WATER-IN-OIL EMULSIONS CONTAINING SURFACTANT, SILICONE GUM AND/OR LATEX, AND SILOXYSILICATE RESIN

FIELD OF THE INVENTION

[0001] The present invention relates to water-in-oil (w/o) emulsions (compositions) comprising (1) at least one surfactant, preferably at least one low HLB surfactant, (2) at least one silicone gum and/or at least one latex comprising polymer comprising at least one styrene group, and (3) at least one siloxysilicate resin The compositions have beneficial cosmetic properties including good or improved wear, sebum resistance and/or water resistance properties. Significantly, the compositions also have good or improved stability properties and/or good or improved removal properties.

DISCUSSION OF THE BACKGROUND

[0002] Mascara compositions are commonly used to enhance the appearance of eyelashes. Conventional mascara compositions generally use waxes to form crystalline network structures to enhance curl, volume, length, thickness, and/or colors to eyelashes. However, conventional mascara compositions including waxes tend to become less resistant to oil and/or sebum, causing smearing, flaking, and/or color transferring after wearing for a certain amount of time.

[0003] Mascaras are in particular prepared on the basis of two types of formulations: aqueous mascaras referred to as cream mascaras, in the form of a dispersion of waxes in water, and anhydrous or low-water-content mascaras, referred to as water-resistant mascaras (referred to as "waterproof), in the form of dispersions of waxes in organic solvents.

[0004] The aqueous mascaras mainly contain a surfactant system, for example based on triethanolamine stearate, which makes it possible to obtain a stable dispersion of particles of wax agglomerated in an aqueous phase. This system piays an important part in the obtaining of such a dispersion, in particular at the interface in the interactions between particles of wax.

[0005] Anhydrous mascaras tend to have the disadvantages of, among other things, being dry, having poor flexibility and/or having poor consistency. Also, consumers have difficulty removing such mascaras from eyelashes.

[0008] WO 2019/122102 is directed to a direct emulsion for use on lips containing at least 10% silicone resin.

[0007] WO 2014/048883 is directed to a slurry powder cosmetic composition containing particulates coated with a binder composition, a silicone gel composition, and the evaporation residue of an alcohol based composition and a method for making the composition.

[0008] WO 2010/149493 is directed to composition for making up and/or caring for keratin materials, comprising at least one fatty phase, at least one silicone resin and at least one styrene/acrylate copolymer.

[0009] WO 2014/143757 is directed to compositions containing a silicone resin emulsion containing 0.5 wt % to 95 wt % of a silicone resin or pressure sensitive adhesive (PSA), 0.1 to 90 wt % of a ethylene oxide/propylene oxide block copolymer, and sufficient amount of water to sum to 100 weight percent. [0010] US 10,441 ,527 is directed to fluid compositions containing multiple components, the first of which can include a copolymer which is a cross- linked siloxane (e.g. a cross-linked aminosiloxane), a silicone polyether copolymer (e.g. an (AB)n silicone polyether copolymer), and/or a saccharide siloxane copolymer, and the second of which can include organopoiysiloxane resin and/or an acrylate copolymer.

[0011] FR 2968983 is directed to compositions fluid anhydrous compositions containing at ieast one organopoiysiloxane elastomer powder coated with silicone resin; at Ieast one organopoiysiloxane elastomer vehicle in a first oil; at ieast one wax; at Ieast one organic lacquer; and at least a second oil.

[0012] US 2006/0078578 is directed to film forming compositions containing dispersed non-quaternary montmorillonite mineral and a film forming component.

[0013] There is a need to develop a cosmetic composition, in particular for making up the eyelashes, making it possible to obtain a good wearing, water- and sebum-resistant and stable and/or easy-to-remove product.

SUMMARY OF THE INVENTION

[0014] The present invention relates to water-in-oil (w/o) emulsions for hair, eyelashes and/or eyebrows comprising (1) at Ieast one surfactant, (2) at Ieast one silicone gum and/or at Ieast one latex comprising polymer comprising at Ieast one styrene group, and (3) at Ieast one sioxysilicate resin. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at Ieast one colorant. [0015] The present invention relates to water-in-oii (w/o) emulsions for hair, eyelashes and/or eyebrows comprising at least one low HLB surfactant, at least one silicone gum, and at least one siloxysilicate resin. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[0016] The present invention relates to water-in-oil (w/o) emulsions for hair, eyelashes and/or eyebrows comprising at least one low HLB surfactant, at least one silicone gum, at ieast one siloxysiiicate resin, and at least one wax. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at Ieast one colorant. Most preferably, the composition comprises 26% or less by weight of wax.

[0017] The present invention relates to water-in-oii (w/o) emulsion compositions for hair, eyelashes and/or eyebrows comprising at Ieast one latex comprising polymer comprising at Ieast one styrene group, wherein the composition comprises from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at Ieast one styrene group, and at Ieast one siloxysiiicate resin. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at Ieast one colorant.

[0018] The present invention relates to water-in-oil (w/o) emulsion compositions for hair, eyelashes and/or eyebrows comprising at Ieast one latex comprising polymer comprising at Ieast one styrene group, wherein the composition comprises from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at Ieast one styrene group, at ieast one siloxysiiicate resin, and at Ieast one wax. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[0019] The present invention also relates to methods of treating, caring for and/or making up hair, eyelashes, and/or eyebrows by applying compositions of the present invention to hair, eyelashes, and/or eyebrows in an amount sufficient to treat, care for and/or make up the hair, eyelashes, and/or eyebrows. Preferably, the composition is a composition for eyelashes. Most preferably, the composition Is a mascara composition further comprising at least one colorant.

[0020] The present invention also relates to methods of improving the stability of a water-in-oil (w/o) emulsion comprising at least one silicone gum and at least one siloxysilicate resin, and optionally at least one wax, by adding at least one low HLB surfactant to the emulsion in an amount sufficient to increase stability properties of the emulsion. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 28% or less by weight of wax, if present.

[0021] The present invention also relates to methods of making a water-in-oil (w/o) emulsion for hair, eyelashes and/or eyebrows comprising combining at least one low HLB surfactant, at least one silicone gum, at least one siloxysilicate resin, and optionally at least one wax, to form the emulsion. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% or less by weight of wax, if present. [0022] The present invention also relates to methods of improving the removal properties (from hair, eyebrows and/or eyelashes) of a water-in-oil (w/o) emulsion composition comprising at least one siloxysilicate resin, and optionally at least one wax, by adding at least one latex comprising polymer comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight with respect to the totai weight of the composition of the polymer comprising at least one styrene group to the composition. Preferably, the composition Is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[0023] The present invention also relates to methods of making a water-in-oii (w/o) emulsion composition for hair, eyelashes and/or eyebrows comprising combining at least one latex comprising polymer comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight with respect to the totai weight of the composition of the polymer comprising at least one styrene group to the composition, at least one siloxysilicate resin, and optionally at least one wax, to form the composition. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

DETAILED DESCRIPTION OF THE INVENTION

[0024] As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations, [0025] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about” meaning within 10% of the indicated number.

[0026] "Film former" 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 former has evaporated, absorbed into and/or dissipated on the substrate.

