AU715324B2 - Skin whitening compositions with sunscreen agents - Google Patents

Description

AUSTRALIA

PATENTS ACT 1990

ORIGINAL

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C C COMPLETE SPECIFICATION STANDARD PATENT TITLE OF INVENTION SKIN WHITENING COMPOSITIONS WITH SUNSCREEN AGENTS

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Name and Address of Applicant: UNILEVER AUSTRALIA LIMITED of 20-22 CAMBRIDGE STREET, EPPING NSW 2121 The following statement is a full description of this invention, including the best method of performing it known to me:- J 6277 (C) SKIN WHITENING COMPOSITIONS

WITH

SUNSCREEN AGENTS Field of the Invention The present invention relates to cosmetic compositions particularly useful for whitening skin and for protecting exposed skin against sunburn, cancer and even photoaging.

Background of the Invention A variety of whitening agents have been formulated in cosmetic compositions to remove darkened spots and enhance overall skin whitening. Placenta extract has been suggested more recently as a whitening agent. See U.S. 4,696, 813 owned by Sansho Seiyiku Company Limited of Japan. The whitening effect of many of these cosmetics has been unsatisfactory.

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The ideal whitening cosmetic composition should combine the whitening enhancement of the whitening agent and the blocking action of a sunscreen active.

Sunscreen compositions are also commonly used to protect exposed skin against sunburn, cancer and even photoaging. The active agent in the compositions functions by blocking passage of erythematogenic radiation to prevent its penetration into the skin.

Guerrero et al.

UNUS #96-0208-EA Sunscreen agents may be categorized in the following groups in the order of decreasing effectiveness as either highly chromophoric monomeric organic compounds, inorganic compounds and minimally chromophoric polymeric organic solvents. U.S. Patent No. 5,219,558 (Wooden, Jr.) and U.S. Patent No. 4,919,934 (Deafner) disclose chromophoric monomeric organic compounds such as the commercially common sunscreens octyl methoxycinnamate (Parsol MCX)(R), benzophenone-3 (Oxybenzone) and octyl dimethyl PABA.

Problems associated with such organic compounds include skin irritation.

Adverse allergic reaction can result in some people who are sensitive to the' chromophoric groups of the organic molecules. Moreover, it has been observed that i because of the mechanism of the actives, increasing the concentration of the organic sunscreen does not necessarily increase SPF and indeed it has been shown it may actually decrease the protective factor. This negative response has been attributed by some to micellar interference with the sunscreen over concentration. Thus it is desirable to minimize the level of such organic compounds. However, total replacement of chromophoric compounds, while may be desirable, is presently not feasible because high SPF compositions also require certain types of aesthetics.

Inorganic particulate compounds such as titanium dioxide, polyethylene, etc.

have been employed as sunscreen agents. The problem with the use of inorganic compounds is that high SPF values can only be achieved with high concentrations of these materials. Aesthetics unfortunately suffer as such high concentrations and clear formulas become opaque. High loading of the inorganic particulates can also form visible white foams on the skin perceived by consumers as a negative.

Polymeric organic particulates are a final category of these sunscreen materials. U.S. Patent No. 5,008,100 (Zecchino) supports oil and water emulsions Guerrero et al. UNUS #96-0208-EA containing polyethylene particles of a peractive sunscreen agent along with the traditional chromophoric organic compounds. Similar to the inorganic materials, polymeric particles are limited in their sunscreen effectiveness. Large amounts of such materials will have an adverse effect upon the formula aesthetics.

It is therefore an object of the present invention to provide a whitening composition which also functions as a sunscreen to maximize the sun protection factor, yet minimize the level of chromophoric monomeric organic compounds.

Another object of the invention is to provide a whitening composition in the form of an oil and water emulsion that exhibits improved aesthetics when applied to the skin.

Yet another object of the invention is to provide a whitening composition which enhances the whitening effect on skin while providing sun protection which has a much lower human irritancy rate than compositions of equivalent SPFs.

These and other objects of the present invention will more readily become apparent from the description and examples which follow.

