MXPA03002168A - Cosmetic method. - Google Patents

Abstract

In accordance with the present invention, there is provided a cosmetic method for providing improved hydration of the skin wherein the method comprises topically applying a protease enzyme to the skin, and simultaneously or sequentially applying a polyhydric alcohol to the skin; provides a cosmetic method for providing improved hydration to the skin wherein the method comprises topically applying a polyhydric alcohol to the skin, and simultaneously or sequentially applying a protease enzyme topically on the skin, and a cosmetic method is provided to provide improved hydration to skin wherein the method comprises topically applying the skin a cosmetic composition comprising (a) from about 0.0001% to about 1%, by weight, of protease enzyme, and (b) from about 0.1% to about 20%, in weight, polyhydric alcohol, finally a cosmetic method is provided to provide improved skin hydration ue comprises applying topically to the skin a first cosmetic composition comprising from about 0.0001% to about 1%, by weight, of protease enzyme, and either simultaneously or sequentially applying topically to the skin a second cosmetic composition comprising from about 0.1% to about 20%, by weight, of polyhydric alcohol

Description

COSMETIC METHOD TECHNICAL FIELD The present invention relates to the use of cosmetic compositions comprising a protease enzyme and a polyhydric alcohol to improve skin hydration, skin smoothness and skin smoothness.

BACKGROUND OF THE INVENTION The skin is made up of several layers of cells that cover and protect the fibrous proteins of keratin and collagen that form the skeleton of its structure. It is known that the outermost layer of these layers, referred to as the stratum corneum, is composed of bundles of 25 nm proteins surrounded by 8 nm thick layers. Anionic surfactants and organic solvents typically penetrate the stratum corneum membrane and, by delipidization (ie, removing the lipids from the stratum corneum), destroy their integrity. This destruction of the topography of the surface of the skin produces a rough sensation and may eventually allow the surfactant or solvent to interact with the keratin, creating irritation. Dry, stinging or scaly skin may also be produced from the deficiency to maintain an adequate water gradient across the stratum corneum. Most of the water needed to maintain the water gradient, which is sometimes considered the plasticizer of the stratum corneum, comes from the inside of the body. If the humidity is too low, such as in cold weather, insufficient water remains in the outer layers of the stratum corneum to plasticize the tissue, and the skin begins to peel and becomes a skin that has itching. The use of protease enzymes in cosmetic compositions is known to provide a benefit for skin care. It is believed that protease enzymes function primarily by providing a desquamatory action to the cosmetic composition. It is believed that proteases remove damaged (ie, dry) skin cells on the surface of the skin, thereby reducing the harshness associated with them. The protease removes the effect of previous damage to the skin, giving the skin a fresher, more youthful appearance and feel. The descriptions describing the cosmetic compositions comprising protease enzymes have been focused to date on the stabilization of the enzyme within the composition. These descriptions include the encapsulation of the enzymes before inclusion within the cosmetic composition (GB 1, 255, 284 and JP 10-251 122); regulating the pH of the cosmetic composition in such a way that the enzyme remains inactive until it is used (WO 97/47238); and use of precursors or other active ingredients within the composition to stabilize the enzyme (EP 0710478 and EUA 1690764). However, the method favored in the art for stabilizing protease enzymes in cosmetic compositions is to dramatically reduce the availability of water within the composition by formulating the aqueous phase of any composition with very high levels of polyhydric alcohols such as glycerin, described in JP 1283213, JP 329421 1. Unfortunately, such systems have unacceptable aesthetics for cosmetic products. This has been overcome until recently by the formulation of the aqueous phase within a water-in-oil emulsion (EUA 5, 932, 234 and EUA 5, 830, 449) or within a triple water-in-oil-in-water emulsion (EP 0779071). An additional solution has been to store the product inside two different chambers in a single package wherein the first chamber contains the enzyme stabilized at high levels of polyhydric alcohol and the second chamber contains an aqueous cosmetic composition such that when the two phases are dispense and mix, the final aqueous composition has acceptable aesthetics (WO 97/27841). While the foregoing technique provides useful advantages in the stabilization of enzymes, particularly protease enzymes, within a range of cosmetic compositions it does not sufficiently teach the use of cosmetic compositions comprising a protease enzyme and a polyhydric alcohol to improve hydration of the skin, softness of the skin and smoothness of the skin. It is also known to use polyhydric alcohols such as glycerin in cosmetic compositions to provide skin moisturizing benefits. Despite this, there is still a desire to provide additional improvements in skin moisturization (hydration), softness of the skin and smoothness of the skin. It has now surprisingly been found that by applying a protease enzyme to the skin and, simultaneously or sequentially applying a polyhydric alcohol to the skin, a significant improvement in skin moistening can be observed (as measured by the improved hydration to the skin), as well as the smoothness of the skin and smoothness of the skin over what could be expected from the use of polyhydric alcohol alone. Without wishing to adhere to the theory, it is believed that the desquamation effect of the protease enzyme removes the dead layers of skin from the upper part, revealing the healthy lower layers which are easier to hydrate by the polyhydric alcohol.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the first aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin wherein the method comprises applying topically to the skin a protease enzyme, and simultaneously or sequentially, applying topically to the skin a polyhydric alcohol. According to a second aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin wherein the method comprises applying topically to the skin a polyhydric alcohol, and simultaneously or sequentially, applying topically to the skin a enzyme protease. According to a third aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin wherein the method comprises applying topically to the skin a cosmetic composition comprising (a) from about 0.0001% to about 1%, in weight, of enzyme protease; and (b) from about 0.1% to about 20%, by weight, of polyhydric alcohol. According to a fourth aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin comprising topically applying to the skin a first cosmetic composition comprising from about 0.0001% to about 1%, by weight, of enzyme protease, and either simultaneously or sequentially apply topically to the skin a second cosmetic composition comprising from about 0.1 to about 20%, by weight, of polyhydric alcohol. The methods of the present invention provide significant improvements in the benefits of skin hydration, skin smoothness and skin smoothness.

DETAILED DESCRIPTION OF THE INVENTION All percentages and ratios used in the present invention are by weight of the total composition and all measurements were made at 25 ° C, unless otherwise designated. Unless otherwise indicated all percentages, ratios and levels of ingredients referred to in the present invention are based on the actual amount of the ingredient, and do not include solvents, fillers or other materials which may be combined with the ingredient in commercially available products. available. The length of the chain and degree of ethoxylation are also specified on a basis of average weight. All publications cited in the present invention are incorporated herein by reference in their entirety, unless otherwise indicated. The term "enzyme" as used in the present invention means the enzyme, wild type or variant, either modified per se, or chemically modified by the conjugation of polymer portions. The term "protease enzyme" as used in the present invention refers to any enzyme whose substrate is a protein. As used in the present invention, the term "wild type" refers to an enzyme produced by non-mutated hosts. As used in the present invention, the term "variant" means an enzyme having an amino acid sequence which differs from that of the wild type enzyme due to the genetic mutation of the host that produces that enzyme. As used in the present invention, "enzyme activity" refers to the activity of 20 μ? of a solution of the enzyme (50 ppm) when reacted with the surface of a suitable proteinaceous substrate disc of 1 cm in diameter, at room temperature for a period of 30 minutes. By adjusting the pH of the pH buffer solution of the enzyme, it is possible to compare the effect of pH on enzyme activity. For enzymes for use in the present invention, suitable activity is defined as greater than 20% of the complete reaction within the first 30 minutes, preferably greater than 50%, more preferably greater than 75%. By using this measurement it is defined that the pH regulators of the enzyme with a pH lower than 5.5 are not suitable for use with this enzyme. The term "skin hydration" as used in the present invention refers to an improvement in the moisture content of the skin, which can be determined either by technical measurements such as through the use of a commometer, etc., or measurements made by a visual expert, for example Fitzpatrick skin dryness scale or by the own evaluation made by the consumer. The "water activity aw" of a medium containing water is the ratio of water pressure in the vapor state of the product "PH20 of the product" to the vapor pressure of pure water "pure PH20" at the same temperature. This can also be expressed as the ratio of the number of water molecules "NH2O" to the total number of molecules.

"NH2O + N dissolved substances", which takes into account the Dissolved substance molecules "N dissolved substances".

It is given by the following formulas: aw = Product of PH? Q = NH3O. PH20 NH20 + N dissolved substances Several methods can be used to measure activity of the Water. The most common is the manometric method, by means of which the pressure of steam is measured directly.

The elements of these compositions are described in greater detail below.

