurant 10 10 10 Propylene glycol Structurant/ Skinfeel - — 13 Paraffin wax Structurant - 1 3 Glycerol monostearate Structurant 27.6 ^ 27.6 \| Palmitic-stearic acid Structurant 8.4 8.4 14 Sodium cocoyl sethionate , Surfactant 27 27 30 Sodium sc ear a tie Structurant - - 5 Cocamidopropyl betaine Surfactant 5 5 5 Petrolatum Emollient - 13 - Sunflower seed oil Emollient 7.5 - - Polyquaternium- 6 Skin feel 2.5 - 2.5 Isononyl feruiate Sunscreen 10 - - Octyl methoxycinnamate Sunscreen - - 10 Octocrylene Sunscreen - 7 - Titanium dioxide - - 0.5 Miscellaneous salts - 2 Perfume 1 Water 2 2 4 Using the formulations noted, following results were obtained: Water soluble anIonia euneoreen Example 1. Example 3 Example 3 Example 4 Comparative 1 Comparative 2 Comparative 3 (1) Phenylbenzimidaz ole sulfonic acid 4.7 SPF 4.9 SPF (2) Sulfonic acid and octycrylene mixture 5.5 SPF (3) Sodium ferulate 5.2 SPF Non-water soluble sunscreent (1) Isononyl ferulate 1.1 SPF (2) Octyl me thoxycinnama te 1 SPF (3) Octycrylene 1 SPF As can be clearly seen from the Table above, where water soluble or mixture of at least one water soluble anionic sunscreen and non-water soluble sunscreen was used, SPF was significantly higher (e.g., 4.7 SPF, 4.9 SPF, 5.5 SPF, 5.2 SPF) compared to when non-water soluble sunscreen was used (e.g., 1.1 SPF, 1 SPF, 1SPF). Clearly, this is an unexpected selection based on the specific type of sunscreen used. Example 5 The following liquid formulations were prepared using various anionic surfactant systems and 2-phenyl benzimidazole sulfonic acid as noted below. Table 3 Liquid Compositions Containing Water-Soluble tTV Absorbers CoaponanCs Function 20% SOS 20% APG 20% SLES Sodium dodecyl sulfate -Surfactant 20 - - Alkyl polyglucoside (glucopon 600 UP) Surfactant - 20 - Sodium lauryl ether sulfate (S'teol CA 230) Surfactant — — 20 2-phenylbenzimidazole sulfonic acid sodium salt Sunscreen 4 4 4 Water To 100% To 100% TO 100% The following results were obtained: Surfactant SPF 20% SDS 8.9 20% APG 7.7 20% SLES 3.4 Again, it can be clearly seen that enhanced SPF can be also found in liquid systems. In comparison, applicants also tested in vitro SPF in a liquid product produced by SKINTEK®, Performance Brands Inc. in Sunrise, Florida. The product is called "Soap Screen®. The Soap Screen® product contains known "oily" sunscreens, e.g., octyl methoxycinnamate, octyl salicylate and oxybenzone. When in-vitro SPF was measured it was found to be 1.1, i.e., well below the SPF of sunscreens used in liquids of subject invention. Example 6 - Lather In order to show less degrading effect on lather by sunscreens of invention compared to more "oily" sunscreens, applicants conducted the following experiment: Stoppered 100 ml graduated cylinders were prepared. One cylinder (cylinder A) contained 10 ml of 1% sodium lauryl ether sulfate and 1% 2-phenylbenzimida2ole-5-sulfonic acid neutralized with a stoichiometric amount of sodium hydroxide and .the other (cylinder 3) .contained 10 ml of 1% sodium lauryl ether sulfate and 1% ethyl hexyl paramethoxy cinnamate. The cylinders were shaken for 10 seconds, then the foam height was observed. Immediately following shaking both cylinders contained the same volume of foam (approximately 70 ml) but the foam in cylinder B decayed more rapidly than the foam in cylinder A. Time (min) Cylinder A Cylinder B 0 70 70 1 70 55 5 70 50 10 65 45 15 65 35 20 65 30 25 65 26 30 65 20 As clearly seen, lather from cylinder,. B. degraded, over 30 minutes while degradation in cylinder A (with more "soluble" sunscreen of 'invention) was almost negligible. WE CLAIM ; 1. A personal wash bar composition comprising : (a) 20 to 85% by wt. first anionic surfactant which is fatty acid soap or synthetic anionic; (b) 0 to 25% by wt. second surfactant; (c) 0 to 15% by wt. free fatty acid; (d) 0 to 20% by wt. of a water soluble structurant which is neither soap nor non-soap detergent and has MP ( melting point) in the range 40 to 100°C and (e) 0.1 to 10% of a sunscreen and/or salt thereof wherein sunscreen and/or salt thereof has SPF greater than 2 to 25, wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H2O at neutral pH; and wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds. 2. A composition as claimed in claim 1 wherein first surfactant (a) is acyl isethionate and second surfactant (b) is soap. 3. A composition as claimed in claim 1 wherein first surfactant (a) is soap. 4. A composition as claimed in claim 1, comprising 1 to 20% second surfactant. 5. A composition as claimed in claim 1, comprising 1 to 15% free fatty acid. 6. A composition as claimed in claim 1, wherein water soluble structurant is polyalkylene glycol. 7. A composition as claimed in claim 1, wherein sun screen and/or salt thereof is glycerol monostearate. 8. A composition as claimed in claim 1, wherein sunscreen component is selected from the group consisting of phenylbenzimidazole sulphonic acid anionic salt or mixtures thereof; ferulic acid, anionic salt or mixtures thereof; and benzephenone, anionic salt or mixtures thereof. 9. A composition as claimed in claim 1, wherein SPF is 3 to 20. 10. A composition as claimed in claim 1, wherein SPF is 4 to 15. 11. A personal wash liquid composition comprising : (a) 10-80% first anionic surfactant (b) 0-15% second surfactant selected from the group consisting of anionic different from first, amphoteric/zwitteronic, cationic and mixtures thereof; (c) 0.1 to 10% anionic sunscreen; (d) balance water, wherein SPF is greater than 2 to 25; wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H20 at neutral pH; and wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds. Dated this 4th day of September 2002 DR. SANCHITA GANGULI of S. MAJUMDAR & CO. (Applicant's Agent)

Full Text

FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
COMPLETE SPECIFICATION
(See section 10; rule 13)

1. Title of the invention.

PERSONAL WASH BAR COMPOSITION

2 Applicant

(a) Hindustan Lever Limited,
(b) 165/166, Backbay Reclamation, Mumbai 400 020 Maharashtra, India.
(c) an Indian Company incorporated under the Indian Companies Act, 1933.

