CN1454081A - Cosmetic method - Google Patents

Abstract

The present invention provides a cosmetic method for improving skin hydration, wherein the method comprises topically applying a protease to the skin and simultaneously or sequentially topically applying to the skin a skin care active selected from vitamin B group ₃ fennel, vitamin E acetate, panthenol, and mixtures thereof. The present invention also provides a cosmetic method for improving skin hydration, wherein the method comprises topically applying to the skin a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof, and simultaneously or The proteases are then applied topically to the skin. Additionally, the present invention provides a cosmetic method for improving skin hydration, wherein the method comprises topically applying to the skin a cosmetic composition comprising (a) from about 0.0001% to about 1% by weight of a protease; and (b) from about 0.1% to about 20% by weight of a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof. Finally, the present invention provides a cosmetic method for improving skin hydration comprising topically applying to the skin a first cosmetic composition comprising from about 0.0001% to about 1% by weight of a protease and simultaneously or sequentially applying to the skin Topically applying a second cosmetic composition comprising from about 0.1% to about 20% by weight of a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof.

Description

Beauty method

field of invention

The present invention relates to the use of cosmetic compositions comprising proteases and selected skin care actives to improve skin hydration, skin suppleness and skin smoothness.

Background of the invention

The skin is composed of several layers of cells that cover and protect the keratin and collagen fibrils that make up its structural backbone. The outermost of these layers is called the stratum corneum, and they are known to consist of 25nm protein bundles surrounded by an 8nm thick layer. Anionic surfactants and organic solvents generally penetrate the stratum corneum membrane and destroy its integrity by degreasing (ie, the removal of lipids from the stratum corneum). This disruption of the skin's surface structure results in roughness and, eventually, the reaction of surfactants or solvents with keratin, causing irritation.

Dry, itchy or flaky skin can result from not maintaining a proper moisture gradient across the stratum corneum. Water that is sometimes considered a stratum corneum plasticizer to maintain a water gradient, most of which comes from the body. If moisture is too low, such as in cold weather, insufficient moisture remains in the outer layer of the stratum corneum to properly plasticize the tissue, and the skin begins to flake and become itchy.

It is known to employ proteases in cosmetic compositions to provide care to the skin. It is believed that the protease acts primarily by imparting a peeling effect to the cosmetic composition. The protease is thought to remove damaged (eg, dry) skin cells on the skin surface, thereby reducing the roughness associated therewith. This protease removes previous damaging effects on the skin, giving it a fresh, more youthful look and feel.

To date, publications describing cosmetic compositions containing proteases have focused on stabilizing the enzymes in the composition. These disclosures include encapsulating enzymes prior to incorporation into cosmetic compositions (GB 1,255,284 and JP 10-251122); buffering cosmetic compositions so that enzymes remain inactive until use (WO 97/47238); and Precursors or other active substances are used to stabilize the enzymes (EP 0710478 and SU 1690764). However, in the prior art, an advantageous approach for stabilizing proteases in cosmetic compositions is by formulating the aqueous phase of the composition with very high levels of polyols, allowing the water available in the composition to be drawn into the Significantly reduced, these methods are disclosed in JP1283213, JP3294211. Unfortunately, such systems have unacceptable aesthetic properties for cosmetic products. To date, this problem has been overcome by formulating the aqueous phase into a water-in-oil emulsion (US Patent No. 5,932,234 and US Patent No. 5,830,449) or into a triple water-in-oil-in-water emulsion (EP 0779071). Another solution is to keep the product in two different compartments within a single package, where the first compartment contains the stabilized enzyme in a high polyol content and the second compartment contains the aqueous cosmetic composition, so that when When the two phases are dispensed and mixed, the final aqueous composition is aesthetically acceptable (WO 97/27841). Although the prior art provides useful and improved methods for stabilizing enzymes, especially proteases, in cosmetic compositions, there is insufficient guidance therein that cosmetic compositions containing proteases and polyols are effective in improving skin hydration, skin softness and skin smoothness.

It is also known to use skin care actives such as vitamins in cosmetic compositions to provide various skin care benefits. Nevertheless, there remains a need to provide further improved skin moisturization (hydration), skin softness and skin smoothness. It has now been surprisingly found that by applying to the skin a protease and simultaneously or sequentially applying to the skin a skin care active selected from vitamin _B3 components, vitamin E acetate or panthenol or mixtures thereof, more than just Significantly improved skin moisturization (measured by improved skin hydration), as well as skin softness and skin smoothness, expected with skin care actives. Without being bound by theory, it is believed that the desquamation action of the protease removes the dead skin surface layer, exposing the underlying healthy skin layer, which is more easily hydrated by the skin care actives.

Summary of the invention

A first aspect of the present invention provides a cosmetic method for improving skin hydration, the method comprising topically applying a protease to the skin, and simultaneously or sequentially topically applying to the skin a composition containing vitamin _B3 components, vitamin E acetate, Skin care actives of panthenol and its mixtures.

A second aspect of the present invention provides a cosmetic method for improving skin hydration, the method comprising topically applying to the skin a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof, and simultaneously Or the protease is applied topically to the skin in sequence.

In a third aspect the present invention provides a cosmetic method for improving skin hydration, wherein the method comprises topically applying to the skin a cosmetic composition comprising (a) from about 0.0001% to about 1% by weight of a protease; and (b) from about 0.1% to about 20% by weight of a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof.

A fourth aspect of the present invention provides a cosmetic method of improving skin hydration, the method comprising topically applying to the skin a first cosmetic composition comprising from about 0.0001% to about 1% by weight of a protease, and simultaneously or sequentially topically applying A second cosmetic composition comprising from about 0.1% to about 20% by weight of an active skin care material selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof is applied.

The methods of the present invention provide significantly improved skin hydration, skin softness and skin smoothness benefits.

Detailed description of the invention

All percentages and ratios used herein are by weight of the total composition and all measurements made are at 25°C, unless otherwise specified. Unless otherwise specified, all percentages, ratios and amounts of ingredients referred to herein are based on the actual content of the ingredients and do not include solvents, fillers or other substances that may be combined with these ingredients in commercially available products. Chain length and degree of ethoxylation are also based on weight averages.

All publications cited herein are incorporated by reference in their entirety unless otherwise indicated.

As used herein, the term "enzyme" refers to a wild-type enzyme or a variant thereof, or chemically modified by conjugation to a polymer moiety.

The term "protease" as used herein refers to any enzyme whose substrate is a protein.

As used herein, the term "wild-type" refers to an enzyme produced by an unchanged host.

As used herein, the term "variant" refers to an enzyme having an amino acid sequence that differs from that of the wild-type enzyme due to genetic variation in the host producing the enzyme.

The term "enzyme activity" as used herein refers to the activity of 20 µl of enzyme solution (50 ppm) reacting with the surface of a suitable protein substrate disc with a diameter of 1 cm at room temperature for 30 minutes. By adjusting the pH of the enzyme buffer solution, the effect of pH on enzyme activity can be compared. For enzymes used in the present invention, suitable activity is defined as greater than 20%, preferably greater than 50%, more preferably greater than 75% completion of the reaction within 30 minutes. By using this measurement method, it was determined that enzyme buffers with a pH of less than 5.5 were not suitable for the use of the enzyme.

The term "skin hydration" as used herein refers to improving the moisture content of the skin, which can be measured by technical means such as using a keratometer, etc., or visually measured by an expert, such as the Fitzpatrick Skin Dryness Scale Assessment, or by the consumer themselves. Evaluate.

The "water activity _aw " of an aqueous matrix is the ratio of the water _vapor pressure of _the product " ^PH2O product" to the vapor pressure of pure water " ^PH2O pure water" at the same temperature. It can also be expressed as the number of water molecules " ^N H ₂ O" and the total number of molecules

The ratio of " ^N H ₂ O + ^N _solubles ", which takes into account the molecular " ^N _solubles " of dissolved substances.

It is expressed by the following equation:

Various methods can be used to measure water activity. The most common is the manometer method, by which the vapor pressure is measured directly.

The ingredients of these compositions are described in more detail below.

Beauty method

The method of the present invention comprises applying to the skin a protease together with a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof. The protease and skin care active can be applied to the skin simultaneously or sequentially.

Accordingly, in one aspect the present invention provides a cosmetic method for improving skin hydration comprising topically applying to the skin a protease and simultaneously or sequentially topically applying to the skin a skin care active selected from the group consisting of vitamins B ₃ components, vitamin E acetate, panthenol, and mixtures thereof.