[0027] "T ransfer 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 mascara compositions, smudges occur when eyelashes contact skin around the eye area and mascara transfers to the contacted skin area. 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 such as hair, eyelashes or eyebrows followed by rubbing a material, for example, a sheet of paper, against the hair, eyelashes or eyebrows 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 hair, eyelashes or eyebrows of an individual to an item of clothing or skin after the expiration of a certain amount of time following application of the composition to the hair, eyelashes or eyebrows. 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 hair, eyelashes or eyebrows. 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 hair, eyelashes or eyebrows.

[0028] "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 hair, eyelashes or eyebrows 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 hair, eyelashes or eyebrows 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.

[0029] "Waterproof as used herein refers to the ability to repel water and permanence with respect to wafer. Waterproof properties may be evaluated by any method known in the art for evaluating such properties. For example, a mascara composition may be applied to false eyelashes, 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 false eyelashes 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, e.g., eyelashes, in a preferred embodiment of the present invention, little or no composition is transferred from the wearer.

[0030] “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, acyloxyaiky groups, oxya!kylene 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.

[0031] “Volatile”, as used herein, means having a flash point of less than about 100°C.

[0032] “Non-volatile”, as used herein, means having a flash point of greater than about 100°C,

[0033] “Stability,” as used herein, means that the emulsion does not phase separate at room temperature over a period of at least 2 months,

[0034] “Removal properties,” as used herein, refers to removing compositions from hair, eyebrows and/or eyelashes. “Easy removal properties” for a removal process refer to processes which are not as time-consuming and/or which do not substantially damage hair, eyebrows and/or eyelashes. Removal properties can be evaluated, for example, by comparing removability of a composition using a removal solvent (for example, a water-based composition containing soap/surfactant or an oil-based composition) with removability of other compositions (including commercially-available compositions) using the same solvent. For example, compositions being evaluated can be applied to hair, eyebrows and/or eyelashes (real or artificial), and allowed to dry for a designated period of time (for example, 15 minutes). Then, the number of strokes it takes to completely remove the composition from the hair, eyebrows and/or eyelashes using a removal solvent and cotton pad can be counted and compared with other compositions.

[0035] The compositions and methods of the present invention can comprise, consist of, or consist essentiaily 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 essentiaily of or “consist of low HLB surfactant(s) comprising a backbone and pendant group(s), wherein (1) the backbone is hydrophobic and one or more pendant groups is/are hydrophilic, (2) the backbone is hydrophilic and one or more pendant groups is/are hydrophobic, or (3) both (1) and (2) are present in the surfactant component. Also for example, the film-forming component of the emulsion composition can “consist essentially of or “consist of latex(es) comprising polymer comprising at least one styrene group and siloxysilicate resin(s).

[0036] The “surfactant component” of the emulsion composition of the present invention comprises at least one low HLB surfactant comprising a backbone and pendant group(s), wherein (1) the backbone is hydrophobic and one or more pendant groups is/are hydrophilic or (2) the backbone is hydrophilic and one or more pendant groups is /are hydrophobic, it may optionally further contain one or more additional surfactants. Preferably, the surfactant component contains a majority (greater than 50% by weight) of low HLB surfactant comprising a backbone and pendant group(s), wherein (1) the backbone is hydrophobic and one or more pendant groups is/are hydrophilic or (2) the backbone is hydrophilic and one or more pendant groups is/are hydrophobic, preferably greater than 60% by weight, preferably greater than 70% by weight, preferably greater than 80% by weight, preferably greater than 90% by weight, and may contain up to 100% by weight of these surfactants, all percentages being based on total weight of the low HLB surfactant(s) with respect to the total weight of the surfactant component. Ail ranges and subranges within the percentages set forth above are included herein such as, for example, 10%-100% by weight, 25%~9G% by weight, 50%~85% by weight, etc,

[0037] The “surfactant component” of the emulsion composition of the present invention preferably comprises from 1% to 15% by weight with respect to the total weight of the composition, preferably 2% to 10% by weight with respect to the total weight of the composition, and preferably from 3% to 8% by weight with respect to the total weight of the composition, including ail ranges and subranges therebetween.

[0038] The “film-forming component” of the emulsion composition of the present invention comprises at least one siloxysilicate resin. Preferably, it further comprises at least one latex comprising polymer comprising at least one styrene group. It may optionally further contain one or more additional film-forming agents. Preferably, the film-forming component contains a majority (greater than 50% by weight) of polymer comprising at least one styrene group and siloxysilicate resin, preferably greater than 80% by weight, preferably greater than 70% by weight, preferably greater than 80% by weight, preferably greater than 90% by weight, and may contain up to 100% by weight of these film-forming agents, ail percentages being based on total weight of the two types of film-forming agents with respect to the total weight of the film-forming component. All ranges and subranges within the percentages set forth above are included herein such as, for example, 10%-100% by weight, 25%-90% by weight, 50%~85% by weight, etc.

[0039] The “film-forming component” of the emulsion composition of the present invention preferably comprises from 1% to 15% by weight with respect to the total weight of the composition, preferably 2% to 10% by weight with respect to the total weight of the composition, and preferably from 3% to 8% by weight with respect to the total weight of the composition, including ail ranges and subranges therebetween.

[0040] For purposes of the methods of the present invention directed to improving long wear properties of an emulsion composition which ’’consists essentially of” identified film forming agents, the “basic and novel property” of such methods is improving long wear (for example, sebum and/or water resistance).

[0041] For purposes of the emulsion compositions and components of the present invention which do not contain at least one latex comprising polymer comprising at least one styrene group and which ’’consist essentially of identified ingredients, the “basic and novel properties” of such compositions and component is stability.

[0042] For purposes of the emulsion compositions and components of the present invention which "consist essentially of identified ingredients and contain at least one latex comprising polymer comprising at least one styrene group, the “basic and novel properties” of such compositions and component is removal properties.

[0043] For purposes of the methods of the present Invention directed to improving stability of an emulsion composition which ’’consists essentially of identified ingredients, the “basic and novel property” of such methods is improving stability of an emulsion composition.

[0044] For purposes of the methods of the present invention directed to improving removal properties of an emulsion composition which ’’consists essentially of” identified ingredients, the “basic and novel property” of such methods is improving removal properties of a composition.

[0045] As indicated above, some compositions of the present invention comprise latex,” which is a colloidal dispersion of polymer particles in an aqueous liquid phase. “Latex” is generally obtained by suspension or emulsion polymerization or copolymerization of monomers according to processes that are well known to those of ordinary skill in the art. Such monomers may be chosen in particular from styrene, butadiene, acrylonitrile, chloroprene, vinyl acetate, urethanes, isoprene, isobutylene, and acrylic or methacrylic acid, maleic acid, crotonic acid or itaconic acid or esters or amides thereof. LATEX AND/OR SILICONE GUM [0047] In accordance with the present invention, water-in-oil emulsion compositions comprising (1) at least one latex comprising polymer comprising at least one styrene group, wherein the composition comprises from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at least one styrene group, and/or (2) at least one silicone gum are provided.

[0048] LATEX COMPRISING POLYMER COMPRISING AT

LEAST ONE STYRENE GROUP

[0049] In accordance with preferred embodiments of the present invention, water-in-oil emulsion compositions comprising at least one latex comprising polymer comprising at least one styrene group, wherein the composition comprises from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at least one styrene group, are provided. According to preferred embodiments, the latex is an aqueous dispersion of styrene/acrylate copolymer.

