ANHYDROUS COSMETIC COMPOSITIONS WITH DERMATOLOGICALLY ACTIVE AGENTS

Abstract: Novel cosmetic compositions containing topical delivery systems for polar dermatologically active agents are disclosed. Active agents, for example, skin revitalizing alpha hydroxy acids are absorbed or adsorbed on to preferably porous carrier particles with the assistance of a viscous polar solvent such as glycerin, if necessary, and dispersed in an anhydrous cosmetic base along with a film-forming system. Such compositions can be formulated into a variety of different cosmetic products, for example eye shadows, eye treatment primers and lip treatments, each providing significant immediate cosmetic benefits and longer term dermatologic activity.

Description: ANHYDROUS COSMETIC COMPOSITIONS WITH DERMATOLOGICALLY ACTIVE AGENTS TECHNICAL FIELD The present invention relates to cosmetic compositions including delivery systems that provide new ways of delivering dermatologically active agents to cosmetically significant areas of the stratum corneum. Compositions of the invention are particularly, but not exclusively, useful as eye enhancers to provide cosmetic benefits to eye areas such as the eyelids, under eye areas and to the canthus or outer eye corner and are also useful for cosmetic treatment of the lips and other topical areas. The invention includes novel film-forming systems to assist delivery of the active agent. These film-forming systems yield supplementary enhancements and are useful independently of the delivery system. BACKGROUND The eyes themselves are the focus of any person's identity and personality as well as a focal point of attention for others. In any face-to-face encounter, the eyes provide a powerful medium of unspoken communication. The appearance of the eyelids and facial areas around the eyes is critical to the appearance of the eyes, and hence to the impression one person receives of another. Accordingly, eye-treatment compositions comprise an important segment of the cosmetics industry. The eyes are cosmetically a sensitive and sometimes difficult area to treat. They are subject to congenital defects, deficiencies and disorders and the appearance of the eye areas can quickly deteriorate owing to aging, the effects of weather, diet and so on. Quality cosmetic treatment of eye areas can bring great visual and psychological benefits to an individual by making striking improvements in their appearance. Some common eye area problems include wrinkling, cracking, formation of fine lines, blotching and discoloration. These problems may blemish the upper and lower eyelids, particularly the under eye area and also the corners of the eye, especially the outer corner known as "the canthus" that are prone to form cracks and lines, often inelegantly referenced as "crow's feet". In response to these problems, the cosmetics industry has offered a wide range of remedies to conceal, fill, color or otherwise modulate the appearance of unattractive eye areas. Mascaras, eyeliners and other eyelash treatments are used to enhance and define the appearance of the eyelashes, eyebrows and the edges of the eyelids and can have a beneficial and sometimes theatrical impact on the eyes as a whole. More significant to the purposes of the present invention are cosmetics used for treating the major dermal areas in the vicinity of the eye, notably the eyelids, the under-eye area and the outer eye corner areas. Such cosmetics are eye shadows, eye creams, and eyeliners. Although general use cosmetics such as foundations and makeups can be used in the eye area, caution is needed because of the risk of contaminating the eye with stinging or irritating allergenic ingredients or of inducing swelling or bacterial infection. A wide range of eye treatment cosmetics is available at any cosmetics outlet and the patent literature is replete with hundreds if not thousands of proposals and solutions to the various problems that arise in providing a desired level of cosmetic enhancement of the eye area. See for example Mercado U.S. Patent No. 4,783,333 and Giezendanner U.S. Patent 5,073,364, the disclosures of which are hereby incorporated herein by reference thereto. However, at the date of this application none of these proposals and solutions provides a wholly satisfactory cosmetic eye area treatment for many users. Existing eye shadows usually begin to fade within a few hours of application, can develop distinct creases on susceptible complexions and may be readily subject to water damage from tears, rain, perspiration or the like. Eye shadow primers can alleviate these problems but provide no structural der atological benefits. Other eye cosmetics can be difficult to apply smoothly or evenly, or may have an unpleasant or tacky feel, or poor film-forming capabilities (being hard to spread) , or have high drag or may be difficult to remove. Few eye cosmetics provide long term structural dermatological improvements, except for special-purpose eye creams and moisturizers, containing skin revitalizing ingredients. Generally, such eye creams are intended for use at night and will not hold eye shadow satisfactorily so that they cannot be used for normal daytime wear because they do not provide significant enhancement of appearance. Theoretically, it would be desirable to avoid separate application steps for cos etically effective and der atologically active ingredients by directly incorporating a dermatologically active ingredient into an eye cosmetic composition. However, there are difficulties. The term M dermatologically active" is used herein to describe materials that act on the skin to provide a long term improvement of one kind or another, being an improvement that endures or begins after the cosmetic makeup is removed. Thus, dermatological activity is to be distinguished from cosmetic properties that are only effective while the cosmetic is present on the skin. There are many chemicals which have a profound physiological effect on the skin. One group of such dermatologically active compounds is alpha hydroxy carbolic acids of relatively low molecular weight, for example with 10 carbon or less. Popularly called "alpha hydroxy acids", these acids are known to have a number of useful effects on the skin. Referenced "AHΛ's" herein, which is a common abbreviation in both the popular press and the technical literature, alpha hydroxy acids can moisturize dry skin and improve various disorders including acne and psoriasis and other skin anomalies. AHΛ's are also effective in revitalizing the skin. Depending upon the concentration and length of application they can cause, or stimulate, exfoliation which is the removal of outer keratinous or horny tissue layers, and stimulate renewal of new skin layers to provide a significant improvement in the appearance of the skin. Some AHA's that have been, used to provide these benefits are the simplest alpha hydroxy acid, namely glycolic acid, as well as lactic acid, citric acid and malic acid. These acids are also known as "fruit acids" because they are found in fruits and in the case of glycolic acid, in sugar cane. There are many other AHA's, or equivalent alpha keto acids and the like, that are known, or have been suggested for use in revitalizing skin or otherwise providing useful dermatological skin functions. Some beta hydroxy acids, for example salicylic acid, also have useful dermatological properties. Some such "skin acids" are disclosed in Yu et al . U.S. Patent No. 5,091,171 the disclosure of which is hereby incorporated herein by reference thereto. While the poor cosmetic condition of the eye areas of many individuals suggests these areas as a prime target for the use of such beneficial dermatologic agents as AHA's, there are problems in using AHΛ's in the eye area. The AHA's of interest are usually quite hydrophilic, dissolve readily in water and, in the case of lactic acid become liquid around room temperature (about 16.8 °C) . Such hydrophilicity is usually incompatible with common hydrophobic eye cosmetics such as eye shadows, or eye primers. The anhydrous nature of such eye cosmetics means that small quantities of active hydrophilic agents for example ΛHΛ's may either lose their activity due to chemical or physico-chemical combination, or fail to be delivered to the skin surface in an adequately hydrophilic or aqueous environment to be effective. In addition, preferred environments for such agents are significantly acidic, a condition which is difficult to provide at skin surfaces treated with anhydrous, or substantially hydrophobic, cosmetics. A critical problem with any eye cosmetic is to avoid irritation of, or stimulation of allergic or pathogenic reactions in the eye. AHA's can be very acidic and are known to be significantly irritating, even when applied to durable areas of the skin. Avoiding irritation is of special significance to products intended for daily use, in the eye or other sensitive skin areas. One way of delivering dermatologically or cosmetically active agents in a cosmetic vehicle is by containing the active agents in or on a suitable particulate carrier. Of particular interest for use as a carrier are small porous polymeric particles or microspheres. A problem with this approach is that having employed an affinity between a medium containing the active agent and the microsphere to O 96/21422 PO7US96/01560 -8 - get the active agent loaded into the microsphere, it is then necessary to overcome that affinity to release the active agent. It is also important that the delivery vehicle not possess a greater affinity for the dermatologically active agent than does the carrier, otherwise the active agent may discharge prematurely from the porous carrier into the vehicle and be dissipated. Schaefer et al . U.S. Patent 5,292,512 discloses a cosmetic composition for topical application in which dermatologically active agents such as acne treatments, for example retinoids and benzoyl peroxide, hormones, antifungal, antibiotics and so on are absorbed on carrier particles for delivery to the skin. Typical carrier particles are organic polymeric microspheres. Active products are introduced into the microspheres by dissolving them in a suitable solvent such as water, glycerol or the like (column 4 lines 47-54) . The objective of Schaefer et al . is to deliver the active products into the sebaceous follicles for release beneath the epidermis. To this end Schaefer et al . employs rather small microspheres of which 80% have a diameter of between 3 μm and 10 μm which is apparently of an appropriate size to travel into the follicles past the epidermus. (See column 1 line 45 to column 2 line 40.) Schaefer et al . provides no 96/21422 PCIYUS96/01560 -9- means for the delivery of dermatologically active agents to the outer surface of the stratum corneu nor any means for the controlled release of active agents, especially hydrophilic active agents from an anhydrous cosmetic composition at that surface. Schaefer et al . provides subdermal penetration not surface release. Schaefer et al . 