FR3113588A1 - WATER-IN-OIL EMULSIONS CONTAINING LOW HLB SURFACTANT, SILICONE GUM AND SILOXYSILICATE RESIN - Google Patents

Abstract

Water-in-oil emulsions containing low HLB surfactant, silicone gum and siloxysilicate resin Disclosed herein are water-in-oil (W/O) emulsion compositions for hair, eyelashes and/or eyebrows including at least one low HLB surfactant, at least one silicone gum, and at least one siloxysilicate resin , as well as methods of making and using such emulsions. Preferably, the composition is a composition for eyelashes, for example a mascara composition additionally including at least one colorant. Figure for abstract: none

Description

WATER-IN-OIL EMULSIONS CONTAINING LOW HLB SURFACTANT, SILICONE GUM AND SILOXYSILICATE RESIN

Field of invention

The present invention relates to water-in-oil (w/o) emulsions (compositions) comprising at least one low HLB surfactant, at least one silicone gum and at least one siloxysilicate resin. The compositions have beneficial cosmetic properties including good or improved wear, sebum resistance and/or water resistance. Importantly, the compositions also have good or improved stability properties.

Discussion of context

Mascara compositions are commonly used to accentuate the appearance of eyelashes. Conventional mascara compositions generally use waxes to form crystal lattice structures to accentuate curl, volume, length, thickness, and/or color of eyelashes. However, conventional mascara compositions including waxes tend to become less resistant to oil and/or sebum, causing smudging, flaking, and/or color transfer after wearing for a period of time.

Mascaras are in particular prepared on the basis of two types of formulations: aqueous mascaras designated by cream mascaras, in the form of a dispersion of waxes in water, and anhydrous or low water content mascaras, designated by water-resistant mascaras (qualified as “water repellent”), in the form of dispersions of waxes in organic solvents.

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

Anhydrous mascaras tend to have the disadvantages of being dry, having poor flexibility and/or having poor consistency, among others. Also, consumers experience difficulty in removing such mascaras from the eyelashes.

Document WO 2019/122102 relates to a direct emulsion for use on lips containing at least 10% silicone resin.

Document WO 2014/046883 relates to a cosmetic composition in slip powder containing particles coated with a binder composition, a silicone gel composition, and the evaporation residue of an alcohol-based composition and a process for realization of the composition.

Document WO 2010/149493 relates to a composition for making up and/or taking care of keratinous materials, comprising at least one fatty phase, at least one silicone resin and at least one styrene/acrylate copolymer.

Document WO 2014/143757 relates to compositions containing a silicone resin emulsion containing 0.5% by weight to 95% by weight of a silicone resin or a pressure-sensitive adhesive (AAC), 0.1 to 90% by weight of an ethylene oxide/propylene oxide block copolymer, and sufficient water to make up 100 percent.

US 10,441,527 is directed to fluid compositions containing multiple components, the first of which may include a copolymer which is a cross-linked siloxane (e.g. a cross-linked aminosiloxane), a silicone polyether copolymer (e.g. a silicone polyether copolymer (AB )n), and/or a saccharide siloxane copolymer, and the second of which may include an organopolysiloxane resin and/or an acrylate copolymer.

Document FR 2968983 relates to fluid anhydrous compositions containing at least one organopolysiloxane elastomer powder coated with a silicone resin; at least one organopolysiloxane elastomeric vehicle in a first oil; at least one wax; at least one organic lacquer; and at least a second oil.

Document US 2006/0078578 relates to film-forming compositions containing a non-quaternary montmorillonite mineral and a film-forming component.

There is a need to develop a cosmetic composition, in particular for making up eyelashes, making it possible to obtain a product that wears well, is resistant to water and to sebum and is stable.

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, and at least one siloxysilicate resin. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

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 least one siloxysilicate resin, and at least a wax. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% by weight wax or less.

The present invention also relates to methods for 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 , take care of and/or make up the hair, eyelashes, and/or eyebrows. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

The present invention also relates to methods for 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 enhance emulsion stability properties. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% by weight wax or less, if present.

The present invention also relates to processes for producing a water-in-oil (w/o) emulsion for hair, eyelashes and/or eyebrows comprising the combination of 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 an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% by weight wax or less, if present.

Detailed description of the invention

As used herein, the term "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

Other than in the working examples, or unless otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions must be understood as being modified in all cases by the term "approximately", meaning to the nearest 10% the number indicated.

"Film former" or "film former" as used herein means a polymer or resin which leaves a film on the substrate to which it is applied, for example, after a solvent accompanying the film former has evaporated, absorbed and /or dissipated on the substrate.

"Polymer" as used herein means a compound that is made up of two or more monomers.

"Transfer resistance" as used herein refers to the quality exhibited by compositions which are not readily removed by contact with another material, such as, for example, clothing or skin, for example. "Smudge resistance" is a type of "transfer resistance" - in the context of mascara compositions, smudges occur when eyelashes come in contact with the skin around the eye area and the mascara transfers to the eye area. area of skin in contact. Transfer resistance can be evaluated by any method known in the art for evaluating it. For example, the transfer resistance of a composition can be evaluated by a test which can involve applying the composition to a 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 after application, such as 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 a transfer from an individual's hair, eyelashes or eyebrows to clothing. or the skin after the expiration of a certain amount of time after applying the composition to the hair, eyelashes or eyebrows. The amount of composition transferred to the substrate (eg, collar, skin, or paper) can then be assessed and compared. For example, a composition may be transfer resistant if a major portion of the product is left on the hair, eyelashes or eyebrows of the wearer. Additionally, 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 from the substrate to the hair, eyelashes or eyebrows.

"Long-lasting" compositions as used herein refer to compositions where the color remains the same or substantially the same as when applied, as seen with the naked eye, after a extended period. Long-lasting properties can be evaluated by any method known in the art for evaluating such properties. For example, long duration can be assessed by a test involving applying a composition to human hair, eyelashes or eyebrows and evaluating the color of the composition after an extended period. For example, the color of a composition can be evaluated immediately after application to the hair, eyelashes or eyebrows and these characteristics can then be re-evaluated and compared after a certain period of time. Additionally, these characteristics can be evaluated against other compositions, such as commercially available compositions.