[0050] In particular, the latex preferably comprises a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one CrC ₁₈ alkyl (meth)acrylate monomer, preferably C _r Ci ₂ alkyl (meth)acrylate, and preferably C _r Ci _G alkyl (meth)acrylate. The C ₁ C ₁₈ alkyl (meth)acrylate monomer is preferably chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, octyl acrylate, 2- ethylhexyl acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate. As styrene monomer that may be used in the invention, examples that may be mentioned include styrene and α-methylstyrene.

[0051] According to preferred embodiments, the polymer comprising at least one styrene group is at least one high molecular weight polymer comprising at least one styrene group. As used herein, “high molecular weight” means more than 100,000 Da weight average molecular weight, preferably more than 120,000 Da, preferably more than 135,000 Da, and preferably more than 150,000 Da, including ail ranges and subranges therebetween such as, for example, 100,000 Da - 500,000 Da, 120,000 Da to 800,000 Da, 150,000 Da to 200,000 Da, etc. [0052] Any styrene acrylate copolymer or derivative thereof may be suitable for use in the compositions of the present invention. The iatex comprising polymer comprising at least one styrene group preferably has a glass transition temperature (Tg) ranging from about -15°C to about 90°C, such as from about 0°C to about 50°C, such as from about 5°C to about 25°C, such as from about 10°C to about 20°C, including all ranges and subranges therebetween. For example, a copolymer comprising (1) styrene and ammonium acrylates, (2) acrylates, and/or (3) acrylic groups are suitable, A particularly preferred copolymer is a styrene/acrylates/ammonium methacrylate copolymer or a styrene acrylic copolymer, commercial examples of which include SYNTRAN 5620 and SYNTRAN 5760 (with or without paraben), by interpolymer Corporation; JONCRYL 77, by BASF Performance Chemicals; and RHOPLEX P376, by Dow Chemical Company.

[0053] Preferably, the Iatex comprising polymer comprising at least one styrene group is present in the compositions of the present invention in an amount ranging from about 5% to about 15%, more preferably from about 5% to about 12%, and preferably from about 5% to about 8%, by weight, based on the total weight of the composition, including ail ranges and subranges in between. The Iatex comprising polymer comprising at least one styrene group comprises (1) polymer comprising at least one styrene group; and (2) liquid phase carrier for the polymer,

[0054] According to preferred embodiments, the polymer comprising at least one styrene group is present in an amount ranging from about 2% to about 6%, preferably from about 2,25% to about 5.5%, and preferably from about 2.5% to about 5%, by weight, based on the total weight of the composition, including all ranges and subranges in between.

[0055] Surprisingly, it has been found that water-in-oil (w/o) emulsion compositions comprising at least one siioxysilicaie resin, and optionally at least one wax, containing the polymer comprising at least one styrene group in amounts both below and above the identified concentration range have inferior removal properties as compared to such emulsions containing the polymer comprising at ieast one styrene group in amounts falling within the identified concentration range. Also surprisingly, it has been found that such increase in removability properties within the identified concentration range is generally independent of the amount of siioxysilicaie resin present in the emulsions.

[0056] SILICONE GUM

[0057] According to preferred embodiments of the present invention, compositions comprising at least one silicone gum resin are provided. The silicone gum can, for example, correspond to the formula:

[0058] in which:

[0059] R ₇ , R _8, R _{1 1} and R ₁₂ are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms,

[0060] R ₉ and R ₁₀ are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms and aryl radicals, [0061] X is chosen from alkyl radicals comprising from 1 to 6 carbon atoms, a hydroxy! radical and a vinyl radical,

[0082] n and p are preferably chosen so as to give the silicone gum a viscosity of from 25,000 cSt to 20,000,000 cSt, preferably from 30,000 cSt to 5,000,000 cSt, preferably from 35,000 cSt to 1 ,000,000 cSt, preferably from 40,000 cSt to 750,000 cSt, preferably from 50,000 cSt to 500,000 cSt and preferably from 60,000 cSt to 300,000 cSt, including ail ranges and subranges therebetween. A particularly preferred range is from 60,000 cSt to 300,000 cSt (corresponding to a molecular weight of 60,000-110,000), with mixtures of two silicone gums within this range being preferred, the weight ratio of the two silicone gums preferably ranging from about 2:1 to 1 :2, with a weight ratio of the two silicone gums of about 1 :1 being preferred. So, for example, a silicone gum having a viscosity of 60,000 cSt and a silicone gum having a viscosity of 300,000 cSt at a weight ratio of about 1 : 1 is preferred. Of course, any two silicone gums falling within the identified viscosity ranges and ratios can be used.

[0083] In general, n and p can each take values ranging from 0 to 10,000, such as from 0 to 5,000.

[0084] Among the silicone gums which can be used according to the invention, mention may be made of those for which:

[0085] the substituents R ₇ to R ₁₂ and X represent a methyl group, p = 0 and n = 2 700, such as the product sold or made under the name SE30 by the company General Electric, [0066] the substituents R ₇ to R ₁₂ and X represent a methyl group, p = 0 and n = 2 300, such as the product sold or made under the name AK 500000 by the company Wacker,

[0067] the substituents R ₇ to R ₁₂ represent a methyl group, the substituent X represents a hydroxyl group, p = 0 and n = 2 700, as a 13% solution in cyclopentasiloxane, such as the product sold or made under the name Q2-1401 by the company Dow Corning,

[0068] the substituents R ₇ to R ₁₂ represent a methyl group, the substituent X represents a hydroxyl group, p = 0 and n = 2 700, as a 13% solution in poiydimethyisiloxane, such as the product sold or made under the name Q2-1403 by the company Dow Corning, and

[0069] the substituents R ₇ , R ₈ , R ₁₁ , R ₁₂ and X represent a methyl group and the substituents R ₉ and R ₁₀ represent an aryl group, such that the molecular weight of the gum Is about 600000, for instance the product sold or made under the name 761 by the company Rhone- Poulenc (Rhodia Chimie).

[0070] In preferred embodiments, the silicone gum correspond to the following formula:

[0071] In this formula the terminal Si’s can also be other than methyl and may be represented with substitutions on the repeating Si such that the R group is an alkyl of 1 to 6 carbon atoms , which may be linear, branched and/or functionalized selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, vinyl, ally!, cycohexyl, phenyl, and mixtures thereof. The silicone gums employed in the present invention may be terminated by triorganosiiyl groups of the formula R’ ₃ where R' is a radical of monovalent hydrocarbons containing from 1 to 6 carbon atoms, hydroxyl groups, alkoxyl groups and mixtures thereof. [0072] The at least one silicone gum is preferably present in the compositions of the present invention an amount which is equal to or less than the amount of siioxysilicate resin present, preferably in an amount of less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight, preferably less than 3% by weight, including ail ranges and subranges therebetween such as, for example, 1% to 15% by weight, 3% to 12% by weight, 1% to 5% by weight 1% to 3% by weight 2% to 8% by weight, etc., all weights being based on the weight of the composition as a whole.