Another aspect of the present invention provides a cosmetic method for improving skin hydration, the method comprising topically applying to the skin a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof, followed by applying The protease is applied topically on the skin.

It is also possible to deliver the protease and the skin care active to the skin simultaneously, meaning substantially simultaneously, from a single cosmetic composition.

It is also possible to sequentially deliver the protease and the skin care active to the skin in two separate cosmetic compositions. Sequential means that the two compositions are delivered sequentially in any order, wherein the second composition is delivered within one hour of delivery of the first composition. Preferably, the enzyme composition is applied to the skin first. It is furthermore preferred that the skin care active substance composition is applied before the buffered solution of the enzyme composition evaporates.

Accordingly, another aspect of the present invention provides a cosmetic method of improving skin hydration comprising topically applying to the skin a cosmetic composition comprising from about 0.0001% to about 1%, preferably from about 0.001% to about 0.5% , more preferably from about 0.005% to about 0.1% by weight of protease and from about 0.1% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 8% by weight of skin care actives, said skin care actives Selected from vitamin B ₃ components, vitamin E acetate, panthenol, and mixtures thereof.

Alternatively, the skin care active and protease can be delivered sequentially to the skin in two separate cosmetic compositions.

Accordingly, another aspect of the present invention provides a cosmetic method of improving skin hydration, the method comprising topically applying to the skin a first cosmetic composition comprising from about 0.1% to about 1%, preferably from about 0.001% to About 0.5%, more preferably about 0.005% to about 0.1% protease by weight, and simultaneously or sequentially topically applied to the skin containing about 0.1% to about 20%, preferably about 1% to about 10%, more preferably about 2% to A second cosmetic composition of about 8% by weight of a skin care active selected from the group consisting of vitamin _B3 components, vitamin E acetate, panthenol, and mixtures thereof.

The compositions of the present invention are suitable for topical application to the skin or hair. In particular, the composition may be in the form of a lotion, lotion, hairspray or the like. Preferably, the cosmetic composition may be an emulsion of one or more oil phases in an aqueous continuous phase.

protease

An essential component for use in the method of the present invention is a protease.

According to the Recommendations (1992) of the International Union of Biochemistry and Molecular Biology (IUBMB), proteases are classified by the enzyme classification number E.C.3.4 (carboxylate hydrolase). Suitable proteases are also described in the following PCT publications: WO 95/30010, published September 9, 1995, Procter & Gamble Company; WO 95/30011, published September 9, 1995, Procter & Gamble Company; WO 95/29979, 1995 Released September 9, 2010, Procter & Gamble Company. Preferred proteases for use in the present invention are subtilisin, chymotrypsin and elastase-type proteases.

Particularly preferred for use in the present invention are proteases of the subtilisin class. Subtilisins are naturally produced by the microorganisms Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus amylosaccharicus, Bacillus licheniformis, Bacillus lentus (a strain) and Bacillus subtilis .

Particularly preferred subtilis-like enzymes are bacterial serine proteases and variants thereof obtained from Bacillus amyloliquefaciens, Bacillus licheniformis ^and /or Bacillus subtilis, including Novo Industries A/S Alcalase®, ^Esperase® , ^Savinase® (Copenhagen , Denmark), Gist-brocades ^{' Maxatase®} , Maxacal® ^{and Maxapem 15®} (Protein Engineered Maxacal®) (Delft, Netherlands), and subtilisins BPN and BPN', which are commercially available.

Particularly preferred are proteases obtained from Bacillus amyloliquefaciens and variants thereof. One known enzyme is BPN'. The wild-type BPN' obtained from Bacillus amyloliquefaciens has the following amino acid sequence characteristics: 1 10 20AlaGlnSer ValProTyr GlyValSer GlnIleLys AlaProAla Leu HisSerGlnGly

30 40TyrThrGly SerAsnVal LysValAla ValIleAsp SerGlyIle Asp SerSerHisPro

50 60AspLeuLys ValAlaGly GlyAlaSer MetValPro SerGluThr Asn ProPheGlnAsp

70 80AsnAsnSer HisGlyThr HisValAla GlyThrVal AlaAlaLeu Asn AsnSerIleGly

90 100ValLeuGly ValAlaPro SerAlaSer LeuTyrAla ValLysVal Leu GlyAlaAspGly

110 120SerGlyGln TyrSerTrp IleIleAsn GlyIleGlu TrpAlaIle Ala AsnAsnMetAsp

                                                                                 

                                                  

                                                                           

                                                                    

210 220ProGlyVal SerIleGln SerThrLeu ProGlyAsn LysTyrGly Ala TyrAsnGlyThr

230 240SerMetAla SerProHis ValAlaGly AlaAlaAla LeuIleLeu Ser LysHisProAsn

250 260TrpThrAsn ThrGlnVal ArgSerSer LeuGluAsn ThrThrThr Lys LeuGlyAspSer

270 275PheTyrTyr GlyLysLys GlyLeuIle AsnAsnVal GlnAlaAla Ala Gln

A variant of BPN', hereinafter referred to as "Protease A", is disclosed in U.S. Patent No. 5,030,378 (issued to Venegas on July 9, 1991) and is characterized by the amino acid sequence of BPN' with the following mutations:

a.) Gly at Gly166 is replaced by Asn, Ser, Lys, Arg, His, Gln, Ala or Glu; Gly at Gly169 is replaced by Ser; Met at Met222 is replaced by Gln, Phe, Cys, His, Asn, Glu, Ala or Thr replaced; or

b.) Gly at Gly166 is replaced by Lys, and Met at Met222 is replaced by Cys; or

c.) Gly at Gly160 is replaced by Ala, and Met at Met222 is replaced by Ala.

Other BPN' variants, hereinafter referred to as "Protease B", are disclosed in European Patent EP-B-251,446 (granted December 28, 1994, published January 7, 1988) to Genencor International, Inc. (San Francisco, California) Among them, wild-type BPN' amino acids are characterized by mutations in one or more of the following amino acids: Tyr21, Thr22, Ser24, Asp36, Ala45, Ala48, Ser49, Met50, His67, Ser87, Lys94, Va195, Gly97, Ser101 , Gly102, Gly103, Ile107, Gly110, Met124, Gly127, Gly128, Pro129, Leu135, Lys170, Tyr171, Pro172, Asp197, Met199, Ser204, Lys213, Tyr214, Gly215 and Ser221; Two or more amino acid mutations in , Ala152, Asn155, Glu156, Gly166, Gly169, Phe189, Tyr217 and Met222, and neither of them can occur in Asp32, Ser33, Tyr104, Ala152, Asn155, Glu156, Gly166, On Gly169, Phe189, Tyr217 and Met222 amino acids.

Another preferred BPN' variant protease, hereinafter referred to as "Protease D", was disclosed in WO 95/10615 by Genencor International on April 20, 1995, and is characterized by its wild-type BPN' amino acid, which is at Asn76 With a mutation and at one or more of the following amino acids: Asp99, Ser101, Gln103, Tyr104, Ser105, Ile107, Asn109, Asn123, Leu126, Gly127, Gly128, Leu135, Glu156, Gly166, Glu195, Asp197, Ser204 , Gln206, Pro210, Ala216, Tyr217, Asn218, Met222, Ser260, Lys26 5 and/or Ala274.

Another preferred BPN' variant protease, hereinafter referred to as "Protease F", is disclosed in U.S. Patent No. 4,760,025, filed July 26, 1988 by Estell et al., and is characterized by its wild-type BPN' amino acid, With mutations at one or more of the following amino acid positions: Asp32, Ser33, His64, Tyr104, Asn155, Glu156, Gly166, Gly169, Phe189, Tyr217 and Met222.

Preferred proteolytic enzymes are selected from the group consisting of Alcalase ^(R) , BPN', Protease A, Protease B, Protease D, and Protease F, and mixtures thereof. Among them, Protease F is most preferred.

Compositions for use in the present invention contain 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 protease.

skin care actives

Preferred ingredients of the present invention are skin care actives, preferably at levels of from about 0.1% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 8%, by weight.

The skin care actives used in the present invention are selected from panthenol, vitamin E acetate and vitamin _B3 components.

Preferred skin care actives for use herein are vitamin _B3 components from the standpoint of providing improved skin hydration.

Vitamin B ₃ components

Compositions of the present invention preferably comprise from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, more preferably from about 1% to about 8%, most preferably From about 1.5% to about 6% vitamin _B3 compound.