The following specification (particularly) describes the nature of this invention (and the manner in which it is to be performed)

PERSONAL WASH SUNSCREEN COMPOSITIONS WHICH DEPOSIT AND
LATHER WELL
The invention relates to personal wash compositions which deposit high levels of sunscreen (SPF >2) while maintaining good lather (i.e., suffer minimal lather degradation over time relative to composicions with more "oily" sunscreens). Enhanced deposition is found from both bar and liquid compositions and is based on the solubility or 'non-solubility of the sunscreen used.
It is a difficult task to deposit significant levels of sunscreen from skin cleansers. Moreover, most sunscreens severely defoam the cleanser composition. Therefore, previous attempts to deliver sunscreen from cleansers resulted in cleanser having low levels of protection (i.e., SPF One reason deposition has been so difficult to achieve is that most of sunscreens used are either water insoluble
oils or insoluble fine solid particles (e.g., ZnO, Ti02).
Such sunscreens are generally dispersed into dilute suspensions by surfactants present in the cleanser. As a 'result, and without wishing to be bound by theory, it is believed that most of the sunscreen.will remain suspended, the suspended sunscreen will be removed when skin is rinsed, and little will be left to deposit or. the skin. Further,

dispersions of the sunscreens into the wash liquid cends to defoarn the liquor. In addition, incorporation of oily sunscreen in bars also generally increases softness, stickiness and mush.
Unexpectedly, applicants have found a novel class of sunscreens which can be delivered and provide superior sun protection. These sunscreens can be deposited even in presence of anionic surfactants. Unlike most sunscreens, these are much more soluble in water than the usual "oily" suras'creen and- provide .measurable sun protection even at low levels of addition (e.g., 0.1-15%, preferably 0.5 to 12%, more preferably 1.0 to 10% by wt.). Moreover, since they are more soluble in water, they do not defoarn cleanser during wash process.
More specifically, applicants have found specific sunscreen agents which are organic molecules absorbing light in the UV range. These sunscreens are water-soluble UV absorbers (greater than or equal to 0.1% preferably greater than 0.5% water solubility on a weight to weight basis at neutral pH). The sunscreens include a functional group that is anionic or at least part of the sunscreen becomes anionic (e.g., anionic functional group incorporated at sufficiently high pK) at suitable pH (e.g., pH J: 3, preferably greater than -., preferably 4 to 10) and the sunscreens are water soluble or become soluble at suitable pH (again about 3 to 10). Examples cf such molecules include: pher.yibenzimidazole suiphonic acid, anionic salts cf said acid which form at pH of 7 and above and mixtures thereof (forming at pH between 4 and 7); ferulic 'acid, its anionic salts and mixtures thereof; benzophenone-4, its anionic

salts and mixtures thereof; and benzophenone-9, 'its anionic salts and mixtures thereof. Preferably, the sunscreen agents are used.in the form of their salts generally at pH 7 and above.
While not wishing to be bound by theory, these anionic organic sunscreen molecules are believed to bind to positively charged sites on proteins within the skin thereby accounting for enhanced deposition.- Because molecules deposited through binding from solution cover the surface uniformly, the UV protection is also believed to be more effective than protection obtained from oily or particulate sunscreens where the deposition may be localized to small areas of skin and leave some areas unprotected. Moreover, because the agents are more soluble in water than oily components, they cause less defoaming than the oily or particulate sunscreen agents. As noted above, oily, particulate sunscreens are believed to suspend in surfactants and more readily wash off when rinsed, thereby leading to lower deposition. Oily agents also lead to mushier bars. The specific sunscreen agents of the invention avoid these problems.
Some of the organic sunscreen materials of the invention are not new. For example, WO 14053 to Cussons Int. Ltd. teaches personal wash compositions containing sunscreen agents including phenylbenzimidazole sulphonic acid (which is recited among a list of sunscreen agents which may be used (page 7).
The reference does net recognize that the sulphonic acid sunscreen agent or salts thereof provide superior sun

protection relative to other sunscreens including even those used in the reference itself (see Examples 1-3 of reference). The higher water solubility also makes the sunscreens less dsfoaming and more soluble for personal wash products where foaming.is considered a desirable attribute.
U.S. Patent Nos. 4,933,174 and U.S. 4,701,321 by J. Bernstein (assigned to Amethyst Investment Group, Inc.) teaches a liquid PW composition, which comprises nonionic and amphoteric surfactants, and sunscreen materials including aminobenzoic acid, the esters of an aminobenzoic acid, homosalate, 2-hydroxy-4-methoxylbenzophenone (oxybenzone) or 2-ethoxyethyl p-methoxycinnamate (cinoxate). Nonionic and amphoteric surfactants instead of anionic surfactants are used to enhance the deposition of sunscreen agents. Repeated washing and bathing with the compositions leaves a long-lasting layer of sunscreens in the stratum corneum of the skin. The reference fails to recognize that specific anionic sunscreens (e.g., anionic salts) of the invention, particularly when used in systems comprising anionic surfactants, deposit better than other sunscreens.
"The noted U.S. patents also do not specifically include phenyibenzimidazole sulphonic acid, benzophenone-4 or any of the other materials suitable for our invention as candidates for the sunscreen agents claimed. These patents further require that formulations contain only nonionic or amphoteric surfactant and further requires that the compositions be used repeatedly over many weeks to achieve the claimed effects.