's loaded microspheres are formulated in various hydrophilic or hydrophobic gel compositions and are reported to provide excellent antiacne properties, presumably due to the penetration of the active ingredient loaded carrier particles into sebaceous follicles. Schaefer et al . 's compositions are clearly intended as single purpose preparations providing improved delivery of a specified active agent and lack independent cosmetic benefits. If the user wants to obtain cosmetic benefits additional to acne or other therapeutic treatments, a cosmetic preparation will need to be applied separately which cosmetic may be incompatible with the acne treatment. Schaefer et al . do not attempt to incorporate active-agent-loaded microspheres into a cosmetic base or to address the problems that may arise in doing so. More specifically Schaefer et al . do not address the problem of delivering a hydrophilic active agent to the skin surface from a cosmetic composition including an anhydrous base which base provides its own useful cosmetic properties independently of, or additional to, cosmetic properties associated with delivery of the active agent. SUMMARY OF THE INVENTION The invention, as claimed, is intended to provide a remedy. It solves the problem of how to deliver a dermatologically active hydrophilic agent to eye and other sensitive skin surface areas in an essentially hydrophobic cosmetic composition. To solve this problems, the invention provides a cosmetic composition in which a dermatologically active hydrophilic agent constituted in a liquid hydrophilic medium is either adsorbed or absorbed into or onto a suitable particulate carrier. This carrier-active-agent system can be incorporated into a substantially anhydrous cosmetic base, for example cream suspension. The anhydrous base preferably comprises one or more film-forming agents to provide a novel cosmetic composition which can be topically applied to deliver the hydrophilic agent to the skin. Preferred embodiments of the invention provide solutions to the problem of providing a useful cosmetic composition containing an effective concentration of a dermatologically active agent which can provide controlled release of the dermatologically active agent to the skin. Cosmetic compositions according to the invention can be formulated into a wide range of cosmetics products, for example, pigmented eye shadows, non-pigmented eye shadow primers, lipsticks, moisturizers, lip treatments, foundations, and the like. These new cosmetics products in addition to having valuable cosmetic properties, have dermatological activity and provide lasting benefits. Thus, for example, an eye shadow can be formulated with a skin revitalizing agent, for example an alpha hydroxy acid, to provide both immediate and long-term improvements to the eye lids. Tests and studies reported hereinbelow show that such cosmetic compositions containing microsphere-loaded dermatologically active agents, for example AHA's, pursuant to the invention, can effectively deliver the AHA's to the skin in an active form, out of a substantially anhydrous vehicle in which a film-forming agent or system is dispersed. The data reported herein show that AHΛ's incorporated in the compositions of the invention are effectively delivered to the skin and provide valuable dermatological benefits, for example skin revitalization, as evidenced by a substantial increase in moisturization after four or more weeks of use. It has been surprisingly found that the dermatologically active agents are successfully released from the microsphere carrier vehicle, in spite of the alien hydrophobic environment of the cream or gelled vehicle in which they were formulated for the tests. The hydrophobicity of the vehicle should tend to inhibit the hydrophilic active medium from egressing from the microsphere. While not being bound by any particular theory, it is a concept of the invention that the spreading and massaging actions that normally accompany topical application of the product act to bring AHA-loaded microspheres into contact with the skin where skin moisture draws the AHA-containing hydrophilic medium out of the microspheres. When the cosmetic compositions of the invention are applied to particular skin areas, such as around the eyes and on the lips, they are subject to a constant kneading action as the eyelids are blinked and the lips are moved or wiped, providing continual turnover of the microspheres contacting the skin surface, and replenishment of the AHA-containing hydrophilic medium supplied to that surface. Further, pursuant to theory, it appears that the film- forming nature of the anhydrous base produces a water-loss barrier on the skin's surface inhibiting transpiration of water from the skin. This control of water loss enables the upper cutaneous level of the skin to increase its water content thereby promoting the egress of the dermatologically active agent from the carrier into the skin. Additionally, any water or other suitable solvent for the dermatologically active agent that is introduced by subsequent application of a secondary cosmetic product using the inventive composition as a primer can also assist the egress of the active agent from the carrier to the s.kin. Organic polymeric microsphere tend to be slippery and do not adhere to the skin. Strong adhesive properties can be provided to the microspheres by incorporating them into anhydrous cosmetic compositions containing suitable film- forming agents, including novel film-forming systems pursuant to the invention. When such a film system is used in cosmetic compositions containing microspheres, a good anhydrous film can be obtained with excellent spreadability and no tackiness or drag. Other valuable cosmetic properties are obtainable with the compositions of the invention. Fine lines in the skin, can be both cosmetically masked or concealed by a filling and light-diffusing action of the microspheres while also being dermatologically reduced by a skin revitalization action of the AHA's. Preferred formulations can also diffuse light to reduce the appearance of dark circles beneath the eyes and provide a soft focus effect. Preferred embodiments of the invention can also enhance the water barrier properties of skin surfaces to which they are applied, potentially promoting the action of dermatologically active hydrophilic agents delivered through the cosmetic and increasing the durability of cosmetics applied over- the inventive product. Many of the foregoing properties can be combined into a single multi-functional cosmetic composition providing both immediate and long-term benefits to consumers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Some embodiments of the invention and one or more ways of practicing the invention, including the best mode contemplated by the inventor of carrying out the invention, will now be described in more detail. Some illustrative, non-limiting examples of preferred embodiments of the invention will also be described. Preferred embodiments of the invention relate to novel cosmetic compositions containing an effective quantity of a polar dermatologically active agent, a sufficient quantity of suitable adsorbing or absorbing carrier to support the dermatologically active agent and one or more film-forming agents in a substantially anhydrous vehicle or base formulated to deliver the dermatologically active agent to the surface of the stratum corneum. This composition provides properties which enables a wearer or user to enjoy their usual, cosmetically assisted, attractive appearance while, at the same time, gaining one or more dermatological benefits which will endure after removal of the cosmetic. The essentially or substantionally anhydrous base provides a medium or vehicle for dispersal of the active-agent loaded carrier particles which medium can be liquid or semi-solid, for example, a dispersant or solvent for other cosmetic ingredients bringing desired cosmetic properties to the composition. The anhydrous base can thus comprise a more or less volatile hydrophobic cosmetic solvent in which a gelling agent is optionally dispersed to provide a desired consistency. Absorbent carrier. Pursuant to the invention, a variety of materials can be employed as a carrier for delivering a dermatologically active ingredient or