COSMETIC COMPOSITIONS CONTAINING RUTILE AND ANATASE TITANIUM OXIDE AND EMOLLIENTS

Abstract: According to the present invention there is provided a cosmetic composition suitable for topical application to the skin comprising: (a) mixture of rutile and anatase titanium oxide; and (b) no more than about 3.5 %, by weight, of emollients. The present compositions provide good coverage while at the same time being less streaky or cakey.

Description: COSMETIC COMPOSITIONS CONTAINING RUTILE AND ANATASE TITANIUM OXIDE AND EMOLLIENTS The present invention relates to cosmetic compositions and more particularly, to pigmented foundation make-up compositions and concealers. Background of the Invention Skin is subject to abuse by many extrinsic (environmental) factors as well as intrinsic (chronoaging) factors. Whether extrinsic or intrinsic, this abuse can result in wrinkling of the skin. To many people, skin wrinkles are a melancholy reminder of the disappearance of youth. Attempts have therefore been made to reduce the appearance of wrinkles. These treatments range from cosmetic creams and moisturisers to various forms of cosmetic surgery. However, these treatments have not always been successful. In particular, attempts to cover up wrinkles using cosmetic foundations often result in a facial appearance which is too clearly evident to the observer that large amounts of make-up have been applied. Prior approaches can even result in an undesirable accentuation of the appearance of wrinkles as some cosmetics deposit more in the creases of the skin thereby increasing the contrast between the wrinkles and the rest of the skin. Cosmetic surgery is expensive, not always successful, and, for many people, it is undesirable to resort to surgical procedures for cosmetic purposes. Skin is also subject to a number of other blemishes, discolourations and minor skin diseases such as acne, hyperpigmentation (more commonly known as liver spots) and other flare-ups. These features are often perceived as imperfections and can cause embarrassment or distress in some individuals. Make-up compositions intended to cover up wrinkles, blemishes and other imperfections are generally available in the form of liquid or cream suspensions, emulsions, gels, pressed powders or anhydrous oil and wax compositions. Many consumers prefer the ease and convenience of liquid compositions. Cosmetic make-up compositions are described in US-A- 3,444,291 , US-A-4,486,405, US-A-4,804,532, US-A-3,978,207, US-A- 4,659,562, US-A-5, 143,722 and Nakamura et al., Preprints of the XlVth I.F.S.C.C. Congress, Barcelona, 1986, Vol. I, 51-63 (1986). Cosmetic make-up compositions often comprise titanium oxide which can have a number of functions. Most commonly titanium oxide is used as an ultra violet filtering agent, as a colourant or as an opacifying agent. For example, JP-A-07/267824 describes the use titanium oxide in cosmetics for providing compositions that do not cause the face to appear unnaturally white under photographic flash light, US-B-5, 700,451 which describes sunscreen composition comprising titanium oxide as an ultra violet filtering agent, US-B-5, 599, 547 which describes mascara compositions comprising titanium oxide as a colourant and JP-A-02/9810 which describes a mixture of both anatase and rutile crystalline forms of titanium oxide for use as an ultra violet blocker. 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 and imperfections, and wrinkles. A foundation composition can also help to moisturise the skin, to balance the oil level of the skin and to provide protection against the adverse effects of sunlight, wind and the harsh environment. Ideally, foundation compositions should be easy to apply, should give a smooth, blemishless appearance to the skin and should not feel 'thick' or 'cakey' when in use. However, with many foundation compositions it is difficult to achieve a smooth application. This leads to an uneven distribution of the compositions which can cause the skin to appear 'streaky' or highly 'made-up'. In addition, some compositions, especially liquid compositions, can cause the unpleasant feeling that the skin is 'caked' with make-up. It would therefore be desirable to provide a cosmetic composition, and in particular a foundation composition which significantly reduces the appearance of wrinkles and which does not cause the face to appear streaky, cakey or highly made-up. Surprisingly, it has now been found that cosmetic compositions comprising a mixture of both rutile and anatase