TITLE OF THE INVENTION

WATER-IN-OIL EMULSIONS SUITABLE AS EYELINERS

FIELD OF THE INVENTION

[0001] The present invention relates to water-in-oil (w/o) emulsion compositions (emulsions) suitable as eyeliner compositions (eyeliners) comprising at least one clay filler, at least one oil, at least one coloring agent (colorant) and at least one surfactant having lipophilic properties (at least one surfactant which has an HLB value which is about 8 or less). The compositions can have beneficial cosmetic properties including continuous and/or homogeneous deposit upon application to keratinous materials (good or improved application properties), good wear properties (waterproof and/or long-lasting), and/or minimization or inhibition of the umbrella effect when the compositions are used in combination with a brush applicator having fibers such as a polybutylene terephthalate (PBT) fibers (good or improved umbrella effect properties).

DISCUSSION OF THE BACKGROUND

[0002] Eyeliners generally are anhydrous compositions, in the form of dispersions of waxes in organic solvents. Because of their structure, such anhydrous compositions can be long-lasting and waterproof. It is also known for eyeliners to be in the form of an aqueous composition, containing aqueous gelling agents and polymers. However, such compositions can have drawbacks.

[0003] For example, aqueous gelled compositions tend not to be waterproof or have other inferior wear properties, while anhydrous compositions can result in an “umbrella effect” when used in combination with a brush applicator having fibers such as polybutylene terephthalate (PBT) fibers. “Umbrella effect” is where fibers of the brush applicator splay out in a disorganized manner after use and contact with an eyeliner formulation, similar to an umbrella, making use of the applicator more difficult or impossible over time.

[0004] US 3,639,572 relates to an eyeliner which is an aqueous dispersion of water-insoluble polymer, polyhydric alcohol, pigment, and inorganic silicate.

[0005] US 5,013, 543 relates to a liquid eyeliner containing pigment, water, alcohol, film former, and plasticizer.

[0006] There is a need to develop a cosmetic composition, in particular a composition suitable for use as an eyeliner, making it possible to obtain good wear properties upon application, where the composition is also capable of minimizing the umbrella effect described above.

SUMMARY OF THE INVENTION

[0007] The present invention relates to water-in-oil (w/o) emulsion compositions suitable for use as eyeliner compositions comprising at least one clay filler, at least one oil, at least one coloring agent, and at least one surfactant having lipophilic properties. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes.

[0008] The present invention relates to water-in-oil (w/o) emulsion compositions suitable for use as eyeliner compositions comprising at least one hectorite filler, at least one oil, at least one coloring agent, and at least one sorbitan ester surfactant having lipophilic properties.

Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes.

[0009] The present invention also relates to methods of making up the eyes by applying compositions of the present invention to keratinous material around the eyes in an amount sufficient to make up the eyes. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes.

[0010] The present invention also relates to methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to keratinous material, wherein the method comprises applying compositions of the present invention to keratinous material with the applicator brush. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0011] The present invention also relates to methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to keratinous material, wherein the method comprises preparing a water-in-oil (w/o) emulsion composition suitable for use as an eyeliner composition comprising combining at least one clay filler, at least one oil, at least one coloring agent, and at least one surfactant having lipophilic properties to form a water-in-oil emulsion composition effective in inhibiting splaying of the fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil emulsion composition to keratinous material. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0012] The present invention also relates to methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply an eyeliner to keratinous material, wherein the method comprises preparing a water-in-oil (w/o) emulsion composition suitable for use as an eyeliner composition comprising combining at least one hectorite filler, at least one oil, at least one coloring agent, and at least one sorbitan ester surfactant having lipophilic properties to form a water-in-oil emulsion composition effective in inhibiting splaying of the fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil eyeliner emulsion composition to keratinous material. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0013] The present invention also relates to methods of making water-in-oil (w/o) emulsion compositions of the present invention as described in the preceding two paragraphs.

[0014] The present invention also relates to kits comprising (1 ) an applicator brush; and (2) water-in-oil (w/o) emulsion compositions of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0015] In the following description of the invention and the claims appended hereto, it is to be understood that the terms used have their ordinary and accustomed meanings in the art, unless otherwise specified.

[0016] “About” as used herein means within 10% of the indicated number (e.g. “about 10%” means 9% - 11 % and “about 2%” means 1.8% - 2.2%).

[0017] “A” or “an” as used herein means “at least one.”

[0018] “At least one” means one or more and thus includes individual components as well as mixtures/combinations.

[0019] As used herein, all ranges provided are meant to include every specific range within, and combination of subranges between, the given ranges. Thus, a range from 1-5, includes specifically 1 , 2, 3, 4 and 5, as well as subranges such as and 2-5, 3-5, 2-3, 2-4, 1 -4, etc.

[0020] “Film former”, “film-forming polymer” or “film-forming agent” or “co-film former” as used herein means a polymer or resin that leaves a film on the substrate to which it is applied, for example, after a solvent accompanying the film former has evaporated, absorbed into and/ or dissipated on the substrate.

[0021] “Polymer” as used herein means a compound which is made up of at least two monomers.

[0022] “Viscosity” as used herein can be determined by any means known in the art, and is measured at 25°C and at atmospheric pressure. For example, viscosity can be measured with a rheometer Rheomat 180 with a mobile adapted to the viscosity of the product to be tested (for example spindle M3 and M4), with rotation speed ranging from 5 to 1000 rpm, with shear rate of about 200 S’ ¹ , and with Torque ranging from 0.25 to 10 mNm, for 10 min. Preferred viscosity of compositions of the present invention range from about 100,000 cps (centipoise) to about 350,000 cps, preferably from about 125,000 cps to about 300,000 cps, and preferably from about 160,000 cps to about 250,000 cps, including all ranges and subranges therebetween.

[0023] "Transfer resistance" as used herein refers to the quality exhibited by compositions that are not readily removed by contact with another material, such as, for example, an item of clothing or the skin, for example. “Smudge resistance” is a type of “transfer resistance” - in the context of eye compositions, smudges occur when skin around the eye area contacts another material and transfers cosmetic material to the contacted material. Transfer resistance may be evaluated by any method known in the art for evaluating such. For example, transfer resistance of a composition may be evaluated by a test which may involve application of the composition to human keratin material, followed by rubbing a material, for example, a sheet of paper, against the keratin material, after expiration of a certain amount of time following application, such as 2 minutes after application. Similarly, transfer resistance of a composition may be evaluated by the amount of product transferred from a wearer to any other substrate, such as transfer from the skin around the eyes of an individual to an item of clothing or other skin after the expiration of a certain amount of time following application of the composition. The amount of composition transferred to the substrate (e.g., collar, skin or paper) may then be evaluated and compared. For example, a composition may be transfer resistant if a majority of the product is left on the wearer’s keratin material. Further, the amount transferred may be compared with that transferred by other compositions, such as commercially available compositions. In a preferred embodiment of the present invention, little or no composition is transferred to the substrate from the keratin material.

