WO2009134511A1 - Topical compositions for improving appearance of keratinous surfaces - Google Patents

Topical compositions for improving appearance of keratinous surfaces Download PDF

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Publication number
WO2009134511A1
WO2009134511A1 PCT/US2009/034297 US2009034297W WO2009134511A1 WO 2009134511 A1 WO2009134511 A1 WO 2009134511A1 US 2009034297 W US2009034297 W US 2009034297W WO 2009134511 A1 WO2009134511 A1 WO 2009134511A1
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Prior art keywords
skin
composition
dermal filler
silicone
dimethicone
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PCT/US2009/034297
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French (fr)
Inventor
Isabelle R. Afriat
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Elc Management Llc
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Publication of WO2009134511A1 publication Critical patent/WO2009134511A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/726Glycosaminoglycans, i.e. mucopolysaccharides
    • A61K31/728Hyaluronic acid
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/735Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/08Anti-ageing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/91Injection

Definitions

  • This invention is in the field of topical compositions for treatment of keratinous surfaces such as skin, nails, or hair.
  • Hyaluronic acid is a glycosaminoglycan. It is found in skin and known to provide volume and plumpness to the dermis and epidermis. It is also widely used as an injectable filler by plastic surgeons who treat patients who desire to plump out lines and wrinkles and are willing to have such materials injected into their dermis.
  • Examples of hyaluronic acid based dermal fillers include RestylaneTM, PerlaneTM, or JuvedermTM. When these fillers are injected into skin folds such as lines and wrinkles they provide a plumping effect. As the hyaluronic acid is gradually reabsorbed back into the body, the filling effect generally lasts only from 3 to 6 months.
  • hyaluronic acid based fillers provide slow re-absorption back into the body is because they have a high molecular weight. For that same reason these types of ingredients cannot be absorbed into the skin when topically applied. Skin pores will permit entry of only small molecular weight materials.
  • Other dermal fillers have been developed that are more permanent. For example,
  • Sculptra which is poly-L-lactic acid.
  • This is a polymeric form of lactic acid that is approved for injection into the dermis of AIDs patients that have lipoatrophy.
  • This polymeric material plumps up the dermis and is said to promote collagen synthesis. It is biodegradable and lasts from 2 to 3 years.
  • Another example of a permanent dermal filler is ArtecollTM, which is injectable polymethylmethacrylate. ArtecollTM is a permanent dermal filler, that is, it never biodegrades. That means that the physician who administers the material must be very skilled because there is simply no margin for error. Any "mistakes" must be cut out of the skin, which creates scars and disfigurement.
  • injectable fillers Because of the expense and requirement for physician administered injections some people who use injectable fillers are sporadic users - that is they obtain such injections only when planning to attend one big event such as a family wedding or public appearance. Other users of injectable fillers are beauty junkies or those that can afford the expense of dermal filler injections and maintenance to obtain the desired look.
  • dermal fillers that have certain properties have been found to be effective when topically applied. If such dermal fillers have certain characteristics they can be applied topically and absorbed into the skin to provide a plumping effect that, with continued use, approximates the effect seen with injectable fillers.
  • the invention is directed to a topical composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of absorption into the epidermal layers of the skin in an amount sufficient to plump the keratinous surface to which the composition is applied.
  • the invention is further directed to a method for ameliorating the effects of skin lines, wrinkles, or laxity by applying a topical composition comprising at least one injectable dermal filler capable of absorption into the epidermal layers of the skin in an amount sufficient to plump the skin.
  • the invention is directed to a non-dermal filler topical composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin.
  • the invention is further directed to a method for providing a plumping effect to skin comprising applying to the skin surface a non-dermal filler composition comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin.
  • Dermat filler when used herein means a dermal filler that is suitable for, or generally used, as an injectable dermal filler, that is in the latter case, pharmaceutically approved for injection into the dermis for plumping out lines, wrinkles, skin depressions and the like.
  • Dermatis means the layer of skin beneath the epidermis and connected to it by the basement membrane.
  • the dermis consists of connective tissue and cushions the body from stress and strain.
  • Epidermis or “Epidermal layers” with respect to skin means the outermost avascular layer of the skin comprised of stratified squamous epithelium and the underlying basal lamina.
  • the epidermis general consists of 4 to 5 sub-layers - stratum corneum, stratum lucidum (on soles of feet and palms only), stratum granulosum, stratum spinosum, and stratum basale.
  • injectable means, with respect to the dermal filler, that it may be injected into the dermis with a syringe and needle such that it is deposited in the appropriate layer of skin to provide a plumping effect that may be temporary or permanent depending on the dermal filler that is used.
  • Non-dermal filler with respect to the composition means that it is not suitable for injection into the skin layers or dermis to provide plumping, line or depression filling, or other cosmetic dermato logical effects.
  • “Plumping” with respect to the term “skin” or “keratinous surface” means that the surface depressions, lines, wrinkles, etc. become more filled in and less visible to the naked eye, much in the manner that such depressions, lines, and wrinkles would become filled in if the dermal filler were injected into the dermis.
  • Suitable hyaluronic acid based dermal fillers are those that are capable of partial or complete absorption into the epidermal layers of the skin.
  • the hyaluronic acid dermal filler is preferably cross linked, more preferably covalently cross linked. It is generally present in an amount sufficient to provide an effect on the epidermis, ranging from about 0.001 to 99%, preferably from about 0.01 to 95%, more preferably from about 0.05 to 90% by weight of the total composition.
  • the hyaluronic acid dermal filler may be in the liquid or solid form. Preferably it is in the solid particulate form with particles ranging from about 0.001 to about 50 microns, preferably from about 0.05 to 5 microns, more preferably from about 0.075 to 1 micron.
  • any one or more of the carbon atoms may be substituted with an aromatic group.
  • specific examples of such compounds suitable for reacting with the hyaluronic acid include, but are not limited to: 2, 2'(ethylenedioxy) bis (ethylamine), l,3-diamino-2- hydroxypropanone; 1,3-diaminoacetone; 2,5-diaminobenzenesulfonic acid; 3,5- diaminobenzoic acid; 2,6-diaminopyridine; 2,5-diaminopyridine; 2,6-diaminopurine; and so on.
  • the hyaluronic acid may be cross linked.
  • the degree of cross linking may range from 0 to 100%.
  • One particularly suitable cross linking agent is carbodiimide (also referred to as CDI), although other cross linking agents may be suitable.
  • Suitable hyaluronic acid based dermal fillers may be made according to Examples 1 through 8 of U.S. Patent Application No. 2007/0224277 Al .
  • one type of hyaluronic acid is prepared in Example 1 by dissolving hyaluronic acid in water to produce a solution having a concentration of 1 mg/ml, adding 2'(ethylenedioxy)bis(ethylamine), then adjusting the pH of the solution to 6.5 by adding 0.1 M NaCl.
  • CDI is added dropwise while stirring the reaction mixture at 4° C. for 30 minutes and subsequently at room temperature (25° C.) for 24 hours.
  • the solution containing hyaluronan particles is then purified by dialysis for 6 days with distilled water and freeze dried.
  • dermal fillers based upon polymeric hydroxyacids such as poly-L- lactic acid sold by Dermik Laboratories under the trademark SculptraTM.
  • Particles of polymeric alpha hydroxyl acids are suitable for topical administration.
  • Such polymeric hydroxyl acids may be in liquid or solid form.
  • examples of such polymeric materials include those set forth in U.S. Patent No. 5,824,333, which is hereby incorporated by reference in its entirety. In one preferred embodiment such particles have a size ranging from about 0.001 to 25 microns, preferably from about 0.001 to 5 microns. III.
  • the dermal fillers used in the non-dermal filler compositions and methods of the invention may be incorporated into a wide variety of topical cosmetic compositions suitable for application to skin, hair, or nails, such as creams, lotions, gels, sprays, shampoos, conditioners, mousses, foundation makeup, blush, concealer, lipstick, mascara, eyeliner, eye shadow, nail color, and so on.
  • topical compositions may be in the form of emulsions, anhydrous compositions, or aqueous based gels.
  • compositions may comprise from about 0.001 to 99%, preferably from about 0.01-95%, more preferably from about 0.1 to 90% water and from about 0.001 to 99%, preferably from about 0.01 to 95%, more preferably from about 0.1 to 90% by weight of the total composition of oil.
  • the aqueous phase may contain one or more aqueous phase structuring agents, that is, an agent that increases the viscosity or, or thickens, the aqueous phase of the composition. This is particularly desirable when the composition is in the form of a serum or gel.
  • the aqueous phase structuring agent should be compatible with the dermal filler particularly when the dermal filler is water soluble, and also compatible with the other ingredients in the formulation. Suitable ranges of aqueous phase structuring agent, if present, are from about 0.01 to 30%, preferably from about 0.1 to 20%, more preferably from about 0.5 to 15% by weight of the total composition. Examples of such agents include various acrylate based thickening agents, natural or synthetic gums, polysaccharides, and the like, including but not limited to those set forth below.
  • L_ 1 Polysaccharides
  • Polysaccharides may be suitable aqueous phase thickening agents.
  • examples of such polysaccharides include naturally derived materials such as agar, agarose, alicaligenes polysaccharides, algin, alginic acid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum, pectin, trehelose, gelatin, and so on. 2.
  • Acrylate Polymers such as agar, agarose, alicaligenes polysaccharides, algin, alginic acid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid,
  • One type includes acrylic polymeric thickeners comprised of monomers A and B wherein A is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and B is selected from the group consisting of a Ci_ 22 alkyl acrylate, a Ci_ 22 alky methacrylate, and mixtures thereof are suitable.
  • the A monomer comprises one or more of acrylic acid or methacrylic acid
  • the B monomer is selected from the group consisting of a C 1-10 , most preferably Ci_ 4 alkyl acrylate, a C 1-10 , most preferably Ci_ 4 alkyl methacrylate, and mixtures thereof.
  • the B monomer is one or more of methyl or ethyl acrylate or methacrylate.
  • the acrylic copolymer may be supplied in an aqueous solution having a solids content ranging from about 10-60%, preferably 20-50%, more preferably 25-45% by weight of the polymer, with the remainder water.
  • the composition of the acrylic copolymer may contain from about 0. 1-99 parts of the A monomer, and about 0.1-99 parts of the B monomer.
  • Acrylic polymer solutions include those sold by Seppic, Inc., under the tradename Capigel. Also suitable are acrylic polymeric thickeners that are copolymer of A, B, and C monomers wherein A and B are as defined above, and C has the general formula:
  • Z is -(CH 2 ) m ; wherein m is 1-10, n is 2-3, o is 2-200, and R is a Ci O _3o straight or branched chain alkyl.
  • Examples of the secondary thickening agent above are copolymers where A and B are defined as above, and C is CO, and wherein n, o, and R are as above defined.
  • Examples of such secondary thickening agents include acrylates/steareth-20 methacrylate copolymer, which is sold by Rohm & Haas under the tradename Acrysol ICS-I .
  • acrylate based anionic amphiphilic polymers containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain.
  • the hydrophilic unit contains an ethylenically unsaturated anionic monomer, more specif ⁇ cially a vinyl carboxylic acid such as acrylic acid, methacrylic acid or mixtures thereof, and where the allyl ether unit containing a fatty chain corresponds to the monomer of formula
  • R denotes H or CH 3
  • B denotes the ethylenoxy radical
  • n is zero or an integer ranging from 1 to 100
  • R denotes a hydrocarbon radical selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals which contain from 8 to 30 carbon atoms, preferably from 10 to 24, and even more particularly from 12 to 18 carbon atoms. More preferred in this case is where R denotes H, n is equal to 10 and R denotes a stearyl (C 18) radical.
  • Anionic amphiphilic polymers of this type are described and prepared in U.S. Patent Nos.
  • anionic amphiphilic polymers polymers formed of 20 to 60% by weight acrylic acid and/or methacrylic acid, of 5 to 60% by weight lower alkyl methacrylates, of 2 to 50% by weight allyl ether containing a fatty chain as mentioned above, and of 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
  • a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
  • polymers are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (having 10 EO units) ether of stearyl alcohol or steareth-10, in particular those sold by the company Allied Colloids under the names SALCARE SC80 and SALCARE SC90, which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth- 10 allyl ether (40/50/10).
  • acrylate copolymers such as Polyacrylate-3 which is a copolymer of methacrylic acid, methylmethacrylate, methylstyrene isopropylisocyanate, and PEG-40 behenate monomers; Polyacrylate-10 which is a copolymer of sodium acryloyldimethyltaurate, sodium acrylate, acrylamide and vinyl pyrrolidone monomers; or Polyacrylate- 11 , which is a copolymer of sodium acryloyldimethylacryloyldimethyl taurate, sodium acrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, and acrylamide monomers.
  • Polyacrylate-3 which is a copolymer of methacrylic acid, methylmethacrylate, methylstyrene isopropylisocyanate, and PEG-40 behenate monomers
  • Polyacrylate-10 which is a copolymer of sodium acryloyl
  • crosslinked acrylate based polymers where one or more of the acrylic groups may have substituted long chain alkyl (such as 6-40, 10-30, and the like) groups, for example acrylates/Cio-30 alkyl acrylate crosspolymer which is a copolymer of C 10-30 alkyl acrylate and one or more monomers of acrylic acid, methacrylic acid, or one of their simple esters crosslinked with the allyl ether of sucrose or the allyl ether of pentaerythritol.
  • Such polymers are commonly sold under the Carbopol or Pemulen tradenames and have the CTFA name carbomer.
  • aqueous phase thickening agent acrylate based polymeric thickeners sold by Clariant under the Aristoflex trademark such as Aristoflex AVC, which is ammonium acryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the same polymer has found in AVC dispersed in mixture containing caprylic/capric triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; or Aristoflex HMB which is ammonium acryloyldimethyltaurate/beheneth-25 methacrylate crosspolymer, and the like.
  • Aristoflex AVC ammonium acryloyldimethyltaurate/VP copolymer
  • Aristoflex AVL which is the same polymer has found in AVC dispersed in mixture containing caprylic/capric triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate
  • Aristoflex HMB ammonium
  • aqueous phase thickening agents are various polyethylene glycols (PEG) derivatives where the degree of polymerization ranges from 1,000 to 200,000. Such ingredients are indicated by the designation "PEG” followed by the degree of polymerization in thousands, such as PEG-45M, which means PEG having 45,000 repeating ethylene oxide units.
  • PEG derivatives include PEG 2M, 5M, 7M, 9M, 14M, 2OM, 23M,
  • polyglycerins which are repeating glycerin moieties where the number of repeating moieties ranges from 15 to 200, preferably from about 20-100.
  • suitable polyglycerins include those having the CFTA names polyglycerin-20, polyglycerin- 40, and the like.
  • the composition will comprise an oil phase.
  • Oily ingredients are desirable for the skin moisturizing and protective properties. Oils, if present, will form a barrier on the skin so that the dermal filler present in the composition remains on the skin.
  • Suitable oils include silicones, esters, vegetable oils, synthetic oils, including but not limited to those set forth herein.
  • the oils may be volatile or nonvolatile, and are preferably in the form of a pourable liquid at room temperature.
  • volatile means that the oil has a measurable vapor pressure, or a vapor pressure of at least about 2 mm. of mercury at 20° C.
  • nonvolatile means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20° C.
  • Suitable volatile oils generally have a viscosity ranging from about 0.5 to 5 centistokes 25° C. and include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof. Volatile oils may be used to promote more rapid drying of the skin care composition after it is applied to skin. Volatile oils are more desirable when the skin care products containing the dermal filler are being formulated for consumers that have combination or oily skin.
  • the term "combination" with respect to skin type means skin that is oily in some places on the face (such as the T-zone) and normal in others. (a).
  • Volatile Silicones Cyclic silicones are one type of volatile silicone that may be used in the composition.
  • Such silicones have the general formula:
  • n 3-6, preferably 4, 5, or 6.
  • linear volatile silicones for example, those having the general formula:
  • Cyclic and linear volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric.
  • the Dow Corning linear volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids include hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviated cst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5 cst), dodecamethylpentasiloxane (2 cst) and mixtures thereof, with all viscosity measurements being at 25° C.