titanium oxide and wherein the compositions comprise no more than about 3.5% emollients provide good coverage of blemishes and wrinkles while having reduced streakiness and cakiness. Summary of the Invention According to the present invention there is provided a cosmetic composition suitable for topical application to the skin comprising: (a) mixture of rutile and anatase titanium; and (b) no more than about 3.5%, by weight, of emollients. The present compositions provide good coverage while at the same time being less streaky or cakey. All concentrations and ratios herein are by weight of the cosmetic composition, unless otherwise specified. All averages are weight averages unless otherwise specified. Detailed Description of the Invention The cosmetic compositions of the present invention comprise a mixture of rutile and anatase titanium oxide and are further characterised in that they comprise 3.5% or less emollient. These elements will be described in more detail below. As used herein the term "cakey" means an undesirable, localised collection of make-up. As used herein the term "streaky" means undesirable areas of contrasting make-up. As used herein the term "coverage" means the concealing of blemishes and wrinkles on the skin by a make-up composition. Titanium Oxide Titanium oxide is an inorganic oxide that conforms to the general formula: Ti0 2 Titanium oxide is polymorphous, that is, it can exist in several crystalline states. An essential feature of the present compositions is that they comprise a mixture of anatase and rutile crystalline forms of titanium oxide. Rutile titanium oxide has a density of about 4.30 g/cm 3 and a tetragonal, hexagonal close packed structure. The refractive index of rutile titanium oxide is 2.72. Rutile titanium oxide is commercially available from sources such as Kobo Products Inc., South Plainfield, New Jersey, USA, under the trade name Kobo RPTD 11S2 and from U.S. Cosmetics Corp., Dayville, USA under the trade name T-CR 837, SAT rutile titanium dioxide. Anatase titanium oxide has a density of about 3.90 g/cm 3 and a tetragonal, cubic close packed structure. The refractive index of anatase titanium oxide is 2.55. Anatase titanium oxide is available from Kobo Products Inc. under the trade name Kobo RBTD 11S2, from Whittaker, Clark, Daniels, South Plainfield, New Jersey, USA, under the trade name Ti02 9729, and from Cardre Inc., South Plainfield, New Jersey, USA, under the trade name Carde 70429. It is preferred that the ratio of rutile titanium oxide to anatase titanium oxide in the mixture is in the range of from about 1 :100 to about 100:1 , preferably from about 1 :50 to about 50:1 , more preferably from about 1 :20 to about 20:1 , even more preferably from about 1 :10 to about 10:1 , even more preferably still from about 5:1 to about 1 :5. Particularly preferred is when the ratio of rutile titanium oxide to anatase titanium oxide is from about 3:1 to about 1 :3, especially from about 1.5:1 to about 1 :1.5. Generally the mixture of rutile and anatase titanium oxide will comprise from about 0.1 % to about 50%, preferably from about 0.5% to about 40%, more preferably from about 1 % to about 20%, even more preferably from about 5% to about 10%, by weight, of the total composition. The rutile and anatase titanium oxide in the mixture preferably consist essentially of particles having a size of greater than 0.05μm. It is preferred that at least about 50%, preferably at least about 75%, more preferably at least about 90%, of the particles have a particle size of greater than 0.05μm. For providing optimal coverage it is preferred that the rutile and anatase titanium oxide in the mixture have a weight average particle size in the range of from about 0.06 μm to about 3.0 μm, more preferably from about 0.1 μm to about 0.75 μm, even more preferably from about 0.2 μm to about 0.60 μm. Emollient A second essential feature of the compositions of the present invention is that they comprise no more than about 3.5%, preferably no more than about 3%, more preferably no more than about 2%, even more preferably no more than about 1%, by weight, emollient. As used herein the term "emollient" means non-volatile, non-silicone containing, oily, skin conditioning materials that are substantially insoluble in water. The term "oily" as used herein, means a material that has a straight or branched aliphatic chain of greater than 8 carbon atoms, particularly those with 8 to 30 carbon atoms. The term "non-volatile" 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. The