"Vitamin _B3 compound" as used herein refers to a compound having the formula:

In the formula, R is -CONH ₂ (such as nicotinamide), -COOH (such as nicotinic acid) or -CH ₂ OH (such as nicotinic alcohol); and derivatives thereof; salts of any of the above components. Examples of derivatives of the aforementioned vitamin _B3 compounds include nicotinic acid esters, including non-vasodilating nicotinic acid esters/nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide, and nicotinamide N-oxide.

Suitable esters of niacin include nicotinic acid esters of C ₁ -C ₂₂ , preferably C ₁ -C ₁₆ , more preferably C ₁ -C ₆ alcohols. These alcohols are suitably straight-chain or branched, cyclic or acyclic, saturated or unsaturated (including aromatic), substituted or unsubstituted. These esters are preferably non-vasodilating. As used herein, "non-vasodilating" means that the esters generally do not produce significant redness when applied to the skin (most people do not experience significant redness, although these compounds may cause See vasodilation). Non-vasodilating esters of niacin include tocopheryl nicotinate and inositol hexapicotinate; tocopheryl nicotinate is preferred. A more complete description of vitamin _B3 compounds can be obtained from WO 98/22085.

Examples of the aforementioned vitamin _B3 compounds are known in the art and are commercially available from various sources, such as from Sigma Chemical Company (St. Louis, MO); ICN Biomedicals, Inc. (Irvin, CA) and Aldrich Chemical Company ( Milwaukee, WI). One or more vitamin _B3 compounds may be used in the present invention. Preferred vitamin _B3 compounds are niacinamide and tocopheryl nicotinate. Niacinamide is preferred.

Preferred skin care actives of the present invention are complexes comprising niacinamide, retinyl palmitate and panthenol. Very highly preferred, compositions suitable for use in the present invention contain a multivitamin consisting of: from about 1% to about 5% by weight of a vitamin _B3 compound or derivative thereof; and from about 0.1% to about 1% by weight From about 0.1% to about 1% by weight of the retinol compound or derivatives thereof conjugated with panthenol or derivatives thereof.

optional ingredients

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

carrier

The compositions of the present invention include a safe and effective amount of a dermatologically acceptable carrier suitable for topical application to the skin or hair, wherein the base material and optional other materials are added such that the base material and optional ingredients Deliver to skin or hair at appropriate concentration. The carrier may thus act as a diluent, dispersant, or solvent, etc., for the essential components to ensure that they can be applied and distributed in proper concentration, in balance, to the chosen target.

The carrier can be solid, semi-solid or liquid. Highly preferred carriers are liquids or semisolids, such as emulsions, lotions and gels. Preferably, the carrier is in the form of a lotion, emulsion or gel, more preferably a material of sufficient consistency or yield point to prevent the particles from settling. The carrier may itself be inert or have dermatological advantages of its own. The carrier should also be physically and chemically compatible with the essential ingredients and should not adversely affect the stability, potency or other usefulness associated with the compositions of the present invention.

The type of carrier used in the present invention will depend on the desired product form of the composition. Topical compositions suitable for use in the present invention may be prepared in a variety of product forms, such as are known in the art. These forms include, but are not limited to, lotions, creams, gels, sticks, salves, pastes and mousses. These product forms can include several carriers including, but not limited to, solutions, emulsions and gels.

Preferred carriers contain a dermatologically acceptable hydrophilic diluent. Suitable hydrophilic diluents include water, organic hydrophilic diluents such as _C1 - _C4 monohydric alcohols and low molecular weight diols and polyols including propylene glycol, polyethylene glycol (e.g. having a molecular weight of 200-600), polypropylene glycol (such as having a molecular weight of 425-2025), glycerin, butanediol, 1,2,4-butanetriol, sorbitol ester, 1,2,6-hexanetriol, ethanol, isopropanol, sorbitol ester, ethyl alcohol Oxylated ethers, propoxylated ethers, and mixtures thereof. The diluent is preferably a liquid. Water is a particularly preferred diluent. The composition preferably includes at least 20% hydrophilic diluent.

Preferred carriers include an emulsion comprising a hydrophilic phase, especially an aqueous phase, and a hydrophobic phase, such as a lipid, oil or oily material. As is known to those skilled in the art, the hydrophilic phase can be dispersed in the hydrophobic phase and vice versa to form a hydrophilic or hydrophobic dispersed and continuous phase, respectively, depending on the composition. In emulsion technology, the term "dispersed phase" is a term well known to those skilled in the art and means that this phase exists as small particles or droplets suspended in and surrounded by a continuous phase. The dispersed phase is also referred to as the internal or discontinuous phase. The emulsion may be or include (eg, as a three-phase or other multi-phase emulsion) an oil-in-water or water-in-oil emulsion, such as a water-in-silicone emulsion. Oil-in-water emulsions typically comprise from about 1% to 60% (preferably about 1% to 30%) dispersed hydrophobic phase and from about 1% to 99% (preferably about 40% to 90%) continuous hydrophilic phase; water-in-oil emulsions Typically comprise about 1% to 98% (preferably not about 40% to 90%) dispersed hydrophilic phase and about 1% to 50% (preferably about 1% to 30%) continuous hydrophobic phase. Preferred compositions of the invention are oil-in-water emulsions.

Polyol

Compositions suitable for use in the present invention contain at least one polyol or mixture thereof at 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%, even more preferably From about 5% to about 12% by weight.

For the purposes of the present invention, a polyol may be any organic compound containing two or more alcohol functional groups or an alkoxylated derivative thereof. It is also preferred that the polyol is present in the continuous phase if the composition has the form of an oil-in-water emulsion.

Suitable polyols for use in the present invention include polyalkylene glycols, more preferably alkylene polyols and derivatives thereof, including propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and derivatives thereof , sorbitol, hydroxypropyl sorbitol, erythritol, threitol, pentaerythritol, xylitol, sorbitol, mannitol, hexanediol, butanediol (such as 1,3-butanediol) diol), hexanetriol (e.g. 1,2,6-hexanetriol), trimethylolpropane, neopentyl glycol, glycerol, ethoxylated glycerol, propane-1,3-diol, propane Oxylated glycerol, and mixtures thereof. Alkoxylated derivatives of any of the above polyols are also suitable for use in the present invention.

Preferred polyhydric alcohols of the present invention are selected from the group consisting of glycerin, butylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, hexanetriol, ethoxylated glycerol and propoxylated glycerol, and mixtures thereof. The most preferred polyols for use in the present invention are glycerin, butylene glycol, propylene glycol, polyethylene glycol, and mixtures thereof.

Vitamin A

Another class of suitable skin care actives is the retinoids. As used herein, "retinoids" include all natural and/or synthetic vitamin A analogs or retinol-like compounds that possess vitamin A biological activity on the skin, as well as geometric and stereoisomers of these compounds.

The retinoids are preferably retinoids, retinol esters (such as _C2 - _C22 alkyl esters of retinoids, including retinyl palmitate, retinyl acetate, retinyl propionate), retinyl Aldehydes, and/or retinoic acid (including all-trans retinoic acid and/or 13-cis-retinoic acid), retinoids excluding retinoic acid are more preferred. These compounds are known in the art and are commercially available from various sources such as 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, retinyl propionate, retinoic acid and retinyl palmitate. Retinoids may be used as substantially pure material, or as extracts obtained from natural (eg plant) sources by suitable means of physical and/or chemical isolation.

The composition preferably contains from about 0.005% to 2%, more preferably from about 0.01% to 2%, of retinoids. Retinol is most preferably used in an amount of about 0.01% to 0.15%; retinol ester is most preferably used in an amount of about 0.01% to 2%, such as about 1%.

Very highly preferred, compositions suitable for use in the present invention contain a multivitamin consisting of: from about 1% to about 5% by weight of a vitamin _B3 compound or derivative thereof; and from about 0.1% to about 1% by weight From about 0.1% to about 1% by weight of the retinol compound or derivatives thereof conjugated with panthenol or derivatives thereof.

additional humectant

The compositions of the present invention may include additional humectants, preferably present in an amount of from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, especially from about 0.5% to about 10%.

Preferred humectants include, but are not limited to, those selected from the group consisting of urea, D or DL panthenol, calcium pantothenate, royal jelly, vitamin _B5 , vitamin _B5 derivatives, panthenyl ethyl ether, vitamin _B15 , pyridoxine, A compound of pantothenyl lactose complex vitamin B, hexa-1,2,6-triol, guanidine or its derivatives. Highly preferred humectants are urea, panthenol, and mixtures thereof. The compounds listed above may be added alone or in combination.