  • Suitable branched volatile silicones include alkyl trimethicones such as methyl trimethicone, a branched volatile silicone having the general formula:
  • Methyl trimethicone may be purchased from Shin-Etsu Silicones under the tradename TMF- 1.5, having a viscosity of 1.5 centistokes at 25° C. (b). Volatile Paraff ⁇ nic Hydrocarbons
  • volatile oils are various straight or branched chain paraffmic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbon atoms.
  • Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and Cg_ 2 o isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference.
  • Preferred volatile paraffmic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60 to 260° C, and a viscosity of less than about 10 cst. at 25° C.
  • Such paraffinic hydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation.
  • Suitable C 12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A.
  • Non- Volatile Oils A variety of nonvolatile oils are also suitable for use in the compositions of the invention.
  • the nonvolatile oils generally have a viscosity of greater than about 5 to 10 centistokes at 25° C, and may range in viscosity up to about 1,000,000 centipoise at 25° C.
  • Examples of nonvolatile oils include, but are not limited to:
  • esters Suitable esters are mono-, di-, and triesters.
  • the composition may comprise one or more esters selected from the group, or mixtures thereof.
  • Monoesters are defined as esters formed by the reaction of a monocarboxylic acid having the formula R-COOH, wherein R is a straight or branched chain saturated or unsaturated alkyl having 2 to 45 carbon atoms, or phenyl; and an alcohol having the formula
  • R-OH wherein R is a straight or branched chain saturated or unsaturated alkyl having 2-30 carbon atoms, or phenyl. Both the alcohol and the acid may be substituted with one or more hydroxyl groups. Either one or both of the acid or alcohol may be a "fatty" acid or alcohol, and may have from about 6 to 30 carbon atoms, more preferably 12, 14, 16, 18, or 22 carbon atoms in straight or branched chain, saturated or unsaturated form.
  • monoester oils examples include hexyl laurate, butyl isostearate, hexadecyl isostearate, cetyl palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl isononanoate, steary lactate, stearyl octanoate, stearyl stearate, isononyl isononanoate, and so on.
  • diesters Suitable diesters are the reaction product of a dicarboxylic acid and an aliphatic or aromatic alcohol or an aliphatic or aromatic alcohol having at least two substituted hydroxyl groups and a monocarboxylic acid.
  • the dicarboxylic acid may contain from 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated or unsaturated form.
  • the dicarboxylic acid may be substituted with one or more hydroxyl groups.
  • the aliphatic or aromatic alcohol may also contain 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated, or unsaturated form.
  • one or more of the acid or alcohol is a fatty acid or alcohol, i.e. contains 12-22 carbon atoms.
  • the dicarboxylic acid may also be an alpha hydroxy acid.
  • the ester may be in the dimer or trimer form.
  • diester oils that may be used in the compositions of the invention include diisotearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, dioctyl malate, and so on.
  • Triesters Suitable triesters comprise the reaction product of a tricarboxylic acid and an aliphatic or aromatic alcohol or alternatively the reaction product of an aliphatic or aromatic alcohol having three or more substituted hydroxyl groups with a monocarboxylic acid.
  • the acid and alcohol contain 2 to 30 carbon atoms, and may be saturated or unsaturated, straight or branched chain, and may be substituted with one or more hydroxyl groups.
  • one or more of the acid or alcohol is a fatty acid or alcohol containing 12 to 22 carbon atoms.
  • triesters include esters of arachidonic, citric, or behenic acids, such as triarachidin, tributyl citrate, triisostearyl citrate, tri C 12 - 13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.
  • esters of arachidonic, citric, or behenic acids such as triarachidin, tributyl citrate, triisostearyl citrate, tri C 12 - 13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.
  • Esters suitable for use in the composition are further described in the C.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition, 2006, under the classification of "Esters", the text of which is hereby incorporated by reference in its entirety.
  • nonvolatile hydrocarbon oils include paraffinic hydrocarbons and olefins, preferably those having greater than about 20 carbon atoms.
  • hydrocarbon oils include C24-28 olefins, C30-45 olefins, C20-40 isoparaffins, hydrogenated polyisobutene, polyisobutene, polydecene, hydrogenated polydecene, mineral oil, pentahydrosqualene, squalene, squalane, and mixtures thereof.
  • such hydrocarbons have a molecular weight ranging from about 300 to 1000 Daltons.
  • Glyceryl Esters of Fatty Acids Synthetic or naturally occurring glyceryl esters of fatty acids, or triglycerides, are also suitable for use in the compositions. Both vegetable and animal sources may be used. Examples of such oils include castor oil, lanolin oil, C 10-18 triglycerides, caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil, sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil, walnut oil, and the like.
  • oils include castor oil, lanolin oil, C 10-18 triglycerides, caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil, sesame oil, camelina sativa oil, tamanu seed oil, coconut oil
  • glyceryl esters such as fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, mono-, di- or triesters of polyols such as glycerin.
  • a fatty (C 12 - 22 ) carboxylic acid is reacted with one or more repeating glyceryl groups, glyceryl stearate, diglyceryl diiosostearate, polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryl tetraisostearate, glyceryl trioctanoate, diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on. 4.
  • glyceryl groups glyceryl stearate, diglyceryl diiosost
  • Nonvolatile silicone oils both water soluble and water insoluble, are also suitable for use in the composition.
  • Such silicones preferably have a viscosity ranging from about greater than 5 to 800,000 cst, preferably 20 to 200,000 cst at 25° C.
  • Suitable water insoluble silicones include amine functional silicones such as amodimethicone.
  • such nonvolatile silicones may have the following general formula:
  • R and R' are each independently Ci_ 3 o straight or branched chain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy, and x and y are each independently 1- 1 ,000,000; with the proviso that there is at least one of either x or y, and A is alkyl siloxy endcap unit.
  • A is a methyl siloxy endcap unit; in particular trimethylsiloxy, and R and R are each independently a Ci_3o straight or branched chain alkyl, phenyl, or trimethylsiloxy, more preferably a Cr 22 alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl, or trimethylsiloxy, and resulting silicone is dimethicone, phenyl dimethicone, diphenyl dimethicone, phenyl trimethicone, or trimethylsiloxyphenyl dimethicone.
  • alkyl dimethicones such as cetyl dimethicone, and the like wherein at least one R is a fatty alkyl (C12, C 14 , C 16 , C 18 , C 2 o, or C 22 ), and the other R is methyl, and A is a trimethylsiloxy endcap unit, provided such alkyl dimethicone is a pourable liquid at room temperature.
  • Phenyl trimethicone can be purchased from Dow Corning Corporation under the tradename 556 Fluid.
  • Trimethylsiloxyphenyl dimethicone can be purchased from Wacker-Chemie under the tradename PDM-1000.
  • Cetyl dimethicone also referred to as a liquid silicone wax, may be purchased from Dow Corning as Fluid 2502, or from DeGussa Care & Surface Specialties under the trade names Abil Wax 9801, or 9814.
  • fluorinated oils may also be suitable for use in the compositions including but not limited to fluorinated silicones, fluorinated esters, or perfluropoly ethers.
  • fluorinated silicones such as trimethylsilyl endcapped fluorosilicone oil, polytrifluoropropylmethylsiloxanes, and similar silicones such as those disclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated by reference.
  • Perfluoropolyethers include those disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated by reference, which are commercially available from Montefluos under the trademark Fomblin.
  • oil phase structuring agent means an ingredient or combination of ingredients, soluble or dispersible in the oil phase, which will increase the viscosity, or structure, the oil phase.
  • compatible means that the oil phase structuring agent and dermal filler derivative are capable of being formulated into a cosmetic product that is generally stable.
  • the structuring agent may be present in an amount sufficient to provide a liquid composition with increased viscosity, a semi-solid, or in some cases a solid composition that may be self- supporting.
  • the structuring agent itself may be present in the liquid, semi-solid, or solid form. Suggested ranges of structuring agent are from about 0.01 to 70%, preferably from about 0.05 to 50%, more preferably from about 0.1-35% by weight of the total composition.
  • Suitable oil phase structuring agents include those that are silicone based or organic based. They may be polymers or non-polymers, synthetic, natural, or a combination of both. 1.
  • Silicone Structuring Agents may be silicone based, such as silicone elastomers, silicone gums, silicone waxes, linear silicones having a degree of polymerization that provides the silicone with a degree of viscosity such that when incorporated into the cosmetic composition it is capable of increasing the viscosity of the oil phase.
  • silicone structuring agents include, but are not limited to: (a). Silicone Elastomers
  • Silicone elastomers suitable for use in the compositions of the invention include those that are formed by addition reaction-curing, by reacting an SiH-containing diorganosiloxane and an organopolysiloxane having terminal olefmic unsaturation, or an alpha-omega diene hydrocarbon, in the presence of a platinum metal catalyst.
  • Such elastomers may also be formed by other reaction methods such as condensation-curing organopolysiloxane compositions in the presence of an organotin compound via a dehydrogenation reaction between hydroxyl-terminated diorganopolysiloxane and SiH-containing diorganopolysiloxane or alpha omega diene; or by condensation-curing organopolysiloxane compositions in the presence of an organotin compound or a titanate ester using a condensation reaction between an hydroxyl-terminated diorganopolysiloxane and a hydrolysable organosiloxane; peroxide- curing organopolysiloxane compositions which thermally cure in the presence of an organoperoxide catalyst.
  • One type of elastomer that may be suitable is prepared by addition reaction-curing an organopolysiloxane having at least 2 lower alkenyl groups in each molecule or an alpha- omega diene; and an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in each molecule; and a platinum-type catalyst. While the lower alkenyl groups such as vinyl, can be present at any position in the molecule, terminal olefmic unsaturation on one or both molecular terminals is preferred.
  • the molecular structure of this component may be straight chain, branched straight chain, cyclic, or network.
  • organopolysiloxanes are exemplified by methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylpolysiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy- terminated dimethylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl(3,3,3-trifluoropropyl) polysiloxanes, and dimethyl
  • Curing proceeds by the addition reaction of the silicon-bonded hydrogen atoms in the dimethyl methylhydrogen siloxane, with the siloxane or alpha-omega diene under catalysis using the catalyst mentioned herein.
  • the methyl hydrogen siloxane must contain at least 2 silicon-bonded hydrogen atoms in each molecule in order to optimize function as a crosslinker.
  • the catalyst used in the addition reaction of silicon-bonded hydrogen atoms and alkenyl groups is concretely exemplified by chloroplatinic acid, possibly dissolved in an alcohol or ketone and this solution optionally aged, chloroplatinic acid-olef ⁇ n complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and carrier-supported platinum.
  • Suitable silicone elastomers for use in the compositions of the invention may be in the powder form, or dispersed or solubilized in solvents such as volatile or nonvolatile silicones, or silicone compatible vehicles such as paraffinic hydrocarbons or esters.
  • silicone elastomer powders include vinyl dimethicone/methicone silesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP- 102, KSP- 103, KSP- 104, KSP- 105, hybrid silicone powders that contain a fluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro-silicone elastomer, and hybrid silicone powders that contain a phenyl group such as
  • Shin-Etsu's KSP-300 which is a phenyl substituted silicone elastomer; and Dow Coming's DC 9506.
  • silicone elastomer powders dispersed in a silicone compatible vehicle include dimethicone/vinyl dimethicone crosspolymers supplied by a variety of suppliers including Dow Corning Corporation under the tradenames 9040 or 9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Silicones under the tradenames KSG-15, 16, 18.
  • KSG- 15 has the CTFA name cyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer.
  • KSG- 18 has the INCI name phenyl trimethicone/dimethicone/phenyl vinyl dimethicone crossoplymer.
  • Silicone elastomers may also be purchased from Grant Industries under the Gransil trademark. Also suitable are silicone elastomers having long chain alkyl substitutions such as lauryl dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu under the tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44.
  • Cross-linked organopolysiloxane elastomers useful in the present invention and processes for making them are further described in U.S. Pat. No.
  • silicone gums are also suitable for use as an oil phase structuring agent.
  • the term "gum” means a silicone polymer having a degree of polymerization sufficient to provide a silicone having a gum-like texture. In certain cases the silicone polymer forming the gum may be crosslinked.
  • the silicone gum typically has a viscosity ranging from about 500,000 to 100 million cst at 25° C, preferably from about 600,000 to 20 million, more preferably from about 600,000 to 12 million cst. All ranges mentioned herein include all subranges, e.g. 550,000; 925,000; 3.5 million.
  • silicone gums that are used in the compositions include, but are not limited to, those of the general formula wherein:
  • Ri to R 9 are each independently an alkyl having 1 to 30 carbon atoms, aryl, or aralkyl; and X is OH or a C i-3o alkyl, or vinyl; and wherein x, y, or z may be zero with the proviso that no more than two of x, y, or z are zero at any one time, and further that x, y, and z are such that the silicone gum has a viscosity of at least about 500,000 cst, ranging up to about 100 million centistokes at 25° C. Preferred is where R is methyl or OH.
  • Such silicone gums may be purchased in pure form from a variety of silicone manufacturers including Wacker-Chemie or Dow Corning, and the like. Such silicone gums include those sold by Wacker-Belsil under the trade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096.
  • a silicone gum where X is OH, also referred to as dimethiconol, is available from Dow Corning Corporation under the trade name 1401.
  • the silicone gum may also be purchased in the form of a solution or dispersion in a silicone compatible vehicle such as volatile or nonvolatile silicone.
  • An example of such a mixture may be purchased from Barnet Silicones under the HL-88 tradename, having the INCI name dimethicone.
  • alkyl silicone waxes that are typically referred to as alkyl silicone waxes which are semi-solids or solids at room temperature.
  • alkyl silicone wax means a polydimethylsiloxane having a substituted long chain alkyl (such as C16 to 30) that confers a semi-solid or solid property to the siloxane.
  • examples of such silicone waxes include stearyl dimethicone, which may be purchased from DeGussa Care & Surface Specialties under the tradename Abil Wax 9800 or from Dow Corning under the tradename 2503.
  • Another example is bis-stearyl dimethicone, which may be purchased from Gransil Industries under the tradename Gransil A-18, or behenyl dimethicone, behenoxy dimethicone.
  • silicone polyamide means a polymer comprised of silicone monomers and monomers containing amide groups as further described herein.
  • the silicone polyamide preferably comprises moieties of the general formula:
  • X is a linear or branched alkylene having from about 1-30 carbon atoms;
  • R 1 , R 2 , R 3 , and R 4 are each independently Ci_ 3 o straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more Ci_ 3 o alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
  • Ci_2o alkyl which may be substituted with one or more hydroxy groups, or
  • R5, R 6 , and R 7 are each independently a C 1-10 linear or branched alkylenes, and T is CRg wherein R 8 is hydrogen, a trivalent atom N, P, or Al, or a Ci_ 3 o straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more Ci_ 3 o alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
  • Ri, R 2 , R3, and R 4 are Ci_io, preferably methyl; and X and Y is a linear or branched alkylene.
  • a and b are each independently sufficient to provide a silicone polyamide polymer having a melting point ranging from about 60 to 120° C, and a molecular weight ranging from about 40,000 to 500,000 Daltons.
  • One type of silicone polyamide that may be used in the compositions of the invention may be purchased from Dow Corning Corporation under the tradename Dow Corning 2-8178 gellant which has the CTFA name nylon-611/dimethicone copolymer which is sold in a composition containing PPG-3 myristyl ether.
  • polyamides such as those purchased from Arizona Chemical under the tradenames Uniclear and Sylvaclear. Such polyamides may be ester terminated or amide terminated. Examples of ester terminated polyamides include, but are not limited to those having the general formula:
  • each R 3 is independently an organic group containing at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and each R 4 is independently a hydrogen atom, a C 1-10 alkyl group or a direct bond to R 3 or to another R 4 , such that the nitrogen atom to which R 3 and R 4 are both attached forms part of a heterocyclic structure defined by R 4 -N-R 3 , with at least 50% of the groups R 4 representing a hydrogen atom.
  • ester and amide terminated polyamides that may be used as oil phase gelling agents include those sold by Arizona Chemical under the tradenames Sylvaclear A200V or A2614V, both having the CTFA name ethylenediamine/hydrogenated dimer dilinoleate copolymer/bis-di-Ci 4 _i8 alkyl amide; Sylvaclear AF1900V; Sylvaclear C75V having the CTFA name bis-stearyl ethylenediamine/neopentyl glycol/stearyl hydrogenated dimer dilinoleate copolymer; Sylvaclear PA1200V having the CTFA name Polyamide-3; Sylvaclear PE400V; Sylvaclear WF 1500V; or Uniclear, such as Uniclear IOOVG having the INCI name ethylenediamine/stearyl dimer dilinoleate copolymer; or ethylenediamine/stearyl dimer ditallate copoly
  • oil phase structuring agent may be one or more natural or synthetic waxes such as animal, vegetable, or mineral waxes.