term "insoluble" as used herein shall mean materials having a solubility of no greater than 0.1 mg/cm 3 at 25°C and one atmosphere. Examples of emollients include C 8 to C 30 carboxylic acids; C., to C 30 alkyl esters of C 8 to C 30 carboxylic acids; C 8 to C 30 alkyl esters of C, to C 30 carboxylic acids; C, to C 6 diol monoesters and diesters of C 8 to C 30 carboxylic acids and monoglycerides, diglycerides and triglycerides of C 8 to C 30 carboxylic acids. Examples of these materials include stearic acid, palmitic acid, diisopropyl adipate, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, methyl isostearate, isodecyl neopentanoate, isononyl isononanoate, C 12-15 alkyl benzoate, diethylhexyl maleate, cetyl ricinoleate, jojoba oil, and cocoa butter. Further examples of emollients include hydrocarbons having a straight or branched chain carbon chain of 10 to 24 carbon atoms in length such as mineral oils, petrolatum and squalane. Still further examples of emollients include straight or branched chain alcohols having from 10 to 30 carbon atoms such as stearyl alcohol, isostearyl alcohol, behenyl alcohol, cetyl alcohol, and isocetyl alcohol. Other examples of emollients include liquid, polyol carboxylic acid esters. 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. Examples of these materials include 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, and sucrose octaoleate. While it is essential that the compositions of the present invention comprise no more than about 3.5% emollients, it is preferred, from the viewpoint of the stability, that the compositions do comprise small amounts of emollient material, especially emollients having a carbon chain of greater than 16 carbon atoms. Generally, the compositions of the present invention will comprise from 0% to about 2%, preferably from about 0.01% to about 1%, more preferably from about 0.1% to about 0.75%, by weight, of emollient. Preferred emollients for use herein include arachidyl behenate, trihydroxy stearin, and synthetic wax. The cosmetic compositions of the present invention will also comprise a vehicle for the titanium oxide which is suitable for topical application to the skin. The vehicle can comprise any material known in the art which is safe for topical application to the skin. The vehicle can take any form which is suitable for use as a cosmetic, for example, emulsion, gel, cream, lotion, suspension, and the like. Preferably, the present compositions are in the form of an emulsion having at least one aqueous phase and at least one oil phase. More preferably, the cosmetic compositions of the present invention are in the form of water-in-oil emulsions. If the compositions herein comprise an oil phase it will generally comprise from about 20% to about 95%, more preferably from about 30% to about 70% by weight of oil phase, and from about 5% to about 80%, more preferably from about 30% to about 70% by weight of aqueous phase. The aqueous phase preferably comprises from about 40% to about 95%, more preferably from about 60% to about 80% by weight of aqueous phase of water. The total level of water in the compositions herein is preferably in the range of from about 10% to about 60%, more preferably from about 20% to about 50% by weight of composition. The compositions of the present invention will generally comprise a mixture of volatile silicones and non-volatile silicones. Generally these silicones will be present in an oil phase. Preferably the oil phase will comprise 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 will generally comprise from about 75% to about 99.99%, more preferably from about 90% to about 99.95% by weight of the oil phase of volatile silicones. A description of various volatile silicones is found in Todd, et al.. "Volatile Silicone Fluids for Cosmetics", 91 Cosmetics and Toiletries 27-32 (1976), herein incorporated by reference. Suitable volatile silicones include cyclic and linear volatile polyorganosiloxanes. 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 2 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 present invention include: Dow Corning 344, Dow Corning 245, 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 preferably will have an average viscosity of from about 10 to about 100,000 cps at 25°C, more preferably from about 100 to about 10,000 cps, even more preferably 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, July 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 endcapped 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. However, 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 Company as a Viscasil (RTM) series and from Dow Corning as the Dow Corning 200 series. Preferably, the viscosity ranges from about 10 mm 2 .s _1 to about 100,000 mm 2 .