WATER-IN-OIL EMULSIONS SUITABLE AS EYELINERS

Abstract

The invention relates to water-in-oil (w / o) emulsion compositions, preferably eyeliner compositions, containing at least one clay filler, at least one oil, at least one coloring agent (dye) and at least one surfactant having lipophilic properties, as well as methods for preparing and using such emulsions. Figure for abstract: none

Description

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 having an HLB value of about 8 or less). The compositions may have beneficial cosmetic properties, including continuous and / or homogeneous deposition upon application to keratinous materials (good or better application properties), good staying power (water-resistant and / or durable), and / or minimization or inhibition of umbrella effect when the compositions are used in combination with a brush applicator having fibers such as polybutylene terephthalate (PBT) fibers (good or better umbrella effect properties). BACKGROUND DISCUSSION

[0002] Eyeliners are generally anhydrous compositions, in the form of dispersions of waxes in organic solvents. Due to their structure, such anhydrous compositions can be durable and water-resistant. It is also known that eyeliners are in the form of an aqueous composition, containing aqueous gelling agents and polymers. However, such compositions may have disadvantages.

[0003] For example, aqueous gel compositions tend not to be water resistant or have other inferior staying power 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. The "umbrella effect" occurs when the fibers of the brush applicator stretch in a disorganized manner after use and contact with an eyeliner formula, similar to an umbrella, making use of the applicator more difficult or impossible over time.

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

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

[0006] There is a need to develop a cosmetic composition, in particular a composition suitable for use as an eyeliner, allowing good holding properties to be obtained during 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 an eyeliner composition 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 (film-forming) agent. 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 an eyeliner composition 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 (film-forming) agent. Preferably, the composition is substantially free of waxes.

[0009] The present invention also relates to methods of applying eye makeup by applying the compositions of the present invention to a keratinous material around the eyes in an amount sufficient to apply eye makeup. 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 the separation of the fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to a keratinous material, wherein the method comprises applying the compositions of the present invention to a 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 the separation of the fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to a keratinous material, wherein the method comprises preparing a water-in-oil (w / o) emulsion composition suitable for use as an eyeliner composition. comprising 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 to inhibit the separation of the fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil emulsion composition to a keratinous material. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film-forming (film-forming) agent. 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 the spread of fibers of an applicator brush during or after use of the applicator brush to apply an eyeliner to a keratinous material, wherein the method comprises preparing a water-in-oil (w / o) emulsion composition suitable for use as an eyeliner composition 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 to inhibit the spread of fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil emulsion composition to a keratinous material. Preferably, the composition is an eyeliner. Preferably, the composition further comprises at least one film-forming (film-forming) agent.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 preparing water-in-oil (w / o) emulsion compositions of the present invention as described in the two preceding 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 thereto, it is to be understood that the terms used have their ordinary and customary meanings in the art, unless otherwise specified.

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

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

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

[0019] As used herein, all proposed ranges are intended to include each specific range within the given ranges, and all combinations of subranges therein. Thus, a range of 1 to 5 specifically includes 1, 2, 3, 4, and 5, as well as subranges 2 to 5, 3 to 5, 2 to 3, 2 to 4, 1 to 4, etc.

[0020] “Film former”, “film-forming polymer” or “film-forming agent” 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-forming material has evaporated, been absorbed into, and / or dissipated on the substrate.

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

[0022] "Viscosity" as used herein may be determined by any means known in the art, and is measured at 25°C and atmospheric pressure. For example, viscosity may be measured using a Rheomat 180 rheometer with a spindle adapted to the viscosity of the product to be tested (e.g., spindles M3 and M4), with a rotation speed ranging from 5 to 1000 rpm, a shear rate of about 200 s*, and a torque ranging from 0.25 to 10 mNm, for 10 min. The preferred viscosity of the compositions of the present invention ranges from about 100,000 cps (centipoise) to about 350,000 cps, preferably from about 125,000 cps to about 300,000 cps, and most preferably from about 160,000 cps to about 250,000 cps, including all intermediate ranges and sub-ranges.

[0023] "Transfer resistance," as used herein, refers to the quality displayed by compositions that are not readily removed by contact with another material, such as clothing or skin, for example. "Stain resistance" is a type of "transfer resistance" - in the context of eye compositions, staining occurs when the skin around the eyes contacts another material and transfers the cosmetic material to the contacting material. Transfer resistance may be evaluated by any method known in the art for evaluating it. For example, the transfer resistance of a composition may be evaluated by a test that may involve applying the composition to a human keratinous material, followed by rubbing a material, for example, a sheet of paper, against the keratinous material, after a certain time has elapsed following application, for example, 2 minutes after application.Similarly, the transfer resistance of a composition can be assessed by the amount of product transferred from a wearer to any other substrate, such as transfer from the skin around an individual's eyes to clothing or other skin after a certain time has elapsed following application of the composition. The amount of composition transferred to the substrate (e.g., collar, skin, or paper) can then be assessed and compared. For example, a composition may be . transfer resistant if a majority of the product is left on the user's keratinous material. Furthermore, the amount transferred can be compared to 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 keratinous material.

