CA2258781A1 - Cosmetic compositions - Google Patents

Abstract

A cosmetic composition in the form of a water-in-oil emulsion comprising: (a) continuous oil phase; (b) discontinuous aqueous phase; and (c) willow bark extract. The compositions of the invention provide regulation of the oily and/or shiny appearance of the skin.

Description

CA 022~8781 1998-12-18 W 097/4937S PCTrUS97/09700 COSMETIC COMPOSITIONS

Field of the Invention The present invention relates to cosmetic compositions and more particularly, to pigmented foundation make-up compositions ànd concealers.

Backaround of the Invention A foundation composition can be applied to the face and other parts of the body to even skin tone and texture and to hide pores, imperfections, fine lines and the like. A foundation composition is also applied to moisturize the skin, to balance the oil level of the skin and to provide protection againstthe adverse effects of sunlight, wind and the harsh environment. Make-up compositions are generally available in the form of liquid or cream suspensions, emulsions, gels, pressed powders or anhydrous oil and wax compositions. Such cosmetic make-up compositions are described in US-A-3,444,291, US-A~,486,405, US-A4,804,532, US-A-3,978,207, US-A-4,659,562, US-A-5,143,722 and Nakamura et al., Preprints of the XlVth l.F.S.C.C. Congress, Barcelona, 1986, Vol. I, 51~3 (1986).

Founddlions in the form of water-in-oil emulsions are well known and provide good coverage and good skin feel, wear and appearance. It is also important for water-in-oil foundation compositions to provide oil and shine control which effects the appearance of the skin. Persons with an oily skin type or combined skin type typically manifest an oily and/or shiny a~",earance between cleansings. The oily or shiny appearance generally inaeases as the day progresses following cleansing of the skin. In order to avoid such appearance, individuals must throughout the day either cleanse the skin, blot the skin, apply oil absorbing powders to the skin, or take some ~ other measure to minimize the appearance of oil or shine.

An oily or combination skin type presents a particular challenge to the formulation of make-up intended for facial use, including foundations. This is bec~se as oil accummulates on the facial skin of such individuals, oil breakthrough occurs (the oil is not masked by the make-up such that an oily CA 022~8781 1998-12-18 W O 97149375 PCTrUS97/09700 or shiny skin appearance results), and the covarage and wear resistance of the make-up tends to be reduced. Attempts have been made to provide foundations which balance the oil level of the skin. Clays, talcs, silicas, starches, polymers, and other similar materials have been suggested for use in cosmetic compositions for absorbing sebum and controlling oily skin.
However, many compositions known in the art either provide benefits that are very limited, in terms of degree of efficacy, duration of efficacy, or both.Therefore, it would be desirable to provide a foundation composition having even greater oil/shine control and improved skin appearance.

Hungarian Patent Specification No. 190 391 discloses cosmetic compositions containing mixtures of plant extracts including condensed water-alcohol essence of willow tree bark. The cosmetic compositions disclosed can be used to achieve various benefits including soothing sensitive skin, pore-tightening, skin regeneration, improving blood circulation, and providing antiseptic and anti-perspirant activity. The examples given are oil-in-water emulsions.

It has now surprisingly been found that by incorporating willow bark extract into a water-in-oil emulsion a cosmetic composition is provided which exhibits improved oil and~or sebum control and improved skin appearance.

Willow bark is known to be rich in salicins and tannins and has been reported to have analgesic, antiseptic and anti-inflammatory properties.
Therefore the compositions of the present invention also provide anti-bacterial and anti-ir,na",n,atory activity.

It is accordingly a primary object of the present invention to provide a cosmetic composition having improved oil and/or shine control and improved appearance when applied to the skin.

It is a further object of the present invention to provide a cosmetic composition having anti-bacterial and anti-inflammatory activity.

CA 022~8781 1998-12-18 WO 97/49375 PCT~US97/09700 SummarY of the Invention In accordance with one aspect of the present invention, there is provided a ~ cosmetic composition in the form of a water-in-oil emulsion comprising:

la) continuous oil phase and;

(b) discontinùous aqùeous phase; and (c) willow bark extract.

The cosmetic compositions of the present invention provide improved oil and/or shine and/or sebum/skin oil control and improved skin appearance when applied to the skin. In addition, the compositions may also provide anti-inflammatory and anti-bacterial efficacy.

Accor~ing to a second aspect of the present invention there is also provided the use of such compositions for regulating the oily and/or shiny appearance of skin, especially facial skin.

According to a further aspect of the present invention there is provided the use of willow bark extract for regulating the oily and/or shiny appearance of skin.

AccorcJ;ng to a further aspect of the present invention there is provided the use of willow bark extract for regul~ting the sebum or skin oil of facial skin.

All levels and ratios are by weight of total composition, unless otherwise in~ e~ Chain lengths and degrees of alkoxylation are also specified on a weight average basis.

Detailed DescriPtion of the Invention The cosmetic composition according to the present invention comprises a continuous oil phase, a discontinuous aqueous phase and willow bark extract. The composition is in the form of a water-in-oil emulsion.

. .

CA 022~8781 1998-12-18 W O 97/49375 PCT~US97109700 Willow Bark Extract The willow tree has brown ridged bark which is rich in salicins and tannins.
It has been reported to have various properties including analgesic, antiseptic and anti-infla~ l,alory activity. Willowbark extract can prepared by solvent extraction of freshly collected bark. Various solvents can be used in the extraction process including water, propylene glycol and ethanol. The extract is conce,1trated by vacuum distillation. Willowbark extract is commercially available from Brooks Industries as both free Willowbark extract and Brookosome Willowbark. The Willowbark extract is preferably present in the internal aqueous phase of the water-in-oil emulsion of the present invention. It is particularly valuable in the compositions herein for providing improved oillshine control and improved skin appearance.

The willow bark extract is present in the compositions of the present invention in an amount that is safe and effective for regulating the oil/shiny appearance of the skin and preferably at a level of from about 0.1% to about 20%, more preferably from about 1% to about 15%, and especially from about 1% to about 10% by weight of composition.

As used herein, "safe and effective amount" means a sufficient amount of a compound, composition or other material described by this phrase to significantly induce a positive modification in the condition being treated, butlow enough to avoid undue side effects (e.g., significant skin irritation or sensiti~tion), within the scope of sound judgement of the skilled person.
The safe and effective amount of the compound, composition or other material inay vary with the particular skin being treated, the age and physical condition of the biological subject being treated, the severity of the condition, the duration of l,ea~",en~, the nature of concurrent therapy, the specific compound, composition, or other material employed, the particular cosmetically acceptable topical carrier utilized, and the factors within the knowledge and expertise of the skilled person.

As used herein, "regulating the oily and/or shiny appearance of skin" means preventing, retarding and/or arresting the appearance of oil and/or shine on CA 022~8781 1998-12-18 W O 97/49375 PCT~US97109700 the skin. By regulating the oily and/or shiny appearance of the skin, one or more of the following benefits are achieved: there is a noticeable decrease in the visible oil, shine, or highlights on the skin; the skin is substantially free from visible oiliness, shine, or highiights; the skin has a substantially matte finish; the user has a more uniform complexion. Regulating the oily and/or shiny appearance of the skin may result in more uniform and lasting coverage of the skin by the composition, increased wear resistance of the composition and/or a decrease in the incidence or severity of skin oil breaking through the co",posilion so as to become visibly apparent.