Additional humectants suitable for use in the present invention are sodium 2-pyrrolidone-5-carboxylate (NaPCA), guanidine; glycolic and glycolic acid salts (such as ammonium and quaternary alkylammonium); lactic acid and lactate salts (such as ammonium and tetravalent alkylammonium); any form of aloe vera (eg, aloe gel); hyaluronic acid and its derivatives (eg, salt derivatives, such as sodium hyaluronate); lactamide monoethanolamine; acetamide monoethanolamine; Urea; panthenol and its derivatives; and mixtures thereof.

At least some (up to about 5% by weight of the composition) of the additional wetting agent may be added in the form of a mixture with a special crosslinked hydrophobic acrylate or methacrylate copolymer, preferably present in an amount of 0.1% to 10%, it can be added to the aqueous phase or to the dispersed phase. The copolymers are particularly valuable for reducing shine and controlling oil while helping to provide effective wetting and are disclosed in detail in WO 96/03964, which is incorporated herein by reference.

The compounds listed above may be added alone or in combination. Preferred additional humectants are selected from urea, panthenol, and mixtures thereof.

emollient

The oil-in-water emulsions of the present invention generally contain 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 dermatologically acceptable Emollients.

Emollients lubricate the skin, increase the smoothness and suppleness of the skin, prevent or relieve dryness of the skin, and/or protect the skin. Emollients are generally oily or waxy substances immiscible with water, and emollients with high molecular weight can impart viscosity to topical compositions. A wide variety of suitable emollients are known and find use in the present invention. Sagarin, "Cosmetics, Science and Technology", 2nd Edition, Vol. 1, pp. 32-43 (1972), contains many examples of substances suitable for use as emollients. All emollients discussed in International Application WO 00/24372 are considered suitable for use in the present invention, although preferred examples are described in more detail below:

i) Linear and branched chain hydrocarbons having from about 7 to about 40 carbon atoms, such as dodecane, squalane, cholesterol, hydrogenated polyisobutene, isohexadecane, isoeicosane, isooctylhexadecane , isohexylpentacene, and C ₇ -C ₄₀ isoparaffins, which are C ₇ -C ₄₀ branched chain hydrocarbons. Branched chain hydrocarbons suitable for use in the present invention are selected from the group consisting of etacrocane, petrolatum, and mixtures thereof. Suitable for use herein are branched chain aliphatic hydrocarbons sold under the tradename Permethyl( ^R) and commercially available from Presperse Inc., PO Box 735, South Plainfield, NJ 07080, USA.

ii) C ₁ -C ₃₀ alcohol esters of C 1 -C ₃₀ carboxylic acids, C 12-15 alkylbenzoic acids and _{C 2} -C ₃₀ dicarboxylic acids, such as isononyl isononanoate, isostearyl pivalate Isodecyl Caprylate, Isodecyl Isononanoate, Tridecyl Isononanoate, Myristyl Octanoate, Octyl Nonanoate, Octyl Isononanoate, Myristyl Myristate, Myristyl Neopentanoate Alkyl esters, myristyl caprylate, isopropyl myristate, myristyl propionate, isopropyl stearate, isopropyl isostearate, methyl isostearate, behenic acid Behenyl esters, dioctyl maleate, diisopropyl adipate and diisopropyl dilinoleate, and mixtures thereof.

iii) C ₁ -C ₃₀ mono- and poly-esters of sugars and related substances. These esters are derived from sugars or polyols and one or more carboxylic acid moieties. Depending on the constituent acids and sugars, these esters can be in liquid or solid form at room temperature. Examples include: glucose tetraoleate, galactose tetraoleate of oleic acid, sorbitol tetraoleate, sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, sorbitan hexaester (wherein the carboxylic acid ester part is palm oleate and arachidonic acid ester in a molar ratio of 1:2) and sucrose octaester (wherein the carboxylic acid esterified part is in a molar ratio of 1:3 : 4 laurate, linoleate and behenate). Other materials include cottonseed oil or soybean oil fatty acid esters of sucrose. Further examples of these materials are disclosed in WO 96/16636, which is incorporated herein by reference. A particularly preferred material is known in INCI under the name sucrose polycotton oleate.

iv) Vegetable oils and hydrogenated vegetable oils. Examples of vegetable oils and hydrogenated vegetable oils include safflower oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil, linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed Oils, partially and fully hydrogenated exogenous oils, and mixtures thereof.

v) Soluble or colloid-soluble moisturizers. Examples include uronic acid and starch-grafted sodium polyacrylates, such as ^Sanwet® IM-1000, IM-1500, and IM-2500, available from Celanese Superabsorbent Materials, Portsmith, VA, USA, and described in USA-A- 4,076,663 in.

Preferred softeners suitable for use in the present invention are isohexadecane, isoctydecane, petrolatum, isononyl isononanoate, isodecyl octanoate, isodecyl isononanoate, tridecyl isononanoate, Tetraalkyl esters, octyl isononanoate, myristyl myristate, methyl isostearate, isopropyl isostearate, C12-15 alkyl benzoate, and mixtures thereof. Particularly preferred for use herein are isohexadecane, isononyl isononanoate, methyl isostearate, isopropyl isostearate, petrolatum or mixtures thereof. Castor oil is not a preferred emollient for use in the present invention due to its poor skin feel properties.

Emulsifier/Surfactant

The compositions of the present invention preferably contain emulsifiers and/or surfactants which generally assist in dispersing and suspending the dispersed phase in the continuous aqueous phase. Surfactants are also suitable if the product is to be used for skin cleansing purposes. For convenience, emulsifiers will hereinafter be subsumed under the term "surfactant", such that "surfactant" will be used to refer to a surface-active substance, whether used as an emulsifier or for other surfactants. Purposes such as skin cleansing. Known or conventional surfactants may be used in the composition provided that the material selected is chemically and physically compatible with the essential components of the composition and provides the desired properties. Suitable surfactants include non-silicone derived materials, and mixtures thereof. All surfactants discussed in International Application WO 00/24372 are considered suitable for use in the present invention.

The compositions of the present invention preferably contain from about 0.05% to about 15% of a surfactant or mixture of surfactants. The choice of the precise surfactant or mixture of surfactants will depend on the pH of the composition and the other components present.

Preferred surfactants are nonionic. Among the nonionic surfactants suitable for use in the present invention are those which can be broadly defined as condensation products of long chain alcohols, for example _C8-30 alcohols, with sugar or starch polymers, ie glycosides. Other suitable nonionic surfactants include condensation products of alkylene oxides with fatty acids (ie, alkylene oxide esters of fatty acids). These materials have the general formula RCO(X) _n OH where R is C _10-30 alkyl and X is -OCH ₂ CH ₂ - (ie derived from ethylene glycol or oxide) or -OCH ₂ CHCH ₃ -( ie derived from propylene glycol or oxide), and n is an integer from about 6 to about 200. Other nonionic surfactants are the condensation products of alkylene oxides with 2 moles of fatty acids (ie, alkylene oxide diesters of fatty acids). These materials have the general formula RCO(X) _n OOCR where R is C _10-30 alkyl and X is -OCH ₂ CH ₂ - (ie derived from ethylene glycol or oxide) or -OCH ₂ CHCH ₃ -( ie derived from propylene glycol or oxide), and n is an integer from about 6 to about 100. Emulsifiers suitable for use in the present invention are most preferably fatty acid ester mixtures based on a mixture of sorbitan fatty acid esters and sucrose fatty acid esters, especially sorbitan (sorbitan) stearate and sucrose cocoate mixture. This is commercially available from ICI under the tradename Arlatone 2121. Further suitable examples include cetearyl alcohol mixtures, cetearyl glycoside mixtures such as those available under the tradename Montanov 68 from Seppic and Emulgade PL68/50 from Henkel.

Hydrophilic surfactants suitable for use in the present invention may include (in place of nonionic surfactants) or in addition various cationic, anionic, zwitterionic and amphoteric surfactants, such as those known in the art. See, e.g., "Detergents and Emulsifiers" by McCutcheon, North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. 5,011,681 issued April 30, 1991 to Ciotti et al; U.S. Patent No. 4,421,769 to Dixon et al No., issued December 20, 1983; and US Patent No. 3,755,560, issued August 28, 1973, to Dickert et al. A wide variety of anionic surfactants are also suitable for use in the present invention. See, eg, US Patent No. 3,929,678, issued December 30, 1975 to Laughlin et al.