[0024] “Long-lasting” compositions as used herein refer to compositions where the color remains the same or substantially the same as at the time of application, as visible to the naked eye, after an extended period of time. Long-lasting properties may be evaluated by any method known in the art for evaluating such properties. For example, long-lasting may be evaluated by a test involving the application of a composition to human keratinous material such as the lips and evaluating the color of the composition after an extended period of time. For example, the color of a composition may be evaluated immediately after application to keratinous materials such as the lips and these characteristics may then be re-evaluated and compared after a period of time. Further, these characteristics may be evaluated relative to other compositions, such as commercially available compositions.

[0025] “Water resistant” as used herein refers to the ability to repel water and permanence with respect to water. Water resistance 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 period of time, such as, for example, 20 minutes. At the end of the predetermined period, the substrate may be removed from the water and passed over a material such as a sheet of paper, for example. The extent of residue left on the material may then be evaluated and compared to other compositions, such as, for example, commercially available compositions. For example, a composition may be water resistant if a majority of the product is left on the user or on the keratinous material or substrate to which the composition has been applied.In a preferred embodiment of the present invention, little or no composition is transferred from the user or keratinous 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, sulfonate groups, thiosulfate groups, siloxane groups and polysiloxane groups. The substituent(s) may be further substituted.

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

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

[0029] “Makeup result” as used herein refers to compositions where the color remains the same or substantially the same as at the time of application, as seen with the naked eye, after an extended period of time. The “makeup result” may be evaluated by assessing long-lasting properties using any method known in the art for assessing such properties as those discussed above.

[0030] The term "Makeup" as used herein refers to the decoration (e.g., color) of the keratinous material to which it is applied.

[0031] The compositions and methods of the present invention may 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 may "consist essentially of" or "consist of" one or more surfactants having lipophilic properties (e.g., sorbitan esters), or surfactants having HLB values ​​less than a stated value (e.g., an HLB value less than 8, 7, 6, 5, or 4).

[0032] Within the meaning of the emulsion compositions and components of the present invention which "consist essentially of" compounds of identified ingredients, the "fundamental and novel properties" of these compositions and components are the minimization of the umbrella effect.

[0033] “Exempt” or “substantially free” or “devoid of” as used herein means that although it is preferred that no amount of the specific component be present in the composition, it is possible for there to be very small amounts thereof in the compositions of the invention provided that such amounts do not materially affect at least one, preferably most, of the beneficial properties of the conditioning compositions of the invention. Thus, for example, "wax-free" means that an effective amount (i.e., greater than trace amounts) of wax is omitted from the composition (i.e., about 0% by weight), "substantially wax-free" means that wax is present in amounts not greater than 1% by weight, and "wax-free" 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 to all other ingredients identified throughout the application and in this paragraph, such as, for example, film formers (the . compositions of the invention that are "free of film formers," "substantially free of film formers," and "free of film formers" have meanings consistent with the discussion within this paragraph), even if not specifically discussed for each identified ingredient. The discussed examples of the use of such language are intended to be provided by way of example, not limitation.

[0034] Reference is made herein to trademarked names of materials including, but not limited to, polymers and optional components. The inventors herein do not intend to be limited to the materials described and referenced by a certain trademarked name. Equivalent materials (e.g., those obtained from a different source under a different catalog name or (reference) number) to those referenced by a trademarked name may be substituted and used 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 levels of component or composition refer to the active level of that component or composition, and are exclusive of impurities, e.g., residual solvents or by-products, which may be present in commercially available sources.

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

[0037] CLAY CHARGE

[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 selected from, for example, ammonium, calcium, magnesium, aluminum, 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 (e.g., under the trade name Bentone® such as Bentone® 27 and Bentone® 38), with preference being disteardimonium hectorite or stearalkonium hectorite.

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

[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 are generally 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 sub-ranges as discussed / defined above.

[0043] In accordance with preferred embodiments, the optimal amount of at least one clay filler present in the compositions of the present invention may vary depending on the type of applicator used in conjunction with the compositions. For example, the use of a felt tip applicator in conjunction with compositions may result in an optimal concentration of at least one clay (e.g., hectorite) of about 4% to about 5% by weight, while 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] The 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 based on the total weight of the composition, including all intermediate ranges and sub-ranges as defined / discussed above.

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

[0048] According to some embodiments, the oil carrier (oil component) comprises one or more volatile silicone oils. According to some embodiments, the oil carrier (component) may "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 room temperature viscosity of less than or equal to 6 cSt 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 mixtures thereof. Other volatile oils that may be used include KF 96A having a viscosity of 6 cSt, 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] [Tables 1] Compound Flash point (°C) Viscosity (cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5) 55 2.5 Octamethylcyclotetrasiloxane 93 7 (cyclotetramethylsiloxane or D4) 63 1.7 Dodecamethylcyclohexasiloxane (D6) 94 6 Decamethyltetrasiloxane (L4) 56 1.5 Shin Etsu KF-96 A PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) Dow Corning PDMS DC 200 (2 cSt) Dow Corning 87 2

[0052] Furthermore, 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 WO03 / 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 more volatile than the decamethyltetrasiloxane.

[0053] According to other embodiments, the oily phase (component) comprises one or more volatile hydrocarbon solvents such as hydrocarbon oils, volatile esters and volatile ethers. Examples of such volatile non-silicone oils include, but are not limited to, compounds such as propylene carbonate and volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof and in particular, C8-C16 branched alkanes such as C8-C16 isoalkanes (also known as isoparaffins), isododecane, isodecane, and for example, oils sold under the brands 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.