Unexpectedly, applicants have found that when specific sunscreen and'/or their salts are used in personal wash compositions, they are more water soluble than many oily particulate sunscreens normally useci (e.g., "normal" oils having solubility of less than 0.1% wt. by wt. water compared to more soluble -"salts" of subject invention) ; they provide enhanced sun protection factor or SPF (e.g. SPF greater than 2, to about 25, preferably greater than 3 to 20, more preferably from about 4 to "i5); and the sunscreen does not depress foaming (e.g., foaming does not depress over time compared with more oily components whose lather does depress more quickly over time),
Generally, using the sunscreens of invention, foaming does not depress more than about 50%, preferably more than 30%, preferably more than about 25% over 30 minutes time using test as defined in examples.
More specifically, the present invention provides a pergonal wash composition, particularly personal wash compositions which may be in bar or liquid form. In one embodiment the compositions are bars comprising:
(1) .20% to 85% by wt of first Anionic surfactant which may be fatty acid"soap or a synthetic anionic;
(2) 0-25% preferably 1-20% second surfactant selected
c„ | n—- -| ■■- ..
from the group consisting of second anionic surfactant (different from first), nonionic, amphoteric, cationic and mixture thereof;
(3) 0-15% free fatty acid;
(4) 0-20% water soluble structiarant (e.g., polyalkylene glycol, EO-PO copolymers);

(5) 0 to 40%, preferably .0-35% alkanoate (e.g.,
glycerol monostearate) having chain length of C12
to C24; and
(6) 0.1 to 10% of a sunscreen agent, anionic salt
(e.g., functional group attached to sunscreen
agent which, in solution, yields negative charge
such as, for example, sulfates, sulfonates,
carboxylates, phosphates, phosphonates, etc.), or
mixtures thereof (at least some portion of the
: sunscreen-.must be ,in ,i-t,s ..salt, form; .however, this is inherently accomplished by specifying minimum pH values) ; wherein sunscreen agent (by which is meant overall equilibrium of the acid form of the sunscreen, its salt and mixtures) has a water solubility of greater than or equal to 0.1%, preferably greater than 0.5% on.weight to weight basis as measured at pH 7;
wherein said sunscreen has SPF of greater than 2 to 25; and
wherein composition does not degrade more than 50% lather, preferably no more than 35%, more preferably no more than 25% over 30 minutes as defined in -examples.
Bars generally will have 1-15%, preferably 2-12% water.
In a second embodiment, composition may be liquid composition comprising:
(I! 10-301 anionic surfactant;
(2) 0-25% of second surfactant selected from group consisting of anionic different from first,

nonionic, amphoteric/zwitterionic, caiionic and
mixtures thereof; and (3) 0.1 to 10% of a sunscreen agent, salt thereof or
mixtures as defined above; wherein sunscreen agent has a water solubility of greater than or equal to 0.1%, preferably greater than 0.5% on weight to weight basis as measured at pH 7; wherein said sunscreen has SPF of greater than 2 to 25; and
wherein composition does not degrade more than 50% lather, preferably no more than 35%, more preferably no more than 25% over 30 minutes as defined in examples.
The present invention is based on applicants unexpected finding that certain sunscreen agents and/or salts thereof are anionic, water-soluble compounds which provide enhanced SPF while simultaneously not depressing foam relative to more oily, less water soluble sunscreen compounds (e.g., those which are generally less soluble and have solubility of less than 0.5% wt. for wt. water) . These "more" water-soluble sunscreen agents and/or anionic salts thereof (counterions may exist to anionic group as well) provide unexpectedly enhanced effect whether used in bar or liquid cleanser compositions.
In one embodiment, the invention comprises bar compositions comprising:
(1) 20 to 85% by wt. of a first anionic surfactant which is fatty acid soap or synthetic anionic;
(2) 0 to 25% by wt. of a second surfactant selected from the group consisting of a second anionic

(differing from the first), nonionic surfactant, amphcteric/zwitterionic surfactant, "cationic surfactant and mixtures thereof;
(3) 0 to 15% by wt. free fatty acid (particularly where bar is a predominantly fatty acid soap bar) ;
(4) 0 to 20% of a water-soluble structurant which is neither soap nor non-soap detergent and has MW in the range 40 to 100°C (e.g., polyalkylene glycol EO-PO copolymers);
(5) 0 to 40% glycerol monoalkanoate of C12-C24 chain
length; and
(6) 0.1 to 10% of a sunscreen agent and/or salt
thereof (providing anionic charge) wherein
sunscreen and/or salt thereof has SPF greater than
2 to 25, preferably greater than 3 to 20, more
preferably greater than about 4 to 15;
wherein sunscreen agent and/or salt has solubility of greater than or equal to 0.1%, preferably greater than 0.5% on weight to weight basis as measured neutral pH; and
wherein sunscreen agent and/or salt has lather which does not substantially degrade over time relative to more oily components.
In second embodiment of the invention, compositions may >e liquid cleanser comprising:
(1) 10-80% first anionic surfactant; and
(2) 0 to 25% second surfactant selected from the croup consisting of anionic different from first, nonionic, amphoteric/zwitterionic, cationic and mixtures thereof;