agent, for example an alpha hydroxy acid to the skin in an active agent form while protecting the active from other cosmetic ingredients that may deactivate it. Suitable carrier materials include but are not limited to polymeric organic microspheres and inorganic particulates. Some commercially available microspherical powders useful in the preparation of the cosmetic materials of this invention include organic polymeric materials for example polyethylene, polypropylene and copolymers thereof, polyurethane, polyesters, polya ides, poly ethylmethacrylate, nylon, ethylene acrylates copolymers and polyvinylidene copolymers. Substantially any non-toxic, non-irritating, cosmetically compatible organic polymeric material that can be provided in a satisfactorily adsorbent or absorbent form for the purposes of this invention, and which is compatible with the anhydrous vehicle, can be used. Some examples of inorganic particulates include talc, clays, organic modified clays, kaolin, mica, calcium salicylate and various carbonates of various metals, for example calcium and magnesium. The carrier particles should not be too large or their presence as a component of the composition will be apparent to the user and may give a particulate coarse or sandy, rather than, smooth feel to the cosmetic. Thus, at least eighty percent of the particles should not exceed 50 and preferably not exceed 20 microns. Nor should the particles be too small, or they may be absorbed in the sebaceous follicles, which is not desired, and will provide too small a storage volume for the passenger dermatologically active agent. Within the limits of providing a satisfactorily cosmetic feel upon spreading, the carrier particles should be relatively large to be able to release passenger active from either the surface or through surface openings from interior volumes of the particles. Preferably, at least eighty percent of the carrier particles are in excess of 10 microns in diameter. A particularly preferred range for at least eighty percent of the particles is from 10 to 20 microns, more preferably from 10 to 15 microns. A useful average particle size is from 12 to 20 microns. A porous carrier particle is particularly preferred whereby a liquid phase can be absorbed within the particle to occupy, for example, from 10 to 90 percent of the particle's volume, rather than simply being retained on the particle's surface. An absorbent matrix powder serving as a carrier for topical delivery of the dermatologically active agent or dermatologically active solution can comprise porous synthetic organic polymeric microspheres, for example a cosmetically acceptable polyamide such as nylon 12, in a proportion of from about 0.1 to about 40.0 percent, preferably from about 5.0 to about 20.0 percent, and more preferably from about 6.5 to about 10.0 percent by weight of the cosmetic composition. In addition to carrying AHA's, or other dermatologically active hydrophilic agents, the organic polymeric microspheres impart desirable feel properties for example creamy, powdery and silky qualities to consumer formulations, and enhance the light-scattering qualities of the formulation. When discharged of AHA or other dermatologically active agents the organic polymeric microspheres are available to absorb skin oils, helping control oil breakthrough. Dermatologically Active Agents. Examples of suitable dermatologically active agents which can be delivered to the skin by the compositions of the invention include, but are not limited to, the following: anesthetics, for example, benzyl alcohol, lidocaine and menthol; astringents, for example, witch hazel, benzoic acid and aluminum or aluminum/zirconium salts; keratolytics, for example resorcinol, salicylic acid, ascorbic acid and acetic acid; exfoliants, for example, lactic acid, glycolic acid and other alpha or beta hydroxy acids; vasoconstrictors, for example, phenylepinephine hydrochloride; external analgesics, for example, tripelenna ine hydrochloride and camphor; anti-inflammatory agents, for example, salts of glycyrrhizic acid, alpha bisabolol; salicylate derivatives and ibuprofen; anti-irritants, for example, allantoin, proteins, trimethyl glycine, glycine, ascorbic acid, ferulic acid, sodium lactate; bleaching agents, for example, magnesium ascorbyl phosphate, hydrogen .peroxide, kojic acid and hydroquinone; lipolytic agents, for example, caffeine, aminophylline and other xanthine bases; pigmentation enhancers, for example, dihydroxy acetone; sunscreens, for example diethanolamine paramethoxycinnamate, glyceryl aminobenzoate, 2- hydroxy-4-methoxy-benzophenone-5-sulfonic acid, 2- phenylbenzimidazole sulfonic acid; moisturizers and humectants, for example panthenol, lactamiodopropyl trimonium chloride, salts of pyrolidone carboxylic acid, and polyethylene glycol, with molecular weights of from about 40 to about 10,000 daltons, propylene glycol/ethylene glycol copolymers, glycerine, polyglyceryl polymers, mono-, di-, tri- or polysaccharides or reduced mono-, di-, tri- or polysaccharides or their derivatives, propylene glycol, polypropylene glycol with molecular weights from about 100 to about 10,000 daltons, hygroscopic amino acids, peptides and polypeptides or their derivatives, glycosoamino glycans, amides or esters of alpha or beta hydroxy acids, ethoxylated derivatives of glycerin, propylene glycol, butanol or pentanol, inositol and choline chloride; nutrients, for example, vitamin C, vitamin B, folic acid, and minerals for example calcium, magnesium, iron, zinc, manganese, selenium and phosphorus. Equivalents to the foregoing examples and other guidelines herein will suggest other dermatologically active agents suitable for including in the compositions of the invention. Some such agents are listed in the OTC Monographs and the Physician's Desk Reference which are hereby included herein by reference thereto. Some of these agents, and others, are disclosed in Schaefer et al . U.S. Patent No. 5,292,512 the disclosure of which is also incorporated herein by reference thereto. As discussed above Schaefer et al.'s cosmetic delivery system is quite distinct from that of the present invention. Schaefer et al . employs ultra microscopic carrier particles small enough to enter skin intrusions or openings to deliver the particles loaded with active agents subcutaneously into sebaceous or follicular openings in the skin. Schaefer et al.'s carrier particles are necessarily below 10 microns in diameter in order to be transported into the sebaceous follicular openings for εubcertaneous and systemic delivery. Since the active material is to be absorbed onto or absorbed into a particulate carrier which in turn is dispersed in an essentially anhydrous cosmetic base or vehicle, it is preferred that the dermatologically active agent or ingredient be polar and have little or no affinity for the components of the essentially anhydrous base. One or more dermatologically active agents in a range of from about 0.01 to about 10.0 percent by weight of the composition can be incorporated into preferred embodiments of the current composition. More preferably these agents can be added from about 0.5 to about 8.0 percent and still more preferably from about 1.0 to about 5.0 percent. Other active agents can be used in equivalent proportions depending upon their activity however proportions are preferred in the sensitive eye area. Preferred dermatologically active agents are classes of exfoliants known as alpha and beta hydroxy acids respectively. These materials can be used to both moisturize and revitalize the skin resulting in better structural and visual qualities. These benefits may begin to be apparent only after long-term use of the cosmetic composition of the invention on a regular, for example daily, basis for a period of from days to weeks, for example, beginning at fourteen or twenty-one days and continuing until from three to six months of daily or twice daily applications or even continuing indefinitely. To this end, the novel, substantially anhydrous eye or lip cosmetic composition of this embodiment of the invention contains, as dermatologically active hydrophilic agent, at least one alpha hydroxy acid ("AHA" herein) , for example lactic acid, citric, malic, mixed fruit acids, or mixtures thereof, supported on a matrix, or in a porous particulate carrier. The AHA is preferably supported on the carrier particles so as to be present in surface pores of the carrier particles and also in interior pores communicating with those surface pores, whereby the AHA bearing hydrophilic medium can be released at the particle surface and withdrawn from the carrier particle by skin moisture, possibly by capillary action. Some other alpha hydroxy acids which can be used in practicing this invention include a straight or branched chain aliphatic acid with not more than three substituents in the aliphatic backbone, said substituents being non-basic and being selected from the group consisting of hydroxy, aldehyde, keto, carboxyl, chloro and nitro. Acidity and water or hydroalcoholic solubility are desirable characteristics of the alpha hydroxy acids used in the present invention. Some preferred alpha hydroxy acids contain at least one hydrophobic moiety being a carbon atom having four substantially non-polar bonds for example carbon-carbon or carbon-hydrogen bonds. Such hydrophobicity is believed useful to balance the electronegative hydroxy and carboxyl radicals for improved biological compatibility and efficiency. Some other alpha hydroxy aliphatic acids are preferably nonocarboxylic acids selected from the group consisting of 2-hydroxy-n-butanoic acid, 2-hydroxy-isobutanoic, 