WO2008058982A1

WO2008058982A1 - Cosmetic composition

Info

Publication number: WO2008058982A1
Application number: PCT/EP2007/062315
Authority: WO
Inventors: Asuka Nishimura; Yusuke Nomoto; Masatoshi Sakurai
Original assignee: Hindustan Unilever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2006-11-16
Filing date: 2007-11-14
Publication date: 2008-05-22
Anticipated expiration: 2009-05-16
Also published as: AR063852A1; GB0622847D0; JP2010510187A

Abstract

A cosmetic composition is provided which includes a water-soluble sulfo-substituted polysaccharide, a phospholipid and a carrier. The composition exhibits sunscreen protective properties. The preferred sulfo-substituted polysaccharide is sodium stearoxy pg- hydroxy ethyl cellulose sulfonate.

Description

COSMETIC COMPOSITION

BACKGROUND OF THE INVENTION

The invention concerns cosmetic compositions having sunscreen properties, particularly those in emulsion form.

Sunscreen compositions are commonly used during outdoor work or leisure for protection of exposed skin against sunburn, cancer and even photoaging. Many effective sunscreen preparations are sold commercially or are described in cosmetic or pharmaceutical literature. In general, sunscreen preparations are formulated as creams, lotions or oils containing as the active agent an ultraviolet radiation absorbing chemical compound. The active agent functions by blocking passage of erythematogenic radiation thereby preventing its penetration into the skin.

The ideal sunscreen formulation should be non-toxic and non-irritating to skin tissue and be capable of convenient application in a uniform continuous film. The product should be sufficiently chemically and physically stable so as to provide an acceptable shelf life upon storage. It is particularly desirable that the preparation should retain its protective effect over a prolonged period after application. Thus, the active agent when present on the skin must be resistant to chemical or photodegradation, to absorption through the skin, and to removal by perspiration, skin oil, or water. For aesthetic reasons, the product should be substantially odorless (or be capable of being scented) and be non-staining to the skin or clothing.

Sunscreen agents in the order of decreasing effectiveness may be categorized as either highly chromophoric monomeric organic compounds, inorganic compounds and minimally chromophoric polymeric organic solids.

Chromophoric monomeric organic compounds are subject to certain problems. One of the more important problems is that of skin irritation. Some people are quite sensitive to organic molecules with chromophoric groups. Adverse allergic reactions can result. Therefore, it would be quite desirable to minimize the level of such compounds in sunscreen compositions. Total replacement of chromophoric organic compounds, while desirable, is presently not feasible for high sun protective factor (SPF) compositions that also require certain types of aesthetics. lnorganic particulate compounds such as titanium dioxide have been employed as sunscreen agents. In fact, titanium dioxide is quite popular with marketers advertising them as "natural sunscreens". Illustrative of this technology is US 5 215 749 and US 5 188 831 , both to Nicoll et al. The problem with inorganic particulate compounds is that high SPF values can only be achieved with high concentrations of these materials. Unfortunately aesthetics suffer at such high concentrations. Clear formulas become opaque. High loadings also tend to form visible white films on the skin which consumers perceive negatively.

Accordingly it is an object of the present invention to provide a cosmetic composition with sunscreen properties in the form of an oil and water emulsion which minimizes the level of potentially irritating organic sunscreens while maximizing the sunscreen protective factor efficiency.

Another object of the present invention is to provide the benefits of at least some sun protection in a cosmetic composition.

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 cosmetic composition is provided which includes:

(i) from 0.001 to 10% by weight a water-soluble sulfo-substituted polysaccharide; (ii) from 0.001 to 5% by weight of a phospholipid; and (iii) a cosmetically acceptable carrier vehicle.

