WO1999038486A1 - Cosmetic compositions - Google Patents

Cosmetic compositions Download PDF

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Publication number
WO1999038486A1
WO1999038486A1 PCT/US1998/021521 US9821521W WO9938486A1 WO 1999038486 A1 WO1999038486 A1 WO 1999038486A1 US 9821521 W US9821521 W US 9821521W WO 9938486 A1 WO9938486 A1 WO 9938486A1
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WO
WIPO (PCT)
Prior art keywords
composition according
polyol
carboxylic acid
skin
silicone
Prior art date
Application number
PCT/US1998/021521
Other languages
French (fr)
Inventor
Petra Helga Beck
Lee Ellen Drechsler
Frank Cselik
Michael David Bell
Susan Frances Marshall
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU62562/98A priority Critical patent/AU6256298A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR9814929-6A priority patent/BR9814929A/en
Priority to JP2000529221A priority patent/JP2003517996A/en
Priority to EP98952257A priority patent/EP1051149A1/en
Priority to KR1020007008360A priority patent/KR20010024893A/en
Priority to AU98002/98A priority patent/AU9800298A/en
Priority to CA002319161A priority patent/CA2319161A1/en
Publication of WO1999038486A1 publication Critical patent/WO1999038486A1/en

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    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/362Polycarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31Hydrocarbons
    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • 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
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/925Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair

Definitions

  • the present invention relates to cosmetic compositions.
  • cosmetic compositions which provide improved moisturization, skin feel, skin softness, skin smoothness benefits, together with excellent rub-in and absorption characteristics.
  • the compositions also display excellent stability characteristics at normal and elevated temperatures.
  • Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure.
  • the outermost of these layers, referred to as the stratum corneum is known to be composed of 25nm protein bundles surrounded by 8nm thick layers.
  • Anionic surfactants and organic solvents typically penetrate the stratum corneum membrane and, by delipidization (i.e. removal of_the lipids from the stratum corneum), destroy its integrity. This destruction of the skin surface topography leads to a rough feel and may eventually permit the surfactant or solvent to interact with the keratin, creating irritation.
  • compositions which will assist the stratum corneum in maintaining its barrier and water-retention functions at optimum performance in spite of deleterious interactions which the skin may encounter in washing, work, and recreation.
  • Conventional cosmetic cream and lotion compositions as described, for example, in Sagarin, Cosmetics Science and Technology, 2nd Edition, Vol.l, Wiley Interscience (1972) and Encyclopaedia of Chemical Technology, Third Edition, Volume 7 are known to provide varying degrees of emolliency, barrier and water-retention (moisturizing) benefits. However, they can also suffer negatives in terms of skin feel (i.e. not providing the desired skin softness or skin smoothness benefits) and have poor rub-in and slow absorption into the skin.
  • compositions which will assist the stratum corneum in maintaining its water gradient, but which do so with improved skin feel, skin softness and skin smoothness and improved absorption into the skin.
  • Polyol fatty acid polyester compounds are known for use in skin care compositions.
  • EP-A-458600, EP-A-466410, EP-A-519727 and EP-A-587288 disclose compositions containing polyol fatty acid polyester compounds for use in skin care compositions.
  • branched chain hydrocarbon such as isohexadecane are known for use in skin care compositions.
  • compositions herein also providing excellent moisturisation, rub-in and absorption characteristics.
  • a cosmetic composition suitable for topical application to the skin or hair comprising:
  • liquid, polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing from about 4 to about 8 hydroxyl groups, and wherein each carboxylic acid moiety has from about 8 to about 22 carbon atoms, and wherein said liquid polyol carboxylic acid ester has a complete melting point of less than about 30°C; and
  • compositions of the invention provide improved skin feel, skin softness and skin smoothness benefits and/or improved rub-in/absorption characteristics.
  • a cosmetic method of treatment of the skin comprising applying to the skin a composition according to the present invention.
  • compositions of the present invention comprises a liquid polyol carboxylic acid ester component together with a branched chain hydrocarbon as well as various optional ingredients as indicated below. All levels and ratios are by weight of total composition, unless otherwise indicated. Chain length and degrees of ethoxylation are also specified on a weight average basis.
  • skin conditioning agent means a material which provides a “skin conditioning benefit”.
  • skin conditioning benefit means any cosmetic conditioning benefit to the skin including, but not limited to, moisturization, humectancy (i.e. the ability to retain or hold water or moisture in the skin), emolliency, visual improvement of the skin surface, soothing of the skin, softening of the skin, improvement in skin feel, and the like.
  • complete melting point means a melting point as measured by the well-known technique of Differential Scanning Calorimetry (DSC).
  • the complete melting point is the temperature at the intersection of the baseline, i.e. the specific heat line, with the line tangent to the trailing edge of the endothermic peak.
  • a scanning temperature of 5°C/minute is generally suitable in the present invention for measuring the complete melting points. However, it should be recognised that more frequent scanning rates may be deemed appropriate by the analytical chemist skilled in the art in specific circumstances.
  • a DSC technique for measuring complete melting points is also described in US Patent No. 5,306,514, to Letton et al., issued April 26, 1994.
  • nonocclusive means that the component as so described does not substantially or block the passage of air and moisture through the skin surface.
  • compositions herein comprise a liquid, polyol carboxylic acid ester.
  • compositions of the present invention preferably comprise from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 0.5% to 4 about 10% by weight of the polyol ester.
  • the level of polyol ester by weight of the oil in the composition is preferably from about 1% to about 85%, more preferably from about 5% to about 75%).
  • the weight ratio of the liquid carboxylic acid polyol ester to the emollient material is preferably in the range of from about 5:1 to about 1 :5, more preferably in the range of from 3:1 to about 1:3.
  • the polyol ester preferred for use herein is a nonocclusive liquid or liquifiable polyol carboxylic acid ester.
  • These polyol esters are derived from a polyol radical or moiety and one or more carboxylic acid radicals or moieties. In other words, these esters contain a moiety derived from a polyol and one or more moieties derived from a carboxylic acid.
  • These carboxylic acid esters can also be derived from a carboxylic acid.
  • These carboxylic acid esters can also be described as liquid polyol fatty acid esters, because the terms carboxylic acid and fatty acid are often used interchangeably by those skilled in the art.
  • the preferred liquid polyol polyesters employed in this invention comprise certain polyols, especially sugars or sugar alcohols, esterified with at least four fatty acid groups.
  • the polyol starting material must have at least four esterifiable hydroxyl groups.
  • preferred polyols are sugars, including monosaccharaides and disaccharides, and sugar alcohols.
  • monosaccharides containing four hydroxyl groups are xylose and arabinose and the sugar alcohol derived from xylose, which has five hydroxyl groups, i.e., xylitol.
  • the monosaccharide, erythrose is not suitable in the practice of this invention since it only contains three hydroxyl groups, but the sugar alcohol derived from erythrose, i.e., erythritol, contains four hydroxyl groups and accordingly can be used.
  • Suitable five hydroxyl group-containing monosaccharides are galactose, fructose, and sorbose.
  • Sugar alcohols containing six -OH groups derived from the hydrolysis products of sucrose, as well as glucose and sorbose, e.g., sorbitol, are also suitable.
  • disaccharide polyols which can be used include maltose, lactose, and sucrose, all of which contain eight hydroxyl groups.
  • Preferred polyols for preparing the polyesters for use in the present invention are selected from the group consisting of erythritol, xylitol, sorbitol, glucose, and sucrose. Sucrose is especially preferred.
  • the polyol starting material having at least four hydroxyl groups is esterified on at least four of the -OH groups with a fatty acid containing from about 8 to about 22 carbon atoms.
  • fatty acids include caprylic, capric, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, arachidic, arachidonic, behenic, and erucic acid.
  • the fatty acids can be derived from naturally 5 occurring or synthetic fatty acids; they can be saturated or unsaturated, including positional and geometrical isomers. However, in order to provide liquid polyesters preferred for use herein, at least about 50%) by weight of the fatty acid incorporated into the polyester molecule should be unsaturated. Oleic and linoleic acids, and mixtures thereof, are especially preferred.
  • the polyol fatty acid polyesters useful in this invention should contain at least four fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acid, but it is preferable that the polyester contain no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterified with fatty acid, i.e., the polyol moiety is substantially completely esterified.
  • the fatty acids esterified to the polyol molecule can be the same or mixed, but as noted above, a substantial amount of the unsaturated acid ester groups must be present to provide liquidity.
  • sucrose fatty triester would not be suitable for use herein because it does not contain the required four fatty acid ester groups.
  • a sucrose tetra-fatty acid ester would be suitable, but is not preferred because it has more than two unesterified hydroxyl groups.
  • a sucrose hexa-fatty acid ester would be preferred because it has no more than two unesterified hydroxyl groups.
  • Highly preferred compounds in which all the hydroxyl groups are esterified with fatty acids include the liquid sucrose octa- substituted fatty acid esters.
  • polyol fatty acid polyesters containing at least four fatty acid ester groups suitable for use in the present invention: glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof.
  • the preferred liquid polyol polyesters preferred for use herein have complete melting points below about 30°C, preferably below about 27.5°C, more preferably below about 25°C. Complete melting points reported herein are measured by Differential Scanning Calorimetry (DSC). 6
  • the polyol fatty acid polyesters suitable for use herein can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification of the polyol with methyl, ethyl or glycerol fatty acid esters using a variety of catalysts; acylation of the polyol with a fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. See U.S. Patent No. 2,831,854; U.S. Patent No. 4,005,196, to Jandacek, issued January 25, 1977.
  • a second essential component of the present invention is a branched chain hydrocarbon having an weight average molecular weight of from about 100 to about 15,000 , preferably from about 100 to 1000.
  • Preferred for use in the compositions herein are branched chain hydrocarbons selected from isododecane, isohexadecane, isoeicosane, isooctahexacontane, isohexapentacontahectane, isopentacontaoctactane, and mixture thereof, especially isohexadecane and isooctacontane, and mixtures thereof.
  • the branched chain aliphatic hydrocarbon is preferred herein from the viewpoint of providing improved skin feel and absorption characteristics.
  • branched chain aliphatic hydrocarbons sold under the trade name Permethyl (RTM) and commercially available from Presperse Inc., P.O. Box 735, South Plainfield, N.J. 07080, U.S.A. Particularly suitable from the viewpoint of improved skin fell, spreadability and application characteristics is a mixture of isohexadecane and isooctahexacontane.
  • RTM Permethyl
  • the branched chain hydrocarbon is present in the compositions herein at a level of from about 0.1%) to about 15%>, preferably from about 0.1 % to about 10%, especially from about 0.1% to about 5% by weight of composition.
  • the present compositions can be used for any suitable purpose.
  • the present compositions are suitable for topical application to the skin or hair.
  • the skin care compositions can be in the form of creams, lotions, gels, and the like.
  • the cosmetic compositions herein are in the form of an oil-in- water emulsion of one or more oil phases in an aqueous continuous phase, each oil phase comprising a single oily component or a mixture of oily components in miscible or homogeneous form but said different oil phases containing different materials or combinations of materials from each other.
  • the overall level of oil phase components in the compositions of the invention is preferably from about 0.1 % to about 60%, preferably from about 1% to about 30% and more preferably from about 1% to about 10% by weight.
  • compositions preferably comprise, as either all or a portion of the oil phase or oil phases referred to above a first silicone-containing phase comprising a crosslinked polyorganosiloxane polymer and a silicone oil, wherein the composition comprises 0.1% to about 20%), preferably from about 0.5%) to about 10%, more preferably from about 0.5% to about 5%>, by weight of composition, of the combination of crosslinked silicone and silicone oil.
  • the first silicone-containing phase comprises from about 10% to about 40%, more preferably from about 20% to about 30%, by weight of the first silicone-containing phase, of the crosslinked polyorganosiloxane polymer and from about 60% to about 90%, preferably from about 70% to about 80%, by weight of the first silicone-containing phase, of the silicone oil.
  • the crosslinked polyorganosiloxane polymer comprises polyorganosiloxane polymer crosslinked by a crosslinking agent.
  • Crosslinking agents for use herein include any crosslinking agents useful for the preparation of crosslinked silicones. Suitable crosslinking agents herein include those represented by the following general formula:
  • R ⁇ is methyl, ethyl, propyl or phenyl
  • R2 is H or -(CH2) n CH-CH2 where n is in the range of from about 1 to about 50, z is in the range of from about 1 to about 1000, preferably from about 1 to about 100 and R is an alkyl group having from 1 to 50 carbon atoms.
  • crosslinking agent has the general formula
  • R1 , R2 and z are as defined above.
  • the crosslinking agent has the following general formula: R1
  • z is in the range from about 1 to about 1000, preferably from about 1 to about 100.
  • the crosslinked polysiloxane polymer preferably comprises from about 10% to about 50%, more preferably from about 20%) to about 30%, by weight the crosslinked polysiloxane polymer, of crosslinking agent.
  • Suitable polyorganosiloxane polymers for use herein include those represented by the following general formula:
  • R ⁇ is methyl, ethyl, propyl or phenyl
  • R3 and R4 are independently selected from methyl, ethyl, propyl and phenyl
  • R is an end-gap, such as an optionally hydroxy-substituted alkyl group having from 1 to 50 carbon atoms, preferably an alkyl group having from 1 to 5 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms
  • p is an integer in the range of from about 1 to about 2000, preferably from about 1 to about 500
  • q is an integer in the range of from about 1 to about 1000, preferably from about 1 to about 500.
  • p and q reflect the number of Si-O linkages in the polymer chain and R ⁇ and R2 and R3 and R4 may vary going from one monomer unit to the next.
  • suitable polyorganosiloxane polymers for use herein include methyl vinyl dimethicone, methyl vinyl diphenyl dimethicone and methyl vinyl phenyl methyl diphenyl dimethicone.
  • the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer having the general formula:
  • the first silicone-containing phase also comprises a silicone oil.
  • a silicone oil Any straight chain, branched and cyclic silicones suitable for use in skin care compositions can be used herein.
  • the silicone oils can be volatile or non-volatile. Suitable silicone oils for use herein include silicone oils having a weight average molecular weight of about 100,000 or less, preferably about 50,000 or less.
  • the silicone oil is selected from silicone oils having a weight average molecular weight in the range from about 100 to about 50,000, and preferably from about 200 to about 40,000.
  • the silicone oil is selected from dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and phenyl methicone, and mixtures thereof, most preferably phenyl methicone.
  • Suitable materials for use in the first silicone-containing phase are available under the tradename KSG supplied by Shinetsu Chemical Co., Ltd, for example KSG-15, KSG-16, KSG-17, KSG-18. These materials contain a combination of crosslinked polyorganosiloxane polymer and silicone oil. Particularly preferred for use herein, especially in combination with the organic amphiphilic emulsifier material, is KSG-18.
  • KSG-15, KSG-16, KSG-17 and KSG-18 are Cyclomethicone DimethiconeNinyl Dimethicone Crosspolymer, Dimethicone DimethiconeNinyl Dimethicone Crosspolymer, Cyclomethicone Dimethicone/Vinyl Dimethicone Crosspolymer and Phenyl Trimethicone Dimethicone/Phenyl Vinyl Dimethicone Crosspolymer, respectively.
  • compositions herein preferably also comprise a second non-crosslinked silicone- containing phase.
  • the second silicone-containing phase is present in a level of from about 0.1% to about 20%, especially from about 0.1 % to about 10% by weight of composition.
  • Suitable silicone fluids for use in the second silicone-containing phase herein include water-insoluble silicones inclusive of non- volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, and mixtures thereof.
  • the second silicone-containing phase comprises a silicone gum or a mixture of silicones including the silicone gum.
  • silicone gum means high molecular weight silicone-based fluids having a mass-average molecular weight in excess of about 200,000 and preferably from about 200,000 to about 400,000. Silicone oils generally have a molecular weight of less than about 200,000. Typically, silicone gums have a viscosity at 25°C in excess of about 1,000,000 mm ⁇ .s'l.
  • the silicone gums include dimethicones as described by Petrarch and others including 11 US-A-4, 152,416, May 1, 1979 to Spitzer, et al, and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968.
  • Silicone gums for use herein include any silicone gum suitable for use in a skin care composition. Suitable silicone gums for use herein are silicone gums having a molecular weight of from about 200,000 to about 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof.
  • Dimethiconol-based silicones suitable for use herein can have the chemical structure HO(CH 3 )2SiO[(CH3)2SiO] n (CH3)2SiOH where n is from about 2000 to about 40,000, preferably from about 3000 to about 30,000.
  • Exemplary fluorosilicones useful herein can have a molecular weight of from about 200,000 to about 300,000, preferably from about 240,000 to about 260,000 and most preferably about 250,000.
  • Specific examples of silicone gums include polydimethylsiloxane, (polydimethyl- siloxane)(methylvinylsiloxane) copolymer, poly(dimethylsiloxane)(diphenyl)(methyl- vinylsiloxane) copolymer and mixtures thereof.
  • the silicone gum used herein can be incorporated into the composition as part of a mixture of silicones.
  • the silicone gum preferably constitutes from about 5% to about 40%, especially from about 10% to 20% by weight of the silicone mixture.
  • the silicone or silicone mixture preferably constitutes from about 0.1 % to about 20%>, more preferably from about 0.1% to about 15%), and especially from about 0.1 % to about 10% by weight of composition.
  • Suitable silicone gum-based silicone mixtures for use in the second silicone-containing phase of the compositions herein include mixtures consisting essentially of:
  • the silicone-based carriers suitable for use herein include certain silicone fluids.
  • the silicone fluid can be either a polyalkyl siloxane, a polyaryl siloxane, a polyalkylaryl siloxane or a polyether siloxane copolymer. Mixtures of these fluids can also be used and are preferred in certain executions.
  • the polyalkyl siloxane fluids that can be used include, for example, polydimethylsiloxanes with viscosities ranging from about 0.65 to 600,000 mm ⁇ .s'l, preferably from about 0.65 to about 10,000 mm ⁇ .s ⁇ at 25°C. These siloxanes are available, for example, from the General Electric Company as the Niscasil (RTM) series and from Dow Corning as the Dow Corning 200 series.
  • the essentially non-volatile poly- alkylarylsiloxane fluids that can be used include, for example, polymethylphenyl- siloxanes, having viscosities of about 0.65 to 30,000 mm ⁇ .s ⁇ at 25°C.
  • siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid. Also suitable for use herein are certain volatile cyclic polydimethylsiloxanes having a ring structure incorporating from about 3 to about 7 (CH3)2SiO moieties.
  • the viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 29, 1970.
  • the viscosity of the silicone blend constituting the second fluid phase ranges from about 500 mm ⁇ .s ⁇ to about 100,000 mm ⁇ .s"!,. preferably from about 1000 rnmAs"! to about 10,000 nim ⁇ .s" 1.
  • An especially preferred silicone-gum based component for use in the compositions herein is a dimethiconol gum having a molecular weight of from about 200,000 to about 4,000,000 along with a silicone carrier with a viscosity of about 0.65 to 100 mm ⁇ .s"! .
  • An example of this silicone component is Dow Corning Q2-1403 (85% 5 mm ⁇ .s"! Dimethicone Fluid/15% Dimethiconol) and Dow Corning Q2-1401 available from Dow Corning.
  • silicone suitable for use in the second silicone-containing phase herein include polydiorganosiloxane-polyoxyalkylene copolymers containing at least one poly- diorganosiloxane segment and at least one polyoxyalkylene segment, said polydiorgano- siloxane segment consisting essentially of RbSiO(4_b)/2 s ⁇ oxane un i ts wherein b has a value of from about 0 to about 3, inclusive, there being an average value of approximately 13 2 R radicals per silicon for all siloxane units in the copolymer, and R denotes a radical selected from methyl, ethyl, vinyl, phenyl and a divalent radical bonding said polyoxyalkylene segment to the polydiorganosiloxane segment, at least about 95% of all R radicals being methyl; and said polyoxyalkylene segment having an average molecular weight of at least about 1000 and consisting of from about 0 to about 50 mol
  • Preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general formula:
  • R is a chain terminating group, especially selected from hydrogen; hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy, propoxy, butoxy; benzyloxy; aryloxy, such as phenoxy; alkenyloxy, such as vinyloxy and allyloxy; acyloxy, such as acetoxy, acryloxy and propionoxy and amino, such as dimethylamino.
  • the number of and average molecular weights of the segments in the copolymer are such that the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in the copolymer is preferably from about 2.5 to about 4.0.
  • Suitable copolymers are available commercially under the tradenames Belsil (RTM) from Wacker-Chemie GmbH, Geschafts Buffalo S, Postfach D-8000 Kunststoff 22 and Abil (RTM) from Th. Goldschmidt Ltd., Tego House, Victoria Road, Ruislip, Middlesex, HA4 14 OYL, for example Belsil (RTM) 6031 and Abil (RTM) B88183.
  • a particularly preferred copolymer for use herein includes Dow Corning DC3225C which has the CTFA designation Dimethicone/Dimethicone copolyol.
  • a third oil phase is present in an amount of from about 0.1% to about 15%, more preferably from about 1% to about 10% by weight of composition.
  • the third oil phase can be either a separate phase or can form one phase together with either or both of the first and second silicone phases.
  • the third oil phase is a separate phase.
  • the third oil phase preferably comprises a non-silicone organic oil, such as a natural or synthetic oil selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, fatty acids and mixtures thereof, which ingredients are useful for achieving emollient cosmetic properties.
  • the first oil phase component is preferably essentially silicone-free, i.e., it contains no more than about 10%>, preferably no more than about 5%> by weight of silicone-based materials. It will be understood that the oil phase may contain, for example, up to about 25%, preferably up to only about 10% of oil phase soluble emulsifier ingredients. Such ingredients are not to be considered as oil phase components from the viewpoint of determining the oil phase level and required HLB. In preferred embodiments, the overall required HLB of the oil phase is from about 8 to about
  • required HLB being determined by summing the individual required HLB values for each component of the oil phase multiplied by its
  • Suitable first oil phase components for use herein include, for example, optionally hydroxy-substituted Cg-C50 unsaturated fatty acids and esters thereof, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol and cetyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalane, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), oils consisting of greater than 20% cholesterol esters, lanolin and lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed
  • Preferred embodiments herein comprise from about 0.1% to about 10% by weight of an unsaturated fatty acid or ester.
  • Preferred unsaturated fatty acids and esters for use herein are optionally hydroxy substituted Cg-C5Q unsaturated fatty acids and esters, especially esters of ricinoleic acid.
  • the unsaturated fatty acid or ester component is valuable herein in combination with the liquid crystal-forming emulsifier for improving the skin feel and rub-in characteristics of the compositon. Highly preferred in this respect is cetyl ricinoleate.
  • a further preferred component of the compositions herein is an organic amphiphilic surfactant which is capable of forming smectic lyotropic crystals in product or when the product is being applied to the skin at ambient or elevated temperatures.
  • the amphiphilic surfactant is capable of forming liquid crystals at a temperature in the range from about 20°C to about 40°C.
  • the amphiphilic surfactant is capable of forming smectic lyotropic liquid crystals.
  • liquid crystals may not be identifiable on the skin surface or stratum corneum.
  • the amphiphilic surfactant is preferably present at a level of from about 0.1% to about 20%, preferably from about 0.1% to about 10%, by weight.
  • liquid-crystal forming amphiphilic surfactants suitable for use herein contain both hydrophilic and lipophilic groupings and exhibit a marked tendency to adsorb at a surface or interface, i.e. they are surface-active.
  • Amphiphilic surface-active materials for use herein include nonionic (no charge), anionic (negative charge), cationic (positive charge) and amphoteric (both charges) based on whether or not they ionize in aqueous media.
  • liquid crystals are also referred to as anisotropic fluids, a fourth state of matter, surfactant association structure or mesophases. Those terms are often used interchangeably.
  • the term "lyotropic" means a liquid crystalline system containing a polar solvent, such as water.
  • the liquid crystals used herein are preferably lamellar, hexagonal, rod or vesicle structures or mixtures thereof.
  • liquid crystalline phase utilized in the compositions of the invention can be identified in various ways.
  • a liquid crystal phase flows under shear and is characterised by a viscosity that is significantly different from the viscosity of its isotropic solution phase.
  • Rigid gels do not flow under shear like liquid crystals.
  • liquid crystals when viewed with a polarized light microscope, liquid crystals show identifiable birefringence, as, for example, planar lamellar birefringence, whereas when isotropic solutions and rigid gels are viewed under polarized light, both show dark fields.
  • Other suitable means for 16 identifying liquid crystals include X-ray diffraction, NMR spectroscopy and transmission electron microscopy.
  • the organic amphiphilic surfactant preferred for use herein can be described as a liquid, semi-solid or waxy water-dispersible material having the formula X- Y where X represents a hydrophilic, especially nonionic moiety and Y represents a lipophilic moiety.
  • Organic amphiphilic surfactants suitable for use herein include those having a weight average HLB (Hydrophilic Lipophilic Balance) in the range from about 2 to about 12, preferably from about 4 to about 8.
  • Preferred organic amphiphilic surfactants employed herein have a long saturated or unsaturated branched or linear lipophilic chain having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic or alkyl phenyl chains.
  • the hydrophilic group of the amphiphilic material forming the liquid crystal phase is a nonionic group
  • a polyoxyethylene, a polyglycerol, a polyol ester, oxyalkylated or not, and, for example, a polyoxyalkylated sorbitol or sugar ester can be employed.
  • the hydrophilic group of the amphiphilic surfactant forming the liquid crystal phase is an ionic group, advantageously there can be used, as the hydrophilic group, a phosphatidylcholine residue as found in lecithin.
  • Hydrophilic moieties suitable for use herein are selected from: (1) ethers of linear, or branched, polyglycerol having the formula R-(Gly) n -OH where n is a whole number between 1 and 6, R is selected from aliphatic, linear or branched, saturated or unsaturated chains of 12 to 30 carbon atoms, the hydrocarbon radicals of lanolin alcohols and the 2-hydroxy alkyl residue of long chain, alpha-diols, and Gly represents a glycerol residue; (2) polyethoxylated fatty alcohols, for example those of the formula R!
  • R is C12-C30 linear or branched alkyl or alkenyl and x averages from about 0 to about 20, preferably from about 0.1 to about 6, more preferably from about 1 to about 4;
  • polyol mono-, di-,or tri-esters optionally polyalkoxylated
  • the polyols are preferably selected from sugars, C2-C6 alkylene glycols, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols and polypropylene glycols and wherein the polyalkoxylated polyol esters contain from about 2 to about 20 preferably from 17 about 2 to about 4 moles of alkylene oxide (especially ethylene oxide) per mole of polyol ester;
  • amphiphilic surfactants suitable for use herein include Cg-C3Q alkyl and acyl-containing amphoteric, anionic, cationic and nonionic surfactants as set out below.
  • N-alkyl amino acids e.g., sodium N-alkylaminoacetate
  • N-lauroylglutamic acid cholesterol ester e.g., Eldew CL-301 Ajinomoto
  • Acylglutamates e.g., disodium N-lauroylglutamate
  • Sarcosinates e.g., sodium lauryl sarcosinate.
  • Taurates e.g., sodium lauryl taurate. sodium methyl cocoyl taurate
  • Carboxylic acids and salts e.g., potassium oleate; potassium laurate; potassium- 10- undecenoate; potassium 1 l-(p-styryl) - undecanoate
  • Ethoxylated carboxylic salts e.g., sodium carboxy methyl alkyl ethoxylate
  • Ether carboxylic acids e.g., sodium carboxy methyl alkyl ethoxylate
  • Phosphoric acid esters and salts e.g., lecithin; DEA-oleth-10 phosphate
  • Acyl isethionates e.g., sodium 2-lauroyloxyethane sulfonate
  • Alkane sulfonates e.g., branched sodium x-alkane sulfonate (x/1); Sulfosuccinates e.g.,
  • Sulfuric acid esters e.g., sodium 2-ethylhept-6-enyl sulfate; sodium 11-heneicosyl sulfate; sodium 9-heptadecyl sulfate.
  • Alkyl sulfates e.g., MEA alkyl sulfate such as MEA-lauryl sulfate
  • MEA alkyl sulfate such as MEA-lauryl sulfate
  • Alkyl Imidazolines e.g., alkyl hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline (supplier Akzo, Finetex and Hoechst));
  • Ethoxylated Amines e.g., PEG-n alkylamine, PEG-n alkylamino propylamine, Poloxamine, PEG-cocopolyamine, PEG- 15 tallow amine
  • Alkylamines e.g., dimethyl alkylamine; dihydroxyethyl alkylamine dioleate
  • Alkylbenzyl dimethylammonium salts e.g., stearalkonium chloride
  • Alkyl betaines e.g., dodecyl dimethyl ammonio acetate, oleyl betaine
  • Heterocylic ammonium salts e.g., alkylethyl morpholinium ethosulfate
  • Tetraalkylammonium salts e.g., dimethyl distearyl quaternary ammonium chloride
  • Monoglycerides e.g., monoolein; monolinolein; monolaurin; 1-dodecanoyl-glycerol monolaurin; 1, 13-docosenoyl-glycerol monoerucin diglyceride fatty acid (e.g., diglycerol monoisostearate Cosmol 41, fractionated.
  • Nisshin e.g., monoolein; monolinolein; monolaurin; 1-dodecanoyl-glycerol monolaurin; 1, 13-docosenoyl-glycerol monoerucin
  • diglyceride fatty acid e.g., diglycerol monoisostearate Cosmol 41, fractionated.
  • Polyglyceryl esters e.g., triglycerol monooleate (Grindsted TS-T122), diglycerol monooleate (Grindsted TST-T101);
  • Polyhydric alcohol esters and ethers e.g., sucrose cocoate, cetostearyl glucoside (Montanol, Seppic), ⁇ octyl glucofliranoside esters, alkyl glucoside such Cjn-Cio
  • Diesters of phosphoric acid e.g., sodium dioleyl phosphate
  • Alkylamido propyl betaine e.g., cocoamido propyl betaine
  • Amide (e.g., N-(dodecanoylaminoethyl)-2-pyrrolidone); Amide oxide: e.g., 1 , 1 Dihydroperfluorooctyldimethylamine oxide,
  • Ammonio phosphates e.g., didecanoyl lecithin
  • Amine e.g., octylamine
  • N-trimethylammoniodecanamidate N-trimethylammoniododecanamidate
  • Ammonio carboxylates e.g., dodecyldimethylammonioacetate
  • Phosphonic and phosphoric esters and amides e.g., methyl-N-methyl-dodecylphosphonamidate, dimethyl dodecylphosphonate, dodecyl methyl methylphosphonate,
  • Ethoxylated alcohols Polyoxyethylene (Cg) e.g., pentaoxyethylene glycol p-n-octylphenyl ether hexaoxyethylene glycol p-n-octylphenyl ether nonaoxyethylene glycol p-n-octylphenyl ether
  • Polyoxyethylene (CJQ) e-g-- pentaoxyethylene glycol p-n-decylphenyl ether, decyl glyceryl ether, 4-oxatetradecan-l, 2-diol, nonaoxyethylene glycol p-n-decylphenyl ether
  • Polyoxyethylene ( Cj 1 ) e.g.,
  • Preferred organic amphiphilic surfactants for use herein are nonionic amphiphilic surfactants having a hydrophilic moiety as in (3) above, and a lipophilic selected from long saturated or unsaturated branched chain or linear lipophilic chains having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic or alkyl phenyl chains.
  • Highly preferred organic amphiphilic surfactants for use herein are selected from polyhydric alcohol esters and ethers.
  • Especially preferred amphiphilic surfactants for use herein are sugar esters and polyalkoxylated sugar esters.
  • the sugar esters for use in this invention can be classified as hydrocarbyl and alkyl polyoxyalkylene esters of cyclic polyhydroxy saccharides wherein one or more of the hydroxyl groups on the saccharide moiety is substituted with an acyl or polyoxyalkylene group.
  • Hydrocarbyl sugar esters can be prepared in well-known fashion by heating an acid or acid halide with sugar, i.e., by a simple esterification reaction.
  • the sugars employed in the preparation of the sugar esters include monosaccharides, di- saccharides and oligo-saccharides well known in the art, for example, the dextrorotatory and levorotatory forms of glucose, fructose, mannose, galactose, arabinose and xylose.
  • Typical di-saccharides include maltose, cellibiose, lactose, and trehalose.
  • Typical tri- saccharides include raffinose and gentianose. The di-saccharides are preferred for use herein, especially sucrose.
  • Sucrose can be esterified at one or more of its eight hydroxyl groups to provide the sucrose esters useful herein.
  • sucrose When sucrose is combined with an esterification agent in a 1 : 1 mole ratio, sucrose monoesters are formed; and when the ratio of esterification agent to sucrose is 2:1, the di- ester is formed.
  • the respective esters of di-saccharide sugars especially sucrose, wherein the acyl groups contain from about 8 to about 20 21 carbon atoms are especially preferred.
  • Preferred sugar esters herein are sucrose cocoate, sucrose monooctanoate, sucrose monodecanoate, sucrose monolaurate, sucrose monomyristate, sucrose monopalmitate, sucrose monostearate, sucrose monooleate, sucrose monolinoleate, sucrose dioleate, sucrose dipalmitate, sucrose distearate, sucrose dilaurate and sucrose dilinoleate, and mixtures thereof.
  • Sucrose cocoate has been found to be particularly efficacious in the compositions herein.
  • the mono- and di-acyl esters preferably comprise at least about 40%, more preferably from about 50% to about 95% by weight of the total sugar ester mixture.
  • sugar esters suitable for use in the compositions of this invention are the alkyl polyoxyalkylene sugar esters wherein one hydroxyl group is substituted with a Cg-Cj alkyl group and wherein one or more of the hydroxyl groups on the sugar molecule are replaced by an ester or ether substituent containing the moiety [(CH2) x -O] v wherein x is an integer from 2 to about 4, preferably 2, and wherein y is an integer from about 1 to about 50, preferably 8 to 30 polyoxyalkylene substituents.
  • sugar esters wherein the polyoxyalkylene substituent is a polyoxyethylene substituent containing from about 8 to about 30 polyoxyethylene groups.
  • Such materials wherein sorbitan is the sugar moiety are commercially available under the tradename "Tweens”.
  • Such mixed esters can be prepared by first acylating a sugar at a 1:1 mole ratio with a hydrocarbyl acid halide followed by reaction with the corresponding polyoxyalkylene acid halide or alkylene oxide to provide the desired material.
  • the simple polyoxyalkylene ester of di-saccharides, especially sucrose, wherein the polyoxyalkylene groups contain up to about 20 alkylene oxide moieties are another useful class of sugar esters herein.
  • a preferred sugar ester of this class is sorbitol trioleate ethoxylated with 20 moles of ethylene oxide.
  • Mixtures of sugar esters with other polyol esters, eg. glycerol esters, are also suitable for use herein, for example, Palm Oil Sucroglyceride (Rhone-Poulenc).
  • lecithin refers to a material which is a phosphatide.
  • Naturally occurring or synthetic phosphatides can be used.
  • Phosphatidylcholine or lecithin is a glycerine esterified with a choline ester of phosphoric acid and two fatty acids, usually a long chain saturated or unsaturated fatty acid having 16-20 carbons and up to 4 double bonds.
  • Other phosphatides capable of forming lamellar or hexagonal liquid crystals can be used in place of the lecithin or in combination with it.
  • phosphatides are glycerol esters with two fatty acids as in the lecithin, but the choline is replaced by ethanolamine (a cephalin), or serine (-aminopropanoic acid; phosphatidyl serine) or an inositol 22 (phosphatidyl inositol). While the invention herein is exemplified with lecithin, it is understood that these other phosphatides can be used herein.
  • lecithins can be used.
  • American Lecithin Company supplies a Nattermann Phospholipid, Phospholipan 80 and Phosal 75.
  • Other lecithins which can be used alone or in combination with these are: Actifla Series, Centrocap series, Central Ca, Centrol series, Centrolene, Centrolex, Centromix, Centrophase and Centrolphil Series from Central Soya; Alcolec and Alcolec 439-C from American Lecithin; Canaspersa from Canada Packers, Lexin K and Natipide from American Lecithin; and L-Clearate, Clearate LV and Clearate WD from the W.A. Cleary Co.
  • Lecithins are supplied dissolved in ethanol, fatty acids, triglycerides and other solvents. They are usually mixtures of lecithins and range from 15% to 50% of the solution as supplied. Both natural and synthetic lecithins can be used. Natural lecithins are derived from oilseeds such as sunflower seeds, soybeans, safflower seeds and cottonseed. The lecithins are separated from the oil during the refining process. The organic amphiphilic surfactant has been found to be especially valuable herein for improving the stability and skin feel of the compositions of the invention.
  • composition It is preferably incorporated into the composition in an amount of from about 0.1 % to about 20% , preferably from about 0.1% to about 10%>, and more preferably from about 0.1% to about 8% by weight of composition.
  • Highly preferred herein is a fatty acid ester blend based on a mixture of sorbitan or sorbitol fatty acid ester and sucrose fatty acid ester, the fatty acid in each instance being preferably C -C24, more preferably CJO-C20-
  • the preferred fatty acid ester emulsifier from the viewpoint of moisturisation is a blend of sorbitan or sorbitol C ⁇ 6-C20 f att Y ac ⁇ ester with sucrose C ⁇ o _ Ci6 fatty acid ester, especially sorbitan stearate and sucrose cocoate. This is commercially available from ICI under the trade name Arlatone 2121.
  • a highly preferred ingredient of the compositions herein is urea which is preferably present in a level of from about 0.1%) to about 20%, more preferably from about 0.5% to about 10% and especially from about 1% to about 5% by weight of composition.