Oil Phase The composition of the present invention is in the form of a water-in-oil emulsion. The oil phase can comprise silicone oils, non-silicone organic oils, or mixtures thereof.

In prefer,ed embodiments the oil phase comprises a mixture of volatile silicones and non-volatile silicones. The silicones are useful herein for providing skin conditioning properties. The silicone fluid is present in an amount of from about 1% to about 50% by weight. Suitable volatile silicones include cyclic and linear volatile polyorganosiloxanes. The term "nonvolatile" as used herein shall mean the material has a vapour pressure of no more than 0.1 mm Hg at one atmosphere and 25~C. The term "volatile" as used herein shall mean materials which are not nonvolatile or which have a vapour pressure at the same conditions of more than 0.1mm Hg.

A desc,iption of various volatile silicones is found in Todd, et al.. '~/olatileSilicone Fluids for Cosmetics", 91 Cos,netics and Toiletries 27-32 (1976).

Preferred cyclic silicones include cyclic dimethyl siloxane chains containing an average of from about 3 to about 9 silicon atoms, preferably from about 4 to about 5 silicon atoms. Preferred linear silicones include the polydimethylsiloxanes containing an average of from about 3 to about 9 silicon atoms. The linear volatile silicones generally have viscosities of less than about 5 centistokes at 25~C, while the cyclic materials have viscosities of less than about 10 centistokes. Examples of silicone oils useful in the CA 022~8781 1998-12-18 WO 97/49375 PCT~US97/09700 present invention include: Dow Corning 344, Dow Corning 21330, Dow Corning 345, and Dow Corning 200 (manufactured by the Dow Corning Corporation): Silicone 7207 and Silicone 7158 (manufactured by the Union Carbide Corporation). SF:202 (manufactured by General Electric) and SWS-03314 (manufactured by Stauffer Chemical).

The nonvolatile silicones will have vapour pressures as previously defined, and prererably will have an average viscosity of from about 10 to about 100,000 cps at 25~C, more pre~erably from about 100 to about 10,000 cps, even more pre~erably from about 500 to about 6000 cps. Lower viscosity non-volatile silicone conditioning agents, however, can also be used.
Viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, ~uly 20, 1970.

Suitable non-volatile silicone fluids for use herein include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polysiloxanes with amino functional substitutions, polyether siloxane copolymers, and mixtures thereof. The siloxanes useful in the present invention may be substituted and/or e"dc~t.ped with any number of moieties, so long as the material remains suitable for use in a topical cosmetic product, including, for example, methyl, hydroxyl, ethylene oxide, propylene oxide, amino and carboxyl. tlowever, other silicone fluids having skin conditioning properties may be used. The non-volatile polyalkyl siloxane fluids that may be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Co")pany as a Viscasil (RTM) series and from Dow Corning as the Dow Corning 200 series. Preferably, the viscosity ranges from about 10 mm2.s~1 to about 100,000 mm2.s-1 at 25~C.
The polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes. 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. The polyether siloxane copolymer that may be used includes, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.

CA 022~8781 1998-12-18 W O 9714937S PCTrUS97/09700 References disclosing suitable silicone fluids include US-A-2,826,551, Green; US-A-3,964,500, Drakoff, issued June 22nd, 1976; US-A4,364,837, Pader; and GB-A-849,433, Woolston. In addition, Silicone Compounds distributed by Petrarch Systems Inc., 1984 provides an extensive (though not exclusive) listing of suitable silicone fluids.

Preferred non-volatile silicones for use herein include polydiorganosiloxane-polyoxyalkylene copolymers containing at least one polydiorganosiloxane segment and at least one polyoxyalkylene segment. The polydiorganosiloxane segment has the general formula:

RbSiO(4-b)12 siloxane units wherein b has a value of from about 0 to about 3, inclusive, there being an average value of approximately two 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. The polyoxyalkylene segment has an average molecular weight of at least about 500, preferably at least about 1000, and comprising 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 grafted to, or covalently bonded directly or indirectly to a polydiorganosiloxane segment, any terminal portion of said polyoxyalkylene segment not bonded to said polycJiorga"osiloxane segment being satisfed by a terminating radical; the weight ratio of polydiorganosiloxane sey" ,ents to polyoxyalkylene segments in said copolymer pr~ferably having a value of from about 2 to about 8. Such polymers are described in US-A~,268,499.
Preferred for use herein are polydiorganosiloxane-polyoxyalkylene - copolymers having the general formula:

CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 R1 - Rl R1 R1 R1--Si--O--Si--O--'ii--O--li _R1 R1 R1 CH2)z R1 -- --x o _ y (C2H40)a(c3H6o~bR

wherein R1 is selected from C1 to CS alkyl groups, preferably methyl, z is in the range of from 1 to 4, x and y are selected such that the weight ratio of polydiorganosiloxane segments to polyoxalkylene 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.
More prefe" ed for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the formula:

IH3 IH3 fH3 IH3 H3C-- si ~ (si ~)x (si o)y si-- CH3 o (C2H40)a(C3H60)bR

wherein x, y and R are as defined above.

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 4Ø

CA 022~8781 1998-12-18 Suitable copolymers are available commercially under the tradenames Belsil (RTM) from Wacker-Chemie GmbH, Geschaftsbereich S, Posffach D-8000 Munich 22 and Abil (RTM) from Th. Goldschmidt Ltd,. Tego House, Victoria Road, Ruislip, Middlesex, HA4 OYL. Particularly preferred for use herein are Belsil (RTM) 6031, Abil (RTM) B88183, DC3225C, DC5200, Abil WeO9 and Abil EM90. SF1328 commercially available from GE Silicones is also suitable for use herein. A prererled silicone herein is known by its CTFA designation as dimethicone copolyol.

The compositions of the present invention preferably comprises from about 30% to about 90% by weight of composition of oil phase. The oil phase preferably comprises from about 0.01% to about 25%, more preferably from about 0.05% to about 10% by weight of the oil phase of non-volatile silicones. The oil phase preferably comprises from about 75% to about 99.99%, more prererably from about 90% to about 99.95% by weight of the oil phase of volatile silicones.

The oil phase in the water-in-oil emulsions of the present invention can also comprise one or more non-silicone orga"ic oil, such as 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. 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 d~te""iiling the oil phase level.

Suit~hlo or~anic oils for use herein include, for example, optionally hydroxy-substituted Cg-Cso unsaturated fatty acids and esters thereof, C1-C24 esters of Cg-C30 saturated fatty acids such as isopropyl myristate, isopropyl palmitate, cetyl palmitate and octyldodecylmyristate (Wickenol 142), 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), 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, CA 022~878l l998-l2-l8 W 097/49375 PCTrUS97/09700 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, grapeseedoil, 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.

The compositions herein further comprise water, preferably at a level of from about 10% to about 60%, more preferably from about 30% to about 50% by weight of composition.

Optional Inqredients A wide variety of optional ingredients can be incorporated into the compositions. The following are non-limiting examples of numerous ingredients that can be used.

Acidic Skin Care Active The compositions of the present invention comprise an additional acidic skin care active.

Suitable acidic skin care actives can be selected from hydroxycarboxylic acids. As used herein the term acidic skin care active means any skin care active containing an acidic functional group (e.g. carboxy, sulfonic).