[0055] [Tables2] Compound Flash point (°C) Isododecane 43 Propylene glycol n-Butyl ether 60 Ethyl 3-Ethoxypropionate 58 Propylene glycol methyl ether acetate 46 Isopar L (Cn-Ci3 isoparaffin) 62 Isopar H (Cn-Ci2 isoparaffin) 56

[0056] The volatility of solvents / oils can be determined using the evaporation rate as presented in U.S. Patent No. 6,338,839, the contents of which are incorporated herein by reference.

[0057] According to preferred embodiments of the present invention, the oil carrier (component) further comprises at least one non-volatile oil or solvent. Examples of non-volatile oils that can be used in the present invention include, but are not limited to, polar oils such as:

[0058] - vegetable oils based on hydrocarbons, with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have different chain lengths, these chains being able to be linear or branched and saturated or unsaturated; these oils are in particular wheat germ oil, corn oil, sunflower oil, shea butter, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy seed oil, pumpkin oil, sesame seed oil, pumpkin seed oil, avocado oil, hazelnut oil, rapeseed 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 example those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

[0059] - synthetic oils or esters of formula R5COOR6 in which R5 represents a linear or branched higher fatty acid residue containing from 1 to 40 carbon atoms, including from 7 to 19 carbon atoms, and R6 represents a branched hydrocarbon chain containing from 1 to 40 carbon atoms, including from 3 to 20 carbon atoms of carbon, with R6 + R7 ❖ 10, such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate and octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, for example, isostearyl lactate or isostearyl malate; and pentaerythritol esters;

[0060] - synthetic ethers containing from 10 to 40 carbon atoms;

[0061] - C8 to C26 fatty alcohols, for example oleyl alcohol, cetyl alcohol, alcohol stearyl and cetearyl alcohol; and

[0062] - their mixtures.

[0063] Furthermore, 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, particularly Vaseline (petrolatum), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydro squalene and mixtures thereof.

[0064] According to preferred embodiments, however, the compositions of the present invention are substantially free, devoid of, or free of non-volatile oils as discussed / defined above.

[0065] According to preferred embodiments, the compositions of the present invention are substantially free, devoid of or devoid of silicone oils such as, for example, dimethicone and / or cyclomethicone as discussed / defined above.

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

[0067] According to preferred embodiments, the oil component of the compositions of the present invention consists of hydrocarbon oils or solvents such as isododecane.

[0068] According to embodiments of the present invention, compositions further comprising at least one chelating agent are provided.

[0069] By "wax" is meant a lipophilic compound which is solid at room temperature (25°C), with a reversible solid / liquid state change, having a melting point greater than or equal to 30°C.

[0070] The waxes used in accordance with the present invention may be any wax and are not particularly limited. The waxes may be hydrocarbon, fluorinated and / or silicone, of vegetable, mineral, animal and / or synthetic origin.

[0071] Suitable examples of waxes include, but are not limited to, Camauba, candelilla wax, BIS-PEG-12 DIMETHICONE CAN-DELILLATE wax such as, for example, Siliconyl Candelilla Wax marketed by KOSTER KEUNEN, hydrogenated Jojoba wax such as, for example, that marketed by DESERT WHALE, hydrogenated palm oil such as that marketed by SIO, rice bran wax, Sumac wax, ceresin waxes, laurel wax, Chinese insect wax, Shellac wax, hydrogenated olive oil such as Waxolive wax from SOLIANCE, waxes obtained by hydrogenation of olive oil esterified with C12 to C18 fatty chain alcohols such as those sold by 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 sold under the names Phytowax Ricin 16 L64 and Phytowax Ricin 22 L 73 by the company SOPIMH, hydrogenated camelina wax, Ouricury wax, Montan wax, ozokerite waxes such as, for example, SP 1020 P wax marketed by the company Strahl & Pitsch, microcrystalline waxes such as, for example, those sold under the brand name Microwax HW by the company PARAMELT, triglycerides of lauric, palmitic, cetyl and stearic acids (INCI name: hydrogenated coco glycerides) such as, for example, those sold under the brand name Softisan 100 by the company SASOL, polymethylene waxes such as, for example, those 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 Per-formalene 500-L polyethylene by New Phase Technologies,alcohol-polyethylene waxes such as those sold under the brand name Per-formacol 425 Alcohol by the company BARECO, the ethylene / acrylic acid copolymer 95 / 5 sold under the brand name AC 540 wax by the company Honeywell, hydroxyoctacosanyl hydroxystearate such as that sold under the brand name Elfacos C 26 by the company AKZO, octacosanyl stearate such as that sold under the brand name Kester Wax K82H by the company KOSTER KEUNEN, stearyl stearate such as that sold under the name Liponate SS by the company LIPO CHEMICALS, pentaerythritol distearate such as that sold under the name Cutina PES by the company COGNIS, the mixture of dibehenyl adipate, dioctadecyl adipate and dieicosanyl adipate (INCI name C18-C22 dialkyl adipate), the mixture of diethyl 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 dioctadecyl octanedioate (name, INCI: C18-C22 dialkyl octanedioate) such as 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 KEUNEN, polyethylene glycol montanaate with 4 ethylene oxide units (PEG-4) such as for example which is sold under the brand name C1ARIANT Licowaxx KST1, hexanediol disalicylate such as for example for Beta RX-13750 marketed by the company CP Hall,dipentaerythritol hexastearate such as for example that sold under the brand name Hest 2P-6S by the company HETERENE, ditrimethylolpropane tetrabehenate such as for example that sold under the brand name Hest 2T-4B by the company HETERENE, jojoba esters such as for example that sold under the brand name Floraester HIP by the company FLORATECH, mixtures of linear carboxylic acid (C20-40) / saturated hydrocarbons (INCI name: C20-40 acid poly-ethylene), 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, carbonate of dioctadecyl such as Cutina KE 3737, sucrose polybehenate such as Crodaderm B from CRODA, and mixtures thereof,may be cited in particular. These waxes are also described in United States Patent Application Publication No. 2009 / 0142289, the entire contents of which are incorporated herein by reference.