"Water repellent" as used herein refers to the ability to repel water and permanence with respect to water. Water repellency properties can be evaluated by any method known in the art for evaluating such properties. For example, a mascara composition can be applied to false eyelashes, which can then be placed in water for a certain period of time, such as, for example, 20 minutes. When the pre-set time expires, the false eyelashes can be removed from the water and passed over a material, such as, for example, a sheet of paper. The extent of the residue left on the material can then be assessed and compared to other compositions, such as, for example, commercially available compositions. For example, a composition can be water repellent if a major part of the product is left on the wearer, for example, eyelashes. In a preferred embodiment of the present invention, little or no composition is transferred from the wearer.

"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 group, sulfonate groups, thiosulfate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted.

"Volatile", as used herein, means having a flash point of less than about 100°C.

"Non-volatile", as used herein, means having a flash point greater than about 100°C.

"Stability" as used herein, means that the emulsion does not experience phase separation at room temperature for a period of at least 2 months.

"Removal properties", as used herein, refers to removal of compositions from hair, eyebrows and/or eyelashes. "Easy removal properties" for a removal process refers to processes that are not time consuming and/or do not substantially damage hair, eyebrows and/or eyelashes. Stripping properties can be assessed, for example, by comparing the stripping ability of a composition using a stripping solvent (e.g., a water-based composition containing a soap/surfactant or an oil-based composition) with the ability to remove other compositions (including commercial compositions) using the same solvent. For example, the compositions under evaluation can be applied to hair, eyebrows and/or eyelashes (real or artificial), and allowed to dry for a designated period (eg, 15 minutes). Then the number of passes it takes to completely remove the composition from the hair, eyebrows and/or eyelashes using a removal solvent and a cotton swab can be counted and compared to other compositions.

The compositions and methods of the present invention may include, 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" low HLB surfactant(s) comprising a backbone and pendant group(s). , wherein (1) the backbone is hydrophobic and one or more pendant group(s) is/are hydrophilic, (2) the backbone is hydrophilic and one or more pendant group(s) is / are hydrophobic, or (3) (1) and (2) are both present in the surfactant component.

The "surfactant component" of the emulsion composition of the present invention comprises at least one low HLB surfactant comprising a backbone and pendent group(s), wherein (1) the backbone is hydrophobic and one or more pendant group(s) is/are hydrophilic or (2) the backbone is hydrophilic and one or more pendant group(s) is/are hydrophobic. It may optionally also contain one or more additional surfactants. Preferably, the surfactant component contains a major portion (greater than 50% by weight) of low HLB surfactant comprising a backbone and pendent group(s), wherein (1) the backbone is hydrophobic and one or more pendant group(s) is/are hydrophilic or (2) the backbone is hydrophilic and one or more pendant group(s) is/are hydrophobic, preferably more than 60% by weight, preferably more than 70% by weight, preferably more than 80% by weight, preferably more than 90% by weight, and may contain up to 100% by weight of these surfactants, all percentages being based on total weight of low HLB surfactant(s) to total weight of surfactant component. All ranges and subranges within the percentages specified above are included herein such as, for example, 10% to 100% by weight, 25% to 90% by weight, 50% to 85% by weight, etc.

The "surfactant component" of the emulsion composition of the present invention preferably comprises from 1% to 15% by weight based on the total weight of the composition, preferably 2% to 10% by weight based on the total weight of the composition , and preferably from 3% to 8% by weight based on the total weight of the composition, including all ranges and subranges included.

In the sense of the emulsion compositions and components of the present invention which "consist essentially of" identified film-forming agents, the "basic and novel properties" of such compositions and component are long-lasting (e.g., sebum resistance and/or at the water).

In the sense of the methods of the present invention aimed at improving long-lasting properties of an emulsion composition which "consists essentially of" identified film-forming agents, the "basic and new property" of such methods is the improvement of the long-lasting (for example, resistance to sebum and/or water).

In the sense of the emulsion compositions and components of the present invention which "consist essentially of" the identified ingredients, the "basic and novel properties" of such compositions and components are stability.

Within the meaning of the methods of the present invention aimed at improving the stability of an emulsion composition which "consists essentially of" the identified ingredients, the "basic and novel property" of such methods is the improvement of the stability of a emulsion composition.

SILOXYSILICATE RESIN

According to the present invention, compositions comprising at least one siloxysilicate resin are provided. Siloxysilicate resins generally meet the formula;

[(R) ₃ SiO] _x (SiO _4/2 ) _y

where R is an alkyl group preferably comprising 1 to 8 carbon atoms. A non-limiting example of a siloxysilicate in accordance with the present invention is trimethylsiloxysilicate, which can be represented by the following formula:

[(CH ₃ ) ₃ SiO] _x (SiO _4/2 ) _y .

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.

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® .

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, inclusive of all ranges and sub-ranges included such that, 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.

SILICONE GUM

According to the present invention, compositions comprising at least one silicone gum resin are provided. Silicone gum can, for example, correspond to the formula:

in which :

R ₇ , R ₈ , R ₁₁ and R ₁₂ are identical or different, and each is chosen from alkyl radicals comprising from 1 to 6 carbon atoms,

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,

X is chosen from alkyl radicals comprising from 1 to 6 carbon atoms, a hydroxyl radical and a vinyl radical,

n and p are preferably chosen so as to give the silicone gum a viscosity of 25,000 cSt to 20,000,000 cSt, preferably 30,000 cSt to 5,000,000 cSt, preferably 35,000 cSt to 1,000,000 cSt, preferably 40,000 cSt to 750,000 cSt, preferably 50,000 cSt to 500,000 cSt and preferably 60,000 cSt to 300,000 cSt, inclusive of all ranges and sub-ranges included. A particularly preferred range is 60,000 cSt to 300,000 cSt (corresponding to a molecular weight of 60,000 to 110,000), mixtures of two silicone gums within this range being preferred, the weight ratio of the two silicone gums ranging preferably about 2:1 to 1:2, with a weight ratio of the two silicone gums of about 1:1 being preferred. Thus, 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 within the identified viscosity ranges and ratios can be used.