Cosmetic method The methods of the present invention comprise the application to the skin of a protease enzyme together with a polyhydric alcohol. The enzyme protease and polyhydric alcohol can be administered to the skin either from simultaneously or sequentially.

Therefore, in accordance with one aspect of this invention, a cosmetic method is provided to provide improved hydration to the skin that comprises applying a protease enzyme topically to the skin, and simultaneously or sequentially, apply topically to the skin a polyhydric alcohol.

In another aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin comprising topically applying a polyhydric alcohol to the skin and simultaneously or sequentially applying a protease enzyme to the skin. It is also possible to administer the protease enzyme and the polyhydric alcohol to the skin simultaneously from a single cosmetic composition, which essentially means at the same time. It is also possible to administer the enzyme protease and polyhydric alcohol to the skin sequentially from two separate cosmetic compositions. By sequentially it is understood that the two compositions are administered one after the other, in any order, wherein the second composition is added within the first hour of administration of the first composition. It is preferred that the enzyme composition is first applied to the skin. It is further preferred that the polyhydric alcohol composition be added before the pH buffer from the enzyme composition has evaporated. Therefore, in accordance with another aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin comprising topically applying to the skin a cosmetic composition comprising from about 0.0001% to about 1%, preferably about 0.001% to about 0.5%, and more preferably from about 0.005% to about 0.1%, by weight, of a protease enzyme and from about 0.1% to about 20%, preferably from about 0.5% to about 18%, more preferably from about 2% to about 15% and even more preferably from about 5% to about 12%, by weight, of polyhydric alcohol. As an alternative, the polyhydric alcohol and protease enzyme can be administered to the skin from separate cosmetic compositions. Therefore, in accordance with another aspect of the present invention, there is provided a cosmetic method for providing improved hydration to the skin comprising topically applying to the skin a first cosmetic composition comprising a protease enzyme, and simultaneously or sequentially applying topically to the skin a second cosmetic composition comprising polyhydric alcohol. The compositions of the present invention are suitable for topical application to the skin or hair. In particular, the compositions may be in the form of creams, lotions, gels, and the like. Preferably the cosmetic compositions of the present invention are in the form of an emulsion of one or more oil phases in an aqueous continuous phase.

Enzyme protease An essential component used in the methods of the present invention is a protease enzyme.

Protease enzymes are classified under the classification number for enzyme E.C.3.4 (Carboxylic Ester Hydrolases) in accordance with the Recommendations (1992) of the International Union of Biochemistry and Molecular Biology (IUBMB). Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/3001 1 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company. Preferred protease enzymes for use in the present invention are subtilisin, chymotrypsin and elastase type protease enzymes. Subtilisin type proteases are especially preferred for use in the present invention. The subtilisin enzymes are produced naturally by the microorganisms Bacillus alkalophilus, Bacillus amyloliquafacians, Bacillus amylosaccharicus, Bacillus licheniformis, Bacillus lentus and Bacillus subtilis. A particularly preferred subtilisin type enzyme is the bacterial enzyme serin protease, and variants thereof, obtained from Bacillus amyloliquefaciens, Bacillus licheniformis and / or Bacillus subtilis, including from Novo Industries A / S Alcalase®, Esperase®, Savinase® ( Copenhagen, Denmark), Maxatase® by Gist-brocades, Maxacal® and Maxapem 15® (protein designed by Maxacal®) (Delft, The Netherlands), and subtilisin BPN and BPN ', which are commercially available.

Especially preferred are the protease enzymes, and variants thereof, obtained from Bacillus amyloliquefaciens. A known enzyme is BPN '. The wild-type BPN 'from Bacillus amyloliquefaciens is characterized by the amino acid sequence: 1 10 20 There Ola Ser Val Pro Tyr Gly Val Ser Obi De Lys Ala Pro Ala Leu His Ser Gto Qly 30 40 Tyr Thr Gly Ser Asn Val Lys Val Ale Val He Asp Ser Gly lio Asp Ser Ser His Pro 50 60 Asp Leu Lys Val Ala Gfy Gly Ala Ser Met Val Pro Ser Glu Thr Ara Pro Phc Gln Aap 70 SO Am Asn Set Hí «Qry Thr Hli Vel A Gly Thr Val Alt- Al * Leu Ata Asn Ser Ue Gly 90 100 Val Lea Gly Val Ala Pro Ser Ala Ser Leu Tyr Ala Vil L i Val Leu Gly Ala Asp Gly 110 120 Ser Gly Qln Tyr Ser Trp From He Asn Oly He Glu Trp Wing? ß Wing Asn Aen Met Atp 130 140 Val Asn Met Ser Read Gly Gly Pro Ser Gly Ser Wing. Ala Leu Lys Ala Ala Val Asp 150 1 «0 Lys Wing Val Wing Ser Gly Val Val Val Val Wing Wing Wing Gly Asn Glu Gly Thr Ser Gly 170 180 Ser Being Thr Val Gly Tyr Pro Gly Lya Tyr Pro Ser Val lie Wing Val Gly Ala Val 190 200 Asp Ser As Asn Gln Arg Ala Sar P e Ser Ser Val Gly Pro Olu Leu Asp Val Met Ak 210 220 PTO Oly Val Ser Ilc Ghi Ser Thr Leu Pro Gly Asn Lys Tyr Gly Wing Tyr Asn Gly Thr 230 240 Ser Mct Wing Ser Pro His Val Ala Gly Ala Ala Ala Leu Ho Leu Ser Lys His Pro Asn 250 260 Trp Thr Asn Thr Gln Val Arg Ser Ser Leu Glu Asn Thr Thr Thr Lys Leu Gly Asp Ser 270 275 Phe Tyr Tyr Gly Lys Lys Gly Leu He Am Ata Val Gln Ala Ala Ala Qln The variants of BPN ', hereinafter referred to as "Protease A", are described in the patent of E.U.A. No. 5, 030, 378 (issued to Venegas on July 9, 1991) as characterized by the amino acid sequence of BPN 'with the following mutations: a. ) The Gly at position Gly166 is replaced with Asn, Ser, Lys, Arg, His, Gln, Ala or Glu; the Gly in position Gly169 is replaced with Ser; the Met at the Met222 position is replaced with Gln, Phe, Cys, His, Asn, Glu, Ala or Thr; or b. ) The Gly at position Gly166 is replaced with Lys and the Met at position Met222 is replaced with Cys; or c. ) The Gly at position Gly160 is replaced with Ala and the Met at position Met222 is replaced with Ala. Additional variants of BPN1, hereinafter referred to as "Protease B", are described by the European Patent of Genencor International, Inc. (San Francisco, California) EP-B-251, 446 (granted on December 28, 1994 and published on January 7, 1988) as characterized by wild-type BPN 'amino acids with mutations in one or more of the following amino acids: Tyr21, Thr22, Ser24, Asp36, Ala45, Ala48, Ser49, Met50, His67, Ser87 , Lys94, Val95, Gly97, Ser101, Gly 02, Gly 03, Ile107, Gly1 10, Met124, Gly127, Gly128, Pro129, Leu135, Lys170, Tyr171, Pro172, Asp 97, Meti 99, Ser204, Lys213, Tyr214, Gly215, and Ser221; or two or more of the amino acids listed above and Asp32, Ser33, Tyr104, Alai 52, Asn155, Glu156, Gly156, Gly166, Gly169, Phe189, Tyr217, and Met222 where both mutations can not be made in the amino acids Asp32, Ser33, Tyr104 , Ala152, Asn155, Glu156, Gly166, Gly169, Phe189, Tyr217, and et222. Another preferred BPN variant protease, hereinafter referred to as "Protease D", is described in WO 95/10615 published April 20, 1995 by Genencor International as characterized by wild-type BPN 'amino acids with the position Asn76, in combination with mutations in one or more of the selected amino acid positions from the group consisting of Asp99, Ser101, Gln103, Tyr104, Ser105, Ile107, Asn109, Asn123, Leu126, Gly127, Gly128, Leu135, Glu156, Gly166, Glu195, Asp197, Ser204, Gln206, Pro210, Ala216, Tyr217, Asn218, Met222, Ser260, Lys265, and / or Ala274. Another preferred BPN variant protease, hereinafter referred to as "Protease F", is described in the US patent. Number 4, 760, 025, issued to Estell, et al. on July 26, 1988 and characterized by wild-type BPN 'amino acids with mutation at one or more amino acid positions selected from the group consisting of Asp32, Ser33, His64, Tyr104, Asn155, Glu.156, Gly166, Gly169, Phe189, Tyr217, and Met222. The preferred proteolytic enzymes, therefore, are selected from the group consisting of Alcalase®, BPN ', Protease A, Protease B, Protease D, and Protease F, and mixtures thereof. The protease F is the most preferred. The compositions for use in the present invention comprise from about 0.0001% to about 1%, more preferably from about 0.001% to about 0.5%, even more preferably from about 0.005% to about 0.1%, by weight, of the enzyme protease.