Summary of the Invention A composition for enhancing the whitening effect of skin is provided which includes: a) from about 0.1 to about 30% by wt. of an organic sunscreen agent with a chromophoric group active within the ultraviolet radiation range from 290 to 400 nm; Guerrero et al. UNUS #96-0208-EA b) from about 0.1 to about 10% by wt. of an inorganic sunscreen selected from the group consisting of titanium dioxide, zinc oxide, barium sulfate, the ratio of organic sunscreen agent to inorganic sunscreen agent being 1:1 to 3:1; c) from about 0.05 to about 1 wt. of a coactive sunscreen agent selected from the group consisting of ethylene vinyl acetate copolymers; d) from about 0.1 to about 0.5 by wt. of a hydrophobically modified acrylate or methacrylate copolymer formed in an amount form about 50 to 99% by wt. of a monoolefinically unsaturated carboxylic acid or a anhydride monomer of 3 to 6 carbon atoms and in an amount from about 1 to about 50% by wt. formed from a long chain acrylate or methacrylate ester monomer; e) from about 0.05 to about 0.5 wt.% xanthan gum; f) from about 0.1 to about 5 wt. of placenta extract; and Sg) from about 1 to 99.9% of a cosmetically acceptable carrier.

Detailed Description of Preferred Embodiments It has been unexpectedly discovered that the combination of a rheological optimizer blend of a hydrophobically modified acrylate or methacrylate polymer and xanthan gum with a ethylene copolymer compound increases the sun protective factor (SPF) of certain chromophoric organic sunscreen compounds in combination with certain inorganic sunscreen compounds. Because of the boost in SPF from the copolymer mixture, the level of chromatophoric organic compound may be minimized to avoid skin irritancy and the level of inorganic compounds may be reduced to improve aesthetics of the product.

Guerrero et al.

UNUS #96-0208-EA In the preferred embodiment the composition exhibits an SPF of 15 or greater, preferably 15 to 25 with substantially no irritation to the user.

Accordingly a first critical element of the compositions is that of a hydrophobically modified acrylate or methacrylate polymer. The polymer is preferably a copolymer formed from about 50 to 99% by weight of a mono- olefinically unsaturated carboxylic acid or anhydride monomer of 3 to 6 carbon atoms and from about 1 to 50% by weight of a long chain Co 1 -Cao acrylate or methacrylate ester monomer. Optionally, there is included in the monomeric mixture a crosslinking monomer. In a preferred embodiment, amount of the carboxylic monomer is 80 to 99%, but especially 90 to 98% by weight, whereas amount of the acrylate monomer is from 20 down to especially 10 down to 2% by weight, based on the weight of the two monomers. Amounts of the carboxylic monomer and the acrylate ester monomer are based on the combined weight of both components. It should be understood that I more than one carboxylic monomer and more than one acrylate ester can be utilized to form the copolymer.

The preferred acrylic ester monomers having long chain aliphatic groups are derivatives of acrylic acid represented by the formula:

R

1

O

I II

CH

2 =C-C-O-R2 wherein R' is selected from hydrogen, methyl and ethyl groups and R 2 is selected from alkyl groups having from 10 to 30 carbon atoms and oxyalkylene and carbonyloxyalkylene groups, preferably alkyl groups of 10 to 22 carbon atoms. The oxyalkylene and carbonyloxyalkylene groups are particularly oxyethylene and carbonyloxyethylene groups. Representative higher alkyl acrylic esters are decyl Guerrero et al.

UNUS #96-0208-EA acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and myristyl acrylate, and the corresponding methacrylates.

Structures and syntheses of the hydrophobically-modified acrylate or methacrylate polymer can be found in U.S. Patent 3,915,921 (Schlatzer, U.S.

Patent 4,062,817 (Westerman) and U.S. Patent 4,509,949 (Huang et all of which are herewith incorporated by reference.

For purposes of the present invention, the hydrophobically-modified copolymer may be neutralized with a base to convert the free carboxylic acid groups pendent from the copolymer into their respectively neutralized salts. Suitable neutralization agents are alkali metal bases such as sodium hydroxide, potassium hydroxide and lithium hydroxide. Organic amine type bases may also be employed, the most preferable of which is.triethanolamine.

Commercially, the hydrophobically-modified copolymer as described above is available from the B.F. Goodrich Company under the trademark Carbopol 1382®. The INCI name is acrylates/Co-C3o alkyl acrylate cross-polymer.