In general, n and p can each take values from 0 to 10000, such as 0 to 5000.

Among the silicone gums that can be used according to the invention, mention can be made of those for which:

the substituents R ₇ to R ₁₂ and X represent a methyl group, p=0 and n=2700, such as the product sold or manufactured under the name SE30 by the company General Electric,

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 manufactured under the name AK 500,000 by the company Wacker,

the substituents R ₇ to R ₁₂ represent a methyl group, the substituent X represents a hydroxyl group, p = 0 and n = 2700, as a 13% solution in cyclopentasiloxane, such as the product sold or manufactured under the name Q2- 1401 by the Dow Corning company,

the substituents R ₇ to R ₁₂ represent a methyl group, the substituent X represents a hydroxyl group, p = 0 and n = 2700, as a 13% solution in polydimethylsiloxane, such as the product sold or manufactured under the name Q2- 1403 by the Dow Corning Company, and

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 approximately 600,000, for example the product sold or manufactured under the name 761 by Rhône-Poulenc (Rhodia Chimie).

In preferred embodiments, the silicone gum corresponds to the following formula:

In this formula, the terminal Si can also be other than methyl and can be represented with substitutions on the repeated Si such that the group R is an alkyl of 1 to 6 carbon atoms, which can be linear, branched and/or functionalized selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, vinyl, allyl, cycohexyl, phenyl, and mixtures thereof. The silicone gums used in the present invention can be terminated by triorganosilyl groups of formula R' ₃ where R' is a radical of monovalent hydrocarbons containing from 1 to 6 carbon atoms, hydroxyl groups, alkoxyl groups and their mixtures .

The at least one silicone gum is preferably present in the compositions of the present invention in an amount which is less than or equal to the amount of siloxysilicate resin present, preferably in an amount of less than 15% by weight, of preferably less than 10% by weight, preferably less than 5% by weight, preferably less than 3% by weight, including all ranges and sub-ranges included 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.

LOW HLB SURFACTANT

According to the present invention, compositions comprising at least one low HLB surfactant are provided. "HLB" refers to the "hydrophilic-lipophilic balance" associated with emulsifiers. In particular, the "HLB" value relates to the ratio of hydrophilic groups and lipophilic groups in emulsifiers, and also relates to the solubility of emulsifiers. Lower HLB emulsifiers are more soluble in oils (lipophilic material) and are more suitable for use in water-in-oil (w/o) emulsions. Higher HLB emulsifiers are more soluble in water (hydrophilic material) and are more suitable for oil-in-water (O/W) emulsions. In the context of the present invention, a "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 more.

The low HLB surfactant is 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 more.

According to preferred embodiments, the low HLB surfactant is nonionic.

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

A particularly preferred skeleton is a hydrophobic skeleton, based on silicone 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 polymer of polyethylene glycol (PEG).

Another preferred backbone is a hydrophilic, hydrocarbon-based backbone such as a polyethylene glycol 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 C ₈ to C ₂₄ fatty compound, preferably a C ₁₂ to C ₂₀ fatty compound, and preferably a C ₁₆ to C ₁₈ fatty compound such as, for example, stearate, isostearate, laurate, etc.

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.

In preferred embodiments, the surfactant component comprises low HLB surfactant(s) comprising a backbone and pendent group(s), wherein (1) the backbone is hydrophobic and a or more pendant group(s) is/are hydrophilic, (2) the backbone is hydrophilic and one or more pendant group(s) is/are hydrophobic, or (3) ( 1) and (2) are both present in the surfactant component.

The low HLB surfactant of the present invention may be a silicone surfactant, preferably comprising dimethicone (eg, PEG-10 dimethicone or lauryl PEG-9 polydimethylsiloxyethyl dimethicone), or a non-silicone surfactant, free of dimethicone (eg, , PEG-30 dihydroxystearate). The low HLB surfactant of the present invention may have through alkoxylation (eg, ethoxylation or propoxylation) groups such as, for example, (C ₂ H ₄ O)-/polyethylene glycol (PEG) groups, ( C ₃ H ₆ O)-/polypropylene glycol (PPG), etc. Suitable emulsifiers include alkoxylated compounds, partial glycerides of alkoxylated compounds, polyglycerolated compounds, and mixtures thereof, etc.

According to preferred embodiments, the low HLB surfactant can be a silicone surfactant which is an oxyalkylenated organosiloxane. Preferably, the organosiloxane emulsifier is linear.

For example, the low HLB surfactant may have the general formula:

where p is 0 to 40 (the range including all numbers between and subranges such as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is (-- C ₂ H ₄ O) _a -(--C ₃ H ₆ O) _b H in which a is 0 to 25, b is 0 to 25 provided that a and b cannot both be 0 simultaneously, x, y , and z are each independently from 0 to 1 million provided 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 is about 5,000 to about 500,000, 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 lauryl, and the compound is referred to, generically, as cetyl dimethicone copolyol or lauryl dimethicone copolyol respectively. In some cases, the number of ethylene oxide or propylene oxide repeating units in the polymer is also specified, such as a dimethicone copolyol which 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 siloxane backbone. It is also possible for one or more of the methyl groups in the general structure above to be substituted by a longer chain alkyl (e.g. ethyl, propyl, butyl, etc.) or ether, such as as methyl ether, ethyl ether, propyl ether, butyl ether, and the like.