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. References disclosing suitable silicone fluids include US-A-2,826,551 , Green; US-A-3,964,500, Drakoff, issued June 22nd, 1976; US-A-4,364,837, Pader; and GB-A-849,433, Woolston, all of which are incorporated herein by reference. 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_ )/2 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 polydiorganosiloxane segment being satisfied by a terminating radical; the weight ratio of polydiorganosiloxane segments to polyoxyalkylene segments in said copolymer preferably having a value of from about 2 to about 8. Such polymers are described in US-A-4, 268,499, incorporated herein by reference. Preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the general formula: 1 — Si — 0 - " 1 (C 2 H 4 0) a (C 3 H 6 θ) b R wherein R1 is selected from C1 to C5 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 preferred for use herein are polydiorganosiloxane-polyoxyalkylene copolymers having the formula: <- M 3 CH 3 CH 3 CH 3 H 3 ->C Si o ( Si 0)X (Si 0)y Si CH ,3 CH 3 CH 3 C 3 H 6 CH 3 0 (C 2 H 4 0) a (C 3 H 6 0) b R 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 4.0. Suitable copolymers are available commercially under the trade names 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 OYL. Particularly preferred for use herein are Belsil (RTM) 6031 , Abil (RTM) B88183, DC3225C, DC5200, DC5225C, Abil We09, Abil EM90, Abil wax 9801 , BY22-008 (Dow Corning) and SF1328 (GE Silicones). A preferred silicone herein is known by its CTFA designation as dimethicone copolyol. Optional Ingredients 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 can comprise an acidic skin care active, in addition to salicylic acid or salicylic acid derivative. 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 hydroxymonocarboxylic acids having the following chemical structure: R-l (CR 2 OH) m (CH 2 )nCOOH wherein R<| , R 2 = 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=0 or a numerical number up to 23. 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 hydroxymonocarboxylic acid and its related compounds may exist as stereoisomers such as D, L, and DL forms. Typical alkyl, aralkyl and aryl groups for R^ and R 2 include methyl, ethyl, propyl, isopropyl, benzyl and phenyl. The hydrogen atoms of the Ri and R 2 and (CH 2 ) n may be substituted by a nonfunctional element such as F, CI, 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-chloromandelic acid, 3-hydroxybutanoic acid, 4- hydroxybutanoic acid, 2-hydroxyhexanoic acid, 5-hydroxydodecanoic acid, 12- hydroxydodecanoic acid, 10-hydroxydecanoic acid, 16-hydroxyhexadecanoic acid, 2-hydroxy-3-methylbutanoic acid, 2-hydroxy-4-methylpentanoic acid, 3- hydroxy-4-methoxymandelic acid, 4-hydroxy-3-methoxymendelic acid, 2- hydroxy-2-methylbutanoic acid, 3-(2-hydroxyphenyl) lactic acid, 3-(4- hydroxyphenyl) lactic acid, hexahydromandelic 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: HOOC(CHOH) m (CH 2 ) n COOH wherein m=1 ,2,3,4,5,6,7,8 or 9; n=0 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 hydrogen attached to the carbon atom may be substituted by a nonfunctional element such as F, CI, 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 (tartaric acid), arabiraric acid, ribaric acid, xylaric acid and lyxaric acid, glucaric acid (saccharic acid), galactaric acid (mucic acid), mannaric 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 compounds 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: Hydroxycarboxylic 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, citramalic acid, agaricic acid (n- hexadecylcitric acid), quinic acid, uronic acids including glucuronic acid, glucuronolactone, galacturonic acid, galacturonolactone, 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-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, CI, 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 retinoic acid, and azelaic acid. The acidic skin care active can be 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 can be solubilized in water or a hydroalcoholic solution, for example, solutions based upon C 2 -C6 alcohols, diols and polyols, preferred alcohols being selected from ethanol, dipropylene glycol, butylene glycol, hexylene glycol, and mixtures thereof. The compositions of the present invention can also comprise a solubilizing agent for solubilizing the acidic skin care active and/or salicylic acid or salicylic acid derivative. Any solublizing agent suitable for use in a cosmetic composition can be used. A description of suitable solubilizing agents can be found in WO-A-98/10741 , incorporated by reference herein. In addition to the rutile and anatase titanium oxide preferred embodiments of the present invention comprise other pigment or mixtures of pigments. Any pigments suitable for use in cosmetic compositions may be used herein. 