(3) O.1 to 10% of sunscreen and/or salt thereof as defined with bar compositions thereof; and
(4) balance water,
wherein compositions has SPF values, solubility and lather parameters as defined for bar compositions above.
Each of these embodiments is described in more detail below.
BAR COMPOSITIONS
First Anionic
The first anionic surfactant may be a synthetic surfactant or fatty acid soap. Although not preferred, the bar compositions may comprise a "pure" soap composition. Such bars are generally not mild (although they do foam well and have sensory properties preferred by some consumers) and so it is generally preferred to use bars which are predominantly synthetic or which are combinations of synthetic and soap.
The term "soap" is used here in its popular sense, i.e., the alkali metal or alkanol ammonium salts of aliphatic alkane- or alkene monocarboxylic acids. Sodium, potassium, mono-, di and tri-ethanol ammonium cations, or combinations thereof, are suitable for purposes of this invention. In general, sodium soaps are used in the compositions of this invention, but from about 1% to about 25% of the soap may be potassium soaps. The soaps useful herein are the well known alkali metal salts of natural or

synthetic aliphatic {alkanoic or alkanoic) acids' having about 12.to.22,carbon atoms, preferably about 12 to about 18 carbon atoms. They may be described as alkali metal carboxylates of acrylic hydrocarbons having about 12 to about 22 carbqn atoms.
Soaps having the fatty acid distribution of coconut oil may provide the lower end of the broad molecular weight range. Those soaps having the fatty acid distribution of peanut or rapeseed oil, or their hydrogenated derivatives may provide the upper end of the broad molecular weight range.
It is preferred to use soaps having the fatty acid distribution of coconut oil or tallow, or mixtures thereof, since these are among the more readily available fats. The proportion of fatty acids having at least 12 carbon atoms in coconut oil soap is about 85%. The proportion will be greater when mixtures of coconut oil and fats such as tallow, palm oil or non-tropical nut oils or fats are used,
wherein the principle chain lengths are C16 and higher.
Preferred soap for use in the compositions of this invention has at least about 85% fatty acids having about 12-18 carbon atoms.
Coconut oil employed for the soap may be substituted in whole or in part by other "high-lauric" oils, that is, oils or fats wherein at least 50% of the total fatty acids are composed of lauric or myristic acids and mixtures thereof. These oils are general exemplified by the tropical nut oils of the coconut oil class. For instance, they include: palm kernel oil, babassu oil, ouricuri oil, tucum oil, cohune nut

oil, muru-muru oil, jaboty kernel oil, khakan kernel oil, dika nut oil,and ucuhuba butter.
A preferred soap is a mixture of about 15% to about 20% coconut oil and about 80% to about 85% tallow. These mixtures contain about 95% fatty acids haying about 12 to about 18 carbon atoms. The soap may be prepared from coconut oil in which case the fatty acid content is about
85% of C12-C18 chain length.
The soaps may contain unsaturation in accordance with commercially acceptable standards. Excessive unsaturation is normally avoided.
Soaps may be made by the classic kettle boiling process or modern continuous soap manufacturing processes wherein natural fats and oils such as tallow or coconut oil or their equivalents are saponified with an alkali metal hydroxide using procedures well known to those skilled in the art. Alternatively, the soaps may be made by neutralizing fatty
acids, such as lauric (C12), myristic (C14), palmitic (C16) or staric (C18) acid's with an alkali metal hydroxide or -carbonate.
The first anionic detergent active which may be usec may be aliphatic sulfonates., such as a primary alkane (e.g.,
C8-C22) sulfonate, primary alkane (e.g., C8-C22) disuifonate, C8-C22 alkene sulfonate, C8-C22 hydroxy alkane sulfonate or alky'i. glycerol ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate.

The first anionic may also be an alkyl sulfate (e.g.,
C12-C18 alkylsulfate) or alkyl ether sulfate (including alkyl
glycerol ether sulfates). Among the alkyl ether sulfates are those having the formula:
RO(CH2(CK2-0)nS03M
wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons; n has an average value of greater than 1.0, preferably greater than 3: and M is a solubilizing cation such as sodium, potassium ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e|.g., C&-C22 sulfosuccinates); alkyl and acyl taurates, alkyl |and acyl sarcosinates, sulfoacetates, Cg-C22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates,. sulphoacetates, alkyl glycosides and acyl isethionates.
Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
R"'02CCH2CH (SO3M) CO2M;
and

amide-MEA sulfosuccinates of the formula
R4CONHCK2CH202CCH2CK(SO3M)CO2M
4 wherein R ranges from C8-C22 alkyl and M is a
solubilizing cation.
Sarcosinates are generally indicated by the formula
RCON(CK3)CK2C02M, wherein R ranges from C8-C20 alkyl and M is a solubilizing cation.
Taurates are generally identified by formula:
R2CONR3CH2CH2S03M
2 3
wherein R ranges from C8-C20 alkyl, R ranges from C1-
C4 alkyl and H is a solubilizing cation.
Particularly preferred are the Cs-Cig acyl isethionates.
These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to IB carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
Acyl isethionates, when present, will generally range from about 10% to about 70% by weight of the total composition. Preferably, this component is present from about 30% to about 60%.

The acyl isethionate may be an alkoxylated isethionate such as'is'-de-scribed'-in I lardi et ai., U.S. Serial No. 796,748, hereby incorporated by reference. This compound has the general formula:

wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are hydrogen or an alkyl
.L.
group having 1 to 4 carbons and M' is a monovelent cation such as, for example, sodium, potassium or ammonium.
In general the anionic component will comprise from about 10 to 70% of the composition, preferably 20-50% by wt. of the composition.
Second Surfactant
The second surfactant may be any of the anionics defined above except-, that it differs from the first anionic. The second component may also be any of the amphoteric or nonionics discussed below as well as a mixture of the anionic, amphoteric and/or nonionic.
.Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylio. or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido

acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula:

wherein R is alkyl or alkenyl of 7 to 18 carbon atoms:
2 3
R and R are each independently alkyl, hydroxyalkyl or
carboxyalkyl of 1 to 3 carbon atoms;
m is 2 to 4;
n is 0 to 1
X is alkylene of to 3 carbon atoms optionally substituted with hydroxyl, and
Y is —CO2— or —SO3—
Suitable amphoteric detergents within the above general formula include simple betaines of formula:

where m is 2 or 3;
In both formulae R1,R2 and R3 are as defined
previously. R may in particular be a mixture of C12 and C14 alkyl groups derived from coconut so that at least half,
preferably at least three quarters of the groups R have 10
2 3 to 14 carbon atoms. R and R are preferably methyl.
A further possibility is that the amphoteric detergent is a sulphobetaine of formula:

where m is 2 or 3 ,or variants of these in which (CH2)3S03— is replaced by :