Polyhydric Alcohol Compositions for use in the present invention comprise at least one polyhydric alcohol in a concentration of from about 0.1% to about 20%, preferably from about 0.5% to about 18%, more preferably from about 2% to about 15%, and even more preferably from about 5% to about 12% by weight, of polyhydric alcohol, or mixtures thereof.

For the purposes of this invention a polyhydric alcohol is considered any organic compound comprising two, or more, alcohol functions or alkoxylated derivatives thereof. It is further preferred that, in the composition having the form of an oil-in-water emulsion, the polyhydric alcohol be present in the continuous phase. Polyhydric alcohols suitable for use in the present invention include 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, erythritol, threitol, pentaerythritol, xylitol, glucitol, mannitol. , hexylene glycol, butylene glycol (for example, 1, 3-butylene glycol), hexanetriol (for example, 1,2,6-hexanetriol), trimethylol propane, neopentyl glycol, glycerin, ethoxylated glycerin, propan-1,3-diol, propoxylated glycerin and mixtures thereof. The alkoxylated derivatives of any of the above polyhydric alcohols are also suitable for use in the present invention. Preferred polyhydric alcohols of the present invention are selected from glycerin, butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, hexantriol, ethoxylated glycerin and propoxylated glycerin, and mixtures thereof. The most preferred polyhydric alcohols for use in the present invention are glycerin, butylene glycol, propylene glycol, polyethylene glycol and mixtures thereof.

Optional ingredients The compositions used in the present invention may comprise a wide variety of optional ingredients.

Vehicle The compositions of the present invention comprise a safe and effective amount of a dermatologically acceptable vehicle, suitable for topical application to the skin or hair, within which essential materials and other optional materials are incorporated to allow essential materials and optional components are administered to the skin or hair at an appropriate concentration. The vehicle can therefore act as a diluent, dispersant, solvent, or the like for the essential components which ensures that they can be applied and distributed homogeneously on the selected target at an appropriate concentration. The vehicle can be solid, semi-solid or liquid. Highly preferred vehicles are liquid or semi-solid, such as creams, lotions and gels. Preferably the vehicle is in the form of a lotion, cream or gel, more preferably one having a sufficient thickness or having a point of deformation to prevent the particles from settling. The vehicle may itself be inert or it may provide dermatological benefits by itself. The vehicle must also be physically and chemically compatible with the essential components described in the present invention, and must not unduly impair the stability, efficiency or other beneficial uses associated with the compositions of the present invention. The type of vehicle used in the present invention depends on the type of product form desired for the composition. Topical compositions useful in the present invention can be made in a wide variety of product forms such as are known in the art. These include, but are not limited to, lotions, creams, gels, bars, ointments, pastes and foams. These product forms may comprise various types of vehicles including, but not limited to,, solutions, emulsions, and gels. Preferred carriers contain a hydrophilic, dermatologically acceptable diluent. Suitable hydrophilic diluents include water, organic hydrophilic diluents such as C1-C4 monohydric alcohols and low molecular weight polyols and glycols, including propylene glycol, polyethylene glycol (for example of MW 200-600), polypropylene glycol (for example of PM 425-2025 ), glycerol, butylene glycol, 1, 2,4-butanetriol, esters of sorbitol, 1, 2,6-hexametriol, ethanol, iso-propanol, sorbitol esters, ethoxylated ethers, propoxylated esters and combinations thereof. The diluent is preferably liquid. Water is an especially preferred diluent. The composition preferably comprises at least about 20% of the hydrophilic diluent.

Preferred carriers comprise an emulsion comprising a hydrophilic phase, especially an aqueous phase, and a hydrophobic phase eg, a liquid, oil or oily material. As is well known to one skilled in the art, the hydrophilic phase will be dispersed in the hydrophobic phase, or vice versa, to form respectively dispersed and continuous hydrophilic or hydrophobic phases, depending on the ingredients of the composition. In emulsion technology, the term "dispersed phase" is a term well known to one skilled in the art which means that the phase exists as small particles or droplets that are suspended in and surrounded by a continuous phase. The dispersed phase is also known as the internal or discontinuous phase. The emulsion may be or comprise (for example, in a triple emulsion or another multi-phase emulsion) an oil-in-water emulsion or a water-in-oil emulsion such as a water-in-silicone emulsion. Oil-in-water emulsions typically comprise from about 1% to about 60% (preferably from about 1% to about 30%) of the hydrophobic dispersed phase and from about 1% to about 99% (preferably from about 40% to about 90%) of the continuous hydrophilic phase; water-in-oil emulsions typically comprise from about 1% to about 98% (preferably from about 40% to about 90%) of the hydrophilic dispersed phase and from about 1% to about 50% (preferably from about 1% to about 30%) of the continuous hydrophobic phase. Preferred compositions in the present invention are oil-in-water emulsions.

Active for skin care A preferred ingredient of the compositions of the present invention comprises a skin care active at a level of from about 0.1% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 8% , in weigh. The skin care active for use in the present invention is selected from the vitamin B3 component, panthenol, vitamin E, vitamin E acetate, retinol, retinylpropionate, retinyl palmitate, retinoic acid, vitamin C, theobromine. a-hydroxycissic, farnesol, phytantriol, salicylic acid, and mixtures thereof. The preferred active for skin care for use in the present invention from the viewpoint of providing improved hydration to the skin is a component of vitamin B3.

Vitamin B3 Component The compositions of the present invention preferably comprise from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, even more preferably from about 0.5% to about 10%, and even more preferably from about 1% to about 8%, more preferably from about 1.5% to about 6%, of the vitamin B3 compound. As used in the present invention, "vitamin B3 compound" means a compound having the formula: Where R is -CONH2 (for example, niacinamide), -COOH (for example, nicotinic acid) or -CH2OH (for example, nicotinyl alcohol); derived from them; and you leave any of the preceding ones. Exemplary derivatives of the above vitamin B3 compounds include nicotinic acid esters, including non-vasodilating nicotinic acid esters, nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid trioxide, and niacinamide N-oxide. Suitable nicotinic acid esters include C 1 -C 22 nicotinic acid esters. preferably C 6 C 6, more preferably C C alcohols. The alcohols are suitably straight chain or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic), and substituted or unsubstituted. The asters are preferably not vasodilators. As used in the present invention, "non-vasodilator" means that asters do not commonly produce a visible blush response after application to the skin in the present compositions (the majority of the general population may not experience a visible blush response, although such compounds may cause vasodilation not visible to the naked eye). Non-vasodilating nicotinic acid esters include tocopherol nicotinate and inositol hexanicotinate; the tocopherol nicotinate is preferred. A more complete description of the vitamin B3 compounds is given in WO 98/22085. Examples of the aforementioned vitamin B3 compounds are well known in the art and are commercially available from various sources, for example, the Sigma Chemical Company (St. Louis, MO); ICB Biomedicals, Inc. (Irvin, CA) and Aldrich Chemical Company (Milwaukee, Wl). One or more vitamin B3 compounds can be used in the present invention. The preferred vitamin B3 compounds are niacinamide and tocopherol nicotinate. Niacinamide is more preferred.

Retinoids Another active suitable for skin care is a retinoid. As used in the present invention, "retinoid" includes all natural and / or synthetic vitamin A analogs or retinol-like compounds that possess the biological activity of vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds. The retinoid is preferably retinol, retinol esters (for example, C2-C22 alkyl retinol esters, including retinyl palmitate, retinyl acetate, retinyl propionate), retinal, and / or retinoic acid (including all transretinoic acids and or 13-cis-retinoic acid), more preferably retinoids other than retinoic acid. These compounds are well known in the art and are commercially available from various sources, for example, Sigma Chemical Company (St. Louis, MO), and Boehringer Mannheim (Indianapolis, IN). Preferred retinoids are retinol, retinyl palmitate, retinyl acetate, retinyl propionate, retinal, retinoic acid and combinations thereof. More preferred are retinol, retinoic propionate, retinoic acid and retinyl palmitate. The retinoid may be included as the substantially pure material, or as a suitable extract obtained by physical and / or chemical isolation from natural sources (e.g., plant). The compositions preferably contain from or about 0.005% to or about 2%, more preferably from 0.01% to about 2% retinoid. The retinol is most preferably used in an amount of or from about 0.01% to or about 0.15%; the retinol esters are more preferably used in an amount from about 0.01% to about 2% (eg, about 1%). It is highly preferred that compositions suitable for use in the present invention comprise a vitamin complex consisting of from about 1% to about 5%, by weight, of the vitamin B3 compound or its derivatives; and from about 0.1% to about 1%, by weight, of a retinol compound or its derivatives in conjunction with from about 0.1% to about 1%, by weight, of panthenol or its derivatives.