Also, the low HLB surfactant can meet the general formula:

wherein each n is independently 0 to 100 provided there may be at least one PE moiety. In some cases, where each n is independently from 2 to 30, and PE (--C ₂ H ₄ O) _a -(--C ₃ H ₆ O) _b H in which a is 0 to 25, b is 0 to 25 provided that a and b cannot both be 0; and wherein w, x, y, and z are each independently 0 to 1,000,000 provided there is at least one PE. In some embodiments the organosiloxane emulsifier is lauryl PEG-9 polydimethylsiloxyethyl dimethicone. Oxyalkylenated organosiloxane emulsifiers disclosed in US Patent No. 9,095,543 are useful in the present compositions. US Patent No. 9,095,543 is incorporated herein by reference in its entirety.

Additional examples of organosiloxane emulsifiers include, but are not limited to, those having the names C.T.F.A. Bis-Butyldimethicone Polyglyceryl-3; Bis-PEG/PPG-14/14 Dimethicone; Bis-butyldimethicone Polyglyceryl-3; Bis-isobutyl PEG/PPG-10/7 Dimethicone copolymer; Bis-PEG/PPG-18/6 Dimethicone; Bis-PEG/PPG-20/20 Dimethicone; Bis-PEG/PPG-16/16 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; Cetyl PEG/PPG-15/15 Butyl Ether Dimethicone; Cetyl PEG /PPG-7/3 Dimethicone; Cetyl 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; Isopolyglyceryl-3 Dimethicone; Isopolyglyceryl-3 Dimethiconol; Isostearyl Carboxyldecyl PEG-8 Dimethicone; Lauryl Methicone PEG-10 Phosphate; Lauryl PEG-8 Dimethicone; Lauryl 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 P EG-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-3/10 Dimethicone; PEG/PPG-4/12 Dimethicone; PEG/PPG-6/11 Dimethicone; PEG/PPG-8/14 Dimethicone; PEG/PPG-12/16 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-20/6 Dimethicone; PEG/PPG-20/15 Dimethicone; PEG/PPG-20/20 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 Ether Dimethicone; PEG-8 trisiloxane; Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone; PPG-12 Butyl Ether Dimethicone; Quaternium-17 silicone; TEA-Dimethicone PEG-7 Phosphate; PEG/PPG-18 dimethicone, PEG/PPG-18/18 dimethicone; lauryl 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-20/22 butyl ether dimethicone; PEG-9 dimethicone; PEG-3 dimethicone; PEG-9 methyl ether dimethicone; PEG-10 dimethicone; lauryl PEG-9 polydimethylsiloxyethyl dimethicone or mixtures thereof.

Examples of commercial linear organosiloxane emulsifiers are those sold by Dow Corning under the trade name Dow Corning 3225C Formulation Aid having the CTFA name cyclotetrasiloxane (and) cyclopentasiloxane (and) PEG/PPG-18 dimethicone; or 5225C Formulation Aid, designated as CTFA cyclopentasiloxane (and) PEG/PPG-18/18 dimethicone; or Dow Corning 190 Surfactant having the name CTFA PEG/PPG-18/18 dimethicone; or Dow Corning 193 Fluid, Dow Corning 5200 having the name CTFA lauryl PEG/PPG-18/18 methicone; or Abil EM 90 having the name CTFA cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abil EM 97 having the name CTFA bis-cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abil WE 09 having the name CTFA cetyl PEG/PPG-10/1 dimethicone in a mixture also containing polyglyceryl-4 isostearate and hexyl laurate; or KF-6011 sold by Shin-Etsu Silicones having the name CTFA PEG-11 methyl ether dimethicone; KF-6012 sold by Shin-Etsu Silicones with the name CTFA PEG/PPG-20/22 butyl ether dimethicone; or KF-6013 sold by Shin-Etsu Silicones having the name CTFA PEG-9 dimethicone; or KF-6015 sold by Shin-Etsu Silicones having the name CTFA PEG-3 dimethicone; or KF-6016 sold by Shin-Etsu Silicones having the name CTFA PEG-9 methyl ether dimethicone; or KF-6017 sold by Shin-Etsu Silicones having the name CTFA PEG-10 dimethicone; or KF-6038 sold by Shin-Etsu Silicones having the name CTFA lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

Particularly preferred low HLB surfactants are as follows:

Surfactants HLB POLYGLYCERYL-2 DIIOSTEARATE 5.5 GLYCOL DISTEARATE 5 to 6 GLYCERYL STEARATE 5.8 PEG-30 DIPOLYHYDROXYSTEARATE 5.5 PEG-10 DIMETHICONE 4.5 LAURYL PEG-9 POLYDIMETHYLSILOXYETHYL DIMETHICONE 3 PEG-9 POLYDIMETHYLSILOXYETHYL DIMETHICONE 4 PEG-6 DIIOSTEARATE 5

The at least one low HLB surfactant is preferably present in the compositions of the present invention in an amount of from about 1% to about 15%, preferably from about 1.5% to about 10%, and preferably from about 2% to about 8% by weight based on the total weight of the composition, inclusive of all ranges and subranges included.

WATER

According to the present invention, compositions comprising water are provided. The 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. water, and more preferably from about 15% to about 30% by weight water based on the total weight of the composition, including all ranges and subranges included.

OIL

According to the present invention, compositions comprising at least one oil are proposed. The 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. oil, and more preferably from about 15% to about 30% oil by weight based on the total weight of the composition, including all ranges and subranges included.

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.

According to some 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 6 cSt and comprising from 2 to 7 silicon atoms, these silicones being optionally substituted by alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that can be used in the invention include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof. Other volatile oils that can be used include KF 96A with a viscosity of 6 cSt, a commercial product from Shin Etsu with a flash point of 94°C. Preferably, the volatile silicone oils have a flash point of at least 40°C.

Non-limiting examples of volatile silicone oils are listed in Table 2 below.