[0073] SILOXYSILICATE RESIN

[0074] According to the present invention, compositions comprising at least one siioxysilicate resin are provided. Siioxysilicate resins generally have the formula;

[0075] [(R) ₃ 8i0] _x (Si0 _4/2 ) _y

[0078] Where R is an alkyl group preferably comprising 1 to 8 carbon atoms. One non-limiting example of a siioxysilicate in accordance with the present invention is trimethylsiloxysilicate, which may be represented by the following formula:

[0077] [(CH ₃ ) ₃ SiO] _x (SiO _½ ) _y . [0078] In the above formulas, x and y preferably range between numbers such as, 10 and 150, 25 and 125, 35 and 100, and 50 to 80, for example.

[0079] Preferred siloxysilicate resins are commercially available from General Electric, Dow Corning, Wacker, Milliken, Siltech, Grant Industries, Momentive and Shin-Etsu Silicones under the tradename Resin MQ®.

[0080] The at least one siloxysilicate resin is preferably present In the compositions of the present invention in an amount of less than 15% by weight, preferably less than 10% by weight, including all ranges and subranges therebetween such as, for example, 1% to 15% by weight, 3% to 12% by weight, 1% to 10% by weight, 3% to 8% by weight, etc., all weights being based on the weight of the composition as a whole.

[0081] Although not wishing to be bound by any theories, generally speaking compositions comprising at least one latex comprising polymer comprising at least one styrene group and at least one siloxysilicate resin have good or improved removal properties while maintaining beneficial cosmetic properties including good or improved wear, sebum resistance and/or water resistance properties. Given that both the latex and the siloxysilicate resin would be expected to increase long-wear properties of a composition, it would be expected that Increasing concentrations of both in a composition would result in a corresponding increase in removal difficulty. However, contrary to this expectation, it was surprisingly discovered that, at concentrations of from about 2% to about 6%, such amounts of polymer comprising at least one styrene group actually improved removal properties of the compositions, including in mascara compositions containing low wax levels, whereas concentration levels on either side of this range resulted in emulsions having inferior removal properties.

[0082] According to particularly preferred embodiments, the combined amount of siloxysilicate resin and of polymer comprising at least one styrene group present ranges from about 5% to 25% by weight, preferably from about 7.5% to about 20%, preferably about 10% to about 15% by weight based on the total weight of the composition, including all ranges and subranges within these ranges. Also, the weight ratio of siloxysilicate resin to polymer comprising at least one styrene group present preferably ranges from 1 :1 to about 5:1, preferably from about 2:1 to about 4:1.

[0083] SURFACTANT

[0084] According to the present invention, compositions comprising at least one surfactant are provided. Preferably, the at least one surfactant is a low HLB surfactant. “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 are more soluble in oils (lipophilic material) and are more appropriate for use in water-in-oil (W/O) emulsions. Higher HLB emulsifiers are more soluble in water (hydrophilic materia!) and are more appropriate for oil-in-water (O/VV) emulsions. In the context of the present invention, “low HLB surfactant” means a surfactant having an HLB value of less than or equal to 6, preferably less than 5, and preferably less than 4. Preferably, the HLB value is 3 or greater. [0085] The surfactant, in particular a low HLB value surfactant, is preferably present as all or part of a “surfactant component” in the compositions of the present invention. According to preferred embodiments of the present invention, the surfactant component has an HLB value of less than or equal to 6, preferably less than 5, and preferably less than 4. Preferably, the HLB value is 3 or greater.

[0086] According to preferred embodiments, the surfactant, in particular a low HLB surfactant, is nonionic.

[0087] According to preferred embodiments, the surfactant, in particular a low HLB surfactant, comprises a backbone and pendant group(s), wherein (1) the backbone is hydrophobic and one or more pendant groups is/are hydrophilic, or (2) the backbone is hydrophilic and one or more pendant groups is/are hydrophobic. The backbone can be silicone-based or hydrocarbon based. By “backbone,” it is meant that the surfactant comprises a main chain. By “pendant” group(s), it is meant that one or more groups is attached to the backbone or main chain of the surfactant. The pendant group(s) can be attached at any location along the backbone or main chain, for example at one or both terminal ends of the chain, at location(s) not at a terminal end of the chain, or both. According to preferred embodiments, the pendant group(s) include one or more ester group(s) attached to the backbone or main chain.

[0088] An especially preferred backbone is a hydrophobic, silicone- based backbone such as dimethicone. For such a backbone, a preferred pendant group is a hydrophilic group such as one including a plurality of ether groups such as a polyethylene glycol (PEG) polymer. [0089] Another preferred backbone is a hydrophilic, hydrocarbon-based backbone such as a polyethylene glycol (PEG) polymer or a polyglyceryl polymer. For such a backbone, a preferred pendant group is an ester based on a hydrophobic group such as, for example, a C8-C24 fatty compound, preferably a C12-C20 fatty compound, and preferably a C16-C18 fatty compound such as, for example, stearate, isostearate, laurate, etc.

[0090] According to preferred embodiments, compositions of the present invention comprise at least one surfactant comprising a silicone-based backbone and at least one surfactant comprising a hydrocarbon-based backbone.

[0091] According to preferred embodiments, the surfactant component comprises surfactant(s), in particular low HLB surfactant(s), comprising a backbone and pendant group(s), wherein (1) the backbone is hydrophobic and one or more pendant groups is/are hydrophilic, (2) the backbone is hydrophilic and one or more pendant groups is/are hydrophobic, or (3) both (1) and (2) are present in the surfactant component.

[0092] The surfactant, in particular a low HLB surfactant, of the present invention can be a silicone surfactant, preferably comprising dimethicone (for example, PEG-10 dimethicone or lauryl PEG-9 polydimethylsiloxyethyl dimethicone), or a non-silicone surfactant, free of dimethicone (for example, PEG-30 dihydroxystearate). The surfactanat, in particular a low HLB surfactant, of the present invention can have alkoxyiation (for example, ethoxylation or propQxylation) through groups such as, for example, (C ₂ H ₄ 0)- /polyethylene glycol groups (PEG), (C ₃ H ₆ 0)- /polypropylene glycol groups (PPG), etc. Suitable emulsifiers include aikoxy!ated compounds, partial glycerides of alkoxylated compounds, poiyglycerolated compounds, and mixtures thereof, etc.

[0093] According to preferred embodiments, the surfactant, in particular a low HLB surfactant, can be a silicone surfactant which is an oxya!kylenated organosiloxane. Preferably, the organosiloxane emulsifier is linear.

[0094] For example, a low HLB surfactant can have the general formula:

[0095] wherein p is 0-40 (the range including ail numbers between and subranges such as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is (--C ₂ H ₄ 0) ₃ -(~ C ₃ H ₆ O) _b H wherein a is 0-25, b is 0-25 with the proviso that both a and b cannot be 0 simultaneously, x, y, and z are each independently ranging from 0 to 1 million with the proviso that x and y cannot be 0 simultaneously. In some cases, x, y, z, a, and b are such that the molecular weight of the polymer ranges from about 5,000 to about 500,000, from about 10,000 to 100,000, or is about 50,000. In some instances, p is such that the long chain alkyl is cetyl or !auryl, and the compound is called, generically, cetyl dimethicone copolyol or lauryi dimethicone copolyol respectively. In some cases the number of repeating ethylene oxide or propylene oxide units in the polymer are also specified, such as a dimethicone copolyoi that is also referred to as PEG-15/PPG-10 dimethicone, which refers to a dimethicone having substituents containing 15 ethylene glycol units and 10 propylene glycol units on the siioxane backbone, it is also possible for one or more of the methyl groups in the above general structure to be substituted with a longer chain alkyl (e.g. ethyl, propyl, butyl, etc.) or ether, such as methyl ether, ethyl ether, propyl ether, butyl ether, and the like.