Amounts of the hydrophobically-modified acrylate or methacrylate polymer will range from about 0.005 to about preferably from about 0.01 to about more preferably from about 0.1 to about 0.2% by weight.

A second critical element of the composition is the presence of xanthan gum in a similar amount to the amount of the acrylate/methacrylate polymer. The amount of xanthan gum is limited by the undesirable "gummy" feel imported to the emulsion during rub out. Xanthan gum is incorporated in a range of about 0.005 to about 1% by wt., preferably from about 0.01 to about 0.5% by wt., more preferably from about Guerrero et al. UNUS #96-0208-EA 0.1 to about 2% by wt.

A third critical element of the composition is a coactive sunscreen agent such as an ethylene vinyl copolymer compound. Amounts of this material may range from about 0.10 to about 5.00, preferably from about 0.5 to about 3.00, optimally from about 1 to about 2.00 by weight. The preferred compound is supplied by Allied Signal as AC-400 copolymer Preferably the sunscreen coactive and the hydrophobically modified acrylate or methacrylate polymer are present in a ratio of 1:1 to about 1:6.

Organic sunscreen of the invention have at least one chromophoric group absorbing within the ultraviolet range somewhere from 290 to 400 nm. Chromophoric organic sunscreen agents may be divided into the following categories (with specific o examples) including: p-Aminobenzoic acid, its salts and its derivatives (ethyl, isobutyl, glyceryl esters; pdimethylaminobenzoic acid); Anthranilates (o-aminobenzoates; methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, and cyclohexenyl esters); Salicylates (octyl, amyl, phenyl, benzyl, menthyl, glyceryl, and dipropyleneglycol esters); Cinnamic acid derivatives (menthyl and benzyl esters, a-phenyl cinnamonitrile; butyl cinnamoyl pyruvate); Dihydroxycinnamic acid derivatives (umbelliferone, methylumbelliferone, methylaceto-umbelliferone); Trihydroxycinnamic acid derivatives (esculetin, methylesculetin, daphnetin, and the glucosides, esculin and daphnin); Hydrocarbons (diphenylbutadiene, stilbene); Dibenzalacetone and benzalacetophenone; Naptholsulfonates (sodium salts of 2-naphthol-3,6-disulfonic and of 2-naphthol-6,8disulfonic acids); Dihydroxy-naphthoic acid and its salts; o- and p- Hydroxybiphenyldisulfonates; Coumarin derivatives (7-hydroxy, 7-methyl, 3-phenyl); Diazoles (2-acetyl-3-bromoindazole, phenyl benzoxazole, methyl naphthoxazole, Guerrero et al. Guerrro e al.UNUS #96-0208-EA various aryl benzothiazoles); Quinine salts (bisulfate, sulfate, chloride, oleate, and tannate); Quinoline derivatives (8-hydroxyquinoline salts, 2-phenyiquinoline); Hydroxyor methoxy-substituted benzophenones; Uric and vilouric acids; Tannic acid and its derivatives hexaethylether); (Butyl carbityl) (6-propyl piperonyl) ether; Hydroquinone; Benzophenones (Oxybenzone, Sulisobenzone, Dioxybenzone, Benzoresorcinol, 2,2',4,4'-Tetrahydroxybenzophenone, 2,2'-Dihydroxy-4,4'dim ethoxybenzophenone, Octabenzone; 4-1lsopropyl dibenzoylm ethane; Butylm ethoxydibenzoylm ethane; Etocrylene; and 4-isopropyl-dibenzoylmethane).

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4'-t-butyl m methoxyd ibenzoylm ethane, 2-hyd roxy-4-methoxybenzoph en one, octyldimethyl paminobenzoic acid, digalloyltrioleate, 2,2-dihydroxy-4-m ethoxybenzophen one, ethyl 4- [bis(hydroxypropyl)]aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2ethyl hexylsa licylate, glyceryl p-aminobenzoate, 3,3,5-trimrnethylcyclohexylsal icy late, methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate, 2-ethylhexyl pdimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonic acid, 2-(pacid and mixtures thereof.