Compound Flash point
(°C) Viscosity
(cSt) Octyltrimethicone
Hexyltrimethicone
Decamethylcyclopentasiloxane
(cyclopentasiloxane or D5)
Octamethylcyclotetrasiloxane
(cyclotetadimethylsiloxane or D4)
Dodecamethylcyclohexasiloxane (D6)
Decamethyltetrasiloxane (L4)
KF-96 A from Shin Etsu
PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) from Dow Corning
PDMS DC 200 (2 cSt) from Dow Corning 93
79
72

55

93
63
94
56

87 1.2
1.2
4.2

2.5

7
1.7
6
1.5

2

Additionally, a volatile linear silicone oil can be employed in the present invention. Suitable volatile linear silicone oils include those described in U.S. Patent No. 6,338,839 and WO 03/042221, 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 which is more volatile than the decamethyltetrasiloxane.

According to other embodiments, the oil vector preferably comprises one or more non-silicone volatile oils and can be chosen 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 8 to 16 carbon atoms and mixtures thereof and in particular branched C ₈ to C ₁₆ alkanes such as C isoalkanes ₈ to C ₁₆ (also known as isoparaffins), isohexadecane, 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.

Non-limiting examples of non-silicone volatile oils are given in Table 3 below.

Compound Flash point (°C) Isododecane
Propylene glycol n-butyl ether
Ethyl 3-ethoxypropionate
Propylene glycol methyl ether acetate
Isopar L (isoparaffin C ₁₁ -C ₁₃ )
Isopar H (isoparaffin C ₁₁ -C ₁₂ ) 43
60
58
46
62
56

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

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

- hydrocarbon-based vegetable oils with a high triglyceride content consisting of fatty acid esters of glycerol, the fatty acids of which may have various chain lengths, these chains possibly being 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, poppyseed oil, pumpkin oil, sesame seed oil, pumpkin seed oil, avocado oil, hazelnut oil, grapeseed oil, black currant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, oat oil, safflower oil, bancoul oil, passion flower oil or rosehip oil; or caprylic/capric acid triglycerides, for example those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

- 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 7 to 19 carbon atoms, and R ₆ represents a chain based on a branched hydrocarbon containing from 1 to 40 carbon atoms, of which 3 to 20 carbon atoms, with R ₆ + R ₇ ≥ 10, such as, for example, Purcellin's oil (cetostearyl octanoate), isononanoate of isononyl, C ₁₂ to C ₁₅ alkyl benzoate, isopropyl myristate, 2-ethylhexyl palmitate, and octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters, for example isostearyl lactate or diisostearyl malate; and pentaerythritol esters;

- synthetic ethers containing 10 to 40 carbon atoms;

- C ₈ to C ₂₆ fatty alcohols, for example oleyl alcohol, cetyl alcohol, stearyl alcohol, and cetearyl alcohol; And

- their mixtures.

Further, examples of non-volatile oils that can 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.

The compositions of the present invention may optionally further comprise any additive commonly used in the field considered. For example, dispersants, antioxidants, sunscreens, preservatives, fragrances, fibers, fillers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids, additional surfactants, silicone elastomers , pasty compounds, viscosity-increasing agents, eg, fat-soluble/fat-dispersible polymers, additional film-forming agents, colorants, and mixtures thereof may be added. A non-exhaustive list of such ingredients can be found in US Patent Application Publication Nos. 2004/0170586 and 2009/0142289, the entire contents of which are incorporated herein by reference. Additional examples of suitable additional components can be found in the other references which are incorporated by reference in this application. Still further examples of such additional ingredients can be found in the International Cosmetic Ingredient Dictionary and Handbook ( ^9th ed. 2002).

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

A “wax” means a lipophilic compound, solid at room temperature (25°C), with a reversible solid/liquid state change, having a melting point greater than or equal to 30°C.

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

Suitable examples of waxes include, but are not limited to, Carnauba wax, candelilla wax, BIS-PEG-12 DIMETHICONE CANDELILLATE wax such as, for example, Siliconyl Candelilla wax marketed by KOSTER KEUNEN, of hydrogenated jojoba such as for example that marketed by the company DESERT WHALE, hydrogenated palm oil such as that marketed by the company SIO, rice bran wax, Sumac wax, ceresin waxes, wax of laurel, Chinese insect wax, shellac wax, hydrogenated olive oil such as Waxolive from SOLIANCE, waxes obtained by hydrogenation of olive oil esterified with chain fatty alcohols in C ₁₂ to C ₁₈ such as those sold by the company SOPHIM under the brand names Phytowax Olive 12L44, 14L48, 16L55 and 18L57, the waxes obtained by hydrogenation of castor oil esterified with cetyl or behenyl alcohol such as by example those that are v sold under the names Phytowax Ricin 16 L 64 and Phytowax Ricin 22 L 73 by the company SOPHIM, hydrogenated Cameline wax, Ouricury wax, Montan wax, ozokerite waxes such as, for example, Wax SP 1020 P marketed by the company Strahl & Pitsch, microcrystalline waxes such as for example 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 by 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 names of the brand Performalene 400 polyethylene, Performalene 655 polyethylene and Performalene 500-L polyethylene by the company New Phase Technologies, alcohol-polyethylene waxes such as for example e those marketed under the name Performacol 425 Alcohol by the company BARECO, the 95/5 ethylene/acrylic acid copolymer sold under the brand name AC 540 wax by the company Honeywell, hydroxyoctacosanyl hydroxystearate such as for example that sold under the brand name Elfacos C 26 by the company AKZO, octacosanyl stearate such as for example that marketed under the name Kester Wax K 82H by the company KOSTER KEUNEN, stearyl stearate such as for example that marketed under the name Liponate SS by the company LIPO CHEMICALS, pentaerythritol distearate such as for example that marketed under the name Cutina PES by the company COGNIS, the mixture of dibehenyl adipate, dioctadecyl adipate and di-eicosanyl (INCI name C ₁₈ -C ₂₂ dialkyl adipate), the mixture of dilauryl adipate and ditetradecyl adipate (INCI name: C ₁₂ -C ₁₄ dialkyl adipate), the mixture of dioctadecyl sebacate, sebacate of didocosyl and sebacate dieicosyl (INCI name: C ₁₈ -C ₂₂ dialkyl sebacate) and the mixture of dioctadecyl octadecanedioate, didocosyl octanedioate and dieicosyl octanedioate (INCI name: C ₁₈ -C ₂₂ dialkyl octanedioate) such as for example that marketed by the company COGNIS, pentaerythrityl tetrastearate such as for example Liponate PS-4 from Lipo Chemicals company, tetracontanyl stearate such as for example Kester Wax K76H from KOSTER KEUNEN company, stearyl benzoate such as for example Finsolv 116 from company FINETEX, behenyl fumarate such as for example Marrix 222 from AKZO BERNEL, di-(trimethylol-1,1,1-propane) tetrastearate such as for example that 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 montanate with 4 ethylene oxide units (PEG-4) such as for example that which is sold under my name brand Clariant Licowax KST1, hexanediol disalicylate such as for example Betawax RX-13750 marketed by the company CP Hall, dipentaerythritol hexastearate such as for example that which is sold under the brand name Hest 2P-6S by the company HETERENE, ditrimethylolpropane tetrabehenate such as for example that which is sold under the brand name Hest 2T-4B by the company HETERENE, jojoba esters such as for example that which is sold under the brand name Floraester HIP by the company FLORATECH, mixtures of linear carboxylic acid/saturated hydrocarbons (C ₂₀ to C ₄₀ ) (INCI name: C ₂₀ -C ₄₀ acid polyethylene) such as for example Performacid 350 acid from the company NEW PHASE TECHNOLOGIES, a synthetic wax from Fischer-Tropsch type such as that marketed under the name Rosswax 100 by the company ROSS, cetyl alcohol, stearyl alcohol, behenyl alcohol, dioctadecyl carbonate such as for example Cutina KE 3737, polybehenate e of sucrose such as for example Crodaderm B from the company CRODA, and their mixtures, can in particular be mentioned. Such waxes are also described in US Patent Application Publication No. 2009/0142289, the entire contents of which are incorporated herein by reference.