A wide variety of anionic surfactants are also suitable for use in the present invention. See, eg, US Patent No. 3,929,678, issued December 30, 1975 to Laughlin et al. Examples of anionic surfactants include alkyl isethionates (eg C ₁₂ -C ₃₀ ), alkyl and alkyl ether sulfates and their salts, alkyl and alkyl ether phosphates and their salts, alkyl Methyl taurates (eg C ₁₂ -C ₃₀ ) and fatty acid soaps (eg alkali metal salts, eg sodium or potassium salts).

Amphoteric and zwitterionic surfactants are also useful in the present invention. Examples of amphoteric and zwitterionic surfactants useful in the compositions of the present invention are those broadly described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group may be linear or branched, and wherein One aliphatic substituent contains from about 8 to about 22 carbon atoms (preferably _C8 - _C18 ), and one contains an anionic water solubilizing group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. Examples thereof are alkyliminoacetates, and also iminodialkanoates and aminoalkanoates, imidazolinium salts and ammonium derivatives. Other suitable amphoteric and zwitterionic surfactants are selected from the group consisting of betaines, sulphobetaines, hydroxysulphobetaines, and branched and unbranched alkanoyl sarcosinates, and mixtures thereof.

Preferred emulsions of the present invention include silicone-containing emulsifiers or surfactants. A wide variety of silicone emulsifiers are useful herein. These silicone emulsifiers are generally organomodified organopolysiloxanes known to those skilled in the art as silicone surfactants. Suitable silicone emulsifiers include dimethicone copolyols. These materials are polydimethylsiloxanes which have been modified to incorporate chains such as polyether side chains such as polyethylene oxide chains, polypropylene oxide chains, mixtures of these chains, and compounds derived from ethylene oxide and propylene Oxide part of the polyether chain. Other examples include alkyl-modified dimethicone copolyols, ie, compounds containing _C2 - _C30 pendant ring side chains. Other dimethicone copolyols that can be used include units with various cationic, anionic, amphoteric, and zwitterionic side chains.

polymeric thickener

The compositions of the present invention include at least one polymeric thickener.

Polymeric thickeners suitable for use in the present invention preferably have a number average molecular weight greater than 20,000, more preferably greater than 50,000, and particularly preferably greater than 100,000.

Generally, the compositions of the present invention may comprise from about 0.01% to about 10%, preferably from about 0.1% to about 8%, most preferably from about 0.5% to about 5%, by weight of the composition, of polymeric thickeners or mixtures thereof.

Preferred polymeric thickeners suitable for use in the present invention include nonionic thickeners and anionic thickeners or mixtures thereof. Suitable nonionic thickeners include polyacrylamide polymers, crosslinked poly(N-vinylpyrrolidone), polysaccharides, natural or synthetic gums, polyvinylpyrrolidone, and polyvinyl alcohol. Suitable anionic thickeners include acrylic acid/ethyl acrylate copolymers, carboxyvinyl polymers and crosslinked alkyl vinyl ether and maleic anhydride copolymers. Particularly preferred thickeners suitable for use in the present invention are nonionic polyacrylamide polymers, such as polyacrylamide and isoparaffin, and laureth-7, which is commercially available from Seppic Corporation under the tradename Sepigel 305, and acrylic acid/ethyl acrylate copolymer and carboxyvinyl polymers sold under the registered trademark Carbopol resins by the B.F. Goodrich Company, or mixtures thereof. Suitable Carbopol resins may be hydrophobically modified and other suitable resins are disclosed in WO98/22085, or mixtures thereof.

silicone oil

The compositions of the invention preferably comprise at least one silicone oil phase. The silicone oil phase generally comprises from about 0.1% to 20%, preferably from about 0.5% to 10%, more preferably from about 0.5% to 5%, of the composition. The silicone oil phase preferably includes one or more silicone ingredients.

The silicone component can be liquid and includes linear, branched and cyclic silicones. Silicone fluids suitable for use herein include silicones including polyalkylsiloxane fluids, polyarylsiloxane fluids, cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones , amino- and quaternary ammonium-modified siloxanes, polyalkylaryl siloxanes, or polyether siloxane copolymers, and mixtures thereof. The silicone fluid may be volatile or non-volatile. Silicone fluids generally have a weight average molecular weight of less than about 200,000. Suitable silicone fluids have a molecular weight of about 100,000 or less, preferably about 50,000 or less, most preferably about 10,000 or less. Preferred silicone fluids are selected from those having a weight average molecular weight of from about 100 to about 50,000, preferably from about 200 to about 40,000. Typically, silicone fluids have a viscosity at 25°C of from about 0.65 to about 600,000 mm ² .s ⁻¹ , preferably from about 0.65 to about 10,000 mm ² .s ⁻¹ . Viscosity may be measured with a glass capillary viscometer listed in Dow Corning Company Test Method CTM0004 (July 29, 1970). Suitable polydimethylsiloxanes which may be used herein include those commercially available from General Electric Company, for example, in the SF and Viscasil ^(R) series and from Dow Corning in the Dow Corning 200 series. Also suitable are substantially nonvolatile polyalkylarylsiloxanes, such as polymethylphenylsiloxanes having a viscosity at 25° C. of about 0.65 to 30,000 mm ² .s ⁻¹ . These silicones are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid, or from Dow Corning as 556 Cosmetic Grade Fluid. Cyclomethicones suitable for use in the present invention are those having a ring structure incorporating about 3 to 7 ( _CH3 ) _2SiO moieties.

In a preferred embodiment, the silicone fluid is selected from the group consisting of dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, phenylsiloxane, and mixtures thereof.

Silicone gums are also suitable for use in the present invention. The term "silicone gum" as used herein refers to high molecular weight polysiloxanes having a weight average molecular weight in excess of about 200,000, preferably from about 200,000 to about 4,000,000, including nonvolatile polyalkyl and polyaryl siloxane gums. In a preferred embodiment, the silicone oil phase comprises a silicone gum or a silicone mixture comprising a silicone gum. Typically, silicone gums have a viscosity in excess of about 1,000,000 mm ² s ^-1 at 25°C. Such silicone gums include polydimethylsiloxanes as described by Petrarch et al., including US-A-4,152,416 (Spitzer et al., issued May 1, 1979) and Noll, Walter, "Chemistry and Polymers Silicone Technology," New York: Academic Press 1968. Also described silicone gums are General Electric Silicone Rubber Product Data Sheets SE30, SE 33, SE 54 and SE 76. Specific examples of silicone gums include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl base) (methylvinylsiloxane) copolymers, and mixtures thereof. Preferred silicone gums suitable for use herein are those having a molecular weight of from about 200,000 to about 4,000,000 selected from the group consisting of dimethiconol and dimethicone, and mixtures thereof.

The silicone phase in the present invention preferably comprises a silicone gum which is added to the composition as part of a liquid silicone gum mixture. When the silicone gum is added as part of a silicone fluid mixture, the silicone gum preferably comprises from about 5% to 40%, especially from about 10% to 20%, by weight of the silicone fluid mixture. Silicone gum-fluid mixtures suitable for the present invention are mixtures consisting essentially of:

(i) a polysiloxane having a molecular weight of from about 200,000 to about 4,000,000 selected from the group consisting of dimethiconol, fluorosilicone, and dimethicone, and mixtures thereof; and

(ii) is a silicone liquid carrier having a viscosity of from about 0.65 mm ² .s ⁻¹ to about 100 mm ² .s ⁻¹ ,

wherein the ratio of i) to ii) is from about 10:90 to about 20:80, and wherein the silicone gum-based component has from about 100 mm ² .s ⁻¹ to about 100,000 mm ² .s ⁻¹ , A final viscosity of 500 mm ² .s ⁻¹ to about 10,000 mm ² .s ⁻¹ is preferred.

A particularly preferred silicone gum fluid mixture base ingredient suitable for use in the composition is dimethiconol having a molecular weight of about 200,000 to 4,000,000 and a silicone fluid carrier having a viscosity of about 0.65 to 100 mm ² . s ^-1 . An example of such a silicone composition is available from Dow Corning as Dow Corning Q2-1403 (85% 5mm ² .s ^- 1 Dimethicone Fluid/15% Dimethiconol) and Dow Corning Q2 -1401.

Further suitable silicone components in the silicone oils of the present invention are crosslinked polyorganosiloxane polymers, optionally dispersed in a liquid carrier. Typically, when a crosslinked organopolysiloxane polymer is present, the combined weight of this ingredient and its carrier (if present) constitutes from about 0.1% to 20% of the composition, preferably from about 0.5% to 10%, more preferably from about 0.5% to 5%. Such polymers include polyorganosiloxane polymers crosslinked with crosslinking agents. Suitable crosslinkers are disclosed in WO98/22085. Examples of polyorganosiloxane polymers suitable for use in the present invention include methyl vinyl dimethicone, methyl vinyl diphenyl dimethicone and methyl vinyl phenyl methyl Diphenyl Dimethicone.