Suitable commercially available organic sunscreen agents are those identified under the following table.

Guerrero et al. Guerrro e al.UNUS #96-0208-EA TABLE I I. a a.

a a. a a a.

CTFA NAME TRADE NAME SUPPLIER Benzophenone-3 UVINUL M-40 BASF Chemical Co.

Benzophenone-4 UVINUL MS-40 BASF Chemical Co.

Benzophenone-8 SPECTRA-SORB UV-24 American Cyanamid DEA-Methoxycinnamate BERNEL HYDRO Bernel Chemical Ethyl dihydroxypropyl-PABA AMERSCREEN P Amerchol Corp.

Glyceiyl PABA NIPA G.M.P.A. Nipa Labs.

Homosalate KEMESTER HMVS Humko Chemical Menthyl anthranilate SUNAROME UVA Felton Worldwide Octocrylene UVINUL N-539 BASF Chemical Co.

Octyl dimethyl PABA AMERSCOL Amerchol Corp.

Octyl methoxycinnamate PARSOL MCX Bernel Chemical Octyl salicylate SUNAROME WMVO Felton Worldwide PABA PABA National Starch acid EUSOLEX 232 EM Industries TEA salicylate SUNAROME W Felton Worldwide 2-(4-Methylbenzylidene)-camphor EUSOLEX 6300 EM Industries Benzophenone-1 UVINUL 400 BASF Chemical Co.

Benzophenone-2 UVINUL D-50 BASF Chemical Co.

Benzophenone-6 UVINUL D-49 BASF Chemical Co.

Benzophenone-12 UVINUL 408 BASF Chemical Co.

4-Isopropyl dibenzoyl methane EUSOLEX 8020 EM Industries Butyl methoxy dibenzoyl methane PARSOL 1789 Givaudan Roure Etocrylene UVINUL N-35 BASF Chemical Co.

Amounts of the aforementioned sunscreen agents will generally range from ab-out 0.1 to about 30%, preferably from about 2 to about 20%, optimally from about 3 to about 8% by weight.

Inorganic sunscreen compounds useful in the invention include titanium dioxide, Guerrero et al. UNUS #96-0208-EA zinc oxide, barium sulfate and mixtures thereof. Amounts of the material should be present in a range from about 0.50 to about preferably from about 1 to about 4, optimally 2 to about Relative ratios of the organic chromophoric monomeric organic compounds to the inorganic particulate compound will range from about 4:1 to 1:1, optimally from about 3:1 to 1:1 by weight.

The whitening agent useful to enhance the whitening effect of skin may be obtained from placenta extract. Placenta extract may be processed by any means conventionally used in the art such as the method described in U.S. 4,696,813.

Placenta extract is also commercially available under the trademark Placendol Col supplied by Pentapharm/Centerchem and Bio-Bpl supplied by Ikeda Corp. Placenta extract should be present in the composition in an amount from about 0.5 to about wt. preferably 1 to about 5 wt. optimally from about 2 to about 5 wt. Compositions of the present invention may include an aqueous phase or be totally aqueous. Advantageously the pH of such aqueous systems may range from about 8.0 down to Compositions of the present invention may also contain water-soluble vitamins, which may function as electrolytes. The term water-soluble defines substances with a solubility of at least preferably at least optimally at least 5% by weight in water. Illustrative water-soluble vitamins are Niacin, Vitamin B 2 Vitamin B 6 Vitamin C and Biotin. One source for Vitamin C is a product sold under the trademark of Vitazyme C(R) available from the Brooks Company. Niacin, Vitamin B and Biotin are available from Roche Pharmaceuticals. Total amount of vitamins in compositions according to the present invention may range from about 0.001 to about 1%, Guerrero et al.

UNUS #96-0208-EA preferably from about 0.01 to about 0.6, optimally from about 0.1 to about 0.5% by weight.

Two classes of keratolytic agents may also be effectively used in compositions of the present invention. The first category is represented by C7-C30 P-hydroxy carboxylic acids and their salts and esters. Illustrative of this category is salicylic acid as well as the alkalimetal and ammonium salts thereof. Suitable amounts of salicylic acid or salt may range from about 0.001 to about 10%, preferably between about 0.8 and about optimally between about 1 and 1.5% by weight.