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, ferric oxide, ferrous oxide, chromium oxide, chromium hydroxide, manganese violet, acylglutamate iron oxides, ultramarine 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. Other examples of suitable pigments include silica, hydrated silica, silicone- treated silica beads, mica, talc, polyethylene, bentonite, hectorite, kaolin, chalk, nylon 12, diatomaceous earth, attapulgite zinc oxide and the like may be utilized. Of particular usefulness 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, aluminium starch octenyl succinate and mixtures thereof are particularly preferred. Materials suitable for use herein as light-scattering 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. Preferred pigments for use in the compositions herein include nylon 12 and the ferric oxides. 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 lysine, silicones, lauroyl, collagen, polyethylene, lecithin and ester oils. The more preferred pigments are the silicone (polysiloxane) treated pigments. A highly preferred pigment for use herein is a pigment which has been coated with organosilicon component 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 H 2 /g of coated pigment. The pigment preferred for use herein is in particulate form. The pigment is incorporated 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 they 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. A description of coated pigments can be found in WO-A-98/10741 , already incorporated by reference herein. A highly preferred component 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 3% to about 15% by weight of composition. Suitable humectants include glycerine, sorbitol, panthenols, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, alkoxylated glucose derivatives, such as Glucam (RTM) E-20, hexanetriol, polyglycerylmethacrylate lubricant, glucose ethers, and mixtures thereof. Preferred polyglycerylmethacrylate lubricants are marketed by Guardian Chemical Corporation under the trademark "Lubrajel". The "Lubrajels" identified as "Lubrajel DV", "Lubrajel MS", and "Lubrajel CG" are preferred in the present invention. The gelling agents sold under these trademarks contain about 1 % propylene glycol. The panthenol moisturiser can be selected from D-panthenol ([R]-2,4-di- hydroxy-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. The preferred humectant herein is glycerine. Chemically, glycerine is 1 ,2,3- propanetriol and is a product of commerce. 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 hydrophobic 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. Alternatively, the hydrophobic polymer can take the form of a porous particle having a surface area (N 2 -BET) in the range from about 50 to 500, preferably 100 to 300m 2 /g and having the active ingredient absorbed therein. The cross-linked hydrophobic polymer when used herein is preferably 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, moisturising 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 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 solid, 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: where the ratio of x to y is 80:20, R' is -CH 2 CH 2 - and R" is -(CH 2 )ι <| CH3. A suitable hydrophobic 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 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 Microsponges 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 0.05μm and a surface area of 200-300m 2 /g. Again, it is preferably loaded with humectant in the levels described above. 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%, 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 xanthan gum. Among suitable hydrophilic gelling agents are acrylic acid/alkyl 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 colloidally 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 980, Carbopol 951 and Carbopol 981. 