  • waxes will have a higher melting point such as from about 50 to 150° C, more preferably from about 65 to 100° C.
  • waxes examples include waxes made by Fischer- Tropsch synthesis, such as polyethylene or synthetic wax; or various vegetable waxes such as bayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnauba wax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, grape wax, and polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or PEG- 12 carnauba wax; or fatty acids or fatty alcohols, including esters thereof, such as hydroxystearic acids (for example 12-hydroxy stearic acid), tristearin, tribehenin, and so on.
  • hydroxystearic acids for example 12-hydroxy stearic acid
  • One type of structuring agent that may be used in the composition comprises natural or synthetic montmorillonite minerals such as hectorite, bentonite, and quaternized derivatives thereof, which are obtained by reacting the minerals with a quaternary ammonium compound, such as stearalkonium bentonite, hectorites, quaternized hectorites such as Quaternium-18 hectorite, attapulgite, carbonates such as propylene carbonate, bentones, and the like.
  • a quaternary ammonium compound such as stearalkonium bentonite, hectorites, quaternized hectorites such as Quaternium-18 hectorite, attapulgite
  • carbonates such as propylene carbonate, bentones, and the like.
  • silicas silicas, silicates, silica silylate, and alkali metal or alkaline earth metal derivatives thereof.
  • These silicas and silicates are generally found in the particulate form and include silica, silica silylate, magnesium aluminum silicate, and the like.
  • surfactants include silica, silica silylate, magnesium aluminum silicate, and the like.
  • the composition may contain one or more surfactants, especially if in the emulsion form.
  • surfactants may be used if the compositions are anhydrous also, and will assist in dispersing ingredients that have polarity, for example pigments.
  • Such surfactants may be silicone or organic based.
  • the surfactants will aid in the formation of stable emulsions of either the water-in-oil or oil-in- water form. If present, the surfactant may range from about 0.001 to 30%, preferably from about 0.005 to 25%, more preferably from about 0.1 to 20% by weight of the total composition.
  • Silicone Surfactants Suitable silicone surfactants include polyorganosiloxane polymers that have amphiphilic properties, for example contain hydrophilic radicals and lipophilic radicals. These silicone surfactants may be liquids or solids at room temperature.
  • silicone surfactant that may be used is generally referred to as dimethicone copolyol or alkyl dimethicone copolyol.
  • This surfactant is either a water-in-oil or oil-in-water surfactant having an Hydrophile/Lipophile Balance (HLB) ranging from about 2 to 18.
  • HLB Hydrophile/Lipophile Balance
  • the silicone surfactant is a nonionic surfactant having an HLB ranging from about 2 to 12, preferably about 2 to 10, most preferably about 4 to 6.
  • hydrophilic radical means a radical that, when substituted onto the organosiloxane polymer backbone, confers hydrophilic properties to the substituted portion of the polymer.
  • radicals that will confer hydrophilicity are hydroxy-polyethyleneoxy, hydroxyl, carboxylates, and mixtures thereof.
  • lipophilic radical means an organic radical that, when substituted onto the organosiloxane polymer backbone, confers lipophilic properties to the substituted portion of the polymer.
  • organic radicals that will confer lipophilicity are Ci_ 4 o straight or branched chain alkyl, fluoro, aryl, aryloxy, Ci_ 40 hydrocarbyl acyl, hydroxy-polypropyleneoxy, or mixtures thereof.
  • One type of suitable silicone surfactant has the general formula:
  • PE is (-C 2 H 4 O) a -(-C 3 H 6 O) b -H wherein a is 0 to 25, b is 0-25 with the proviso that both a and b cannot be 0 simultaneously, x and y are each independently ranging from 0 to 1 million with the proviso that they both cannot be 0 simultaneously.
  • x, y, z, a, and b are such that the molecular weight of the polymer ranges from about 5,000 to about 500,000, more preferably from about 10,000 to 100,000, and is most preferably approximately about 50,000 and the polymer is generically referred to as dimethicone copolyol.
  • One type of silicone surfactant is wherein p is such that the long chain alkyl is cetyl or lauryl, and the surfactant is called, generically, cetyl dimethicone copolyol or lauryl dimethicone copolyol respectively.
  • the number of repeating ethylene oxide or propylene oxide units in the polymer are also specified, such as a dimethicone copolyol that is also referred to as PEG- 15/PPG-10 dimethicone, which refers to a dimethicone having substituents containing 15 ethylene glycol units and 10 propylene glycol units on the siloxane backbone.
  • PEG- 15/PPG-10 dimethicone which refers to a dimethicone having substituents containing 15 ethylene glycol units and 10 propylene glycol units on the siloxane backbone.
  • one or more of the methyl groups in the above general structure to be substituted with a longer chain alkyl (e.g. ethyl, propyl, butyl, etc.) or an ether such as methyl ether, ethyl ether, propyl ether, butyl ether, and the like.
  • silicone surfactants are those sold by Dow Corning under the tradename
  • crosslinked silicone surfactants that are often referred to as emulsifying elastomers. They are typically prepared as set forth above with respect to the section "silicone elastomers" except that the silicone elastomers will contain at least one hydrophilic moiety such as polyoxyalkylenated groups.
  • these polyoxyalkylenated silicone elastomers are crosslinked organopolysiloxanes that may be obtained by a crosslinking addition reaction of diorganopolysiloxane comprising at least one hydrogen bonded to silicon and of a polyoxyalkylene comprising at least two ethylenically unsaturated groups.
  • the polyoxyalkylenated crosslinked organo- polysiloxanes are obtained by a crosslinking addition reaction of a diorganopolysiloxane comprising at least two hydrogens each bonded to a silicon, and a polyoxyalkylene comprising at least two ethylenically unsaturated groups, optionally in the presence of a platinum catalyst, as described, for example, in U.S. Pat. No. 5,236,986 and U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No. 5,811,487, the contents of which are incorporated by reference.
  • Polyoxyalkylenated silicone elastomers that may be used in at least one embodiment of the invention include those sold by Shin-Etsu Silicones under the names KSG-21 , KSG-20, KSG-30, KSG-31, KSG-32, KSG-33; KSG-210 which is dimethicone/PEG-10/15 crosspolymer dispersed in dimethicone; KSG-310 which is PEG- 15 lauryl dimethicone crosspolymer; KSG-320 which is PEG- 15 lauryl dimethicone crosspolymer dispersed in isododecane; KSG-330 (the former dispersed in triethylhexanoin), KSG-340 which is a mixture of PEG-IO lauryl dimethicone crosspolymer and PEG- 15 lauryl dimethicone crosspolymer.
  • polyglycerolated silicone elastomers like those disclosed in PCT/WO 2004/024798, which is hereby incorporated by reference in its entirety.
  • elastomers include Shin-Etsu's KSG series, such as KSG-710 which is dimethicone/polyglycerin-3 crosspolymer dispersed in dimethicone; or lauryl dimethicone/polyglycerin-3 crosspolymer dispersed in a variety of solvent such as isododecane, dimethicone, triethylhexanoin, sold under the Shin-Etsu tradenames KSG-810, KSG-820, KSG-830, or KSG-840.
  • silicones sold by Dow Corning under the tradenames 9010 and DC9011.
  • One preferred crosslinked silicone elastomer emulsifier is dimethicone/PEG-10/15 crosspolymer, which provides excellent aesthetics due to its elastomeric backbone, but also surfactancy properties.
  • the composition may comprise one or more nonionic organic surfactants.
  • Suitable nonionic surfactants include alkoxylated alcohols, or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide.
  • the alcohol is either a fatty alcohol having 6 to 30 carbon atoms.
  • Steareth 2-100 which is formed by the reaction of stearyl alcohol and ethylene oxide and the number of ethylene oxide units ranges from 2 to 100
  • Beheneth 5-30 which is formed by the reaction of behenyl alcohol and ethylene oxide where the number of repeating ethylene oxide units is 5 to 30
  • Ceteareth 2-100 formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is 2 to 100
  • Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, and so on.
  • alkoxylated alcohols are formed by the reaction of fatty acids and mono-, di- or polyhydric alcohols with an alkylene oxide.
  • Examples include polymeric alkylene glycols reacted with glyceryl fatty acid esters such as PEG glyceryl oleates, PEG glyceryl stearate; or PEG polyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein the number of repeating ethylene glycol units ranges from 3 to
  • nonionic surfactants are formed by the reaction of a carboxylic acid with an alkylene oxide or with a polymeric ether.
  • the resulting products have the general formula: where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl, and n is the number of polymerized alkoxy groups. In the case of the diesters, the two RCO-groups do not need to be identical.
  • R is a C6-30 straight or branched chain, saturated or unsaturated alkyl, and n is from 1-100.
  • Monomeric, homopolymeric, or block copolymeric ethers are also suitable as nonionic surfactants.
  • ethers are formed by the polymerization of monomeric alkylene oxides, generally ethylene or propylene oxide.
  • Such polymeric ethers have the following general formula: wherein R is H or lower alkyl and n is the number of repeating monomer units, and ranges from 1 to 500.
  • Suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives.
  • alkoxylation, in particular ethoxylation of sorbitan provides polyalkoxylated sorbitan derivatives.
  • Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates.
  • the polyalkyoxylated sorbitan can be esterified with C6-30, preferably C12-22 fatty acids. Examples of such ingredients include
  • Certain types of amphoteric, zwitterionic, or cationic surfactants may also be used in the compositions. Descriptions of such surfactants are set forth in U.S. Pat. No. 5,843,193, which is hereby incorporated by reference in its entirety.
  • Humectants It may also be desirable to include one or more humectants in the composition. If present, such humectants may range from about 0.001 to 25%, preferably from about 0.005 to 20%, more preferably from about 0.1 to 15% by weight of the total composition.
  • suitable humectants include glycols, sugars, and the like.
  • Suitable glycols are in monomeric or polymeric form and include polyethylene and polypropylene glycols such as PEG 4-200, which are polyethylene glycols having from 4 to 200 repeating ethylene oxide units; as well as Ci_ 6 alkylene glycols such as propylene glycol, butylene glycol, pentylene glycol, and the like.
  • Suitable sugars are also suitable humectants.
  • sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on.
  • urea is also suitable.
  • the humectants used in the composition of the invention are C 1-6 , preferably C 2 _ 4 alkylene glycols, most particularly butylene glycol.
  • Suitable botanical extracts include extracts from plants (herbs, roots, flowers, fruits, seeds) such as flowers, fruits, vegetables, and so on, including yeast ferment extract, Padina Pavonica extract, thermus thermophilis ferment extract, camelina sativa seed oil, boswellia serrata extract, olive extract, A ⁇ bodopsis Thaliana extract, Acacia Dealbata extract, Acer Saccharinum (sugar maple), acidopholus, acorus, aesculus, agaricus, agave, agrimonia, algae, aloe, citrus, brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear, lemon, lime, pea, seaweed, caffeine, green tea, chamomile, willowbark, mul
  • Glycyrrhiza Glabra Salix Nigra, Macrocycstis Pyrifera, Pyrus Malus, Saxifraga Sarmentosa, Vitis Vinifera, Morus Nigra, Scutellaria Baicalensis, Anthemis Nobilis, Salvia Sclarea, Rosmarinus Officianalis, Citrus Medica Limonum, Panax Ginseng, Siegesbeckia Orientalis, Fructus Mume, Ascophyllum Nodosum, Bifida Ferment lysate, Glycine Soja extract, Beta Vulgaris, Haberlea Rhodopensis, Polygonum Cuspidatum, Citrus Aurantium Dulcis, Vitis Vinifera, Selaginella Tamariscina, Humulus Lupulus, Citrus Reticulata Peel, Punica Granatum, Asparagopsis, Curcuma Longa, Menyanthes Trifoliata, Helianthus Annu
  • sunscreens include chemical UVA or UVB sunscreens or physical sunscreens in the particulate form. Inclusion of sunscreens in the compositions containing the dermal filler will provide additional protection to skin during daylight hours and promote the effectiveness of the dermal filler on the skin. 1. UVA Chemical Sunscreens
  • the composition may comprise one or more UVA sunscreens.
  • UVA sunscreen means a chemical compound that blocks UV radiation in the wavelength range of about 320 to 400 nm.
  • Preferred UVA sunscreens are dibenzoylmethane compounds having the general formula
  • Ri is H, OR and NRR wherein each R is independently H, Ci_2o straight or branched chain alkyl; R 2 is H or OH; and R3 is H, Ci_2o straight or branched chain alkyl.
  • Ri is OR where R is a Ci_2o straight or branched alkyl, preferably methyl; R 2 is H; and R3 is a Ci_2o straight or branched chain alkyl, more preferably, butyl.
  • UVA sunscreen compounds of this general formula include 4- methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert- butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 4,4'- diisopropylbenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoymethane, 2-methyl-5- tert-butyl-4'-methoxydibenzoylmethane, and so on.
  • Avobenzone is commercial available from Givaudan-Roure under the trademark Parsol 1789, and Merck & Co. under the tradename Eusolex 9020.
  • Other types of UVA sunscreens include dicamphor sulfonic acid derivatives, such as ecamsule, a sunscreen sold under the trade name MexorylTM, which is terephthalylidene dicamphor sulfonic acid, having the formula: - ⁇
  • the composition may contain from about 0.001-20%, preferably 0.005-5%, more preferably about 0.005-3% by weight of the composition of UVA sunscreen.
  • the UVA sunscreen is Avobenzone, and it is present at not greater than about 3% by weight of the total composition.
  • UVB sunscreen means a compound that blocks UV radiation in the wavelength range of from about 290 to 320 nm.
  • Octocrylene is 2-ethylhexyl 2- cyano-3,3-diphenylacrylate.
  • the composition may contain no more than about 110% by weight of the total composition of octocrylene. Suitable amounts range from about 0.001-10% by weight.
  • Octocrylene may be purchased from BASF under the tradename Uvinul N-539.
  • benzylidene camphor derivatives as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety.
  • Such benzylidene camphor derivatives have the general formula:
  • R is p-tolyl or styryl, preferably styryl.
  • Particularly preferred is 4-methylbenzylidene camphor, which is a lipid soluble UVB sunscreen compound sold under the tradename Eusolex 6300 by Merck.
  • Also suitable are cinnamate derivatives having the general formula:
  • R and Ri are each independently a Ci_ 2 o straight or branched chain alkyl. Preferred is where R is methyl and Ri is a branched chain C 1-10 , preferably Cg alkyl.
  • the preferred compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate or octyl methoxycinnamate.
  • the compound may be purchased from Givaudan Corporation under the tradename Parsol MCX, or BASF under the tradename Uvinul MC 80. Also suitable are mono-, di-, and triethanolamine derivatives of such methoxy cinnamates including diethanolamine methoxycinnamate.
  • Cinoxate the aromatic ether derivative of the above compound is also acceptable. If present, the Cinoxate should be found at no more than about 3% by weight of the total composition.
  • UVB screening agents are various benzophenone derivatives having the general formula:
  • R through R 9 are each independently H, OH, NaO 3 S, SO 3 H, SO 3 Na, Cl, R", OR" where R" is Ci 20 straight or branched chain alkyl
  • R is Ci 20 straight or branched chain alkyl
  • examples of such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.
  • the benzophenone derivative is Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (also referred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium), and the like. Most preferred is Benzophenone 3.
  • menthyl salicylate derivatives having the general formula:
  • Ri, R 2 , R 3 , and R 4 are each independently H, OH, NH 2 , or Ci 20 straight or branched chain alkyl. Particularly preferred is where Ri, R2, and R 3 are methyl and R 4 is hydroxyl or NH2, the compound having the name homomenthyl salicylate (also known as Homosalate) or menthyl anthranilate. Homosalate is available commercially from Merck under the tradename Eusolex HMS and menthyl anthranilate is commercially available from Haarmann & Reimer under the tradename Heliopan. If present, the Homosalate should be found at no more than about 15% by weight of the total composition.