Specific commercially available crosslinked polyorganosiloxane polymers useful in the present invention are polysiloxane vinyl crosslinked copolymer blends sold under the tradename KSG, such as KSG-15, KSG-16, KSG-17, KSG-18. These materials include combinations of crosslinked polyorganosiloxane polymers and silicone fluids. Particularly preferred for use herein, especially in combination with an organic amphiphilic emulsifier material, is KSG-18. The INCI designations given for KSG-15, KSG-16, KSG-17 and KSG-18 respectively are Cyclomethicone Dimethicone/Vinyl Dimethicone Crosslinked Copolymer, Dimethicone Dimethicone/Vinyl Dimethicone Crosscopolymer, Cyclomethicone Dimethicone/Vinyl Dimethicone Methicone Crosscopolymer and Phenyltrimethicone Dimethicone/Phenylvinyl Dimethicone Crosscopolymer.

Another type of silicone component suitable for use in the silicone oil phase of the present invention includes polydiorganosiloxane-polyoxyalkylene copolymers, which contain at least one polydiorganosiloxane segment and at least one polydiorganosiloxane segment. Oxidized alkylene fragments. Suitable polydiorganosiloxane segments and copolymers thereof are disclosed in WO 98/22085. Suitable polydiorganosiloxane-polyalkylene copolymers are commercially available under the trade name ^Belsil® from Wacker-Chemie GmbH, Geschftsbereich S, Postfach D-8000 Munich 22 and under the trade name ^Abil® from Th. Goldschmidt Ltd., Tego House, Victoria Road, Ruislip, Middlesex, HA4 OYL, such as ^Belsil® 6031 and ^Abil® B88183. Particularly preferred copolymer fluid blends for use in the present invention include Dow Corning DC3225C, which has the CTFA designation Polydimeric Methicone/Dimethicone Copolyol.

sunscreen

The compositions of the invention preferably contain an organic sunscreen. Suitable sunscreens have UVA-absorbing properties, UVB-absorbing properties, or a mixture of both. The exact amount of sunscreen active used will vary depending on the desired sun protection factor, ie, "SPF" of the composition, and the desired level of UV protection. Compositions of the invention preferably have an SPF value of at least 10, preferably at least 15. SPF is commonly used to measure the photoprotective effect of sunscreens against erythema. SPF is defined as the ratio of the ultraviolet energy required to minimize erythema on skin in need of protection to the ultraviolet energy required to minimize erythema on the same individual's unprotected skin. See Federal Register, 43, No 166, pp. 38206-38269 (August 25, 1978). Sunscreens are typically used at levels of from about 2% to about 20%, more typically from about 4% to about 14%. Suitable sunscreens include, but are not limited to, CTFA International Cosmetic Ingredient Dictionary and Handbook (7th Edition, volume 2 pp.1672, published by Wenninger and McEwen (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1997)) those mentioned in.

The compositions herein preferably contain UVA absorbing sunscreen actives which absorb ultraviolet radiation having a wavelength of from about 320 nm to about 400 nm. Suitable UVA absorbing sunscreen actives are selected from dibenzoylmethane derivatives, anthranilate derivatives such as methyl anthranilate and homomenthyl 1-N-acetylanthranilate, and mixtures thereof. Examples of dibenzoylmethane sunscreen actives are described in U.S. Patent No. 4,387,089 (to Depolo); and in "Sunscreen Agents: Development, Evaluation, and Regulation," eds. N.J. Lowe and N.A. Shaath, Marcel Dekker, Inc (1990). The UVA-absorbing sunscreen active is preferably present in an amount that provides broad spectrum UVA protection, either alone or in combination with other UV protection actives that may be present in the composition.

Preferred UVA sunscreen actives are dibenzoylmethane sunscreen actives and derivatives thereof. These substances include, but are not limited to, substances selected from the following: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane Acyl methane, 2,4-dimethyldiphenylmethane, 2,5-dimethyldiphenylmethane, 4,4'-diisopropylbenzoylmethane, 4-(1,1-dimethyl Ethyl)-4'-methoxydibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl -4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4'-tert-butyl-4' -Methoxydibenzoylmethane, and mixtures thereof. Preferred dibenzoyl sunscreen actives include those selected from the group consisting of 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane, 4-isopropyldibenzoyl Acyl methane, and mixtures thereof. A more preferred sunscreen active is 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane.

The sunscreen active substance 4-(1,1-dimethylethyl)-4'-methoxydibenzoylmethane, also known as butylmethoxydibenzoylmethane or avobenzone, Commercially available under the tradename Parsol( ^R) 1789 from Givaudan Roure (International) SA (Basel, Switzerland) and Eusolex ^(R) 9020 from Merck & Co., Inc (Whitehouse Station, NJ). The sunscreen 4-isopropylbenzoylmethane, also known as isopropyldibenzoylmethane, is available from Merck under the tradename ^Eusolex® 8020.

The compositions herein preferably also contain a UVB sunscreen active which absorbs ultraviolet radiation having a wavelength of from about 290 nm to about 320 nm. The compositions contain a UVB sunscreen active in an amount safe and effective to provide UVB protection, alone, or in combination with other UV protection actives that may be present in the composition. The compositions preferably contain from about 0.1% to about 16%, more preferably from about 0.1% to about 12%, most preferably from about 0.5% to about 8%, by weight, of a UVB absorbing organic sunscreen.

A wide variety of UVB sunscreen actives are suitable for use herein. Non-limiting examples of such organic sunscreen actives are described in U.S. Patent No. 5,087,372 (issued to Haffey et al., issued February 11, 1992); and U.S. Patent Nos. 5,073,371 and 5,073,372 (to Turner et al., both published December 17, 1991) and Segarin et al., "Cosmetic Science and Technology," Chapter VIII, pp. 189ff. Other suitable sunscreens are disclosed in US Patent No. 4,937,370 (issued June 26, 1990 to Sabatelli); and US Patent No. 4,999,186 (issued March 12, 1991 to Sabatelli et al.). Preferred UVB sunscreen actives are selected from the group consisting of 2-ethylhexyl-2-cyano-3,2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, parabens Ketone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-tert-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 3-benzylidene camphor , 3-(4-methylbenzylidene)camphor, 3-diphenylacrylate (known as octocrylene), 2-phenylbenzimidazole-5-sulfonic acid (PBSA), cinnamic acid Esters and their derivatives such as 2-ethylhexyl p-methoxycinnamate and octyl p-methoxycinnamate, TEA salicylate, octyldimethyl PABA, camphor derivatives and their derivatives, and their mixture. Preferred organic sunscreen actives are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (known as octocrylene), 2-phenylbenzimidazole-5-sulfonic acid ( PBSA), octyl p-methoxycinnamate, and mixtures thereof. Salt and acid neutralized forms of acidic sunscreens are also suitable for use in the present invention.

Materials that stabilize the UVA sunscreen against photodegradation when exposed to ultraviolet radiation can be added to any of the compositions of the present invention, thereby maintaining its UVA protective efficacy. A number of compounds have been cited for these stabilizing properties and those should be selected for benefit to both the UVA sunscreen and the composition as a whole. Suitable stabilizers include, but are not limited to, those disclosed in US Patent Nos. 5,972,316; 5,968,485; 5,935,556; 5,827,508 and WO00/06110. Examples of stabilizers preferred for use in the present invention include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (known as octocrylene), 2-cyano-3,3 - Ethyl diphenylacrylate, 2-ethylhexyl 3,3-diphenylacrylate, ethyl 3,3-di(4-methoxyphenyl)acrylate, and mixtures thereof. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate is most preferred.

Substances which improve the skin substantivity of those compositions, especially their resistance to washing or rubbing, may also be added to any of the compositions of the invention. A preferred material to provide this benefit is a copolymer of ethylene and acrylic acid. Compositions containing this copolymer are disclosed in US Patent No. 4,663,157 (Brock, issued May 5, 1987).