Suitable hydroxycarboxylic acids can be selected from hydroxy"~onoc~,60xylic acids having the following chemical structure:

R1 (CR20H)m(CH2)nCOOH

wherein R1, R2 = H, alkyl, aralkyl or aryl group of saturated or unsaturated, straight or branched chain or cyclic form, having from 1 to 25 carbon atoms;
m =1,2,3,4,5,6,7,8 or 9; n=O or a numerical number up to 23.

CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 The hydroxymonocarboxylic acid may be present as a free acid, lactone, or salt form, The lactone form could be either inter or intramolecular lactone, however, most common ones are intramolecular lactones with a ring structure formed by elimination of one or more water molecules between a hydroxy group and the carboxylic group. Since the hydroxymonocarboxylic acids are organic in nature, they may form a salt or a complex with an inorganic or organic base such as ammonium hydroxide, sodium or potassium hydroxide, or triethanolamine.

The hydroxymonoca,boxylic acid and its related compounds may exist as stereoisomers such as D, L, and DL forms.

Typical alkyl, aralkyl and aryl groups for R1 and R2 include methyl, ethyl, propyl, isopropyl, benzyl and phenyl. The hydrogen atoms of the R1 and R2 and (CH2)n may be substituted by a nonfunctional element such as F, Cl, Br, I, S or a radical such as a lower alkyl or alkoxy, saturated or unsaturated, having 1 to 9 carbon atoms. Representative hydroxymonocarboxylic acids are 2-hydroxyacetic acid (glycolic acid), 2-hydroxypropanoic acid (lactic acid), 2-methyl 2-hydroxypropanoic acid (methyllactic acid), 2-hydroxybutanoic acid, phenyl 2-hydroxyacetic acid (mandelic acid), phenyl 2-methyl 2-hydroxyacetic acid, 3-phenyl 2-hydroxypropanoic acid (phenyllactic acid), 2,3-dihydroxypropanoic acid (glyceric acid), 2.3.4-trihydroxybutanoic acid, 2,3,4,5-tetrahydroxypentanoic acid, 2,3,4,5,6-pentahydroxyhexanoic acid, 2-hydroxydodecanoic acid (alpha hydroxylauric acid), 2,3,4,5,6,7-hexahydroxyheptanoic acid, diphenyl 2-hydroxyacetic acid (benzilic acid), 4-hydroxymandelic acid, 4-chloro",a~delic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 2-hydroxyhexanoic acid, 5-hydroxydodecanoic acid, 1 2-hydroxydodecanoic acid, 10-hydroxyJeca"oic acid, 16-hydroxyhex~dsc~noic acid, 2-hydroxy-3-methylbutanoic acid, 2-hydroxy4-methylpenta,loic acid, 3-hydroxy4-methoxymandelic acid, 4-hydroxy-3-methoxymendelic acid, 2-hydroxy-2-methylbutanoic acid, 3-(2-hydroxyphenyl) lactic acid, 3-(4-hydroxyphenyl) lactic acid, hexahydromandeJic acid, 3-hydroxy-3-methylpentanoic acid, 4-hydroxydecanoic acid, 5-hydroxydecanoic acid and aleuritic acid.

Another type of hydroxyacid suitable for use herein is a hydroxydicarboxylic acid having the following formula:

. .

CA 022~8781 1998-12-18 HOOC(CHOH)m(CH2)nCOOH

wherein m=1,2,3,4,5,6,7,8 or 9; n=O or an integer up to 23.

The hydroxydicarboxylic acid may also be present as a free acid, lactone or salt form. The hydroxydicarboxylic acid and its related compounds may also exist as stereoisomers such as D, L, DL and meso forms.

The hydl ogen attached to the carbon atom may be substituted by a nonfunctional element such as F, Cl, Br, I, S, or a radical such as a lower saturated or unsaturated alkyl or alkoxy having from 1 to 9 carbon atoms.

Representative hydroxydicarboxylic acids are 2-hydroxypropanedioic acid (tartronic acid), 2-hydroxybutanedioic acid (malic acid), erythraric acid and threaric acid (tallalic acid), arabiraric acid, ribaric acid, xylaric acid and Iyxaric acid, glucaric acid (saccharic acid), g~ct~ric acid (mucic acid), ma("1a,ic acid, gularic acid, allaric acid, altraric acid, idaric acid and talaric acid.

A third type of hydroxyacid suitable for use herein is a miscellaneous group of co",~ounds which is not readily represented by the above generic structure of either the first type or the second type described above.
Included in the third type of hydroxyacids are the following:

HydroxycarL,oxylic acids of formula:

R(OH)m(cOoH)n wherein m, n=1,2,3,4,5,6,7,8 or 9, R=H, alkyl, aralkyl or aryl group of saturated or unsaturated, straight or branched chain or cyclic form, having from 1 to 25 carbon atoms; citric acid, isocitric acid, cil~amalic acid, agaricic acid (n-hexadecylcitric acid), quinic acid, uronic acids including glucuronic acid, glucuronolactone, galacturonic acid, g~l~ctIlronolactone, hydroxypyruvic acid, hydroxypyruvic acid phosphate, ascorbic acid, dihydroascorbic acid, dihydroxytartaric acid, 2-hydroxy-2-methylbutanoic acid, 1-hydroxy-1-cyclopropane carboxylic acid, 2-hydroxyhexanedial, 5-CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 hydroxylysine, 3-hydroxy-2-aminopentanoic acid, tropic acid, 4-hydroxy-2,2-diphenylbutanoic acid, 3-hydroxy-3-methylglutaric acid, and 4-hydroxy-3-pentenoic acid.

The third type of hydroxyacid may also be present as a free acid, lactone or salt form and may also exist as stereoisomers such as D, L, DL and meso forms.

The hydrogen atom attached to the carbon atom may be substituted by a nonfunctional element such as F, Cl, Br, I, S or a radical such as a lower saturated or unsaturated alkyl or alkoxy having from 1 to 9 carbon atoms.

Mixtures of hydroxy acids can also be used in the compositions herein.
Hydroxy acids are useful herein from the viewpoint of reducing wrinkles and improving skin feel and appearance.

Other suitable hydroxy acids for use herein include salicylic acid, retinoic acid, and azelaic acid.

Preferred acidic skin care actives for use herein include salicylic acid, retinoic acid, azelaic acid, lactic acid, glycolic acid, pyruvic acid, and mixtures thereof, more preferably salicylic acid and azelaic acid, and especially salicylic acid. The salicylic acid is useful herein as an anti-acne active.

The acidic skin care active is present at a level of from about 0.1% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.5% to about 3%, by weight of composition.

The acidic skin care active is solubilized in water or a hydroalcoholic solution, for example, solutions based upon C2-C6 alcohols, diols and polyols, preferred alcohols being selected from ethanol, dipropylene glycol, butylene glycql, hexylene glycol, and mixtures thereof. Alcohol is preferably present in the co",positions herein at a level of from about 1% to about 20%. The final aqueous/hydroalcoholic skin care active solution preferably has a pH at a",biont temperature (25~C) of less than about PKa + 1, where PKa is the logarithmic acidity constant for the fully protonated skin care CA 022~878l l998-l2-l8 W O 97/49375 PCTrUS97/09700 active. In preferred embodiments, the pH of the final solution is less than about PKa The logarithmic acidity constant is thus defined by reference to the equilibrium HnA= H+ + Hn 1A-where HnA is the fully protonated acid, n is the number of protons in the fully protonated acid and Hn 1 A- is the conjugate base of the acid corresponding to loss of one proton.