  • the oil phase and organic amphiphilic surfactant when present are premixed in water at a temperature above the Kraft Point of the organic amphiphilic surfactant (but preferably below about 60°C) to form a liquid crystal/oil in water dispersion prior to addition of the urea.
  • the urea is found to be especially effective herein in combination with the amphiphilic emulsifier surfactant and the polyol fatty acid polyester for providing outstanding skin moisturisation and softening in the context of an 23 oil-in-water skin care emulsion composition. Moreover, it is surprisingly found that the urea is rendered more stable to hydrolytic degradation, thereby allowing an increase in compositional pH.
  • a wide variety of optional ingredients such as further emollients, non-occlusive moisturizers, humectants, gelling agents, neutralizing agents, perfumes, colouring agents and surfactants, can be added to the skin compositions herein.
  • compositions of the present invention can comprise emollient materials selected from compounds of formula:
  • R ⁇ is selected from H or CH3, R ⁇ , R3 and R4 are independently selected from C1 -C20 straight chain or branched chain alkyl, and x is an integer of from 1-20.
  • Preferred emollients for use herein are described in WO98/22085. Particularly preferred emollients for use herein are isononyl isononanoate, methyl isostearate, isopropyl isostearate, or mixtures thereof.
  • the emollient material is preferably present in the compositions at a level of from about 0.1%) to about 10%, preferably from about 0.1 % to about 5%, especially from about 1% to about 3%> by weight of composition.
  • compositions herein can comprise a humectant.
  • Suitable humectants for use herein include sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose derivatives, hexanetriol, glycerine, glycine, hyaluronic acid, arginine, Ajidew (NaPCA), water-soluble polyglycerylmethacrylate lubricants and panthenols.
  • a preferred humectant herein is glycerine (sometimes known as glycerol or glycerin). Glycerine is especially preferred in the compositions of the invention from the viewpoint of boosting moisturisation. Also preferred for use herein is butylene glycol. Particularly preferred from the viewpoint of boosting moisturisation is a combination of glycerine and urea.
  • the humectant is preferably present at a level of from about 0.1% to about 20%, more preferably from about 1%> to about 15%>, and especially from about 5%> to about 15% by weight of composition.
  • Suitable polyglycerylmethacrylate lubricants for use in the compositions of this invention are available under the trademark Lubrajel (RTM) from Guardian Chemical Corporation,
  • Lubrajels can be described as 24 hydrates or clathrates which are formed by the reaction of sodium glycerate with a methacrylic acid polymer. Thereafter, the hydrate or clathrate is stabilized with a small amount of propylene glycol, followed by controlled hydration of the resulting product.
  • Lubrajels are marketed in a number of grades of varying glycerate: polymer ratio and viscosity. Suitable Lubrajels include Lubrajel TW, Lubrajel CG and Lubrajel MS, Lubrajel WA, Lubrajel DV and so-called Lubrajel Oil.
  • At least part (up to about 5%> by weight of composition) of the humectant can be incorporated in the form of an admixture with a particulate cross-linked hydrophobic acrylate or methacrylate copolymer, itself preferably present in an amount of from about 0.1%) to about 10%, which can be added either to the aqueous or disperse phase.
  • This copolymer is particularly valuable for reducing shine and controlling oil while helping to provide effective moisturization benefits and is described in further detail by WO96/03964, incorporated herein by reference.
  • compositions of the invention can also contain a hydrophilic gelling agent at a level preferably from about 0.01%> to about 10%, more preferably from about 0.02% to about 2%o, and especially from about 0.02% to about 0.5%.
  • the gelling agent preferably has a viscosity (1% aqueous solution, 20 C, Brookfield RVT) of at least about 4000 mPa.s, more preferably at least about 10,000 mPa.s and especially at least 50,000 mPa.s.
  • Suitable hydrophilic gelling agents can generally be described as water-soluble or coUoidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, guar gum, hydroxypropyl guar gum and xanthan gum.
  • cellulose ethers e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose
  • polyvinylpyrrolidone polyvinylalcohol
  • guar gum hydroxypropyl guar gum
  • xanthan gum xanthan gum
  • Preferred hydrophilic gelling agents herein are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a coUoidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00%) of a crosslinking agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 954, Carbopol 980, Carbopol 951 and Carbopol 981.
  • Carbopol 934 is a water-soluble polymer of acrylic acid crosslinked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule.
  • a most preferred polymer is Carbopol 954.
  • CFA Designation Acrylates/ 10-30 25 Alkyl Acrylate Crosspolymer
  • a combination of the polyalkenyl polyether cross-linked acrylic acid polymer and the hydrophobically modified cross-linked acrylic acid polymer is also suitable and is preferred for use herein.
  • the gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures.
  • non-ionic polyacrylamide polymers which may be substituted, branched or unbranched. These polymers are non-ionic water dispersible polymers which can be formed from a variety of monomers including acrylamide and methacrylamide which are unsubstituted or substituted with one or two alkyl groups (preferably C r C 5 ).
  • acrylate amides and methacrylate amides in which the amide nitrogen is unsubstituted, or substituted with one or two C,-C 5 alkyl groups (preferably: methyl, ethyl or propyl), for example, acrylamide, methacrylamide, N- methacrylamide, N-methylmethacrylamide, N,N-dimethylmethacrylamide and N,N- dimethylacrylamide.
  • C,-C 5 alkyl groups preferably: methyl, ethyl or propyl
  • acrylamide, methacrylamide, N- methacrylamide, N-methylmethacrylamide, N,N-dimethylmethacrylamide and N,N- dimethylacrylamide These monomers are generally disclosed in US Pat. No. 4,963,348 to Bolich, Jr. et al., issued Oct, 16., 1990, incorporated by reference herein.
  • These copolymers may optionally be formed using conventional neutral crosslinking agents such as dialkenyl compounds.
  • crosslinking agents for cationic polymers is disclosed in US Pat. No. 4,628,078 to Glover et al. issued Dec. 9, 1986 and US Pat. No. 4,599,379 to Flesher et al. issued Jul. 8, 1986 both of which are incorporated by reference herein.
  • These non-ionic co-polymers have a molecular weight greater than about 1,000,000 preferably greater than about 1,500,000 and range up to about 30,000,000.
  • these non-ionic polyacrylamides are predispersed in a water-immiscible solvent such as mineral oil and the like, containing a high HLB surfactant (HLB from about 7 to about 10) which helps to facilitate water dispersibility of the polyacrylamide.
  • HLB high HLB surfactant
  • Most preferred for use herein is the non-ionic polymer under the CTFA designation: polyacrylamide and isoparaffin and laureth-7, available under the trade name Sepigel 305 from Seppic Corporation.
  • Other polyacrylamide polymers useful herein include multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids. Commercially available examples of these multi-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H, from Lipo Chemicals, Inc., (Patterson, NJ).
  • Neutralizing agents suitable for use in neutralizing acidic group containing hydrophilic gelling agents herein include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine. 26
  • the compositions of the invention are in emulsion form and are preferably formulated so as to have a product viscosity of at least about 4,000 mPa.s and preferably in the range from about 4,000 to about 300,000 mPa.s, more preferably from about 8,000 to about 200,000 mPa.s and especially from about 10,000 to about 100,000 mPa.s and even more especially from about 10,000 to about 50,000 mPa.s (25°C, neat, Brookfield RVT Spindle No. 5).
  • compositions of the invention can also contain from about 0.1% to about 10%, preferably from about 1%> to about 5%> of a panthenol moisturizer.
  • the panthenol moisturizer can be selected from D-panthenol ([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]- 3,3-dimethylbutamide), DL-panthenol, calcium pantothenate, royal jelly, panthetine, pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B complex.
  • Highly preferred from the viewpoint of skin care and tack reduction is D- panthenol.
  • compositions of the present invention can additionally comprise from about 0.001%> to about 0.5%, preferably from about 0.002% to about 0.05%, more preferably from about 0.005% to about 0.02% by weight of carboxymethylchitin.
  • Chitin is a polysaccharide which is present in the integument of lobsters and crabs and is a mucopolysaccharide having beta (1-4) linkages of N-acetyl-D-glucosamine.
  • Carboxymethylchitin is prepared by treating the purified chitin material with alkali followed by monochloracetic acid. It is sold commercially in the form of a dilute (approximately 0.1% to 0.5% by weight) aqueous solution under the name Chitin Liquid available from A & E Connock Ltd., Fordingbridge, Hampshire, England.
  • keratolytic agents/desquamation agents such as salicylic acid; proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives preferably at a level of from about 0.1 %> to about 5%, such as Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, EDTA, Euxyl (RTM) K400, Bromopol (2-bromo-2-nitropropane-l,3-diol) and phenoxypropanol; anti-bacterials such as Irgasan (RTM) and phenoxyethanol (preferably at levels of from 0.1%) to about 5%>); soluble or colloidally-soluble moisturising agents such as hylaronic acid and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials,
  • sunscreening agents are also useful herein.
  • a wide variety of sunscreening agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 5,073,372, to Turner et al, issued December 17, 1991; U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology.
  • sunscreens which are useful in the compositions of the instant invention are those selected from 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p- aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4- isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789, and mixtures thereof.
  • sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra.
  • One of the chromophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range.
  • sunscreens include those selected from 4- ⁇ , ⁇ -(2-ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-N,N- (2-ethylhexyl)methylaminobenzoic acid ester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)- methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.
  • the sunscreens can comprise from about 0.5% to about 20%> of the compositions useful herein. Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of 28 photoprotection of a sunscreen against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
  • compositions of the present invention can additionally comprise from about 0.1 %> to about 5%> by weight of aluminium starch octenylsuccinate.
  • Aluminium starch octenylsuccinate is the aluminium salt of the reaction product of octenylsuccinic anhydride with starch and is commercially available under the trade name from Dry Flo National Starch & Chemical Ltd. Dry Flo is useful herein from the viewpoint of skin feel and application characteristics.
  • pigments which, where water-insoluble, contribute to and are included in the total level of oil phase ingredients.
  • Pigments suitable for use in the compositions of the present invention can be organic and/or inorganic. Also included within the term pigment are materials having a low colour or lustre such as matte finishing agents, and also light scattering agents. Examples of suitable pigments are iron oxides, acyglutamate iron oxides, ultramarine blue, D&C dyes, carmine, and mixtures thereof. Depending upon the type of composition, a mixture of pigments will normally be used.
  • the preferred pigments for use herein from the viewpoint of moisturisation, skin feel, skin appearance and emulsion compatibility are treated pigments.
  • the pigments can be treated with compounds such as amino acids, silicones, lecithin and ester oils.
  • compositions herein can also comprise colorants.
  • ⁇ -carotene which can be used at a level of from 0.00001 to 0.005%. At the higher levels ⁇ -carotene is additionally valuable as an anti-oxidant for reducing skin damage by free radicals.
  • compositions of the present invention can also comprise a safe and effective amount of a vitamin B3 compound.
  • the compositions of the present invention preferably comprise from about 0.01% to about 50%>, more preferably from about 0.1 %> to about
  • vitamin B3 compound means a compound having the formula:
  • R is -CONH2 (i.e., niacinamide), -COOH (i.e., nicotinic acid) or -CH2OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing.
  • exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
  • Suitable esters of nicotinic acid include nicotinic acid esters of C1 -C22- preferably C ⁇ - Ci g, more preferably Cj-Cg alcohols.
  • the alcohols are suitably straight-chain or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic), and substituted or unsubstituted.
  • the esters are preferably non-vasodilating. As used herein, "non-vasodilating" means that the ester does not commonly yield a visible flushing response after application to the skin in the subject compositions (the majority of the general population would not experience a visible flushing response, although such compounds may cause vasodilation not visible to the naked eye).
  • Non-vasodilating esters of nicotinic acid include tocopherol nicotinate and inositol hexanicotinate; tocopherol nicotinate is preferred.
  • a more complete description of vitamin B3 compounds is given in WO 98/22085.
  • vitamin B3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Company
  • vitamin B3 compounds may be used herein. Preferred vitamin B3 compounds -ire niacinamide and tocopherol nicotinate. Niacinamide is more preferred.
  • the compositions of the present invention also contain a retinoid.
  • the vitamin B3 compound and retinoid provide unexpected benefits in regulating skin condition, especially in therapeutically regulating signs of skin aging, more especially wrinkles, lines, and pores. Without intending to be bound or otherwise limited by theory, it is believed that the vitamin B3 compound increases the conversion of certain retinoids to trans-retinoic acid, which is believed to be the biologically active form of the retinoid, to provide synergistic regulation of skin condition (namely, increased conversion for retinol, retinol esters, and retinal).
  • the vitamin B3 compound unexpectedly mitigates redness, inflammation, dermatitis and the like which may otherwise be associated with topical application of retinoid (often referred to, and hereinafter alternatively referred to as "retinoid dermatitis").
  • retinoid dermatitis also referred to, and hereinafter alternatively referred to as "retinoid dermatitis"
  • the combined vitamin B3 compound and retinoid tend to increase the amount and activity of 30 thioredoxin, which tends to increase collagen expression levels via the protein AP-1. Therefore, the present invention enables reduced active levels, and therefore reduced potential for retinoid dermatitis, while retaining significant positive skin conditioning benefits.
  • higher levels of retinoid may still be used to obtain greater skin conditioning efficacy, without undesirable retinoid dermatitis occurring.
  • retinoid includes all natural and/or synthetic analogs of Vitamin A or retinol-like compounds which possess the biological activity of Vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds.
  • the retinoid is preferably retinol, retinol esters (e.g., C2 - C22 alkyl esters of retinol, including retinyl palmitate, retinyl acetate, retinyl proprionate), retinal, and/or retinoic acid (including all- trans retinoic acid and/or 13-cis-retinoic acid), more preferably retinoids other than retinoic acid.
  • retinol retinol esters
  • retinyl esters e.g., C2 - C22 alkyl esters of retinol, including retinyl palmitate, retinyl acetate, retinyl proprionate
  • retinal and
  • retinoids are retinol, retinyl palmitate, retinyl acetate, retinyl proprionate, retinal and combinations thereof. More preferred are retinol and retinyl palmitate.
  • the retinoid may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources.
  • compositions preferably contain from or about 0.005% to or about 2%>, more preferably 0.01% to or about 2%, retinoid.
  • Retinol is most preferably used in an amount of from or about 0.01% to or about 0.15%; retinol esters are most preferably used in an amount of from or about 0.01% to or about 2% (e.g., about 1%).
  • the pH of the compositions is preferably from about 4 to about 9, more preferably from about 6 to about 8.0.
  • the balance of the composition is water or an aqueous carrier suitable for topical application to the skin.
  • the water content of the compositions herein is generally from about 30% to about 98.89%>, preferably from about 50% to about 95% and especially from about 60% to about 90%> by weight.
  • compositions of the invention are preferably in the form of a moisturising cream or lotion, which can be applied to the skin as a leave-on product.
  • the invention is illustrated by the following examples: Examples I to IV
  • Oil in water emulsions are prepared from the following ingredients using conventional formulating techniques.
  • Arlatone 2121 1 1.0 1.0 1.0 1.0 1.0
  • Arlatone 212l' 0.0 0.50 1.50 0.60 0.50 1.00
  • Carbopol 954 4 0.70 0.63 0.68 0.60 0.70 0.61 NaOH (40% Soln) 0.80 1.00 0.80 0.85 0.75 0.90 32
  • compositions as set out in examples I to X are made as follows:
  • a first premix of thickening agents, methyl paraben when present, glycerine/TiO2 premix, Arlatone 2121 when present, and other water soluble ingredients apart from urea is prepared by admixing in water and heating to about 80°C.
  • a second premix of the oil phase ingredients including the emulsifiers, oil-soluble preservatives, other than silicone gum is prepared by mixing and heating and is added to the aqueous premix.
  • the silicone gum is added to the resulting mixture which is then cooled to about 60°C.
  • the NaOH solution, Glydant Plus when present, EDTA, silicone gum, and then urea solution are then added to the resulting oil-in- water 34 emulsion and the mixture is cooled before adding minor ingredients.
  • the composition is ready for packaging.
  • compositions as set out in examples XI and XII are made as follows:
  • a first premix of thickening agents (except Sepigel when present), methyl paraben, glycerine/TiO2 premix, Arlatone 2121 when present, and other water soluble ingredients apart from urea, is prepared by admixing in water and heating to about 80°C.
  • a second premix of the oil phase ingredients including the emulsifiers, oil-soluble preservatives, other than silicone gum and cyclomethicone is prepared by mixing and heating and is added to the aqueous premix and the mixture homogenised. The silicone gum is added to the resulting mixture which is then cooled to about 60°C.
  • Sepigel and cyclomethicone are added between 60° and 55°C to the resulting oil-in- water emulsion.
  • EDTA and urea solution (lg dissolved in 1ml of water) are added and the mixture is neutralised with NaOH when necessary.
  • the mixture is further cooled under stirring before adding minor ingredients.
  • the composition is ready for packaging.
  • compositions display improved skin feel, skin smoothness, skin softness and skin care characteristics together with reduced greasiness and excellent rub-in and fast absorption characteristics.