[0096] Further the surfactant, in particular a low HLB surfactant, can have the general formula:

[0097] wherein each n is independently 0-100 with the proviso that there must be at least one PE radical. In some instances, where each n Independently ranges from about 2 to 30, and PE wherein a is 0-25, b is 0-25 with the proviso that both a and b cannot simultaneously be 0; and wherein w, x, y, and z are each independently 0 to 1 ,000,000 with the proviso that there is at least one PE. In some embodiments the organosiloxane emulsifier is lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone. Oxyaikylenated organosiioxane emulsifiers disclosed in U.S, Pat, No. 9,095,543 are useful in the instant compositions, U.S, Pat. No. 9,095,543 is incorporated herein by reference in its entirety. [0098] Further examples of organosiloxane emulsifiers include but are not limited to those having C.T.F.A. names Bis-Butyidimethicone Polyglyceryi-3; Bis-PEG/PPG-14/14 Dimethicone; Bis-butyldimethicone Poiyg lycery!-3 ; Bis- isobutyi PEG/PPG- 10/7 Dimethicone copolymer; Bis-PEG/PPG-18/6 Dimethicone; Bis-PEG/PPG-20/20 Dimethicone; Bis-PEG/PPG-18/16 PEG/PPG- 16/16 Dimethicone; Bis(PPG-7 Undeceneth-21 -Dimethicone; Cetyl Dimethicone PEG-7 Acetate; Cetyl PEG-8 Dimethicone; Cetyl PEG/PPG-15/16 Butyl Ether Dimethicone; Cetyi PEG/PPG-15/15 Butyl Ether Dimethicone; Cetyl PEG/PPG- 7/3 Dimethicone; Cetyi PEG/PPG-10/1 Dimethicone; Dimethicone PEG-15 Acetate; Dimethicone PEG-7 Cocoate; Dimethicone PEG-7 Phosphate; Dimethicone PEG-10 Phosphate; Dimethicone PEG/PPG-7/4 Phosphate; Dimethicone PEG/PPG-12/4 Phosphate; Dimethicone PEG-7 Undecylenate; Lauryl Dimethicone PEG-10 Phosphate; Isopoiygiyceryi-3 Dimethicone; lsopoiygiyceryl-3 Dimethiconol; isostearyl Carboxyidecyl PEG-8 Dimethicone; Lauryl Methicone PEG-10 Phosphate; Lauryl PEG-8 Dimethicone; Lauryi PEG- 10 Methyl Ether Dimethicone; Lauryl PEG/PPG-18/18 Methicone; PEG-6 Methyl Ether Dimethicone; PEG-7 Methyl Ether Dimethicone; PEG-9 Methyl Ether Dimethicone; PEG-10 Methyl Ether Dimethicone; PEG-11 Methyl Ether Dimethicone; PEG-11 Methyl Ether Dimethicone, PEG-32 Methyl Ether Dimethicone; PEG-PEG/PPG-28/21 Acetate Dimethicone; PEG/PPG-22/22 Butyl Ether Dimethicone; PEG/PPG-23/23 Butyl Ether Dimethicone; PEG/PPG- 24/18 Butyl Ether Dimethicone; PEG/PPG-3/1G Dimethicone; PEG/PPG-4/12 Dimethicone; PEG/PPG-6/11 Dimethicone; PEG/PPG-8/14 Dimethicone; PEG/PPG-12/18 Dimethicone; PEG/PPG-12/18 Dimethicone; PEG/PPG-14/4 Dimethicone; PEG/PPG-15/5 Dimethicone; PEG/PPG-15/15 Dimethicone; PEG/PPG-16/2 Dimethicone; PEG/PPG-16/8 Dimethicone; PEG/PPG-17/18 Dimethicone; PEG/PPG-18/12 Dimethicone; PEG/PPG-19/19 Dimethicone; PEG/PPG-20/8 Dimethicone: PEG/PPG-2Q/15 Dimethicone; PEG/PPG-2G/20 Dimethicone; PEG/PPG-20/29 Dimethicone; PEG/PPG-22/23 Dimethicone; PEG/PPG-22/24 Dimethicone; PEG/PPG-25/25 Dimethicone; PEG/PPG-27/27 Dimethicone; PEG/PPG-30/10 Dimethicone; PEG/PPG-10/3 Oleyl bther Dimethicone; PEG-8 trisiioxane; Polygiyceryl-3 Poiydimethyisiioxyethyl Dimethicone; PPG-12 Butyl Ether Dimethicone; Silicone Quatemium-17; TEA- Dimethicone PEG-7 Phosphate; PEG/PPG-18 dimethicone, PEG/PPG-18/18 dimethicone; iauryi PEG/PPG-18/18 methicone; cetyl PEG/PPG-14/14 dimethicone; bis-cetyl PEG/PPG-14/14 dimethicone; cetyl PEG/PPG-10/1 dimethicone; PEG-11 methyl ether dimethicone; PEG/PPG-2Q/22 butyl ether dimethicone; PEG-9 dimethicone; PEG-3 dimethicone; PEG-9 methyl ether dimethicone; PEG-10 dimethicone; lauryl PEG-9 poiydimethyisiioxyethyi dimethicone. or mixtures thereof.

[0099] Examples of commercial linear organosiloxane emulsifiers are those sold by Dow Corning under the tradename Dow Corning 3225C Formulation Aid having the CTFA name cyclotetrasiloxane (and) cyciopentasiloxane (and) PEG/PPG-18 dimethicone; or 5225C Formulation Aid, having the CTFA name cyciopentasiioxane (and) PEG/PPG-18/18 dimethicone: or Dow Corning 190 Surfactant having the CTFA name PEG/PPG-18/18 dimethicone; or Dow Corning 193 Fluid, Dow Corning 5200 having the CTFA name iauryl PEG/PPG-18/18 methicone; or Abil EM 90 having the CTFA name cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abil EM 97 having the CTFA name bis-cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abi! WE 09 having the CTFA name cetyl PEG/PPG-10/1 dimethicone in a mixture also containing poiyglyceryi-4 isostearate and hexyl !aurate; or KF-6Q11 sold by Shin-Etsu Silicones having the CTFA name PEG-11 methyl ether dimethicone; KF-6012 sold by Shin-Etsu Silicones having the CTFA name PEG/PPG-20/22 butyl ether dimethicone; or KF-6Q13 sold by Shin-Etsu Silicones having the CTFA name PEG-9 dimethicone; or KF-6015 sold by Shin- Etsu Silicones having the CTFA name PEG-3 dimethicone; or KF-6016 sold by Shin-Etsu Silicones having the CTFA name PEG-9 methyl ether dimethicone; or KF-6017 sold by Shin-Etsu Silicones having the CTFA name PEG-10 dimethicone; or KF-6038 sold by Shin-Etsu Silicones having the CTFA name iauryl PEG-9 polydimethylsiloxyethyl dimethicone.