[0024] "Long wear" compositions as used herein, refers to compositions where color remains the same or substantially the same as at the time of application, as viewed by the naked eye, after an extended period of time. Long wear properties may be evaluated by any method known in the art for evaluating such properties. For example, long wear may be evaluated by a test involving the application of a composition to human keratin material and evaluating the color of the composition after an extended period of time. For example, the color of a composition may be evaluated immediately following application to keratin material and these characteristics may then be re-evaluated and compared after a certain amount of time. Further, these characteristics may be evaluated with respect to other compositions, such as commercially available compositions.

[0025] "Waterproof" as used herein refers to the ability to repel water and permanence with respect to water. Waterproof properties may be evaluated by any method known in the art for evaluating such properties. For example, a composition may be applied to a substrate, which may then be placed in water for a certain amount of time, such as, for example, 20 minutes. Upon expiration of the pre-ascertained amount of time, the substrate may be removed from the water and passed over a material, such as, for example, a sheet of paper. The extent of residue left on the material may then be evaluated and compared with other compositions, such as, for example, commercially available compositions. For example, a composition may be waterproof if a majority of the product is left on the wearer or keratin material or substrate to which composition had been applied. In a preferred embodiment of the present invention, little or no composition is transferred from the wearer or keratin material to the other material.

[0026] “Substituted” as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen containing groups, ester groups, thiol groups, sulphonate groups, thiosulphate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted.

[0027] “Volatile”, as used herein, means having a flash point of less than about 100°C.

[0028] “Non-volatile”, as used herein, means having a flash point of greater than about 100°C.

[0029] “Makeup Result” as used herein, refers to compositions where color remains the same or substantially the same as at the time of application, as viewed by the naked eye, after an extended period of time. “Makeup Result” may be evaluated by evaluating long wear properties by any method known in the art for evaluating such properties such as those discussed above.

[0030] “Making up” as used herein means to provide decoration (for example, color) to the keratin material to which they are applied.

[0031] The compositions and methods of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful. For example, the surfactant component of the emulsion composition can “consist essentially of” or “consist of” one or more surfactants having lipophilic properties (e.g., sorbitan esters), or surfactants having HLB values below an indicated value (e.g., an HLB value of less than

8, 7, 6, 5 or 4). [0032] For purposes of the emulsion compositions and components of the present invention which ’’consist essentially of’ identified ingredients, the “basic and novel properties” of such compositions and component is minimization of umbrella effect.

[0033] "Free" or "substantially free" or "devoid of" as it is used herein means that while it is preferred that no amount of the specific component be present in the composition, it is possible to have very small amounts of it in the compositions of the invention provided that these amounts do not materially affect at least one, preferably most, of the advantageous properties of the conditioning compositions of the invention. Thus, for example, "free of wax” means that an effective amount (that is, more than trace amounts) of wax is omitted from the composition (that is, about 0% by weight), "substantially free of wax" means that wax is present in amounts not greater than 1 % by weight, and "devoid of wax" means that wax is present in amounts not greater than 0.5% by weight, based on the total weight of the composition. The same nomenclature applies for all other ingredients identified throughout the application and in this paragraph such as, for example, film formers (compositions of the invention which are "free of film formers," "substantially free of film formers," and "devoid of film formers" have meanings consistent with the discussion within this paragraph), even if not specifically discussed for each identified ingredient. Discussed examples of the use of such language are intended to be exemplary, not limiting.

[0034] Referred to herein are trade names for materials including, but not limited to polymers and optional components. The inventors herein do not intend to be limited by materials described and referenced by a certain trade name. Equivalent materials (e.g., those obtained from a different source under a different name or catalog (reference) number) to those referenced by trade name may be substituted and utilized in the methods described and claimed herein.

[0035] All percentages and ratios are calculated by weight unless otherwise indicated. All percentages are calculated based on the total weight of a composition unless otherwise indicated. All component or composition levels are in reference to the active level of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources.

[0036] All U.S. patents or patent applications disclosed herein are expressly incorporated by reference in their entirety.

[0037] CLAY FILLER

[0038] According to the present invention, water-in-oil (w/o) emulsion compositions comprising at least one clay filler are provided.

[0039] Suitable clay fillers include silicate clays such as, for example, silicate clays containing at least one cation which may be chosen from, for example, ammonium, calcium, magnesium, aluminium, sodium, potassium, and lithium cations, and mixtures thereof.

[0040] Non-limiting examples of such products include smectite clays such as montmorillonites, hectorites, bentonites, beidellites, saponites, vermiculites, stevensite, and chlorites. Preferred clays are hectorites such as those commercially available from Elementis (for example, under the Bentone® tradename such as Bentone® 27 and Bentone® 38, Most preferred is disteardimonium hectorite or stearalkonium hectorite.

[0041] Other specific examples of silicate clays which may be used in the present invention can be chosen from, for example, lithium magnesium silicate, aluminum calcium sodium silicate, calcium magnesium silicate, sodium magnesium silicate, calcium aluminum borosilicate, magnesium aluminum silicate, sodium potassium aluminum silicate, and sodium silver aluminum silicate.

[0042] Preferably, the at least one clay filler is present in an amount sufficient to thicken a composition of the present invention to a desired viscosity. Such amounts generally are preferably from about 0.1 % to about 15% by weight, preferably from about 1 % to about 10% by weight, preferably from about 2% to about 6% by weight, and preferably from about 3% to about 5% by weight, based on the total weight of the composition, including all ranges and subranges as discussed/defined above.

[0043] In accordance with preferred embodiments, the optimal amount of the at least one clay filler present in the compositions of the present invention may vary depending upon the type of applicator used in conjunction with compositions. For example, using a felt tip applicator in conjunction with compositions can result in an optimal concentration of at least one clay (e.g., hectorite) of about 4% to about 5% by weight, whereas the optimal amount of the clay (e.g., hectorite) may be slightly higher (about 5% to about 6% by weight) for a brush applicator.

[0044] SOLVENT [0045] According to the present invention, water-in-oil (w/o) emulsion compositions comprising at least oil or solvent are provided.