The acidity constant for this equilibrium is therefore Ka = [H+l [Hn-1A ]
[HnA]

and PKa = -1~910Kn For the purposes of this specification, acidity constants are defined at 25~C
and at zero ionic strength. Literature values are taken where possible (see Stability Constants of Metal-lon Complexes, Special Publication No. 25, The Chemical Society, London); where doubt arises they are determined by potentiometric titration using a glass electrode.

The PKa Of the acidic skin care active used herein is preferably in the range of from about 1 to about 5.5, more preferably from about 2 to about 4.5, especially from about 2 to about 4.

The pH of the aqueous phase is less than about pH 6, preferably from about pH 2 to about pH 5, more preferably from about pH 2.5 to about pH 4. At pH
values of IBSS than about 5 the aqueous phase is prarerably free of acid labile species such as polyacrylic or polymethacrylic acids or esters.

The compositions of the present invention can also comprise a solubilizing agent for solubilizing the acidic skin care active. Any solublizing agent CA 022~8781 1998-12-18 W 097/49375 PCT~US97109700 suitable for use in a cosmetic composition can be used. Preferably the solubilizing agent herein is selected from polyoxyethylene-polyoxypropylene ethers of C4 to C22 alcohols, pyrrolidone-based solubilising agents, polyethylene glycol based nonionic surfactants having an HLB of greater than about 15, preferably greater than about 18, and mixtures thereof.

Pyrrolidone-based solubilising agents suitable for use herein include polyvinylpyrrolidone or C1-C4 alkyl polyvinylpyrrolidone having a molecular weight (viscosity average) in the range from about 1500 to about 1,500,000, prefe,ably from about 3000 to about 700,000, more preferably from about 5000 to about 100,000. Suitable examples of pyrrolidone-based solubilising agents are polyvinylpyrrolidone (PVP) (or povidone) and butylated polyvinylpyrrolidone. The most preferred pyrrolidone-based solubilising agent herein is polyvinylpyrrolidone. PVP is commercially available under the trade name Luviskol (RTM) from BASF. A preferred PVP solubilising agent herein is Luviskol K17 which has a viscosity-average molecular weight of about 9,000. Other pyrrolidone-based solubilising agents for use herein include C~-C1g alkyl or hydroxyalkyl pyrrolidones such as lauryl pyrrolidone.

The pyrrolidone-based solubilising agent is preferably present in the composition hereln in a level of from about 0.1% to about 10%, more preferably from about 0.1% to about 5%, especially from about 0.5% to about 2% by weight of ~mposition. The weight ratio of acidic skin care active: pyrrolidone-based solubilising agent is preferably in the range from about 10:1 to about 1:10, more preferably from about 5:1 to about 1:5.

P,el~r,ecl embodiments of the invention additionally comprise from about 0.01% to about 5% by weight of an additional acid or salt thereof which is soluble in water at-pH values of less than or equal to the PKa Of the corresponding acid, for example, an acid selected from citric acid, boric acid, and salts, and mixtures thereof. These materials are valuable herein in con,bi"ation with the pyrrolidone-based complexing agent from the viewpoint of aiding solubilization of the acidic skin care active. Particularly preferred herein from this viewpoint is a sodiurn salt of citric acid. In preferred embodiments, the acid or salt thereof is soluble to a ievel of at least 5% w/w at 25~C.

.

CA 022~8781 1998-12-18 A particularly preferred solubilizing agent in the compositions of the present invention is a nonionic surfactant selected from poiyoxyethylene-polyoxypropylene ethers of C4-C22 alcohols, and mixtures thereof. The nonionic surfactant is valuable herein as a solubilising agent for the acidic skin care active in the discontinuous aqueous phase. Suitable polyoxyethylene-polyoxypropylene ethers of C4-C22 alcohols for use herein include those having the general formula:

R(OCHCH2)x(OCH2CH2)yOH

wherein x is in the range of from about 1 to about 35, preferably from about 1 to about 10, y is in the range of from about 1 to about 45, preferably from about 1 to about 30 and R is a straight chain or branched chain C4 to C22 alkyl group, or a mixture thereof. In preferred embodiments (x+y) is greater than or equal to 5, preferably greater than or equal 10, more preferably greater than or equal to 15. The ratio of x:y is in the range from 1: 1 to 1: 10.

Examples of suitable R groups in the above formula include cetyl, butyl, stearyl, cetearyl, decyl, lauryl and myristyl.

Examples of suitable polyoxyethylene-polyoxypropylene alcohol ethers include (using CTFA designations) PPG4-Ceteth-1, PPG~-Ceteth-5, PPG-4-Ceteth-10, PPG4-Ceteth-20, PPG-5-Ceteth-20, PPG-8-Ceteth-1, PPG-8-Ceteth-2, PPG-8-Ceteth-5, PPG-8-Ceteth-10, PPG-8-Ceteth-20, PPG-2-Buteth-3, PPG-2-Buteth-5, PPG-5-Buteth-7, PPG-9-Buteth-12, PPG-28-Buteth-35! PPG-12-Buteth-16, PPG-15-Buteth-20, PPG-20-Buteth-30, PPG-24-Buteth-27, PPG-26-Buteth-26, PPG-33-Buteth45, PPG-2-Ceteareth-9, PPG4-Ceteareth-12, PPG-10-Ceteareth-20, PPG-2-Deceth-10, PPG4-Deceth4, PPG-6-Deceth4, PPG-6-Deceth-9, PPG-8-Deceth~, PPG-2-lsodeceth-4, PPG-2-lsodecelll-6, PPG-2-lsodeceth-9, PPG-2-lsodeceth-12, PPG-3-lsodeceth-1, PPG4-Laureth-5, PPG4-Laureth-2, PPG4-Laureth-7, PPG-5-Laureth-5, PPG-25-Laureth-25, PPG-3-Myreth-11, PPG-3-Myreth-3 and PPG-9-Steareth-3.

CA 022~878l l998-l2-l8 W 097/49375 PCTrUS97109700 Preferred polyoxyethylene-polyoxypropylene ethers for use herein are ethers of C8 to C16 alcohols having the formula (I) wherein x is from 2 to 12 and y is from 10 to 30 and where the ratio of x:y is in the range of from about 1:2 to about 1:8.

Particularly preferred polyoxyethylene-polyoxypropylene ethers of C4 to C22 alcohols for use herein are those having the formula (I) above wherein R is cetyl and wherein x is in the range of from about 4 to about 8, and wherein y is in the range of from about 15 to about 25, and the ratio of x:y is in the range of from about 1:3 to about 1:5. A particularly preferred ether from the viewpoint of improving solubilisation of the acidic skin care active isPPG-5-Ceteth-20, which is available under the tradename Procetyl AWS.

The solubilizing agent herein is preferably present at a level of from about 0.1% to about 15%, more preferably from about 1% to about 10%, especially from about 2% to about 8% by weight of composition.