  • Various amino benzoic acid derivatives are suitable UVB absorbers including those having the general formula:
  • R 1 , R 2 , and R3 are each independently H, Ci_2o straight or branched chain alkyl which may be substituted with one or more hydroxy groups. Particularly preferred is wherein Ri is H or Ci_8 straight or branched alkyl, and R 2 and R3 are H, or Ci_8 straight or branched chain alkyl.
  • PABA ethyl hexyl dimethyl PABA
  • Padimate O ethyldihydroxypropyl PABA
  • Padimate O should be found at no more than about 8% by weight of the total composition.
  • Salicylate derivatives are also acceptable UVB absorbers. Such compounds have the general formula: wherein R is a straight or branched chain alkyl, including derivatives of the above compound formed from mono-, di-, or triethanolamines. Particular preferred are octyl salicylate, TEA-salicylate, DEA-salicylate, and mixtures thereof.
  • the amount of the UVB chemical sunscreen present may range from about 0.001- 45%, preferably 0.005-40%, more preferably about 0.01-35% by weight of the total composition.
  • compositions of the invention may be formulated to have a certain SPF
  • compositions of the invention may contain particulate materials in the form of pigments, inert particulates, or mixtures thereof. If present, suggested ranges are from about 0.01-75%, preferably about 0.5-70%, more preferably about 0.1-65% by weight of the total composition. In the case where the composition may comprise mixtures of pigments and powders, suitable ranges include about 0.01-75% pigment and 0.1-75% powder, such weights by weight of the total composition. 1. Powders
  • the particulate matter may be colored or non-colored (for example white) non- pigmented powders.
  • Suitable non-pigmented powders include bismuth oxychloride, titanated mica, fumed silica, spherical silica, polymethylmethacrylate, micronized teflon, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium aluminum silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate, calcium silicate, dextran,
  • the above mentioned powders may be surface treated with lecithin, amino acids, mineral oil, silicone, or various other agents either alone or in combination, which coat the powder surface and render the particles more lipophilic in nature.
  • the particulate materials may comprise various organic and/or inorganic pigments.
  • the organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthroquinone, and xanthine dyes which are designated as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc.
  • Organic pigments generally consist of insoluble metallic salts of certified color additives, referred to as the Lakes.
  • Inorganic pigments include iron oxides, ultramarines, chromium, chromium hydroxide colors, and mixtures thereof. Iron oxides of red, blue, yellow, brown, black, and mixtures thereof are suitable.
  • the composition may contain 0.001-8%, preferably 0.01-6%, more preferably 0.05-5% by weight of the total composition of preservatives.
  • preservatives include such as benzoic acid, benzyl alcohol, benzylhemiformal, benzylparaben, 5-bromo-5- nitro-l,3-dioxane, 2-bromo-2-nitropropane-l,3-diol, butyl paraben, phenoxyethanol, methyl paraben, propyl paraben, diazolidinyl urea, calcium benzoate, calcium propionate, caprylyl glycol, biguanide derivatives, phenoxyethanol, captan, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, chloroacetamide, chlorobutanol, p-chloro-m- cresol, chlorophene, chlorothymol, chloroxylenol,
  • compositions of the invention may contain vitamins and/or coenzymes, as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, more preferably 0.05-5% by weight of the total composition is suggested.
  • Suitable vitamins include ascorbic acid and derivatives thereof such as ascorbyl palmitate, tetrahexydecyl ascorbate, and so on; the B vitamins such as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymes such as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and derivatives thereof are suitable.
  • retinyl palmitate examples are retinyl palmitate, retinol. retinoic acid, as well as Vitamin A in the form of beta carotene.
  • Vitamin E and derivatives thereof such as Vitamin E acetate, nicotinate, or other esters thereof.
  • Vitamins D and K are suitable.
  • Suitable antioxidants are ingredients which assist in preventing or retarding spoilage.
  • antioxidants suitable for use in the compositions of the invention are potassium sulfite, sodium bisulfite, sodium erythrobate, sodium metabisulfite, sodium sulfite, propyl gallate, cysteine hydrochloride, butylated hydroxytoluene, butylated hydroxyanisole, and so on.
  • collagen fortifiers means an ingredient that either stimulates or promotes collagen synthesis in the skin or inhibits degradation of collagen in the skin. If present suggested ranges of collagen fortifier are from about 0.001 to 80%, preferably from about 0.01 to 75%, preferably from about 0.05 to 30% by weight of the total composition.
  • Suitable collagen fortifiers include, but are not limited to, copper peptides, emodin, vitamin C, acetyl hexapeptide-8 (argirilene), palmitoyl pentapeptide (a.k.a.
  • Matrixyl® Ceramide-2
  • pollen various isoflavones including those from soy products, marine collagen, brown algae, fatty acid esters of ascorbic acid such as ascorbyl palmitate or tetrahexadecyl ascorbate, tocopherol, managanese, and so on.
  • Ingredients that are known in the art to promote collagen synthesis in skin or inhibit degradation of skin collagen are know in the art and included within the definition of "collagen fortifier” when used herein, even if not mentioned specifically.
  • M. Elastin Fortifier Elastin Fortifier
  • elastin fortifiers are also suitable for use in the invention.
  • the term "elastin fortifier” means an ingredient that stimulates or promotes synthesis of elastin in the skin or inhibits the degradation of skin elastin. If present the elastin fortifier may range from about 0.001 to 50%, preferably from about 0.005 to 40%, more preferably from about 0.05 to 35% by weight of the total composition.
  • elastin fortifiers include, but are not limited to, zinc, boswellic acids, ursolic acid, various types of alpha hydroxyl acids such as citric or lactic acids, aloe, panthenol, and the like.
  • Ingredients that stimulate or promote elastin synthesis or inhibit degradation of skin elastin are well known in the art and are included within the term "elastin fortifier” when used herein, even if not specifically mentioned herein.
  • GAG Fortifer Also suitable for use in the compositions of the invention are various types of ingredients that promote GAG (or glycosaminoglycan) synthesis. If present, suggested ranges are from about 0.001 to 50%, preferably from about 0.005 to 40%, more preferably from about 0.01 to 35% by weight of the total composition.
  • GAG fortifiers include botanical extracts from Centella genus such Centella Asiatica, glucosamine, manganese, Guto Kola extract, Hibiscus extract and so on. Ingredients that promote GAG synthesis are well known in the art and included within the definition of "GAG Fortifier" as used herein, even though not specifically mentioned herein. IV.
  • the Cosmetic Compositions are well known in the art and included within the definition of "GAG Fortifier" as used herein, even though not specifically mentioned herein. IV.
  • compositions of the invention containing the dermal fillers may be found in a variety of forms, such as anhydrous compositions, aqueous based solutions, serums, gels, skin creams or lotions, or color cosmetic compositions such as foundation makeup, mascara, lip color, blush, eyeshadow, and the like.
  • the dermal filler may be solubilized or dispersed in the oil phase of the emulsion; or if the dermal filler is water soluble it may be solvated in polar solvents, typically ingredients referred to as humectants such as glycerine or alkylene glycols prior to formation of an anhydrous emulsion.
  • the dermal filler may be found in the water phase or the oil phase of the emulsion depending on the type of derivative.
  • certain hydrophilic derivatives such as dermal filler acetate salt and the like are water soluble and will generally be solubilized in the water phase of the emulsion.
  • Certain other derivatives are lipophilic in nature and will more likely be found in the oil phase of the emulsion.
  • Suitable serums or gels will generally comprise from about 1-99% water, and optionally from about 0.001-30% of an aqueous phase thickening agent.
  • the other ingredients mentioned herein may be present in the percentage ranges set forth.
  • Typical skin creams or lotions comprise from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants.
  • the surfactants are nonionic and may be in the form of silicones or organic nonionic surfactants.
  • Typical color cosmetic compositions such as foundations, blush, eyeshadow and the like will preferably contain from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants in addition to from about 0.1 to 65% of particulates that are pigments or a combination of pigments and powders.
  • Typical mascara compositions generally contain from about 5-98% water, 1-85% oil, and from about 0.1 to 20% surfactant in addition to natural or synthetic polymers that are film forming, such as aqueous dispersions of acrylic copolymers, aqueous dispersions of polyurethane, or silicone resins. V. The Methods
  • the invention further comprises treating skin for improvement by applying to the skin the compositions of the invention.
  • the compositions may be applied in the forms mentioned herein, as part of skin care regimens.
  • the composition may be applied to the skin as a night cream or cream applied to skin prior to a period of bodily rest such as a nap or sleep.
  • the composition may be applied two times a day, in the morning and in the evening after cleansing the skin.
  • the composition may be applied to the skin over skin care products, in the form of foundations or other color cosmetics.
  • the dermal filler is formulated into a day cream and a night cream, so that the consumer using the regimen applies the dermal filler to the skin twice a day as part of a standard skin care routine.
  • the dermal filler is applied to the skin in the form of a toner, over which a skin cream or lotion is applied.
  • the dermal filler is applied to the skin in the form of a skin cleanser.
  • treating skin for improvement means that the skin to which the composition is applied will exhibit one or more of improvements such as increase in skin tone (reduction of laxity), reduction in wrinkles, skin plumping, and so on.
  • composition is prepared by combining the water phase and oil phase ingredients separately, then emulsifying to form an emulsion.
  • a water in silicone oil emulsion skin serum is prepared as follows:
  • composition is prepared by combining the oil phase ingredients and water phase ingredients separately, then mixing well to emulsify.
  • Oil-in- water (O/W) and water-in-oil (W/O) emulsion mascaras are prepared as follows:
  • the mascaras are made by combining the oily phase ingredients except for the cyclomethicone and dimethicone and heating to about 90° C. until solids melt.
  • the cyclomethicone and dimethicone are added to the mixture and the heat maintained at about 60° C.
  • the water phase ingredients are combined and heated to about 60° C. and combined with the mixture.
  • the phases are emulsified to form the final mixture.
  • Emulsion foundation makeup compositions are prepared as follows:
  • the water, oil and pigment phases are separately prepared by low shear mixing.
  • the phases are combined with high shear blending to form a foundation makeup composition.
  • EXAMPLE 5 Anhydrous emulsion skin treatment serums and gels may be prepared as follows:
  • compositions were prepared by combining the dermal filler and glycerin. The remaining ingredients were combined and mixed well, followed by addition of the dermal filler in glycerin.
  • the composition was prepared by grinding the pigments in a portion of the oil. The remaining ingredient were combined with heat and mixed well, incorporating the pigment grind into the composition.
  • the composition was a semi-solid beige colored composition suitable for use as a foundation.
  • a lipstick composition is prepared as follows:
  • the composition is prepared by grinding the pigments in a portion of the cetyl esters.
  • the waxes and oils were separately combined with heat and mixed well.
  • the pigment grind was added to the mixture and stirred well.
  • the mixture was poured into molds and allowed to cool to room temperature.
  • compositions are prepared by grinding the pigments in a portion of the oil.
  • oils and waxes were combined with heat and mixed well.
  • the pigment grind was added.
  • the compositions are pressed into pans.
  • the skin models were maintained in an incubator at 37° C. and fixed after 24 hours by staining with Alcian Blue cationic dye.
  • the skin samples were viewed under the microscope. It was observed that the intensity of the blue in the epidermis was significantly increased for the skin treated with the cross-linked hyaluronic acid particles compared to the control treated with PBS. The intensity of the blue color was greater with the high concentration of hyaluronic acid particles. Thus, the hyaluronic acid particles are absorbed by the skin and appear to provide a plumping effect in the skin samples.

Abstract

A topical non-dermal filler composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin and methods for plumping skin by applying the composition of the invention.

Description

TOPICAL COMPOSITIONS FOR IMPROVING APPEARANCE OF KERATINOUS SURFACES
Technical Field
This invention is in the field of topical compositions for treatment of keratinous surfaces such as skin, nails, or hair.
Background of the Invention Hyaluronic acid is a glycosaminoglycan. It is found in skin and known to provide volume and plumpness to the dermis and epidermis. It is also widely used as an injectable filler by plastic surgeons who treat patients who desire to plump out lines and wrinkles and are willing to have such materials injected into their dermis. Examples of hyaluronic acid based dermal fillers include Restylane™, Perlane™, or Juvederm™. When these fillers are injected into skin folds such as lines and wrinkles they provide a plumping effect. As the hyaluronic acid is gradually reabsorbed back into the body, the filling effect generally lasts only from 3 to 6 months. The reason that hyaluronic acid based fillers provide slow re-absorption back into the body is because they have a high molecular weight. For that same reason these types of ingredients cannot be absorbed into the skin when topically applied. Skin pores will permit entry of only small molecular weight materials. Other dermal fillers have been developed that are more permanent. For example,
Sculptra, which is poly-L-lactic acid. This is a polymeric form of lactic acid that is approved for injection into the dermis of AIDs patients that have lipoatrophy. This polymeric material plumps up the dermis and is said to promote collagen synthesis. It is biodegradable and lasts from 2 to 3 years. Another example of a permanent dermal filler is Artecoll™, which is injectable polymethylmethacrylate. Artecoll™ is a permanent dermal filler, that is, it never biodegrades. That means that the physician who administers the material must be very skilled because there is simply no margin for error. Any "mistakes" must be cut out of the skin, which creates scars and disfigurement. Because of the expense and requirement for physician administered injections some people who use injectable fillers are sporadic users - that is they obtain such injections only when planning to attend one big event such as a family wedding or public appearance. Other users of injectable fillers are beauty junkies or those that can afford the expense of dermal filler injections and maintenance to obtain the desired look.
Any type of topically applied product that plumps skin in the way injectable fillers do would be of great interest to cosmetics companies. However, formulating this type of product has its difficulties because the skin is such an effective barrier against most ingredients. One of the reasons why most ingredients are not well absorbed into the skin is because of size. Usually, very low molecular weight molecules or small particles are likely to be better absorbed by skin. Simply applying injectable dermal fillers topically to the skin will not provide any appreciable effect because these substances are simply too large to be absorbed into the skin.
Most unexpectedly, however, dermal fillers that have certain properties have been found to be effective when topically applied. If such dermal fillers have certain characteristics they can be applied topically and absorbed into the skin to provide a plumping effect that, with continued use, approximates the effect seen with injectable fillers.
The invention is directed to a topical composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of absorption into the epidermal layers of the skin in an amount sufficient to plump the keratinous surface to which the composition is applied.
The invention is further directed to a method for ameliorating the effects of skin lines, wrinkles, or laxity by applying a topical composition comprising at least one injectable dermal filler capable of absorption into the epidermal layers of the skin in an amount sufficient to plump the skin.
Summary of the Invention The invention is directed to a non-dermal filler topical composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin.
The invention is further directed to a method for providing a plumping effect to skin comprising applying to the skin surface a non-dermal filler composition comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin.
Detailed Description I. Definitions "Dermal filler" when used herein means a dermal filler that is suitable for, or generally used, as an injectable dermal filler, that is in the latter case, pharmaceutically approved for injection into the dermis for plumping out lines, wrinkles, skin depressions and the like.
"Dermis" means the layer of skin beneath the epidermis and connected to it by the basement membrane. The dermis consists of connective tissue and cushions the body from stress and strain.
"Epidermis" or "Epidermal layers" with respect to skin means the outermost avascular layer of the skin comprised of stratified squamous epithelium and the underlying basal lamina. The epidermis general consists of 4 to 5 sub-layers - stratum corneum, stratum lucidum (on soles of feet and palms only), stratum granulosum, stratum spinosum, and stratum basale. "Injectable" means, with respect to the dermal filler, that it may be injected into the dermis with a syringe and needle such that it is deposited in the appropriate layer of skin to provide a plumping effect that may be temporary or permanent depending on the dermal filler that is used.
"Non-dermal filler" with respect to the composition means that it is not suitable for injection into the skin layers or dermis to provide plumping, line or depression filling, or other cosmetic dermato logical effects. "Plumping" with respect to the term "skin" or "keratinous surface" means that the surface depressions, lines, wrinkles, etc. become more filled in and less visible to the naked eye, much in the manner that such depressions, lines, and wrinkles would become filled in if the dermal filler were injected into the dermis. II. The Dermal Filler
A. Hyaluronic Acid Based Fillers
Suitable hyaluronic acid based dermal fillers are those that are capable of partial or complete absorption into the epidermal layers of the skin. The hyaluronic acid dermal filler is preferably cross linked, more preferably covalently cross linked. It is generally present in an amount sufficient to provide an effect on the epidermis, ranging from about 0.001 to 99%, preferably from about 0.01 to 95%, more preferably from about 0.05 to 90% by weight of the total composition. The hyaluronic acid dermal filler may be in the liquid or solid form. Preferably it is in the solid particulate form with particles ranging from about 0.001 to about 50 microns, preferably from about 0.05 to 5 microns, more preferably from about 0.075 to 1 micron.