DETAILED DESCRIPTION OF THE INVENTION

Now it has been discovered that an increased sun protective factor is achievable in a water and oil emulsion formulated with a water-soluble sulfo-substituted polysaccharide and a phospholipid. The combination also improves water repellency of the formulation. This invention is not only suitable for cosmetics with sunscreen as a primary purpose, but also extends to general cosmetic formulas. These include foundations, face powders, eye shadow, mascara, anti-aging creams/lotions and skin-lightening products. Accordingly, a first component of the present invention is that of a water-soluble sulfo- substituted polysaccharide. Preferably the polysaccharide will be a cellulose with a first substituent group being sulfated or sulfonated hydrophilic moiety (particularly a CrC₅ sulfoalkyl or salt thereof) and a second substituent group being a C₈-C₄O alkyl or substituted alkyl hydrophobic moiety, wherein the hydrophilic and hydrophobic moiety substitution are in a molar ratio from 1 :100 to 100:1. The degree of substitution per each monosaccharide of the polysaccharide may range from 0.001 to 2.0.

Amounts of the sulfo-substituted polysaccharide may range from 0.001 to 10%, preferably from 0.5 to 5%, more preferably from 0.25 to 1% by weight of the cosmetic composition.

A particularly preferred substituted sulfo-substituted polysaccharide has the chemical name sodium hydroxyethylcellulose hydroxypropylstearoylether hydroxypropylsulfonate, which is recognized under the INCI nomenclature of Sodium Stearoxy PG-Hydroxyethyl Cellulose Sulfonate, and commercially available from the Kao Corporation under the name POIZ 310. The structure is as follows.

A further important component of compositions according to the present invention is a phospholipid (known also as a phosphatide). Examples of suitable phosphatides are lecithin, phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl inositol, diphosphatidyl glycerol and mixtures thereof. Lysophosphoglycerides may also serve as the phosphatide. Preferred from among the foregoing list is lecithin. Suitable lecithin may be derived from soy bean, egg yolk and can be hydrogenated or not hydrogenated. Hydroxylated lecithin, lyso-lecithin and sphingomyelin also may be utilized. Amounts of the phosphatide may range from 0.001 - A -

to 5%, preferably from 0.01 to 2%, preferably from 0.1 to 1 %, optimally from 0.3 to 0.8% by weight of the cosmetic composition.

Although in many preferred formulations, inorganic and organic sunscreens are absent, some amounts of these materials may be formulated with the compositions of the present invention.

Suitable inorganic sunscreen agents are particularly titanium dioxide and zinc oxide. Other inorganic powders useful for the invention include iron oxide, talc, mica, barium sulphate, calcium carbonate, zirconium oxide, cerium oxide, hydroxyapatite, sericite and combinations thereof. These agents in powder form should be particulates having an average particle size ranging from 0.005 to 5 micron (i.e. 5 nm to 5,000 nm), preferably from 0.01 to 1 micron and optimally from 15 to 100 nm. Advantageously the agents should be of the oil-dispersible variety exhibiting hydrophobic surface properties. Hydrophobicity may be achieved by applying a hydrophobic coating to the inorganic sunscreen agent particles. Typical coatings include metal soaps such as aluminum stearate, aluminum laurate or zinc stearate; or coatings with organosilicone compounds. The most preferred agent is titanium dioxide. Amounts of the inorganic sunscreen agent may range from 0.01 to 20%, preferably from 0.5 to 10%, optimally from 1 to 5% by weight of the cosmetic composition.

Organic sunscreen agents suitable for this invention have at least one chromophoric group absorbing within the ultraviolet ranging from 280 to 400 nm. Chromophoric organic sunscreen agents may be divided into the following categories (with specific examples) including: p-aminobenzoic acid, its salts and its derivatives (ethyl, isobutyl and glyceryl esters; p-dimethylaminobenzoic 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, alpha-phenyl cinnamonitrile; butyl cinnamoyl pyruvate); dihydroxycinnamic acid derivatives (umbelliferone, methylumbelliferone and methylaceto-umbelliferone); trihydroxycinnamic acid derivatives (esculetin, methylesculetin, daphnetin and the glucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene and stilbene); dibenzalacetone and benzalacetophenone; naphtholsulfonates (sodium salts of 2-naphthol-3,6-disulfonic and of 2-naphthol-6,8- disulfonic acids); dihydroxy-naphthoic acid and its salts; o- and p- hydroxybiphenyldisulfonates; coumarin derivatives (7-hydroxy, 7-methyl and 3-phenyl); diazoles (2-acetyl-3-bromoindazole, phenyl benzoxazole, methyl naphthoxazole and various aryl benzothiazoles); quinine salts (bisulfate, sulfate, chloride, oleate and tannate); quinoline derivatives (8-hydroxyquinoline salts and 2-phenylquinoline); hydroxy- or methoxy-substituted benzophenones; uric and vilouric acids; tannic acid and its derivatives (e.g. hexaethylether); (butyl carbityl) (6-propyl piperonyl) ether; hydroquinone; benzophenones (oxybenzone, sulisobenzone, dioxybenzone, benzoresorcinol, 2, 2', 4,4'- tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and octabenzone); 4-isopropyldibenzoylmethane; butylmethoxydibenzoylmethane; etocrylene; and 4-isopropyl-dibenzoylmethane.