Prefe.,ed embodiments herein comprise a pigment or mixture of pigments.
The pigment used herein must be compatible with any acidic skin care active which is present in the co""~osition and have excellent overall colour stability. Suitable pigments for use herein can be inorganic and/or organic.
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, rutile titanium dioxide, anatase titanium d,oxide, ferric oxide, ferrous oxide, chromium oxide, .:I.ro,.,i~m hydroxi-le, manganese violet, acylglutamate iron oxides, ul~,~",arine blue, D&C dyes, carmine, and mixtures thereof. Depending upon the type of make-up composition, eg. foundation or blusher, a mixture of pigments will normally be used.

The foundation composition can also include at least one matte finishing agent. The function of the matte finishing agent is to hide skin defects and reduce shine. Such cosmetically acceptable inorganic agents, i.e., those included in the CTFA Cosmetic Ingredient Dictionary, Third Ed., as silica, hydrated silica, silicone-treated silica beads, mica, talc, polyethylene, titanium dioxide, bentonite, hectorite, kaolin, chalk, diatomaceous earth, attapulgite zinc oxide and the like may be utilized. Of particular usefulness CA 022~8781 1998-12-18 W O 97t49375 PCTrUS97/09700 as a matte finishing agent is low lustre pigment such as titanated mica (mica coated with titanium dioxide) coated with barium sulfate. Of the inorganic components useful as a matte finishing agent low lustre pigment, talc, polyethylene, hydrated silica, kaolin, titanium dioxide and mixtures thereof are particularly preferred. Materials suitable for use herein as light-scallerir19 agents can be generally described as spherical shaped inorganic materials having a particle size of up to about 100 microns, preferably from about 5 to about 50 microns, for example spherical silica particles.

Other examples of pigments include lakes of organic colorants such as FD&C Red No. 7 calcium lake, FD&C Yellow No. 5 aluminium lake, D&C
Red No. 9 barium lake, and D&C Red No. 30.

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 such as Iysine, silicones, lauroyl, collagen, polyethylene, lecithin and ester oils. Themore prefer,ed pigments are the silicone (polysiloxane) treated pigments.

A highly prefer,ed pigment for use herein is a pigment which has been coated with organosilicon co"lponent selected from a polyorganosiloxane or a silane wherein the coated pigment has a hydrogen potential of less than about 2.0, preferably less than about 1.0, more preferably less than about 0.5 ml, and especially less than about 0.1ml H2/g of coated pigment. The pigment preferled for use herein is in particulate form. The pigment is i"cGr~.orated into the continuous oil phase in the compositions herein. The coatings used can be bonded to the pigment surface by covalent bonding, physical adsorption or adhesion, preferably by covalent bonding to the surface of the pigment. The function of the coatings herein is to hydrophobically-modify the pigments so that thay are "wettable" in the continuous silicone phase of the water-in-silicone emulsions. The coated pigment is also useful herein from the viewpoint of reducing hydrogen gas evolution and improving product stability.

Without wishing to be limited by theory it is believed that although the pigments are present in the oil phase of the water-in-oil emulsion, hydrogen ions from the aqueous phase can pass through the interface of the emulsion CA 022~878l l998-l2-l8 W 097/49375 PCT~US97/09700 into the oil phase, where they are available to react with the pigment coatings, e.g. to give off hydrogen gas. However, by using organosilicon-coated pigments having a hydrogen potential of less than about 2 ml H2/g of coated pigment, hydrogen gas generation is reduced.

The hydrogen potential of the coated pigment is measured herein using the following test method:

A dispersion of the coated pigment containing 209 of coated pigment is placed in a flask on a magnetic stirrer and 100ml of a 2% ethanolic solution of potassium hydroxide is added with stirring at ambient temperature. The hydrogen gas which is evolved is collected in a second flask at ambient te,,,,uera~ure and pressure (25~C, 1At). The hydrogen gas released can therefore be volumetrically measured.

A wide variety of organosilicon components can be used for treating the pigments herein. A suitable polyorganosiloxane herein is selected from:

(A) material of the formula:

(R1 )3Sio-(Si(R2R3)0)p-Si(R2R3)0A2 wherein p is 1 to 1000, preferably from 1 to 100, A2 is hydrogen or an alkyl group having from 1 to 30 carbon atoms, R1 is a C1-C30 alkyl, prefer~bly methyl, R2 and R3 are independently selected from a C1-C30 alkyl and a phenyl, preferably wherein R2 and R3 are both methyl or wherein R2 is methyl and R3 is phenyl; or (B) material of the formula:
(R1 )3SiO(Si(R2)(H)-O)j-Si(R1 )3 wherein i is 1 to 1000, preferably 1 to 100, and wherein R1 and R2 are as defined above for formula (A).

In prefe~,ed embodiments the organosilicon component is selected from a silane. The silane can be selected from material of the formula:

CA 022~8781 1998-12-18 W 097/49375 PCTrUS97tO9700 (C) A1 SiX1X2X3 wherein A is an alkyl or alkenyl group having from 1 to 30 carbon atoms, and X1, X2 and X3 are independently C1-C4 alkoxy ~referably methoxy or ethoxy, or halo, preferably chloro.

When the pigment herein is treated with silane material having the formula (C) described herein above a pigment having the following formula (1) is produced:

P-o-si(oH)(A)-[-o-si(oH)(A)-]o-1 oo-~H

wherein P is an atom in the pigment surface and each A is an alkyl or alkenyl group having up to 30 carbon atoms. A number of ~dj-cent polysiloxane chains as shown in formula (1) can be cross-linked through oxygen atoms to form a polysiloxane chain with up to 100 repeating -Si(-OP)-O-units that extend along the pigment surface, in addition to the polysiloxane chain which extends away from the pigment surface.
Examples of linear or branched alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and so forth up to octadecyl. "Alkenyl" includes carbon chains with one or more double bonds; examples of such groups include ethylene, propylene, acrylyl, methacrylyl, and residues of unsaturated fatty acids such as oleic (C17C33-), linoleic (C17H31-), and linoleniC (C17H29-) When the pigment herein is treated with polyorganosiloxane material having the formu~a (A) described hereinabove a pigment having the following formula (2) is produced:

P-o-(Si(R2R3)o)p-Si(R1 )3 (2) wherein p is 1-1000, preferably 1 to 100, R1, R2 and R3 are as defined above for formula (A) and P is an atom in the pigment surface.

CA 022~8781 1998-12-18 W O 97/49375 PCT~US97/09700 When the pigment herein is treated with polyorganosiloxane material having the formula (B) described hereinabove a pigment having the following formula (3) is produced:

(R1 )3SiO-[Si(R2)(-OP)-0-~p-Si(R1 )3 (3) wherein each P is an atom in the pigment surface, p is from 1 to 1000, preferably from 1 to 100, R1 and R2 are as defined above ir formula (B) and in which each of the up to 100 repeating (Si-0) units is bonded through an oxygen atom to the pigment surface.

The pigment (or a mixture of two or more pigments) can be coated by placing it in dry, finely divided form in a mixer, adding the organosilicon compo"ent, and mixing. The organosilicon coating is preferably present at a level of from about 0.01% to about 5%, more prtferably from about 0.1%
to about 4%, and especially from about 0.5% to about 2%, by weight of the organosilicon coated pigment.

The most preferred coated pigment from the viewpoint of reducing hydrogen gas evolution and improving product stability is Cardre 70429.