[00100] Particularly preferred low HLB surfactants are as follows:

[00101] The at least one surfactant, in particular a low HLB surfactant, is preferably present in the compositions of the present invention in an amount of about 1% to about 15%, preferably from about 1.5% to about 10%, and preferably from about 2% to about 8% by weight with respect to the total weight of the composition, including all ranges and subranges therebetween.

[00102] WATER [00103] According to the present invention, compositions comprising water are provided. Compositions of the present invention comprise sufficient water to form a water-in-oil emulsion, preferably from about 5% to about 80% water, more preferably from about 10% to about 50% water, and more preferably from about 15% to about 30% water by weight with respect to the total weight of the composition, including all ranges and subranges therebetween.

[00104] OIL

[001 OS] According to the present invention, compositions comprising at least one oil are provided. Compositions of the present invention comprise sufficient oil to form a water-in-oil emulsion, preferably from about 5% to about 80% oil, more preferably from about 10% to about 50% oil, and more preferably from about 15% to about 30% oil by weight with respect to the total weight of the composition, including all ranges and subranges therebetween.

[00106] 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.

[00107] According to certain embodiments, the oil carrier comprises one or more volatile silicone oils. 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, dodecamethyicyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethyipentasiloxane 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.

[00108] Non-limiting examples of volatile silicone oils are listed in Table 1 below.

[00109] Table 1

[00110] 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. 8,338,839 and W003/042221, the contents of which are incorporated herein by reference. In one embodiment the volatile linear silicone oii is decamethyltetrasiloxane. in another embodiment, the decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.

[00111] According to other embodiments, the oil carrier comprises one or more non-silicone volatile oils and may be selected from volatile hydrocarbon oils, volatile esters and volatile ethers. Examples of such volatile non-silicone oils include, but are not limited to, volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures and in particular branched C ₈ to C ₁₆ alkanes such as C ₈ to C ₁₆ isoalkanes (also known as isoparaffins), isododecane, isodecane, and for example, the oils sold under the trade names of Isopar or Permethyl. Preferably, the volatile non-silicone oils have a flash point of at least

40°C.

[00112] Non-!imiting examples of volatile non-silicone volatile oils are given in Table 2 below.

Table 2

[00113] 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.

[00114] According to other embodiments of the present invention, the oil carrier comprises at least one non-volatile oil. Examples of non-volatile oils that may be used in the present invention include, but are not limited to, polar oils such as:

[00115] - 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 oii, barley oil, quinoa oil, olive oil, rye oii, safflower oii, candlenut oil, passion flower oii or musk rose oil; or capry!ic/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;

[00116] - 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 ₇ > 10, such as, for example, Purceilin oil (cetostearyl octanoaie), isononyl isononanoate, C ₁₂ to C ₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricino!eates of alcohols or of polyalcohols; hydrcxylated esters, for instance isostearyl lactate or diisostearyi malate; and pentaerythritol esters:

[00117] - synthetic ethers containing from 10 to 40 carbon atoms;

[00118] - C ₈ to C ₂₆ fatty alcohols, for instance oleyl alcohol, cetyl alcohol, stearyl alcohol, and cetearly alcohol; and

[00119] - mixtures thereof.

[00120] 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.

[00121] Compositions of the present invention can optionally further comprise any additive usually used in the field(s) under consideration. For example, dispersants, antioxidants, sunscreens, preserving agents, fragrances, fibers, fillers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, vitamins, essentia! fatty acids, additional surfactants, silicone eiastomers, pasty compounds, viscosity increasing agents, for example, liposoluble/lipodispersibl e polymers, additional film forming agents, colorants, 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).

[00122] According to preferred embodiments of the present invention, compositions further comprising at least one wax are provided.

[00123] “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.

[00124] 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.

[00125] 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, ceresln waxes, laurel wax, Chinese insect wax, Shellac wax, hydrogenated olive oil such as Waxolive from the company SGLIANCE, 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,

18L55 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 84 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, microcrystaliine waxes such as for example that sold under the brand name Microwax HW by the company PARAMELT, triglycerides of lauric, palmitic, cetyiic 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 Girebelle 303 by the company SASOL, polyethylene waxes such as for example those sold under the brand names Performalene 400 polyethylene, Performalene 655 polyethylene and Performaiene 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 AG 540 wax by the company Honeywell, hydroxyoctacosanyl hydroxy-stearate such as for example that sold under the brand name Elfacos C 26 by the company AKZG, 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, pentaeryihritol distearate such as for example that marketed under the name Cutina RES by the company COGNIS, the mixture of dibehenyl adipate, dioctadecyl adipate and di-eicosanyl adipate (INC! name C18-C22 dialkyl adipate), the mixture of dilauryl adipate and ditetradecyi adipate (INC! name: C12-C14 dia!kyl adipate), the mixture of dioctadecyl sebacate, didocosyl sebacate and dieicosyl sebacate (INC! name: C18-C22 dialkyl sebacate) and the mixture of dioctadecyl octadecanedioate, didocosyi octanedioate and dieicosyl octanedioate (INC! 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, tetracontanyi stearate such as for example Kester Wax K76H from the company KOSTER KEUNEN, stearyl benzoate such as for example Finsolv 116 from the company F!NETEX, behenyl fumarate such as for example Marrix 222 from the company AKZO BERNEL, di-(trimethyiol-1,1 ,1- propane) tetrastearate such as for example that which is offered under the name "HEST 2T-48" by the company HETERENE, didotriaconianyl distearate such as for example Kester Wax K82D from the company KOSTER KEUNEN, polyethylene glycol montanate with 4 ethylene oxide units (PEG-4) such as for example that which is sold under the brand name Clariant Licowax KST 1 , hexanediol disalicyiate 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-8S by the company HETERENE, ditrimethylo!propane 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 (INC! 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, steary! 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.

[00126] 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, 18L55 and 18L57), rice bran wax, cetyl, stearyl and behenyl alcohols, laurel wax and Ouricury wax are preferably used.

[00127] Examples of suitable silicone waxes include, but are not limited to, silicone waxes such as alkyl- or a!koxydimethicones having an alkyl or aikoxy chain ranging from 10 to 45 carbon atoms, pojy(di)methyisiloxane esters which are solid at 30°C and whose ester chain comprising at least 10 carbon atoms, di(1 ,1 ,1-trimethylolpropane) tetrastearate, which is sold or manufactured by Heterene under the name HEST 2T-48; alkylated silicone acrylate copolymer waxes comprising at least 40 mole % of siloxy units having the formula (R ₂ R'SiO _1/ 2) _x (R"SiO _3/2 )y, where x and y have a value of 0.05 to 0.95, R is an alky group having from 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, R is a monovalent hydrocarbon having 9-40 carbon atoms, R" is a monovalent hydrocarbon group having 1 to 8 carbon atoms, an aryl group such as those disclosed in U.S. patent application 2007/0149703, the entire contents of which is hereby incorporated by reference, with a particular example being C30-C45 alkyldimethylsilyl polypropylsilsesquioxane; and mixtures thereof.

[00128] If at least one latex comprising polymer comprising at least one styrene group is present in the composition, 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.