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

Examples of suitable silicone waxes include, but are not limited to, silicone waxes such as alkyl- or alkoxydimethicones having an alkyl or alkoxy chain ranging from 10 to 45 carbon atoms, poly(di)methylsiloxane esters which are solid at 30°C and whose ester chain comprises at least 10 carbon atoms, di(1,1,1-trimethylolpropane) tetrastearate, which is sold or manufactured by Heterene under the name HEST 2T-4S; alkylated silicone-acrylate copolymer waxes comprising at least 40 mol% 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 from 0.05 to 0.95, R is an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group, or an amino group, R is a monovalent hydrocarbon having 9 to 40 carbon atoms, R'' is a monovalent hydrocarbon group having 1 to 8 carbon atoms, an aryl group such as those disclosed in US patent application 2007/0149703, the entire contents of which are incorporated herein by reference, a particular example being an alkyl( C ₃₀ to C ₄₅ )dimethylsilylpolypropylsilsesquioxane; and their mixtures.

If present, the wax(es) is (are) preferably present in an amount of at least 5% by weight, preferably about 5 to 26% by weight, preferably from about 7 to about 23% by weight, and preferably from about 10 to about 20% by weight based on the total weight of the composition, including all ranges and subranges therein .

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 at least one dispersion of film-forming particles in aqueous phase as additional film-forming agent. The dispersion of film-forming particles in aqueous phase is more generally known under the name of latex.

“Latex” is a colloidal dispersion of polymer particles in an aqueous liquid phase. The “latex” is generally obtained by polymerization or copolymerization in suspension or emulsion of monomers according to processes which are well known to those skilled in the art. Such monomers can 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 their esters or amides.

An example of a suitable latex is a polymer comprising a latex comprising at least one styrene group as an additional film-forming agent.

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 C ₁ to C ₁₈ alkyl (meth)acrylate monomer, preferably C ₁ to C ₁₂ alkyl (meth)acrylate, and preferably C ₁ to C ₁₀ alkyl (meth)acrylate. The C ₁ to 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 the styrene monomer which can be used in the invention, examples which can be mentioned include styrene and α-methylstyrene.

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 a weight average molecular weight of 100,000 Da, preferably greater than 120,000 Da, preferably greater than 135,000 Da, and preferably greater than 150,000 Da, including including all included ranges and sub-ranges such as, for example, 100,000 Da – 500,000 Da, 120,000 Da to 600,000 Da, 150,000 Da to 200,000 Da, etc.

Any styrene-acrylate copolymer or derivative thereof may be suitable for use in the compositions of the present invention. The polymer comprising latex 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, including all included ranges and sub-ranges. For example, a copolymer comprising (1) styrene and ammonium acrylates, (2) acrylates, and/or (3) acrylic groups is suitable. A particularly preferred copolymer is styrene/acrylates/ammonium methacrylate copolymer or styrene acrylic copolymer, commercial examples of which include SYNTRAN 5620 and SYNTRAN 5760 (with or without paraben), from Interpolymer Corporation; JONCRYL 77, by BASF Performance Chemicals; and RHOPLEX P376, by Dow Chemical Company.

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 the film-forming particles in aqueous phase mentioned 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 fat-soluble. Acceptable film formers are known in the art and include, but are not limited to, those disclosed in U.S. Patent Publication No. 2004/0170586, the entire contents of which are incorporated herein by reference.

Specific examples of film formers include, but are not limited to, proteins, such as proteins of plant origin, such as, for example, wheat or soy proteins; or proteins of animal origin, such as keratins, for example keratin hydrolysates and sulfonic keratins; cellulose polymers, such as, for example, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose or ethylhydroxyethylcellulose; arabic gums, guar gum, xanthan derivatives or karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; shellac resin, sandarac gum, dammars, elemis or copals; muccopolysaccharides, such as chondroitin sulphates, and mixtures thereof.