The total conc~n~(a~ion of the coated pigment may be from about 0.1 to about 25% by weight and is preferably from about 1 to about 15%, more preferably from about 8% to about 12% by weight of the total composition, the exact concerlt~dlion being dependent to some extent upon the specifi mixture of pigments selected for use in a foundation make-up or blusher to achieve the desired shades. The prefer~ed compositions contain from about 2% to about 20% by weight of titanium dioxide and most preferably from about 5% to about 10% by weight of titanium dioxide.

A highly preferled cGmpol~.cnt of the compositions herein is a humectant or mixture of humectants. The humectant or mixture of humectants herein is present in an amount of from about 0.1% to about 30% preferably from about 1% to about 25%, and more preferably from about 1% to about 10%
by weight of composition. Suitable humectants are selected from glycerine and polyglycerylmethacrylate lubricant having a viscosity at 25~C of 300,000 to 1,100,000 cps; a specific gravity at 25~C of 1 to 1.2g/ml, a pH of ~.0 to CA 022~8781 1998-12-18 5.5; a bound water content of 33 to 58%; and, a free water content from 5 to 20%.

The humectant can be incorporated at least partly into the oil phase of the water-in-oil emulsion. The oil phase preferably comprises from about 0.1%
to about 10%, more preferably from about 0.1% to about 3% by weight of humectant on a composition basis. The humectant can be introduced into the oil phase in the form of a mixture with or incorporated within a particulate lipophilic or hydrophobic carrier material.

Polyglycerylmethacrylate lubricants having the desired properties are marketed by Guardian Chemical Corporation under the trademark "Lubrajel". The "Lubrajels" identified as "Lubrajel D\/', "Lubrajel MS", and "Lubrajel CG" are preferred in the present invention. The gelling agents sold under these trademarks contain about 1% propylene glycol.

Other suitable humectants include sorbitol, panthenols, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, alkoxylated glucose derivatives, such as Glucam (RTM) E-20, hexanetriol, and glucose ethers, and mixtures thereof.

The panthenol moisturiser can be selected from D-panthenol ([Rl-2,4-dihydroxy-N-[3-hydroxypropyl)]-3,3~ir"e~hylbutamide), DL-panthenol, calcium pantotl,enate, royal jelly, panthetine, pantotheine, panthenyl ethyl ether, pangamic acid, pyridoxin, pantoyl lactose and Vitamin B complex.

The preferred humectant herein is glycerine. Chemically, glycerine is 1,2,3-propanetriol and is a product of commerce.

A preferred component of the compositions herein, in addition to the organic amphiphilic surfactant is a polyol ester skin conditioning agent.

The compositions of the present invention p~eferably comprise from about 0.01% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 1% to about 10% by weight of the polyol ester. The level of polyol ester by weight of the oil in the composition is preferably fromabout 1% to about 30%, more preferably from about 5% to about 20%.

CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 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, bec~use 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, especi~lly 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 hydroxyigroups, but the sugar alcohol derived from erythrose, i.e., erythritol, contains four hydroxyl groups and accordingly can be used. Suitable five hydroxyl group-coi,taining monosaccl,a,ides are galactose, fructose, and s~r60se. 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, xyiitol, sorbitol, glucose, and sucrose. Sucrose is especially prefer,~d.

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, CA 022~8781 1998-12-18 W O 97/49375 PCT~US97/09700 ricinoleic, linoleic, linolenic, eleostearic, arachidic, arachidonic, behenic, and erucic acid. The fatty acids can be derived from naturally 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 incol~Jorated 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 hydroxylgroups 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, sl ~hst~ntially all of the hydroxyl groups of the polyol are esterified with fatty acid, i.e., the polyol moiety is subs~anlially 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 prefer~ed because it has more than two unesterified hydroxyl groups. A
sucrose hexa-fatty acid ester would be prefer,ed because it has no more than two unesterified hydroxyl groups. Highly prererled compounds in which all the hydroxyl groups are esterified with fatty acids include the liquidsucrose 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: 911 ~cose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the 9 ~nc-tose tetraesters of oleic acid, the arabinosetetraesters of linoleic acid, xylose tetralinoleate, g~l~ctose 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.

CA 022~8781 1998-12-18 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).

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; U.S. Patent No. ~,005,196, to Jandacek, issued January 25, 1977.

The make-up compositions of the present invention can also comprise a particulate cross-linked hydrophobic acrylate or methacrylate copolymer.
This copolymer is particularly valuable for reducing shine and controlling oil while helping to provide effective moisturization benefits. The cross-linked hydlu,vhobic polymer is preferably in the form of a copolymer lattice with at least one active ingredient dispersed uniformly throughout and entrapped within the copolymer lattice. Altematively, the hydrophobic polymer can take the form of a porous particle having a surface area (N2-BET) in the range from about 50 to 500, preferdbly 100 to 300m2/9 and having the active ingredient absorbed therein.

The cross-linked hydrophobic polymer when used herein is in an amount of from about 0.1% to about 10% by weight and is preferably incorporated in the external silicone-containing oil phase. The active ingredient can be one or more or a mixture of skin compatible oils, skin compatible humectants, emollients, moisturizing agents and sunscreens. The polymer material is in the form of a powder, the powder being a combined system of particles.
The system of powder particles forms a lattice which includes unit particles of less than about one micron in average diameter, agglomerates of fused CA 022~8781 1998-12-18 W O 97/49375 PCTrUS97/09700 unit particles of sizes in the range of about 20 to 100 microns in average diameter and aggregates of clusters of fused agglomerates of sizes in the range of about 200 to 1,200 microns in average diameter.

The powder material of the present invention which can be employed as the carrier for the active ingredient can be broadly described as a cross-linked "post absorbed" hydrophobic polymer lattice. The powder preferably has entrapped and dispersed therein, an active which may be in the form of a soiid, liquid or gas. The lattice is in particulate form and constitutes free flowing discrete solid particles when loaded with the active material. The lattice may contain a predetermined quantity of the active material. The polymer has the structural formula:

CH3 ~ CH3 CH2 C . C - CH2--C=O C=O
O O
R' - R" - Y
o C =O

where the ratio of x to y is 80:20, R' is -CH2CH2- and R" is -(CH2)1 1 CH3.

A suitable hyJropl,obic polymer for use herein is a highly crosslinked polymer, more particularly a highly cross-linked polymethacrylate copolymer such as that manufactured by the Dow Corning Corporation, Midland.
Michigan, USA, and sold under the trademark POLYTRAP (RTM) . It is an ultralight free-flowing white powder and the particles are capable of absorbing high levels of lipophilic liquids and some hydrophilic liquids while at the same time maintaining a free-flowing powder character. The powder structure consists of a lattice of unit particles less than one micron that are fused into agglomerates of 20 to 100 microns and the agglomerates are loosely clustered into macro-particles or aggregates of about 200 to about CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 1200 micron size. The polymer powder is capable of containing as much as four times its weight of fluids, emulsions, dispersions or melted solids.

Adsorption of actives onto the polymer powder can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active is added to the powder and the spoon is used to gently fold the active into the polymer powder. Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel containing the polymer and then tumbling the materials until a consistency is achieved. More elaborate blending equipment such as ribbon or twin cone blenders can also be employed. The preferred active ingredient for use herein is glycerine. Preferably, the weight ratio of humectant: carrier is from about 1:4 to about 3:1.