[0046] Compositions of the present invention comprise sufficient oil to form a water-in-oil emulsion, preferably from about 15% to about 70% oil, preferably from about 20% to about 60% oil, preferably from about 25% to about 50% oil, preferably from about 30% to about 45% oil, and preferably from about 30% to about 40% oil, by weight with respect to the total weight of the composition, including all ranges and subranges therebetween as defined/discussed above.

[0047] Suitable oils include volatile and/or non-volatile oils. Such oils can be any acceptable oil including but not limited to silicone oils and/or hydrocarbon oils.

[0048] According to certain embodiments, the oil carrier (oil component) comprises one or more volatile silicone oils. According to certain embodiments, the oil carrier (component) can “consist essentially of” or “consist of” volatile hydrocarbon oils, volatile silicone oils, or mixtures thereof.

[0049] Examples of such volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature less than or equal to 6cSt and having from 2 to 7 silicon atoms, these silicones being optionally substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that may be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and their mixtures. Other volatile oils which may be used include KF 96A of 6 cSt viscosity, a commercial product from Shin Etsu having a flash point of 94°C. Preferably, the volatile silicone oils have a flash point of at least 40°C.

[0050] Non-limiting examples of volatile silicone oils are listed in

Table 1 below.

[0051] Table 1

[0052] Further, a volatile linear silicone oil may be employed in the present invention. Suitable volatile linear silicone oils include those described in U.S. patent no. 6,338,839 and W003/042221 , the contents of which are incorporated herein by reference. In one embodiment the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, the decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

[0053] According to other embodiments, the oil phase (component) comprises one or more volatile hydrocarbon solvents such as hydrocarbon oils, volatile esters and volatile ethers. Examples of such volatile solvents include, but are not limited to, compounds like propylene carbonate and volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures and in particular branched C ₈ to Ci ₆ alkanes such as C ₈ to C isoalkanes (also known as isoparaffins), isododecane, isodecane, and for example, the oils sold under the trade names of Isopar or Permethyl. Preferably, the volatile hydrocarbon solvents have a flash point of at least 40°C.

[0054] Non-limiting examples of volatile hydrocarbons are given in Table 2 below.

Table 2

[0055] The volatility of the solvents/oils can be determined using the evaporation speed as set forth in U.S. patent no. 6,338,839, the contents of which are incorporated by reference herein.

[0056] According to preferred embodiments of the present invention, the oil carrier (component) further comprises at least one nonvolatile oil or solvent. Examples of non-volatile oils that may be used in the present invention include, but are not limited to, polar oils such as:

[0057] - hydrocarbon-based plant oils with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have varied chain lengths, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheat germ oil, corn oil, sunflower oil, karite butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, avocado oil, hazelnut oil, grape seed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; or caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

[0058] - synthetic oils or esters of formula R ₅ COOR ₆ in which R ₅ represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R ₆ represents a branched hydrocarbon-based chain containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms, with R ₆ + R? > 10, such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C ₁₂ to C ₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricinoleates of alcohols or of polyalcohols; hydroxylated esters, for instance isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

[0059] - synthetic ethers containing from 10 to 40 carbon atoms;

[0060] - C ₈ to C ₂ 6 fatty alcohols, for instance oleyl alcohol, cetyl alcohol, stearyl alcohol, and cetearyl alcohol; and

[0061] - mixtures thereof.

[0062] Further, examples of non-volatile oils that may be used in the present invention include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons and hydrocarbon waxes including polyolefins, in particular Vaseline (petrolatum), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene, and mixtures thereof.

[0063] According to preferred embodiments, however, compositions of the present invention are substantially free of, devoid of, or free of non-volatile oils as discussed/defined above.

[0064] According to preferred embodiments, compositions of the present invention are substantially free of, devoid of, or free of silicone oils such as, for example, dimethicone and/or cyclomethicone as discussed/defined above.

[0065] According to preferred embodiments, the oil component of the compositions of the present invention consist of volatile oils, preferably volatile hydrocarbon oils or solvents such as isododecane.

[0066] According to preferred embodiments, the oil component of the compositions of the present invention consist of hydrocarbon oils or solvents such as isododecane.

[0067] According to some embodiments of the present invention, compositions further comprising at least one wax are provided.

[0068] “Wax” means a lipophilic compound, solid at ambient temperature (25°C), with a reversible solid/liquid change of state, having a melting point greater than or equal to 30°C.