Specific examples of suitable film-forming agents also include silicone resins which are not siloxysilicates such as, for example, T-propyl silsesquioxanes and MK resins (for example, polymethylsilsesquioxanes), silicone esters such as those disclosed in U.S. Patent Nos. 6,045,782, 5,334,737, and 4,725,658, the disclosures of which are incorporated herein by reference, the polymers comprising a backbone selected from vinyl polymers, methacrylic polymers, and acrylic polymers and at least one chain selected from pendant siloxane groups and pendant fluorochemical groups such as those disclosed in U.S. Patent Nos. 5,209,924, 4,693,935, 4,981,903, 4,981,902, and 4,972,037, and WO 01/32737, the disclosures of which incorporated herein by reference are polymers such as those described in U.S. Patent No. 5,468,477, the disclosure of which is incorporated herein by reference (a non-limiting example of such polymers is poly(di methylsiloxane)-g-poly(isobutyl methacrylate), which is commercially available from 3M under the trade name VS 70 IBM), and mixtures thereof.

Specific examples of suitable polymers further include, but are not limited to, polyalkylenes, polyvinylpyrrolidone (PVP) or vinylpyrrolidone (VP) homopolymers or copolymers, copolymers of a C ₂ to C ₃₀ alkene, such as C ₃ to C ₂₂ , and their combinations. As specific examples of the VP copolymers which can be used in the invention, mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP), VP/ethyl methacrylate/ methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate, and mixtures thereof.

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 moiety chain or as a graft, and at least two groups capable of establishing hydrogen interactions. Non-limiting examples of polyorganosiloxane copolymers are disclosed, for example, in U.S. Patent No. 8,945,525, the disclosure of which is incorporated herein by reference in its entirety.

Additional polyorganosiloxane copolymers which can be used in long-lasting lip compositions of the present invention include those described in US 5,874,069, US 5,919,441, US 6,051,216, and US 5,981,680, of which the entire contents are incorporated herein by reference in their entirety.

A preferred polyorganosiloxane copolymer for use in the present invention contains at least one moiety selected from formula (III):

and the formula (IV)

in which :

(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;

(b) X is straight or branched chain alkylene having 1 to 30 carbons;

(c) Y is selected from the group consisting of straight or branched chain alkylenes having 1 to 40 carbons;

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

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

Particularly preferred polyorganosiloxane copolymers useful herein are commercially available from Dow Corning under the tradenames DC ^8178® and DC ^8179® , which are known by the INCI designation Nylon-611/Dimethicone Copolymer.

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, inclusive of all ranges and subranges, all weights being based on the weight of the composition as a whole.

Suitable fillers and/or viscosity increasing agents include silicate clays such as, for example, silicate clays containing at least one cation which may be selected from calcium, magnesium, aluminum, sodium, potassium, and lithium cations, and their mixtures. Non-limiting examples of such products include smectite clays such as montmorillonites, hectorites, bentonites, beidellites, saponites, vermiculites, stevensite, and chlorites. Preferred clays are synthetic silicate clays, most preferably lithium magnesium sodium silicate, commercially available from Rockwood under the tradename ^Laponite® . Other preferred examples of silicate clays which can be used in the present invention are selected from lithium magnesium silicate, calcium sodium aluminum silicate, calcium magnesium silicate, sodium magnesium silicate, calcium aluminum borosilicate, magnesium aluminum silicate, sodium potassium aluminum silicate, and sodium silver aluminum silicate.

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

According to preferred embodiments of the present invention, the compositions may further comprise a desired agent. The desired agent can be, for example, any colorant (pigment, tint, etc.), fiber or any additional film-forming agent known in the art.

Acceptable colorants include pigments, tints, such as oil soluble tints, pearlescent pigments, and pearlescent agents.

Representative oil-soluble dyes that can be used in accordance with the present invention include Sudan Red, DC Red 7, DC Green 6, β-carotene, soybean oil, Sudan Brown, DC Yellow 11, DC Violet 2, DC Orange 5, anneto , and quinoline yellow.

Representative pearlescent pigments include white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent 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 pearlescent pigments based on bismuth oxychloride.

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.

Suitable fibers include, but are not limited to, fibers which provide an improved elongation effect. A "fiber" should be understood as designating an object of length L and diameter D such that L is much larger than D, D being the diameter of the circle in which the cross section of the fiber is inscribed. In particular, the L/D ratio (or form factor) is chosen in the range going from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150. The fibers which can be used in the composition of the invention may be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or structured, for example, braided, hollow or solid. 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 blunt and/or polished to avoid injuries. 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.

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

According to other preferred embodiments, methods for 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 treating, caring for and/or enhancing the appearance of 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 with clothing or other objects (e.g. , a finishing coat). 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 which is dry or has been dried before application, or to which a base coat has been previously applied.

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 an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant.

According to a preferred embodiment of the present invention, methods for 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 a stability property of the emulsion are provided. Preferably, the composition is an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% by weight or less wax, if present.

According to a preferred embodiment of the present invention, methods for producing a water-in-oil (w/o) emulsion for hair, eyelashes and/or eyebrows comprising the combination of 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 an eyelash composition. Most preferably, the composition is a mascara composition further comprising at least one colorant. Most preferably, the composition comprises 26% by weight wax or less, if present.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, etcetera used in the specification and the claims are to be understood as being modified in all cases by the term "about". Accordingly, unless otherwise indicated, the numerical parameters specified in the following specification and appended claims are approximations which may vary depending on the desired properties sought to be achieved in the present invention.

Notwithstanding that the numerical ranges and parameters specifying the broad scope of the invention are approximations, the numerical values specified in the 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. Percentages are given on a weight basis.

Example 1 – Composition of typical mascara

Total %100.00 Phase Chemical name % w/w AT Low HLB surfactants 5 AT Raincoats 15 AT Silicon gum 2 AT Oils 25 AT Conservatives 1 AT Colorants -- Iron oxides 8 AT Water QS AT Polyol 2 AT Trimethylsiloxsilicate 8 AT clays 3 B Styrene/Acrylates/Ammonium Methacrylate Copolymer 4

Typical procedure for preparing compositions of the present invention:

In a metal container A, all phase A materials were added and heated to 90°C.