Abstract

A cosmetic composition suitable for topical application to the skin or hair comprising: (a) a liquid, polyol carboxylic acid ester having a polyol moiety and a least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing from about 4 to about 8 hydroxyl groups, and wherein each carboxylic acid moiety has from about 8 to about 22 carbon atoms, and wherein said liquid polyol carboxylic acid ester has a complete melting point of less than about 30 °C; (b) a branched chain aliphatic hydrocarbon having a weight average molecular weight of from about 100 to about 15,000. The compositions herein provide improved skin feel, skin smoothness, skin softness and skin care benefits.

Description

Cosmetic Compositions
Technical Field
The present invention relates to cosmetic compositions. In particular it relates to cosmetic compositions which provide improved moisturization, skin feel, skin softness, skin smoothness benefits, together with excellent rub-in and absorption characteristics. The compositions also display excellent stability characteristics at normal and elevated temperatures.
Background of the Invention
Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure. The outermost of these layers, referred to as the stratum corneum, is known to be composed of 25nm protein bundles surrounded by 8nm thick layers. Anionic surfactants and organic solvents typically penetrate the stratum corneum membrane and, by delipidization (i.e. removal of_the lipids from the stratum corneum), destroy its integrity. This destruction of the skin surface topography leads to a rough feel and may eventually permit the surfactant or solvent to interact with the keratin, creating irritation.
It is now recognised that maintaining the proper water gradient across the stratum corneum is important to its functionality. Most of this water, which is sometimes considered to be the stratum corneum's plasticizer, comes from inside the body. If the humidity is too low, such as in a cold climate, insufficient water remains in the outer layers of the stratum corneum to properly plasticize the tissue, and the skin begins to scale and becomes itchy. Skin permeability is also decreased somewhat when there is inadequate water across the stratum corneum. On the other hand, too much water on the outside of the skin causes the stratum corneum to ultimately sorb three to five times its own weight of bound water. This swells and puckers the skin and results in approximately a two to three fold increase in the permeability of the skin to water and other polar molecules.
Thus, a need exists for compositions which will assist the stratum corneum in maintaining its barrier and water-retention functions at optimum performance in spite of deleterious interactions which the skin may encounter in washing, work, and recreation. 2 Conventional cosmetic cream and lotion compositions as described, for example, in Sagarin, Cosmetics Science and Technology, 2nd Edition, Vol.l, Wiley Interscience (1972) and Encyclopaedia of Chemical Technology, Third Edition, Volume 7 are known to provide varying degrees of emolliency, barrier and water-retention (moisturizing) benefits. However, they can also suffer negatives in terms of skin feel (i.e. not providing the desired skin softness or skin smoothness benefits) and have poor rub-in and slow absorption into the skin.
Thus, there remains a need for compositions which will assist the stratum corneum in maintaining its water gradient, but which do so with improved skin feel, skin softness and skin smoothness and improved absorption into the skin.
Polyol fatty acid polyester compounds are known for use in skin care compositions. For example, EP-A-458600, EP-A-466410, EP-A-519727 and EP-A-587288 disclose compositions containing polyol fatty acid polyester compounds for use in skin care compositions. In addition, branched chain hydrocarbon such as isohexadecane are known for use in skin care compositions.
It has now been surprisingly found that by incorporating a particular polyol fatty acid polyester material into a cosmetic emulsion composition together with a particular branched chain hydrocarbon such as isohexadecane, a composition is provided which provides enhanced skin feel, skin softness and skin smoothness benefits. The compositions herein also providing excellent moisturisation, rub-in and absorption characteristics.
Summary of the Invention
According to one aspect of the present invention there is provided a cosmetic composition suitable for topical application to the skin or hair comprising:
(a) liquid, polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing from about 4 to about 8 hydroxyl groups, and wherein each carboxylic acid moiety has from about 8 to about 22 carbon atoms, and wherein said liquid polyol carboxylic acid ester has a complete melting point of less than about 30°C; and
(b) a branched chain hydrocarbon having a weight average molecular weight of from about 100 to about 15,000. 3 The compositions of the invention provide improved skin feel, skin softness and skin smoothness benefits and/or improved rub-in/absorption characteristics.
According to a further aspect of the present invention there is provided a cosmetic method of treatment of the skin comprising applying to the skin a composition according to the present invention.
Detailed Description of the Invention
The compositions of the present invention comprises a liquid polyol carboxylic acid ester component together with a branched chain hydrocarbon as well as various optional ingredients as indicated below. All levels and ratios are by weight of total composition, unless otherwise indicated. Chain length and degrees of ethoxylation are also specified on a weight average basis.
The term "skin conditioning agent", as used herein means a material which provides a "skin conditioning benefit". As used herein, the term "skin conditioning benefit" means any cosmetic conditioning benefit to the skin including, but not limited to, moisturization, humectancy (i.e. the ability to retain or hold water or moisture in the skin), emolliency, visual improvement of the skin surface, soothing of the skin, softening of the skin, improvement in skin feel, and the like.
The term "complete melting point", as used herein means a melting point as measured by the well-known technique of Differential Scanning Calorimetry (DSC). The complete melting point is the temperature at the intersection of the baseline, i.e. the specific heat line, with the line tangent to the trailing edge of the endothermic peak. A scanning temperature of 5°C/minute is generally suitable in the present invention for measuring the complete melting points. However, it should be recognised that more frequent scanning rates may be deemed appropriate by the analytical chemist skilled in the art in specific circumstances. A DSC technique for measuring complete melting points is also described in US Patent No. 5,306,514, to Letton et al., issued April 26, 1994.
The term "nonocclusive" as used herein, means that the component as so described does not substantially or block the passage of air and moisture through the skin surface.
Liquid polyol carboxylic acid ester As an essential component the compositions herein comprise a liquid, polyol carboxylic acid ester.
The compositions of the present invention preferably comprise from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 0.5% to 4 about 10% by weight of the polyol ester. The level of polyol ester by weight of the oil in the composition is preferably from about 1% to about 85%, more preferably from about 5% to about 75%). From the viewpoint of providing improved skin softness and smoothness benefits, the weight ratio of the liquid carboxylic acid polyol ester to the emollient material is preferably in the range of from about 5:1 to about 1 :5, more preferably in the range of from 3:1 to about 1:3.
The polyol ester preferred for use herein is a nonocclusive liquid or liquifiable polyol carboxylic acid ester. These polyol esters are derived from a polyol radical or moiety and one or more carboxylic acid radicals or moieties. In other words, these esters contain a moiety derived from a polyol and one or more moieties derived from a carboxylic acid. These carboxylic acid esters can also be derived from a carboxylic acid. These carboxylic acid esters can also be described as liquid polyol fatty acid esters, because the terms carboxylic acid and fatty acid are often used interchangeably by those skilled in the art.
The preferred liquid polyol polyesters employed in this invention comprise certain polyols, especially sugars or sugar alcohols, esterified with at least four fatty acid groups.
Accordingly, the polyol starting material must have at least four esterifiable hydroxyl groups. Examples of preferred polyols are sugars, including monosaccharaides and disaccharides, and sugar alcohols. Examples of monosaccharides containing four hydroxyl groups are xylose and arabinose and the sugar alcohol derived from xylose, which has five hydroxyl groups, i.e., xylitol. The monosaccharide, erythrose, is not suitable in the practice of this invention since it only contains three hydroxyl groups, but the sugar alcohol derived from erythrose, i.e., erythritol, contains four hydroxyl groups and accordingly can be used. Suitable five hydroxyl group-containing monosaccharides are galactose, fructose, and sorbose. Sugar alcohols containing six -OH groups derived from the hydrolysis products of sucrose, as well as glucose and sorbose, e.g., sorbitol, are also suitable. Examples of disaccharide polyols which can be used include maltose, lactose, and sucrose, all of which contain eight hydroxyl groups.
Preferred polyols for preparing the polyesters for use in the present invention are selected from the group consisting of erythritol, xylitol, sorbitol, glucose, and sucrose. Sucrose is especially preferred.
The polyol starting material having at least four hydroxyl groups is esterified on at least four of the -OH groups with a fatty acid containing from about 8 to about 22 carbon atoms. Examples of such fatty acids include caprylic, capric, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, arachidic, arachidonic, behenic, and erucic acid. The fatty acids can be derived from naturally 5 occurring or synthetic fatty acids; they can be saturated or unsaturated, including positional and geometrical isomers. However, in order to provide liquid polyesters preferred for use herein, at least about 50%) by weight of the fatty acid incorporated into the polyester molecule should be unsaturated. Oleic and linoleic acids, and mixtures thereof, are especially preferred.
The polyol fatty acid polyesters useful in this invention should contain at least four fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acid, but it is preferable that the polyester contain no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterified with fatty acid, i.e., the polyol moiety is substantially completely esterified. The fatty acids esterified to the polyol molecule can be the same or mixed, but as noted above, a substantial amount of the unsaturated acid ester groups must be present to provide liquidity.
To illustrate the above points, a sucrose fatty triester would not be suitable for use herein because it does not contain the required four fatty acid ester groups. A sucrose tetra-fatty acid ester would be suitable, but is not preferred because it has more than two unesterified hydroxyl groups. A sucrose hexa-fatty acid ester would be preferred because it has no more than two unesterified hydroxyl groups. Highly preferred compounds in which all the hydroxyl groups are esterified with fatty acids include the liquid sucrose octa- substituted fatty acid esters.
The following are non-limiting examples of specific polyol fatty acid polyesters containing at least four fatty acid ester groups suitable for use in the present invention: glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof. As noted above, highly preferred polyol fatty acid esters are those wherein the fatty acids contain from about 14 to about 18 carbon atoms.
The preferred liquid polyol polyesters preferred for use herein have complete melting points below about 30°C, preferably below about 27.5°C, more preferably below about 25°C. Complete melting points reported herein are measured by Differential Scanning Calorimetry (DSC). 6 The polyol fatty acid polyesters suitable for use herein can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification of the polyol with methyl, ethyl or glycerol fatty acid esters using a variety of catalysts; acylation of the polyol with a fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. See U.S. Patent No. 2,831,854; U.S. Patent No. 4,005,196, to Jandacek, issued January 25, 1977.
A second essential component of the present invention is a branched chain hydrocarbon having an weight average molecular weight of from about 100 to about 15,000 , preferably from about 100 to 1000. Preferred for use in the compositions herein are branched chain hydrocarbons selected from isododecane, isohexadecane, isoeicosane, isooctahexacontane, isohexapentacontahectane, isopentacontaoctactane, and mixture thereof, especially isohexadecane and isooctacontane, and mixtures thereof. The branched chain aliphatic hydrocarbon is preferred herein from the viewpoint of providing improved skin feel and absorption characteristics. Suitable for use herein are branched chain aliphatic hydrocarbons sold under the trade name Permethyl (RTM) and commercially available from Presperse Inc., P.O. Box 735, South Plainfield, N.J. 07080, U.S.A. Particularly suitable from the viewpoint of improved skin fell, spreadability and application characteristics is a mixture of isohexadecane and isooctahexacontane. The branched chain hydrocarbon is present in the compositions herein at a level of from about 0.1%) to about 15%>, preferably from about 0.1 % to about 10%, especially from about 0.1% to about 5% by weight of composition.
The present compositions can be used for any suitable purpose. In particular, the present compositions are suitable for topical application to the skin or hair. In particular, the skin care compositions can be in the form of creams, lotions, gels, and the like. Preferably the cosmetic compositions herein are in the form of an oil-in- water emulsion of one or more oil phases in an aqueous continuous phase, each oil phase comprising a single oily component or a mixture of oily components in miscible or homogeneous form but said different oil phases containing different materials or combinations of materials from each other. The overall level of oil phase components in the compositions of the invention is preferably from about 0.1 % to about 60%, preferably from about 1% to about 30% and more preferably from about 1% to about 10% by weight.
The present compositions preferably comprise, as either all or a portion of the oil phase or oil phases referred to above a first silicone-containing phase comprising a crosslinked polyorganosiloxane polymer and a silicone oil, wherein the composition comprises 0.1% to about 20%), preferably from about 0.5%) to about 10%, more preferably from about 0.5% to about 5%>, by weight of composition, of the combination of crosslinked silicone and silicone oil.
The first silicone-containing phase comprises from about 10% to about 40%, more preferably from about 20% to about 30%, by weight of the first silicone-containing phase, of the crosslinked polyorganosiloxane polymer and from about 60% to about 90%, preferably from about 70% to about 80%, by weight of the first silicone-containing phase, of the silicone oil.
The crosslinked polyorganosiloxane polymer comprises polyorganosiloxane polymer crosslinked by a crosslinking agent. Crosslinking agents for use herein include any crosslinking agents useful for the preparation of crosslinked silicones. Suitable crosslinking agents herein include those represented by the following general formula:
1
(R)3Si — o Si — O Si(R)3 R2
where R\ is methyl, ethyl, propyl or phenyl, R2 is H or -(CH2)nCH-CH2, where n is in the range of from about 1 to about 50, z is in the range of from about 1 to about 1000, preferably from about 1 to about 100 and R is an alkyl group having from 1 to 50 carbon atoms.
Preferably the crosslinking agent has the general formula
R1
(CH3)3Si — O - - Si — O Si(CH3)3 R2
where R1 , R2 and z are as defined above.
In especially preferred embodiments, the crosslinking agent has the following general formula: R1
(CH3)3Sι — 0 - Si — O - Sι(CH3)3
Ro
where z is in the range from about 1 to about 1000, preferably from about 1 to about 100.
The crosslinked polysiloxane polymer preferably comprises from about 10% to about 50%, more preferably from about 20%) to about 30%, by weight the crosslinked polysiloxane polymer, of crosslinking agent.
Any polyorganosiloxane polymers suitable for use in skin care compositions can be used herein. Suitable polyorganosiloxane polymers for use herein include those represented by the following general formula:
-
R3 R-,
|
(R)3Sι — o - Si — O — Si — O Si(R)3
1
R4 R2
. .
Figure imgf000010_0001
P wherein R\ is methyl, ethyl, propyl or phenyl, R2 is H or -(CH2)nCH=CH2, where n is in the range of from about 1 to about 50, R3 and R4 are independently selected from methyl, ethyl, propyl and phenyl, R is an end-gap, such as an optionally hydroxy-substituted alkyl group having from 1 to 50 carbon atoms, preferably an alkyl group having from 1 to 5 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, p is an integer in the range of from about 1 to about 2000, preferably from about 1 to about 500, q is an integer in the range of from about 1 to about 1000, preferably from about 1 to about 500.
In preferred embodiments the polyorganosiloxane is selected from polymers having the following general structure:
(CH3)3Si - 0 Si - Si — O \- Si(CH3)3
RΛ wherein Ri , R2, R3, R4, p and q are as defined above.
As defined herein, p and q reflect the number of Si-O linkages in the polymer chain and R\ and R2 and R3 and R4 may vary going from one monomer unit to the next. For example, suitable polyorganosiloxane polymers for use herein include methyl vinyl dimethicone, methyl vinyl diphenyl dimethicone and methyl vinyl phenyl methyl diphenyl dimethicone.
In order to achieve crosslinking between the polyorganosiloxane polymer and the crosslinking agent, an (-Si-H) group must crosslink with a -Si-(CH2)nCH=CH2 group, so that for any specific crosslink, the group R2 must be different in the polyorganosiloxane polymer and the crosslinking agent. For example, for any specific crosslink, when R2 is - (CH2)n H=CH2 in the polyorganosiloxane polymer, R2 must be H in the crosslinking agent, and vice versa. However, there can be mixtures of R2 for each of the polyorganosiloxane polymer and crosslinking agent. In preferred embodiments, the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer having the general formula:
CH-- C6H5 CH3
I
(CH3)3Si — O -[ Si — O —Si — O Si — o- Si(CH3)3 CH3 I
C6H5 R-y
wherein R2 is selected from -CH=CH2 or H, preferably -CH=CH2, and wherein 1 is an integer in the range of from about 1 to about 1000, preferably from about 1 to about 500, m is an integer in the range from 0 to about 1000, preferably from about 0 to about 500, and n is an integer in the range of from about 1 to about 1000, preferably from about 1 to about 100.
In particularly preferred embodiments the polyorganosiloxane polymer is selected from an alkylarylpolysiloxane polymer having the general formula:
CH-, C6H5 CH3
I
(CH3)3Si — o - Si Si — O Si — o - Si(CH3)3 f
CH-, C6H5 CH=CH2
wherein 1, m and n are as defined above. In preferred embodiments m is in the range of from about 1 to about 1000, preferably from about 200 to about 800. 10 The first silicone-containing phase also comprises a silicone oil. Any straight chain, branched and cyclic silicones suitable for use in skin care compositions can be used herein. The silicone oils can be volatile or non-volatile. Suitable silicone oils for use herein include silicone oils having a weight average molecular weight of about 100,000 or less, preferably about 50,000 or less. Preferably the silicone oil is selected from silicone oils having a weight average molecular weight in the range from about 100 to about 50,000, and preferably from about 200 to about 40,000. In preferred embodiments, the silicone oil is selected from dimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and phenyl methicone, and mixtures thereof, most preferably phenyl methicone.
Suitable materials for use in the first silicone-containing phase are available under the tradename KSG supplied by Shinetsu Chemical Co., Ltd, for example KSG-15, KSG-16, KSG-17, KSG-18. These materials contain a combination of crosslinked polyorganosiloxane polymer and silicone oil. Particularly preferred for use herein, especially in combination with the organic amphiphilic emulsifier material, is KSG-18. The assigned INCI names for KSG-15, KSG-16, KSG-17 and KSG-18 are Cyclomethicone DimethiconeNinyl Dimethicone Crosspolymer, Dimethicone DimethiconeNinyl Dimethicone Crosspolymer, Cyclomethicone Dimethicone/Vinyl Dimethicone Crosspolymer and Phenyl Trimethicone Dimethicone/Phenyl Vinyl Dimethicone Crosspolymer, respectively.
Compositions herein preferably also comprise a second non-crosslinked silicone- containing phase. In preferred embodiments the second silicone-containing phase is present in a level of from about 0.1% to about 20%, especially from about 0.1 % to about 10% by weight of composition. Suitable silicone fluids for use in the second silicone-containing phase herein include water-insoluble silicones inclusive of non- volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, and mixtures thereof.
In preferred embodiments the second silicone-containing phase comprises a silicone gum or a mixture of silicones including the silicone gum. As used herein, the term "silicone gum" means high molecular weight silicone-based fluids having a mass-average molecular weight in excess of about 200,000 and preferably from about 200,000 to about 400,000. Silicone oils generally have a molecular weight of less than about 200,000. Typically, silicone gums have a viscosity at 25°C in excess of about 1,000,000 mm^.s'l. The silicone gums include dimethicones as described by Petrarch and others including 11 US-A-4, 152,416, May 1, 1979 to Spitzer, et al, and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. Silicone gums for use herein include any silicone gum suitable for use in a skin care composition. Suitable silicone gums for use herein are silicone gums having a molecular weight of from about 200,000 to about 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof.
Dimethiconol-based silicones suitable for use herein can have the chemical structure HO(CH3)2SiO[(CH3)2SiO]n(CH3)2SiOH where n is from about 2000 to about 40,000, preferably from about 3000 to about 30,000.
Exemplary fluorosilicones useful herein can have a molecular weight of from about 200,000 to about 300,000, preferably from about 240,000 to about 260,000 and most preferably about 250,000. Specific examples of silicone gums include polydimethylsiloxane, (polydimethyl- siloxane)(methylvinylsiloxane) copolymer, poly(dimethylsiloxane)(diphenyl)(methyl- vinylsiloxane) copolymer and mixtures thereof.
The silicone gum used herein can be incorporated into the composition as part of a mixture of silicones. When the silicone gum is incorporated as part of a mixture of silicones, the silicone gum preferably constitutes from about 5% to about 40%, especially from about 10% to 20% by weight of the silicone mixture. The silicone or silicone mixture preferably constitutes from about 0.1 % to about 20%>, more preferably from about 0.1% to about 15%), and especially from about 0.1 % to about 10% by weight of composition. Suitable silicone gum-based silicone mixtures for use in the second silicone-containing phase of the compositions herein include mixtures consisting essentially of:
(i) a silicone having a molecular weight of from about 200,000 to about 4,000,000 selected from dimethiconol, fluorosilicone and dimethicone and mixtures thereof; and (ii) a silicone-based carrier having a viscosity from about 0.65 mm^.s'l to about lOO mm^.s"!, 12 wherein the ratio of i) to ii) is from about 10:90 to about 20:80 and wherein said silicone gum-based component has a final viscosity of from about 500 mm^.s"! to about 10,000 mm2.--1.
The silicone-based carriers suitable for use herein include certain silicone fluids. The silicone fluid can be either a polyalkyl siloxane, a polyaryl siloxane, a polyalkylaryl siloxane or a polyether siloxane copolymer. Mixtures of these fluids can also be used and are preferred in certain executions.