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4'-t-butyl methoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethyl p- aminobenzoic acid, digalloyltrioleate, 2,2-dihydroxy-4-methoxybenzophenone, ethyl A- [bis(hydroxypropyl)]aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2- ethylhexylsalicylate, glyceryl p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate, methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate, 2-ethylhexyl p- dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonic acid, 2-(p- dimethylaminophenyl)-5-sulfoniobenzoxazoic acid and mixtures thereof.

Amounts of the organic sunscreen agent may range from 0.1 to 10%, preferably from 0.2 to 2%, more preferably from 0.6 to 1.5%, optimally from 0.8 to 1% by weight of the cosmetic composition.

Cosmetic compositions of the present invention will have a cosmetically acceptable carrier vehicle in amounts from 10 to 99% by weight. Carriers include water, oils and mixtures thereof. Advantageously the carrier is an emulsion containing an oil and a water phase. Most preferred are oil-in-water emulsions. Water constituting the latter phase will be present in an amount from 20 to 99% by weight thereof. Preferably the level of water may range from 50 to 95%, optimally between 70 and 90% by weight of the cosmetic composition.

Emollient materials may form the oil component according to the present invention.

These emollient materials may be selected from hydrocarbons, silicones, fatty alcohols, synthetic or natural esters and combinations thereof. Amounts of the emollient oil will range from 0.5 to 50%, preferably from 1 to 20%, optimally from 5 to 10% by weight of the cosmetic composition.

Hydrocarbons encompass mineral oil, terpenes (such as squalene), Cn-Ci₃ isoparaffins, polyalphaolefins (especially isohexadecane) and petroleum jelly.

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 3 to 9, preferably from 4 to 5, silicon atoms. Examples of commercially available volatile silicone oils are Dow Corning® 344 and Dow Corning® 345.

Non-volatile silicone oils useful as an emollient material include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. The essentially non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from about 5 x 10^"6 to 0.1 m²/s at 25⁰C. Among the preferred non-volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 1 x 10^"5 to about 4 x 10^"4 m²/s at 25⁰C.

Silicone copolyols are useful as emollient and emulsifying materials within the context of the present invention. Particularly preferred is Dow Corning® 3225C fluid, a mixture of cyclomethicone and dimethicone copolyol having viscosity at 25⁰C of 600-2000 cps and a specific gravity of 0.963.

Among the ester emollients are:

(1 ) Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms. Examples thereof include isoarachidyl neopentanoate, isononyl isononanoate, oleyl myristate, oleyl stearate, octyl stearate and oleyl oleate.

(2) Ether-esters such as fatty acid esters of ethoxylated fatty alcohols.

(3) Polyhydric alcohol esters. Ethylene glycol mono and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 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, and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters.

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

(5) Mono-, di- and triglyceride esters such as PEG-8 caprylic/capric triglyceride.

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

Natural esters which may be employed as emollients include sunflower seed oil, safflower oil, cotton seed oil, rape seed oil, palm kernel oil, palm oil and mixtures thereof.

Fatty alcohols may also serve as emollients. These are typically formed from 10 to 30 carbon atoms and include cetyl, myristyl, palmityl, stearyl, isostearyl, hydroxystearyl, oleyl, linoleyl, behenyl alcohols and mixtures thereof.