Examples of suitable dermal fillers include those set forth in U.S. Patent Application 2007/0224277 Al, which is hereby incorporated by reference in its entirety. More specifically, such dermal fillers are made by amidating hyaluronic acid with alkylene oxide containing di-, tri-, or polyamino compounds including those having the formula: NH2 - (CH2)n - (O - CH2 - CH2)m - (CH-OH)x - NH2 wherein n = 0 to 50, m = 0 - 12 x = 0 - 10
In the formula above any one or more of the carbon atoms may be substituted with an aromatic group. Specific examples of such compounds suitable for reacting with the hyaluronic acid include, but are not limited to: 2, 2'(ethylenedioxy) bis (ethylamine), l,3-diamino-2- hydroxypropanone; 1,3-diaminoacetone; 2,5-diaminobenzenesulfonic acid; 3,5- diaminobenzoic acid; 2,6-diaminopyridine; 2,5-diaminopyridine; 2,6-diaminopurine; and so on.
In addition to the amidation step the hyaluronic acid may be cross linked. The degree of cross linking may range from 0 to 100%. One particularly suitable cross linking agent is carbodiimide (also referred to as CDI), although other cross linking agents may be suitable. Suitable hyaluronic acid based dermal fillers may be made according to Examples 1 through 8 of U.S. Patent Application No. 2007/0224277 Al . For example, one type of hyaluronic acid is prepared in Example 1 by dissolving hyaluronic acid in water to produce a solution having a concentration of 1 mg/ml, adding 2'(ethylenedioxy)bis(ethylamine), then adjusting the pH of the solution to 6.5 by adding 0.1 M NaCl. CDI is added dropwise while stirring the reaction mixture at 4° C. for 30 minutes and subsequently at room temperature (25° C.) for 24 hours. The solution containing hyaluronan particles is then purified by dialysis for 6 days with distilled water and freeze dried. B. Polymeric Hydroxy Acids
Also suitable are dermal fillers based upon polymeric hydroxyacids such as poly-L- lactic acid sold by Dermik Laboratories under the trademark Sculptra™. Particles of polymeric alpha hydroxyl acids are suitable for topical administration. Such polymeric hydroxyl acids may be in liquid or solid form. Examples of such polymeric materials include those set forth in U.S. Patent No. 5,824,333, which is hereby incorporated by reference in its entirety. In one preferred embodiment such particles have a size ranging from about 0.001 to 25 microns, preferably from about 0.001 to 5 microns. III. Other Ingredients The dermal fillers used in the non-dermal filler compositions and methods of the invention may be incorporated into a wide variety of topical cosmetic compositions suitable for application to skin, hair, or nails, such as creams, lotions, gels, sprays, shampoos, conditioners, mousses, foundation makeup, blush, concealer, lipstick, mascara, eyeliner, eye shadow, nail color, and so on. The topical compositions may be in the form of emulsions, anhydrous compositions, or aqueous based gels. If present in the emulsion form, the compositions may comprise from about 0.001 to 99%, preferably from about 0.01-95%, more preferably from about 0.1 to 90% water and from about 0.001 to 99%, preferably from about 0.01 to 95%, more preferably from about 0.1 to 90% by weight of the total composition of oil. A. Aqueous Phase Structuring Agent
In the case where the compositions are in the form of aqueous solutions, dispersions or emulsions, in addition to water the aqueous phase may contain one or more aqueous phase structuring agents, that is, an agent that increases the viscosity or, or thickens, the aqueous phase of the composition. This is particularly desirable when the composition is in the form of a serum or gel. The aqueous phase structuring agent should be compatible with the dermal filler particularly when the dermal filler is water soluble, and also compatible with the other ingredients in the formulation. Suitable ranges of aqueous phase structuring agent, if present, are from about 0.01 to 30%, preferably from about 0.1 to 20%, more preferably from about 0.5 to 15% by weight of the total composition. Examples of such agents include various acrylate based thickening agents, natural or synthetic gums, polysaccharides, and the like, including but not limited to those set forth below. L_ 1. Polysaccharides
Polysaccharides may be suitable aqueous phase thickening agents. Examples of such polysaccharides include naturally derived materials such as agar, agarose, alicaligenes polysaccharides, algin, alginic acid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum, pectin, trehelose, gelatin, and so on. 2. Acrylate Polymers
Also suitable are different types of synthetic polymeric thickeners. One type includes acrylic polymeric thickeners comprised of monomers A and B wherein A is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and B is selected from the group consisting of a Ci_22 alkyl acrylate, a Ci_22 alky methacrylate, and mixtures thereof are suitable. In one embodiment the A monomer comprises one or more of acrylic acid or methacrylic acid, and the B monomer is selected from the group consisting of a C1-10, most preferably Ci_4 alkyl acrylate, a C1-10, most preferably Ci_4 alkyl methacrylate, and mixtures thereof. Most preferably the B monomer is one or more of methyl or ethyl acrylate or methacrylate. The acrylic copolymer may be supplied in an aqueous solution having a solids content ranging from about 10-60%, preferably 20-50%, more preferably 25-45% by weight of the polymer, with the remainder water. The composition of the acrylic copolymer may contain from about 0. 1-99 parts of the A monomer, and about 0.1-99 parts of the B monomer. Acrylic polymer solutions include those sold by Seppic, Inc., under the tradename Capigel. Also suitable are acrylic polymeric thickeners that are copolymer of A, B, and C monomers wherein A and B are as defined above, and C has the general formula:
,£""""0""""' ^ K I lτ ^- ) iJcT" R-
wherein Z is -(CH2)m; wherein m is 1-10, n is 2-3, o is 2-200, and R is a CiO_3o straight or branched chain alkyl. Examples of the secondary thickening agent above, are copolymers where A and B are defined as above, and C is CO, and wherein n, o, and R are as above defined. Examples of such secondary thickening agents include acrylates/steareth-20 methacrylate copolymer, which is sold by Rohm & Haas under the tradename Acrysol ICS-I . Also suitable are acrylate based anionic amphiphilic polymers containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain. Preferred are those where the hydrophilic unit contains an ethylenically unsaturated anionic monomer, more specifϊcially a vinyl carboxylic acid such as acrylic acid, methacrylic acid or mixtures thereof, and where the allyl ether unit containing a fatty chain corresponds to the monomer of formula
CH2 = CR5CH2OBnR in which R denotes H or CH3, B denotes the ethylenoxy radical, n is zero or an integer ranging from 1 to 100, R denotes a hydrocarbon radical selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals which contain from 8 to 30 carbon atoms, preferably from 10 to 24, and even more particularly from 12 to 18 carbon atoms. More preferred in this case is where R denotes H, n is equal to 10 and R denotes a stearyl (C 18) radical. Anionic amphiphilic polymers of this type are described and prepared in U.S. Patent Nos. 4,677,152 and 4,702,844, both of which are hereby incorporated by reference in their entirety. Among these anionic amphiphilic polymers, polymers formed of 20 to 60% by weight acrylic acid and/or methacrylic acid, of 5 to 60% by weight lower alkyl methacrylates, of 2 to 50% by weight allyl ether containing a fatty chain as mentioned above, and of 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide. One commercial example of such polymers are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (having 10 EO units) ether of stearyl alcohol or steareth-10, in particular those sold by the company Allied Colloids under the names SALCARE SC80 and SALCARE SC90, which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth- 10 allyl ether (40/50/10). Also suitable are acrylate copolymers such as Polyacrylate-3 which is a copolymer of methacrylic acid, methylmethacrylate, methylstyrene isopropylisocyanate, and PEG-40 behenate monomers; Polyacrylate-10 which is a copolymer of sodium acryloyldimethyltaurate, sodium acrylate, acrylamide and vinyl pyrrolidone monomers; or Polyacrylate- 11 , which is a copolymer of sodium acryloyldimethylacryloyldimethyl taurate, sodium acrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, and acrylamide monomers.
Also suitable are crosslinked acrylate based polymers where one or more of the acrylic groups may have substituted long chain alkyl (such as 6-40, 10-30, and the like) groups, for example acrylates/Cio-30 alkyl acrylate crosspolymer which is a copolymer of C 10-30 alkyl acrylate and one or more monomers of acrylic acid, methacrylic acid, or one of their simple esters crosslinked with the allyl ether of sucrose or the allyl ether of pentaerythritol. Such polymers are commonly sold under the Carbopol or Pemulen tradenames and have the CTFA name carbomer. One particularly suitable type of aqueous phase thickening agent are acrylate based polymeric thickeners sold by Clariant under the Aristoflex trademark such as Aristoflex AVC, which is ammonium acryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the same polymer has found in AVC dispersed in mixture containing caprylic/capric triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; or Aristoflex HMB which is ammonium acryloyldimethyltaurate/beheneth-25 methacrylate crosspolymer, and the like.
3. High Molecular Weight PEG or Polyglycerins
Also suitable as the aqueous phase thickening agents are various polyethylene glycols (PEG) derivatives where the degree of polymerization ranges from 1,000 to 200,000. Such ingredients are indicated by the designation "PEG" followed by the degree of polymerization in thousands, such as PEG-45M, which means PEG having 45,000 repeating ethylene oxide units. Examples of suitable PEG derivatives include PEG 2M, 5M, 7M, 9M, 14M, 2OM, 23M,
25M, 45M, 65M, 9OM, 115M, 160M, 180M, and the like.
Also suitable are polyglycerins which are repeating glycerin moieties where the number of repeating moieties ranges from 15 to 200, preferably from about 20-100. Examples of suitable polyglycerins include those having the CFTA names polyglycerin-20, polyglycerin- 40, and the like. B. Oils
In the event the compositions of the invention are in emulsion form, the composition will comprise an oil phase. Oily ingredients are desirable for the skin moisturizing and protective properties. Oils, if present, will form a barrier on the skin so that the dermal filler present in the composition remains on the skin. Suitable oils include silicones, esters, vegetable oils, synthetic oils, including but not limited to those set forth herein. The oils may be volatile or nonvolatile, and are preferably in the form of a pourable liquid at room temperature. The term "volatile" means that the oil has a measurable vapor pressure, or a vapor pressure of at least about 2 mm. of mercury at 20° C. The term "nonvolatile" means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20° C.
1. Volatile Oils
Suitable volatile oils generally have a viscosity ranging from about 0.5 to 5 centistokes 25° C. and include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof. Volatile oils may be used to promote more rapid drying of the skin care composition after it is applied to skin. Volatile oils are more desirable when the skin care products containing the dermal filler are being formulated for consumers that have combination or oily skin. The term "combination" with respect to skin type means skin that is oily in some places on the face (such as the T-zone) and normal in others. (a). Volatile Silicones Cyclic silicones are one type of volatile silicone that may be used in the composition.
Such silicones have the general formula:
Figure imgf000012_0002
where n=3-6, preferably 4, 5, or 6. Also suitable are linear volatile silicones, for example, those having the general formula:
■CH^SU-O fSii;Cai}r-O]p--isi!CH ,;J where n=0, 1, 2, 3, 4, or 5, preferably 0, 1, 2, 3, or 4.
Cyclic and linear volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric. The Dow Corning linear volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids include hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviated cst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5 cst), dodecamethylpentasiloxane (2 cst) and mixtures thereof, with all viscosity measurements being at 25° C. Suitable branched volatile silicones include alkyl trimethicones such as methyl trimethicone, a branched volatile silicone having the general formula:
Figure imgf000012_0001
(CR^S§O — SiO — Si(CH3)3
OSi(CH3),
Methyl trimethicone may be purchased from Shin-Etsu Silicones under the tradename TMF- 1.5, having a viscosity of 1.5 centistokes at 25° C. (b). Volatile Paraffϊnic Hydrocarbons
Also suitable as the volatile oils are various straight or branched chain paraffmic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and Cg_2o isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference.
Preferred volatile paraffmic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60 to 260° C, and a viscosity of less than about 10 cst. at 25° C. Such paraffinic hydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Various C16 isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R), are also suitable.
C. Non- Volatile Oils A variety of nonvolatile oils are also suitable for use in the compositions of the invention. The nonvolatile oils generally have a viscosity of greater than about 5 to 10 centistokes at 25° C, and may range in viscosity up to about 1,000,000 centipoise at 25° C. Examples of nonvolatile oils include, but are not limited to:
1. Esters Suitable esters are mono-, di-, and triesters. The composition may comprise one or more esters selected from the group, or mixtures thereof.
(a) Monoesters
Monoesters are defined as esters formed by the reaction of a monocarboxylic acid having the formula R-COOH, wherein R is a straight or branched chain saturated or unsaturated alkyl having 2 to 45 carbon atoms, or phenyl; and an alcohol having the formula
R-OH wherein R is a straight or branched chain saturated or unsaturated alkyl having 2-30 carbon atoms, or phenyl. Both the alcohol and the acid may be substituted with one or more hydroxyl groups. Either one or both of the acid or alcohol may be a "fatty" acid or alcohol, and may have from about 6 to 30 carbon atoms, more preferably 12, 14, 16, 18, or 22 carbon atoms in straight or branched chain, saturated or unsaturated form. Examples of monoester oils that may be used in the compositions of the invention include hexyl laurate, butyl isostearate, hexadecyl isostearate, cetyl palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl isononanoate, steary lactate, stearyl octanoate, stearyl stearate, isononyl isononanoate, and so on.
(b). Diesters Suitable diesters are the reaction product of a dicarboxylic acid and an aliphatic or aromatic alcohol or an aliphatic or aromatic alcohol having at least two substituted hydroxyl groups and a monocarboxylic acid. The dicarboxylic acid may contain from 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated or unsaturated form. The dicarboxylic acid may be substituted with one or more hydroxyl groups. The aliphatic or aromatic alcohol may also contain 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated, or unsaturated form. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol, i.e. contains 12-22 carbon atoms. The dicarboxylic acid may also be an alpha hydroxy acid. The ester may be in the dimer or trimer form. Examples of diester oils that may be used in the compositions of the invention include diisotearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, dioctyl malate, and so on.
(c). Triesters Suitable triesters comprise the reaction product of a tricarboxylic acid and an aliphatic or aromatic alcohol or alternatively the reaction product of an aliphatic or aromatic alcohol having three or more substituted hydroxyl groups with a monocarboxylic acid. As with the mono- and diesters mentioned above, the acid and alcohol contain 2 to 30 carbon atoms, and may be saturated or unsaturated, straight or branched chain, and may be substituted with one or more hydroxyl groups. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol containing 12 to 22 carbon atoms. Examples of triesters include esters of arachidonic, citric, or behenic acids, such as triarachidin, tributyl citrate, triisostearyl citrate, tri C12-13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.
Esters suitable for use in the composition are further described in the C.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition, 2006, under the classification of "Esters", the text of which is hereby incorporated by reference in its entirety.
2. Hydrocarbon Oils
It may be desirable to incorporate one or more nonvolatile hydrocarbon oils into the composition. Suitable nonvolatile hydrocarbon oils include paraffinic hydrocarbons and olefins, preferably those having greater than about 20 carbon atoms. Examples of such hydrocarbon oils include C24-28 olefins, C30-45 olefins, C20-40 isoparaffins, hydrogenated polyisobutene, polyisobutene, polydecene, hydrogenated polydecene, mineral oil, pentahydrosqualene, squalene, squalane, and mixtures thereof. In one preferred embodiment such hydrocarbons have a molecular weight ranging from about 300 to 1000 Daltons.