The polyalkyl siloxane fluids that can be used include, for example, polydimethylsiloxanes with viscosities ranging from about 0.65 to 600,000 mm^.s'l, preferably from about 0.65 to about 10,000 mm^.s^ at 25°C. These siloxanes are available, for example, from the General Electric Company as the Niscasil (RTM) series and from Dow Corning as the Dow Corning 200 series. The essentially non-volatile poly- alkylarylsiloxane fluids that can be used include, for example, polymethylphenyl- siloxanes, having viscosities of about 0.65 to 30,000 mm^.s^ at 25°C. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid. Also suitable for use herein are certain volatile cyclic polydimethylsiloxanes having a ring structure incorporating from about 3 to about 7 (CH3)2SiO moieties.
The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 29, 1970. Preferably the viscosity of the silicone blend constituting the second fluid phase ranges from about 500 mm^.s^ to about 100,000 mm^.s"!,. preferably from about 1000 rnmAs"! to about 10,000 nim^.s" 1.
An especially preferred silicone-gum based component for use in the compositions herein is a dimethiconol gum having a molecular weight of from about 200,000 to about 4,000,000 along with a silicone carrier with a viscosity of about 0.65 to 100 mm^.s"! . An example of this silicone component is Dow Corning Q2-1403 (85% 5 mm^.s"! Dimethicone Fluid/15% Dimethiconol) and Dow Corning Q2-1401 available from Dow Corning. Another class of silicone suitable for use in the second silicone-containing phase herein include polydiorganosiloxane-polyoxyalkylene copolymers containing at least one poly- diorganosiloxane segment and at least one polyoxyalkylene segment, said polydiorgano- siloxane segment consisting essentially of RbSiO(4_b)/2 s^oxane units wherein b has a value of from about 0 to about 3, inclusive, there being an average value of approximately 13 2 R radicals per silicon for all siloxane units in the copolymer, and R denotes a radical selected from methyl, ethyl, vinyl, phenyl and a divalent radical bonding said polyoxyalkylene segment to the polydiorganosiloxane segment, at least about 95% of all R radicals being methyl; and said polyoxyalkylene segment having an average molecular weight of at least about 1000 and consisting of from about 0 to about 50 mol percent polyoxypropylene units and from about 50 to about 100 mol percent polyoxyethylene units, at least one terminal portion of said polyoxyalkylene segment being bonded to said polydiorganosiloxane segment, any terminal portion of said polyoxyalkylene segment not bonded to said polydiorganosiloxane segment being satisfied by a terminating radical; the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in said copolymer having a value of from about 2 to about 8. Such polymers are described in US-A-4,268,499.
Preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general formula:
CH- CH- CH- CH-
H3C - Si -o- (si o) (Si O) -si CH- y
CH- CH- 3H6 CH-
O ( C2H4°> a < C3H60> bR wherein x and y are selected such that the weight ratio of polydiorgano-siloxane segments to polyoxalkalkylene segments is from about 2 to about 8, the mol ratio of a:(a+b) is from about 0.5 to about 1, and R is a chain terminating group, especially selected from hydrogen; hydroxyl; alkyl, such as methyl, ethyl, propyl, butyl, benzyl; aryl, such as phenyl; alkoxy such as methoxy, ethoxy, propoxy, butoxy; benzyloxy; aryloxy, such as phenoxy; alkenyloxy, such as vinyloxy and allyloxy; acyloxy, such as acetoxy, acryloxy and propionoxy and amino, such as dimethylamino.
The number of and average molecular weights of the segments in the copolymer are such that the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in the copolymer is preferably from about 2.5 to about 4.0.
Suitable copolymers are available commercially under the tradenames Belsil (RTM) from Wacker-Chemie GmbH, Geschaftsbereich S, Postfach D-8000 Munich 22 and Abil (RTM) from Th. Goldschmidt Ltd., Tego House, Victoria Road, Ruislip, Middlesex, HA4 14 OYL, for example Belsil (RTM) 6031 and Abil (RTM) B88183. A particularly preferred copolymer for use herein includes Dow Corning DC3225C which has the CTFA designation Dimethicone/Dimethicone copolyol.
In preferred embodiments, a third oil phase is present in an amount of from about 0.1% to about 15%, more preferably from about 1% to about 10% by weight of composition. The third oil phase can be either a separate phase or can form one phase together with either or both of the first and second silicone phases. Preferably, the third oil phase is a separate phase.
The third oil phase preferably comprises a non-silicone organic oil, such as a natural or synthetic oil selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, fatty acids and mixtures thereof, which ingredients are useful for achieving emollient cosmetic properties. The first oil phase component is preferably essentially silicone-free, i.e., it contains no more than about 10%>, preferably no more than about 5%> by weight of silicone-based materials. It will be understood that the oil phase may contain, for example, up to about 25%, preferably up to only about 10% of oil phase soluble emulsifier ingredients. Such ingredients are not to be considered as oil phase components from the viewpoint of determining the oil phase level and required HLB. In preferred embodiments, the overall required HLB of the oil phase is from about 8 to about
12, especially from about 9 to about 11, required HLB being determined by summing the individual required HLB values for each component of the oil phase multiplied by its
W/W percentage in the oil phase (see ICI Literature on HLB system; ICI reference paper ref 51/0010/303/15m., first printed in 1976, revised in 1984 and May 1992).
Suitable first oil phase components for use herein include, for example, optionally hydroxy-substituted Cg-C50 unsaturated fatty acids and esters thereof, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol and cetyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalane, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26 1976), oils consisting of greater than 20% cholesterol esters, lanolin and lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, shea butter, shorea butter, and sunflower seed oil and C1.C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylmalate, diisostearyldimerate and triisostearyltrimerate. Of the above, highly preferred are the mineral oils, petrolatums, unsaturated fatty acids and esters thereof and mixtures thereof. 15
Preferred embodiments herein comprise from about 0.1% to about 10% by weight of an unsaturated fatty acid or ester. Preferred unsaturated fatty acids and esters for use herein are optionally hydroxy substituted Cg-C5Q unsaturated fatty acids and esters, especially esters of ricinoleic acid. The unsaturated fatty acid or ester component is valuable herein in combination with the liquid crystal-forming emulsifier for improving the skin feel and rub-in characteristics of the compositon. Highly preferred in this respect is cetyl ricinoleate.
Amphiphilic Surfactant
A further preferred component of the compositions herein is an organic amphiphilic surfactant which is capable of forming smectic lyotropic crystals in product or when the product is being applied to the skin at ambient or elevated temperatures. Preferably the amphiphilic surfactant is capable of forming liquid crystals at a temperature in the range from about 20°C to about 40°C. Preferably the amphiphilic surfactant is capable of forming smectic lyotropic liquid crystals. Once application of the product to the skin has been completed, liquid crystals may not be identifiable on the skin surface or stratum corneum. The amphiphilic surfactant is preferably present at a level of from about 0.1% to about 20%, preferably from about 0.1% to about 10%, by weight.
The liquid-crystal forming amphiphilic surfactants suitable for use herein contain both hydrophilic and lipophilic groupings and exhibit a marked tendency to adsorb at a surface or interface, i.e. they are surface-active. Amphiphilic surface-active materials for use herein include nonionic (no charge), anionic (negative charge), cationic (positive charge) and amphoteric (both charges) based on whether or not they ionize in aqueous media.
In the literature, liquid crystals are also referred to as anisotropic fluids, a fourth state of matter, surfactant association structure or mesophases. Those terms are often used interchangeably. The term "lyotropic" means a liquid crystalline system containing a polar solvent, such as water. The liquid crystals used herein are preferably lamellar, hexagonal, rod or vesicle structures or mixtures thereof.
The liquid crystalline phase utilized in the compositions of the invention can be identified in various ways. A liquid crystal phase flows under shear and is characterised by a viscosity that is significantly different from the viscosity of its isotropic solution phase. Rigid gels do not flow under shear like liquid crystals. Also, when viewed with a polarized light microscope, liquid crystals show identifiable birefringence, as, for example, planar lamellar birefringence, whereas when isotropic solutions and rigid gels are viewed under polarized light, both show dark fields. Other suitable means for 16 identifying liquid crystals include X-ray diffraction, NMR spectroscopy and transmission electron microscopy.
In general terms, the organic amphiphilic surfactant preferred for use herein can be described as a liquid, semi-solid or waxy water-dispersible material having the formula X- Y where X represents a hydrophilic, especially nonionic moiety and Y represents a lipophilic moiety.
Organic amphiphilic surfactants suitable for use herein include those having a weight average HLB (Hydrophilic Lipophilic Balance) in the range from about 2 to about 12, preferably from about 4 to about 8. Preferred organic amphiphilic surfactants employed herein have a long saturated or unsaturated branched or linear lipophilic chain having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic or alkyl phenyl chains. When the hydrophilic group of the amphiphilic material forming the liquid crystal phase is a nonionic group, a polyoxyethylene, a polyglycerol, a polyol ester, oxyalkylated or not, and, for example, a polyoxyalkylated sorbitol or sugar ester, can be employed. When the hydrophilic group of the amphiphilic surfactant forming the liquid crystal phase is an ionic group, advantageously there can be used, as the hydrophilic group, a phosphatidylcholine residue as found in lecithin.
Hydrophilic moieties suitable for use herein are selected from: (1) ethers of linear, or branched, polyglycerol having the formula R-(Gly)n-OH where n is a whole number between 1 and 6, R is selected from aliphatic, linear or branched, saturated or unsaturated chains of 12 to 30 carbon atoms, the hydrocarbon radicals of lanolin alcohols and the 2-hydroxy alkyl residue of long chain, alpha-diols, and Gly represents a glycerol residue; (2) polyethoxylated fatty alcohols, for example those of the formula R! (C2 H4θ)x OH wherein R is C12-C30 linear or branched alkyl or alkenyl and x averages from about 0 to about 20, preferably from about 0.1 to about 6, more preferably from about 1 to about 4;
(3) polyol mono-, di-,or tri-esters, optionally polyalkoxylated, wherein the polyols are preferably selected from sugars, C2-C6 alkylene glycols, glycerol, polyglycerols, sorbitol, sorbitan, polyethylene glycols and polypropylene glycols and wherein the polyalkoxylated polyol esters contain from about 2 to about 20 preferably from 17 about 2 to about 4 moles of alkylene oxide (especially ethylene oxide) per mole of polyol ester;
(4) natural and synthetic phosphoglycerides, glycolipids and sphingolipids, for example cerebrosides, ceramides and lecithin. Examples of amphiphilic surfactants suitable for use herein include Cg-C3Q alkyl and acyl-containing amphoteric, anionic, cationic and nonionic surfactants as set out below.
Amphoteric
N-alkyl amino acids (e.g., sodium N-alkylaminoacetate); N-lauroylglutamic acid cholesterol ester (e.g., Eldew CL-301 Ajinomoto) Anionic
Acylglutamates (e.g., disodium N-lauroylglutamate); Sarcosinates (e.g., sodium lauryl sarcosinate. Grace, Seppic); Taurates (e.g., sodium lauryl taurate. sodium methyl cocoyl taurate); Carboxylic acids and salts (e.g., potassium oleate; potassium laurate; potassium- 10- undecenoate; potassium 1 l-(p-styryl) - undecanoate);
Ethoxylated carboxylic salts (e.g., sodium carboxy methyl alkyl ethoxylate); Ether carboxylic acids;
Phosphoric acid esters and salts (e.g., lecithin; DEA-oleth-10 phosphate); Acyl isethionates (e.g., sodium 2-lauroyloxyethane sulfonate); Alkane sulfonates (e.g., branched sodium x-alkane sulfonate (x/1); Sulfosuccinates e.g.,
Sodium dibutyl sulfosuccinate,
Sodium di-2-pentyl sulfosuccinate,
Sodium di-2-ethylbutyl sulfosuccinate, Sodium di-hexyl-sulfosuccinate,
Sodium di-2 ethylhexyl sulfosuccinate (AOT),
Sodium di-2-ethyldodecyl sulfosuccinate,
Sodium di-2-ethyloctadecyl sulfosuccinate,
Dioctyl sodium sulfosuccinate, Disodium laureth sulfosuccinate (MacKanate El, Mclntyre Group Ltd.)
Sulfuric acid esters (e.g., sodium 2-ethylhept-6-enyl sulfate; sodium 11-heneicosyl sulfate; sodium 9-heptadecyl sulfate).
Alkyl sulfates (e.g., MEA alkyl sulfate such as MEA-lauryl sulfate) 18 Cationic
Alkyl Imidazolines (e.g., alkyl hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline (supplier Akzo, Finetex and Hoechst));
Ethoxylated Amines (e.g., PEG-n alkylamine, PEG-n alkylamino propylamine, Poloxamine, PEG-cocopolyamine, PEG- 15 tallow amine);
Alkylamines (e.g., dimethyl alkylamine; dihydroxyethyl alkylamine dioleate)
Quaternaries:
Alkylbenzyl dimethylammonium salts (e.g., stearalkonium chloride);
Alkyl betaines (e.g., dodecyl dimethyl ammonio acetate, oleyl betaine); Heterocylic ammonium salts (e.g., alkylethyl morpholinium ethosulfate);
Tetraalkylammonium salts (e.g., dimethyl distearyl quaternary ammonium chloride
(Witco));
Bis-isostearamidopropyl hydroxypropyl diammonium chloride (Schercoquat 21AP from
Scher Chemicals); 1.8-Bis (decyldimethylammonio)-3, 6 dioxaoctane ditosylate
Nonionic Surfactants
Ethoxylated glycerides;
Monoglycerides (e.g., monoolein; monolinolein; monolaurin; 1-dodecanoyl-glycerol monolaurin; 1, 13-docosenoyl-glycerol monoerucin diglyceride fatty acid (e.g., diglycerol monoisostearate Cosmol 41, fractionated. Nisshin
Oil Mills Ltd.);
Polyglyceryl esters (e.g., triglycerol monooleate (Grindsted TS-T122), diglycerol monooleate (Grindsted TST-T101);
Polyhydric alcohol esters and ethers (e.g., sucrose cocoate, cetostearyl glucoside (Montanol, Seppic), β octyl glucofliranoside esters, alkyl glucoside such Cjn-Cio
(Henkel));
Diesters of phosphoric acid (e.g., sodium dioleyl phosphate);
Alkylamido propyl betaine (e.g., cocoamido propyl betaine);
Amide: (e.g., N-(dodecanoylaminoethyl)-2-pyrrolidone); Amide oxide: e.g., 1 , 1 Dihydroperfluorooctyldimethylamine oxide,
Dodecyldimethylamine oxide, 2-Hydroxydodecyldimethylamine oxide, 2-Hydroxydodecyl-bis (2-hydroxyethyl) amine oxide, 2-Hydroxy-4-oxahexadecyldimethylamine oxide, Ethoxylated amides (e.g., PEG-n acylamide); 19
Ammonio phosphates (e.g., didecanoyl lecithin);
Amine (e.g., octylamine);
Ammonio amides e.g.,
N-trimethylammoniodecanamidate, N-trimethylammoniododecanamidate,
Ammonio carboxylates e.g., dodecyldimethylammonioacetate,
6-didodecylmethylammoniohexanoate,
Phosphonic and phosphoric esters and amides e.g., methyl-N-methyl-dodecylphosphonamidate, dimethyl dodecylphosphonate, dodecyl methyl methylphosphonate,
N,N-dimethyl dodecylphosphonic diamide
Ethoxylated alcohols Polyoxyethylene (Cg) e.g., pentaoxyethylene glycol p-n-octylphenyl ether hexaoxyethylene glycol p-n-octylphenyl ether nonaoxyethylene glycol p-n-octylphenyl ether Polyoxyethylene (CJQ) e-g-- pentaoxyethylene glycol p-n-decylphenyl ether, decyl glyceryl ether, 4-oxatetradecan-l, 2-diol, nonaoxyethylene glycol p-n-decylphenyl ether Polyoxyethylene ( Cj 1 ) e.g.,
Tetraoxyethylene glycol undecyl ether Polyoxyethylene (Ci 2) e.g.,
3, 6, 9, 13-tetraoxapentacosan 1, 11-diol,
3, 6, 10-trioradocosan-l, 8-diol,
3, 6, 9, 12, 16-pentaoxaoctacosan 1, 14-diol,
3,6,9,12, 15-pentaoxanonacosan-l, 17-diol, 3 , 7-dioxanonadecan- 1 , 5 -diol,
3, 6, 12, 15, 19-hexaoxahentriacontan-l, 16-diol, pentaoxyethylene glycol dodecyl ether, monaoxyethylene glycol p-n-dodecylphenyl ether, Polyoxyethylene(Ci4) e.g., 3, 6, 9, 12, 16-pentaoxaoctacosan-l, 14-diol,
3, 6, 9, 12,15,19-heraoxatriacontan-l, 17-diol, 20 Sulfone diimines e.g., decyl methyl sulfone diimine Sulfoxides e.g.,
3-decyloxy-2-hydroxypropyl methyl sulfoxide 4-decyloxy-3-hydroxy butyl methyl sulfoxide
Sulfoximines e.g.,
N-methyl dodecyl methyl sulfoximine
Preferred organic amphiphilic surfactants for use herein are nonionic amphiphilic surfactants having a hydrophilic moiety as in (3) above, and a lipophilic selected from long saturated or unsaturated branched chain or linear lipophilic chains having from about 12 to about 30 carbon atoms such as oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric, coconut, stearic or alkyl phenyl chains.
Highly preferred organic amphiphilic surfactants for use herein are selected from polyhydric alcohol esters and ethers. Especially preferred amphiphilic surfactants for use herein are sugar esters and polyalkoxylated sugar esters.
The sugar esters for use in this invention can be classified as hydrocarbyl and alkyl polyoxyalkylene esters of cyclic polyhydroxy saccharides wherein one or more of the hydroxyl groups on the saccharide moiety is substituted with an acyl or polyoxyalkylene group. Hydrocarbyl sugar esters can be prepared in well-known fashion by heating an acid or acid halide with sugar, i.e., by a simple esterification reaction.
The sugars employed in the preparation of the sugar esters include monosaccharides, di- saccharides and oligo-saccharides well known in the art, for example, the dextrorotatory and levorotatory forms of glucose, fructose, mannose, galactose, arabinose and xylose. Typical di-saccharides include maltose, cellibiose, lactose, and trehalose. Typical tri- saccharides include raffinose and gentianose. The di-saccharides are preferred for use herein, especially sucrose.
Sucrose can be esterified at one or more of its eight hydroxyl groups to provide the sucrose esters useful herein. When sucrose is combined with an esterification agent in a 1 : 1 mole ratio, sucrose monoesters are formed; and when the ratio of esterification agent to sucrose is 2:1, the di- ester is formed. Especially preferred are the mono-, di- and tri- acyl sugar esters and mixtures thereof wherein the acyl substituents contain from about 8 to about 24, preferably from about 8 to about 20 carbon atoms and 0,1 or 2 unsaturated moieties. Of the mono-acyl and di-acyl sugar esters, the respective esters of di-saccharide sugars, especially sucrose, wherein the acyl groups contain from about 8 to about 20 21 carbon atoms are especially preferred. Preferred sugar esters herein are sucrose cocoate, sucrose monooctanoate, sucrose monodecanoate, sucrose monolaurate, sucrose monomyristate, sucrose monopalmitate, sucrose monostearate, sucrose monooleate, sucrose monolinoleate, sucrose dioleate, sucrose dipalmitate, sucrose distearate, sucrose dilaurate and sucrose dilinoleate, and mixtures thereof. Sucrose cocoate has been found to be particularly efficacious in the compositions herein. In mixtures of mono-acyl with di-, and tri-acyl sugar esters, the mono- and di-acyl esters preferably comprise at least about 40%, more preferably from about 50% to about 95% by weight of the total sugar ester mixture. Other sugar esters suitable for use in the compositions of this invention are the alkyl polyoxyalkylene sugar esters wherein one hydroxyl group is substituted with a Cg-Cj alkyl group and wherein one or more of the hydroxyl groups on the sugar molecule are replaced by an ester or ether substituent containing the moiety [(CH2)x-O]v wherein x is an integer from 2 to about 4, preferably 2, and wherein y is an integer from about 1 to about 50, preferably 8 to 30 polyoxyalkylene substituents. Especially preferred herein are sugar esters wherein the polyoxyalkylene substituent is a polyoxyethylene substituent containing from about 8 to about 30 polyoxyethylene groups. Such materials wherein sorbitan is the sugar moiety are commercially available under the tradename "Tweens".
Such mixed esters can be prepared by first acylating a sugar at a 1:1 mole ratio with a hydrocarbyl acid halide followed by reaction with the corresponding polyoxyalkylene acid halide or alkylene oxide to provide the desired material. The simple polyoxyalkylene ester of di-saccharides, especially sucrose, wherein the polyoxyalkylene groups contain up to about 20 alkylene oxide moieties are another useful class of sugar esters herein. A preferred sugar ester of this class is sorbitol trioleate ethoxylated with 20 moles of ethylene oxide. Mixtures of sugar esters with other polyol esters, eg. glycerol esters, are also suitable for use herein, for example, Palm Oil Sucroglyceride (Rhone-Poulenc).
As used herein, the term "lecithin" refers to a material which is a phosphatide. Naturally occurring or synthetic phosphatides can be used. Phosphatidylcholine or lecithin is a glycerine esterified with a choline ester of phosphoric acid and two fatty acids, usually a long chain saturated or unsaturated fatty acid having 16-20 carbons and up to 4 double bonds. Other phosphatides capable of forming lamellar or hexagonal liquid crystals can be used in place of the lecithin or in combination with it. These phosphatides are glycerol esters with two fatty acids as in the lecithin, but the choline is replaced by ethanolamine (a cephalin), or serine (-aminopropanoic acid; phosphatidyl serine) or an inositol 22 (phosphatidyl inositol). While the invention herein is exemplified with lecithin, it is understood that these other phosphatides can be used herein.
A variety of lecithins can be used. American Lecithin Company supplies a Nattermann Phospholipid, Phospholipan 80 and Phosal 75. Other lecithins which can be used alone or in combination with these are: Actifla Series, Centrocap series, Central Ca, Centrol series, Centrolene, Centrolex, Centromix, Centrophase and Centrolphil Series from Central Soya; Alcolec and Alcolec 439-C from American Lecithin; Canaspersa from Canada Packers, Lexin K and Natipide from American Lecithin; and L-Clearate, Clearate LV and Clearate WD from the W.A. Cleary Co. Lecithins are supplied dissolved in ethanol, fatty acids, triglycerides and other solvents. They are usually mixtures of lecithins and range from 15% to 50% of the solution as supplied. Both natural and synthetic lecithins can be used. Natural lecithins are derived from oilseeds such as sunflower seeds, soybeans, safflower seeds and cottonseed. The lecithins are separated from the oil during the refining process. The organic amphiphilic surfactant has been found to be especially valuable herein for improving the stability and skin feel of the compositions of the invention. It is preferably incorporated into the composition in an amount of from about 0.1 % to about 20% , preferably from about 0.1% to about 10%>, and more preferably from about 0.1% to about 8% by weight of composition. Highly preferred herein is a fatty acid ester blend based on a mixture of sorbitan or sorbitol fatty acid ester and sucrose fatty acid ester, the fatty acid in each instance being preferably C -C24, more preferably CJO-C20- The preferred fatty acid ester emulsifier from the viewpoint of moisturisation is a blend of sorbitan or sorbitol C\ 6-C20 fattY ac^ ester with sucrose Cιo_Ci6 fatty acid ester, especially sorbitan stearate and sucrose cocoate. This is commercially available from ICI under the trade name Arlatone 2121.
A highly preferred ingredient of the compositions herein is urea which is preferably present in a level of from about 0.1%) to about 20%, more preferably from about 0.5% to about 10% and especially from about 1% to about 5% by weight of composition.
In preferred embodiments, the oil phase and organic amphiphilic surfactant when present are premixed in water at a temperature above the Kraft Point of the organic amphiphilic surfactant (but preferably below about 60°C) to form a liquid crystal/oil in water dispersion prior to addition of the urea. The urea is found to be especially effective herein in combination with the amphiphilic emulsifier surfactant and the polyol fatty acid polyester for providing outstanding skin moisturisation and softening in the context of an 23 oil-in-water skin care emulsion composition. Moreover, it is surprisingly found that the urea is rendered more stable to hydrolytic degradation, thereby allowing an increase in compositional pH.