2-hydroxy- n-pentanoic, 2-hydroxy-isopentanoic, 2-hydroxy-n-hexanoic acid, 2-hydroxy-isohexanoic acid. Di- or polyhydric analogs thereof can also be used, for example, 2,X-dihydroxy analogs thereof where "X" is an integer from 3 to 6, as appropriate for the respective monohydroxy acid, indicating the carbon atom location of a second hydroxyl substituent in a carbon atom other than the number one or two carbon atoms. Preferably, such dihydroxy acids balance the additional electronegativity attributable to the second hydroxyl with a further hydrophobic moiety as described above. While some dermatologically active agents possess properties, for example a low enough melting point, that enable them to be absorbed or adsorbed directly into or onto the carrier matrix, others are in crystaline form at room temperature, and are preferably dissolved in a suitable hydrophilic solvent system for the active agent. Preferably also the solvent system should have little or no affinity for the essentially anhydrous base. This is important to retaining both the solvent and its dermatologically active solute in or on the carrier and to preserving the intended functionality of the dermatologically active agent. Additionally, the solvent should be suitably vicous to further help retard the migration of the dermatologically active agent from the carrier. Also, the solvent should be inert or inactive with respect to, or at least not negatively impact the functionality of the dermatologically active agent. Hydrophilic Solvents. Some classes of liquid hydrophilic solvents or disperse phase media that can be used alone or in combinations as adjuvants to assist the loading of the dermatologically active agent or agents onto or into the particular carrier include but are not limited to water, alcohols and ethers. A suitable class of alcohols comprises mono-, di-, tri- or polyhydroxy alcohols having the formula: (OH) I R - (CH) χ - (C) v - (CH 2 ). - R 1 | | (OH) (OH) where R = H, CH 3 , or a saturated, unsaturated, cyclic or branched alkyl radical containing from 1 to 20 carbons; X = 0 to 1 , 000 , 000 ; Y = 0 to 100 ; Z = 0 to 10 ; and R 1 = H , CH 3 , O-CH j , 0 -CH 2 -CH 3 Suitable examples of such compounds include glycerin, propylene glycol, dipropylene glycol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, neopentanol, diglycerol, polyglycerol, sorbitol, polyethylene glycerol, and polyol. Suitable ethers include unsubstituted and substituted ethers for example UCON (trademark) fluid, Union Carbide Corp. or DOWANOL (trademark) fluids, Dow Chemical Company or CARBITOL (trademark) and CELLOSOLVE (trademark) solvents from Union Carbide. In principle, suitable viscous, hydrophilic solvents or blends of solvents can be used with the dermatologically active agent in a proportion of from about 99 parts: 1 part to about 1 part: 99 parts. However, preferred proportions are chosen to exploit the physical or physico-chemical characteristics of the solvent to deliver the dermatologically active agent an active form in a liquid phase for uptake by absorbent carrier particles. To this end, while a minor proportion of solvent may have merit in some circumstances, major properties of solvent are preferred, for example a proportion of from about 1:1 to about 1:20 parts agent to solvent, on a weight basis. Whereas such proportions can be efficacious for intercellularly active agents, more potent intracellularly active agents, for example hydrophilic or water-soluble hormones such as corticosteroids may be present in smaller relative proportions, for example from about 1:999 to 1:20 parts agent to solvent. A preferred solvent for a dermatologically active agent for example an alpha hydroxy acid (AHA) is glycerin. The solvent's viscosity helps retain the AHA within or on the particulate carrier while the hydrophilicity permits skin moisture to draw dissolved AHA out of or off of the microparticle. Film-forming agents. Preferably, the invention provides for a film-forming agent to assist with the adhesion of the loaded particulate carrier onto the skin and to help form an occlusive barrier to enhance the buildup of water on or near the surface of the skin. By film-forming is meant that an essentially continuous layer of product is formed on the surface of the skin. By occlusive is meant that a barrier is placed on the surface of the skin which barrier substantially blocks or retards the loss of volatile materials from the skin's surface and enables them to build up in the upper layers of the skin. For the purpose of this invention, the barrier film is preferably hydrophobic. Some classes of suitable cosmetic film-forming agents that can be used alone or in combination include but are not limited to metallic soaps, waxes and film-forming emollients. Some non-limiting examples of each of these classes of cosmetic film-forming agents will now be described. Others will be known to those skilled in the art. Metallic soaps are useful materials which function to aid adhesion and to promote the formation of a hydrophobic film. The metallic soap gelling agent or agents can be an alkaline earth or aluminum alkanoate of from six to twenty carbon atoms, for example, the laurate, oleate, or stearate salts of calcium, magnesium, zinc, aluminum or lithium or mixtures thereof. A cosmetic metal soap, for example zinc laurate, can be used in a proportion of from about 1.0 to about 5.0 percent, preferably about 3.0 percent by weight of the composition. Metallic soap functions as an ionic gelling agent, aids adhesion and adds to hydrophobic film formation. Other useful film-forming agents are waxes. Many waxes which can function as suitable film-forming agents in the compositions of present invention are well known in the cosmetic art. Typically these materials are composed of the formula R-X, in which R is a long chain saturated, unsaturated, cyclic or branched chain alkyl radical of from C 8 to C, 000000 , X is -H, -OR 1 or -C-OR 11 , where R 1 is H, or a saturated, unsaturated, cyclic or branched chain alkyl radical of from C,, to C ≥tι ; R 11 is H or residue of a mono-, di-, tri- or polyhydroxy compound capable of forming a mono-, di-, tri or polyester. Preferred waxes have melting points which exceed 100 °F. Materials such as glyceryl wax esters, beeswax, ceresin wax, carnauba wax, candelilla wax and other cosmetically acceptable waxes can be used. A total wax content of from 0 to 10.0 percent is adequate for formulating satisfactory cosmetics, pursuant to the invention. Preferably, total wax content does not exceed 5.0 percent and more preferably not 3.0 percent. Suitable waxes are, for example, glyceryl tribehenate, ceresin wax and microcrystalline wax used in proportions of from about 0.00 to about 5.00 percent, preferably about 0.1 to 1.5 percent. More preferably from about 0.25 to 0.5 percent of waxes such as glyceryl tribehenate and a somewhat higher proportion of about 1 to 2 percent of a ceresin was are used. The low wax content attainable with cosmetic compositions according to the invention has the advantage of providing low drag and enhanced removability. Useful wax functions are adhesion, imparting a creamy feel to the product, film forming and increasing viscosity. Other useful film-forming agents are emollients. These materials are usually liquid at temperatures between 32 °F an 100 "F. Emollients useful in the present invention include those with the following formula c n H (2n + 2 . χ) , where n is an integer from 6 to greater than 1 million and x is 0 or an even integer no greater than n and may include saturated, unsaturated, branched and cyclic hydrocarbon chains. Examples include: mineral oil, petrolatum, PERMETHYL (trademark) fluids, and polybutylenes. Further useful film-forming emollients include the mono-, di-, tri- or poly-branched, -cyclic, -saturated or - unsaturated alkyl esters or ethers of di, tri or polyhydroxy compounds for example ethylene glycol, propylene glycol, glycerin, sorbitol or polyol. Examples of such emollients include but are not limited to vegetable oils for example soybean oil, babassu oil, castor oil, cottonseed oil, Chinese tallow oil, crambe oil, perilla oil, Danish rapeseed oil, rice bran oil, palm oil, palm kernel oil, olive oil, linseed oil, coconut oil, sunflower oil, safflower oil, peanut oil, and corn oil. Preferred saturated and unsaturated vegetable oils are those having fatty acid components with 6 to 24 carbon atoms. Additional suitable emollient film-forming agents include esters of the formula: R.-C-OR, or R.