Optionally there may be present in the sunscreen emulsion compositions of the present invention a variety of other materials. Examples include fatty acids, humectants, thickeners/viscosifiers, surfactants, preservatives, biologically active materials and other adjunct ingredients. These are described more fully below.

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. Amounts may range from 0.1 to 20%, preferably from 1 to 10%, optimally from 2 to 5% by weight of the cosmetic composition.

Humectants of the polyhydric alcohol-type can be formulated into 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 (known also as glycerin), polyalkylene glycols and more 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, isoprene glycol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of humectant may range anywhere from 0.5 to 30%, preferably between 1 and 15% by weight of the cosmetic composition.

Thickeners/viscosifiers in amounts from 0.01 to 5% by weight of the cosmetic composition may also be included. As known to those skilled in the art, the precise amount of thickeners can vary depending upon the consistency and thickness of the composition which is desired. Exemplary thickeners are xanthan gum, sodium carboxymethyl cellulose, hydroxyalkyl and alkyl celluloses (particularly hydroxypropyl cellulose), and cross-linked acrylic acid polymers (Carbomers) such as those sold by Noveon Corporation under the Carbopol and Ultrez trademarks.

Surfactants or emulsifiers can be formulated into cosmetic compositions of the present invention. Total concentration of the surfactant may range from 0.1 to 40%, preferably from 1 to 20%, optimally from 1 to 5% by weight of the cosmetic 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 Ci₀-C₂O fatty alcohol or acid hydrophobe condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; the C₂-Ci₀ alkyl phenols condensed with from 2 to 20 moles of alkylene oxide; mono- and di- fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di- C₈-C₂₀ fatty acids; and polyoxyethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and saccharide fatty amides (e.g. methyl gluconamides) are also suitable nonionic surfactants.

Preferred anionic surfactants include soap, alkyl ether sulfate and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C₈-C₂₀ acyl isethionates 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 disodium EDTA, 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 0.01 % to 2% by weight of the cosmetic composition.

Anti-oxidants may be included within the compositions of the present invention. Representative anti-oxidants include butyl hydroxytoluene (BHT), butyl hydroxyanisole (BHA), tocopherols, nordihydrogualaretin, propyl gallate and fatty acid esters of ascorbic acid.

Compositions of the present invention may also contain vitamins and flavanoids. Illustrative water-soluble vitamins are niacinamide, vitamin B₂, vitamin B₆, vitamin C and biotin. Among the useful water-insoluble vitamins are vitamin A (retinol), vitamin A palmitate, ascorbyl tetraisopalmitate, vitamin E (tocopherol), vitamin E acetate and DL- panthenol. A particularly suitable vitamin B₆ derivative is pyridoxine palmitate. Among the preferred flavanoids are glucosyl hesperidin and rutin. Total amount of vitamins or flavanoids when present in compositions according to the present invention may range from 0.001 to 10%, preferably from 0.01 % to 1 %, optimally from 0.1 to 0.5% by weight of the cosmetic composition.

Desquamation agents are further optional components. Illustrative are the alpha- hydroxycarboxylic acids and beta-hydroxycarboxylic acids and salts of these acids. Among the former are salts of glycolic acid, lactic acid and malic acid. Salicylic acid is representative of the beta-hydroxycarboxylic acids. Amounts of these materials when present may range from 0.1 to 15% by weight of the cosmetic composition.

A variety of herbal extracts may optionally be included in compositions of this invention.

Illustrative are citrus unshui, chinpi, saxifrage sarmentosa, camu camu, pomegranate, white birch (Betula Alba), green tea, chamomile, licorice and extract combinations thereof. The extracts may either be water soluble or water-insoluble carried in a solvent which respectively is hydrophilic or hydrophobic. Water and ethanol are the preferred extract solvents.

Colorants, fragrances, opacifiers and abrasives may also be included in compositions of the present invention. Each of these substances may range from 0.05 to 5%, preferably between 0.1 and 3% by weight of the cosmetic composition.

The term "comprising" is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

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.