Also suitable as a highly cross-linked polymethacrylate copolymer is Microspor,ges 5640. This takes the form of generally spherical particles of cross-linked hydrophobic polymer having a pore size of from about 0.01 to about 0.05,um and a surface area of 200-300m2/g. Again, it is preferably loaded with humectant in the levels desc, ibed above.

The compositions of the invention can also co"~ain a hydrophilic gelling agent at a level preferably from about 0.01% to about 10%, more preferably from about 0.02% to about 2%, 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- colloidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose), polyvinylalcohol, polyquaternium-10, guar gum, hydroxypropyl guar gum and xa~ ,an gum.

Among suitable hydrophilic gelling agents are acrylic acid/alkyl acrylate - copolymers and the carboxyvinyl polymers sold by the B.F. GoodrichCompany under the trade mark of Carbopol resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00% of a CA 022~8781 1998-12-18 W O 97/49375 PCT~US97109700 crosslinking agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, 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. 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 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 for use herein. Other suitable gelling agents suitable for use herein are oleogels such as trihydroxystearin and aluminium magnesium hydroxy stearate. The gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures.

Pteferat~ly the acidic group containing hydrophilic gelling agents are neutralized.
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.

The make-up compositions herein can additionally comprise an emollient.
Emollients suitable for the compositions of the present invention include natural and synthetic oils selected from mineral, vegetable, and animal oils, fats and waxes, fatty acid esters, fatty alcohols, alkylene glycol and polyalkylene glycol ethers and esters, fatty acids and mixtures thereof.

Suitable emollients for use herein include, for example, optionally hydroxy-substituted Cg-Cso unsaturated fatty acids and esters thereof, C1-C24 esters of Cg-C30 saturated fatty acids such as isopropyl myristate, cetyl palmitate and octyldodecylmyristate (Wickenol 142), 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), lanolin and lanolin derivatives, such as lanolin alcohol ethoxylated, hydroxylated and acetylated lanolins, cholesterol and derivatives thereof, animal and CA 022~8781 1998-12-18 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, and sunflower seed oil and C1 C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearyimalate, diisostearyldimerate and triisostearyltrimerate.

Preferred emollients are selected from hydrocarbons such as isohexadec~ne, mineral oils, petrolatum and squalane, lanolin alcohol, and stearyl alcohol. These emollients may be used independently or in mixtures and may be present in the composition of the present invention in an amount from about 1% to about 30% by weight, and pr~ferably are present in an amount from about 5% to about 15% by weight of the total composition.

The composition may also contain additional materials such as, for example, fragrances, sun-screens, preservatives, electrolytes such as sodium chloride, proteins, antioxidants, chelating agents and water-in-oil emulsifiers as appropriate.

Another optional component of the make-up composition is one or more ultraviolet absorbing agents. Ultraviolet absorbing agents, often described as sunscreening agents, can be present in a concenl~&lion in the range of between about 1% and about 12% by weight, based on the total weight of cGi"posiliGn. Prefer~bly, the UV absorbing agents constitute between about 2% and 8% by weight. More preferably, the UV absorbing agents can be presenl in the comp~si(iGIl in a concenl~alion range of between about 4%
and about 6% by weight. Of the ultraviolet absorbing agents suitable for use herein, benzophenone-3, octyl dimethyl PABA (Padimale 0), Parsol MCX, and mixtures thereof are particularly prerer,ed.

Another optional but preferred component herein is one or more additional chelating agents, preferably in the range of from about 0.02% to about 0.10% by weight, based on the total weight of the composition. Preferably, the chelating agent is present in a concenlralion in the range of between about 0.03% and about 0.07% by weight, based on the total weight of the ....

CA 022~8781 1998-12-18 W 097/49375 PCT~US97/09700 composition. Among the chelating agents that may be included in the composition is tetrasodium EDTA.

Another optional but preferred component of the foundation composition is one or more preservatives. The preservative CGi ,cen~, a~ion in the foundation composition, based on the total weight of that composition, is in the range of between about 0.05% and about 0.8% by weight, preferably between about 0.1% and about 0.3% by weight. Suitable preservatives for use herein include sodium bei,~oale, phenoxyethanol, methyl paraben and propyl paraben, and mixtures thereof.

The composition preferably comprises from about 20% to about 95%, more preferably from about 30% to about 70% by weight of the oil phase, and from about 5% to about 80%, more prererably from about 30% to about 70%
by weight of the ~ eous phase. The aqueous phase preferably comprises from about 40% to about 90%, more ~.rererably from about 60% to about 80% by weight of aqueous phase of water.

The cosmetic compositions of the present invention can be in the form of foundations, blushers, concealers, compact powders, and the like, prefer~bly as foundations and concealers.

Method of ~Jse The cor~positions herein are used for regulating the oily and/or shiny appearance of skin. The compositions herein can be used by topically applying to the areas of skin to be treated an effective amount of the co",positions. As used herein the term "effective amount" means an amount sufficient to re~ul~te the oily and/or shiny appearance of skin as defined herein.

The co",posilion can be applied for several days, weeks, months or years at appropriate intervals. The compositions are preferably applied from about four times a day to about once every three days, more preferably from about twice a day to once every other day, especially about once a day. Typically, in each application, an effective amount of co""~osition is delivered to the skin by topically applying (in terms of mg/cm2 skin) from about 0.01 to about CA 022~8781 1998-12-18 5 mg composition/cm2, more preferably from about 1 to about 2 mg composition/cm2 skin.

The compositions are generally applied by lightly massaging the composition into the skin typically in the amounts described above.

The present invention further relates to the use of willow bark extract for regulating the oily and/or shiny appearance of mammalian skin. The willow bark extract can be used by topically applying to the areas of skin to be treated an effective amount of the willow bark extract. Typicaily, an effective amount of willow bark extract on the skin is achieved by topically applying (in terms of mg active/cm2 skin) from about 0.0004 mg/cm2 to about 0.8 mg/cm2 of willow bark extract to the skin to be treated, more preferably from about 0.004 mg/cm2 to about 0.4 mg/cm2 of willow bark extract, especially from about 0.04 mg/cm2 to about 0.2 mg/cm2 of willow bark extract.
The table below shows examples of cosmetic compositions of the present invention.

Phase A (%,wlw) (%,wlw) (%,wlw) (%,wlw) (%,wlw) (%,wlw) Cyclomethicone(DC 15.75 7.749 7.59 16.75 5.25 11.99 2-1330) Cyclomethicone/Dim 10.00 15.00 17.20 10.00 18.50 10.00 ethicone copolyol (90: 1 O) (DC3225C) SEFA Cotlonate1 0.00 0.00 2.00 0.00 2.00 4.00 Phase B
Microsponge 56402 o.oo 0.50 0.75 0.00 0.50 0.75 Mica 0.10 0.00 0.00 0.10 0.10 0.10 Titanium Dioxide 8.25 8.25 8.25 8.25 8.25 8.25 (Cardre 70429)3 Zinc Oxide 8 0.00 0.00 4.00 4.00 0.00 4.00 Dimethicone Phase C
Dryflow4 0.00 2.50 0.00 0.00 0.00 0.00 Phase D
Yellow Iron Oxide 2.10 2.10 2.00 2.10 2.10 2.10 Red Iron Oxide 0.90 0.90 0.24 0.90 0.60 0.90 .. .~ .