[0069] The waxes used in accordance with the present invention can be any wax and is not particularly limited. The waxes can be hydrocarbon, fluorinated and/or silicone, and be of plant, mineral, animal and/or synthetic origin. [0070] Suitable examples of waxes include, but are not limited to, Carnauba wax, candelilla wax, BIS-PEG-12 DIMETHICONE CANDELILLATE wax such as for example the Siliconyl Candelilla Wax marketed by the company KOSTER KEUNEN, hydrogenated Jojoba wax such as for example that marketed by the company DESERT WHALE, hydrogenated palm oil such as that marketed by the company SIO, rice bran wax, Sumac wax, ceresin waxes, laurel wax, Chinese insect wax, Shellac wax, hydrogenated olive oil such as Waxolive from the company SOLIANCE, waxes obtained by hydrogenation of olive oil esterified with C12 to C18 chain fatty alcohols such as those sold by the company SOPHIM under the brand names Phytowax Olive 12L44, 14L48, 16L55 and 18L57, waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol such as for example those which are sold under the names Phytowax Ricin 16 L 64 and Phytowax Ricin 22 L 73 by the company SOPHIM, hydrogenated Cameline wax, Ouricury wax, Montan wax, ozokerite waxes such as for example Wax SP 1020 P marketed by the company Strahl & Pitsch, microcrystalline waxes such as for example that sold under the brand name Microwax HW by the company PARAMELT, triglycerides of lauric, palmitic, cetylic and stearic acids (INCI name: hydrogenated coco glycerides) such as for example that sold under the brand name Softisan 100 by the company SASOL, polymethylene waxes such as for example that sold under the brand name Cirebelle 303 by the company SASOL, polyethylene waxes such as for example those sold under the brand names Performalene 400 polyethylene, Performalene 655 polyethylene and Performalene 500-L polyethylene by the company New Phase Technologies, alcohol-polyethylene waxes such as for example that marketed under the name Performacol 425 Alcohol by the company BARECO, the 95/5 ethylene/acrylic acid copolymer sold under the brand name AC 540 wax by the company Honeywell, hydroxyoctacosanyl hydroxystearate such as for example that sold under the brand name Elfacos C 26 by the company AKZO, octacosanyl stearate such as for example that marketed under the name Kester Wax K 82H by the company KOSTER KEUNEN, stearyl stearate such as for example that marketed under the name Liponate SS by the company LIPO CHEMICALS, pentaerythritol distearate such as for example that marketed under the name Cutina PES by the company COGNIS, the mixture of dibehenyl adipate, dioctadecyl adipate and di-eicosanyl adipate (INCI name C18-C22 dialkyl adipate), the mixture of dilauryl adipate and ditetradecyl adipate (INCI name: C12-C14 dialkyl adipate), the mixture of dioctadecyl sebacate, didocosyl sebacate and dieicosyl sebacate (INCI name: C18-C22 dialkyl sebacate) and the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyl octanedioate (INCI name: C18-C22 dialkyl octanedioate) such as for example those marketed by the company COGNIS, pentaerythrityl tetrastearate such as for example Liponate PS-4 from the company Lipo Chemicals, tetracontanyl stearate such as for example Kester Wax K76H from the company KOSTER KEUNEN, stearyl benzoate such as for example Finsolv 116 from the company FINETEX, behenyl fumarate such as for example Marrix 222 from the company AKZO BERNEL, di- (trimethylol-1 , 1 ,1 -propane) tetrastearate such as for example that which is offered under the name "HEST 2T-4S" by the company HETERENE, didotriacontanyl distearate such as for example Kester Wax K82D from the company KOSTER KELINEN, polyethylene glycol montanate with 4 ethylene oxide units (PEG-4) such as for example that which is sold under the brand name Clariant Licowax KST1 , hexanediol disalicylate such as for example Betawax RX-13750 marketed by the company CP Hall, dipentaerythritol hexastearate such as for example that which is sold under the brand name Hest 2P-6S by the company HETERENE, ditrimethylolpropane tetrabehenate such as for example that which is sold under the brand name Hest 2T-4B by the company HETERENE, Jojoba esters such as for example that which is sold under the brand name Floraester HIP by the company FLORATECH, mixtures of linear (C20-40) carboxylic acid/saturated hydrocarbons (INCI name: C20-40 acid polyethylene) such as for example Performacid 350 acid from the company NEW PHASE TECHNOLOGIES, synthetic wax of the Fischer-Tropsch type such as that marketed under the name Rosswax 100 by the company ROSS, cetyl alcohol, stearyl alcohol, behenyl alcohol, dioctadecyl carbonate such as for example Cutina KE 3737, saccharose polybehenate such as for example Crodaderm B from the company CRODA, and mixtures thereof, can in particular be cited. Such waxes are also described in U.S. patent application publication no. 2009/0142289, the entire contents of which is hereby incorporated by reference.

[0071] Waxes of plant origin such as carnauba wax, candelilla wax, hydrogenated jojoba wax, sumac wax, waxes obtained by hydrogenation of olive oil esterified with C12 to C18 chain fatty alcohols sold by the company SOPHIM in the Phytowax range (12L44, 14L48, 16L55 and 18L57), rice bran wax, cetyl, stearyl and behenyl alcohols, laurel wax and Ouricury wax are preferably used.

[0072] If present, the wax(es) are preferably present in a quantity of at least 5% by weight, preferably from about 5 to about 35% by weight, preferably from about 7.5 to about 30% by weight, and preferably from about 10 to about 25% by weight relative to the total weight of the composition, including all ranges and subranges therebetween.

[0073] According to preferred embodiments, however, compositions of the present invention are substantially free of, devoid of, or free of wax as discussed/defined above.

[0074] COLORANT

[0075] According to present invention, water-in-oil (w/o) emulsion compositions comprising at least one coloring agent (colorant) are provided. Acceptable colorants include pigments, dyes (for example, liposoluble dyes), nacreous pigments, and pearling agents.

[0076] Representative liposoluble dyes which may be used according to the present invention include Sudan Red, DC Red 17, DC Green 6, li-carotene, soybean oil, Sudan Brown, DC Yellow 11 , DC Violet 2, DC Orange 5, annatto, and quinoline yellow.

[0077] Representative nacreous pigments include white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment chosen from those mentioned above, and nacreous pigments based on bismuth oxychloride. [0078] Representative pigments include white, colored, inorganic, organic, polymeric, nonpolymeric, coated and uncoated pigments. Representative examples of mineral pigments include titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, and ferric blue. Representative examples of organic pigments include carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium.

[0079] Preferably, the at least one colorant (coloring agent) is present in a composition of the present invention in an amount sufficient to color keratinous material upon application of a composition of the present invention to a keratinous material. Such amounts generally are preferably from about 0.1 % to about 50% by weight, preferably from about 1 % to about 40% by weight, preferably from about 5% to about 35% by weight, and preferably from about 10% to about 25% by weight, based on the total weight of the composition, including all ranges and subranges as discussed/defined above.

[0080] SURFACTANT

[0081] According to the present invention, water-in-oil (w/o) emulsion compositions comprising at least one surfactant having lipophilic properties are provided. Generally speaking, acceptable surfactants (emulsifiers) can be chose from ionic emulsifiers, nonionic emulsifiers, and mixtures thereof.

[0082] “HLB” refers to the “hydrophilic-lipophilic balance” associated with emulsifiers. In particular, “HLB” value relates to the ratio of hydrophilic groups and lipophilic groups in emulsifiers, and also relates to solubility of the emulsifiers. Lower HLB emulsifiers (less than 8 and preferably less than 6) are more soluble in oils (lipophilic material) and are more appropriate for use in water-in-oil (W/O) emulsions. Higher HLB emulsifiers (greater than 8 and preferably greater than 9) are more soluble in water (hydrophilic material) and are more appropriate for oil-in-water (O/W) emulsions. “Surfactant having lipophilic properties” as used herein refers to a surfactant which has an HLB value which is about 8 or less.

[0083] According to preferred embodiments, compositions of the present invention comprise at least one surfactant which has an HLB value which is about 8 or less, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4 and preferably less than 3.

[0084] According to preferred embodiments, compositions of the present invention comprise a surfactant component (total surfactants present) which has an HLB value which is less than 8, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4 and preferably less than 3. Preferably, the surfactant component contains only one surfactant.

[0085] According to preferred embodiments, compositions of the present invention comprise a surfactant component which “consists essentially of” surfactants having an HLB value of about 8 or less, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4 and preferably less than 3 as defined/discussed above. Preferably, the surfactant component contains only one surfactant. [0086] According to preferred embodiments, compositions of the present invention comprise a surfactant component which “consists of” surfactants having an HLB value of about 8 or less, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4 and preferably less than 3 as defined/discussed above. Preferably, the surfactant component contains only one surfactant.