The second class of keratolytic agent is the C2-C25 a-hydroxy alkanoic acids.

Illustrative of this group of materials are glycolic, lactic, a-hydroxyoctanoic acids and salts and esters thereof. The salts may be selected from alkalimetal, ammonium and C,-C20 alkyl or alkanolammonium counterions. Levels of a-hydroxyalkanoic acids may range from about 0.001 to about 10%, preferably between about 0.2 and optimally between about 0.4 and 0.5% by weight.

Compositions of the present invention may either be aqueous or anhydrous.

Preferably the compositions are aqueous, especially water and oil emulsions of the W/O or O/W variety. Water when present will be in amounts which may range from about 5 to about 90%, preferably from about 35 to about 65%, optimally between about 40 and 55% by weight.

Besides water, relatively volatile solvents may also be incorporated within compositions of the present invention. Most preferred are monohydric C,-C3 alkanols.

These include ethyl alcohol, methyl alcohol and isopropyl alcohol. The amount of monohydric alkanol may range from about 5 to about 50%, preferably from about to about 40%, optimally between about 25 to about 35% by weight.

Guerrero et al. UNUS #96-0208-EA Emollient materials in the form of silicone oils and synthetic esters may be incorporated into compositions of the present invention. Amounts of the emollients may range anywhere from about 0.1 to about 30%, preferably between about 1 and by weight.

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 or linear polydimethylsiloxanes containing from about 3 to about 9, preferably from about 4 to about 5, silicon atoms.

Linear volatile silicone materials generally have viscosities less than about centistokes at 25*C while cyclic materials typically have viscosities of less than about :10 centistokes.

e9 Nonvolatile 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 viscosities of from about 5 to about 100,000 centistokes at 250C.

Among the preferred non-volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 10 to about 400 centistokes at S: 250C.

Among the ester emollients are: Alkenyl or alkyl esters of branched or straight chain fatty acids having 9 to 22 carbon atoms. Examples thereof include isononyl isonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate, among others.

Guerrero et al.

UNUS #96-0208-EA Ether-esters such as fatty acid esters of ethoxylated fatty alcohols.

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 monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty esters, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and pentaerythritol fatty acid esters are satisfactory polyhydric alcohol esters.

Wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate.

Sterols esters, of which cholesterol fatty acid esters are examples thereof.

o The most preferred esters are octyldodecyl neopentanoate (available as Elefac I- 205®) and isononyl isononanoate.

Fatty acids having from 10 to 30 carbon atoms may also be included in the compositions of this invention. Illustrative of this category are pelargonic, lauric, myristic, palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic, ricinoleic, arachidic, behenic and erucic acids.

Humectants of the polyhydric alcohol-type may also be included in the compositions of this invention. The humectant aids in increasing the effectiveness of the emollient, reduces scaling, stimulates removal of built-up scale and improves skin feel. Typical polyhydric alcohols include glycerol, polyalkylene glycols and more Guerrero et al.

UNUS #96-0208-EA preferably alkylene polyols and their derivatives, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol, hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, glycerol homopolymers, propoxylated glycerol and mixtures thereof. For best results the humectant is preferably 1,3 butylene glycol. The amount of humectant may range anywhere from 0.5 to 30%, preferably between 1 and 15% by weight of the composition.

Collectively the water, solvents, silicones, esters, fatty acids, humectants and/or thickeners are viewed as cosmetically acceptable carriers for the compositions of the invention. Total amount of carrier will range from about 1 to 99.9%, preferably from about 80 to 99% by weight.

p Cosmetic compositions of the present invention may be in any form. These forms may include lotions, creams, roll-on formulations, mousses, aerosol sprays and pad-applied formulations.

Surfactants may also be present in cosmetic compositions of the present invention. Total concentration of the surfactant will range from about 0.1 to about preferably from about 1 to about 20%, optimally from about 1 to about 5% by weight of the total 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 C 1 o-C 20 fatty alcohol or acid hydrophobe condensed with from about 2 to about 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C 2 -Co 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- C 8

-C

2 0 fatty acids; and polyoxyethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and saccharide fatty amides methyl gluconamides) Guerrero et al.