3. Glyceryl Esters of Fatty Acids Synthetic or naturally occurring glyceryl esters of fatty acids, or triglycerides, are also suitable for use in the compositions. Both vegetable and animal sources may be used. Examples of such oils include castor oil, lanolin oil, C10-18 triglycerides, caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil, sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil, walnut oil, and the like. Also suitable are synthetic or semi-synthetic glyceryl esters, such as fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, mono-, di- or triesters of polyols such as glycerin. In an example, a fatty (C 12-22) carboxylic acid is reacted with one or more repeating glyceryl groups, glyceryl stearate, diglyceryl diiosostearate, polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryl tetraisostearate, glyceryl trioctanoate, diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on. 4. Nonvolatile Silicones
Nonvolatile silicone oils, both water soluble and water insoluble, are also suitable for use in the composition. Such silicones preferably have a viscosity ranging from about greater than 5 to 800,000 cst, preferably 20 to 200,000 cst at 25° C. Suitable water insoluble silicones include amine functional silicones such as amodimethicone. For example, such nonvolatile silicones may have the following general formula:
Figure imgf000016_0001
wherein R and R' are each independently Ci_3o straight or branched chain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy, and x and y are each independently 1- 1 ,000,000; with the proviso that there is at least one of either x or y, and A is alkyl siloxy endcap unit. Preferred is where A is a methyl siloxy endcap unit; in particular trimethylsiloxy, and R and R are each independently a Ci_3o straight or branched chain alkyl, phenyl, or trimethylsiloxy, more preferably a Cr22 alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl, or trimethylsiloxy, and resulting silicone is dimethicone, phenyl dimethicone, diphenyl dimethicone, phenyl trimethicone, or trimethylsiloxyphenyl dimethicone. Other examples include alkyl dimethicones such as cetyl dimethicone, and the like wherein at least one R is a fatty alkyl (C12, C14, C16, C18, C2o, or C22), and the other R is methyl, and A is a trimethylsiloxy endcap unit, provided such alkyl dimethicone is a pourable liquid at room temperature. Phenyl trimethicone can be purchased from Dow Corning Corporation under the tradename 556 Fluid. Trimethylsiloxyphenyl dimethicone can be purchased from Wacker-Chemie under the tradename PDM-1000. Cetyl dimethicone, also referred to as a liquid silicone wax, may be purchased from Dow Corning as Fluid 2502, or from DeGussa Care & Surface Specialties under the trade names Abil Wax 9801, or 9814.
5. Fluorinated Oils
Various types of fluorinated oils may also be suitable for use in the compositions including but not limited to fluorinated silicones, fluorinated esters, or perfluropoly ethers. Particularly suitable are fluorosilicones such as trimethylsilyl endcapped fluorosilicone oil, polytrifluoropropylmethylsiloxanes, and similar silicones such as those disclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated by reference. Perfluoropolyethers include those disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated by reference, which are commercially available from Montefluos under the trademark Fomblin.
D. Oil Phase Structuring Agents
In the case where the composition is anhydrous or in the form of an emulsion, it may be desirable to include one or more oil phase structuring agents in the cosmetic composition. The term "oil phase structuring agent" means an ingredient or combination of ingredients, soluble or dispersible in the oil phase, which will increase the viscosity, or structure, the oil phase. The term "compatible" means that the oil phase structuring agent and dermal filler derivative are capable of being formulated into a cosmetic product that is generally stable.
The structuring agent may be present in an amount sufficient to provide a liquid composition with increased viscosity, a semi-solid, or in some cases a solid composition that may be self- supporting. The structuring agent itself may be present in the liquid, semi-solid, or solid form. Suggested ranges of structuring agent are from about 0.01 to 70%, preferably from about 0.05 to 50%, more preferably from about 0.1-35% by weight of the total composition. Suitable oil phase structuring agents include those that are silicone based or organic based. They may be polymers or non-polymers, synthetic, natural, or a combination of both. 1. Silicone Structuring Agents A variety of oil phase structuring agents may be silicone based, such as silicone elastomers, silicone gums, silicone waxes, linear silicones having a degree of polymerization that provides the silicone with a degree of viscosity such that when incorporated into the cosmetic composition it is capable of increasing the viscosity of the oil phase. Examples of silicone structuring agents include, but are not limited to: (a). Silicone Elastomers
Silicone elastomers suitable for use in the compositions of the invention include those that are formed by addition reaction-curing, by reacting an SiH-containing diorganosiloxane and an organopolysiloxane having terminal olefmic unsaturation, or an alpha-omega diene hydrocarbon, in the presence of a platinum metal catalyst. Such elastomers may also be formed by other reaction methods such as condensation-curing organopolysiloxane compositions in the presence of an organotin compound via a dehydrogenation reaction between hydroxyl-terminated diorganopolysiloxane and SiH-containing diorganopolysiloxane or alpha omega diene; or by condensation-curing organopolysiloxane compositions in the presence of an organotin compound or a titanate ester using a condensation reaction between an hydroxyl-terminated diorganopolysiloxane and a hydrolysable organosiloxane; peroxide- curing organopolysiloxane compositions which thermally cure in the presence of an organoperoxide catalyst.
One type of elastomer that may be suitable is prepared by addition reaction-curing an organopolysiloxane having at least 2 lower alkenyl groups in each molecule or an alpha- omega diene; and an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in each molecule; and a platinum-type catalyst. While the lower alkenyl groups such as vinyl, can be present at any position in the molecule, terminal olefmic unsaturation on one or both molecular terminals is preferred. The molecular structure of this component may be straight chain, branched straight chain, cyclic, or network. These organopolysiloxanes are exemplified by methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylpolysiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy- terminated dimethylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl(3,3,3-trifluoropropyl) polysiloxanes, and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl(3 ,3 ,-trifluoropropyl)siloxane copolymers, decadiene, octadiene, heptadiene, hexadiene, pentadiene, or tetradiene, or tridiene. Curing proceeds by the addition reaction of the silicon-bonded hydrogen atoms in the dimethyl methylhydrogen siloxane, with the siloxane or alpha-omega diene under catalysis using the catalyst mentioned herein. To form a highly crosslinked structure, the methyl hydrogen siloxane must contain at least 2 silicon-bonded hydrogen atoms in each molecule in order to optimize function as a crosslinker. The catalyst used in the addition reaction of silicon-bonded hydrogen atoms and alkenyl groups, and is concretely exemplified by chloroplatinic acid, possibly dissolved in an alcohol or ketone and this solution optionally aged, chloroplatinic acid-olefϊn complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and carrier-supported platinum.
Examples of suitable silicone elastomers for use in the compositions of the invention may be in the powder form, or dispersed or solubilized in solvents such as volatile or nonvolatile silicones, or silicone compatible vehicles such as paraffinic hydrocarbons or esters. Examples of silicone elastomer powders include vinyl dimethicone/methicone silesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP- 102, KSP- 103, KSP- 104, KSP- 105, hybrid silicone powders that contain a fluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro-silicone elastomer, and hybrid silicone powders that contain a phenyl group such as
Shin-Etsu's KSP-300, which is a phenyl substituted silicone elastomer; and Dow Coming's DC 9506. Examples of silicone elastomer powders dispersed in a silicone compatible vehicle include dimethicone/vinyl dimethicone crosspolymers supplied by a variety of suppliers including Dow Corning Corporation under the tradenames 9040 or 9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Silicones under the tradenames KSG-15, 16, 18. KSG- 15 has the CTFA name cyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG- 18 has the INCI name phenyl trimethicone/dimethicone/phenyl vinyl dimethicone crossoplymer. Silicone elastomers may also be purchased from Grant Industries under the Gransil trademark. Also suitable are silicone elastomers having long chain alkyl substitutions such as lauryl dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu under the tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44. Cross-linked organopolysiloxane elastomers useful in the present invention and processes for making them are further described in U.S. Pat. No. 4,970,252 to Sakuta et al, issued Nov. 13, 1990; U.S. Pat. No. 5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No. 5,654,362 to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese Patent Application JP 61-18708, assigned to PoIa
Kasei Kogyo KK, each of which are herein incorporated by reference in its entirety. It is particularly desirable to incorporate silicone elastomers into the compositions of the invention because they provide excellent "feel" to the composition, are very stable in cosmetic formulations, and relatively inexpensive. (b). Silicone Gums
Also suitable for use as an oil phase structuring agent are one or more silicone gums. The term "gum" means a silicone polymer having a degree of polymerization sufficient to provide a silicone having a gum-like texture. In certain cases the silicone polymer forming the gum may be crosslinked. The silicone gum typically has a viscosity ranging from about 500,000 to 100 million cst at 25° C, preferably from about 600,000 to 20 million, more preferably from about 600,000 to 12 million cst. All ranges mentioned herein include all subranges, e.g. 550,000; 925,000; 3.5 million.
The silicone gums that are used in the compositions include, but are not limited to, those of the general formula wherein:
Figure imgf000021_0001
Ri to R9 are each independently an alkyl having 1 to 30 carbon atoms, aryl, or aralkyl; and X is OH or a C i-3o alkyl, or vinyl; and wherein x, y, or z may be zero with the proviso that no more than two of x, y, or z are zero at any one time, and further that x, y, and z are such that the silicone gum has a viscosity of at least about 500,000 cst, ranging up to about 100 million centistokes at 25° C. Preferred is where R is methyl or OH.
Such silicone gums may be purchased in pure form from a variety of silicone manufacturers including Wacker-Chemie or Dow Corning, and the like. Such silicone gums include those sold by Wacker-Belsil under the trade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096. A silicone gum where X is OH, also referred to as dimethiconol, is available from Dow Corning Corporation under the trade name 1401. The silicone gum may also be purchased in the form of a solution or dispersion in a silicone compatible vehicle such as volatile or nonvolatile silicone. An example of such a mixture may be purchased from Barnet Silicones under the HL-88 tradename, having the INCI name dimethicone.
(c). Silicone Waxes
Another type of oily phase structuring agent includes silicone waxes that are typically referred to as alkyl silicone waxes which are semi-solids or solids at room temperature. The term "alkyl silicone wax" means a polydimethylsiloxane having a substituted long chain alkyl (such as C16 to 30) that confers a semi-solid or solid property to the siloxane. Examples of such silicone waxes include stearyl dimethicone, which may be purchased from DeGussa Care & Surface Specialties under the tradename Abil Wax 9800 or from Dow Corning under the tradename 2503. Another example is bis-stearyl dimethicone, which may be purchased from Gransil Industries under the tradename Gransil A-18, or behenyl dimethicone, behenoxy dimethicone.
(d). Polyamides or Silicone Polyamides
Also suitable as oil phase structuring agents are various types of polymeric compounds such as polyamides or silicone polyamides. The term silicone polyamide means a polymer comprised of silicone monomers and monomers containing amide groups as further described herein. The silicone polyamide preferably comprises moieties of the general formula:
Figure imgf000022_0001
X is a linear or branched alkylene having from about 1-30 carbon atoms; R1, R2, R3, and R4 are each independently Ci_3o straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more Ci_3o alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
and Y is:
(a) a linear or branched alkylene having from about 1-40 carbon atoms which may be substituted with: (i) one or more amide groups having the general formula RiCONRi, or
(ii) C5-6 cyclic ring, or
(iii) phenylene which may be substituted with one or more C1-10 alkyl groups, or
(iv) hydroxy, or
(v) C3_8 cycloalkane, or (vi) Ci_2o alkyl which may be substituted with one or more hydroxy groups, or
(vii) C1-10 alkyl amines; or
(b) TR5R6R7 wherein R5, R6, and R7, are each independently a C1-10 linear or branched alkylenes, and T is CRg wherein R8 is hydrogen, a trivalent atom N, P, or Al, or a Ci_3o straight or branched chain alkyl which may be substituted with one or more hydroxyl or halogen groups; phenyl which may be substituted with one or more Ci_3o alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having the general formula:
Figure imgf000024_0001
Preferred is where Ri, R2, R3, and R4 are Ci_io, preferably methyl; and X and Y is a linear or branched alkylene. Preferred are silicone polyamides having the general formula
Figure imgf000024_0002
wherein a and b are each independently sufficient to provide a silicone polyamide polymer having a melting point ranging from about 60 to 120° C, and a molecular weight ranging from about 40,000 to 500,000 Daltons. One type of silicone polyamide that may be used in the compositions of the invention may be purchased from Dow Corning Corporation under the tradename Dow Corning 2-8178 gellant which has the CTFA name nylon-611/dimethicone copolymer which is sold in a composition containing PPG-3 myristyl ether.
Also suitable are polyamides such as those purchased from Arizona Chemical under the tradenames Uniclear and Sylvaclear. Such polyamides may be ester terminated or amide terminated. Examples of ester terminated polyamides include, but are not limited to those having the general formula:
RJ— O — i C — R— C — N — R-*- X sr— C — R3— C — O — R-s
' Ii Ii ■" Il Si
0 0 0 0
wherein n denotes a number of amide units such that the number of ester groups ranges from about 10% to 50% of the total number of ester and amide groups; each Ri is independently an alkyl or alkenyl group containing at least 4 carbon atoms; each R2 is independently a C4-42 hydrocarbon group, with the proviso that at least 50% of the R2 groups are a C30-
42 hydrocarbon; each R3 is independently an organic group containing at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and each R4 is independently a hydrogen atom, a C1-10 alkyl group or a direct bond to R3 or to another R4, such that the nitrogen atom to which R3 and R4 are both attached forms part of a heterocyclic structure defined by R4-N-R3, with at least 50% of the groups R4 representing a hydrogen atom.
General examples of ester and amide terminated polyamides that may be used as oil phase gelling agents include those sold by Arizona Chemical under the tradenames Sylvaclear A200V or A2614V, both having the CTFA name ethylenediamine/hydrogenated dimer dilinoleate copolymer/bis-di-Ci4_i8 alkyl amide; Sylvaclear AF1900V; Sylvaclear C75V having the CTFA name bis-stearyl ethylenediamine/neopentyl glycol/stearyl hydrogenated dimer dilinoleate copolymer; Sylvaclear PA1200V having the CTFA name Polyamide-3; Sylvaclear PE400V; Sylvaclear WF 1500V; or Uniclear, such as Uniclear IOOVG having the INCI name ethylenediamine/stearyl dimer dilinoleate copolymer; or ethylenediamine/stearyl dimer ditallate copolymer. Other examples of suitable polyamides include those sold by Henkel under the Versamid trademark (such as Versamid 930, 744, 1655), or by Olin Mathieson Chemical Corp. under the brand name Onamid S or Onamid C.
(d). Natural or Synthetic Organic Waxes
Also suitable as the oil phase structuring agent may be one or more natural or synthetic waxes such as animal, vegetable, or mineral waxes. Preferably such waxes will have a higher melting point such as from about 50 to 150° C, more preferably from about 65 to 100° C. Examples of such waxes include waxes made by Fischer- Tropsch synthesis, such as polyethylene or synthetic wax; or various vegetable waxes such as bayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnauba wax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, grape wax, and polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or PEG- 12 carnauba wax; or fatty acids or fatty alcohols, including esters thereof, such as hydroxystearic acids (for example 12-hydroxy stearic acid), tristearin, tribehenin, and so on.
(e). Montmorillonite Minerals
One type of structuring agent that may be used in the composition comprises natural or synthetic montmorillonite minerals such as hectorite, bentonite, and quaternized derivatives thereof, which are obtained by reacting the minerals with a quaternary ammonium compound, such as stearalkonium bentonite, hectorites, quaternized hectorites such as Quaternium-18 hectorite, attapulgite, carbonates such as propylene carbonate, bentones, and the like.
(f). Silicas and Silicates
Another type of structuring agent that may be used in the compositions are silicas, silicates, silica silylate, and alkali metal or alkaline earth metal derivatives thereof. These silicas and silicates are generally found in the particulate form and include silica, silica silylate, magnesium aluminum silicate, and the like. E. Surfactants
The composition may contain one or more surfactants, especially if in the emulsion form. However, such surfactants may be used if the compositions are anhydrous also, and will assist in dispersing ingredients that have polarity, for example pigments. Such surfactants may be silicone or organic based. The surfactants will aid in the formation of stable emulsions of either the water-in-oil or oil-in- water form. If present, the surfactant may range from about 0.001 to 30%, preferably from about 0.005 to 25%, more preferably from about 0.1 to 20% by weight of the total composition.
1. Silicone Surfactants Suitable silicone surfactants include polyorganosiloxane polymers that have amphiphilic properties, for example contain hydrophilic radicals and lipophilic radicals. These silicone surfactants may be liquids or solids at room temperature.