-O-C- (CH,) -C-O-R, 0 II 0 i " 0 i ' wherein R, and R z are saturated, unsaturated, branched or cyclic alkyl radicals of 2 to 24 carbon atoms and n is an integer from 0 to about 20. Silicone-based auxiliary film-forming agents. The novel cosmetic compositions of the invention may also contain a silicone material to provide some measure of auxiliary film- forming ability. Suitable silicone materials are preferably insoluble in water and cyclo ethicone, polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polysiloxane gums, amino functional polysiloxanes and polyethersiloxane copolymers. Teachings directed to additional suitable silicone materials can be found in U.S 4,788,006; U.S. 4,341,799; 4,152,416; 3,964,500; 3,208,911; 4,364,837 and U.S. 4,465,619, the disclosures of all of which are hereby incorporated herein by reference there to. Polyalkylene oxide auxiliary film-forming agents. Another class of suitable auxiliary film-forming agents comprises substances formed by the polymerization of alkylene oxide monomers of the formula 0 / \ H(CH 2 ) n - HC - CH 2 where n is an integer from 0 to about 3. These materials can be either a homogeneous polymer or a copolymer of two or more monomers. Examples of homogeneous polymers include polypropylene oxide and polybutylene oxide. Typically, the molecular weights of these materials is between 100 and 10,000 daltons. Additionally, these materials can be condensed with a mono or polyhydroxyalkyl alcohol as exemplified by the UCON (trademark) fluids from Union Carbide Corp. The film-forming agent can be used alone or in combination with other film-forming agents to achieve desired aesthetic properties in the final preparation. A preferred range of film-forming agents is from 1 to 99%, more preferably from about 1 to 50% by weight of the composition. Suitable non-hardening film formers, for example dimethicone, can be used in proportions of from about 0.5 to about 5.0 percent, preferably about 0.6 to 1.5 percent, and more preferably about 1.0 percent. Preferred functions include film forming, skin protectant or water-barrier forming agent, lubricious and silky emollient. Film enhancing agents, for example aluminum-myristate- treated mica, in a proportion of from about 4.0 to about 20.0 percent by weight of the composition, preferably about 5.0 to 8.0 percent, and more preferably 6.5 percent can be used. Preferred film enhancer functions include adhesion to skin, imparting of a creamy and silky feel to the composition and enhancing hydrophobic film formation. Although strong adhesive properties can be introduced into anhydrous cosmetics compositions by incorporating waxy fil - forming agents, too high a wax content causes drag and an undesired tacky feel when the cosmetic is applied, and may result in a cosmetic that is difficult to remove. To solve this problem, the invention also provides a novel film-forming system which comprises relatively high proportions of a particulate mineral gelling agent, for example a bentonite-clay based gelling agent, and of a metallic soap gelling agent, such for example as zinc laurate, while using only a small proportion of wax, if any. When this film system is used in cosmetic compositions containing microspheres a good anhydrous film can be obtained with excellent spreadability and no tackiness or drag. These desirable properties appear to result from a unique combination of the skin-adhering properties of the metal soap with "ball-bearing" type lubricity properties of the microspheres. In one practical embodiment of the invention carrier loading of our AHA is achieved by dissolving the AHA in glycerine and absorbing the glycerine-dissolved AHA on porous microspheres or fine polymer particles. This system is intended for use in a hydrophobic environment where the AHAs remain in storage contained in the porous microspheres. When applied to the skin, as the cosmetic is rubbed or massageα into cne skin, microspheres are brushed across the skin surface, bringing them into contact with moisture which releases the hydrophilic AHA-glycerine system from the microporous polymer particles. Once discharged of the glycerine-AHA system, the now-hollow microspheres are available to absorb oil, moderating oil- breakthrough tendencies. The AHΛ is preferably loaded on the carrier particles, for example, porous nylon particles in a liquid medium which should be sufficiently viscous to be held in the particles' pores during formulation. Lactic acid melts at 16.8 °C and can be absorbed into porous carrier particles, without the need for any adjuvant, at temperatures above this melting point, by blending in appropriate proportions, for example, near 1:1 by weight, until the lactic acid is absorbed. Other acids, such as a mixture of fruit acids, can be similarly loaded on to carrier particles by agitating ie. blending, by using fine powders with a sufficiently small particle size to be contained in the carrier's pores. Skin revitalization benefits brought by AHA's resulting in better structural and visual qualities of the skin, which benefits may begin to be apparent only after long-term use of the cosmetic composition of the invention on a regular, for example daily, basis for a period of weeks for example, four or six weeks or more. To this end, the novel, substantially anhydrous eye or lip cosmetic composition of this embodiment of the invention contains, as dermatologically active hydrophilic agent, at least one AHA, for example lactic acid or mixed fruit acids, supported on a matrix, or porous particulate carrier in powder form, of a synthetic organic polymer, for example nylon. The AHA is preferably present in surface pores of the carrier particles and also in interior pores communicating with those surface pores, so that the AHA can be released at the particle surface and withdrawn from the carrier particle by skin moisture. The invention also provides a low-wax, or zero-wax, cream- to-powder film-forming vehicle for the foregoing AHA-loaded system. This low-wax vehicle is made possible by a unique combination of a relatively high proportion of a gelling agent such as a bentonite and a high proportion of a metal soap, preferably in a volatile solvent system such as a cyclomethicone, for example dimethicone or a non-polar solvent, for example a volatile hydrocarbon. Surprisingly, by including the AHA-loaded microspheres in the system, a vehicle with good film-forming abilities yet which is low in drag or tackiness is obtained, apparently due to the "rolling slip" effect referenced above. Metal soaps alone are notably tacky or adhesive, and these adhesive properties are in fact used, or exploited, to hold the cosmetic base to the skin and, in the case of a primer composition, to provide an adequately adhesive base for a finishing layer of for example, eyeshadow. A desirable result obtained with such novel cosmetics is a silky smooth powdery feel. Also, by virtue apparently of its adhesive yet non-tacky properties novel eye enhancers according to the invention are surprisingly long lasting, as shown by comparative data. Whereas traditional eye makeups may need refreshing after a few hours and are usually fading noticeably in about six hours, eye cosmetics produced according to the invention can endure satisfactorily for over 12 hours without unacceptable fading. Cream-to-powder products according to the invention are quick drying. The solvent evaporates off in a matter of a few seconds to provide a silky smooth powder film. Inclusion of a light- diffusing agent scatters light in the shadows between wrinkles cracks or other skin defects and helps give the product a soft focus appearance. Such eye enhancers pursuant to the invention work synergistically the film-forming system and AHΛ loaded porous microspheres to provide an enhanced appearance on application, giving the skin an illusion of improved skin quality while the alpha hydroxy acid released on contact with the skin actively conditions or revitalizes the skin, so that after a period of regular use, which may be as low as four weeks, the appearance of the skin without cosmetics is improved. -36- Absorbing the AHA into pores in microsphere particles, using glycerin as an AHA solvent, effectively isolates the hydrophilic ingredients from the hydrophobic, without creating a separate aqueous phase for dispersion. Another benefit of microsphere utilization is the reduced diffusion into sensitive eye tissue due to the binding effect of the microsphere. A preferred hydrophobic vehicle for the active-agent-loaded microsphere particles is a silicone gel, which is preferably formulated using a volatile silicone solvent such as a dimethicone. A preferred gelling agent is a bentonite powder. As described above, the invention preferably employs a low wax, cosmetic film-forming system comprising, in weight percent based on the weight of the composition, from 5.0 to 13.0 percent of a particulate mineral gelling agent, for example a bentonite, and at least 1.0 percent of a metallic soap gelling agent, with no more than 5.0 percent of a cosmetic wax material, if present, dispersed in a volatile cosmetic solvent, preferably a cyclomethicone in a proportion of from about 30.0 to 70.0 percent. A volatile solvent, for example a cyclomethicone, preferably the penta er form, can be used as a hydrophobic vehicle, for example for a cream-to-powder composition. Suitable proportions are from about 20.0 to about 70.0 percent by weight of the composition, preferably about 30 to 40 percent, and more preferably about, 33.0 percent. Functions as a wetting agent while quickly evaporating upon application. Some alternative or additional volatile silicone solvents are described hereinbelow. A gelling agent suitable for a volatile solvent, for example quaternium-18 bentonite, from about 1.0 to about 15.0 percent, more preferably from about 3 to 10 percent, and more preferably about 5.0 to 6.0 percent. Physically stabilizes the composition and functions as a pigment- suspension vehicle and to absorb oil and reduce shine. Wetting agents. A wetting agent, for example sorbitan isostearate, from about 1.0 to about 10.0 percent by weight of the composition, preferably about 3.5 to 4.5 percent, and more preferably about 4.0 percent can be used. Preferred wetting agents allow for increased capacity of solid material, and impart a hydrophobic film. Additional polymeric microspheres. Synthetic polymeric microspheres additional to the AHA carrier powder, for example poly ethylmethacrylate, can be used in a proportion of from about 8.0 to about 20.0 percent by weight of the composition, preferably about 10.0 to 15.0 percent, and more preferably 12.0 percent. Such additional polymeric microspheres act as feel enhancers, providing a "ball bearing" feel on application, and a velvety, dry feel after application and