UNUS #96-0208-EA are also suitable nonionic surfactants.

Preferred anionic surfactants include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C8-C20 acyl isethionates, C8-C20 alkyl ether phosphates and combinations thereof.

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 incompatibilities between the preservatives and other ingredients in the emulsion. Preservatives are preferably employed in amounts ranging from about 0.01% to about 2% by weight of the composition.

Minor adjunct ingredients may also be present in the cosmetic compositions.

S: Among them may be the water-insoluble vitamins such as Vitamin A Palmitate, Vitamin E Acetate and DL-panthenol.

Another adjunct ingredient can be that of an enzyme. Particularly preferred is superoxide dismutase, commercially available as Biocell SOD from the Brooks Company, USA.

Guerrero et al. UNUS #96-0208-EA Natural vegetable materials from renewable resources are often desirable in cosmetic compositions. For instance, cosmetic compositions of the present invention may include O-glucan derived from oats, commercially available under the trademark Microat SF from Nurture Inc., Missoula, Montana.

Colorants, fragrances, opacifiers and abrasives may also be included in compositions of the present invention. Each of these substances may range from about 0.05 to about preferably between 0.1 and 3% by weight.

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 weight unless otherwise indicated.

I* *o o* Ce o Guerrero et al. Guerrro e al.UNUS #96-0208-EA Example 1 A typically fully formulated whitening lotion according to the present invention is prepared as conventionally known and is described below: 00 00 *ee@ @00.0.

0 00 0 .0 00 *0 S 0@ 00 *0 S

OS

Ingredient WIW Deionized Water 51.8 Glycerine Butylene Glycol 0.9 Disodium EDTA 0.1 Methyl paraben 0.3 Xanthan Gum 0.1 Ca rbopol 13820 Tioveil AQ 2.4 Polym ethyl methacrylate Isononyl Isononanoate 2.3 Pentaerythrityl Tetraoctanoate Isostearic Acid 1.2 Elefac 1 2 0 5 3.8 Steareth 21 1.2 Steareth 2 0.3 Cetyl Alcohol Arlacel 165 VS (GMS/PEG)R) 1.7 Trilaureth-4 phosphate 0.20 P ropyl paraben 0.2 HEthyleneNinyl Acetate Copolymer 0.2 .5 0 Se S

S

S.

5

S

5055 Guerrero et al.

UNUS #96-0208-EA Xalifin 15(R) 0.2 Parsol MCX(R) Dow Corning 344(R) Gransil PM 5 6 Vitamin E Acetate 0.1 Triethanolamine Phenoxyethanol 0.7 Placenta extract Sodium Hyalurononate 0.95 Seamollient 0.25 DL-Panthenol 0.3 The foregoing descriptions and examples illustrate selected embodiments of the present invention. In like thereof, various modifications will be suggested to one skilled in the art, all of which are within the spirit and purview of this invention.

Guerrero et al. UNUS #96-0208-EA Example 2 Samples of the compositions according to Example 1, were prepared incorporating 0.05 wt.% and 0.15 wt.% Carbopol 13 82

R

to provide a SPF of 16.

Each of the samples were stored in an oven at 250C, 43 0 C and under alternating temperature, 40C to 430C. Stabilities of the samples were visibly observed an determined with a Brookfield Viscosity, Spindle #3 at 20 rpm at 250C. PH values were measured for each of the samples. These measurements were conducted for up to at least 6 weeks.

.o The sample containing only 0.05 wt.% Carbopol 138 2

R

phase separated in less than two weeks and the titanium dioxide precipitated out of the system.

The sample within the invention was observed to have no syneresis, phase separation, or aggregation of TiO 2 for up to at least 6 weeks at a SPF of 16.

Guerrero et al.

UNUS #96-0208-EA Sample 2A Sample 2B Ingredient %I %WI

WI

Deionized Water 51.8 56.8 Glycerine 3.0 Butylene Glycol 0.9 0.9 Disodium EDTA 0.1 0.1 Methylparaben 0.3 0.3 Xanthan Gum 0.1 0.1 Carbopol 1382 7.5 Tioveil AQ 2.4 2.4 Polymethylmethacrylate 1.0 Isononyl Isononanoate 2.3 2.3 Pentaerythrityl Tetraoctanoate 1.0 Isostearic Acid 1.2 1.2 Elefac 1-205R) 3.8 3.8 Steareth-21 1.2 1.2 Steareth-2 0.3 0.3 Cetyl Alcohol 1.0 Arlacel 165 VS (GMS/PEG)(R) 1.7 1.7 Trilaureth-4 phosphate 0. 0.