[0087] By way of example, the following emulsifiers have been reported to have the following HLB values:

[0088] Glycol Distearate HLB = 1 ;

[0089] Sorbitan Trioleate HLB = 1.8;

[0090] Propylene Glycol Isostearate HLB = 2.5;

[0091] Glycol Stearate HLB = 2.9;

[0092] Sorbitan Sesquioleate HLB = 3.7;

[0093] Glyceryl Stearate HLB = 3.8;

[0094] Lecithin HLB = 4;

[0095] Sorbitan Oleate HLB = 4.3;

[0096] Sorbitan Monostearate NF HLB = 4.7;

[0097] Sorbitan Stearate HLB = 4.7;

[0098] Sorbitan Isostearate HLB = 4.7;

[0099] Steareth-2 HLB = 4.9;

[0100] Oleth-2 HLB = 4.9;

[0101] Glyceryl Laurate HLB = 5.2;

[0102] Ceteth-2 HLB = 5.3;

[0103] PEG-30 Dipolyhydroxystearate HLB = 5.5;

[0104] Glyceryl Stearate SE HLB = 5.8; [0105] Sorbitan Stearate (and) Sucrose Cocoate HLB = 6;

[0106] PEG-4 Dilaurate HLB = 6;

[0107] Methyl Glucose Sesquistearate HLB = 6.6; and [0108] Polyglyceryl-4 Isostearate = 8.2 (about 8 or less). [0109] Preferred surfactants include, but are not limited to, sorbitan esters (esterified sorbitol) such as those derived from sorbitol and fatty acids (8 carbon atoms or greater) such as, for example, lauric acid, palmitic acid, stearic acid, oleic acid, etc.

[0110] Preferred sorbitan esters can have one or more fatty chains, for example 1 -3 fatty chains (for example, 1 fatty acid chain is present in sorbitan monostearate, whereas 3 chains are present in sorbitan trioleate). A preferred sorbitan ester is sorbitan sesquioleate.

[0111] Preferably, the at least one surfactant is present in a composition of the present invention in an amount from about 0.1 % to about 20% by weight, preferably from about 0.5% to about 15% by weight, preferably from about 1 % to about 10% by weight, and preferably from about 2.5% to about 7.5% by weight, based on the total weight of the composition, including all ranges and subranges as discussed/defined above, in particular ranges and subranges in which 3% by weight, 3.5% by weight, or 4% by weight are the lower end of the range such as, for example, 3% to 20% by weight, 3% to 12.5% by weight, 3% to 6% by weight, 4% to 15% by weight, 4% to 7.5% by weight, etc.

[0112] According to preferred embodiments of the present invention, the surfactant component of the invention compositions contains a surfactant, such as for example a sorbitan ester surfactant as discussed above, in a range in which 2.5% by weight, 3% by weight, 3.5% by weight, or 4% by weight are the lower end of the range such as, for example, 2.5% to 20% by weight, 2.5% to 15% by weight, 2.5% to 10% by weight, 3% to 20% by weight, 3% to 12.5% by weight, 3% to 7% by weight, 3.5% to 20% by weight, 3.5% to 11 % by weight, 3.5% to 7% by weight, 4% to 15% by weight, 4% to 7.5% by weight, etc. According to further preferred embodiments, the surfactant component of the invention compositions contains only one surfactant in the above amountsWhile not wishing to be bound by any theory, Applicants believe that the surfactants/surfactant component, in particular the sorbitan surfactants discussed above, in combination with the at least one clay in the compositions of the present invention allows for formation of a water-in-oil emulsion of appropriate viscosity while minimizing interaction between the oil portion of the composition and the applicator which, in turn, minimizes the “umbrella effect” or splaying discussed above. Further, Applicants believe that the presence of one surfactant in the above-identified significant amounts allows for improved pigment wetting in the invention compositions which, in turn, results in improved color intensity upon application. WATER

[0113] According to the present invention, water-in-oil (w/o) emulsion compositions comprising water are provided.

[0114] Compositions of the present invention comprise sufficient water to form a water-in-oil emulsion, preferably from about 5% to about 80% water, preferably from about 10% to about 70% water, preferably from about 20% to about 60% water, preferably from about 25% to about 50% water, and preferably from about 30% to about 40% water, by weight with respect to the total weight of the composition, including all ranges and subranges therebetween as defined/discussed above.

[0115] OTHER INGREDIENTS

[0116] Compositions of the present invention can optionally further comprise any additive usually used in the field(s) under consideration. For example, waxes, dispersants, antioxidants, sunscreens, preserving agents, fragrances, fibers, non-clay fillers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, humectants, vitamins, essential fatty acids, silicone elastomers, film formers, pasty compounds, viscosity increasing agents, for example, liposoluble/lipodispersible polymers, and mixtures thereof can be added. A non-exhaustive listing of such ingredients can be found in U.S. patent application publication nos. 2004/0170586 and 2009/0142289, the entire contents of which are hereby incorporated by reference. Further examples of suitable additional components can be found in the other references which have been incorporated by reference in this application. Still further examples of such additional ingredients may be found in the International Cosmetic Ingredient Dictionary and Handbook (9 ^th ed. 2002), with specific reference to solvents for the aqueous/water or oil phases such as, for example, glycerine, alcohols and low carbon (below C8) alkyl glycols (such as proylene glycol) and high carbon (C8 or greater) alkyl glycols (such as caprylyl glycol).

[0117] For example, according to preferred embodiments, waterin-oil (w/o) emulsions of the present invention further comprise at least one film forming agent (film former). The film-forming agent can be a hydrocarbon film forming agent or a silicone film forming agent.

[0118] Compositions of the present invention may comprise at least one hydrocarbon-containing film-forming agent. As used herein, “hydrocarbon-containing film forming agent” refers to a film forming agent comprising at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, or 99% hydrocarbon by weight. According to one or more embodiments, the hydrocarbon-containing film forming agent comprises less than about 5%, or less than about 1 %, silicone or siloxane groups, and preferably contains no silicone or siloxane groups.

[0119] Hydrocarbon-containing film forming agents are known in the art, and any hydrocarbon-containing film forming agent may be used.

[0120] Examples of acceptable classes of hydrocarbon- containing film-forming agents include acrylic polymers, acrylate copolymers, vinyl pyrrolidone (VP) containing homopolymers and copolymers, polyurethanes, polyolefins and mixtures thereof.

[0121] Acrylic Polymers

[0122] Acceptable acrylic polymer film forming agents are known in the art and include, but are not limited to, those disclosed in U.S. patent application 2004/0170586 and U.S. patent application 2011/0020263, the entire contents of which are hereby incorporated by reference.