evaporation of the solvent. Additional functions include light scattering and impartation of a powdery feel to the product. Oily esters. An oily, low-volatility solvent ester, for example isononyl isononanoate, is useful for volatility and molecular weight control of the solvent system in a proportion of from about 1.0 to about 10.0 percent by weight, preferably from about 4.0 to 6.0 percent, and more preferably about 5.0 percent of a solvent. Preferred solvents also function as lipophilic emollients, aid in the solubilization of the ingredients and are miscible with the volatile carrier solvent (for example dimethicone) . Moisturizers. One or more oil soluble moisturizers, for example lauryl PCΛ, in a proportion of from about 0.4 to about 2.5 percent, preferably about 0.5 percent, or cetyl dimethicone, in a proportion of from about 1.0 to about 5.0 percent by weight of the composition, can be used to enhance moisturization. Cetyl dimethicone provides a light, dry feel and aids film formation. Oil absorbents. Kaolin or other oil absorbents in a proportion of from about 0.50 to about 3.0 percent by weight of the composition, preferably about 0.7 to 1.5 percent, and more preferably 1.00 percent can be used. Preferred oil absorbent functions include absorption of excess skin oils, skin adhesion, light diffusion, and opacification. Opacifiers. An opacifier, for example titanium dioxide, can be used in a proportion of from about 0.10 to about 5.0 percent by weight of the composition, preferably about 0.3 to 1.0 percent, and more preferably 0.50 percent to provide coverage and help mask skin defects. Plasticizers. A volatile polar activator solvent for the gellant, for example hexylene glycol, can be used in a proportion of from about 0.75 to about 1.75 percent by weight of the composition, preferably about 0.85 percent. This will act as a binder plasticizing agent, solvent and softener while providing resistance to moisture and oxidation. Preservatives. Preservatives such as, for example, methyl or propyl paraben, can be used in proportions of, for example, 0.1 to 0.3 percent by weight, as is known to those skilled in the art. Further optional ingredients. Other optional ingredients can be used, as is known to those skilled in the art including pigments and fragrances. Some further optional ingredients are: vitamin E linoleate, in a percentage of about 0.10 percent as a supplemental moisturizer; vitamin E acetate, at about 0.10 percent functions as a free radical scavenger and an antioxidant; retinyl pal itate, at about 0.1 percent functions as a derivative of retinoic acid to reduce fine lines; ceramides at a percentage below about 0.3 percent function as a skin firmer; sphingolipids serve the function of skin firming at a percentage below about 0.3 percent, function to improve the skin's barrier thereby increasing moisturization and decreasing penetration of irritant substances. Alternative volatile silicone solvents. A class of cyclomethicone compounds that is preferred for use in the cosmetic compositions of this invention is illustrated by compounds of the formula -[R.R 2 SiO] n -, in which R and R is each lower alkyl having from one to four carbon atoms with or without innocuous substitutes selected from the group consisting of halo, hydroxyl, carboxyl or methoxy and n is from 3 to 6; which compounds are cyclized. The volatile cyclomethicone solvent used can be a single one of the foregoing compounds or a mixture thereof and the compound or compounds can be a homopolymer in which all n monomeric units are similar, or a heteropolymer in which they are different. Some preferred cyclomethicones are dimethicones especially homopolymers in which n is 4 or 5; and R and R is each methyl such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Depending upon the character of the end product composition, for example, composite eye enhancer, eye shadow primer, lipstick, blush, makeup and the like, other optional ingredients can be used, as known to those skilled in the art, in proportions known to those skilled in the art. Such ingredients include, but are not limited to, fragrance, color, pigments, preservatives, wetting agents, oil absorbents, opacifiers, and antioxidants. The following Examples illustrate the practice of the invention in more detail. The proportions of ingredients used in the Examples are set forth in the various Tables, as identified in the Examples. Table I sets forth the ingredients used in Examples 1 and 2. TABLE I PHASE DESCRIPTION Example 1 Example 2 A Lactic acid 20 A Mixed fruit acid 20 complex A Glycerin 20 20 B Nylon 12 60 60 Example 1 Lactic Acid Powder Blend In Example 1 porous Nylon-12 microspheres are loaded with lactic acid using a glycerin solvent. Glycerin is mixed in a blender with an equal amount of lactic acid to form phase A using the proportions set forth in Table II. Nylon-12 powder is then added to phase A in a ratio of two parts phase A to three parts Nylon-12. The glycerin lactic acid phase is substantially completely absorbed by the Nylon-12 microspheres, increasing their density, to produce a free flowing powder. This combination is blended for one hour to produce a physically stable, mildly tacky, lactic acid powder blend which is subsequently used in Example 9. Example 2 Mixed Fruit Acid Powder Blend Example 1 is repeated using mixed fruit acids in place of lactic acid in the proportions indicated in Table I. A physically stable, mildly tacky powder is obtained and used in Example 10. TABLE II PHASE DESCRIPTION Example 3 B Zinc laurate 27.27 B Mica-aluminum 59.23 myristate B Kaolin 9.00 B Titanium dioxide 4.50 Example 3 Dry Mix for Eve Enhancer A dry mix for use in eye enhancer compositions is prepared in a single phase using the ingredients referred to in Table II. Powdered zinc laurate is combined with aluminum [ yristate] coated mica, kaolin, and titanium dioxide and blended until a smooth homogenous powder is obtained. Table III sets forth the ingredients used in Examples 4-5. TABLE III PHASE DESCRIPTION EXAMPLE 4 EXAMPLE 5 A Nylon - 12 80.00 50.00 C Mixed fruit acid 50.00 C Lactic acid 20.00 Example 4 Solventless Nylon-12 Carrier Lactic Acid Blend In this example, porous Nylon-12 microspheres are loaded with lactic acid without the use of solvents. The phase A ingredient is slowly added to the phase B ingredient while mixing on a blender at room temperature. The preparation yields a 4:1 Nylon-12/lactic acid blend utilized in Example 7. Example 5 Solventless Nylon-12 Carrier Mixed Fruit Acids Blend Example 4 is repeated, substituting mixed fruit acids for lactic acid and reducing the proportion nylon-12 utilized, to yield a product with a 1:1 ratio of nylon-12 to mixed fruit acids. This preparation is utilized in Example 6. Table IV sets forth the ingredients used in Examples 6-8. TABLE IV PHASE DESCRIPTION Example 6 Example 7 Example 8 A Dimethicone 0.50 0.50 0.50 A Sorbitan isostearate 4.00 4.00 4.00 A Isononyl isononanoate 5.00 5.00 5.00 A Lauryl Lauryldone 3.00 3.00 0.50 A SL88 dimethicone 10.00 10.00 A Cetyl dimethicone 10.00 10.00 3.10 A Glyceryl tribehenate 0.17 A Ceresin, low melting 0.76 A Microcrystalline wax 0.17 A Propylparaben 0.10 0.10 0.10 A Methylparaben 0.30 0.30 0.30 A Cyclomethicone 18.00 B Zinc laurate 3.00 3.00 3.00 B Mica-aluminum myristate12.00 11.52 12.00 B Kaolin 1.00 1.00 1.00 B Titanium dioxide 1.00 B Nylon 12 5.00 C 4:1 Nylon-12/lactic acid blend 5.00 C 1:1 Nylon-12/mixed fruit acids 5.00 5.00 B MBX8C (PMMA) polymethyl methacrylate 5.87 12.00 12.00 D Tioxogel CYM 34.10 34.258 34.20 E Tocopherol linoleate 0.10 0.10 E Tocopherol acetate 0.10 0.10 E Retinyl pal itate 0.10 0.10 B Yellow (55-0242) 0.03 B Red (55-0241) 0.02 B Black (55-0016) 0.002 Example 6 Solventless Nylon-12/Mixed Fruit Acid Blend in an Anhydrous Base Example 6 incorporates the composition prepared as in Example 5 in an anhydrous base according to the percentages listed in Table III. The phase B ingredients are dispersed by mixing for at least three minutes at high speed. Once -4b- dispersed, phase B is added to phase C and blended at low speed for one minute. Phase A ingredients are mixed and heated to 65 degrees Celsius until clear. When phase A is clear, the blended phase B and C mixture is added, in a propeller type mixer until uniform and free of lumps. Once this mix is uniform, phase D ingredients are added and the mix is again blended to uniformity. Example 7 Solventless Nylon-12 Carrier Lactic Acid Blend in an Anhydrous Base Example 6 is repeated with the addition of Nylon-12 at phase B, to further enhance the feel of the composition, and the substitution of solventless nylon-12 carrier lactic acid blend, as prepared in Example 4, for solventless nylon-12 carrier mixed fruit acid blend as prepared in Example 5. The acid blend substitution yields a composition with a higher percentage of alpha hydroxy acid. Example 8 Solventless Nylon-12/Mixed Fruit Acid Blend in an Anhydrous Base as a Color Primer Example 8 utilizes the procedure designated in Example 6 with the inclusion of a phase E comprising additives and colorants. This final phase involves the mixture being brought to 45 degrees Celsius at which point the phase E ingredients are added and blended until uniform. The cetyl dimethicone and dimethicone are substantially replaced with cyclomethicone. The less volatile cetyl dimethicone and dimethicone lead to the production of a creamy composition whereas the more volatile cyclomethicone produces a composition that will rub out into a cream to powder vehicle. Various coloring agents can be used as is evidenced by the inclusion of several coloring agents as phase B ingredients. Table V sets forth the