Guerrero et al.

UNUS #96-0208-EA Propylparaben 0.2 EthyleneNinyl Acetate Copolymer 0.2 0.2 Xalifin 15" 1 0.2 0.2 Parsol MCXI" 5.0 Dow Coming 344(R) 5.5 Gransil PM 56(R) 1.0 Vitamin E Acetate 0.1 0.1 Triethanolamine 0.5 Phenoxyethanol 0.7 0.7 Placenta extract 3.0 Sodium Hyaluronate 0.95 0.95 Seamollient"R) 0.25 0.25 DL-Panthenol 0.3 0.3 The SPF determinations were carried out using an Corporation, Ayer, Massachussets.

SPF 290 Analyzer from Optometrics The SPF 290 Analyzer provides in-vitro SPF determinations for sunscreen products.

The data generated has been found to provide a ranking method that aids in the development and optimization of sunscreen formulations.

The SPF 290's optical scanning system consists of a xenon light source, an integrating collection sphere, color compensating filters, diffusion gratings, a monochrometer, and a detector connected to a computer.

Guerrero et al. UNUS #96-0208-EA During testing, the light emitted by the xenon bulb encounters the product and substrate and is collected in the integrating sphere. The light, now, passes through a monochrometer optimized for efficiency in the UV range. The radiation exiting the monochrometer impacts upon a photosensitive surface, generating a signal that is proportional to the intensity of the radiation striking the surface. A blank piece of substrate is used as a reference. The SPF 290 Analyzer records 23 data points as the monochrometer moves from 290 to 400 nm. in 5 nm. intervals. As a result of the measurements performed on the substrate as well as on the substrate with the sample product, a Monochromatic Protection Factor is developed. The MPF is, then, defined as the ratio of the signal at a specific wavelength of the substrate with sample to the original reference substrate without sample.

Samples 3A through 3G demonstrate the critical interrelationships among the active sunscreen ingredients Parsol MCX(R), Tioveil the rheology modifiers Xanthan Gum and Carbopol 1382(R and the structure builder EthyleneNinyl Acetate Copolymer (A-C 400R) Copolymer).

3A 3B 3C 3D 3E 3F Ingredient W/W Deionized Water qs qs qs qs qs qs qs Glycerine 3.0 3.0 3.0 3.0 3.0 3.0 Butylene Glycol 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Methylparaben 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Xanthan Gum 0.09 0.09 0.09 0.09 Guerrero et al. Guerrro e al.UNUS #96-0208-EA

C

C

C

Carbopol 1382R) 6.2 6.2 6.2 6.2 6.2 Tioveil AQ 2.4 2.4 2.4 2.4 2.4 2.4 Polymethylmethacrylate 1.0 1.0 1.0 1.0 1.0 1.0 Isononyl Isononanoate 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Pentaerythrityl Tetraoctanoate 1.0 1.0 1.0 1.0 1.0 1.0 Isostearic Acid 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Elefac 1-205(R) 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Steareth-21 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Steareth-2 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Cetyl Alcohol 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Behenyl Alcohol 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Arlacel 165 VS(R) (GMS/PEG) 1.7 1.7 1.7 1.7 1.7 1.7 1.7 Trilaureth-4 Phosphate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Propylparaben 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Ethylene/Vinyl Acetate Copol. 0.2 0.2 0.2 0.2 0.2 Xalifin 15(R) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Parsol MCX(R) 5.0 5.0 5.0 5.0 5.0 Dow Corning 344R) 5.5 5.5 5.5 5.5 5.5 5.5 Gransil PM 56R) 1.0 1.0 1.0 1.0 1.0 1.0 Vitamin E Acetate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethanolamine 0.5 0.5 0.5 0.5 0.5 0. 5 10.5 I Guerrero et al.