[0072] 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 wax, cetyl, stearyl and behenyl alcohols, laurel wax and Ouricury wax are preferably used.

[0073] If present, the wax(es) are preferably present in an amount 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 intermediate ranges and sub-ranges.

[0074] According to preferred embodiments, however, the compositions of the present invention are substantially free, devoid of or free from wax as discussed / defined above.

[0075] COLORANT

[0076] According to the present invention, water-in-oil (w / o) emulsion compositions comprising at least one coloring agent (dye) are provided. Acceptable colorants include pigments, dyes (e.g., fat-soluble dyes), pearlescent pigments, and pearlescent agents.

[0077] Representative fat-soluble dyes that may be used according to the present invention include Sudan Red, DC Red 17, DC Green 6, B-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, annatto, and quinoline yellow.

[0078] Pearlescent pigments such as titanium or bismuth oxychloride coated mica, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment selected from those mentioned above, and bismuth oxychloride based pearlescent pigments may also be used.

[0079] Representative pigments include white, colored, inorganic, organic, polymeric, non-polymeric, coated, and uncoated pigments. Representative examples of inorganic 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, D & C type pigments, and cochineal carmine lakes, barium.

[0080] Preferably, the at least one colorant (coloring agent) is present in a composition of the present invention in an amount sufficient to color a keratinous material upon application of a composition of the present invention to a keratinous material. Such amounts are generally 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 sub-ranges as discussed / defined above.

[0081] SURFACTANT

[0082] According to the present invention, water-in-oil (w / o) emulsion compositions comprising at least one surfactant having lipophilic properties are provided. Generally, acceptable surfactants (emulsifiers) may be selected from ionic emulsifiers, non-ionic emulsifiers and mixtures thereof.

[0083] “HLB” means the “hydrophilic-lipophilic balance” associated with emulsifiers. In In particular, the "HLB" value relates to the ratio of hydrophilic groups to lipophilic groups in emulsifiers, as well as the solubility of the emulsifiers. Emulsifiers with lower HLB (less than 8 and preferably less than 6) are more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (W / O) emulsifiers. Emulsifiers with higher HLB (more than 8 and preferably more than 9) are more soluble in water (hydrophilic material) and are more suitable for oil-in-water (O / W) emulsions. "Surfactant having lipophilic properties," as used herein, means a surfactant whose HLB value is about 8 or less.

[0084] According to preferred embodiments, the compositions of the present invention comprise at least one surfactant whose HLB value 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.

[0085] According to preferred embodiments, the compositions of the present invention comprise a surfactant component (total surfactants present) whose HLB value 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 a single surfactant.

[0086] According to preferred embodiments, the 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 a single surfactant.

[0087] According to preferred embodiments, the 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 a single surfactant.

[0088] For example, the following emulsifiers have been reported to have the following HLB values:

[0089] Glycol distearate HLB = 1; Sorbitan trioleate HLB = 1.8;

[0091] Propylene glycol isostearate HLB = 2.5;

[0092] Glycol stearate HLB = 2.9; Sorbitan sesquioleate HLB = 3.7;

[0094] Glyceryl stearate HLB = 3.8;

[0095] Lecithin HLB = 4; Sorbitan oleate HLB = 4.3;

[0097] Sorbitan monostearate NF HLB = 4.7;

[0098] Sorbitan stearate HLB = 4.7;

[0099] Sorbitan isostearate HLB = 4.7;

[0100] Steareth-2 HLB = 4.9;

[0101] Oleth-2 HLB = 4.9;

[0102] Glyceryl laurate HLB = 5.2;

[0103] Ceteth-2 HLB = 5.3;

[0104] PEG-30 dipolyhydroxystearate HLB = 5.5;

[0105] Glyceryl stearate SE HLB = 5.8;

[0106] Sorbitan stearate (and) sucrose cocoate HLB = 6;

[0107] PEG-4 dilaurate HLB = 6;

[0108] Methylglucose sesquistearate HLB = 6.6;

[0109] Polyglyceryl-4 isostearate = 8.2 (about 8 or less).

[0110] Preferred surfactants include, but are not limited to, sorbitan esters (esterified sorbitol) such as those derived from sorbitol and fatty acids (8 or more carbon atoms), such as, for example, lauric acid, palmitic acid, stearic acid, oleic acid, etc.

[0111] Preferred sorbitan esters may have one or more fatty chains, for example 1 to 3 fatty chains (for example, 1 fatty acid chain is present in sorbitan monostearate, while 3 chains are present in sorbitan trioleate). The preferred sorbitan ester is sorbitan sesquioleate.