A wide variety of optional ingredients such as further emollients, non-occlusive moisturizers, humectants, gelling agents, neutralizing agents, perfumes, colouring agents and surfactants, can be added to the skin compositions herein.
The compositions of the present invention can comprise emollient materials selected from compounds of formula:
2 o
//
C — (CH2)χ — C
R3 OR4
wherein R^ is selected from H or CH3, R^, R3 and R4 are independently selected from C1 -C20 straight chain or branched chain alkyl, and x is an integer of from 1-20. Preferred emollients for use herein are described in WO98/22085. Particularly preferred emollients for use herein are isononyl isononanoate, methyl isostearate, isopropyl isostearate, or mixtures thereof. The emollient material is preferably present in the compositions at a level of from about 0.1%) to about 10%, preferably from about 0.1 % to about 5%, especially from about 1% to about 3%> by weight of composition.
The compositions herein can comprise a humectant. Suitable humectants for use herein include sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose derivatives, hexanetriol, glycerine, glycine, hyaluronic acid, arginine, Ajidew (NaPCA), water-soluble polyglycerylmethacrylate lubricants and panthenols. A preferred humectant herein is glycerine (sometimes known as glycerol or glycerin). Glycerine is especially preferred in the compositions of the invention from the viewpoint of boosting moisturisation. Also preferred for use herein is butylene glycol. Particularly preferred from the viewpoint of boosting moisturisation is a combination of glycerine and urea.
In the present compositions, the humectant is preferably present at a level of from about 0.1% to about 20%, more preferably from about 1%> to about 15%>, and especially from about 5%> to about 15% by weight of composition.
Suitable polyglycerylmethacrylate lubricants for use in the compositions of this invention are available under the trademark Lubrajel (RTM) from Guardian Chemical Corporation,
230 Marcus Blvd., Hauppage, N.Y. 11787. In general, Lubrajels can be described as 24 hydrates or clathrates which are formed by the reaction of sodium glycerate with a methacrylic acid polymer. Thereafter, the hydrate or clathrate is stabilized with a small amount of propylene glycol, followed by controlled hydration of the resulting product. Lubrajels are marketed in a number of grades of varying glycerate: polymer ratio and viscosity. Suitable Lubrajels include Lubrajel TW, Lubrajel CG and Lubrajel MS, Lubrajel WA, Lubrajel DV and so-called Lubrajel Oil.
At least part (up to about 5%> by weight of composition) of the humectant can be incorporated in the form of an admixture with a particulate cross-linked hydrophobic acrylate or methacrylate copolymer, itself preferably present in an amount of from about 0.1%) to about 10%, which can be added either to the aqueous or disperse phase. This copolymer is particularly valuable for reducing shine and controlling oil while helping to provide effective moisturization benefits and is described in further detail by WO96/03964, incorporated herein by reference.
The compositions of the invention can also contain a hydrophilic gelling agent at a level preferably from about 0.01%> to about 10%, more preferably from about 0.02% to about 2%o, and especially from about 0.02% to about 0.5%. The gelling agent preferably has a viscosity (1% aqueous solution, 20 C, Brookfield RVT) of at least about 4000 mPa.s, more preferably at least about 10,000 mPa.s and especially at least 50,000 mPa.s.
Suitable hydrophilic gelling agents can generally be described as water-soluble or coUoidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, guar gum, hydroxypropyl guar gum and xanthan gum.
Preferred hydrophilic gelling agents herein, are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a coUoidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00%) of a crosslinking agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 954, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic acid crosslinked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule. A most preferred polymer is Carbopol 954. Also suitable for use herein are hydrophobically-modified cross-linked polymers of acrylic acid having amphipathic properties available under the Trade Name Carbopol 1382, Carbopol 1342 and Pemulen TR-1 (CTFA Designation: Acrylates/ 10-30 25 Alkyl Acrylate Crosspolymer). A combination of the polyalkenyl polyether cross-linked acrylic acid polymer and the hydrophobically modified cross-linked acrylic acid polymer is also suitable and is preferred for use herein. The gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures.
Further useful gelling agents herein, are non-ionic polyacrylamide polymers which may be substituted, branched or unbranched. These polymers are non-ionic water dispersible polymers which can be formed from a variety of monomers including acrylamide and methacrylamide which are unsubstituted or substituted with one or two alkyl groups (preferably CrC5). Preferred are acrylate amides and methacrylate amides in which the amide nitrogen is unsubstituted, or substituted with one or two C,-C5 alkyl groups (preferably: methyl, ethyl or propyl), for example, acrylamide, methacrylamide, N- methacrylamide, N-methylmethacrylamide, N,N-dimethylmethacrylamide and N,N- dimethylacrylamide. These monomers are generally disclosed in US Pat. No. 4,963,348 to Bolich, Jr. et al., issued Oct, 16., 1990, incorporated by reference herein. These copolymers may optionally be formed using conventional neutral crosslinking agents such as dialkenyl compounds. The use of such crosslinking agents for cationic polymers is disclosed in US Pat. No. 4,628,078 to Glover et al. issued Dec. 9, 1986 and US Pat. No. 4,599,379 to Flesher et al. issued Jul. 8, 1986 both of which are incorporated by reference herein. These non-ionic co-polymers have a molecular weight greater than about 1,000,000 preferably greater than about 1,500,000 and range up to about 30,000,000. Preferably as a result of being synthesised by reverse phase emulsion polymerisation, these non-ionic polyacrylamides are predispersed in a water-immiscible solvent such as mineral oil and the like, containing a high HLB surfactant (HLB from about 7 to about 10) which helps to facilitate water dispersibility of the polyacrylamide. Most preferred for use herein is the non-ionic polymer under the CTFA designation: polyacrylamide and isoparaffin and laureth-7, available under the trade name Sepigel 305 from Seppic Corporation. Other polyacrylamide polymers useful herein include multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids. Commercially available examples of these multi-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H, from Lipo Chemicals, Inc., (Patterson, NJ).
Neutralizing agents suitable for use in neutralizing acidic group containing hydrophilic gelling agents herein include sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine. 26 The compositions of the invention are in emulsion form and are preferably formulated so as to have a product viscosity of at least about 4,000 mPa.s and preferably in the range from about 4,000 to about 300,000 mPa.s, more preferably from about 8,000 to about 200,000 mPa.s and especially from about 10,000 to about 100,000 mPa.s and even more especially from about 10,000 to about 50,000 mPa.s (25°C, neat, Brookfield RVT Spindle No. 5).
The compositions of the invention can also contain from about 0.1% to about 10%, preferably from about 1%> to about 5%> of a panthenol moisturizer. The panthenol moisturizer can be selected from D-panthenol ([R]-2,4-dihydroxy-N-[3-hydroxypropyl)]- 3,3-dimethylbutamide), DL-panthenol, calcium pantothenate, royal jelly, panthetine, pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B complex. Highly preferred from the viewpoint of skin care and tack reduction is D- panthenol.
The compositions of the present invention can additionally comprise from about 0.001%> to about 0.5%, preferably from about 0.002% to about 0.05%, more preferably from about 0.005% to about 0.02% by weight of carboxymethylchitin. Chitin is a polysaccharide which is present in the integument of lobsters and crabs and is a mucopolysaccharide having beta (1-4) linkages of N-acetyl-D-glucosamine. Carboxymethylchitin is prepared by treating the purified chitin material with alkali followed by monochloracetic acid. It is sold commercially in the form of a dilute (approximately 0.1% to 0.5% by weight) aqueous solution under the name Chitin Liquid available from A & E Connock Ltd., Fordingbridge, Hampshire, England.
Other optional materials include keratolytic agents/desquamation agents such as salicylic acid; proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives preferably at a level of from about 0.1 %> to about 5%, such as Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, benzyl alcohol, EDTA, Euxyl (RTM) K400, Bromopol (2-bromo-2-nitropropane-l,3-diol) and phenoxypropanol; anti-bacterials such as Irgasan (RTM) and phenoxyethanol (preferably at levels of from 0.1%) to about 5%>); soluble or colloidally-soluble moisturising agents such as hylaronic acid and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in USA-A-4,076,663; vitamins such as vitamin A, vitamin C, vitamin E and vitamin K; alpha and beta hydroxyacids; aloe vera; sphingosines and phytosphingosines, cholesterol; skin whitening agents; N-acetyl cysteine; colouring agents; perfumes and perfume solubilizers and additional surfactants/emulsifiers such as 27 fatty alcohol ethoxylates, ethoxylated polyol fatty acid esters, wherein the polyol can be selected from glycerine, propyleneglycol, ethyleneglycol, sorbitol, sorbitan, polypropyleneglycol, glucose and sucrose. Examples include glyceryl monohydroxy stearate and stearyl alcohol ethoxylated with an average of from 10 to 200 moles of ethyleneoxide per mole of alcohol and PEG-6 caprylic/capric glycerides.
Also useful herein are sunscreening agents. A wide variety of sunscreening agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 5,073,372, to Turner et al, issued December 17, 1991; U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology. Preferred among those sunscreens which are useful in the compositions of the instant invention are those selected from 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p- aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4- isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789, and mixtures thereof.
Still other useful sunscreens are those disclosed in U.S. Patent No. 4,937,370, to Sabatelli, issued June 26, 1990; and U.S. Patent No. 4,999,186, to Sabatelli et al, issued March 12, 1991. The sunscreening agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra. One of the chromophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range. These sunscreening agents provide higher efficacy, broader UN absorption, lower skin penetration and longer lasting efficacy relative to conventional sunscreens. Especially preferred examples of these sunscreens include those selected from 4-Ν,Ν-(2-ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-N,N- (2-ethylhexyl)methylaminobenzoic acid ester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)- methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.
Generally, the sunscreens can comprise from about 0.5% to about 20%> of the compositions useful herein. Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of 28 photoprotection of a sunscreen against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978.
The compositions of the present invention can additionally comprise from about 0.1 %> to about 5%> by weight of aluminium starch octenylsuccinate. Aluminium starch octenylsuccinate is the aluminium salt of the reaction product of octenylsuccinic anhydride with starch and is commercially available under the trade name from Dry Flo National Starch & Chemical Ltd. Dry Flo is useful herein from the viewpoint of skin feel and application characteristics.
Other optional materials herein include pigments which, where water-insoluble, contribute to and are included in the total level of oil phase ingredients. Pigments suitable for use in the compositions of the present invention can be organic and/or inorganic. Also included within the term pigment are materials having a low colour or lustre such as matte finishing agents, and also light scattering agents. Examples of suitable pigments are iron oxides, acyglutamate iron oxides, ultramarine blue, D&C dyes, carmine, and mixtures thereof. Depending upon the type of composition, a mixture of pigments will normally be used. The preferred pigments for use herein from the viewpoint of moisturisation, skin feel, skin appearance and emulsion compatibility are treated pigments. The pigments can be treated with compounds such as amino acids, silicones, lecithin and ester oils.
The compositions herein can also comprise colorants. Especially preferred in this respect is β-carotene which can be used at a level of from 0.00001 to 0.005%. At the higher levels β-carotene is additionally valuable as an anti-oxidant for reducing skin damage by free radicals.
The compositions of the present invention can also comprise a safe and effective amount of a vitamin B3 compound. The compositions of the present invention preferably comprise from about 0.01% to about 50%>, more preferably from about 0.1 %> to about
10%), even more preferably from about 0.5% to about 10%>, and still more preferably from about 1% to about 5%, most preferably from about 2% to about 5%>, of a vitamin B3 compound.
As used herein, "vitamin B3 compound" means a compound having the formula:
Figure imgf000030_0001
29 wherein R is -CONH2 (i.e., niacinamide), -COOH (i.e., nicotinic acid) or -CH2OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing. Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
Suitable esters of nicotinic acid include nicotinic acid esters of C1 -C22- preferably C\- Ci g, more preferably Cj-Cg alcohols. The alcohols are suitably straight-chain or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic), and substituted or unsubstituted. The esters are preferably non-vasodilating. As used herein, "non-vasodilating" means that the ester does not commonly yield a visible flushing response after application to the skin in the subject compositions (the majority of the general population would not experience a visible flushing response, although such compounds may cause vasodilation not visible to the naked eye). Non-vasodilating esters of nicotinic acid include tocopherol nicotinate and inositol hexanicotinate; tocopherol nicotinate is preferred. A more complete description of vitamin B3 compounds is given in WO 98/22085.
Examples of the above vitamin B3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Company
(St. Louis, MO); ICN Biomedicals, Inc. (Irvin, CA) and Aldrich Chemical Company (Milwaukee, WI). One or more vitamin B3 compounds may be used herein. Preferred vitamin B3 compounds -ire niacinamide and tocopherol nicotinate. Niacinamide is more preferred.
Retinoids
In a preferred embodiment, the compositions of the present invention also contain a retinoid. The vitamin B3 compound and retinoid provide unexpected benefits in regulating skin condition, especially in therapeutically regulating signs of skin aging, more especially wrinkles, lines, and pores. Without intending to be bound or otherwise limited by theory, it is believed that the vitamin B3 compound increases the conversion of certain retinoids to trans-retinoic acid, which is believed to be the biologically active form of the retinoid, to provide synergistic regulation of skin condition (namely, increased conversion for retinol, retinol esters, and retinal). In addition, the vitamin B3 compound unexpectedly mitigates redness, inflammation, dermatitis and the like which may otherwise be associated with topical application of retinoid (often referred to, and hereinafter alternatively referred to as "retinoid dermatitis"). Furthermore, the combined vitamin B3 compound and retinoid tend to increase the amount and activity of 30 thioredoxin, which tends to increase collagen expression levels via the protein AP-1. Therefore, the present invention enables reduced active levels, and therefore reduced potential for retinoid dermatitis, while retaining significant positive skin conditioning benefits. In addition, higher levels of retinoid may still be used to obtain greater skin conditioning efficacy, without undesirable retinoid dermatitis occurring.
As used herein, "retinoid" includes all natural and/or synthetic analogs of Vitamin A or retinol-like compounds which possess the biological activity of Vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds. The retinoid is preferably retinol, retinol esters (e.g., C2 - C22 alkyl esters of retinol, including retinyl palmitate, retinyl acetate, retinyl proprionate), retinal, and/or retinoic acid (including all- trans retinoic acid and/or 13-cis-retinoic acid), more preferably retinoids other than retinoic acid. These compounds are well known in the art and are commercially available from a number of sources, e.g., Sigma Chemical Company (St. Louis, MO), and Boerhinger Mannheim (Indianapolis, IN). Preferred retinoids are retinol, retinyl palmitate, retinyl acetate, retinyl proprionate, retinal and combinations thereof. More preferred are retinol and retinyl palmitate. The retinoid may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources.
The compositions preferably contain from or about 0.005% to or about 2%>, more preferably 0.01% to or about 2%, retinoid. Retinol is most preferably used in an amount of from or about 0.01% to or about 0.15%; retinol esters are most preferably used in an amount of from or about 0.01% to or about 2% (e.g., about 1%).
The pH of the compositions is preferably from about 4 to about 9, more preferably from about 6 to about 8.0. The balance of the composition is water or an aqueous carrier suitable for topical application to the skin. The water content of the compositions herein is generally from about 30% to about 98.89%>, preferably from about 50% to about 95% and especially from about 60% to about 90%> by weight.
The compositions of the invention are preferably in the form of a moisturising cream or lotion, which can be applied to the skin as a leave-on product. The invention is illustrated by the following examples: Examples I to IV
Oil in water emulsions are prepared from the following ingredients using conventional formulating techniques. Ingredient Ex I Ex II Ex III Ex IV 31
(% w/w) (% w/w) (% w/w) (% w/w)
Cetyl Alcohol 0.72 0.17 » 0.72 0.72
Stearyl Alcohol 0.48 0.4- > 0.48 0.48
Stearic acid 0.1 0.1 0.1 0.1
PEG- 100 Stearate 0.1 0.1 0.1 0.1
Arlatone 21211 1.0 1.0 1.0 1.0
Isohexadecane 1.33 1.33 1.33 1.5
Silicone Q214032 2.0 2.0 2.0 2.0
Fatty acid ester of sugar3 0.67 0.67 0.67 1.5
Glycerin 7.0 7.0 7.0 9.0
Urea 2.0 0 0 2.0
Carbopol 9544 0.68 0.5 0.5 0.68
Carbopol 13825 0.1 0.1 0.1 0.1
TiO2 0.75 0.75 0.75 0.15
D-Panthenol 0 0 0.5 0
Tocopherol Acetate 0 0 0.5 0
Niacinamide 2.0 2.0 2.0 0
Retinol 0 0 0.04 0
BHT 0 0 0.05 0
Glydant Plus 0.1 0.1 0.1 0.1
EDTA 0.1 0.1 0.1 0.1
NaOH 0.1 0.1 0.1 0.1
NaCl 0.02 0.02 0.02 0.02
Distilled water qs lOO qs lOO qs lOO qs lOO
Examples V to X
Ingredient Ex V Ex VI Ex VII Ex VIII Ex IX Ex X
(% w/w) (%w/w) (% w/w) (% w/w) (% w/w) (% w/w)
Deionised Water to 100 to 100 to 100 to 100 to 100 to 100
Glycerine 9.00 5.00 8.00 6.50 7.50 9.00
Urea 1.40 1.80 2.20 1.98 1.60 2.00
Kronos (Ti02) 0.15 0.15 0.15 0.15 0.15 0.15
Arlatone 212l' 0.0 0.50 1.50 0.60 0.50 1.00
Carbopol 13825 0.05 0.20 0.08 0.12 0.05 0.09
Carbopol 9544 0.70 0.63 0.68 0.60 0.70 0.61
Figure imgf000033_0001
NaOH (40% Soln) 0.80 1.00 0.80 0.85 0.75 0.90 32
Hydrofol Acid 0.08 0.09 0.10 0.12 0.13 0.10
Myrj 59? 0.09 0.10 0.09 0.12 0.10 0.10
Stearyl Alcohol 0.50 0.38 0.40 0.32 0.48 0.48
Cetyl Alcohol 1.20 0.85 1.00 0.72 0.72 0.72
Propyl Paraben 0.29 0.25 0.15 0.15 0.18 0.00
Finsolv TN 0.00 1.2 0.00 0.5 0.5 0.00
SEFA Cottonate9 0.2 1.50 1.50 0.75 1.80 1.50
Isohexadecane 1.33 0.2 0.75 2.25 1.00 1.00
Methyl Paraben 0.20 0.20 0.20 0.20 0.20 0.00
Phenoxytol 0.40 0.40 0.40 0.40 0.40 0.00
EDTA 0.10 0.10 0.10 0.10 0.10 0.10
DC Q2-140310 2.00 1.60 1.60 1.80 1.50 3.00
NaCl 0.02 0.02 0.02 0.02 0.02 0.00
Isononyl Isononanoate 0.00 0.00 0.00 0.00 0.00 1.50
Glydant Plus 0.00 0.00 0.00 0.00 0.00 0.10
Examples XI to XII
Ingredients Ex XI Ex XII
(%w/w) (%w/w)
Sepigel 305 1.0 1.0
Xanthan Gum 1400 CP1 0.28 0.28
Glycerine 7.0 7.0
Urea 2.0 2.0
PEG-30 2.4 2.4
Glyceryl Monosterate 1.5 1.5
Propylene Glycol Monosterate 1.5 1.5
Cetearyl Alcohol 1.0 1.0
Polyglyceryl-2-Sesquilsosterate 0.8 0.8
Isohexadecane 12.0 4.0
SEFA Cottonate9 2.0 2.0
Lanolin Oil 4.0 8.0
DC 345 1.0 1.0
Dimethicone 350 1.0 1.0
Kronos (TiO2)6 - 0.5 β-carotene 0.0015 0.0015
Figure imgf000034_0001
Tetrasodium EDTA 0.1 0.1 33
Methylparaben 0.3 0.3 Phenoxyethanol 0.4 0.4 Propylparaben 0.1 0.1 Distilled water
Figure imgf000035_0001
qs lOO qs lOO
1. Supplied by ICI Surfactants, PO Box 90, Wilton Centre, Middlesborough, Cleveland, TS6 8JE
2. Supplied by Dow Corning, Kings Court, 185 Kinds Rd, Reading, Berks, RG1 4EX 3. A C1-C30 monoester or polyester of sugars and one or more carboxylic acid moieties as described herein, preferably a sucrose polyester in which the degree of esterification is 7-8, and in which the fatty acid moieties are C18 mono- and/or di- unsaturated and behenic, in a molar ratio of unsaturates:behenic of 1 :7 to 3:5, more preferably the octaester of sucrose in which there are about 7 behenic fatty acid moieties and about 1 oleic acid moiety in the molecule, e.g. sucrose ester of cottonseed oil fatty acids, e.g. SEFA Cottonate.
4. B.F. Goodrich, 9911 Brecksville Road, Brecksville, OH 44141, USA
5. B.F. Goodrich, 9911 Brecksville Road, Brecksville, OH 44141, USA
6. Supplied by Kronos, 4 Place Ville Marie # 500, Montreal, Quebec, Canada 7. PEG 100 Stearate supplied by ICI, PO Box 90, Wilton Centre, Middlesborough, Cleveland, TS6 8JE.
8. C12-C15 Alkyl Benzoate Ester supplied by Finetex Inc., PO Box 216, Elmwood Park, New Jersey 07407, USA.
9. Supplied by Procter & Gamble, Winton Hill Technical Centre, Cincinnati, OH, USA.
10. Supplied by Dow Corning, Kings Court, 185 Kinds Rd, Reading, Berks, RG1 4EX.
The compositions as set out in examples I to X are made as follows:
A first premix of thickening agents, methyl paraben when present, glycerine/TiO2 premix, Arlatone 2121 when present, and other water soluble ingredients apart from urea, is prepared by admixing in water and heating to about 80°C. A second premix of the oil phase ingredients including the emulsifiers, oil-soluble preservatives, other than silicone gum is prepared by mixing and heating and is added to the aqueous premix.
The silicone gum is added to the resulting mixture which is then cooled to about 60°C. The NaOH solution, Glydant Plus when present, EDTA, silicone gum, and then urea solution (lg dissolved in 1ml of water) are then added to the resulting oil-in- water 34 emulsion and the mixture is cooled before adding minor ingredients. The composition is ready for packaging.
The compositions as set out in examples XI and XII are made as follows:
A first premix of thickening agents (except Sepigel when present), methyl paraben, glycerine/TiO2 premix, Arlatone 2121 when present, and other water soluble ingredients apart from urea, is prepared by admixing in water and heating to about 80°C. A second premix of the oil phase ingredients including the emulsifiers, oil-soluble preservatives, other than silicone gum and cyclomethicone is prepared by mixing and heating and is added to the aqueous premix and the mixture homogenised. The silicone gum is added to the resulting mixture which is then cooled to about 60°C. When present, Sepigel and cyclomethicone are added between 60° and 55°C to the resulting oil-in- water emulsion. Afterwards, EDTA and urea solution (lg dissolved in 1ml of water) are added and the mixture is neutralised with NaOH when necessary. The mixture is further cooled under stirring before adding minor ingredients. The composition is ready for packaging.
The compositions display improved skin feel, skin smoothness, skin softness and skin care characteristics together with reduced greasiness and excellent rub-in and fast absorption characteristics.