[0123] “Acrylic polymer film formers” as used herein refers to polymers that are film forming agents and which are based upon one or more (meth)acrylic acid (and/or corresponding (meth)acrylate) monomers or similar monomers. In further embodiments, the acrylic polymer film formers do not contain any silicone or siloxane groups.

[0124] Non-limiting representative examples of such film forming agents include copolymers containing at least one apolar monomer, at least one olefinically unsaturated monomer, and at least one vinylically functionalized monomer.

[0125] For the apolar monomers, acrylic monomers which comprise acrylic and methacrylic esters with alkyl groups composed of 4 to 14 C atoms, preferably 4 to 9 C atoms are preferred. Examples of monomers of this kind are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n- nonyl acrylate, isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, and their branched isomers, such as, for example, 2-ethylhexyl acrylate, 2- ethylhexyl methacrylate.

[0126] For olefinically unsaturated monomers, it is preferred to use monomers having functional groups selected from hydroxyl, carboxyl, sulphonic acid groups, phosphonic acid groups, acid anhydrides, epoxides, and amines. Particularly preferred examples of olefinically unsaturated monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, betaacryloyloxypropionic acid, trichloracrylic acid, vinylacetic acid, vinylphosphonic acid, itaconic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate.

[0127] For vinylically functionalized compounds, preferred monomers include monomers which are copolymerizable with one or both of the previously discussed monomers and include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, sec-butyl acrylate, tertbutyl acrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tert-butylphenyl acrylate, tert-butylphenyl methacrylate, dodecyl methacrylate, isodecyl acrylate, lauryl acrylate, n- undecyl acrylate, stearyl acrylate, tridecyl acrylate, behenyl acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-butoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,5-dimethyladamantyl acrylate, 4-cumylphenyl methacrylate, cyanoethyl acrylate, cyanoethyl methacrylate, 4-biphenyl acrylate, 4-biphenyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, tetrahydrofurfuryl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, methyl 3-methoxyacrylate, 3-methoxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-phenoxyethyl methacrylate, butyldiglycol methacrylate, ethylene glycol acrylate, ethylene glycol monomethylacrylate, methoxy-polyethylene glycol methacrylate 350, methoxy-polyethylene glycol methacrylate 500, propylene glycol monomethacrylate, butoxydiethylene glycol methacrylate, ethoxytriethylene glycol methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, N-(1 -methylundecyl)acrylamide, N-(n- butoxymethyl)acrylamide, N-(butoxymethyl)methacrylamide, N- (ethoxymethyl)acrylamide, N-(n-octadecyl)acrylamide, and also N, N-dialkyl- substituted amides, such as, for example, N,N-dimethylacrylamide, N,N- dimethylmethacrylamide, N-benzylacrylamides, N-isopropylacrylamide, N- tert-butylacrylamide, N-tert-octylacrylamide, N-methylolacrylamide, N- methylolmethacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers, such as vinyl methyl ether, ethyl vinyl ether, vinyl isobutyl ether, vinyl esters, such as vinyl acetate, vinyl chloride, vinyl halides, vinylidene chloride, vinylidene halide, vinylpyridine, 4-vinylpyridine, N-vinylphthalimide, N-vinyllactam, N- vinylpyrrolidone, styrene, a- and p-methylstyrene, a-butylstyrene, 4-n- butylstyrene, 4-n-decylstyrene, 3,4-dimethoxystyrene, macromonomers such as 2-polystyrene-ethyl methacrylate (molecular weight Mw of 4000 to 13 000 g/mol), poly(methyl methacrylate)ethyl methacrylate (Mw of 2000 to 8000 g/mol).

[0128] Vinylpyrrolidone Polymers

[0129] Acceptable vinylpyrrolidone polymers include vinylpyrrolidone homopolymers and vinylpyrrolidone copolymers. Such homopolymers and copolymers can be crosslinked or non-crosslinked. For example, particularly suitable polymers are vinylpyrrolidone homopolymers such as the Polymer ACP-10. Further examples include copolymers produced from alpha-olefin and vinylpyrrolidone in which the copolymer contains vinylpyrrolidone and an alkyl component, preferably containing at least one C4-C30 moiety (substituted or unsubstituted) in a concentration preferably from 10 to 80 percent of the copolymer. Suitable examples of commercially available copolymers include those available from Ashland under the Ganex name such as, for example, VP/eicosene (GANEX V-220) and VP/tricontanyl copolymer (GANEX WP660).

[0130] Silicone-Containing Film Forming Agent

[0131] Compositions of the present invention may comprise at least one silicone-containing film forming agent. As used herein, “silicone- containing film forming agent” refers to a film forming agent that contains silicone. In one or more embodiments, “silicone-containing film forming agent” includes polymers that contain at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 99% silicone by weight. Silicone-containing film forming agents are known in the art, and any silicone-containing film forming agent may be used.

[0132] Examples of acceptable classes of silicone-containing film forming agents include silicone resins, silicone acrylate copolymers, and mixtures thereof.

[0133] Silicone Resin

[0134] As used herein, the term “resin” means a crosslinked or non-crosslinked three-dimensional structure. Silicone resin nomenclature is known in the art as "MDTQ" nomenclature, whereby a silicone resin is described according to the various monomeric siloxane units which make up the polymer.

[0135] Each letter of "MDTQ" denotes a different type of unit. The letter M denotes the monofunctional unit (CH ₃ ) ₃ SiO 2. This unit is considered to be monofunctional because the silicone atom only shares on oxygen when the unit is part of a polymer. The "M" unit can be represented by the following structure:

[0137] At least one of the methyl groups of the M unit may be replaced by another group, e.g., to give a unit with formula [R(CH ₃ ) ₂ ]SiO _1/2 , as represented in the following structure:

[0139] wherein R is chosen from groups other than methyl groups. Non-limiting examples of such groups other than methyl groups include alkyl groups other than methyl groups, alkene groups, alkyne groups, hydroxyl groups, thiol groups, ester groups, acid groups, ether groups, wherein the groups other than methyl groups may be further substituted.

[0140] The symbol D denotes the difunctional unit (CH ₃ ) ₂ SiO ₂ / ₂ wherein two oxygen atoms bonded to the silicone atom are used for binding to the rest of the polymer. The "D" unit, which is the major building block of dimethicone oils, can be represented as:

[0142] At least one of the methyl groups of the D unit may be replaced by another group, e.g., to give a unit with formula [ (CH3) ₂ ]SiO-i/ ₂ . [0143] The symbol T denotes the trifunctional unit, (CH ₃ )SiO _3/2 and can be represented as:

[0144]

[0145] At least one of the methyl groups of the T unit may be replaced by another group, e.g., to give a unit with formula [R(CH ₃ ) ₂ ]SiOi/ ₂ .