[0112] Preferably, the at least one surfactant is present in a composition of the present invention in an amount of about 0.1% to about 20% by weight, preferably about 0.5% to about 15% by weight, preferably about 1% to about 10% by weight, and preferably about 2.5% to about 7.5% by weight, based on the total weight of the composition, including all ranges and sub-ranges as discussed / defined above, in particular the ranges and sub-ranges in which 3% by weight, 3.5% by weight or 4% by weight are the lower limit 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.

[0113] According to preferred embodiments of the present invention, the surfactant component of the compositions of the invention 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 constitutes the lower limit 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. In other preferred embodiments, the surfactant component of the compositions of the invention contains only one surfactant in the above amounts. Although not wishing to theorize, applicants believe that the surfactants / surfactant components, particularly the sorbitan surfactants discussed above, in combination with at least one clay in the compositions of the present invention allow for the formation of a water-in-oil emulsion of appropriate viscosity while minimizing the interaction between the oil portion of the composition and the applicator which, in turn, minimizes the "umbrella effect" or gap discussed above.Furthermore, Applicants believe that the presence of a surfactant in the significant amounts identified above provides improved pigment wetting in the compositions of the invention, which in turn results in improved color intensity upon application. WATER.

[0114] According to the present invention, water-in-oil (w / o) emulsion compositions comprising water are provided.

[0115] The 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 based on the total weight of the composition, including all intermediate ranges and sub-ranges as defined / discussed above.

[0116] OTHER INGREDIENTS

[0117] The composition of the invention may also include any additive commonly used in the field(s) under consideration. For example, waxes, dispersants, antioxidants, sunscreens, preservatives, perfumes, 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, paste-like compounds, viscosity increasing agents, for example, fat-soluble / fat-dispersible polymers, and derivatives thereof may be added. A non-exhaustive list of such ingredients is available in US Patent Application Publication Nos. 2004 / 0170586 and 2009 / 0142289, the entire contents of which are incorporated by reference.Other examples of suitable additional components can be found in the other references which have been incorporated by reference into this application. Further examples of such additional ingredients are contained in the International Cosmetic Ingredient Dictionary and Handbook (9th 2002), with specific reference to solvents for aqueous / water or oily phases such as . such as, for example, glycerin, alcohols and low carbon (below C8) alkyl glycols (such as propylene glycol) and high carbon (C8 or higher) alkyl glycols (such as caprylyl glycol).

[0118] For example, according to preferred embodiments, the water-in-oil (w / o) emulsions of the present invention further comprise at least one film-forming agent (a film-former). The film-forming agent may be a hydrocarbon film-forming agent or a silicone film-forming agent.

[0119] The compositions of the present invention may comprise at least one hydrocarbon-containing film-forming agent. As used herein, a "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% by weight of hydrocarbons. In one or more embodiments, the hydrocarbon-containing film-forming agent comprises less than about 5%, or less than about 1%, of siloxane or silicone groups, and preferably does not contain siloxane or silicone groups.

[0120] Film-forming agents containing hydrocarbons are known in the art and any film-forming agent containing hydrocarbons may be used.

[0121] 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.

[0122] Acrylic polymers

[0123] Acceptable acrylic polymer film-forming agents are known in the art and include, but are not limited to, those disclosed in US Patent Application 2004 / 0170586 and US Patent Application 2011 / 0020263, the entire contents of which are incorporated herein by reference.

[0124] "Acrylic polymer film formers" as used herein refer to polymers that are film-forming agents and are based on one or more (meth)acrylic acid (and / or corresponding (meth)acrylate) monomers or similar monomers. In other embodiments, the acrylic polymer film formers do not contain siloxane or silicone groups.

[0125] Representative non-limiting 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.

[0126] 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 such monomers are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, methacrylate hexyl, 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.

[0127] For olefinically unsaturated monomers, it is preferable to use monomers having functional groups selected from hydroxyl, carboxyl, sulfonic acid, phosphonic acid, acid anhydrides, epoxides and amines. Particularly preferred examples of unsaturated olefinic monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, beta-acryloyloxypropionic acid, trichloroacrylic 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.

[0128] For vinylically functionalized compounds, preferred monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, sec-butyl acrylate, tert-butyl acrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, dodecyl methacrylate, isodecyl acrylate, n-undecyl acrylate, stearyl acrylate, tridecyl acrylate, behenyl acrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, acrylate phenoxyethyl, 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, 3-methyl 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 500 methacrylate, propylene glycol monomethacrylate, butoxydiethylene glycol methacrylate, methacrylate, ethoxytriethylene glycol, dimethylaminopropylacrylamide, dimethylaminopro-pylmethacrylamide, N-(l-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 4000 to 13000 g / mol), poly(methyl methacrylate) ethyl methacrylate (Mw 2000 to 8000 g / mol).