Claims

35 CLAIMS
1. A composition suitable for topical application to the skin or hair comprising:
(a) a liquid, polyol carboxylic acid ester having a polyol moiety and at least 4 carboxylic acid moieties, wherein the polyol moiety is selected from sugars and sugar alcohols containing from about 4 to about 8 hydroxyl groups, and wherein each carboxylic acid moiety has from about 8 to about 22 carbon atoms, and wherein said liquid polyol carboxylic acid ester has a complete melting point of less than about 30┬░C; and (b) a branched chain aliphatic hydrocarbon having a weight average molecular weight of from about 100 to about 15,000.
2. A composition according to Claim 1 wherein the branched chain hydrocarbon has an average molecular weight of from about 200 to about 1000.
3. A composition according to Claim 1 or 2 wherein the branched chain hydrocarbon is selected from isododecane, isohexadecane, isoeicosane, isooctahexacontane, iso- hexapentacontahectane, isopentacontaoctactane, and mixture thereof.
4. A composition according to any of Claims 1 to 3 wherein said branched chain hydrocarbon is isohexadecane.
5. A composition according to any of Claims 1 to 4 comprising from about 0.1% to about 15%, preferably from about 0.1% to about 10%>, more preferably from about
0.1%) to about 5% by weight of the branched chain aliphatic hydrocarbon.
6. A composition according to any of Claims 1 to 5 wherein said liquid polyol carboxylic acid ester contains no more than about 2 free hydroxyl groups.
7. A composition according to any of Claims 1 to 6 wherein said carboxylic acid moieties contain from about 14 to about 18 carbon atoms.
8. A composition according to any of Claims 1 to 7 wherein said polyol moiety is selected from erythritol, xylitol, sorbitol, glucose, sucrose, and mixtures thereof.
9. A composition according to any of Claims 1 to 8 wherein said polyol moiety is sucrose.
10. A composition according to any of Claims 1 to 9 wherein said liquid polyol carboxylic acid ester has a complete melting point below about 27.5┬░C. 36
11. A composition according to any of Claims 1 to 10 wherein said liquid polyol carboxylic acid polyester has a complete melting point below about 25┬░C.
12. A composition according to any of Claims 1 to 11 wherein said liquid carboxylic acid polyol ester is selected from sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, and mixtures thereof.
13. A composition according to any of Claims 1 to 12 comprising from about 0.1% to about 15%), preferably from about 0.1 %> to about 10%, more preferably from about 0.1%) to about 5% by weight of the liquid, polyol carboxylic acid ester.
14. A composition according to any of Claims 1 to 13 wherein the weight ratio of said liquid carboxylic acid polyol ester to the branched chain aliphatic hydrocarbon is in the range from about 5:1 to 1 :5, preferably from about 3 : 1 to about 1 :3.
15. A composition according to any of Claims 1 to 14 wherein the composition is in the form of an emulsion, preferably an oil-in-water emulsion.
16. A composition according to Claim 15 additionally comprising a silicone- containing phase.
17. A composition according to Claim to 16 wherein the silicone-containing phase comprises a silicone or mixture of silicones in a level of from 0.1% to 20% by weight, preferably from about 0.1% to about 15%, more preferably from 0.1% to about 10% by weight of composition, and wherein the silicone or silicone mixture comprises a silicone gum having a molecular weight of from about 200,000 to about 4,000,000.
18. A composition according to any of the preceding claims additionally containing an oil component comprising 20% or greater of cholesterol esters.
19. A composition according to Claim 18 wherein the oil component is selected from lanolin or lanolin derivatives.
20. A cosmetic method of treatment of the skin comprising applying to the skin a composition according to any of Claims 1 to 19.
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JP2003113045A (en) * 2001-09-28 2003-04-18 Toho Chem Ind Co Ltd Composition for hair
JP2004529949A (en) * 2001-05-15 2004-09-30 ピーアンドジー−クレイロール・インコーポレイテッド Two-part aqueous composition for oxidative coloring of hair
US7252830B2 (en) 2003-10-06 2007-08-07 The Gillette Company Moisturizing compositions

Families Citing this family (9)

* Cited by examiner, † Cited by third party
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AU5771200A (en) * 1999-06-28 2001-01-31 Procter & Gamble Company, The Cosmetic compositions
WO2001000170A1 (en) * 1999-06-28 2001-01-04 The Procter & Gamble Company Cosmetic compositions
JP2003104827A (en) * 2001-09-28 2003-04-09 Kose Corp Cosmetic
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WO2009107062A2 (en) 2008-02-25 2009-09-03 The Procter & Gamble Company Hair care compositions comprising sucrose polyesters
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2196785A1 (en) * 1972-08-21 1974-03-22 Henkel & Cie Gmbh
EP0547897A2 (en) * 1991-12-19 1993-06-23 Unilever Plc Cosmetic composition
WO1996016636A1 (en) * 1994-11-28 1996-06-06 The Procter & Gamble Company Topical skin care compositions containing thickened polyol carboxylic acid esters as skin conditioning agents
WO1997007782A1 (en) * 1995-08-29 1997-03-06 The Procter & Gamble Company High lather styling shampoos
EP0835651A2 (en) * 1996-10-11 1998-04-15 L'oreal Oil in water cosmetic emulsion with high electrolyte content
EP0839522A1 (en) * 1996-11-04 1998-05-06 L'oreal Cleaning composition in the form of a transparent washable gel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2196785A1 (en) * 1972-08-21 1974-03-22 Henkel & Cie Gmbh
EP0547897A2 (en) * 1991-12-19 1993-06-23 Unilever Plc Cosmetic composition
WO1996016636A1 (en) * 1994-11-28 1996-06-06 The Procter & Gamble Company Topical skin care compositions containing thickened polyol carboxylic acid esters as skin conditioning agents
WO1997007782A1 (en) * 1995-08-29 1997-03-06 The Procter & Gamble Company High lather styling shampoos
EP0835651A2 (en) * 1996-10-11 1998-04-15 L'oreal Oil in water cosmetic emulsion with high electrolyte content
EP0839522A1 (en) * 1996-11-04 1998-05-06 L'oreal Cleaning composition in the form of a transparent washable gel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004529949A (en) * 2001-05-15 2004-09-30 ピーアンドジー−クレイロール・インコーポレイテッド Two-part aqueous composition for oxidative coloring of hair
JP2003113045A (en) * 2001-09-28 2003-04-18 Toho Chem Ind Co Ltd Composition for hair
JP4648600B2 (en) * 2001-09-28 2011-03-09 東邦化学工業株式会社 Hair composition
US7252830B2 (en) 2003-10-06 2007-08-07 The Gillette Company Moisturizing compositions

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JP2003517996A (en) 2003-06-03
WO1999038485A1 (en) 1999-08-05
KR20010024893A (en) 2001-03-26
AU9800298A (en) 1999-08-16
EP1051149A1 (en) 2000-11-15
CN1286627A (en) 2001-03-07
CA2319161A1 (en) 1999-08-05
AU6256298A (en) 1999-08-16
BR9814929A (en) 2000-10-17

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