Additional humectants The compositions of the present invention may comprise additional humectants which are preferably present at a level of from about 0.01% to about 20%, more preferably from about 0.1% to about 15% and especially from about 0.5% to about 10%. Preferred humectants include, but are not limited to, compounds selected from urea, Panthenol D or DL, calcium pantothenate, royal jelly, panthenol, pantothein, panthenilether, pangamic acid, pyridoxine, pantonyl lactose complex, Vitamin B, hexane-1, 2,6, -triol, guanidine or its derivatives. Highly preferred humectants are urea, panthenol and mixtures thereof. The compounds listed above can be incorporated in particular or in combination. Additional suitable humectants useful in the present invention are 2-pyrrolidone-5-carboxylate (NaPCA), guanidine; glycolic acid and glycolate salts (for example ammonium and quaternary alkylammonium); lactic acid and lactate salts (for example ammonium and quaternary alkylammonium); aloe vera and any of its varieties of forms (for example, aloe vera gel); hyaluronic acid and derivatives thereof (e.g., salts derived such as sodium hyaluronate); lactamide monoethanolamine, acetamide monoethanolamine; urea; panthenol and derivatives thereof; and mixtures thereof. At least part (up to about 5% by weight of the composition) of an additional humectant can be incorporated in the form of a mixture with a hydrophobic crosslinked acrylate or methacrylate copolymer in particle form, which is preferably present in an amount of approximately 0.1% to approximately 10%, which can be added either to the aqueous phase or to the dispersed phase. This copolymer is particularly valuable for reducing the gloss and controlling the oil while helping to provide effective wetting benefits and is described in more detail by WO 96/03964, incorporated herein by reference. The compounds listed above can be incorporated in particular or in combination. The preferred additional humectants are selected from urea, panthenol and mixtures thereof.

Emollients The oil-in-water emulsions of the present invention generally comprise from about 1% to about 20%, preferably from about 1.5% to about 15%, more preferably from about 0.1% to about 8%, especially from about 0.5% to about 5%. % of a dermatologically acceptable emollient. Emollients tend to lubricate the skin, increase the softness and elasticity of the skin, prevent or alleviate the dryness of the skin, and / or protect the skin. Emollients are typically not miscible in water, oily or waxy materials and emollients with high molecular weights can confer tack properties to a topical composition. A wide variety of suitable emollients are known and can be used in the present invention. Sagarin, Cosmetics and Technology. 2nd edition, Volume 1, pp. 32-43 (1972), contains numerous examples of suitable materials as an emollient. All emollients discussed in the application WO 00/24372 should be considered as suitable for use in the present invention even though the preferred examples are outlined in more detail below: i) Straight or branched chain hydrocarbons having approximately 7 to about 40 carbon atoms, such as dodecane, squalane, cholesterol, hydrogenated polyisobutylene, isohexadecane, isoeicosane, isooctahexacontane, isohexapentacontahectane, and C7-C40 isoparaffins, which are branched C7-C4o hydrocarbons. Branched chain hydrocarbons suitable for use in the present invention are selected from isopentacontaoctactane, petrolatum, and mixtures thereof. Suitable for use in the present invention are the branched chain aliphatic hydrocarbons sold under the trade name Permethyl (RTM) and commercially available from Presperse Inc., P.O. Box 735, South Plainfield, N.J. 07080, E.U.A. ii) C1-C30 alcohol esters of C1-C30 carboxylic acids, C-12-C15 alkyl benzoates, and C2-C30 dicarboxylic acids, for example isononyl isononanoate, isostearyl neopentanoate, isodecyl octanoate, isodecyl isononanoate, tridecyl isononanoate, myristyl octanoate, octyl pelargonate, octyl isononanoate, myristyl myristate, myristyl neopentanoate, myristyl octanoate, isopropyl myristate, myristyl propionate, isopropyl stearate, isopropyl isostearate, isostearate methyl, behenyl behenate, dioctyl maleate, diisopropyl adipate, and diisopropyl dilinoleate and mixtures thereof. iii) Mono- and poly-esters of sugars of C1-C30 and related materials. These asters are derived from a sugar or polyol portion and one or more portions of carboxylic acids. Depending on the constituent acid and sugar, these esters can be either liquid or solid at room temperature. Examples include: glucose tetraoleate, galactose tetraesters of oleic acid, sorbitol tetraoleate, sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, sorbitol hexaester in which the portions of carboxylic acid ester are pamitoleate and arachididate in a 1: 2 molar ratio, and the octaester of sucrose wherein the esterified carboxylic acid moieties are laurate, linoleate and behenate in a 1: 3: 4 molar ratio. Other materials include sucrose fatty acid esters of cottonseed oil or soybean oil. Other examples of such materials are described in WO 96/16636, incorporated herein by reference. A particularly preferred material is known by the name INCI polysemilladealgodonate sucrose. iv) Vegetable agents and hydrogenated vegetable oils. Examples of vegetable oils and hydrogenated vegetable oils include safflower oil, coconut oil, cottonseed oil, shad oil, palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil, flax seed oil, rice bran oil, pine oil, oil of sesame, sunflower seed oil, partially or completely hydrogenated oils from the preceding sources, and mixtures thereof. v) Soluble wetting agents or colloidally soluble wetting agents. Examples include hyaluronic acid and sodium polyacrylates grafted with starch such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in EUA-A-4. , 076, 663. Preferred emollients for use in the present invention are isohexadecane, isooctacontane, petrolatum, isononyl isononanoate, isodecyl octanoate, isodecyl isononanoate, tridecyl isononanoate, myristyl octanoate, octyl isononanoate, myristyl myristate, isostearate. of methyl, isopropyl isostearate, d2-C-15 alkyl benzoates and mixtures thereof. Particularly preferred emollients for use in the present invention are isohexadecane, isononyl isononanoate, methyl isostearate, isopropyl isostearate, petrolatum, or mixtures thereof. Due to its poor properties with respect to skin feel, castor oil is not a preferred emollient for use in the present invention.

Surface-active emulsifiers / surfactants The compositions in the present invention preferably contain an emulsifier / or surfactant, generally to help disperse and suspend the dispersed phase within the continuous aqueous phase. A surfactant may also be useful if the product is intended for skin cleansing. For convenience, hereinafter emulsifiers will be referred to under the term 'surfactants', so 'surfactant agent (s)' will be used to refer to surface active agents if used as an emulsifier or for other agent purposes. surfactant such as skin cleansing Known or conventional surfactants can be used in the composition, with the proviso that the selected agent is chemically and physically compatible with the essential components of the composition, and provides the desired characteristics. Suitable surfactants include materials derived from non-silicone materials, and mixtures thereof All of the surfactants discussed in the application WO 00/24372 should be considered as suitable for use in the present invention.