[0129] Vinylpyrrolidone polymers

[0130] Acceptable vinylpyrrolidone polymers include vinylpyrrolidone homopolymers and vinylpyrrolidone copolymers. These homopolymers and copolymers may be crosslinked or uncrosslinked. For example, particularly suitable polymers are vinylpyrrolidone homopolymers such as ACP-10 polymer. Other examples include copolymers produced from alpha-olefin and vinylpyrrolidone wherein the copolymer contains vinylpyrrolidone and an alkyl component, preferably containing at least one C4-C30 moiety (substituted or unsubstituted) at a preferred concentration of 10 to 80 percent of the copolymer. Commercially available copolymers include those available from Ashland under the name GANEX, such as VP / eicosene (GANEX V-220) and VP / tricontanyl copolymer (GANEX WP660).

[0131] Film-forming agent containing silicone

[0132] The compositions of the present invention may comprise at least one silicone-containing film-forming agent. As used herein, a “silicone-containing film-forming agent” refers to a film-forming agent that contains silicone. In one or more embodiments, a “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.

[0133] Examples of acceptable classes of silicone-containing film-forming agents include silicone resins, silicone acrylate copolymers and their blends.

[0134] Silicone resin

[0135] As used herein, the term "resin" refers to a crosslinked or non-crosslinked three-dimensional structure. The nomenclature for silicone resins is known in the art as the "MDTQ" nomenclature, by which a silicone resin is described according to the various siloxane monomeric units that comprise the polymer.

[0136] Each letter in "MDTQ" denotes a different type of motif. The letter M denotes the monofunctional motif (CH3)3SiOi / 2. This motif is considered monofunctional because the silicone atom only shares oxygen when the motif is part of a polymer. The "M" motif can be represented by the following structure: h3cx If O ■ y-? 1LC | Eyelash

[0137] At least one of the methyl groups of the M unit may be replaced by another group, for example to give a unit of formula [R(CH3)2]SiOi / 2, as represented in the following structure:

[0138] wherein R is selected 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.

[0139] The symbol D denotes the difunctional unit (CH3)2SiO2 / 2 in which two oxygen atoms bonded to the silicone atom are used to link to the rest of the polymer. The "D" unit, which is the major building block of dimethicone oils, can be represented as follows:

[0140] At least one of the methyl groups of the D unit may be replaced by another group, for example to give a unit of formula [R(CH3)2]SiOi / 2.

[0141] The symbol T denotes the trifunctional unit, (CH3)SiO3 / 2 and can be represented as follows:

[0142] At least one of the methyl groups of the T unit may be replaced by another group, for example to give a unit of formula [R(CH3)2]SiOi / 2.

[0143] Finally, the letter Q denotes a tetrafunctional SiO4 / 2 unit in which the silicon atom can be bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.

[0144] Thus, a large number of different silicone polymers can be manufactured. Furthermore, it would be clear to those 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 polymer chain, the degree of crosslinking and the size of any side chain.

[0145] Non-limiting examples of silicone polymers include siloxysilicates and silsesquioxanes.

[0146] According to preferred embodiments, the compositions of the present invention comprise at least one silicone resin selected from the group consisting of siloxysilicates, silsesquioxanes and mixtures thereof.

[0147] A non-limiting example of siloxysilicate is trimethylsiloxysilicate, which can be represented by the following formula:

[0148] [(CH3)3SiO]x(SiO4 / 2)y

[0149] (i.e., MQ units) where x and y can, for example, range from 50 to 80. Silsesquioxanes, on the other hand, can be represented by the following formula:

[0150] (CH3SiO3 / 2).x

[0151] (i.e., T patterns) in which x may, for example, have a value of up to several thousand.

[0152] MQ resin, 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 trade name SR1000 and from Wacker under the trade name TMS 803. TMS is also commercially available from Dow Chemical in a solvent, such as cyclomethicone. However, according to the present invention, TMS may be used as a 100% active material, i.e., not in a solvent.

[0153] Suitable silicon resins comprising at least one T unit according to the present invention are disclosed, for example, in US Patent Application Publication Nos. 2007 / 0166271, 2011 / 0038820, 2011 / 0002869, and 2009 / 0214458, the entire contents of which are incorporated herein by reference in their entirety.

[0154] When the silicone resin contains at least one T unit, it may be, for example, a T, MT, MTQ or MDTQ resin.

[0155] According to preferred embodiments, the unit composition of the silicone resin may be at least 50% T units, at least 70% T units, at least 80% T units, or at least 90% T units.

[0156] In the units M, D and T 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)SiO3 / 2 is selected from silsesquioxanes of formula: ((R')SiO3 / 2)x, wherein x ranges from 100 to 500 and R' is selected, independently per trifunctional unit, from a hydrocarbon group containing from 1 to 10 carbon atoms or a hydroxyl group, provided that at least one R' is a hydrocarbon group. According to preferred embodiments, the hydrocarbon group containing from 1 to 10 carbon atoms is a methyl group.According to preferred embodiments, at least one silicone resin comprising at least one trifunctional unit of formula (R)SiO3 / 2 is selected from silsesquioxanes of the formula: ((R')SiO3 / 2)x, in which x ranges from 100 to 500 and R' is selected, independently per unit, from CH3, a hydrocarbon group containing from 2 to 10 carbon atoms, or a hydroxyl group, provided that at least one R' is a hydrocarbon group.

[0157] 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%, based on 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 hydroxyl functions of up to 20%. In certain embodiments, the total weight of hydroxyl functions may range from 4% to 8% and the total weight of hydroxyl functions may range up to 10%.