[00129] If at least one latex comprising polymer comprising at least one styrene group is not present in the composition, the wax(es) are preferably present in a quantity of at least 5% by weight, preferably from about 5 to 28% by weight, preferably from about 7 to about 23% by weight, and preferably from about 10 to about 20% by weight relative to the total weight of the composition, including all ranges and subranges therebetween. [00130] According to preferred embodiments, the compositions of the present invention comprise at least one additional film forming agent. According to preferred embodiments, the compositions of the present invention comprise, as additional film forming agent, either instead of or in addition to the dispersion of film forming particles in aqueous phase discussed above, one or more film-forming agents suitable for use in compositions for application to eyebrows and/or eyelashes. Such film-forming agents can be, for example, water-soluble or liposoluble. Acceptable film-forming are known in the art and include, but are not limited to, those disclosed in U.S. patent application publication no. 2004/0170586, the entire contents of which is hereby incorporated by reference.

[00131] Specific examples of film-forming agents include, but are not limited to, proteins, such as proteins of plant origin, such as, for example, wheat or soya proteins; or proteins of animal origin, such as keratins, for example keratin hydrolysates and sulfonic keratins; cellulose polymers, such as, for example, hydroxyethylcellulose, hydroxypropylcellulose, methyicellulose or ethyl hydroxyethylcellulose ; gums arable, guar gum, xanthan derivatives or karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic add and its derivatives; shellac resin, gum sandarac, dammars, elemis or copals; muccopolysaccharides, such as chondroitin sulfates, and mixtures thereof.

[00132] Specific examples of suitable film-forming agents also include silicone resins which are not siloxysilicates such as, for example, T-propy! siisesquioxanes and MK resins (for example, polymethylsilsesquioxanes), silicone esters such as those disclosed in U.S. Pat Nos. 6,045,782, 5,334,737, and 4,725,658, the disclosures of which are hereby incorporated by reference, polymers comprising a backbone chosen from vinyl polymers, methacryiic polymers, and acrylic polymers and at least one chain chosen from pendant siloxane groups and pendant fluorochemical groups such as those disclosed in U.S. Pat. Nos. 5,209,924, 4,893,935, 4,981 ,903, 4,981 ,902, and 4,972,037, and WO 01/32737, the disclosures of which are hereby incorporated by reference, polymers such as those described in U.S. Pat. No. 5,468,477, the disclosure of which is hereby incorporated by reference (a non-limiting example of such polymers is poiy(dimethyisiloxane)-g~poly(isobutyl methacrylate), which is commercially available from 3M Company under the tradename VS 70 IBM) , and mixtures thereof.

[00133] Specific examples of suitable polymers further include, but are not limited to, polyalkylenes, polyvinylpyrrolidone (PVR) or vinylpyrrolidone (VP) homopolymers or copolymers, copolymers of a Cz to C ₃₀ , such as C ₃ to C22 alkene, and combinations thereof. As specific examples of VP copolymers which can be used in the invention, mention may be made of VP/vinyl acetate, VP/ethyl methacrylate, buty!ated polyvinylpyrrolidone (PVR), VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate copolymer, and mixtures thereof.

[00134] According to preferred embodiments, the compositions of the present invention comprise at least one polyorganosiloxane copolymer. The polyorganosiloxane copolymer useful herein is preferably a polymer (homopolymer or copolymer) having at least one moiety which contains: at least one polyorganosiloxane group consisting of 1 to about 1000 organosiloxane units in the chain of the moiety or in the form of a graft, and at least two groups capable of establishing hydrogen interactions. Non-limiting examples of polyorganosiloxane copolymers are disclosed, for example in US. Pat. No. 8,945,525, the disclosure of which is hereby incorporated by reference in its entirety.

[00135] Additional polyorganosiloxane copolymers which may be used in the long-wear lip compositions of the present invention include those described in documents US 5,874,069, US 5,919,441 , US 6,051 ,216, and US 5,981,680, the entire contents of which are hereby Incorporated by reference in their entirety.

[00136] A preferred polyorganosiloxane copolymer for use in the present invention contain at least one moiety chosen from formula (HI): and formula (IV)

in which:

[00138] (a) R ¹ . R ² , R ³ and R ⁴ are the same or different and may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, a siloxane chain, and phenyl;

[00139] (b) X is a linear or branched chain aikylene having 1 -30 carbons;

[00140] (c) Y is selected from the group consisting of linear or branched chain alkylenes having 1 -40 carbons;

[00141] (d) m is a number between 1 and 700;

[00142] (e) n is a number between 1 and 500.

[00143] Particularly preferred polyorganosiloxane copolymers useful herein are commercially available from Dow Corning under the tradenames DC 8178® and DC 8179®, which are known under the I NCI denomination of Nylon-611/Dimethicone Copolymer.

[00144] If present, the polyorganosiloxane copolymer is preferably present in the compositions of the present invention in an amount ranging from about 1 % to about 35% by weight, preferably from about 5% to about 25% by weight, and preferably from about 7% to about 15% by- weight, including all ranges and subranges therebetween, all weights being based on the weight of the composition as a whole.

[00145] Suitable fillers and/or viscosity increasing agents include silicate clays such as, for example, silicate clays containing at least one cation which may be chosen from calcium, magnesium, aluminium, sodium, potassium, and lithium cations, and mixtures thereof. Non-limiting examples of such products include smectite days such as montmorilionites, hectorites, bentonites, beideilites, saponites, vermiculites, stevensite, and chlorites. Preferred days are synthetic silicate days, most preferably lithium magnesium sodium silicate, commercially available from Rockwood under the tradename Laponite®. Other preferred examples of silicate clays which may be used in the present invention are chosen from lithium magnesium silicate, aluminum calcium sodium silicate, calcium magnesium silicate, sodium magnesium silicate, calcium aluminum borosiiicate, magnesium aluminum silicate, sodium potassium aluminum silicate, and sodium silver aluminum silicate.

[00148] If present, the filler and/or viscosity increasing agent is preferably present in the compositions of the present invention in an amount of from 0.1% to 10% by weight, preferably in an amount of from 0.5% to 7%, preferably in an amount of from 1 % to 5% by weight, based on the total weight of the composition.

[00147] According to preferred embodiments of the present invention, the compositions can further comprise a desired agent. The desired agent can be, for example, any colorant (pigment, dye, etc.), fiber or any additonai film forming agent known in the art.

[00148] Acceptable colorants include pigments, dyes, such as liposoluble dyes, nacreous pigments, and pearling agents.

[00149] Representative liposoluble dyes which may be used according to the present invention include Sudan Red, DC Red 17, DC Green 8, b- carotene, soybean oil, Sudan Brown, DC Yellow 11 , DC Violet 2, DC Orange 5, annatto, and quinoline yellow.

[00150] 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.

[00151] Representative pigments include white, colored, inorganic, organic, polymeric, nonpoiymeric, 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,

[00152] Suitable fibers Include, but are not limited to, fibers which enable improvement of the lengthening effect. "Fiber" should be understood to mean an object of length L and diameter D such that L is much greater than D, D being the diameter of the circle in which the cross-section of the fibre is inscribed. In particular, the L/D ratio (or form factor) is selected in the band ranging from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150. The fibers utilisabie in the composition of the invention can be fibers of synthetic or natural origin, mineral or organic. They can be short or long, unitary or structured, for example, braided, hollow or full. They can be of any shape and in particular of circular or polygonal cross-section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunted and/or polished to avoid injury. They can be rigid or non-rigid fibers. They can be of synthetic or natural origin, mineral or organic. They can be surface treated or not, coated or not, and colored or not.