The compositions of the present invention preferably comprise from about 0.5% to about 15% of a surfactant or mixtures of surfactants. The exact surfactant or mixtures of surfactants chosen will depend on the pH of the composition and other components present. Preferred surfactants are nonionic surfactants. Among the nonionic surfactants which are useful in the present invention are those which can be broadly defined as condensation products of long-chain alcohols, for example C8-C30 alcohols, with sugar or starch polymers, ie glycosides. Other useful nonionic surfactants include the condensation products of the alkylene oxides with fatty acids (for example alkylene oxide esters of fatty acids). These materials have the general formula RCO (X) nOH wherein R is an alkyl group of Cm-C30, X is -OCH2CH2- (for example derived from ethylene glycol or oxide) or -OCH2CHCH3- (e.g. from propylene glycol or from oxide), and n is an integer from about 6 to about 200. Other nonionic surfactants are the condensation products of the alkylene oxides with 2 moles of fatty acids (eg, alkylene oxide diesters of acids fatty). These materials have the general formula RCO (X) nOOCR wherein R is a C10-C3o alkyl group, X is -OCH2CH2- (for example derived from ethylene glycol or oxide) or -OCH2CHCH3- (e.g. from propylene glycol or from oxide), and n is an integer from about 6 to about 100. An emulsifier for use in the present invention is more preferably a mixture of fatty acid ester based on a mixture of fatty acid ester of sorbitan and ester of sucrose fatty acid, especially a mixture of sorbitan stearate and sucrose cocoate. This is commercially available from ICI under the trade name Arlatone 2121. Even more suitable examples include a mixture of cetearyl alcohols, cetearyl glycosides such as those available under the trade name Montanov 68 from Seppic and Emulgade PL 68/50 available from from Henkel. The hydrophilic surfactants useful in the present invention may alternatively or additionally include any of a wide variety of cationic, anionic, zwitterionic, and amphoteric surfactants such as those known in the art. See, for example, McCutcheon's, Detergent and Emulsifiers. North American Edition (1986), published by Allured Publishing Corporation; Patent of E.U.A. No. 5, 01 1, 681 to Ciotti et al., Filed on April 30, 1991; Patent of E.U.A. No. 4, 421, 769 to Dixon et al., Presents December 20, 1983; and Patent of E.U.A. No. 3, 755, 560 to Dickert et al., Filed August 28, 1973. A wide variety of anionic surfactants are also useful in the present invention. See, for example, U.S. Patent. No. 3, 929, 678 to Laughlin et al., Filed December 30, 1975. A wide variety of anionic surfactants are also useful in the present invention. See, for example, U.S. Patent. No. 3, 929, 678 to Laughlin et al., Filed December 30, 1975. Exemplary anionic surfactants include alkyl (eg, C12-C30) isethionates, alkyl and alkyl ether sulfates and salts of the same, alkyl and alkyl ether phosphates and salts thereof, alkylmethyl taurates (e.g., C12-C30), and soaps (e.g., alkali metal salts, e.g., sodium or potassium salts) fatty acids. Amphoteric and zwitterionic surfactants are also useful in the present invention. Examples of amphoteric and zwitterionic surfactants which can be used in the compositions of the present invention are those which are widely described as derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical can be a straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 22 carbon atoms (preferably Ca-Ci8) and one contains an anionic water solubilizing group, for example, carboxyl, sulfonate, sulfate, phosphate, or phosphonate. Examples are alkyl imino acetates, and iminodialkanoates and aminoalkanoates, imidazolinium and ammonium derivatives. Other suitable amphoteric and zwitterionic surfactants are those selected from the group consisting of branched and unbranched alkanol betaines, sultaines, hydroxysultaines, and sarcosinates, and mixtures thereof. Preferred emulsions of the present invention include an emulsifier or surfactant that contains silicone. A wide variety of silicone emulsifiers are used in the present invention. These silicone emulsifiers are typically organically modified organopolysiloxanes, also known to those skilled in the art as silicone surfactants. Useful silicone emulsifiers include dimethicone copolyols. These materials are polydimethyl siloxanes which have been modified to include polyether side chains such as polyethylene oxide chains, polypropylene oxide chains, mixtures of these chains, and polyether chains containing portions derived from both ethylene oxide as propylene oxide. Other examples include alkyl-modified dimethicone copolyols, for example, compounds containing pendant C2-C30 side chains. Even other useful dimethicone copolyols include materials having various cationic, anionic, amphoteric, and zwitterionic pendant moieties.

POLYMER THICKENING AGENTS The compositions of the present invention may comprise at least one polymeric thickening agent. The polymeric thickening agents useful in the present invention preferably have an average molecular weight number greater than 20,000, more preferably greater than 50,000 and especially greater than 100,000. In general, the compositions of the present invention may comprise from about 0.01% to about 10%, preferably from about 0.1% to about 8% and more preferably from about 0.5% to about 5% by weight of the composition of the polymeric thickening agent, or mixtures thereof. Preferred polymeric thickening agents for use in the present invention include nonionic thickeners and anionic thickening agents, or mixtures thereof. Suitable nonionic thickening agents include polyacrylamide polymers, crosslinked poly (N-vinylpyrrolidones), polysaccharides, natural or synthetic gums, polyvinylpyrrolidone, and polyvinylalcohol. Suitable anionic thickening agents include copolymers of acrylic acid / ethyl acrylate, carboxyvinyl polymers and crosslinked copolymers of alkylvinyl ethers and maleic anhydride. Particularly preferred thickeners for use in the present invention are nonionic polyacrylamide polymers such as polyacrylamide and isoparaffin and laureth-7, available under the tradename Sepigel 305 from Seppic Corporation, and copolymers of acrylic acid / ethyl acrylate and the carboxyvinyl polymers sold by the BF Goodrich Company under the registered name of Carbopol resins, or mixtures thereof. Suitable Carbopol resins can be hydrophobically modified, and other suitable resins are described in WO 98/22085, or mixtures thereof.

Silicone oil The present compositions preferably comprise at least one phase of silicone oil. The phase (s) of silicone oil generally comprises from about 0.1% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 0.5% to about 5%, of the composition. The, or each, silicone oil phase preferably comprises one or more silicone components. The silicone components can be fluid, including straight chain, branched and cyclic silicones. Suitable fluid silicones useful in the present invention include fluid polyalkyl siloxane inclusive silicones, fluid polyaryl siloxane, linear and cyclic polyalkylsiloxanes, polyalkoxylated silicones, modified ammonium and quaternary ammonium silicones, polyalkylalkyl siloxanes or polyol siloxane copolymers and mixtures of the same. Fluid silicones can be volatile or non-volatile. Fluid silicones generally have an average molecular weight of less than about 200,000. Suitable fluid silicones have a molecular weight of about 100,000 or less, preferably about 50,000 or less, more preferably about 10,000 or less. Preferably the fluid silicone is selected from fluid silicones having an average molecular weight in the range of from about 100 to about 50,000 and preferably from about 200 to about 40,000.

Typically, the fluid silicones have a viscosity ranging from about 0.65 to about 600,000 mm2.s "1, preferably from about 0.65 to about 10,000 mm2.s" 1 to 25 ° C. The viscosity can be measured by means of a capillary tube viscometer as set forth in the Dow Corning Corporate Test Method CTM0004 of July 29, 1970. The polydimethyl siloxanes that can be used in the present invention include those available, for example, from the General Electric Company as the SF and Viscasil series (RTM) and from Dow Corning as the Dow Corning 200 series. Non-volatile polyalkylaryl siloxanes are also useful., for example, polymethylphenylsiloxanes, having viscosity from about 0.65 to 30,000 mm2. s "1 to 25 ° C. These siloxanes are available, for example, from the General Electric Company as SF 1075 methylphenyl fluid or from Dow Corning as a 556 fluid grade cosmetic. The cyclic polydimethylsiloxanes for use in the present invention are those having an incorporated ring structure of from about 3 to about 7 portions (CH 3) 2 S 0 0. In preferred embodiments, the fluid silicone is selected from dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, phenyl methicone, and mixtures thereof. The term "silicone rubber" in the present invention means silicones of high molecular weight having an average molecular weight in excess of about 200,000 and preferably from about 200,000 to about 4,000,000. Non-volatile polyalkyl gums and polyaryl siloxane gums. Preferred, a silicone oil phase comprises a silicone gum or a mixture of silicones including silicone gum. Typically, silicone rubbers have a viscosity at 25 ° C in excess of about 1,000,000 mm2.s "1. Silicone gums include dimethicones as described by Petrarch and others including EUA-A-4, 152, 416, from May 1, 1979 to Spitzer, et al., and Noli, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. The silicone gums that are also described are from data sheets of silicone rubber products. of General Electric SE 30, SE 33, SE 54 and SE 76. Specific examples of silicone rubber include polydimethylsiloxane, copolymer of (polydimethylsiloxane) (methylvinylsiloxane), copolymer of poly (dimethylsiloxane) - (diphenyl) (methylvinylsiloxane) and Mixtures thereof Preferred silicone rubbers for use in the present invention are silicone gums having a molecular weight of about 200,000 to about 4,000,000 selected from dimethiconol, and dimethicone and mixtures thereof. silicone preferably in the present invention comprises a silicone gum incorporated within the composition as part of a mixture of silicone-silicone rubber fluid. When the silicone rubber is incorporated as part of a mixture of fluid silicone-silicone rubber, the silicone rubber preferably constitutes from about 5% to about 40%, especially from about 10% to 20% by weight of the rubber blend Silicone-silicone fluid. Suitable blends of silicone-silicone fluid rubber are mixtures consisting essentially of: (i) A silicone having a molecular weight of about 200,000 to about 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof; and (i) A vehicle which is a fluid silicone, the vehicle having a viscosity of about 0.65 mm2.s ~ 1 to about 100 mm2.s "1, wherein the ratio of i) to i i) is about 10:90 to about 20:80 and wherein said component based on silicone rubber has a final viscosity of about 100 mm2.s * 1 to about 100,000 mm2.s "1, preferably 500 mm2.s" 1 to about 10,000 mm2.s "1. A specially preferred fluid silicone-silicone rubber-based component blend for use in the compositions in the present invention is a dimethiconol gum having a molecular weight of from about 200,000 to about 4,000,000 together with a fluid silicone carrier having a viscosity of approximately 0.65 to 100 mm2.s "1. An example of this silicone component is Dow Corning Q2-1403 (85% fluid dimethicone 5 mm2.s ~ / 15% dimethiconol) and Dow Corning Q2-1401 available from Dow Corning.