CA 022~8781 1998-12-18 W 097/49375 PCT~US97/09700 Btack Iron oxide 0.60 0.60 0.12 0.60 0.30 0.60 Cyclomethicone(DC 1.00 1.00 1.00 1.00 1.00 1.00 2-1 330) Phase E
Durachem5 0.00 0.10 0.00 0.00 0.00 0.00 Waxenol6 0.00 0.00 0.30 0.00 0.00 0.00 Phase F
Cyclometl ,i~ne 1.00 1.00 1.00 1.00 1.00 1.00 (DC2-1 330) ThixinR/ 0.30 0.30 0.30 0.30 0.30 0.30 Propyl Paraben 0.00 0.00 0.25 0.00 0.00 0.00 Phase G
EthyleneBrassylate 0.00 0.00 0.00 0.00 0.10 0.00 Rose Water 0.00 0.001 0.00 0.00 0.00 0.01 Co"cenl, ale Phase H
Ethanol 4.00 4.00 0.00 4.00 4.00 4.00 Polyvinylpyrrolidone 1.00 1.00 1.00 1.00 1.00 1.00 (Luviskol K17)8 Salicylic Acid 0.50 0.50 1.50 1.45 1.00 1.00 Dipropylene glycol 0.00 0.00 0.00 0.00 7.00 8.00 Glycerine 6.00 6.00 6.00 6.00 6.00 6.00 Carbowax 400(PEG 0.00 0.00 0.00 0.00 3.00 0.00 8)g Procetyl AWS10 3.00 3.00 3.00 3.00 0.00 0.00 Glycyrrhizic acid 0.00 0.00 0.10 0.00 0.00 0.10 Phase I
Deionised Water to 100 Na4EDTA 0.10 0.10 0.10 0.10 0.10 0.10 Sodium Citrate 0.30 0.30 0.30 0.30 0.30 0.30 Sodium Chloride 0.30 0.30 0.30 0.30 0.30 0.30 Citric Acid 1.00 1.00 0.00 0.00 0.50 0.00 Methyl Paraben 0.00 0.00 0.20 0.00 0.00 0.00 r l~; ~e J
Zinc Oxide 0.00 0.00 0.42 0.42 0.00 0.28 Willow Bark 5.00 10.00 2.50 5.00 5.00 5.00 Extract1 ~
Total: 100 100 100 100 100 100 CA 022~8781 1998-12-18 W 097/49375 PCTrUS97/09700 1. Supplied by Procter & Gamble 2. Supplied by Dow Corning Ltd, Avco House, Castle Street, Reading RG1 7DZ, UK

3. Supplied by Cardre Incorporated, 70 Tyler Pl., South Plainfield, NJ07090, - USA

4. Supplied by Dow Corning Ltd, Avco House, Castle Street, Reading RG1 7DZ, UK

5. Supplied by Astor-Stag Ltd., Tavistock Road, Wets Drayton, Middlesex UB7 7RA, UK

6. Supplied by Caschem Inc., 40 Avenue A, Bayonne, NJ07002, USA

7. Trihydroxystearin, supplied by Rheox Ltd, Barons Court, Manchester Road, Wilmslow, SK9 1BQ, UK

8. Supplied by BASF, Earl Road, Cheadle Hulme, Cheadle, Cheshire, SK8 9. Supplied by Union Carbide, 39 Old Ridgebury Road, Danbury 10. Supplied by Croda Chemicals Ltd., Cowick Hall, Snaith, Goole, North Humberside, DN14 9M

11. Supplied by Brooks Industries, 70 Tyler Place, South Plainfield, NJ
07090, USA

The formulations of Examples I to Vl can be prepared as follows. The various c~ll,ponents listed in the Table have been segregated into groups.

In the first step, the mixture of components of phase A is stirred for a~,pr~xi,nately 15 minutes with shear mixing until homogeneous. With high speed shear mixing, the materiaJs of phase B are added gradually to A and the batch is mixed for about 30 minutes. Phase C is added and the resulting mixture is ground for approximately 15 minutes.

The components from phase D are then added and the resulting mixture is ground until fully dispersed.

The waxy phase E is then added to the batch and the batch is heated to 85~C with mixing until the waxes have melted and then cooled to 50~C with stirring. Phase F premix is then added to the batch and homogenised for 10 minutes. The batch is cooled to room temperature with stirring. Phase G is added to the batch and homogenised for 10 minutes.

.. . . .

CA 022~8781 1998-12-18 W 097/49375 PCTrUS97109700 The water phase is prepared as follows. The components of phase I are mixed until dissolved. The components of phase H except for the ethanol are mixed together under high speed shear until dissolved. Phase H is cooled and ethanol is added. The solution is mixed until clear. Phase I is added to phase H and mixed followed by addition of phase J under mixing.

The water phase is finally added to the oil phase slowly whilst homogenising at a low speed with stirring. When all of the water phase has been added high shear is applied to the batch for approximately 5 minutes to increase the viscosity of the final product.

The resulting make-up co,nposition is ready for packaging.

The cosmetic cG",posilions of the Examples exhibit improved oil control and facial skin appearance together with improved anti-bacterial and anti-infla"",~atory activity.

Claims (13)

What is claimed is:

1. Cosmetic composition for topical application to the skin in the form of a water-in-oil emulsion comprising:

(a) continuous oil phase;
(b) discontinuous aqueous phase; and (c) willow bark extract.

2. Cosmetic composition according to Claim 1 comprising from about 0.1% to about 10% by weight of the willow bark extract.

3. Cosmetic composition according to Claim 1 or 2 additionally comprising from about 0.1% to about 10%, preferably from about 0.1% to about 5% by weight of acidic skin care active.

4. Cosmetic composition according to Claim 3 wherein the acidic skin care active is solubilised in the aqueous phase.

5. Cosmetic composition according to Claim 3 or 4 wherein the acidic skin care active is selected from salicylic acid, azelaic acid, retinoic acid, lactic acid, glycolic acid, pyruvic acid, and mixtures thereof.

6. Cosmetic composition according to any of Claims 3 to 5 wherein the acidic skin care active is salicylic acid.

7. Cosmetic composition according to any of Claims 1 to 6 additionally comprising from about 0.1% to about 30%, preferably from about 0.1% to about 25%, more preferably from about 1% to about 15% by weight of pigment.

8. Cosmetic composition according to any of Claims 1 to 7 additionally comprising from about 0.1% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.5% to about 2%, by weight, of pyrrolidone-based solubilising agent.

9. Cosmetic composition according to Claim 8 wherein the pyrrolidone-based solubilising agent is polyvinylpyrrolidone.

10 Cosmetic composition according to any of Claims 1 to 9 additionally comprising from about 0 01% to about 5%, by weight, of citric acid or salt thereof.

11. Cosmetic composition according to any of Claims 1 to 10 wherein the oil phase comprises from about 0.01% to about 25% by weight of oil phase of non-volatile silicones and from about 75% to about 99.99%
by weight of the oil phase of volatile silicones.

12. Use of willow bark extract for regulating the oily and/or shiny appearance of mammalian skin.

13. Use of a composition according to any of Claims 1 to 11 for regulating the oily and/or shiny appearance of mammalian skin.