Phenoxyethanol UNUS #96-0208-EA *r Placenta Extract 3.0 3.0 3.0 3.0 3.0 3.0 Sodium Hyaluronate 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Seamollient" 0.25 0.25 0.25 0.25 0.25 0.25 0.25 DL-Panthenol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Fragrance 0.06 0.06 0.06 0.06 0.06 0.06 0.06 The corresponding in-vitro SPF for samples values are depicted on the chart below.

3A 3B 3C 3D 3E 3F 3G SPF 21.5 4.7 11.7 16.1 16.2 11.8 15.4 From the above SPF results, it can be seen that a significantly higher SPF (sample 3A) was achieved when the active sunscreening ingredients Parsol MCX(R), Tioveil AQ the rheology modifiers Xanthan Gum, Carbopol 1382(R)) and the structure builder EthyleneNinyl Acetate Copolymer A-C400 CopolymerR) were used in the same formulation.

In practical terms, such a combination will allow the achievement of prototypes of a specific SPF value using a very significantly lower concentration of potentially irritating organic sunscreening agents.

Claims (5)

1. A cosmetic composition for enhancing the whitening effect of the skin comprising: a) from about 0.1 to about 30% by wt. of an organic sunscreen agent with a chromophoric group active within the ultraviolet radiation range from 290 to 400 nm; b) from about 0.1 to about 10% by wt. of an inorganic sunscreen selected from the group consisting of titanium dioxide, zinc oxide and barium sulfate and mixtures thereof, the ratio of organic sunscreen agent to inorganic sunscreen agent being 1:1 to 3:1; c) from about 0.05 to about 1 wt. of a coactive sunscreen agent selected from the group consisting of ethylene/vinyl acetate copolymers; d) from about 0.1 to about 0.5 of a hydrophobically modified acrylate or methacrylate copolymer formed in an amount form about 50 to 99% by wt. of a monoolefinically unsaturated carboxylic acid or a anhydride monomer of 3 to 6 carbon atoms and in an amount from about 1 to about 50% by wt. formed from a long chain acrylate or methacrylate ester monomer; from about 0.05 to about 0.5 wt.% xanthan gum; e from about 0.5 to about 5 wt. of placenta extract; and g) from about 1 to 99.9% of a cosmetically acceptable carrier.

2. A composition according to claim 1, wherein the SPF of the composition is 15 or greater. g b Guerrero et al. UNUS #96-0208-EA

3. A composition according to claim 1 wherein the organic sunscreen agent is selected from the group consisting of benzophenone-3, benzophenone-4, benzophenone-6, benzophenone-8, benzophenone-12, butyl methoxy dibenzoyl methane, PABA, octyl dimethyl PABA, octyl methoxycinnamate and combinations thereof.

4. A composition according to claim 1 further comprising from about 0.5 to about by weight of water insoluble vitamins.

5. A method for enhancing the whitening effect of skin comprising the steps of: applying a cosmetic composition comprising: a) from about 0.1 to about 30% by wt. of an organic sunscreen agent with a chromophoric group active within the ultraviolet radiation range from 290 to 400 nm, b) from about 0.1 to about 10% by wt. of an inorganic sunscreen selected from the group consisting of titanium dioxide, zinc oxide and barium sulfate and mixtures thereof, the ratio of organic sunscreen agent to inorganic sunscreen agent being 1:1 to 3:1, c) from about 0.05 to about 1 wt. of a sunscreen coactive selected from the group consisting of ethylene/vinyl acetate copolymers, d) from about 0.1 to about 0.5 of a hydrophobically modified acrylate or methacrylate copolymer formed in an amount form about 50 to 99% by wt. of a monoolefinically unsaturated carboxylic acid or a anhydride monomer of 3 to 6 carbon atoms and in an amount from about 1 to about 50% by Guerrero et UNUS #96-0208-EA wt. formed from a long chain acrylate or methacrylate ester monomer, e) from about 0.05 to about 0.5 wt.% xanthan gum, f) from about 0.5 to about 5 wt. of placenta extract, and g) from about 1 to 99.9% of a cosmetically acceptable carrier, to substantially enhance the whitening effect of skin. F. .O BIN yereay