Additional silicone components suitable for use in a silicone oil phase are crosslinked polyorganosiloxane polymers, optionally dispersed in a fluid carrier. In general, when present, the crosslinked polyorganosiloxane polymers, together with their carrier (if present) comprise from 0.1% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 0.5% to about 5%. % of the composition Said polymers comprise polyorganosiloxane polymers crosslinked by a crosslinking agent. Suitable crosslinking agents are described in WO 98/22085. Examples of polyorganosiloxane polymers suitable for use in the present invention include methyl vinyl dimethicone, methylvinyl diphenyl dimethicone and methylvinyl phenyl methyl! diphenyl dimethicone. The commercially available cross-linked polyorganosiloxane polymers available for use in the present invention are crosslinked vinyl silicone blends available under the trade name KSG supplied by Shinetsu Chemical Co., Ltd., for example KSG-15, KSG-16, KSG-17, KSG. -18. These materials contain a combination of cross-linked polyorganosiloxane polymer and fluid silicone. Particularly preferred for use in the present invention especially in combination with the organic amphiphilic emulsifier material is KSG-18. The INCI names assigned for (KSG-15, KSG-16, KSG-17 and KSG-18 are crosslinked polymer of cyclomethicone dimethicone / vinyl dimethicone, crosslinked polymer of dimethicone dimethicone / vinyl dimethicone, crosslinked polymer of cyclomethicone dimethicone / vinyl dimethicone and polymer crosslinked of phenyl trimethicone dimethicone / phenyl vinyl dimethicone, respectively Another class of silicone component suitable for use in the silicone oil phase in the present invention includes polyorganosiloxane-polyoxyalkylene copolymers containing at least one polyorganosiloxane segment and at least one polyoxyalkylene segment The suitable polyorganosiloxane segments and copolymers thereof are described in WO 98/22085. Suitable polyorganosiloxane-polyalkylene copolymers are commercially available under the trade names Belsil (RTM) from Wacker-Chemie GmbH, Geschaftsbereich S , Postfach D-8000 Munich 22 and Abil (RTM) from Th. G oldschmrdt Ltd., Tego House, Victoria Road, Ruislip, Middlesex, HA4 OYL, for example Belsil (RTM) 6031 and Abil (RTM) B88183. A particularly preferred fluid copolymer mixture for use in the present invention includes Dow Corning DC3225C which has the CTFA designation of Dimethicone / Dimethicone copolyol.

Sunblockers The compositions of the present invention preferably comprise an organic sunblock. Suitable sunscreens may have UVA absorbing properties, UVB absorbing properties or a mixture thereof. The exact amount of active sunscreen will vary depending on the desired Sun Protection Factor, ie the "SPF" of the composition as well as the desired level of UV protection. The compositions of the present invention preferably comprise an SPF of at least 10, preferably at least 15. SPF is a commonly used measurement of the photoprotection of a sunscreen against erythema. The SPF is defined as a ratio of the ultraviolet energy required to produce minimal erythema on the protected skin in relation to that required for the products of the same minimal erythema on unprotected skin in the same individual. See Federal Register (Federal Register), 43, No. 166, pp. 38206-38269, August 25, 1978). The amounts of sunscreen typically used are from about 2% to about 20%, more typically from about 4% to about 14%. Suitable sunscreens include, but are not limited to, those found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 7th Edition, volume 2 pp. 1672, edited by Wenninger and cEwen (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1997). The compositions of the present invention preferably comprise UVA absorbing sunscreen active agents which absorb UV ation having a wavelength of about 320 nm to about 400 nm. Sunscreen actives that absorb suitable UVAs are selected from dibenzoylmethane derivatives, anthranilate derivatives such as methylanthranilate and homomethyl, 1-N-acetylanthranilate, and mixtures thereof. Examples of active dibenzoylmethane sunblockers are described in the U.S. Patent. No 4, 387, 089 issued to Depolo; and in Sunscreens: Development, Evaluation, and Regulatory Aspects edited by N. J. Lowe and N. A. Shaath, Marcel Dekker, Inc. (1990). The active UVA absorbing sunscreen preferably is presented in an amount to provide a broad protection of the UVA spectrum either independently, or in combination with, other UV protective assets which may be present in the composition. Preferred UVA sunblock assets are active dibenzoylmethane sunblocks and their derivatives. These include, but are not limited to, those selected from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-methyldibenzoylmethane, 2,5-methyldibenzoylmethane, 4,4'-diisopropylbenzoylmethane. 4- (1,1-dimethylethyl) -4'-methoxydibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4- dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4'-tert-butyl-4'-methoxydibenzoylmethane, and mixtures thereof. Preferred dibenzoyl sunblock actives include those selected from 4- (1,1-dimethylethyl) -4'-methoxydibenzoylmethane, 4-isopropyldibenzoylmethane, and mixtures thereof. A most preferred active sunblock is 4- (1,1-dimethylethyl) -4'-methoxydibenzoylmethane.

The active sunblock 4- (1,1-dimethylethyl) -4'-methoxydibenzoylmethane, which is also known as butyl methoxydibenzoylmethane or Avobenzone, is commercially available under the names of Parsol® 1789 from Givaudan Roure ( International) SA (Basel, Switzerland) and Eusolex® 9020 from Merck & Co., Inc. (Whitehouse Station, NJ). Sunblock 4-isopropyldibenzoylmethane, which is also known as sopropyldibenzoylmethane, is commercially available from Merck under the name Eusolex® 8020. The compositions of the present invention preferably additionally comprise an active UVB sunblock which absorbs radiation UV having a wavelength of about 290 nm to about 320 nm. The compositions comprise an amount of the active sunblock UVB which is safe and effective to provide protection against UVB independently, or in combination with other UV protective assets, which may be present in the compositions. The compositions preferably comprise from about 0.1% to about 16%, more preferably from about 0.1% to about 12%, and more preferably from about 0.5% to about 8% by weight, of organic sunscreen that absorbs UVB. A wide variety of active UVB sunblocks are suitable for use in the present invention. Non-limiting examples of said organic sunblock actives are described in the U.S. Patent. No. 5, 087, 372 issued February 1, 1992 to Haffey et al., And U.S. Patents. Nos. 5, 073, 371 and 5, 073, 372 both issued on December 17, 1991 to Turner et al. and Segarin, et al., in Chapter VIII, pages 189 et seq., of Cosmetic Science and Technology. Even other useful sunscreens are those described in the U.S. Patent. No 4, 937, 370, to Sabatelli, issued on June 26, 1990; and the U.S. Patent. No. 4, 999, 186, to Sabatelli et al., Issued March 12, 1991. Preferred active sunblockers against UVB are selected from 2-ethylhexyl-2-cyano-3,2-ethylhexyl N, N- dimethyl-p-aminobenzoate, p-aminobenzoic acid, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 3-benzylidene camfor, 3- (4-methylbenzylidene) camphor, 3- diphenylacrylate (referred to as octocrylene), 2-phenyl-benzimidazole-5-sulfonic acid (PBSA), cinnamates and their derivatives such as 2-ethylhexyl-p-methoxycinnamate and octyl-p-methoxycinnamate, TEA salicylate, octyl dimethyl PABA, camphor derivatives and its derivatives, and mixtures thereof. Preferred active organic sunblocks are 2-ethylhexyl-2-cyano-3, 3-d-ifenylacrylate (referred to as octocrylene), 2-phenyl-benzimidazole-5-sulfonic acid (PBSA), octyl-p-methoxycinnamate, and mixtures thereof. the same. Neutralized salt and acid forms of acidic sun blockers are also useful in the present invention. An agent can also be added to any of the compositions useful in the present invention to stabilize the UVA sunblock to prevent it from photo-degrading during exposure to UV radiation and thus maintaining its protection efficiency against UVA. A wide range of compounds that provide these stabilizing properties have been cited and should be chosen to complement both the UVA sunblock and the composition as a whole. Suitable stabilizing agents include, but are not limited to, those described in U.S. Pat. Nos. 5, 972, 316; 5, 968, 485; 5, 935, 556; 5, 827, 508 and WO 00/061 10. Preferred examples of stabilizing agents for use in the present invention include 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate (referred to as octocrylene), etl-2. -cyano-3, 3-diphenylacrylate, 2-ethylhexyl-3, 3-diphenylacrylate, ethyl-3, 3-bis (4-methoxyphenyl) acrylate, and mixtures thereof. 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate is the most preferred. An agent can also be added to any of the compositions useful in the present invention to improve the substantivity of the skin of those compositions, particularly to improve their resistance to being washed by water, or rubbed. A preferred agent which can provide this benefit is a copolymer of ethylene and acrylic acid. The compositions comprising this copolymer are described in the patent of E.U.A. 4, 663, 157, to Brock, issued May 5, 1987. In addition to the organic sunblock compositions of the present invention, inorganic physical sunblocks may additionally be comprised. Non-limiting examples of suitable physical sunscreens are described in CTFA International Cosmetic Ingredient Dictionary, 6th Edition, 1995, p. 1026-28 and 1 103, Sayre, R. M. et al., "Physical Sunscreens", J. Soc. Cosmet. Chem., Vol 41, no 2, pp. 103-109 (1990). Preferred inorganic physical sunblocks are zinc oxide and titanium dioxide, and mixtures thereof. When used, physical sunscreens are present in an amount such that the present compositions are transparent on the skin (ie, non-whitening), preferably less than or equal to about 5%. When titanium dioxide is used, it may have an anatase, rutile, or amorphous structure. The physical particles of the sunscreen, for example titanium dioxide and zinc oxide, may be uncoated or coated with a variety of materials including but not limited to amino acids, aluminum compounds such as alumina, aluminum stearate, aluminum laurate, and the like; carboxylic acids and their salts, for example stearic acid and its salts; phospholipids such as lecithin; organic silicone compounds; inorganic silicone compounds such as silica and silicates; and mixtures thereof. A preferred titanium dioxide is commercially available from Tayca (Japan) and is distributed by Tri-K Industries (Emerson, NJ) under the micro-ionized MT series (eg MT 100SAS). The compositions of the present invention preferably comprise from about 0.1% to about 10%, more preferably from about 0.1% to about 4%, and more preferably from about 0.5% to about 2.5%, by weight, of inorganic sunscreen.