[0146] Finally, the letter Q means a tetrafunctional unit SiO ₄ / ₂ in which the silicon atom is bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.

[0147] Thus, a vast number of different silicone polymers can be manufactured. Further, it would be clear to one skilled in the art that the properties of each of the potential silicone polymers will vary depending on the type(s) of monomer(s), the type(s) of substitution(s), the size of the polymeric chain, the degree of cross linking, and size of any side chain(s).

[0148] Non-limiting examples of silicone polymers include siloxysilicates and silsesquioxanes.

[0149] According to preferred embodiments, compositions of the present invention comprise at least one silicone resin selected from the gorup consisting of siloxysilicates, silsesquioxanes, and mixtures thereof.

[0150] A non-limiting example of a siloxysilicate is trimethylsiloxysilicate, which may be represented by the following formula:

[0151] [(CH ₃ ) ₃ XSiXO] _x X(SiO _4/2 ) _y

[0152] (i.e, MQ units) wherein x and y may, for example, range from 50 to 80. Silsesquioxanes, on the other hand, may be represented by the following formula: [0153] (CH ₃ SiO _3/2 ).x

[0154] (i.e. , T Units) wherein x may, for example, have a value of up to several thousand.

[0155] Resin MQ, which is available from Wacker, General Electric and Dow Corning, is an example of an acceptable commercially- available siloxysilicate. For example, trimethylsiloxysilicate (TMS) is commercially available from General Electric under the tradename SR1000 and from Wacker under the tradename TMS 803. TMS is also commercially available from Dow Chemical in a solvent, such as for example, cyclomethicone. However, according to the present invention, TMS may be used in the form of 100% active material, that is, not in a solvent.

[0156] Suitable silicon resins comprising at least one T unit in accordance with the present invention are disclosed, for example, in U.S. patent application publication numbers 2007/0166271 , 2011/0038820, 2011/0002869, and 2009/0214458, the entire contents of which are hereby incorporated by reference in their entirety.

[0157] Where the silicone resin contains at least one T unit, it may thus be, for example, a T, MT, MTQ or MDTQ resin.

[0158] According to preferred embodiments, the unit composition of the silicone resin can be at least 50% T units, or at least 70% T units, or at least 80% T units, or at least 90% T units.

[0159] In the M, D and T units listed as examples above, at least one of the methyl groups may be substituted. According to preferred embodiments, the at least one silicone resin comprising at least one trifunctional unit of formula (R)SiO ₃ /2 is chosen from the silsesquioxanes of formula: ((R')SiO ₃ / ₂ ) _x , in which x ranges from 100 to 500 and R' is chosen, independently by trifunctional unit, from a hydrocarbon-based group containing from 1 to 10 carbon atoms or a hydroxyl group, on the condition that at least one R' is a hydrocarbon-based group. According to preferred embodiments, the hydrocarbon-based group containing from 1 to 10 carbon atoms is a methyl group. According to preferred embodiments, the at least one silicone resin comprising at least one trifunctional unit of formula (R)SiO ₃ / ₂ is chosen from the silsesquioxanes of the formula: ((R')SiO ₃ / ₂ )x, in which x ranges from 100 to 500 and R' is chosen, independently by unit, from CH ₃ , a hydrocarbon-based group containing from 2 to 10 carbon atoms, or a hydroxyl group, on the condition that at least one R' is a hydrocarbon-based group.

[0160] According to preferred embodiments, the T resins may contain M, D and Q units such that at least 80 mol % or at least 90 mol %, relative to the total amount of silicones, are T units. The T resins may also contain hydroxyl and/or alkoxy groups. The T resins may have a total weight of hydroxyl functions ranging from 2% to 10% and a total weight of alkoxy functions that may be up to 20%; in some embodiments, the total weight of hydroxyl functions ranges from 4% to 8% and the total weight of alkoxy functions may be up to 10%.

[0161] The silicone resin may be chosen from silsesquioxanes that are represented by the following formula: ((CH ₃ )SiO ₃ /2)x, in which x may be up to several thousand and the CH ₃ group may be replaced with an R group, as described previously in the definition of the T units. The number x of T units of the silsesquioxane may be less than or equal to 500, or it may range from 50 to 500, including all ranges and subranges therebetween. The molecular weight of the silicone resin may range from about 500, 1000, 5,000, 10,000, 15,000 or 20,000 g/molto about 30,000, 35,000, 40,000, 45,000, 50,000, 75,000 or 100,000 g/mol, including all ranges and subranges therebetween.

[0162] As suitable examples of these silicone resins containing at least one T unit, mention may be made of:

[0163] polysilsesquioxanes of formula ((R)SiO ₃ / ₂ )x (T units) in which x is greater than 100, in which the R groups may independently be methyl or other substituents as defined above;

[0164] polymethylsilsesquioxanes, which are polysilsesquioxanes in which R is a methyl group. Such polymethylsilsesquioxanes are described, for example, in U.S. Pat. No. 5,246,694, the entire contents of which is hereby incorporated by reference in its entirety;

[0165] polypropylsilsesquioxanes, in which R is a propyl group. These compounds and their synthesis are described, for example, in patent application WO 2005/075567, the entire contents of which is hereby incorporated by reference in its entirety; and

[0166] polyphenylsilsesquioxanes, in which R is a phenyl group. These compounds and their synthesis are described, for example, in patent application US 2004/0180011 , the entire contents of which is hereby incorporated by reference in its entirety.

[0167] Examples of commercially available polymethylsilsesquioxane resins that may be mentioned include those sold: [0168] by the company Wacker under the reference Resin MK such as Belsil PMS MK: polymer comprising CH ₃ SiO3/2 repeating units (T units), which may also comprise up to 1 % by weight of (CH ₃ ) ₂ SiO2/2 units (D units) and having an average molecular weight of about 10 000 g/mol. It is thought that the polymer is in a "cage" and "ladder" configuration as represented in the figures below. The average molecular weight of the units in "cage" configuration has been calculated as 536 g/mol. The majority of the polymer is in the "ladder" configuration with ethoxy groups at the ends. These ethoxy groups represent 4.5% by mass of the polymer. As these end groups can react with water, a small and variable amount of SiOH groups may also be present; and

[0169] by the company Shin-Etsu under the references KR- 220L, which are composed of T units of formula CH ₃ SiO ₃ / ₂ and have Si-OH (silanol) end groups, under the reference KR-242A, which comprise 98% of T units and 2% of dimethyl D units and have Si--OH end groups or alternatively under the reference KR-251 comprising 88% of T units and 12% of dimethyl D units and have Si--OH end groups.