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. Preferably 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 and triisostearyltrimerate. The compositions of the present invention may also comprise additional materials such as, for example, fragrances, preservatives, electrolytes such as sodium chloride, proteins, antioxidants such as tocopheryl acetate, chelating agents and water-in-oil emulsifiers as appropriate. The compositions of the present invention also preferably comprise one or more ultraviolet filtering agents. Ultraviolet filtering agents, often described as sunscreening agents, can be present in a concentration in the range of between about 1% and about 12% by weight, based on the total weight of composition. Preferably, the UV filtering agents constitute between about 2% and 8% by weight. More preferably, the UV filtering agents can be present in the composition in a concentration range of between about 3% and about 6% by weight. Any UV filtering agent suitable for use in cosmetic compositions may be used herein. Preferred are inorganic filtering agents. More preferred are zinc oxide and micronised titanium oxide, particularly micronised titanium oxide. As used herein the term "micronised titanium oxide" means titanium oxide particles that have a weight average particle size of less than 0.045μm, preferably less than 0.04μm. If present, the micronised titanium oxide will be in addition to the aforementioned rutile and anatase titanium oxides and will be treated separately in any calculations of, for example, average particle size or percentage weight of the composition. 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 concentration in the range of between about 0.03% and about 0.07% by weight, based on the total weight of the composition. Among the chelating agents that may be included in the composition is disodium EDTA. Another optional but preferred component of the foundation composition is one or more preservatives. The preservative concentration 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 benzoate and propyl paraben, and mixtures thereof. The cosmetic compositions of the present invention can be in the form of foundations, blushers, concealers, compact powders, moisturising creams and lotions, tinted moisturising creams and lotions, and the like, preferably as foundations and concealers. Method of Use The cosmetic compositions of the present invention may be used in a conventional manner for cosmetically treating skin. An effective amount of the composition, typically from about 0.1 grams to about 5 grams is applied to the skin. Application of the composition typically includes spreading the composition over the skin with the fingers or with a suitable implement such as a sponge to ensure good coverage. The composition is then left on the skin. The preferred method of treating the skin therefore comprises the steps of: (a) applying an effective amount of the cosmetic composition to the skin, (b) spreading the composition over the skin with hands and fingers or with a suitable implement. Examples The following examples further illustrate the preferred embodiments within the scope of the present invention. All ingredients are expressed on a weight percentage of the active ingredient. Examples l-VI (% w/w) - Liquid Foundations 1. Supplied by Dow Corning, Barry, South Glamorgan, Wales. 2. Ti0 2 9729 supplied by Whittaker, Clark & Daniels, South Plainfield, New Jersey, USA. 3. Kobo RPTD 11 S2 supplied by Kobo Products Inc., Montrose Av., South Plainfield, New Jersey, USA. 4. Supplied by Tayca Corporation, Tokyo 104, Japan. 5. Supplied by Chesham Chemicals Ltd., Cunningham House, Kenton, Harrow, Middlesex, UK. 6. Supplied by Presperse Inc., South Plainfield, New Jersey, USA. 7. Supplied by Caschem Inc. ., Bayonne, New Jersey, USA.. 8. Supplied by Astor Wax Corporation, Titusville, PA 16354, USA. 9. Supplied by NL Chemicals, Hightstown, New Jersey, USA. 10. Supplied by Roche Products Ltd., Welwyn Garden City, Herts, UK. The formulations in examples l-VI are prepared as follows. The mixture of components in Phase A are stirred together using high shear for 5 minutes until homogeneous. Remaining under high shear, the materials of Phase B are gradually added to Phase A and the batch is mixed for about 30 minutes. This mixing breaks down any solid agglomerations. The components of Phase C are then added are the resulting mixture is then ground for approximately a further 15 minutes. If required, the waxy phase D is added and the batch