(a). Dimethicone Copolvols or Alkyl Dimethicone Copolvols
One type of silicone surfactant that may be used is generally referred to as dimethicone copolyol or alkyl dimethicone copolyol. This surfactant is either a water-in-oil or oil-in-water surfactant having an Hydrophile/Lipophile Balance (HLB) ranging from about 2 to 18. Preferably the silicone surfactant is a nonionic surfactant having an HLB ranging from about 2 to 12, preferably about 2 to 10, most preferably about 4 to 6. The term "hydrophilic radical" means a radical that, when substituted onto the organosiloxane polymer backbone, confers hydrophilic properties to the substituted portion of the polymer. Examples of radicals that will confer hydrophilicity are hydroxy-polyethyleneoxy, hydroxyl, carboxylates, and mixtures thereof. The term "lipophilic radical" means an organic radical that, when substituted onto the organosiloxane polymer backbone, confers lipophilic properties to the substituted portion of the polymer. Examples of organic radicals that will confer lipophilicity are Ci_4o straight or branched chain alkyl, fluoro, aryl, aryloxy, Ci_40 hydrocarbyl acyl, hydroxy-polypropyleneoxy, or mixtures thereof.
One type of suitable silicone surfactant has the general formula:
wherein p is 0-40 (the range including all numbers between and subranges such as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is (-C2H4O)a-(-C3H6O)b-H wherein a is 0 to 25, b is 0-25 with the proviso that both a and b cannot be 0 simultaneously, x and y are each independently ranging from 0 to 1 million with the proviso that they both cannot be 0 simultaneously. In one preferred embodiment, x, y, z, a, and b are such that the molecular weight of the polymer ranges from about 5,000 to about 500,000, more preferably from about 10,000 to 100,000, and is most preferably approximately about 50,000 and the polymer is generically referred to as dimethicone copolyol. One type of silicone surfactant is wherein p is such that the long chain alkyl is cetyl or lauryl, and the surfactant is called, generically, cetyl dimethicone copolyol or lauryl dimethicone copolyol respectively.
In some cases the number of repeating ethylene oxide or propylene oxide units in the polymer are also specified, such as a dimethicone copolyol that is also referred to as PEG- 15/PPG-10 dimethicone, which refers to a dimethicone having substituents containing 15 ethylene glycol units and 10 propylene glycol units on the siloxane backbone. It is also possible for one or more of the methyl groups in the above general structure to be substituted with a longer chain alkyl (e.g. ethyl, propyl, butyl, etc.) or an ether such as methyl ether, ethyl ether, propyl ether, butyl ether, and the like. Examples of silicone surfactants are those sold by Dow Corning under the tradename
Dow Corning 3225C Formulation Aid having the CTFA name cyclotetrasiloxane (and) cyclopentasiloxane (and) PEG/PPG- 18 dimethicone; or 5225C Formulation Aid, having the CTFA name cyclopentasiloxane (and) PEG/PPG-18/18 dimethicone; or Dow Coming 190 Surfactant having the CTFA name PEG/PPG-18/18 dimethicone; or Dow Corning 193 Fluid, Dow Corning 5200 having the CTFA name lauryl PEG/PPG- 18/18 methicone; or Abil EM 90 having the CTFA name cetyl PEG/PPG- 14/ 14 dimethicone sold by Goldschmidt; or Abil EM 97 having the CTFA name bis-cetyl PEG/PPG- 14/ 14 dimethicone sold by Goldschmidt; or Abil WE 09 having the CTFA name cetyl PEG/PPG- 10/1 dimethicone in a mixture also containing polyglyceryl-4 isostearate and hexyl laurate; or KF-6011 sold by Shin-Etsu Silicones having the CTFA name PEG-11 methyl ether dimethicone; KF-6012 sold by Shin- Etsu Silicones having the CTFA name PEG/PPG-20/22 butyl ether dimethicone; or KF-6013 sold by Shin-Etsu Silicones having the CTFA name PEG-9 dimethicone; or KF-6015 sold by
Shin-Etsu Silicones having the CTFA name PEG-3 dimethicone; or KF-6016 sold by Shin- Etsu Silicones having the CTFA name PEG-9 methyl ether dimethicone; or KF-6017 sold by Shin-Etsu Silicones having the CTFA name PEG-IO dimethicone; or KF-6038 sold by Shin- Etsu Silicones having the CTFA name lauryl PEG-9 polydimethylsiloxyethyl dimethicone.
(b). Crosslinked Silicone Surfactants
Also suitable are various types of crosslinked silicone surfactants that are often referred to as emulsifying elastomers. They are typically prepared as set forth above with respect to the section "silicone elastomers" except that the silicone elastomers will contain at least one hydrophilic moiety such as polyoxyalkylenated groups. Typically these polyoxyalkylenated silicone elastomers are crosslinked organopolysiloxanes that may be obtained by a crosslinking addition reaction of diorganopolysiloxane comprising at least one hydrogen bonded to silicon and of a polyoxyalkylene comprising at least two ethylenically unsaturated groups. In at least one embodiment, the polyoxyalkylenated crosslinked organo- polysiloxanes are obtained by a crosslinking addition reaction of a diorganopolysiloxane comprising at least two hydrogens each bonded to a silicon, and a polyoxyalkylene comprising at least two ethylenically unsaturated groups, optionally in the presence of a platinum catalyst, as described, for example, in U.S. Pat. No. 5,236,986 and U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No. 5,811,487, the contents of which are incorporated by reference.
Polyoxyalkylenated silicone elastomers that may be used in at least one embodiment of the invention include those sold by Shin-Etsu Silicones under the names KSG-21 , KSG-20, KSG-30, KSG-31, KSG-32, KSG-33; KSG-210 which is dimethicone/PEG-10/15 crosspolymer dispersed in dimethicone; KSG-310 which is PEG- 15 lauryl dimethicone crosspolymer; KSG-320 which is PEG- 15 lauryl dimethicone crosspolymer dispersed in isododecane; KSG-330 (the former dispersed in triethylhexanoin), KSG-340 which is a mixture of PEG-IO lauryl dimethicone crosspolymer and PEG- 15 lauryl dimethicone crosspolymer.
Also suitable are polyglycerolated silicone elastomers like those disclosed in PCT/WO 2004/024798, which is hereby incorporated by reference in its entirety. Such elastomers include Shin-Etsu's KSG series, such as KSG-710 which is dimethicone/polyglycerin-3 crosspolymer dispersed in dimethicone; or lauryl dimethicone/polyglycerin-3 crosspolymer dispersed in a variety of solvent such as isododecane, dimethicone, triethylhexanoin, sold under the Shin-Etsu tradenames KSG-810, KSG-820, KSG-830, or KSG-840. Also suitable are silicones sold by Dow Corning under the tradenames 9010 and DC9011. One preferred crosslinked silicone elastomer emulsifier is dimethicone/PEG-10/15 crosspolymer, which provides excellent aesthetics due to its elastomeric backbone, but also surfactancy properties.
2. Organic Nonionic Surfactants The composition may comprise one or more nonionic organic surfactants. Suitable nonionic surfactants include alkoxylated alcohols, or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide. Preferably the alcohol is either a fatty alcohol having 6 to 30 carbon atoms. Examples of such ingredients include Steareth 2-100, which is formed by the reaction of stearyl alcohol and ethylene oxide and the number of ethylene oxide units ranges from 2 to 100; Beheneth 5-30 which is formed by the reaction of behenyl alcohol and ethylene oxide where the number of repeating ethylene oxide units is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, and so on. Other alkoxylated alcohols are formed by the reaction of fatty acids and mono-, di- or polyhydric alcohols with an alkylene oxide. For example, the reaction products of C6-30 fatty carboxylic acids and polyhydric alcohols which are monosaccharides such as glucose, galactose, methyl glucose, and the like, with an alkoxylated alcohol. Examples include polymeric alkylene glycols reacted with glyceryl fatty acid esters such as PEG glyceryl oleates, PEG glyceryl stearate; or PEG polyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein the number of repeating ethylene glycol units ranges from 3 to
1000.
Also suitable as nonionic surfactants are formed by the reaction of a carboxylic acid with an alkylene oxide or with a polymeric ether. The resulting products have the general formula: where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl, and n is the number of polymerized alkoxy groups. In the case of the diesters, the two RCO-groups do not need to be identical. Preferably, R is a C6-30 straight or branched chain, saturated or unsaturated alkyl, and n is from 1-100.
Monomeric, homopolymeric, or block copolymeric ethers are also suitable as nonionic surfactants. Typically, such ethers are formed by the polymerization of monomeric alkylene oxides, generally ethylene or propylene oxide. Such polymeric ethers have the following general formula: wherein R is H or lower alkyl and n is the number of repeating monomer units, and ranges from 1 to 500.
Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular ethoxylation of sorbitan provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates. For example, the polyalkyoxylated sorbitan can be esterified with C6-30, preferably C12-22 fatty acids. Examples of such ingredients include
Polysorbates 20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and so on. Certain types of amphoteric, zwitterionic, or cationic surfactants may also be used in the compositions. Descriptions of such surfactants are set forth in U.S. Pat. No. 5,843,193, which is hereby incorporated by reference in its entirety.
F. Humectants It may also be desirable to include one or more humectants in the composition. If present, such humectants may range from about 0.001 to 25%, preferably from about 0.005 to 20%, more preferably from about 0.1 to 15% by weight of the total composition. Examples of suitable humectants include glycols, sugars, and the like. Suitable glycols are in monomeric or polymeric form and include polyethylene and polypropylene glycols such as PEG 4-200, which are polyethylene glycols having from 4 to 200 repeating ethylene oxide units; as well as Ci_6 alkylene glycols such as propylene glycol, butylene glycol, pentylene glycol, and the like. Suitable sugars, some of which are also polyhydric alcohols, are also suitable humectants. Examples of such sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Also suitable is urea. Preferably, the humectants used in the composition of the invention are C1-6, preferably C2_4 alkylene glycols, most particularly butylene glycol.
G. Botanical Extracts
It may be desirable to include one or more botanical extracts in the compositions. If so, suggested ranges are from about 0.0001 to 10%, preferably about 0.0005 to 8%, more preferably about 0.001 to 5% by weight of the total composition. Suitable botanical extracts include extracts from plants (herbs, roots, flowers, fruits, seeds) such as flowers, fruits, vegetables, and so on, including yeast ferment extract, Padina Pavonica extract, thermus thermophilis ferment extract, camelina sativa seed oil, boswellia serrata extract, olive extract, Aήbodopsis Thaliana extract, Acacia Dealbata extract, Acer Saccharinum (sugar maple), acidopholus, acorus, aesculus, agaricus, agave, agrimonia, algae, aloe, citrus, brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear, lemon, lime, pea, seaweed, caffeine, green tea, chamomile, willowbark, mulberry, poppy, and those set forth on pages 1646 through 1660 of the CTFA Cosmetic Ingredient Handbook, Eighth Edition, Volume 2. Further specific examples include, but are not limited to, Glycyrrhiza Glabra, Salix Nigra, Macrocycstis Pyrifera, Pyrus Malus, Saxifraga Sarmentosa, Vitis Vinifera, Morus Nigra, Scutellaria Baicalensis, Anthemis Nobilis, Salvia Sclarea, Rosmarinus Officianalis, Citrus Medica Limonum, Panax Ginseng, Siegesbeckia Orientalis, Fructus Mume, Ascophyllum Nodosum, Bifida Ferment lysate, Glycine Soja extract, Beta Vulgaris, Haberlea Rhodopensis, Polygonum Cuspidatum, Citrus Aurantium Dulcis, Vitis Vinifera, Selaginella Tamariscina, Humulus Lupulus, Citrus Reticulata Peel, Punica Granatum, Asparagopsis, Curcuma Longa, Menyanthes Trifoliata, Helianthus Annuus, Hordeum Vulgare, Cucumis Sativus, Evernia Prunastri, Evernia Furfuracea, and mixtures thereof.
H. Sunscreens It may also be desirable to include one or more sunscreens in the compositions of the invention. Such sunscreens include chemical UVA or UVB sunscreens or physical sunscreens in the particulate form. Inclusion of sunscreens in the compositions containing the dermal filler will provide additional protection to skin during daylight hours and promote the effectiveness of the dermal filler on the skin. 1. UVA Chemical Sunscreens
If desired, the composition may comprise one or more UVA sunscreens. The term "UVA sunscreen" means a chemical compound that blocks UV radiation in the wavelength range of about 320 to 400 nm. Preferred UVA sunscreens are dibenzoylmethane compounds having the general formula
Figure imgf000034_0001
wherein Ri is H, OR and NRR wherein each R is independently H, Ci_2o straight or branched chain alkyl; R2 is H or OH; and R3 is H, Ci_2o straight or branched chain alkyl.
Preferred is where Ri is OR where R is a Ci_2o straight or branched alkyl, preferably methyl; R2 is H; and R3 is a Ci_2o straight or branched chain alkyl, more preferably, butyl.
Examples of suitable UVA sunscreen compounds of this general formula include 4- methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert- butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 4,4'- diisopropylbenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoymethane, 2-methyl-5- tert-butyl-4'-methoxydibenzoylmethane, and so on. Particularly preferred is 4-tert-butyl-4'- methoxydibenzoylmethane, also referred to as Avobenzone. Avobenzone is commercial available from Givaudan-Roure under the trademark Parsol 1789, and Merck & Co. under the tradename Eusolex 9020. Other types of UVA sunscreens include dicamphor sulfonic acid derivatives, such as ecamsule, a sunscreen sold under the trade name Mexoryl™, which is terephthalylidene dicamphor sulfonic acid, having the formula: - \
The composition may contain from about 0.001-20%, preferably 0.005-5%, more preferably about 0.005-3% by weight of the composition of UVA sunscreen. In the preferred embodiment of the invention the UVA sunscreen is Avobenzone, and it is present at not greater than about 3% by weight of the total composition.
2. UVB Chemical Sunscreens
The term "UVB sunscreen" means a compound that blocks UV radiation in the wavelength range of from about 290 to 320 nm. A variety of UVB chemical sunscreens exist including alpha-cyano-beta,beta-diphenyl acrylic acid esters as set forth in U.S. Pat. No.
3,215,724, which is hereby incorporated by reference in its entirety. One particular example of an alpha-cyano-beta,beta-diphenyl acrylic acid ester is Octocrylene, which is 2-ethylhexyl 2- cyano-3,3-diphenylacrylate. In certain cases the composition may contain no more than about 110% by weight of the total composition of octocrylene. Suitable amounts range from about 0.001-10% by weight. Octocrylene may be purchased from BASF under the tradename Uvinul N-539.
Other suitable sunscreens include benzylidene camphor derivatives as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety. Such benzylidene camphor derivatives have the general formula:
Figure imgf000036_0001
wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred is 4-methylbenzylidene camphor, which is a lipid soluble UVB sunscreen compound sold under the tradename Eusolex 6300 by Merck. Also suitable are cinnamate derivatives having the general formula:
ft;
Figure imgf000036_0002
wherein R and Ri are each independently a Ci_2o straight or branched chain alkyl. Preferred is where R is methyl and Ri is a branched chain C1-10, preferably Cg alkyl. The preferred compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate or octyl methoxycinnamate. The compound may be purchased from Givaudan Corporation under the tradename Parsol MCX, or BASF under the tradename Uvinul MC 80. Also suitable are mono-, di-, and triethanolamine derivatives of such methoxy cinnamates including diethanolamine methoxycinnamate. Cinoxate, the aromatic ether derivative of the above compound is also acceptable. If present, the Cinoxate should be found at no more than about 3% by weight of the total composition.
Also suitable as UVB screening agents are various benzophenone derivatives having the general formula:
Figure imgf000037_0001
wherein R through R9 are each independently H, OH, NaO3S, SO3H, SO3Na, Cl, R", OR" where R" is Ci 20 straight or branched chain alkyl Examples of such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Particularly preferred is where the benzophenone derivative is Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (also referred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium), and the like. Most preferred is Benzophenone 3.
Also suitable are certain menthyl salicylate derivatives having the general formula:
Figure imgf000037_0002
wherein Ri, R2, R3, and R4 are each independently H, OH, NH2, or Ci 20 straight or branched chain alkyl. Particularly preferred is where Ri, R2, and R3 are methyl and R4 is hydroxyl or NH2, the compound having the name homomenthyl salicylate (also known as Homosalate) or menthyl anthranilate. Homosalate is available commercially from Merck under the tradename Eusolex HMS and menthyl anthranilate is commercially available from Haarmann & Reimer under the tradename Heliopan. If present, the Homosalate should be found at no more than about 15% by weight of the total composition. Various amino benzoic acid derivatives are suitable UVB absorbers including those having the general formula:
Figure imgf000038_0001
wherein R1, R2, and R3 are each independently H, Ci_2o straight or branched chain alkyl which may be substituted with one or more hydroxy groups. Particularly preferred is wherein Ri is H or Ci_8 straight or branched alkyl, and R2 and R3 are H, or Ci_8 straight or branched chain alkyl.