In addition to organic sunscreens, the compositions of the invention may also contain inorganic physical sunblocking substances. Non-limiting examples of suitable physical sunblocking substances are described in CTFA International Cosmetic Ingredient Dictionary, 6 ^th Edition, 1995, pp. 1026-28 and 1103, Sayre, RM et al., "Physical Sunblocks", 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, the physical sunblock is present in an amount such that the compositions of the present invention are clear (ie, non-whitening) on the skin, preferably less than or equal to about 5%. When titanium dioxide is used, it may have an anatase, rutile or amorphous structure. Physical sun blockers such as titanium dioxide and zinc oxide can be uncoated or coated with various substances. These substances include, but are not limited to, amino acids, aluminum compounds such as aluminum oxide, aluminum stearate and aluminum laurate, etc.; carboxylic acids and their salts such as stearic acid and its salts; phospholipids such as lecithin; organopolysiloxane compounds; Silicone compounds such as silicon dioxide and silicates; and mixtures thereof. Preferred titanium dioxide is obtained from Tayca (Japan), supplied by Tri-K Industries (Emerson, NJ) in the micro ionization series (e.g. MT 100SAS).

The compositions of the present invention preferably contain from about 0.1% to about 10%, more preferably from about 0.1% to about 4%, most preferably from about 0.5% to about 2.5%, by weight, of an inorganic sunscreen.

Various optional ingredients such as neutralizing agents, fragrances and coloring agents may also be added to the compositions of the present invention. Preferably, any additional ingredients enhance the skin softness/smoothness of the product. Furthermore, it is preferred that any of these ingredients do not negatively affect the aesthetic properties of the product. Therefore, it is not preferred to use high levels of proteins such as collagen and elastin in compositions suitable for use in the present invention.

The compositions of the present invention also contain from about 0.01% to 10%, preferably from about 0.1% to 5%, of a panthenol humectant. The panthenol wetting agent may be selected from D-panthenol ([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]-3,3-dimethylbutanamide), DL-panthenol , calcium pantothenate, royal jelly, vitamin B ₅ , vitamin B ₅ derivatives, panthenyl ethyl ether, vitamin B ₁₅ , pyridoxine and pantothenyl lactose.

In a preferred embodiment, the composition according to the invention additionally comprises salts selected from alkali metal and alkaline earth metal salts and mixtures thereof, preferably sodium, calcium and magnesium salts, and mixtures thereof. Particularly preferred for use in the present invention are calcium and magnesium salts. The compositions of the present invention preferably comprise from about 5 ppm to 500 ppm salt based on the amount of metal ion.

In a further preferred embodiment, the composition according to the invention may comprise additional enzymes selected from the group consisting of lipases, phospholipases, glycosidases, lactoperoxidases and cellulases and mixtures thereof.

Neutralizing agents suitable for neutralizing acid groups containing hydrophilic gelling agents include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine, aminomethylpropanol, tri-buffer, and triethanolamine .

Other optional materials include keratolytics; water-soluble or water-solubilizable preservatives, preferably at levels from about 0.1% to about 5%, such as Germall 115, methyl, ethyl, propyl and Butyl esters, benzyl alcohol, DMDM hydantoin iodopropyl butyl carbonate available from Lonza under the tradename Glydant Plus, EDTA, ^Euxyl® K400, Bromopol (2-bromo-2-nitropropane-1,3- diol) and phenoxypropanol; antibacterial agents such as ^Irgasan® and phenoxyethanol (preferably in amounts of about 0.1% to about 5% content); soluble or colloid-soluble moisturizing agents such as sugar alkyd and starch grafted sodium polyacrylates such as ^Sanwet® IM-1000, IM-1500 and IM-2500 from Celanese Superabsorbent Materials, Portsmith, VA, USA, described in USA-A-4,076,663; vitamins such as Vitamin A , vitamin C, vitamin E and their derivatives and their synergists "physical sunscreens" such as phytantriol and vitamin K and their components such as fatty alcohol dodecatrienol; alpha and beta hydroxy acids; aloe; sphingosine Alcohols and phytosphingosines, cholesterol; skin lightening agents; N-acetyl cysteine; coloring agents; antibacterial agents such as TCC/TCS, known as triclosan and carbon trichloride; solvent. Examples of alpha hydroxy acids include glycolic acid, lactic acid, malic acid, citric acid, glycolic acid combined with ammonium glycolate, alpha-glycolic acid, alpha-hydroxypantothenic acid, alpha-hydroxycaprylic acid, hydroxycaprylic acid, mixed fruit acids, tri-hydroxycaprylic acid, Alpha hydroxy AHAs, tri-HAs, sugar cane extract, alpha hydroxy and botanicals (including 1-alpha hydroxy acids and glycolic polymers in cross-linked fatty acid alpha-nutrients). Examples of preferred alpha hydroxy acids are glycolic acid and lactic acid. Alpha hydroxy acids are preferably used in amounts of up to 10%.

Compositions of the present invention may additionally include from about 0.1% to 5% by weight of aluminum starch octenylsuccinate. Aluminum starch octenyl succinate is the aluminum salt of the reaction product of octenyl succinic anhydride and starch and is commercially available from National Starch & Chemical Ltd. under the tradename Dry Flo. Considering the skin feel and application characteristics, Dry Flo is suitable for use in the present invention.

Anti-inflammatory agents may be added to the compositions of the present invention in a safe and effective amount, preferably from about 0.1% to about 5%, more preferably from about 0.1% to about 2%, of the composition. Anti-inflammatory agents enhance the skin appearance benefits of the present invention, eg, the anti-inflammatory agents help to provide a more even and acceptable skin tone or color. The exact amount of anti-inflammatory agent used in the composition will depend on the particular anti-inflammatory agent used, since the potency of different anti-inflammatory agents can vary widely.

Compositions of the present invention may also include antioxidant/radical scavengers. Antioxidants/radical scavengers can be used, inter alia, to provide protection against UV radiation, which can cause exacerbated peeling or structural changes 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. Antioxidants/radical scavengers are eg ascorbic acid (vitamin C) and its salts.

The addition of chelating agents can be used, inter alia, to provide protection against ultraviolet radiation, which can cause excessive peeling or structural changes in the stratum corneum, and against other environmental agents that can cause skin damage. Suitable amounts are from about 0.01% to about 1%, more preferably from about 0.05% to about 0.5%, of the composition. Examples of chelating agents suitable for use in the present invention are disclosed in US Patent No. 5,487,884, which is incorporated herein by reference. Preferred chelating agents suitable for use in the compositions of the present invention are ethylenediaminetetraacetic acid (EDTA), furildioxime and derivatives thereof.

The compositions of the present invention may also contain a skin lightening agent. When a skin lightening agent is used, the composition preferably contains from about 0.1% to about 10%, more preferably from about 0.2% to about 5%, still preferably from about 0.5% to about 2% of the skin lightening agent. Suitable skin lightening agents include those known in the art, including kojic acid, arbutin, ascorbic acid and derivatives thereof, such as magnesium ascorbyl phosphate. Skin lightening agents suitable for use herein also include those described in WO 95/34280 and WO 95/23780; both of which are incorporated herein by reference.

Other optional materials include water-soluble or solubilizable preservatives, preferably at levels of from about 0.1% to about 5%, such as Germall 115, methyl, ethyl, propyl and butyl parabens, benzyl alcohol, DMDM hydantoin iodopropyl butylcarbanate, EDTA, ^Euxyl® K400, Bromopol (2-bromo-2-nitropropane-1,3-diol) and phenoxypropanol available from Lonza under the tradename Glydant Plus ; antibacterial agents such as Irgasan ^(R) and phenoxyethanol (preferably in an amount of about 0.1% to about 5% content). Antibacterial agents such as TCC/TCS, known as triclosan and carbon trichloride, are also suitable for use in the compositions of the present invention.

Other materials described in the present invention include pigments which, when water insoluble, assist and are included in the total level of oil phase ingredients. Pigments suitable for use in the compositions of the present invention are organic or inorganic. Included in the term pigments are also materials with a lighter color or sheen, such as matte finishes, and diffusers. The compositions of the present invention preferably contain particulate material having a refractive index of from about 1.3 to about 1.7 dispersed throughout the composition and having an average particle size of from about 2 to about 30 microns. Preferably, particles suitable for use in the present invention have a relatively narrow distribution, meaning that greater than 50% of the particles fall within +/- 3 μm of the respective median. It is also preferred that more than 50%, preferably more than 60%, more preferably more than 70% of the particles fall within the size range of the respective median. Suitable particulate materials are organic or organosiloxanes and preferably organosiloxane polymers. Preferred particles are free flowing solid materials. The so-called "solid" means that the particle is not hollow. The presence of voids in the center of hollow particles can adversely affect the refractive index and thus the visual effect of the particles on the skin or composition. Suitable organic particulate materials include polymethylhexasilane, polyamide, polyethylene, polyacrylonitrile, polyacrylic acid, polymethacrylic acid, polystyrene, polytetrafluoroethylene (PTFE) and poly(vinylidene chloride) as described above. ) made of those substances. Copolymers derived from monomers of the above materials may also be employed. Inorganic materials include silicon dioxide and boron nitride. Representative commercially available examples of particulate materials suitable for use in the present invention are Tospearl® ¹⁴⁵ , which has an average particle size of about 4.5 μm, and EA- ^209® from Kobo, which has an average particle size of about 10 μm. Ethylene/acrylic acid copolymer, Nylon-12 (obtained under the tradename Orgasol 2002 from Elf Atochem, France), or mixtures thereof.