A wide variety of optional ingredients such as neutralizing agents, perfumes, and coloring agents can also be added to the compositions in the present invention. It is preferred that any additional ingredients improve the softness / smoothness benefits of the skin of the product. It is further preferred that any of said ingredients does not adversely impact the aesthetic properties of the product. Since such high levels of proteins such as collagen and elastin are not preferred in the compositions useful in the present invention. The compositions of the invention may also contain from about 0.01% to about 10%, preferably from about 0.1% to about 5% of a panthenol humectant. The panthenol humectant can be selected from D-panthenol ([R] -2,4-dihydroxy-N- [3-hydroxypropyl]] - 3,4-dimethylbutamine), DL-panthenol, calcium pantothenate, royal jelly, pantethine, pantothene, panthenilether, pangamic acid, pyridoxine, and pantoyl lactose. In a preferred embodiment, the compositions of the present invention additionally comprise a salt selected from alkali metal salts and alkaline torric metal salts, and mixtures thereof, preferably sodium, calcium and magnesium salts, and mixtures thereof. Especially preferred for use in the present invention are the calcium and magnesium salts. The compositions in the present invention preferably comprise from about 5 ppm to about 500 ppm of the salt, based on the amount of the metal ion. In a further preferred embodiment, the compositions in the present invention may comprise additional enzymes selected from lipases, phospholipases, glucosidases, lactoperoxidases and cellulases, and mixtures thereof. Neutralizing agents suitable for use in hydrophilic gelling agents containing a neutralizing acid group in the invention include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, amino methyl propanol, pH-tris buffer and triethanolamine. Other optional materials include keratolytic agents; water-soluble preservatives or solubilizers preferably at a level of from about 0.1% to about 5%, such as Germall 115, methyl, methyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, DMDM, hydantoin butylcarbamate iodopropanil available under the name Registered Glydant Plus from Lonza, EDTA, Euxyl (RT) K400, Bromopol (2-bromo-2-nitropropane-1,3-diol) and phenoxypropanol; antibacterials such as Irgasan (RTM) and phenoxyethanol (preferably at levels of from about 0.1% to about 5%); soluble or colloidal soluble wetting agents such as hyaluronic acid and sodium polyacrylates grafted with starch such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in USA-A-4, 076, 663; vitamins such as vitamin A, vitamin C, vitamin E and derivatives thereof and building blocks thereof such as phytatrol and beta hydroxy acids; aloe vera; sphingosines and phytosphingosines, cholesterol; skin lightening agents; N-acetyl cysteine; coloring agents; antibacterial agents such as TCC / TCS, also known as triclosan and trichlorocarbon; perfumes and perfume solubilizers. Examples of alpha hydroxy acids include glycolic acid, lactic acid, malic acid, citric acid, glycolic acid in conjunction with ammonium glycolate, alpha hydroxyethanic acid, alpha hydroxyoctanoic acid, alpha hydroxycaprilic acid, hydroxycaprylic acid, mixed fruit acid, trihydric acid, fruit alphahydroxy, triple fruit acid, cane sugar extract, alpha hydroxy and alpha hydroxy botanicals comprise, 1 -alpha hydroxy acid and glucomer in crosslinked fatty acids alpha nutrium. Preferred examples of alpha hydroxy acids are glycolic acid and lactic acid. It is preferred that alpha hydroxy acids be used at levels up to 10%. The compositions of the present invention may additionally comprise from about 0.1% to about 5% by weight of starch octenylsuccinate with aluminum. Starch octenylsuccinate with aluminum is the aluminum salt of the reaction product of octenylsuccinic anhydride with starch and is commercially available under the trade name from Dry Fio National Starch &; Chemical Ltd. Dry Fio is useful in the present invention from the point of view of skin feel characteristics and application to the skin. A safe and effective amount of an anti-inflammatory agent can be added to the compositions of the present invention, preferably from about 0.1% to about 5%, more preferably from about 0.1% to about 2%, of the composition. The anti-inflammatory agent improves the appearance benefits of the skin of the present invention, for example, said agents contribute to a more uniform and acceptable skin tand color. The exact amount of the anti-inflammatory agent to be used in the compositions will depend on the particular anti-inflammatory agent since said agents vary widely in potency. The compositions of the present invention may additionally include an antioxidant / radical scavenger. The antioxidant / radical scavenger is especially useful for providing protection against UV radiation that can cause increased scaling or changes in texture in the stratum corneum and against other environmental agents that can cause skin damage. Suitable amounts are from about 0.1% to about 10%, more preferably from about 1% to about 5% of the composition. Antioxidant / radical eliminators such as ascorbic acid (vitamin C) and its salts.

The inclusion of a chelating agent is especially useful to provide protection against UV radiation which can contribute to excessive desquamation or changes in the texture of the skin and against other environmental agents that can cause damage to the skin. A suitable amount is from about 0.01% to about 1%, more preferably from about 0.05% to about 0.5%, of the composition. Exemplary chelators that are useful in the present invention are described in the U.S. Patent. No. 5, 487, 884, incorporated herein by reference. Preferred chelants useful in the compositions of the present invention are ethylenediamine tetraacetic acid (EDTA), furyldioxime, and derivatives thereof. The compositions of the present invention may also comprise a skin brightening agent. When used, the compositions preferably comprise from about 0.1% to about 10%, more preferably from about 0.2% to about 5%, also preferably from about 0.5% to about 2%, of a skin-illuminating agent. Suitable skin illuminating agents include those known in the art, including kojic acid, arbutin, ascorbic acid and derivatives thereof, for example, ascorbyl magnesium phosphate. In addition, skin illuminating agents suitable for use in the present invention also include those described in WO 95/34280 and WO 95/23780; each one incorporated here as a reference.