ingredients used in Examples 9-10. TABLE V PHASE DESCRIPTION Example 9 Example 10 A Dimethicone 1.00 1, 00 A Sorbitan isostearate 4.00 4.00 A Isononyl isononanoate 5.00 5.00 A Lauryl PCA 0.50 0.50 A Cetyl dimethicone 2.13 2.13 A Glyceryl tribehenate 0.32 0.32 Λ Ceresin, low melting 1.43 1.43 Λ Microcrystalline wax 0.32 0.32 A Propylparaben 0.10 0.10 A Methylparaben 0.30 0.30 B Cyclomethicone 17.60 17.60 C Dry mix for eye enhancell.00 11.00 D Nylon-12 5.00 5.00 C Mixed fruit acid powder blend 5.00 Lactic acid powder blend 5.00 D MBX8C (PMMA) polymethyl- methacrylate 12.00 12.00 E Tixogel CYM 33.50 33.50 E Tocopherol linoleate 0.10 0.10 E Tocopherol acetate 0.10 0.10 E Retinyl pal itate 0.10 0.10 E Hydrophobic sphingolipido.50 0.50 Tixogel CYM (Hexylene Glycol/Quaterium-18 Bentonite/Cyclomethicone) Example 9 Eve Enhancer with Lactic Acid Example 9 blends the compositions prepared in Examples 1 and 5 and adds to them the ingredients listed in Table III. The procedure for preparing Example 9 is that used in example 8. Example 9 makes use of hydrophobic sphingolipids complex to promote skin firming. Example 10 Eve Enhancer with Mixed Fruit Acids Example 9 is repeated with the substitution of Example 2, mixed fruit acid powder blend, in place of Example 1, lactic acid powder blend. The products of Examples 9 and 10 were tested to determine their dermatologic and cosmetic properties. Some of the results are reported below. Physiological Benefits. Controlled biophysical studies, employing the eye cosmetic composition of Examples 9 (lactic acid) and 10 (mixed fruit acids) , demonstrated valuable structural dermatological improvements. Some controlled tests showed significant increases in the moisture content of the canthus (outer eye corner) and under eye, accompanied by an increase in firmness and a reduction in fine lines and wrinkles. Twenty female subjects per product were treated in a half- face design with the products of Examples 9 and 10. The Example 9 or 10 product alone was applied around one eye and a moisturizing eye cream concentrate was applied, prior to the product, around the other eye. Treatments were applied to the face twice daily, but not on the morning on which measurements were taken. Skin moisturization, firmness and the textural characteristics of the canthus were determined, as described below. Skin moisturization. Impedance measurements of the canthus and under eye area of the cheeks with a dermal phase meter showed average increases of moisture content as set out below in Tables VI and VII, respectively, when compared with baseline measurements taken at week 0 (not reported) : TABLE VI Percent Improvement in Canthus Moisture Content Example 9 Example 9 Example 10 Example 10 Weeks Lactic Acid Lactic Acid MFA MFA of Use Formula Alone + Moisturizer Formula Alone + Moisturizer 2 8.5 9.8 7.6 7.6 4 20.1 24.9 16.2 21.2 6 23.3 29.5 20.8 27.4 Thus, at least a twenty percent moisturization increase was achieved with all compositions after six weeks of use, the lactic acid formulation of Example 9 was more effective than the mixed fruit acid (MFA) formulation of Example 10, and the eye cream moisturizer provided a useful additional motorization benefit, at four or more weeks. Comparable, albeit slightly lower, results were obtained on the under eye, as shown in Table VII, below. TABLE VII Percent Improvement in Under Eve Moisture Content Weeks of Lactic Acid Lactic Acid MFA MFA Use Formula Alone + Moisturizer Formula Alone + Moisturizer 2 5.3 6.3 4.9 5.8 4 14.7 19.3 12.8 15.6 6 20.6 25.6 16.5 22.1 Skin firmness. Using a ballesto eter, the firmness of the canthus was determined at the indicated times and compared with baseline measurements taken at week 0 (not reported) . The results are reported in Table VIII, below: TABLE VIII Percent Improvement in Canthus Firmness Weeks of Lactic Acid Lactic Acid MFA MFA Use Formula Alone + Moisturizer Formula Alone + Moisturizer 2 8.1 10.0 5.5 7.1 4 19.0 20.0 12.1 15.0 6 26.8 29.1 21.8 26.7 These results show a significant, 19 percent increase in firmness obtained with the lactic acid formulation of Example 9, after only four weeks of use. The mixed fruit acid (MFA) formulation of Example 10 was somewhat less effective, but still produced a significant increase in skin firmness. Better results are obtained after six weeks and by using a moisturizer. Skin texture improvements. Using computer-assisted image analysis of replicas of the canthus, measurements were made of decreases in fine lines and wrinkles at the indicated times compared to 0 - week baseline values. The results are reported in Table IX, below: TABLE IX Percent Improvement in Canthus Fine Lines and Wrinkles Weeks of Lactic Acid Lactic Acid MFA MFA Use Formula Alone + Moisturizer Formula Alone + Moisturizer 4 16.0 19.4 14.9 15.6 6 23.2 27.1 20.6 22.3 The results in Table IX show a significant, 16 percent increase in firmness obtained with the lactic acid formulation of Example 9, after only four weeks of use. The mixed fruit acid (MFA) formulation of Example 10 was somewhat less effective, but still produced a significant increase in skin firmness. Better results are obtained after six weeks and by using a moisturizer. Other controlled tests showed that compositions of the invention can be used as an eyeshadow primer to reduce eyeshadow creasing and color loss and to impart water resistance. Eyeshadow creasing. Eyeshadow creasing, or feathering, is a well-known phenomenon frequently exhibited by people with oily skin, which displays itself as an unevenness in color, or displacement of eye shadow into ridges and furrows, that may develop within a few hours of application of eyeshadow. A study enlisting twelve adult women panelists, each having a history of eyeshadow creasing, showed that use of the inventive eye cosmetic composition, as a primer, was effective in controlling creasing of eyeshadow applied over the primer. The inventive eyeshadow primer composition was applied to one eyelid only of each panelist and allowed to dry for one minute, following which a rose-colored eyeshadow was applied to both eyelids. The eyelids were videotaped immediately following application of eyeshadow and a picture of the center of each eyelid was frozen for image analysis. The procedure was repeated three and six hours after the first application. Image analysis showed that primer-treated eyelids exhibited insignificant increases in unevenness of the eye shadow, even after six hours. In contrast, unevenness of eyeshadow coverage increased significantly at both three and six hours on eyelids lacking primer. Eyeshadow color. Other tests showed that the eyeshadow primer composition of Example 9 was effective in controlling eyeshadow color loss. Neither formula changed the color of a superimposed eyeshadow, as measured with a chromameter. The forehead was chosen as a target site for color control tests because of difficulties in safely measuring eyelid color and because of physiological similarities between the forehead and eyelids with regard to the presence of sebum and the like. Eyeshadow and primer were applied to one side of the forehead of each of twelve subjects. Eyeshadow alone was applied to the other. Immediately after each application, color measurements were made with a chromameter and repeated three and six hours later. In addition no color was lost from the primer treated skin, even after six hours. This was in contrast to the unprimed skin which showed statistically significant color loss. Importantly, the color of the eyeshadow was not changed by applying it over the primer composition of the invention. Color losses of the eyeshadow primed with the composition of the invention, were visually insignificant after six hours, and were in fact less than the primed side at three hours. Water resistance. Further tests with twelve subjects demonstrated water resistance. Eyeshadow and the primer composition of the invention were applied as described above to comparative forearm areas. Immediately after taking color measurements, the arm was rinsed, air dried and the measurement was taken again. The resulting data showed a significant loss of blue color from the unprimed site whereas there was no change at the primed site. The control of color loss suggested that significant water resistance was imparted by the primer. Barrier properties and skin deposit of acids Trans-epidermal water loss measurements showed that the products of Examples 9 and 10 can signi icantly reduce water loss and thus provide an increase in the skin's barrier function. This increased barrier function may enhance penetration into the stratum corneum of active ingredients delivered beneath the applied barrier, for example alpha hydroxyacids entrapped in porous microspheres. It is postulated that the alpha hydroxyacid-loaded microspheres of the invention may participate in the enhanced barrier function while simultaneously depositing acids to the skin, the acids being drawn from the microspheres by the affinity of the glycerol solvent for skin moisture. Further studies showed that the products could improve the skin's tone in the short term, up to six hours and imposed no immediate physical threat to polymacon or surfilcon A contact lenses. INDUSTRIAL APPLICABILITY The present invention is particularly suitable for application to modern industrial processes. In particular, it is useful in the cosmetics industry where it can provide new products offering new benefits to consumers, as described herein. While an illustrative embodiment of the invention has been described above, it is, of course, understood that various modifications will be apparent to those of ordinary skill in the art.