Further examples of suitable pigments are titanium dioxide, predispersed titanium dioxide (from Kobo, eg Kobo GWL75CAP), iron oxides, oxides of iron acylated glutamate, ultramarine blue, D&C dyes, carmine, and mixtures thereof. Depending on the type of composition, usually a mixture of pigments can be used. Preferred pigments for use in the present invention are treated pigments in view of wettability, skin feel, skin appearance and emulsion compatibility. These pigments can be treated with compounds such as amino acids, silicones, lecithin and ester oils.

Suitably, the pH of the compositions of the present invention ranges 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, even more preferably from about 8.0 to about 8.6. Preferably, the pH of the final composition is adjusted by adding acids, bases or buffer salts as required.

The cosmetic compositions of the present invention preferably have a water activity greater than 0.85, more preferably greater than 0.9, even more preferably greater than 0.95.

The compositions of the present invention are generally in the form of emulsions and are preferably formulated to have a viscosity of at least about 4,000 mPa.s, preferably from about 4,000 to about 1,000,000 mPa.s, more preferably from about 8,000 to about 350,000 mPa.s, especially about 10,000 to about 250,000 mPa.s, even more preferably about 10,000 to about 150,000 mPa.s (25°C, neat, Brookfield RVT, T Spindle at 5 rpm and Heliopath Stand).

preparation composition

The compositions of the present invention are prepared using standard techniques well known to those skilled in the art. Usually the aqueous and/or oily phases should be prepared separately, adding similar phase separating substances in any order. If the final product is an emulsion, the two phases are mixed under vigorous stirring. If appropriate, any highly volatile or easily hydrolyzed ingredients of the formulation may be added with gentle agitation after emulsification towards the end of the preparation.

Example

The following examples further illustrate preferred embodiments within the scope of the present invention. These examples are given merely to illustrate the invention and are not to be construed as limiting the invention, since many changes can be made therein without departing from the spirit and scope of the invention. All ingredients are expressed as weight percent of active ingredient unless otherwise indicated.

enzyme assembly Example 1 Example 2 Example 3 %w/w %w/w %w/w Protease ¹ 100ppm 200ppm 1000ppm Standard Buffer ^* Appropriate amount Appropriate amount Appropriate amount total 100 100 100

^* Adjust pH to desired value using standard buffers as taught in textbooks such as Handbook of Chemistry and Physics

Composition of skin care actives Example Example Example Example Example Example 4 5 6 7 8 9 %w/w %w/w %w/w %w/w %w/w %w/w Deionized water Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount glycerin 7.00 10.00 12.00 7.00 10.00 12.00 Nicotinamide 2.00 3.50 5.00 2.00 3.50 5.00 panthenol 0.50 0.50 1.00 0.50 0.50 1.00 vitamin E acetate 0.50 0.50 0.50 0.50 0.50 0.50 Isohexadecane 5.40 5.40 5.40 5.40 5.40 5.40 Polyacrylamide and C13-14 Isoparaffin and Laureth-7 ² 2.50 2.50 2.50 2.50 2.50 2.50 Dimethicone and Dimethiconol ³ 2.00 2.00 2.00 2.00 2.00 2.00 Isopropyl isostearate 2.40 2.40 2.40 2.40 2.40 2.40 Sorbitan Stearate and Sucrose Cocoate ⁴ 1.00 1.00 1.00 1.00 1.00 1.00 cetyl alcohol 0.50 0.50 0.50 0.50 0.50 0.50 vaseline 0.00 0.00 0.00 0.00 0.00 0.00 Isopropyl palmitate 0.00 0.00 0.00 0.00 0.00 0.00 Docosanol 0.72 0.72 0.72 0.72 0.72 0.72 SEFA COTTONATE 1.20 1.20 1.20 1.20 1.20 1.20 stearyl alcohol 0.72 0.72 0.72 0.72 0.72 0.72 Benzyl alcohol 0.25 0.25 0.25 0.25 0.25 0.25 Ethyl p-hydroxybenzoate 0.20 0.20 0.20 0.20 0.20 0.20 Propylparaben 0.10 0.10 0.10 0.10 0.10 0.10 Disodium edetate 0.10 0.10 0.10 0.10 0.10 0.10 Polyoxyethylene-100 Stearate ⁴ 0.10 0.10 0.10 0.10 0.10 0.10 stearic acid 0.10 0.10 0.10 0.10 0.10 0.10 sodium hydroxide 0.05 0.05 0.05 0.05 0.05 0.05 100 100 100 100 100 100

1. Genencor International, Palo Alto, California, US

2. Courtesy of Seppic, 75 Quai D'Orsay, Paris

3. Courtesy of Dow Corning, Kings Court, 185 Kinds Rd, Reading, Berks, RG1 4EX

4. Provided by ICI, PO Box 90, Wi1ton Centre, Middlesborough, Cleveland, England. TS6 8JE

Compositions were prepared according to the recipe above. The skin of the participants was treated with 0.1 to 2 micrograms per square centimeter of the enzyme solution (Examples 1-3) followed by 0.8 to 2 micrograms of the skin care active composition (Examples 4-9) for a total area of 35 square centimeters. The level of skin hydration over time was then measured with a keratometer.

The cosmetic methods used in the above examples showed excellent skin hydration, skin softness and skin smoothness benefits.

The cosmetic methods used in the above examples showed excellent skin hydration, skin softness and skin smoothness benefits.

Claims (11)

CLAIMS 1. A cosmetic method for improving skin hydration comprising topically applying a protease to the skin and simultaneously or sequentially topically applying to the skin a skin care active selected from vitamin _B3 components, panthenol and vitamin E acetate. 2. A cosmetic method for improving skin hydration comprising topically applying to the skin a skin care active selected from vitamin _B3 components, panthenol and vitamin E acetate, and simultaneously or sequentially topically applying a protease to the skin. 3. A cosmetic method of providing skin hydration, the method comprising topically applying to the skin a cosmetic composition comprising: (a) about 0.0001% to about 1% by weight protease; and (b) from about 0.1% to about 20% by weight of a skin care active selected from the group consisting of vitamin _B3 components, panthenol, and vitamin E acetate. 4. A cosmetic method for providing skin hydration, the method comprising topically applying to the skin a first cosmetic composition comprising from about 0.0001% to about 1% by weight of protease, and simultaneously or sequentially topically applying to the skin comprising about 0.1% A second cosmetic composition comprising up to about 20% by weight of a skin care active selected from the group consisting of vitamin _B3 components, panthenol and vitamin E acetate. 5. The cosmetic method according to any one of claims 1 to 4, wherein the enzyme is selected from the group consisting of subtilisin, chymotrypsin and elastase-type proteases. 6. Cosmetic method according to any one of claims 1 to 5, wherein said enzyme is selected from bacterial serine proteases and variants thereof obtained from Bacillus amyloliquefaciens, Bacillus licheniformis and/or Bacillus subtilis, These include ^Alcalase® , ^Esperase® , ^Savinase® , ^Maxatase® , ^Maxacal® and ^{Maxapem 15®} (Protein Engineered Maxacal®), and subtilisins BPN and BPN'. 7. The cosmetic method according to any one of claims 1 to 6, wherein the enzyme is selected from the group consisting of Alcalase ⁽ R), BPN', Protease A, Protease B, Protease D and Protease F and mixtures thereof, preferably Protease F. 8. The cosmetic method of claim 3 or 4, wherein the cosmetic composition comprises from about 0.001% to about 0.5%, most preferably from about 0.005% to about 0.1%, by weight of protease. 9. The cosmetic method according to claim 3 or 4, wherein the skin care active is a vitamin _B3 component. 10. The cosmetic method according to claim 3 or 4, wherein the vitamin _B3 component is a complex comprising vitamin _B3 or a derivative thereof; retinol or a derivative thereof and panthenol or a derivative thereof. 11. The cosmetic method of claim 3 or 4, wherein the cosmetic composition comprises from about 1% to about 10%, more preferably from about 2% to about 8%, by weight of the skin care active.