Particularly preferred are PABA, ethyl hexyl dimethyl PABA (Padimate O), ethyldihydroxypropyl PABA, and the like. If present Padimate O should be found at no more than about 8% by weight of the total composition. Salicylate derivatives are also acceptable UVB absorbers. Such compounds have the general formula: wherein R is a straight or branched chain alkyl, including derivatives of the above compound formed from mono-, di-, or triethanolamines. Particular preferred are octyl salicylate, TEA-salicylate, DEA-salicylate, and mixtures thereof.
Generally, the amount of the UVB chemical sunscreen present may range from about 0.001- 45%, preferably 0.005-40%, more preferably about 0.01-35% by weight of the total composition.
If desired, the compositions of the invention may be formulated to have a certain SPF
(sun protective factor) values ranging from about 1-50, preferably about 2-45, most preferably about 5-30. Calculation of SPF values is well known in the art. I. Particulate Materials
The compositions of the invention may contain particulate materials in the form of pigments, inert particulates, or mixtures thereof. If present, suggested ranges are from about 0.01-75%, preferably about 0.5-70%, more preferably about 0.1-65% by weight of the total composition. In the case where the composition may comprise mixtures of pigments and powders, suitable ranges include about 0.01-75% pigment and 0.1-75% powder, such weights by weight of the total composition. 1. Powders
The particulate matter may be colored or non-colored (for example white) non- pigmented powders. Suitable non-pigmented powders include bismuth oxychloride, titanated mica, fumed silica, spherical silica, polymethylmethacrylate, micronized teflon, boron nitride, acrylate copolymers, aluminum silicate, aluminum starch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk, corn starch, diatomaceous earth, fuller's earth, glyceryl starch, hectorite, hydrated silica, kaolin, magnesium aluminum silicate, magnesium trisilicate, maltodextrin, montmorillonite, microcrystalline cellulose, rice starch, silica, talc, mica, titanium dioxide, zinc laurate, zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate, calcium silicate, dextran, kaolin, nylon, silica silylate, silk powder, sericite, soy flour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnut shell powder, or mixtures thereof. The above mentioned powders may be surface treated with lecithin, amino acids, mineral oil, silicone, or various other agents either alone or in combination, which coat the powder surface and render the particles more lipophilic in nature. 2. Pigments The particulate materials may comprise various organic and/or inorganic pigments.
The organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthroquinone, and xanthine dyes which are designated as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc. Organic pigments generally consist of insoluble metallic salts of certified color additives, referred to as the Lakes. Inorganic pigments include iron oxides, ultramarines, chromium, chromium hydroxide colors, and mixtures thereof. Iron oxides of red, blue, yellow, brown, black, and mixtures thereof are suitable.
J. Preservatives
The composition may contain 0.001-8%, preferably 0.01-6%, more preferably 0.05-5% by weight of the total composition of preservatives. A variety of preservatives are suitable, including such as benzoic acid, benzyl alcohol, benzylhemiformal, benzylparaben, 5-bromo-5- nitro-l,3-dioxane, 2-bromo-2-nitropropane-l,3-diol, butyl paraben, phenoxyethanol, methyl paraben, propyl paraben, diazolidinyl urea, calcium benzoate, calcium propionate, caprylyl glycol, biguanide derivatives, phenoxyethanol, captan, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, chloroacetamide, chlorobutanol, p-chloro-m- cresol, chlorophene, chlorothymol, chloroxylenol, m-cresol, o-cresol, DEDM Hydantoin, DEDM Hydantoin dilaurate, dehydroacetic acid, diazolidinyl urea, dibromopropamidine diisethionate, DMDM Hydantoin, and the like. In one preferred embodiment the composition is free of parabens. K. Vitamins and Antioxidants
The compositions of the invention may contain vitamins and/or coenzymes, as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, more preferably 0.05-5% by weight of the total composition is suggested. Suitable vitamins include ascorbic acid and derivatives thereof such as ascorbyl palmitate, tetrahexydecyl ascorbate, and so on; the B vitamins such as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymes such as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and derivatives thereof are suitable. Examples are retinyl palmitate, retinol. retinoic acid, as well as Vitamin A in the form of beta carotene. Also suitable is Vitamin E and derivatives thereof such as Vitamin E acetate, nicotinate, or other esters thereof. In addition, Vitamins D and K are suitable. Suitable antioxidants are ingredients which assist in preventing or retarding spoilage.
Examples of antioxidants suitable for use in the compositions of the invention are potassium sulfite, sodium bisulfite, sodium erythrobate, sodium metabisulfite, sodium sulfite, propyl gallate, cysteine hydrochloride, butylated hydroxytoluene, butylated hydroxyanisole, and so on.
L. Collagen Fortifiers
It is particularly desirable to formulate compositions of the invention that contain ingredients that may be referred to as collagen fortifiers. The term "collagen fortifier" means an ingredient that either stimulates or promotes collagen synthesis in the skin or inhibits degradation of collagen in the skin. If present suggested ranges of collagen fortifier are from about 0.001 to 80%, preferably from about 0.01 to 75%, preferably from about 0.05 to 30% by weight of the total composition. Suitable collagen fortifiers include, but are not limited to, copper peptides, emodin, vitamin C, acetyl hexapeptide-8 (argirilene), palmitoyl pentapeptide (a.k.a. Matrixyl®), Ceramide-2, pollen, various isoflavones including those from soy products, marine collagen, brown algae, fatty acid esters of ascorbic acid such as ascorbyl palmitate or tetrahexadecyl ascorbate, tocopherol, managanese, and so on. Ingredients that are known in the art to promote collagen synthesis in skin or inhibit degradation of skin collagen are know in the art and included within the definition of "collagen fortifier" when used herein, even if not mentioned specifically. M. Elastin Fortifier
Also suitable for use in the invention are elastin fortifiers. The term "elastin fortifier" means an ingredient that stimulates or promotes synthesis of elastin in the skin or inhibits the degradation of skin elastin. If present the elastin fortifier may range from about 0.001 to 50%, preferably from about 0.005 to 40%, more preferably from about 0.05 to 35% by weight of the total composition. Examples of elastin fortifiers include, but are not limited to, zinc, boswellic acids, ursolic acid, various types of alpha hydroxyl acids such as citric or lactic acids, aloe, panthenol, and the like. Ingredients that stimulate or promote elastin synthesis or inhibit degradation of skin elastin are well known in the art and are included within the term "elastin fortifier" when used herein, even if not specifically mentioned herein.
N. GAG Fortifer Also suitable for use in the compositions of the invention are various types of ingredients that promote GAG (or glycosaminoglycan) synthesis. If present, suggested ranges are from about 0.001 to 50%, preferably from about 0.005 to 40%, more preferably from about 0.01 to 35% by weight of the total composition. Examples of GAG fortifiers include botanical extracts from Centella genus such Centella Asiatica, glucosamine, manganese, Guto Kola extract, Hibiscus extract and so on. Ingredients that promote GAG synthesis are well known in the art and included within the definition of "GAG Fortifier" as used herein, even though not specifically mentioned herein. IV. The Cosmetic Compositions
The compositions of the invention containing the dermal fillers may be found in a variety of forms, such as anhydrous compositions, aqueous based solutions, serums, gels, skin creams or lotions, or color cosmetic compositions such as foundation makeup, mascara, lip color, blush, eyeshadow, and the like. In the case where the composition is in the anhydrous form the dermal filler may be solubilized or dispersed in the oil phase of the emulsion; or if the dermal filler is water soluble it may be solvated in polar solvents, typically ingredients referred to as humectants such as glycerine or alkylene glycols prior to formation of an anhydrous emulsion.
If the composition is in the emulsion form, the dermal filler may be found in the water phase or the oil phase of the emulsion depending on the type of derivative. For example, certain hydrophilic derivatives such as dermal filler acetate salt and the like are water soluble and will generally be solubilized in the water phase of the emulsion. Certain other derivatives are lipophilic in nature and will more likely be found in the oil phase of the emulsion. Suitable serums or gels will generally comprise from about 1-99% water, and optionally from about 0.001-30% of an aqueous phase thickening agent. The other ingredients mentioned herein may be present in the percentage ranges set forth.
Typical skin creams or lotions comprise from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants. Preferably the surfactants are nonionic and may be in the form of silicones or organic nonionic surfactants.
Typical color cosmetic compositions such as foundations, blush, eyeshadow and the like will preferably contain from about 5-98% water, 1-85% oil, and from about 0.1 to 20% of one or more surfactants in addition to from about 0.1 to 65% of particulates that are pigments or a combination of pigments and powders.
Typical mascara compositions generally contain from about 5-98% water, 1-85% oil, and from about 0.1 to 20% surfactant in addition to natural or synthetic polymers that are film forming, such as aqueous dispersions of acrylic copolymers, aqueous dispersions of polyurethane, or silicone resins. V. The Methods
The invention further comprises treating skin for improvement by applying to the skin the compositions of the invention. The compositions may be applied in the forms mentioned herein, as part of skin care regimens. For example, the composition may be applied to the skin as a night cream or cream applied to skin prior to a period of bodily rest such as a nap or sleep. The composition may be applied two times a day, in the morning and in the evening after cleansing the skin. The composition may be applied to the skin over skin care products, in the form of foundations or other color cosmetics.
In one embodiment, the dermal filler is formulated into a day cream and a night cream, so that the consumer using the regimen applies the dermal filler to the skin twice a day as part of a standard skin care routine. In another embodiment, the dermal filler is applied to the skin in the form of a toner, over which a skin cream or lotion is applied.
In another embodiment the dermal filler is applied to the skin in the form of a skin cleanser.
The term "treating skin for improvement" means that the skin to which the composition is applied will exhibit one or more of improvements such as increase in skin tone (reduction of laxity), reduction in wrinkles, skin plumping, and so on.
The invention will be further described in connection with the following examples which are set forth for the purposes of illustration only.
EXAMPLE 1
Skin treatment oil-in-water (1), and oil-in- water-in-silicone oil (2), creams are prepared as follows:
Figure imgf000044_0001
Figure imgf000045_0001
Crosslinked hyaluronic acid dermal filler in particle form 1.00 1.00
The composition is prepared by combining the water phase and oil phase ingredients separately, then emulsifying to form an emulsion.
EXAMPLE 2
A water in silicone oil emulsion skin serum is prepared as follows:
Figure imgf000046_0001
The composition is prepared by combining the oil phase ingredients and water phase ingredients separately, then mixing well to emulsify.
EXAMPLE 3 Oil-in- water (O/W) and water-in-oil (W/O) emulsion mascaras are prepared as follows:
Figure imgf000046_0002
Figure imgf000047_0001
The mascaras are made by combining the oily phase ingredients except for the cyclomethicone and dimethicone and heating to about 90° C. until solids melt. The cyclomethicone and dimethicone are added to the mixture and the heat maintained at about 60° C. The water phase ingredients are combined and heated to about 60° C. and combined with the mixture. The phases are emulsified to form the final mixture.
EXAMPLE 4
Emulsion foundation makeup compositions are prepared as follows:
Figure imgf000047_0002
Magnesium sulfate 1.00
Laureth-7 0.25
The water, oil and pigment phases are separately prepared by low shear mixing. The phases are combined with high shear blending to form a foundation makeup composition.
EXAMPLE 5 Anhydrous emulsion skin treatment serums and gels may be prepared as follows:
Figure imgf000048_0001
The compositions were prepared by combining the dermal filler and glycerin. The remaining ingredients were combined and mixed well, followed by addition of the dermal filler in glycerin.
EXAMPLE 6 A foundation makeup is prepared as follows:
Figure imgf000049_0001
The composition was prepared by grinding the pigments in a portion of the oil. The remaining ingredient were combined with heat and mixed well, incorporating the pigment grind into the composition. The composition was a semi-solid beige colored composition suitable for use as a foundation.
EXAMPLE 7
A lipstick composition is prepared as follows:
Figure imgf000049_0002
Figure imgf000050_0001
The composition is prepared by grinding the pigments in a portion of the cetyl esters. The waxes and oils were separately combined with heat and mixed well. The pigment grind was added to the mixture and stirred well. The mixture was poured into molds and allowed to cool to room temperature.
EXAMPLE 8 Powder blush compositions are prepared as follows
Figure imgf000050_0002
The compositions are prepared by grinding the pigments in a portion of the oil.
Separately, the oils and waxes were combined with heat and mixed well. The pigment grind was added. The compositions are pressed into pans.
EXAMPLE 9 Cross linked hyaluronic acid particles were tested for their ability to plump skin. A 2% aqueous solution of cross linked hyaluronic acid was prepared. Skin models from EpiDermFT Full Thickness Skin Model (Mattek) were treated by applying the solution to the top of the skin as follows:
1. 50micro liters of PBS in each well (3 wells) 2. 50 microliters of solution A (3 wells)
3. 100 microliters of solution A (3 wells)
The skin models were maintained in an incubator at 37° C. and fixed after 24 hours by staining with Alcian Blue cationic dye. The skin samples were viewed under the microscope. It was observed that the intensity of the blue in the epidermis was significantly increased for the skin treated with the cross-linked hyaluronic acid particles compared to the control treated with PBS. The intensity of the blue color was greater with the high concentration of hyaluronic acid particles. Thus, the hyaluronic acid particles are absorbed by the skin and appear to provide a plumping effect in the skin samples.
While the invention has been described in connection with the preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

Claims

WE CLAIM:
I . A topical non-dermal filler composition for application to keratinous surfaces comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin. 2. The composition of claim 1 where the dermal filler is a crosslinked hyaluronic acid.
3. The composition of claim 1 wherein the hyaluronic acid based dermal filler is in particulate form.
4. The composition of claim 3 wherein the particle size is greater than about 0.001 to 25 microns. 5. The composition of claim 1 wherein the hyaluronic acid based dermal filler is covalently cross linked.
6. The composition of claim 1 which is a skin cream, lotion, or gel.
7. The composition of claim 1 which is in the water and oil emulsion form.
8. The composition of claim 1 further comprising at least one ingredient selected from (a) a collagen fortifier, (b) an elastin fortifier, (c) a GAG fortifier; and (d) mixtures thereof. .
9. A method for providing a plumping effect to skin comprising applying to the skin surface a topical non-dermal filler composition comprising at least one injectable dermal filler capable of being absorbed into the epidermal layers of the skin in an amount sufficient to plump the skin. 10. The method of claim 9 wherein the dermal filler is crosslinked hyaluronic acid.
I I. The method of claim 10 wherein the cross linked hyaluronic acid has a particle size ranging from about 0.001 to 25 microns.
12. The method of claim 11 wherein the cross linked hyaluronic acid is covalently cross linked. 13. The method of claim 11 wherein the composition is applied to the skin in the form of a skin cream or lotion.
14. The method of claim 11 wherein the composition further comprises at least one ingredient selected from the group consisting of (a) a collagen fortifier, (b) an elastin fortifier, (c) a GAG fortifier; and (d) mixtures thereof.
15. A method for plumping skin comprising topically applying to the skin an injectable dermal filler in the form of covalently cross linked hyaluronic acid particles having a particle size of 0.001 to 25 microns, in an amount sufficient to plump the skin.
PCT/US2009/034297 2008-04-28 2009-02-17 Topical compositions for improving appearance of keratinous surfaces WO2009134511A1 (en)

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JP2014136681A (en) * 2013-01-15 2014-07-28 Kose Corp Water-in-oil type cosmetic for eyelash
US20210022981A1 (en) * 2019-07-24 2021-01-28 Amorepacific Corporation Hyaluronic acid composition for external use on skin and a method for skin moisturizing comprising applying the same onto the skin
GB2596998B (en) * 2019-04-01 2023-10-04 Geltor Inc Topical formulations of recombinant collagens

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JP2014136681A (en) * 2013-01-15 2014-07-28 Kose Corp Water-in-oil type cosmetic for eyelash
GB2596998B (en) * 2019-04-01 2023-10-04 Geltor Inc Topical formulations of recombinant collagens
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