In these formula R1, R2 and R3 are as discussed previously.
The nonionic which may be used as the second component of the invention include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for 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 alkyl (C6-C22) phenols-
ethylene oxide condensates, the condensation products of
aliphatic (C8-C18) primary or secondary linear or branched
alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
The nonionic may also be a sugar amice, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Serial No. 816,419 to Au et al. which is hereby incorporated by-reference or it may be one of the sugar amices described in U.S. Patent No. 5,009,814 to Kelkenberc, hereby incorporated into the subject application by reference.

Other surfactants which may be used are described in U.S. Patent No. 3,723,325 to Parran Jr., which is also incorporated into the subject application by reference.
In general the second component (i.e., second anionic nonionic and/or amphoteric compound or mixture) is incorporated into the composition as less than 20% by weight, preferably 1 to 15% by weight of the composition.
Structurant-
In general, bars of the invention may comprise 0 to 75% structurant (e.g., free fatty acid, water soluble structurant, glycerol monoalkanoate noted below). Preferably, the bar will contain 5% to 65% structurant though none is required.
Free Fatty Acid
Free fatty acids of 8-22 carbon atoms may also be desirably incorporated within the compositions of the present invention. Some of these fatty acids are present to operate as superfatting agent's and others- as skin .feel and creaminess enhancers. Superfatting agents enhance lathering properties and may be selected from fatty acids of carbon atoms numbering 8-18, preferably 10-16, generally in an amount up to 15% by weight (although higher amounts may be used) of the composition. Skin feel and creaminess enhancers, the mosr important of which is stearic acid, are also desirabiv present in these cor.posirions.

Water Soluble Structurant
Another compound which may be used in the bar is water soluble structurant (e.g., polyalkylene glycol).
This component should comprise 0% by wt. to 60%, preferably greater than 5% to 40% by wt. of the bar composition.
The structurant (e-. g., po1yalkylene glycol) has a melting point of 400C to 100°C, preferably 45°C to 100°C, more preferably 50°C to 90°C.
Materials which are envisaged as the water soluble structurant (b) are moderately high molecular weight polyalkylene oxides cf appropriate melting point and in particular polyethylene glycols or mixtures thereof.
Polyethylene glycols (PEG's) which may be used may have a molecular weight in the range 1,500-20,000.
It should be understood that each product (e.g., Union
Carbide's Carbowax® PEG 8,000) represents a distribution of
molecular weights. Thus PEG 8,000, for example, has an average MW range of 7,000-9,000, while PEG 300 has an average MW range fro- 285 to 315. The average MW of the product can be anywhere between the low and high value, and there may still be a good portion of the material with MW below, the low., value and above the high value.
In some embodiments of this invention it is preferred to include a fairly small quantity of polyalkylene glycol

(e.g., polyethylene glycol) with a molecular weight in the range from-50,000 to 50,000, especially molecular weights of around 100,000. Such polyethylene glycols have been found to improve the wear rate of the bars. It is believed that this is because their long polymer chains remain entangled even when the bar composition is wetted during use.
If such high molecular weight polyethylene glycols (or any other water soluble high molecular weight polyalkylene oxides) -are used, the quantity is preferably .from- l%-to-5-% more preferably from 1% or 1.5% to 4% or 4.5% by weight of the composition. These materials will generally be used jointly with a larger quantity of other water soluble structurant (b) such as the above mentioned polyethylene glycol of molecular weight 1,500 to 10,000.
Some polyethylene oxide polypropylene oxide block copolymers melt at temperatures in the required range of 40°C to 100°C, and may be used as part or all of the water soluble structurant (b). Preferred ere are block- copolymers in which polyethylene oxide provides at least 40% by weight of the block copolymer. Such block copolymers may be used in mixtures with polyethylene glycol or other polyethylene glycol water soluble structurant.
Glycerol Monoalkanoate
Another optional structurant which may be used is
glycerol monoalkanoate wherein alkanoate group may be C12-C24
alkyl (e.g., glycerol monostearate) . This may comprise C-60% by wt.,of bar, preferably 5% to 50% by wt.

Sunscreen
The sunscreens of the invention are defined by the fact that they are sunscreens which form salts (at sufficient pH) sc that the salts or an equilibrium of salt and the acid form of the sunscreen have a solubility of greater than 0.1% wt/wt., preferably greater than 0.5% as measured at neutral pH. As noted, in general the pH of the composition has to be high enough to have at least some portion of the anionic salt.
The anionic salts are formed by functional anionic groups well known to those skilled in the art such as sulphates, sulfonates, carboxylates, phosphates, phospnonates and other groups which are well known to provide anionic charges in solution.
Unexpectedly, applicants have found that use of these sunscreens and/or salts which have the defined solubility will provide enhanced S?F (e.g., 2 to 25) relative to other sunscreens while at the same time not depressing the lather function of the final composition.
Examples of such sunscreen compounds include phenylbenzimidazole sulphonic acid and salts thereof; ferulic acid and salts thereof; benzophenone and its salts thereof. Other examples include variants of benzophenone and salts thereof.