Claims: CLAIMS Claim 1. A topically applied essentially anhydrous cosmetic composition comprising: a) an effective amount of at least one dermatologically active polar agent; b) a sufficient quantity of. an adsorbent or absorbent particulate carrier to support said dermatologically active polar agent; and c) a hydrophobic phase cosmetic base, said essentially anhydrous base having a sufficient quantity of a film-forming agent to produce a desired cosmetic film when said cosmetic composition is applied to the skin, said active- agent-loaded carrier being dispersed in said cosmetic base. Claim 2. A cosmetic composition according to claim 1 comprising, in proportions by weight, based upon said weight of said composition: a) from 0.01 to 10 percent of said dermatologically active polar agent; b) from 0.1 to 40.0% of said particulate carrier, at least 80 percent of said carrier particles having a particle size in excess of 10 μm; and c) from 1.0 to 99.0% of said film-forming agent; whereby topical application of said cosmetic composition to the skin produces controlled release of said active agent to the surface of the stratum corneum. Claim 3. A cosmetic composition according to claim 1 further comprising a liquid-phase solvent for said polar active agent, said solvent being substantially immiscible with said hydrophobic phase base in a ratio by weight of said active agent to said solvent of from about 1:99 to about 99:1, said dissolved polar agent being retained by said carrier. Claim 4. A cosmetic composition according to claim 1 wherein said dermatologically active agent comprises one or more substances selected from the group consisting of exfoliating skin acids, water-soluble vitamins, astringents, dentifrices and dental care agents, external analgesics, wart removers, anesthetics, keratolytics, anti- inflammatories, anti-dandruff agents, bleaching agents, chemical sunscreen, moisturizers, deodorants, color enhancers, intercellularly active agents and hormones. Claim 5. A cosmetic composition according to claim 3 wherein said dermatologically active agent is a εkin- revitalizing alpha hydroxy acid or beta hydroxy acid. Claim β. A cosmetic composition according to claim 3 wherein said dermatologically active agent is lactic acid. Claim 7. A cosmetic composition according to claim 5 wherein said dermatologically active agent is incorporated in said cosmetic composition in a proportion of from about 0.1 to about 4.0% by weight. Claim 8. A cosmetic composition according to claim 1 wherein said adsorbent or absorbent carrier is selected from the group consisting of organic synthetic polymeric microspheres, silica, starch, polystyrene, spherical cellulose acetate, polyethylene, styrene, polytetrafluoroethylene, polymethyl methacrylate, acrylate polymers, talc, kaolin, mica, calcium silicates, nylon, magnesium carbonate and other salts, boron nitride, polyvinylidene copolymer, silicone resin, polyurethane, organic modified clays and earthen clays. Claim 9. A cosmetic composition according to claim 8 wherein said absorbent carrier is porous. Claim 10. A cosmetic composition according to claim 3 where said absorbent carrier is nylon 12 present in a proportion of from about 5.0 to about 20.0 percent by weight of the composition. Claim 11. A cosmetic composition according to claim 3 wherein said solvent is selected from the group consisting of glycerin, a water soluble cosmetically compatible glycol; water; alcohol; sodium citrates; PPG 650 oleyl ether; glycereth 4,5; lactates; ethoxydiglycol; nonoxynol 10, 12, 14, 40, 50; octoxynol 11, 40; PEG 4 dilaurate; glycereth 7, 26; methylated cyclodextrin; PEG 40; polysorbate 20; and dimethyl dodecylamine oxide. Claim 12. A cosmetic composition according to claim 3 wherein said solvent is glycerin. Claim 13. A cosmetic composition according to claim 3 wherein said carrier is porous and said solvent has a viscosity of from approximately 5 cps to approximately 100,000 cps to control egress of said active agent from said carrier pores. Claim 14. A cosmetic composition according to claim 1 wherein said film-forming agent is selected from the group consisting of solid, liquid or semi-solid saturated, unsaturated or branched fatty esters, amides, alcohols, soaps, waxes and powders and mixtures thereof. Claim 15. A cosmetic composition according to claim 14 wherein said film-forming agents are selected from the group consisting of glyceryl tribehenate, ceresin, microcrystalline wax, volatile silicone, dimethicone, sorbitan isostearate, isononyl isononanoate, cetyl dimethicone, and zinc laurate. Claim 16. A dermatologically active, hydrophobic, eye-area cosmetic composition having appearance-enhancing cosmetic properties combined with dermatological properties, said cosmetic composition comprising: a) a dermatologically acceptable and innocuous porous particulate carrier having an average particle size in excess of lOμm; b) a dermatologically active hydrophilic agent, said active agent being loaded into pores in said particulate carrier; c) a hydrophobic, non-hardening, film-forming system to provide an opaque film including said active- agent-loaded carrier particles, said opaque film covering the skin when said cosmetic composition is spread on the skin; and d) a film-forming adhesive to hold said opaque film to the skin. Claim 17. A cosmetic composition according to Claim 16 wherein said dermatologically active agent is a skin- revitalizing alpha hydroxyacid. Claim 18. A cosmetic composition according to Claim 17 wherein said alpha hydroxy acid is selected from the group consisting of lactic acid, glycolic acid, citric acid, malic acid, equivalents thereof and mixtures of the foregoing ingredients and is present in a proportion of from 0.5 to 8.0% by weight of the composition. Claim 19. A cosmetic composition according to Claim 16 wherein said particulate carrier is a porous synthetic polymeric organic microsphere, with a particle size of from greater than 10 to 100 microns. Claim 20. A cosmetic composition according to Claim 16 having appearance-enhancing cosmetic properties with opaque coloring pigments comprising from 0.10 to 3.0% of the composition by weight. Claim 21. A cosmetic composition according to Claim 16 wherein said hydrophobic film-forming system comprises: i) a hydrophobic-phase solvent vehicle said active- agent-loaded carrier being dispersed in said hydrophobic phase vehicle; ii) a particulate mineral gelling agent; ϋi) a metallic soap gelling agent; and iv) a cosmetic wax material. Claim 22. A cosmetic composition according to Claim 21 wherein said hydrophobic-phase vehicle is a volatile polysiloxane, said particulate mineral gelling agent is a bentonite gelling agent in a proportion of from about 5.0 to 13.0 percent, said metallic soap gelling agent, is an alkaline earth or aluminum alkanoate of from six to twenty carbon atoms in a proportion of from 1.0 to 5.0 percent and said cosmetic wax material is selected from the group consisting of glyceryl wax esters, ceresin waxes, O 96/21422 PCI7US96/01560 -61- microcrystalline waxes, equivalents thereof and mixtures of the foregoing cosmetic wax ingredients, said proportions being by weight based on the weight of the composition. Claim 23. An eyeshadow or eyeshadow primer being a cosmetic composition according to Claim 16 and having skin-moisture enhancing properties. Claim 24. A topically applied cosmetic composition comprising: a) an effective amount of a dermatologically active hydrophilic agent; b) a porous particulate carrier for said active hydrophilic agent, said carrier having an average particle size in the range of from 10 to 50 microns, said active agent being loaded into pores in said carrier; c) a hydrophobic-phase vehicle, said active-agent- loaded carrier being dispersed in said hydrophobic phase vehicle; and d) a hydrophilic viscous solvent for said active agent, said hydrophilic solvent being substantially immiscible with said hydrophobic phase vehicle said active agent being dissolved in said viscous solvent to provide a viscous solution of said active agent, said viscous solution being retained in said carrier pores; whereby topical application of said cosmetic composition brings said viscous solution into contact with the skin for release of said viscous solution from said carrier by skin moisture and delivery of said active agent to the stratum corneum. Claim 25. A topically applied cosmetic composition according to Claim 24 wherein said dermatologically active hydrophilic agent is an alpha hydroxy acid, chosen from a list that includes mixed fruit acids, lactic acid, glycolic acid, citric acid and malic acid, and is present from 0.5 to 8.0% by weight. Claim 26. A topically applied cosmetic composition according to Claim 24 wherein said porous particulate carrier for said active hydrophilic agent is synthetic organic polymeric microsphere present from 5.0 to 20.0 percent. Claim 27. A topically applied cosmetic composition according to Claim 24 wherein said hydrophobic-phase vehicle is a volatile polysiloxane. Claim 28. A topically applied cosmetic composition according to Claim 24 wherein said hydrophilic viscous solvent is glycerol. Claim 29. Λ low wax, cosmetic film-forming system suitable for incorporation in cosmetic eye enhancer compositions said film-forming composition comprising, in weight percent based on the weight of the composition: a) at least 5.0 percent of a particulate mineral gelling agent for a volatile cosmetic solvent; b) at least 1.0 percent of a metallic soap gelling agent; and c) from 0.0 to 5.0 percent of a cosmetic wax material; dispersed in a volatile cosmetic solvent. Claim 30. A film-forming system according to claim 23 comprising from about 8.0 to 20.0 percent of feel-enhancing synthetic polymeric organic microspheres. Claim 31. A film-forming system according to claim 24 wherein: a) said particulate mineral gelling agent comprises a bentonite gelling agent in a proportion of from about 5.0 to 13.0 percent; b) said metallic soap gelling agent is an alkaline earth alkanoate of from six to twenty carbon atoms in a proportion of from 1.0 to 5.0 percent; c) said cosmetic wax material is selected from the group consisting of glyceryl wax esters, ceresin waxes, microcrystalline waxes, equivalents thereof and mixtures of the foregoing cosmetic wax ingredients; and wherein said volatile cosmetic solvent is a cyclomethicone in a proportion of from 30.0 to 70.0 percent. Claim 32. A film-forming system according to claim 31 comprising from about 8.0 to 20.0 percent of feel-enhancing synthetic polymeric organic microspheres. Claim 33. A cream-to-powder cosmetic composition comprising a major proportion of a low-wax film-forming system according to claim 32. Claim 34. A process for preparing a topically applied cosmetic composition according to claim 1 comprising: a) blending said dermatologically active agent or a solution thereof with said absorbent particulate carrier until said active agent is completely absorbed by said carrier; and b) adding said carrier and dermatologically active agent complex to said hydrophobic cosmetic base.

Inventors: LABOY YOLANDA, SZCZEPANOWSKI ANNA, WILMOTT JAMES MICHAEL, LABOY, YOLANDA, SZCZEPANOWSKI, ANNA, WILMOTT, JAMES, MICHAEL
Applicants: MARY KAY INC, MARY KAY INC.
Application year: 1996
Main classification: A61K7
IPC codes: A61K8, A61Q19