Other optional materials include water soluble preservatives or solubilizers preferably at a level of from about 0.1% to about 5%, such as Germall 15, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, DMDM, hydantoin butylcarbonate iodopropanyl available under the trade name Glydant Plus from Lonza, EDTA, Euxyl (RTM) K400, Bromopol (2-bromo-2-nitropropane-1,3-diol) and phenoxypropanol; antibacterials such as Irgasan (RTM) and phenoxyethanol (preferably at levels from about 0.1% to about 5%). Antibacterial agents such as TCC / TCS, also known as triclosan and trichlorocarbon are also useful in the compositions of the present invention. Other optional materials in the present invention include pigments which, when soluble in water, contribute to and are included in the total level of the oil phase ingredients. Pigments suitable for use in the compositions of the present invention can be organic and / or inorganic. Also included within the term pigment are materials that have a low color or luster such as matte finish agents, and also light dissipating agents. Preferably the compositions of the present invention comprise materials in particular having a refractive index of about 1.3 to about 1.7, the materials in particular being dispersed in the composition and having an average particle size of about 2 to about 30 μ? . Preferably the particles useful in the present invention have relatively narrow distributions, by means of which it is intended that more than 50% of the particles fall within 3 μ? on each side of the respective average values. It is also preferred that more than 50%, preferably more than 60%, more preferably more than 70% of the particles fall within the prescribed size ranges for the respective average values. Suitable particle materials are organic or organosilicon materials and preferably organosilicon polymers. Preferred particles are free-flowing, solid-type materials. By "solid" it is meant that the particles do not have perforations. The prevention in the center of perforated particles can have an adverse effect on the refractive index and therefore on the visual effects of the particles either on the skin or in the composition. Suitable organic particle materials include those made from polymethyl-silsesquioxane, referred to above, polyamide, polythene, polyacrylonitrile, polyacrylic acid, polymethacrylic acid, polystyrene, polytetrafluoroethylene (PTFE) and poly (vinylidene chloride). Copolymers derived from monomers of the aforementioned materials can also be used. Inorganic materials include silica and boron nitride. Commercially available representative examples of the particulate materials useful in the present invention are Tospearl® 145 which has an average particle size of about 4.5 μp? and EA-209® from Kobo of which is an ethylene / acrylic acid copolymer having an average particle size of about 10 μ ??, Nylon-12 available under the registered name Orgasol 2002 from Elf Atochem, France , or mixtures thereof. Additional examples of suitable pigments are titanium dioxide, predispersed titanium dioxide from Kobo for example Kobo GWL75CAP, iron oxides, iron oxides of acylglutamate, ultramarine blue, pigments D & amp;; C, crimson carmine, and mixtures thereof. Depending on the type of composition, a mixture of pigments will normally be used. Preferred pigments for use in the present invention from the viewpoint of wetting, skin feeling, skin appearance and emulsion compatibility are treated pigments. The pigments can be treated with compounds such as amino acids, silicones, lecithin and oils of asters. Suitably, the pH of the compositions in the present invention is in the range of from about 6.1 to about 10.0, preferably from about 7.0 to about 9.0, more preferably from about 8.0 to about 9.0 and even more preferably from about 8.0 to about 8.6 . It is preferred that the pH of the final composition be adjusted by the addition of acidic, basic salts or pH regulators as necessary. The cosmetic compositions in the present invention preferably have a water activity greater than 0.85, more preferably greater than 0.9, and more preferably greater than 0.95.

The compositions of the invention are generally in the form of an emulsion and are preferably formulated so as to have a product viscosity of at least about 4,000 mPa.s and preferably in the range from about 4,000 to about 1,000,000 mPa.s, more preferably from about 8,000 to about 350,000 mPa.s and especially from about 10,000 to about 250,000 mPa.se even more especially from about 10,000 to about 50,000 mPa.s (25 ° C, pure, Brookfield RVT, from spindle in T to 5 rpms and Heliopath Stand).

Preparation of the compositions The compositions of the present invention are prepared by standard techniques well known to those skilled in the art. In general, the aqueous phase and / or the oil phase can be prepared separately, with similar phase-partition materials being added in any order. If the final product is an emulsion, the two phases will then be combined with vigorous stirring. Any ingredients in the formulation with high volatility, or which are susceptible to hydrolysis at elevated temperatures, can be added with gentle mixing towards the end of the process, post-emulsification can be done if applicable.

EXAMPLES The following examples further illustrate the preferred embodiments within the scope of the present invention. These examples are given only for the purpose of illustration and are not considered as limiting the present invention since many variations of the invention are possible without departing from their spirit or scope. Unless indicated otherwise, all ingredients are expressed as a weight percentage of the active ingredient.

Enzymatic compositions * pH adjusted to a desired value using standard pH buffer, outlined in textbooks, eg Handbook of Chemistry and Physics Polyhydric alcohol compositions 2. Supplied by Seppic, 75 Quai 'Orsay, Paris 3. Supplied by Dow Corning, Kings Court, 185 Kinds Rd, Reading, Berks, RG1 4 EX 4. Supplied by ICI, PO Box 90, Wilton Center, Middlesborough, Cleveland, England. TS6 8JE The compositions were prepared based on the formulations described above. Study participants were treated with 0.1-2 micrograms of enzyme solutions (examples 1-3) per square centimeter followed by 0.8-2 micrograms of polyhydric alcohol compositions (examples 4-9) in a total skin area of 35 square centimeters . The hydration levels of the skin were then measured over time using a corneometer. The cosmetic methods used in the aforementioned examples exhibit excellent skin hydration, skin smoothness and skin smoothness benefits.

Claims (10)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A cosmetic method for providing improved hydration to the skin comprising topically applying a protease enzyme to the skin, and, simultaneously or sequentially, applying a polyhydric alcohol topically to the skin. 2. - A cosmetic method for providing improved hydration to the skin which comprises applying topically to the skin a polyhydric alcohol, and simultaneously or sequentially, applying a protease enzyme topically to the skin. 3. - A cosmetic method for providing hydration to the skin comprising topically applying to the skin a cosmetic composition wherein the composition comprises: (a) from about 0.0001% to about 1%, by weight, of a protease enzyme; and (b) from about 0.1% to about 20%, by weight, of a polyhydric alcohol. 4. - A cosmetic method for providing improved hydration to the skin comprising topically applying to the skin a first cosmetic composition comprising from about 0.0001% to about 1%, by weight, of a protease enzyme, and, simultaneously or sequentially , applying topically to the skin a second cosmetic composition comprising from about 0.1% to about 20%, by weight, of a polyhydric alcohol. 5. - A cosmetic method according to any of claims 1 to 4, further characterized in that the enzyme is selected from protease enzymes type subtilisin, chymotrypsin and elastase. 6. - The cosmetic method according to any of claims 1 to 5, further characterized in that the enzyme is selected from bacterial serine protease enzymes, and variants thereof, obtained from Bacillus amyloliquafaciens, Bacillus lichaniformis and / or Bacillus subtilis, including Alcalase®, Esperase®, Savinase®, Maxatase®, Maxacal® and Maxapem 15® (protein designed Maxacal®) and subtilisin BPN and BPN "7. - The cosmetic method according to any of claims 1 to 6, further characterized in that the enzyme is selected from Alcalase®, BPN ', Protease A, Protease B, Protease D, and Protease F, and mixtures thereof, preferably protease F. 8. - The cosmetic method in accordance with claim 3 or 4, further characterized in that the cosmetic composition comprises from about 0.001% to about 0.5% and more preferably from about 0.005% to about 0.1%, and n weight, enzyme protease. 9. - The cosmetic method according to claim 3 or 4, further characterized in that the cosmetic composition comprises from about 0.5% to about 18%, preferably from about 2% to about 15% and more preferably from about 5% to about 12%, in weight, of polyhydric alcohol. 10. - The cosmetic method according to claim 3 or 4, further characterized in that the polyhydric alcohol is selected from glycerin; butylene glycol; propylene glycol; dipropylene glycol; polyethylene glycol; hexanetriol; ethoxylated glycerin; propoxylated glycerin and mixtures thereof. 1. The cosmetic method according to claim 10, further characterized in that the polyhydric alcohol is selected from glycerin, butylene glycol, propylene glycol, polyethylene glycol and mixtures thereof. 12. The cosmetic method according to any of claims 1 to 11, further characterized in that the method further comprises applying to the skin a skin care active selected from a component of vitamin B3, panthenol and sodium acetate. vitamin E. 13.- The cosmetic method in accordance with the claim 12, further characterized in that the active for skin care is a component of vitamin B3. 14. - The cosmetic method according to claim 12 or 13, further characterized in that the active for skin care is a vitamin B3 complex comprising niacinamide, panthenol and retinoic acid compound.