Other Compounds
Skin mildness improvers also preferably used in the composition of the invention are salts of isethionate. Effective salts cations may be selected from the group consisting of alkali metal, alkaline earth metal, ammonium, alkyl ammonium and mono-, di or tri-alkanolammonium ions. Specifically preferred cations include sodium potassium, lithium, calcium, magnesium, ammonium, triethylammonium, monoe.thanolammonium,, diethanaLammonium or triethanolammonium ions.
Particularly preferred as a mildness improver is simple unsubstituted sodium isethionate.
The skin mildness improver will be present from about 0.5% to about 50%. Preferably, the mildness improver is present from about 1% to about 25%, more preferably from about 2% to about 15, optimally from 3% to 10% by weight of the total composition.
Other performance chemicals and adjuncts may be needed with these compositions. The amount of these chemicals and adjuncts may range from about 1% to about 40% by weight of the total composition. For instance, from 2 to 10% of a suds-busing detergent salt may be incorporated. Illustrative of this type additive are salts selected from the group consisting of alkali metal and organic amine higher aliphatic fatty alcohol sulfates, alkyl aryl sulfonates and the hiaher aliphatic fattv acid taurinates.

Adjunct materials including germicides, perfumes, colorants pigments such as titanium dioxide and water may also be present.
The bar compositions of the invention have SPF of greater than 2 to 25, preferably greater than about 3 to 20 and more preferably greater than about 4 to 15.
SPF is defined as per the protocol in the example section.
In addition compositions have lather of which does not degrade more than 50%, preferably more than 35%, preferably more than 25% over 30 minute period.
In a second embodiment, the compositions of the invention may also be liquid compositions as noted above.
LIQUID
First Anionic
In the liquid compositions, the first anionic surfactant may be any of the surfactants as for the bars above except that it will not be "soap" as defined therein.
Second surfactant
The second surfactant may also be one of the above as defined for bars.

Optional
The liquids of this invention may be isotropic single phase liquids or they may be structured as defined and using structurants as defined in U.S. Patent No. 5,952,286 to Puvvada et al. hereby incorporated by reference into the subject invention.
The compositions may contain oils or emollients as noted below.
Vegetable oils: Arachis oil, castor oil, cocoa butter, coconut oil, corn .oil, cotton seed oil, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, sesame seed oil and soybean oil.
Esters: Butyl myristate, cetyl palmitate, decyloleate, glyceryl laurate, glyceryl ricinoleate, glyceryl stearate, glyceryl isostearate, hexyl laurate, isobutyl palmitate, isocetyl stearate, isopropyi isostearate, isopropyi laurate, isopropyi linoleate, isopropyi myristate, isopropyi palmitate, isopropyi stearate, propylene glycol monolaurate, propylene glycol ricinoleate, propylene glycol stearate, and propylene glycol isostearate.
Animal Fats: Acytylatelte lanolin alcohols, lanolin, lard, mink oil and tallow.
Fatty acids and alcohols: Behenic acid, palmitic acid, stearic acid, behenyl alcohol, cetyl alcohol, eicosanyi alcohol and isocetvl alcohol.

Other examples of oil/emollients include mineral oil, petrolatum, silicone oil such as dimethyl polysiloxane, lauryl and myristyl lactate.
It should be understood that where the emollient may also function as a structurant, it should .not be doubly included such that, for example, if the structurant is 15% oleyl alcohol, no more than 5% oleyl alcohol as "emollient" would be added since the emollient (whether functioning as emollient or -structurantl- never comprises more than. 20%, preferably no more than 15% of the composition.
The emollient/oil is generally used in an amount from about 1 to 20%, preferably 1 to 15% by wt. of the composition. Generally, it should comprise no more than 20% of the composition.
In addition, the compositions of the invention may include optional ingredients as follows:
Organic solvents, such as ethanol; auxiliary thickeners, such as carboxymeuhyicellulose, magnesium aluminum silicate, hydroxyethylcellulose, methylcellulose,
(R)
carbopols, glucamides, or Antil from Rhone Poulenc;
perfumes; sequestering agents, such as tetrasodium ethylenediaminetetraacetare (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and peariizers such as zinc stearate,
magnesium stearate, TiO2, EGMS (ethylene glycol monostearate) or Lytror. 621 (Styrene/Acrylate copolymer) ; all of which are useful in enhancing the appearance or cosmetic properties of the product.

The compositions may further comprise antimicrobials such as 2-hydroxy-4, 2 ' 4 ' trich-lorodiphenylether (DP300) ; preservatives such as dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid etc.
The compositions may also comprise coconut acyl mono-or diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may also be used to advantage.
Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate.
Cationic conditioners which may be used include ..
Quatrisoft LM-200 Polyquaternium-24, Merquat Plus 3330 -
(R)
Polyquaternium 39; and Jaguar type conditioners.
Polyethylene glycols which may be used include:
Polyox WSR-205 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750 PEG 7M.
Thickeners which may be used include Amerchol Polymer
HM 1500 (Nonoxynyl Hydroethyl Cellulose); Glucam DOE 120
(R)
(PEG 120 Methyl Glucose Dioleate); Rewoderm (PEG modified
glyceryl cocoate, palmate or tallowate) from Rewo Chemicals;
(R)
Antil 141 (from Gcldschmidt).

Another optional ingredient which may be added are the defloculating polymers such as are taught in U.S. Patent Nc. 5,147,576 to Montague, hereby incorporated by reference.
Another ingredient which may be included are exfoliants such as polyoxyethylene beads, walnut sheets and apricot seeds.
The liquid compositions, like the bar compositions will have SPF values and lather volume as defined for the bars.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word "about".
Where used in the specification, the term "comprising" is intended to include the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more features, integers, steps / "components' or- "groups thereof.
The following examples are intended to further illustrate the invention and are not intended to limit the invention in any way.
Unless indicated otherwise, ail percentages are intended to be percentages by weight.