[00153] if present, the desired agent is preferably present in the compositions of the present invention in an amount of from 0.1% to 30% by weight, preferably in an amount of from 0.5% to 25%, preferably in an amount of from 1 % to 20% by weight, based on the total weight of the composition.

[00154] According to other preferred embodiments, methods of treating, caring for and/or enhancing the appearance of hair, eyebrows or eyelashes by applying compositions of the present invention to the hair, eyebrows or eyelashes in an amount sufficient to treat, care for and/or enhance the appearance of the hair, eyebrows or eyelashes are provided. In accordance with these preceding preferred embodiments, the compositions of the present invention are applied topically to the desired area of the hair, eyebrows or eyelashes in an amount sufficient to treat, care for and/or enhance the appearance of the hair, eyebrows or eyelashes. 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 (for example, a topcoat).

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, or to which a basecoat has been previously applied.

[00155] According to a preferred embodiment of the present invention, compositions having improved cosmetic properties such as, for example, Increased stability are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[00156] According to a preferred embodiment of the present invention, methods of improving the stability properties of a water-in-oil (w/o) emulsion comprising at least one silicone gum and at least one siloxysilicate resin, and optionally at least one wax, by adding at least one low HLB surfactant to the emulsion in an amount sufficient to increase stability properties of the emulsion are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% or less by weight of wax, if present.

[00157] According to a preferred embodiment of the present invention, methods of making a water-in-oil (w/o) emulsion for hair, eyelashes and/or eyebrows comprising combining at least one low HLB surfactant, at least one silicone gum, at least one siloxysilicate resin, and optionally at least one wax, to form the emulsion are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% or less by weight of wax, if present.

[00158] According to a preferred embodiment of the present invention, compositions having improved cosmetic properties such as, for example, increased removability from hair, eyebrows or eyelashes to which they have been applied are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant,

[00159] According to a preferred embodiment of the present invention, methods of improving the removal properties (from hair, eyebrows and/or eyelashes) of a water-in-oil (w/o) emulsion composition comprising at least one siloxysi!icate resin, and optionally at least one wax, by adding at least one latex comprising polymer comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at least one styrene group to the emulsion composition, resulting in increased removal properties of the emulsion composition, are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[00160] According to a preferred embodiment of the present invention, methods of making a water-in-oii (w/o) emulsion composition for hair, eyelashes and/or eyebrows comprising combining at least one latex comprising polymer comprising at least one styrene group in an amount sufficient to add from about 2% to about 6% by weight with respect to the total weight of the composition of the polymer comprising at least one styrene group and at least one siioxysilicate resin, and optionally at least one wax, to form the emulsion composition are provided. Preferably, the composition is a composition for eyelashes. Most preferably, the composition is a mascara composition further comprising at least one colorant.

[00161] 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.

[00162] 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.

[00163] Examples

[00164] Example 1 - Sample Mascara Composition

[00165] Sample procedure for preparing compositions of the present invention:

[00166] In metal container A, All phase A materials were added and heated until 90°C.

[00167] When metal container A was at SOT, homogenized for 30 minutes at 2QQ0RPM.

[00168] After the mixture was uniform and cooled to 45T, added B subsequently, and mixed for 10mins.

[00169] Batch Cooled to SOT.

[00170] Example 2 - Determination of Stability Properties

[00171] “Stability," as used herein, means that the oil and water phases of the emulsion do not phase separate at room temperature over a period of at least 2 months. To determine if invention compositions are stable, a glass jar can be filled with the composition (formula), and placed into a 25° C oven for 2 months. If no separation (clear, white) is observed, the formula is considered stable.

[00172] Alternatively, to simulate a real time equivalency to the 2 month time period, the composition can be placed into a Lumisizer from LUM, and the following protocol can be followed:

[00173] Fill the cuvette with mascara sample. @ 45°C;

[00174] Pre-run at 2000 rpm for 2 min to level the sample surface at 45°C; and

[00175] Run samples at 3000 rpm for 30min and monitor for separation.

[00176] Phase separation by visual assessment can occur by examining the black phase of the composition. For example, unstable compositions can have black sandwich layers as opposed to stable compositions which have a homogeneous black phase.

[00177] Example 3 - Comparative Stability Testing

[00178] Compositions falling with the ranges set forth in the following Table were prepared and tested for stability according to the simulated real time equivalency protocol in example 2, and the results of this testing is also set forth in the Table.

[00179] Example 4 - Comparative Stability and Wear Properties Testing [00180] Compositions falling with the ranges set forth in the following Table were prepared and tested for both stability (according to the same protocol as above) and wear properties according to the following protocol.

[00181] Artificial sebum and water resistance protocol: on fake lashes, apply 3 x 10 strokes of composition with 2 min dry time in between. Lashes then dipped in solvent 1b after application of composition. Lashes then left in the solvent for 1h and then placed in the spinning apparatus where the lashes rub against a sheet of drawing paper. 3 samples of each formula were assessed on one sheet. The deposit was then assessed on a scale of 1-5, with 1= no mascara on lashes, dissolved in solvent; 2 significant transfer onto paper, mascara left in solvent; 3= significant transfer onto paper; 4= low transfer onto paper; and 5= little to no transfer onto paper.

[00182] Removal method protocol: on fake lashes, apply 3 x 10 strokes of composition with 2 min dry time in between. Removal carried out 1 h after application. 1 ,5g of ganrier pink micellar water added to cotton pad. Lashes softly pinched for 10 sec. with the soaked pad and then the cotton pad is removed by softly pulling under a neutral grip.

[001 S3] Example 5A - Sample Mascara Composition Containing Latex

[00184] Sample procedure for preparing compositions of the present invention:

[00185] In metal container A, All phase A materials were added and heated until 90°C.

[00188] When metal container A was at 9Q°C, homogenized for 30 minutes at 20G0RPM,

[00187] After the mixture was uniform and cooled to 45°C, added B subsequently, and mixed for IQmins.

[00188] Batch Cooled to 30°C.

[00189] Example 5B - Determination of Removal Properties

[00190] Water-in-oil emulsions containing the same base ingredients but varying amounts of (1) latex containing styrene/acrylates/ammonium methacrylate copolymer (ranging from 0% to 10%); (2) MQ resin in combination with nylon 611/dimethicone (ranging from 0% to 18.7%); and (3) waxes (ranging from 17% to 25.5%) were prepared and tested for removal properties as follows:

[00191] Compositions were applied to artificial eyelashes and allowed to dry at room temperature. Once dried, the compositions were subjected to contact with removal solvent (makeup remover) using a cotton pad until the composition was completely removed from the eyelashes. The number of strokes it took to completely remove compositions from eyelashes was counted and recorded, with 4 = easy removal; 5 = good removal; 8 = poor removal; and 7 = difficult removal.

[00115] It was found that compositions containing MQ resin, and optionally at least one wax, containing from about 2% to about 6% styrene/acrylates/ammonium methacrylate copolymer possessed easy or good removal properties, whereas compositions containing the copolymer in amounts outside of the 2%-6% range possessed poor or difficult removal properties, it was also found that removal properties were generally not affected by the amount of MQ resin present in the compositions.