is heated to around 85°C with continued mixing until the waxes have melted. The mixture is then cooled to around 65°C with stirring. Phase E is then added to the batch and homogenised for 15 minutes. The batch is then cooled to room temperature with stirring. Phases F, G and H, if present, are added and the mix is further homogenised for 10 minutes. The water phase is prepared by mixing the components of Phase I together with stirring until dissolved. The water phase is then added to the oil phase slowly whilst homogenising and stirring. When all the water phase has been incorporated the shear is increased for about 5 minutes to increase the viscosity of the finished product. The resulting product is then packaged. Examples VI l-VI 11 (% w/w) - Pressed Powders 1 Supplied by US Cosmetics, Dayville, CT 06241 , USA 2 Supplied by US Cosmetics, Dayville, CT 06241 , USA 3 Supplied by Mearl Corporation, Ossming, New Jersey, USA 4 Ti02 9729 supplied by Whittaker, Clark & Daniels, South Plainfield, New Jersey, USA 5 Kobo RPTD 11S2 supplied by Kobo Products Inc . Montrose Av , South Plainfield, New Jersey, USA 6 Supplied by Tayca Corporation, Tokyo 104, Japan 7 Supplied by Lipa Chemicals Inc , Paterson, New Jersey, USA 8 Supplied by ISP Van Dyk, Belleville, New Jersey, USA 9 Supplied by Dow Corning, Barry, South Glamorgan, Wales The formulations in examples VII and VIII, are prepared as follows. The components in Phase A are mixed together under low shear for 30 minutes until homogeneous. The mixture is then milled to ensure an adequate dispersion. Separately, the materials of Phase B are mixed together for 10 minutes. Phase B is then sprayed into the vessel containing Phase A. The complete mixture is then mixed for a further 30 minutes to ensure a homogeneous product. Manual intervention may used if needed during this procedure. Finally, the complete mixture is milled again to ensure a fine, even dispersion. The resulting product is then packaged. All of the above examples show good coverage with reduced streakiness and cakiness.

Claims: Claims: 1. A cosmetic composition comprising: (a) mixture of rutile and anatase titanium oxide; and (b) no more than about 3.5%, by weight, of emollients. 2. A cosmetic composition according to Claim 1 wherein ratio of rutile titanium oxide to anatase titanium oxide in the mixture is in the range of from about 1 :20 to about 20:1 , preferably from about 1 :5 to about 5:1. 3. A cosmetic composition according to Claim 1 or 2 wherein at least about 50%, preferably at least about 90%, of the rutile and anatase titanium oxide particles in the mixture have a particle size of greater than 0.05μm. 4. A cosmetic composition according to any of the preceding claims wherein the rutile and anatase titanium oxide has a weight average particle size of from about 0.06μm to about 3.0μm, preferably from about 0.2μm to about 0.6μm. 5. A cosmetic composition according to any of the preceding claims wherein the mixture of rutile and anatase titanium oxide comprises from about 0.1% to about 50%, preferably from about 5% to about 10%, by weight, of the total composition. 6. A cosmetic composition according to any of the preceding claims wherein the composition comprises no more than about 2%, preferably no more than about 1%, by weight, of emollient . 7. A cosmetic composition according to any of the preceding claims comprising an ultra violet filtering agent. 8. A cosmetic composition according to Claim 7 wherein the ultra violet filtering agent is selected from micronised titanium oxide and zinc oxide. 9. A cosmetic composition according to any of the preceding claims comprising from about 1% to about 30%, preferably from about 5% to about 15%, by weight, humectant. 10. A cosmetic composition according to any of the preceding claims wherein the composition is in the form of a water-in-oil emulsion comprising a continuous oil phase and a discontinuous aqueous phase. 11. A cosmetic method of treating the skin to reduce the appearance of imperfections, blemishes or wrinkles comprising applying an effective amount of a composition according to any of the preceding claims.

Inventors: BROWNE YVONNE BRIDGET, CASSIDY DAVIN MARK, GRAHAM CAROLE, BROWNE, YVONNE, BRIDGET, CASSIDY, DAVIN, MARK, GRAHAM, CAROLE
Applicants: BROWNE YVONNE BRIDGET, CASSIDY DAVIN MARK, GRAHAM CAROLE, PROCTER & GAMBLE, BROWNE, YVONNE, BRIDGET, CASSIDY, DAVIN, MARK, GRAHAM, CAROLE, THE PROCTER & GAMBLE COMPANY
Application year: 1999
Main classification: A61K7
IPC codes: A61K8, A61Q1, A61Q19