When metal container A was at 90°C, it was homogenized for 30 minutes at 2000 rpm.

After the mixture was uniform and cooled to 45°C, B was added later, and mixed for 10 min.

Batch cooled to 30°C.

Example 2 – Determination of stability properties

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

Alternatively, to simulate a real-time equivalence at the 2-month period, the composition can be placed in a LUM Lumisizer, and the following protocol can be followed:

fill the cuvette with a sample of mascara at 45°C;

pre-spin at 2000 rpm for 2 min to level the sample surface at 45°C; And

spin the samples at 3000 rpm for 30 min and monitor the separation.

A phase separation by visual estimation can take place by examination of the black phase of the composition. For example, unstable compositions may have intercalated black layers as opposed to stable compositions which have a homogeneous black phase.

Example 3 - Comparative Stability Test

Compositions falling within the ranges specified in the following table were prepared and tested for stability according to the real-time equivalence protocol simulated in Example 2, and the results of this test are also specified in table.

Ingredient Comparative Inventive Comparison 1 invention 2 invention 3 invention 4 invention 5 HLB value of surfactant component 8.8 5.4 5.2 4.3 4.8 GLYCERYL STEARATE
STEARETH-20 X PEG-10 DIMETHICONE – silicone
X X X X X PEG-30 DIPOLYHYDROXYSTEARATE - no silicone X X X LAURYL PEG-9 POLYDIMETHYLSILOXYETHYL DIMETHICONE – silicone X X non-silicone PEG-6 DIISOSTEARATE X sodium laureth sulphate X X X X X Hectorite 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 Magnesium sulfate 0-1 0-1 0-1 0-1 0-1 Silicon gum 2-8 2-8 2-8 2-8 2-8 MQ Resin 5-10 5-10 5-10 5-10 5-10 Total waxes 23 23 11 11 11-21 Filmogenic 0-5 0-5 0-5 0-5 0-5 Water QS QS QS QS QS Oils 10-30 10-30 10-30 10-30 10-30 Conservatives 1 1 1 1 1 Dyes 5-10 5-10 5-10 5-10 5-10 Polyols 1-3 1-3 1-3 1-3 1-3 Accelerated emulsion stability Unstable emulsion. See sedimentation of hydrophilic pigments at the bottom of the cuvette Stable emulsion. No water phase separation at the bottom of the cuvette Stable emulsion. No water phase separation at the bottom of the cuvette Stable emulsion. No water phase separation at the bottom of the cuvette Stable emulsion. No water phase separation at the bottom of the cuvette

Example 4 – Test comparative stability and wearing properties

Compositions falling within the ranges specified in the following table were prepared and tested for both their stability (according to the same protocol as above) and wearing properties according to the following protocol.

Artificial sebum and water resistance protocol: on false eyelashes, apply 3 x 10 passes of composition with a drying time of 2 min between. Then immerse the eyelashes in a solvent for 1 hour after applying the composition. Then leave the eyelashes in the solvent for 1 hour then place them in the rotating device where the eyelashes rub against a sheet of drawing paper. 3 samples of each formula were estimated on one sheet. The deposit was then estimated on a scale of 1 to 5, with 1 = no mascara on the eyelashes, dissolved in the solvent; 2 = significant transfer to paper, mascara left in the solvent; 3 = significant transfer to paper; 4 = low transfer to paper; and 5 = little or no transfer to paper.

Protocol of the removal process: on false eyelashes, apply 3 x 10 passes of composition with a drying time of 2 min in between. Carry out the elimination 1 hour after application. Add 1.5 g of Garnier pink micellar water to the cotton pad. Gently pinch the eyelashes for 10 s with the soaked pad then remove the cotton pad by gentle traction under a neutral grip.

invention 6 Comparative A Comparative B Comparative C HLB value of surfactant component 4.7 8.8 4.7 4.7 GLYCERYL STEARATE
STEARETH-20 - X - - PEG-10 DIMETHICONE – silicone X X X X PEG-30 DIPOLYHYDROXYSTEARATE- X - X X LAURYL PEG-9 POLYDIMETHYLSILOXYETHYL DIMETHICONE – silicone X - X X sodium laureth sulphate X X X X Silicon gum 2-8 2-8 2-8 0 MQ Resin 5-10 5-10 0 5-10 Filmogenic 3-5 3-5 3-5 3-5 Total waxes 17 26 17 17 Water QS QS QS QS Oils 20-35 20-35 20-35 20-35 Conservatives 1 1 1 1 Dyes 5-10 5-10 5-10 5-10 Polyols 1-3 1-3 1-3 1-3 Lumisizer visual description of stability Steady Separates into 3 layers. Unstable emulsion Stable emulsion with very slight migration of waxes to the surface Stable emulsion with very slight migration of waxes to the surface Water resistance 5 3 5 4 Resistance to artificial sebum 4 4 2 2 Elimination properties > 10 pads 3 pads 4 pads 5 pads

Claims (9)

A stable water-in-oil emulsion composition comprising (a) water, (b) at least one oil, (c) a surfactant component having an HLB value less than or equal to 6, (d) at least one of silicone and (e) at least one siloxysilicate resin. A composition according to claim 1, wherein the siloxysilicate resin is a trimethylsiloxysilicate resin. Composition according to any one of the preceding claims, further comprising at least one wax in an amount less than 26% by weight of the total weight of the composition. Composition according to any one of the preceding claims, further comprising at least one colorant. A composition according to any preceding claim, further comprising at least one silicate clay. Composition according to any one of the preceding claims, in the form of a mascara. A composition according to any preceding claim, wherein the surfactant component 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. A composition according to any preceding claim, wherein the composition comprises at least one silicone gum having a viscosity greater than 60,000 cSt and less than 300,000 cSt. A method of making up eyelashes comprising applying the composition of any one of the preceding claims to eyelashes.