[0158] The silicone resin may be selected from silsesquioxanes which are represented by the following formula: ((CH3)SiO3 / 2)x, where x may be up to several thousand and the CH3 group may be replaced by an R group, as previously described 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 may be between 50 and 500, including all intermediate ranges and sub-ranges. The molecular weight of the silicone resin can vary from about 500, 1,000, 5,000, 10,000, 15,000 or 20,000 g / mol to about 30,000, 35,000, 40,000, 45,000, 50,000, 75,000 or 100,000 g / mol, including all ranges and sub- intermediate beaches.

[0159] As suitable examples of such silicone resins containing at least one T unit, mention may be made of:

[0160] polysilsesquioxanes of formula ((R)SiO3 / 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;

[0161] polymethylsilsesquioxanes, which are polysilsesquioxanes in which R is a methyl group. These polymers are described, for example, in U.S. Patent No. 5,246,694, the entire contents of which are incorporated herein by reference in their entirety;

[0162] polypropylsilsesquioxanes, wherein R is a propyl group. These compounds and their synthesis are described, for example, in patent application OT 2005 / 075567, the entire contents of which are incorporated herein by reference in their entirety; and

[0163] polyphenylsilsesquioxanes, wherein R is a phenyl group. These compounds and their synthesis are described, for example, in US patent application 2004 / 0180011, the entire contents of which are incorporated herein by reference in their entirety.

[0164] Examples of commercially available polymethylsilsesquioxane resins that may be mentioned include those sold:

[0165] by Wacker under the name Resin MK®, such as Belsil PMS MK®: polymer comprising CH3SiO3 / 2 repeating units (T units), which may also comprise up to 1% by weight of (CH3)2SiO2 / 2 (D units) and having an average molecular weight of about 10,000. The polymer is believed to be in a "cage" and "ladder" configuration, as shown in the tables below. The average molecular weight of the units in the "cage" configuration has been calculated to be 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 weight of the polymer. Since these end groups can react with water, a small and variable amount of SiOH groups may also be present; and

[0166] by the company Shin-Etsu under the reference KR-220L® which are composed of T units of formula CH3SiO3 / 2 and comprise Si-OH (silanol) end groups, under the reference KR-242A which comprise 98% of T units and 2% of D dimethyl units and comprise Si-OH end groups, or also under the reference KR-251, comprising 88% of T units and 12% of D dimethyl units and comprise Si-OH end groups.

[0167] Examples of commercially available polypropylsilsesquioxane resins that may be mentioned include those sold:

[0168] by Dow Corning under the reference Dow Corning 670 Fluid or 680 Fluid. Typically, these 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 RnSiO(4 n) / 2 wherein R is independently selected from hydrogen and a monovalent hydrocarbon group comprising 3 carbon atoms, wherein more than 80 mol% of R are propyl groups, n is a value between 1.0 and 1.4, more than 60 mol% of the copolymer comprises RSiO3 / 2 units, and have a hydroxyl or alkoxy content of 0.2 to 10 wt%, for a value between 1 and 4%, preferably between 5 and 10 wt%, and more preferably between 6 and 8 wt%. Preferably, the polypropyl silsesquioxane resin has a molecular weight of 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.

[0169] Examples of commercially available polyphenylsilsesquioxane resins that may be mentioned include those sold:

[0170] by Dow Corning under the reference Dow Corning 217 Flake Resin, which is a polyphenylsilsesquioxane with silanol end groups; and

[0171] by the company Wacker under the reference Belsil SPR 45 VP.

[0172] If present, the oil(s) is / are preferably present in the compositions of the present invention in an amount ranging from about 0.1% to about 15% by weight, preferably from 0.5% to about 12.5% ​​by weight, more preferably from about 1% to about 10% by weight, and most preferably from about 2.5% to about 7.5% by weight, based on the total weight of the composition, including all ranges and sub-ranges as discussed / defined above. Although it is possible for the compositions of the present invention to be free of film-forming agents, this is desired.

[0173] APPLICATOR BRUSH

[0174] 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 applicator brush suitable for liquid cosmetic compositions may be provided and / or used in combination with compositions of the present invention such as, for example, a fiber applicator brush, a felt tip applicator brush, a flock tip applicator brush, etc. Suitable applicator brushes include those for entirely manual application. However, suitable applicator brushes may also include those intended for use with other functionalities, such as, for example, the use of heat, sonic frequency, or shear forces during application.

[0175] Preferably, a fiber applicator brush comprises an applicator brush head that comprises fibers defining a fiber field. The fibers (filaments) can be creped or not creped.

[0176] Preferably, the brush head is produced from plastic, such as nylon, polypropylene, polyurethane, polyethylene, etc., although other materials may be used, including metals, such as aluminum, titanium, etc., and mixtures of all these materials (e.g., a combination of plastics and metals).

[0177] Preferably, the brush head comprises one or more tufts of fibers, including a plurality of fibers (filaments). The tufts may be arranged on the surface of the brush head in a variety of profiles or shapes. For example, tufts may be arranged in diamonds, squares, circles, triangles, snowflakes, etc. Preferably, when the fibers of the tufts are crimped, they may fill spaces between tufts to ensure uniform distribution of the fibers, if desired.

[0178] Each tuft may include any number of fibers, for example, from about 10 to about 360 individual fibers, preferably from 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 more, and a diameter of about 0.002 inches (0.0508 millimeters) to about 0.020 inches (0.508 millimeters) or more. The fiber length may be uniform or non-uniform across the brush head, or even vary in length within the individual tufts.