Protocol
In-Vitro SPF Measurement for Evaluating Skin Cleansing Compositions Containing Sunscreens
This method involves the measurement of the transmission of light across the UV spectrum through a treated substrate. From the transmittance data an estimate of SPF can be obtained.
In-vitro SPF measurements were made on an Optometries SPF 2 90 instrument (Optometries Corp., Ayre MA, USA). The instrument measures diffuse transmittance through a treated substrate at 5 nm increments covering wavelengths from 290 to 400 nm and reports a calculated SPF. Measurements were taken at 6 sites over a 6.5 cm by 6.5 cm piece of each
treated substrate. The substrate used was Vitro-skin™ (IMS Testing Group, Milford, CT,- USA). The Vitro-Skin substrate was pre-hydrated in a desiccator at 80% relative humidity as recommended by the supplier. The vitro-skin substrate was treated by rubbing a wet bar across it. 10. times, then rubbing the Vitro-skin substrate for 15 seconds. After this the substrate was rinsed under tap water for 15 seconds and blotted dry with a paper towel.

Lather Measurements
Lather was measured using stoppered, graduated 100 ml. cylinders. The cylinders were shaken 10 seconds and foam height observed.
Example 1-4 and Comparative 1-3
The following formulations were made where Table 1 represents formulae containing anionic (water-soluble) UV sunscreens and Table 2 represents formulae containing hydrophobic UV absorbers
Table 1 Formulations Containing Anionic (Water-Soluble) UV Absorbers

Components Function Example
1 Example
2 Example
3 Example 4
Polyethylene glvcoi -8000 Structurant 10 10 10 10
Glycerol monostearate Structurar.t 27.6 27.6 27.6 27.5
Palmitic-stearic acid Structurar.t 8.4 8.4 8.4 8.4
Sodium cocoyl isethionate Surfactant 27 27 27 2"
Cocamidgprqpyl betaine Surfactant 5 5 5 -
Sunflower seed oil
Emollient - - - 7.5
Petrolatum Emollient 16 " S -
Polyquaiternium-S Skin feel - = - 2.5
Sodiur; ferulate Sunscreen - - - 10
2-phenlylben:imidazole-5-suifonic acid Sunscreen 4 4 4 -
Octocrylene Sunscreen 1 - - ; -
Water 1 2 2 2 -

Table 2 Formulations Containing Only Hydrophobic UV Absorbers

Consonants Function Comparative
1 Comparative 2 Comparative 3
Polyethylene glycol -8000 Struccurant 10 10 10
Propylene glycol Structurant/ Skinfeel - — 13
Paraffin wax Structurant - 1 3
Glycerol monostearate Structurant 27.6 ^ 27.6 |
Palmitic-stearic acid Structurant 8.4 8.4 14
Sodium cocoyl
sethionate , Surfactant 27 27 30
Sodium sc ear a tie Structurant - - 5
Cocamidopropyl betaine Surfactant 5 5 5
Petrolatum Emollient - 13 -
Sunflower seed oil Emollient 7.5 - -
Polyquaternium- 6 Skin feel 2.5 - 2.5
Isononyl feruiate Sunscreen 10 - -
Octyl methoxycinnamate Sunscreen - - 10
Octocrylene Sunscreen - 7 -
Titanium dioxide - - 0.5
Miscellaneous salts - 2
Perfume 1
Water 2 2 4

Using the formulations noted, following results were obtained:

Water soluble
anIonia euneoreen Example
1. Example
3 Example
3 Example
4 Comparative 1 Comparative
2 Comparative 3
(1) Phenylbenzimidaz
ole sulfonic
acid 4.7 SPF 4.9 SPF
(2) Sulfonic acid and octycrylene mixture 5.5 SPF
(3) Sodium ferulate 5.2 SPF

Non-water soluble sunscreent
(1) Isononyl ferulate 1.1 SPF
(2) Octyl
me thoxycinnama te 1 SPF
(3) Octycrylene 1 SPF

As can be clearly seen from the Table above, where water soluble or mixture of at least one water soluble anionic sunscreen and non-water soluble sunscreen was used, SPF was significantly higher (e.g., 4.7 SPF, 4.9 SPF, 5.5 SPF, 5.2 SPF) compared to when non-water soluble sunscreen was used (e.g., 1.1 SPF, 1 SPF, 1SPF).
Clearly, this is an unexpected selection based on the specific type of sunscreen used.
Example 5
The following liquid formulations were prepared using various anionic surfactant systems and 2-phenyl benzimidazole sulfonic acid as noted below.
Table 3 Liquid Compositions Containing Water-Soluble tTV Absorbers

CoaponanCs Function 20% SOS 20% APG 20% SLES
Sodium dodecyl sulfate -Surfactant 20 - -
Alkyl polyglucoside (glucopon 600 UP) Surfactant - 20 -
Sodium lauryl ether sulfate (S'teol CA 230) Surfactant — — 20
2-phenylbenzimidazole sulfonic acid sodium salt Sunscreen 4 4 4
Water To 100% To 100% TO 100%

The following results were obtained:

Surfactant SPF
20% SDS 8.9
20% APG 7.7
20% SLES 3.4
Again, it can be clearly seen that enhanced SPF can be also found in liquid systems.
In comparison, applicants also tested in vitro SPF in a liquid product produced by SKINTEK®, Performance Brands Inc.
in Sunrise, Florida. The product is called "Soap Screen®.
The Soap Screen® product contains known "oily"
sunscreens, e.g., octyl methoxycinnamate, octyl salicylate and oxybenzone.
When in-vitro SPF was measured it was found to be 1.1, i.e., well below the SPF of sunscreens used in liquids of subject invention.
Example 6 - Lather
In order to show less degrading effect on lather by sunscreens of invention compared to more "oily" sunscreens, applicants conducted the following experiment:
Stoppered 100 ml graduated cylinders were prepared. One cylinder (cylinder A) contained 10 ml of 1% sodium lauryl ether sulfate and 1% 2-phenylbenzimida2ole-5-sulfonic acid neutralized with a stoichiometric amount of sodium hydroxide

and .the other (cylinder 3) .contained 10 ml of 1% sodium lauryl ether sulfate and 1% ethyl hexyl paramethoxy cinnamate. The cylinders were shaken for 10 seconds, then the foam height was observed. Immediately following shaking both cylinders contained the same volume of foam (approximately 70 ml) but the foam in cylinder B decayed more rapidly than the foam in cylinder A.

Time (min) Cylinder A Cylinder B
0 70 70
1 70 55
5 70 50
10 65 45
15 65 35
20 65 30
25 65 26
30 65 20

As clearly seen, lather from cylinder,. B. degraded, over 30 minutes while degradation in cylinder A (with more "soluble" sunscreen of 'invention) was almost negligible.

WE CLAIM ;
1. A personal wash bar composition comprising :
(a) 20 to 85% by wt. first anionic surfactant which is fatty acid soap or synthetic anionic;
(b) 0 to 25% by wt. second surfactant;
(c) 0 to 15% by wt. free fatty acid;
(d) 0 to 20% by wt. of a water soluble structurant which is neither soap nor non-soap detergent and has MP ( melting point) in the range 40 to 100°C and
(e) 0.1 to 10% of a sunscreen and/or salt thereof wherein sunscreen and/or salt thereof has SPF greater than 2 to 25,
wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H2O at neutral pH; and
wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds.
2. A composition as claimed in claim 1 wherein first surfactant (a) is acyl isethionate and second surfactant (b) is soap.
3. A composition as claimed in claim 1 wherein first surfactant (a) is soap.
4. A composition as claimed in claim 1, comprising 1 to 20% second surfactant.
5. A composition as claimed in claim 1, comprising 1 to 15% free fatty acid.
6. A composition as claimed in claim 1, wherein water soluble structurant is polyalkylene glycol.

7. A composition as claimed in claim 1, wherein sun screen and/or salt thereof is glycerol monostearate.
8. A composition as claimed in claim 1, wherein sunscreen component is selected from the group consisting of phenylbenzimidazole sulphonic acid anionic salt or mixtures thereof; ferulic acid, anionic salt or mixtures thereof; and benzephenone, anionic salt or mixtures thereof.
9. A composition as claimed in claim 1, wherein SPF is 3 to 20.
10. A composition as claimed in claim 1, wherein SPF is 4 to 15.
11. A personal wash liquid composition comprising :

(a) 10-80% first anionic surfactant
(b) 0-15% second surfactant selected from the group consisting of anionic different from first, amphoteric/zwitteronic, cationic and mixtures thereof;
(c) 0.1 to 10% anionic sunscreen;
(d) balance water,
wherein SPF is greater than 2 to 25;
wherein sunscreen agent/salt has solubility of greater than or equal to 0.1% as measured in H20 at neutral pH; and
wherein composition lather degrades no more than 50% after 30 minutes as measured in 100ml graduated cylinders which have been shaken for 10 seconds.

Dated this 4th day of September 2002

DR. SANCHITA GANGULI
of S. MAJUMDAR & CO.
(Applicant's Agent)

Documents:

in-pct-2002-01204-mum-cancelled pages-(01-10-2004).pdf

in-pct-2002-01204-mum-claim(granted)-(03-03-2004).doc

in-pct-2002-01204-mum-claims(granted)-(01-10-2004).pdf

in-pct-2002-01204-mum-correspondence 1(04-09-2002).pdf

in-pct-2002-01204-mum-correspondence 2(17-04-2006).pdf

in-pct-2002-01204-mum-correspondence(ipo)(01-11-2006).pdf

in-pct-2002-01204-mum-form 19(23-06-2003).pdf

in-pct-2002-01204-mum-form 1a(19-05-2004).pdf

in-pct-2002-01204-mum-form 2(granted)-(01-10-2004).pdf

in-pct-2002-01204-mum-form 2(granted)-(03-03-2004).doc

in-pct-2002-01204-mum-form 3(04-09-2002).pdf

in-pct-2002-01204-mum-form 5(04-09-2002).pdf

in-pct-2002-01204-mum-form-pct-ipea-409(04-09-2002).pdf

in-pct-2002-01204-mum-form-pct-isa-210(04-09-2002).pdf

in-pct-2002-01204-mum-petition under rule 138(01-10-2004).pdf

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Patent Number

203931

Indian Patent Application Number

IN/PCT/2002/01204/MUM

PG Journal Number

20/2007

Publication Date

18-May-2007

Grant Date

03-Nov-2006

Date of Filing

04-Sep-2002

Name of Patentee

HINDUSTAN LEVER LIMITED

Applicant Address

HINDUSTAN LEVER HOUSE, 165/166, BACKBAY RECLAMATION, MUMBAI 400 020, MAHARASHTRA, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	CROOKHAM, HARRYN CLARK	C/O UNILEVER RESEARCH U.S. INC., 45 RIVER ROAD, EDGEWATER, NJ 07020, U.S.A.
2	LANG, DAVID JOHN	C/O UNILEVER RESEARCH U.S. INC., 45 RIVER ROAD, EDGEWATER, NEW JERSEY 07020, U.S.A.
3	HE, MENGTAO	10814 EAST PALM RIDGE DRIVE, SCOTTSDALE, ARIZONA 85259, USA.
4	KHAN-LODHI, ABID NADIM	C/O UNILEVER RESEARCH U.S. INC., 45 RIVER ROAD, EDGEWATER, NEW JERSEY 07020, U.S.A.

PCT International Classification Number

N/A

PCT International Application Number

PCT/EP01/02223

PCT International Filing date

2001-02-27

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/523248	2000-03-10	U.S.A.