EXAMPLE 1 A representative sunscreen composition of the present invention in the form of a lotion is outlined under table I.

TABLE I

EXAMPLE 2

Illustrated herein is a skin cream according to the present invention.

TABLE

¹ Isohexadecane (Presperse Inc., South Plainfield, NJ)

² Polyacrylamide(and)C13-14 isoparaffin(and) laureth-7 (Seppic Corp, Fairfield, NJ)

³ Dimethicone(and)dimethiconol (Dow Corning Corp. Midland, Ml) ⁴ Sorbitan monostearate and sucrococoate (ICI Americas Inc., Wilmington, DE)

⁵ Sucrose ester of fatty acid

⁶ DMDM hydantoin (and) iodopropynyl butylcarbamate (Lonza Inc., Fairlawn, NJ)

EXAMPLE 3

Experiments were conducted to evaluate the sun protective factor effects with elements of the present invention. Table III reports on the constituents of four evaluated formulas.

TABLE

SPF for each formulation was measured on an Optometric LLC SPF-290 instrument according to a standard FDA procedure (Department of Health and Human Services, FDA, USA: Sunscreen drug products for over-the-counter human use, Final Monograph Federal Register. 64198, 276866-27693, 21 May 1999 (provisional)). The analyzed wavelength ranged from 290 to 400 nm. Each sample at a weight of 0.08 g per 40 cm² was supported on a Transpore™ tape (3M) for the optical anaylsis. Results are recorded in the table below. TABLE IV

Sample A is representative of the present invention. Sample D is formulated identical to sample A except that lecithin was removed. The lower SPF for sample B demonstrated the importance of lecithin. Sample C contains lecithin but none of the sulfo-substituted polysaccharide (i.e. POIZ-310). It is evident that POIZ has importance in raising SPF. These experiments demonstrate the interactivity of POIZ 310 and lecithin.

EXAMPLE 4

A foundation lotion suitable for the present invention is illustrated in table V.

TABLE V

EXAMPLE 5

A liquid face powder according to the present invention is illustrated in table Vl below. TABLE Vl

EXAMPLE 6

A make-up base according to the present invention is provided in table VII.

TABLE VII

EXAMPLE 7

A liquid eye shadow formula according to the present invention is reported in table VIII. TABLE VIII

EXAMPLE 8

A liquid blush according to the present invention is illustrated in table IX below.

TABLE IX

EXAMPLE 9

A water-proof mascara according to the present invention is described in table X below.

TABLE X

EXAMPLE 10

A make-up base for use in cold weather (shittori type) is reported in table Xl below.

TABLE XI

EXAMPLE 11

A gel lotion of the sarasara type according to the present invention is recorded in table XII below.

TABLE XII

Claims

1. A cosmetic composition comprising:

(i) from 0.001 to 10% by weight a water-soluble sulfo-substituted polysaccharide;

(ii) from 0.001 to 5% by weight of a phospholipid; and

(iii) a cosmetically acceptable carrier vehicle.

2. The composition according to claim 1 wherein the water-soluble sulfo-substituted polysaccharide is a cellulose with a first substituent group which is a sulfated or sulfonated hydrophilic moiety and a second substituent group which is a C₈-C₄₀ alkyl or substituted alkyl hydrophobic moiety, wherein the hydrophilic and hydrophobic moiety substitution are in a molar ratio from 1 :100 to 100:1.

3. The composition according to claim 1 wherein the sulfo-substituted polysaccharide is sodium hydroxyethylcellulose hydroxypropylstearoylether hydroxypropylsulfonate.

4. The composition according to claim 1 wherein the phospholipid is lecithin.

5. The composition according to claim 1 further comprising a hydrophobic surface treated inorganic powder.

6. The composition according to claim 5 wherein the hydrophobic surface treated inorganic powder is selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, talc, mica, barium sulfate, calcium carbonate, zirconium oxide, cerium oxide, hydroxyapatite, sericite and combinations thereof.

7. The composition according to claim 1 further comprising an organic sunscreen agent having at least one chromomorphic group absorbing within the ultraviolet ranging from 280 to 400 nm.