[0179] Preferably, the fibers may be produced from a variety of materials, including, but not limited to, natural materials (hair or fur), elastomers, coelastomers, polymers, copolymers, etc., and blends or combinations thereof. For example, the fibers may be composed of polybutylene terephthalate (PBT), polyester or thermoplastic elastomer (TPE) or a TPE / PBT blend.

[0180] METHODS AND KITS

[0181] According to preferred embodiments, methods of making up the eyes by applying the compositions of the present invention to keratinous materials 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.

[0182] 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 them 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.

[0183] According to preferred embodiments, methods of inhibiting the separation of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to a keratinous material, wherein the method comprises applying the compositions of the present invention to a 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.

[0184] According to preferred embodiments, methods of inhibiting the spread of fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to a keratinous material, wherein the method comprises preparing a water-in-oil (w / o) emulsion composition suitable for use as an eyeliner composition comprising 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 to inhibit the spread of fibers of the applicator brush during or after use of the applicator brush to apply the water-in-oil emulsion composition to a 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.

[0185] According to preferred embodiments, methods of inhibiting brush fiber separation during or after use of the brush applicator to apply an eyeliner to a keratinous material are provided, wherein the method comprises preparing a water-in-oil (w / o) emulsion eyeliner composition 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 to inhibit brush fiber separation during or after use of the brush applicator to apply the water-in-oil eyeliner emulsion composition to a keratinous material. Preferably, the composition further comprises at least one film-forming (film-forming) agent. Preferably, the composition is substantially free of waxes.Preferably, the fibers of the applicator brush are polybutylene terephthalate (PBT) fibers.

[0186] According to preferred embodiments, methods of making water-in-oil (w / o) emulsion compositions of the present invention as described in two previous paragraphs are proposed.

[0187] In the context of the preceding embodiments relating to inhibiting fiber spacing, this spacing is associated with the above-discussed "umbrella effect" resulting from the use of a brush applicator having fibers to apply a composition. Therefore, these embodiments are relevant to addressing and minimizing the "umbrella effect".

[0188] 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.

[0189] Unless otherwise stated, all numbers expressing amounts of ingredients, reaction conditions, etc. used in the description and claims are to be understood as being modified in all cases by the term "about". Accordingly, unless otherwise stated, the numerical parameters set forth in the following specification and the appended claims are approximations which may vary depending on the desired properties sought to be achieved by the present invention.

[0190] Although the numerical ranges and parameters exhibiting the broad scope of the invention are approximations, the numerical values ​​presented in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective measurements. The following examples are intended to illustrate the invention without limiting its scope accordingly. Percentages are provided on a weight basis. Examples

[0191] Example 1 - Sample composition:

[0192] [Tables3] Ingredient Amount (% by weight) Preferred Amount (% by weight) Water 25-50% 30-40% Volatile oil (e.g., volatile hydrocarbon oil such as isododecane) 25-50% 30-40% Surfactant (e.g., sorbitan ester such as sorbitan sesquioleate) 1-10% 2.5-7.5% Clay (e.g., hectorite) 1-10% 2-6% Colorant 5-35% 10-25% Preservative / antioxidants (e.g., parabens, phenoxyethanol, vitamins) 0.1-2% 0.5-1.5% Non-volatile, hydrophobic, and / or hydrophilic solvent (e.g., non-volatile oil, humectant such as glycols) 0-20% 1-5% Film formers (e.g., silicone resin(s)) 0-15% 2.5-7.5% Others (e.g. active agents, fibers) 0-10% 0.1-5% Total 100% 100%

Claims

Claims

1. A water-in-oil emulsion comprising from 2% to 6% by weight of the emulsion of at least one hectorite clay filler, at least one oil, at least one coloring agent and from 2.5% to 7.5% by weight of the emulsion of a surfactant component comprising at least one surfactant having an HLB value of 8 or less which is at least one sorbitan ester, wherein the emulsion comprises wax(es) in an amount of not more than 1% by weight, preferably not more than 0.5% by weight based on the total weight of the composition.

2. The water-in-oil emulsion of claim 1, wherein the emulsion further comprises at least one film former, wherein the at least one film former is preferably at least one silicone resin selected from the group consisting of silixoysilicates, silsesquioxanes and mixtures thereof.

3. The water-in-oil emulsion of claim 1, wherein the at least one clay filler is disteardimonium hectorite.

4. The water-in-oil emulsion of claim 1, wherein the at least one surfactant having an HLB value of 8 or less is sorbitan sesquioleate.

5. A water-in-oil emulsion according to claim 1, wherein the at least one oil is at least one volatile hydrocarbon oil, preferably isododecane.

6. A water-in-oil emulsion according to claim 1, which is free from

7. Wax. A kit comprising (1) a fiber applicator brush, preferably polybutylene terephthalate fibers; and (2) the water-in-oil (w / o) emulsion of claim 1.

8. A method of inhibiting the separation of polybutylene terephthalate fibers of an applicator brush during or after use of the applicator brush to apply a cosmetic composition to a keratinous material, wherein the method comprises preparing a water-in-oil (w / o) emulsion composition according to one of claims 1 to 6 and applying the water-in-oil emulsion composition with said applicator brush to a keratinous material.