[0170] Examples of commercially available polypropylsilsesquioxane resins that may be mentioned include those sold:

[0171] by the company Dow Corning under the reference Dow Corning 670 Fluid or 680 Fluid. Typically such commercially available products are polypropylsilsesquioxane diluted in volatile oil such as volatile hydrocarbon oil or volatile silicone oil such as D5. Dow Corning 670 and 680 Fluids have a general formula of R _n SiO(4. _n )/2 wherein R is independently chosen from a hydrogen atom and a monovalent hydrocarbon group comprising 3 carbon atoms, wherein more than 80 mole % of R are propyl groups, n is a value from 1 .0 to 1 .4, more than 60 mole % of the copolymer comprises RSiO ₃ / ₂ units, and having a hydroxyl or alkoxy content from 0.2 to 10% by weight, for example between 1 and 4% by weight, preferably between 5 and 10% by weight, and more preferably between 6 and 8% by weight. Preferably, the polypropylsilsesquioxane resin has a molecular weight from about 5,000, 7,000, 10,000, 15,000, 20,000, 25,000 to about 30,000, 50,000, 75,000, 100,000 g/mol and a Tg of less than about 37 °C, from about -100, -50, -37, or -20 to about 37 °C.

[0172] Examples of commercially available polyphenylsilsesquioxane resins that may be mentioned include those sold:

[0173] by the company Dow Corning under the reference Dow Corning 217 Flake Resin, which is a polyphenylsilsesquioxane with silanol end groups; and

[0174] by the company Wacker under the reference Belsil SPR 45 VP.

[0175] If present, the at least one film former is preferably present in a composition of the present invention in an amount from about 0.1 % to about 15% by weight, preferably from about 0.5% to about 12.5% by weight, preferably from about 1 % to about 10% by weight, and preferably from about 2.5% to about 7.5% by weight, based on the total weight of the composition, including all ranges and subranges as discussed/defined above. Although it is possible for the compositions of the present invention to be free of film forming agents, if desired.

[0176] APPLICATOR BRUSH [0177] According to preferred embodiments of the present invention, an applicator brush is provided and/or used in combination with compositions of the present invention. Any suitable applicator brush for liquid cosmetic compositions can be provided and/or used in combination with compositions of the present invention such as, for example, an applicator brush having fibers, an applicator brush having a felt tip, an applicator brush having a flocked tip, etc. Suitable applicator brushes include those for use with completely manual application. However, suitable applicator brushes can further include those for use with other functionality, such as for example employing heat, a sonic frequency, or shearing forces during application.

[0178] Preferably, an applicator brush having fibers comprises an applicator brush head which comprises fibers defining a fiber field. The fibers (filaments) can be crimped or non-crimped.

[0179] Preferably, the brush head is constructed out of plastics, such as nylon, polypropylene, polyurethane, polyethylene, etc., although other materials may be utilized, including metals, such as aluminum, titanium, etc., and mixtures of all of these materials (e.g., a combination of plastics and metals).

[0180] Preferably, the brush head comprises one or more of tufts of fibers including a plurality of fibers (filaments). The tufts can be arranged in a variety of profiles or shapes on the brush head surface. For example, tufts can be arranged into diamonds, squares, circles, triangles, snowflakes, etc. Preferably, when the fibers of the tufts are crimped, they can fill in spaces between tufts to provide a uniform distribution of fibers, if desired. [0181] Each tuft can include any number of fibers, such as from about 10 to 360 individual fibers, preferably 20 to 180 individual fibers. Preferably, the fibers have a length of about 0.20 inches (5.08 millimeters) to about 1.2 inches (30.48 millimeters) or greater, and a diameter in the range of about 0.002 inches (0.0508 millimeters) to about 0.020 inches (0.508 millimeters) or greater. Fiber length can either be uniform or non-uniform on the brush head, or even vary in length in individual tufts.

[0182] Preferably, the fibers can be constructed out of a variety of materials, including but not limited to natural materials (hair or fur), elastomers, co-elastomers, polymers, co-polymers, etc., and blends or combinations thereof. For example, fibers can be constructed out of polybutylene terephthalate (PBT), polyester or thermoplastic elastomer (TPE) or a TPE/PBT blend.

[0183] METHODS AND KITS

[0184] According to preferred embodiments, methods of making up the eyes by applying compositions of the present invention to keratinous material around the eyes in an amount sufficient to make up the eyes are provided. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes.

[0185] The compositions may be applied to the desired area as needed, preferably once or twice daily, more preferably once daily and then preferably allowed to dry before subjecting to contact such as with clothing or other objects. Preferably, the composition is allowed to dry for about 1 minute or less, more preferably for about 45 seconds or less. The composition is preferably applied to the desired area that is dry or has been dried prior to application.

[0186] According to preferred embodiments, methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to keratinous material, wherein the method comprises applying compositions of the present invention to keratinous material with the applicator brush as described above are provided. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0187] According to preferred embodiments, methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to keratinous material, wherein the method comprises preparing a water-in-oil (w/o) emulsion composition suitable for use as an eyeliner composition comprising combining at least one clay filler, at least one oil, at least one coloring agent, and at least one surfactant having lipophilic properties to form a water-in-oil emulsion composition effective in inhibiting splaying of the fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil emulsion composition to keratinous material are provided. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0188] According to preferred embodiments, methods of inhibiting splaying of fibers of an applicator brush during or after use of the applicator brush to apply an eyeliner to keratinous material, wherein the method comprises preparing a water-in-oil (w/o) emulsion eyeliner composition comprising combining comprising at least one hectorite filler, at least one oil, at least one coloring agent, and at least one sorbitan ester surfactant having lipophilic properties to form a water-in-oil emulsion composition effective in inhibiting splaying of the fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil eyeliner emulsion composition to keratinous material are provided. Preferably, the composition further comprises at least one film forming agent (film former). Preferably, the composition is substantially free of waxes. Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0189] According to preferred embodiments, methods of making water-in-oil (w/o) emulsion compositions of the present invention as described in the preceding two paragraphs are provided.

[0190] In the context of the preceding embodiments directed to inhibition of splaying of fibers, such splaying is associated with the “umbrella effect” discussed above resulting from using a brush applicator having fibers to apply a composition. Accordingly, such embodiments are relevant to ways to address and minimize the “umbrella effect.” [0191] According to preferred embodiments, kits comprising (1) an applicator brush as discussed above; and (2) water-in-oil (w/o) emulsion compositions as discussed above are provided.

[0192] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention.

[0193] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without limiting the scope as a result. The percentages are given on a weight basis.

[0194] Examples

[0195] Example 1 - Sample Composition: