FR3113587A1 - GEL COMPOSITIONS COMPRISING HYDROPHOBIC SILICA AND A COPOLYMER FORMED FROM ACRYLIC MONOMER OF SULFONIC ACID - Google Patents

Abstract

GEL COMPOSITIONS COMPRISING HYDROPHOBIC SILICA AND A COPOLYMER FORMED FROM ACRYLIC MONOMER OF SULFONIC ACID Gel compositions including water, a water-soluble or water-dispersible gelling agent comprising at least one copolymer formed from acrylic sulfonic acid monomer are provided. The compositions further include a film-forming polymer selected from a film-forming acrylic polymer, a film-forming urethane polymer, and combinations thereof. The compositions further include hydrophobic silica and are substantially free of fatty compounds. Figure for abstract: none.

Description

GEL COMPOSITIONS COMPRISING HYDROPHOBIC SILICA AND A COPOLYMER FORMED FROM ACRYLIC SULFONIC ACID MONOMER

FIELD OF THE INVENTION

The present invention relates to gel compositions comprising hydrophobic silica and a copolymer formed from acrylic sulfonic acid monomer. Among other improved or beneficial properties, these compositions have surprisingly good properties including phase stability and water resistance.

CONTEXT DISCUSSION

Makeup compositions, particularly those useful for foundations and primers, are difficult to formulate, especially for use in humid environments. It is difficult to create formulas that are comfortable, water repellent, phase stable, and offer non-transfer properties. The present inventors have surprisingly discovered that by combining particular gelling agents and hydrophobic silica with film formers, an advantageous mixture of properties is obtained.

The present invention relates to gel compositions including water, a water-soluble or water-dispersible gelling agent comprising at least one copolymer formed from acrylic sulfonic acid monomer. The compositions further include a film-forming polymer selected from a film-forming acrylic polymer, a film-forming urethane polymer, and combinations thereof; and hydrophobic silica. The compositions are substantially free of fatty compounds. In some embodiments, the gel compositions include at least about 0.75% by weight of the at least one copolymer formed from acrylic sulfonic acid monomer.

The present invention also relates to methods for treating, caring for and/or making up keratinous materials by applying compositions of the present invention to a keratinous material in an amount sufficient to treat, care for and/or make up the keratinous material.

It is understood that the preceding general description and the following detailed description are both given by way of example and explanation only, and do not limit the invention.

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.

All ingredient percentages are given here on an active substance basis, unless otherwise stated. Additionally, all ingredient percentages are by weight percent unless otherwise noted.

Except in the working examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions shall be understood to be modified in all cases by the term "approximately", meaning within 10% to 15% of the number indicated. For example, about 10% means 8.5% to 11.5%, such as between 9% and 11%.

Numerical ranges include endpoints and are intended to include all combinations and subcombinations. For example, from about 5%, 10% or 15% to about 20%, 50% or 60% means about 5% to about 20%, about 5% to about 50%, about 5% to about 60%, about 10% to about 20%, about 10% to about 50%, about 10% to about 60%, about 15% to about 20%, about 15% to about 50%, or about 15% to about 60%.

All concentrations in this specification are by weight unless specifically stated otherwise.

"Film former" or "film former" as used herein means any material such as, for example, a polymer or resin which leaves a film on the substrate to which it is applied.

A "polymer" as used herein means a compound which is made up of two or more monomers.

The term "keratinous materials" includes materials containing keratin such as hair, skin, eyebrows, lips and nails.

"Substantially free" as used herein means that while it is preferred that no amount of the specific component be present in the composition, it is possible to have very small amounts of it in the compositions of the invention provided that these amounts do not materially affect at least one, preferably most, of the beneficial properties of the conditioning compositions of the invention. In some embodiments, substantially free means less than about 2% of the identified ingredient, such as less than about 1%, such as less than about 0.5%, such as less than about 0.1 % of ingredient. The term “anhydrous” means substantially free of water.

"Substituted", as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups, hydroxyalkyl groups and polysiloxane groups. The substituent(s) may further be 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 of greater than about 100°C.

The term "long-lasting" compositions as used herein refers to compositions where the compositions, after application to a keratinous material, are not transferred or do not stain after contact with another substrate and retain a homogeneous appearance on the material. keratinous for a long period of time. The term "long-lasting" compositions as used herein may also refer to compositions where the color remains the same or substantially the same as at the time of application, as seen with the naked eye, after a long period of time. Long-wear properties can be evaluated by any method known in the art for evaluating such properties. For example, long wear can be assessed by a test involving applying a composition to keratinous materials such as the skin, eyebrows or lips and evaluating the color of the composition after a long period of time. . For example, the color of a composition can be evaluated immediately after application to the keratinous material 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. Additionally, durability properties can be assessed by applying a sample, allowing the sample to dry, and then abrading the sample to determine sample removal/loss.

"Transfer" as used herein refers to the displacement of a fraction of a composition which has been applied to a keratinous material by contact with another substrate, whether of the same nature or of a different nature. . For example, when a composition such as eye shadow, eyeliner or mascara has been applied, the composition can be transferred to the hands by friction or by contact of the hands with the eyes. By way of further example, when a composition such as lipstick has been applied, the composition may be transferred to another person's teeth or hands, or cheek. Regardless of the type of composition, the composition can also be transferred from the keratinous material on which it was applied to another substrate such as napkins, collars, glasses, cups or other containers.

"Transfer resistance" as used herein refers to the quality exhibited by a composition in its transfer resistance. To determine transfer resistance, the amount of composition transferred from a keratinous material to a substrate can be assessed and compared. For example, a composition can be transfer resistant if, after application to a keratinous material such as the lips, skin or eyebrows and contact with a substrate, a major part of the composition remains on 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 to the substrate from the keratinous material.

"Oil resistance" or "sebum resistance" as used herein means resistance to transfer when the composition comes into contact with oil or sebum, respectively.

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 useful in personal care.

In accordance with the present invention, the gel compositions of the present invention include a gelling system which includes one or more copolymers formed from acrylic sulfonic acid monomers.

Copolymer formed from sulfonic acid acrylic monomer

In accordance with the present invention, compositions which include a gelling system which includes at least one copolymer formed from acrylic sulfonic acid monomer are provided.

Suitable copolymers formed from acrylic sulfonic acid monomers include cross-linked acrylamide/sodium acrylamido-2-methylpropanesulfonate (AMPS) copolymers, such as that used in the commercial product Sepigel 305 (CTFA name: polyacrylamide/isoparaffin in C ₁₃ -C ₁₄ /laureth-7) or that used in the commercial product sold under the name Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate/isohexadecane/polysorbate-80) by the company SEPPIC; copolymers of AMPS® and vinylpyrrolidone or vinylformamide, such as that used in the commercial product sold under the name Aristoflex AVC® by the company Clariant (CTFA name: ammonium acryloyldimethyltaurate/VP copolymer) but neutralized with sodium hydroxide or sodium hydroxide; copolymers of AMPS and sodium acrylate, for example the copolymer of AMPS/sodium acrylate, such as that used in the commercial product sold under the name Simulgel EG® by the company SEPPIC or under the brand name Sepinov EM (CTFA name: hydroxyethyl acrylate/sodium acryloyldimethyltaurate copolymer); copolymers of AMPS and hydroxyethyl acrylate, for example the copolymer of AMPS/hydroxyethyl acrylate, such as that used in the commercial product sold under the name Simulgel NS® by the company SEPPIC (CTFA name: copolymer hydroxyethyl acrylate/sodium acryloyldimethyltaurate (and) squalane (and) polysorbate 60), or such as the product sold under the name sodium acrylamido-2-methylpropanesulfonate/hydroxyethyl acrylate copolymer, such as the product commercial Sepinov EMT 10 (INCI name: hydroxyethyl acrylate/sodium acryloyldimethyltaurate copolymer).

In some embodiments, the compositions of the present invention include both (1) a copolymer of AMPS and sodium acrylate and (2) a copolymer of AMPS and hydroxyethyl acrylate.

The one or more copolymers formed from acrylic sulfonic acid monomers may be present in an amount of active content ranging from greater than 0.75% to about 20%, such as about 0.75% , 1.0% or 1.25% by weight to about 1.5%, 3% or 5% by weight relative to the total weight of the composition.

Film-forming polymer

In accordance with the present invention, the compositions include at least one film-forming polymer. By "film-forming" polymer is meant a polymer or resin that leaves a film (e.g., a continuous film) on the substrate to which it is applied, for example, after a solvent accompanying the film-forming agent has evaporated, absorbed into and/or dissipated on or from the substrate. According to some embodiments, the film former, when tested according to the following pick test, forms a conformal coating and/or can be picked or scraped off with a razor blade to be removed as a movie isolated. Five to ten grams of material are placed in the center of a Leneta card stock (black and white opacity chart Chart 2812 available from BYK Additives and Instruments of Geretsried, Germany) and using a 3 mil Drawdown Birdbar (also from Byk), the material is spread over the sheet (8 inches by 3 inches) and left to dry overnight. Film formers which are cosmetically or dermatologically acceptable can be used in the present invention. As used herein, "cosmetically acceptable" or "dermatologically acceptable" is intended to mean that a composition is suitable for use in contact with human tissues such as keratinous materials and mucous membranes without toxicity, incompatibility, instability and/or or excessive allergic response.

The film-forming polymer is selected from a film-forming acrylic polymer, a film-forming urethane polymer, and combinations thereof. In some notable embodiments, the gel compositions include both a film-forming acrylic polymer and a film-forming urethane polymer.

The film-forming polymer (total combined concentration of film-forming acrylic polymer and film-forming urethane polymer) is preferably present in the compositions of the present invention in an amount of active solid content in the range of about 0.1%, 0.2%, 0.25% or 0.5% to approximately 2%, 3%, 4%, 10%, 20% or 25% by weight relative to the total weight of the composition.

By “acrylic”, it is meant that the film-forming polymer is formed from the polymerization, for example, the polymerization by the radical route, of one or more ethylenically unsaturated monomers, namely a vinyl, (meth)acrylic or allylic group. The term "(meth)acryl" and variations thereof, as used herein, means acryl or methacryl.

Suitable film-forming acrylic polymers include those having acrylic acid, acrylamide, methacrylamide, alkyl- and dialkylacrylamide, alkyl- and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate monomers.

The film-forming acrylic polymer can be a latex. By “latex” is meant a colloidal dispersion of polymer particles in an aqueous liquid phase. The “latex” is generally obtained by polymerization or copolymerization in suspension or in emulsion of monomers according to methods 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, d maleic acid, crotonic acid or itaconic acid or esters or amides thereof. The latex may include a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one C ₁ -C ₁₈ alkyl (meth)acrylate monomer, preferably a (meth) C ₁ -C ₁₂ alkyl acrylate, and preferably a C ₁ -C ₁₀ 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 the styrene monomer which can be used in the invention, examples which can be mentioned include styrene and α-methylstyrene.

Suitable examples of film-forming acrylic polymers include EPITEX 66 polymer, an aqueous polyacrylate emulsion available from Dow Chemical and LUVIFLEX SOFT, available from BASF Corporation.

The film-forming acrylic polymer is preferably present in the compositions of the present invention in an amount of active solid content ranging from about 0.1% to about 20%, preferably from about 0.2% to about 10%, preferably from about 0.25% to about 5%, and preferably from about 0.33% to about 3%, by weight relative to the total weight of the composition.

Film-forming urethane polymer

In accordance with the present invention, the compositions include at least one film-forming urethane polymer. By "urethane" polymer is meant polymers formed by reaction of isocyanates and polyols, and having a plurality of -NHCOO- bonds.

The film-forming urethane polymer can exist as a dispersion or a latex. Commercially available examples of such dispersions or latexes include, but are not limited to, aqueous polyurethane dispersions comprising a reaction product of a prepolymer comprising a dihydroxy compound, a polyisocyanate, and a low molecular weight diol and at least two diamine compounds and in which the composition is substantially free of triethanolamine stearate such as, for example, those sold under the name BAYCUSAN® by Bayer such as, for example, BAYCUSAN® C1000 (polyurethane-34), BAYCUSAN® C1001 (polyurethane-34), BAYCUSAN® C1003 (polyurethane-32) and BAYCUSAN® C1004 (polyurethane-35).

In some embodiments, the film-forming urethane polymer is a polyurethane-34, such as polyurethane polymer dispersions sold under the trademark Baycusan™ C1000 by Bayer. It is sold as a 40% polymer solution.

The film-forming urethane polymer is preferably present in the compositions of the present invention in an amount of active solid content ranging from about 0.1% to about 20%, preferably about 0.2% to about 10%, preferably from about 0.25% to about 5%, and preferably from about 0.33% to about 3%, by weight relative to the total weight of the composition.

HYDROPHOBIC SILICA

The inventors have surprisingly discovered that hydrophobic silica, despite having no affinity for water, can be used in the gel compositions of the present invention to enhance the stability and/or the water resistance. Suitable hydrophobic silicas include, but are not limited to, silicas, such as pyrogenic silica with a hydrophobic surface treatment whose particle size is less than 1 micron, preferably less than 500 nm, preferably less than 100 nm. nm, preferably 5 nm to 30 nm, including all ranges and subranges therebetween. It is in fact possible to modify the surface of silica chemically, by a chemical reaction producing a decrease in the number of silanol groups present on the surface of silica. The silanol groups can in particular be replaced by hydrophobic groups: a hydrophobic silica is then obtained. Hydrophobic groups can be:

trimethylsiloxyl groups, which are obtained in particular by treating pyrogenic silica in the presence of hexamethyldisilazane. Silicas treated in this way are called "silica silylate" according to the CTFA (6th edition, 1995). They are for example marketed under the references “AEROSIL R812®” by the company Degussa, “CAB-O-SIL TS-530®” by the company Cabot; or “VM-2270 FINE PARTICLES AEROGEL” by Dow.

dimethylsilyloxyl or polydimethylsiloxane groups, which are in particular obtained by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas treated in this way are called "silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are for example marketed under the references; “AEROSIL R972®”, “AEROSIL R974®” by the Degussa company, “CAB-O-SIL TS-610®”, “CAB-O-SIL TS-720®” by the Cabot company.

Additionally, silica airgel particles can be added to the compositions of the present invention, if desired. Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air. They are generally synthesized via a sol-gel process in a liquid medium and then dried, usually by extraction with a supercritical fluid, the most commonly used being supercritical CO ₂ . This type of drying avoids the contraction of the pores and the material.

The hydrophobic silica airgel particles which can be used in the present invention can have a specific surface area per unit mass (S _M ) ranging from 500 to 1500 m ² /g, preferably from 600 to 1 200 m ² /g and more preferably 600 to 800 m ² /g, and a size expressed as the volume average diameter (D[0.5]) lying within a range of 1 to 1500 μm, more preferably 1 to 1000 µm, preferably 1 to 100 µm, in particular 1 to 30 µm, more preferably 5 to 25 µm, more preferably 5 to 20 µm and still more preferably from 5 to 15 µm.

According to one embodiment, the hydrophobic silica airgel particles that can be used in the present invention have a size, expressed as the volume average diameter (D[0.5]), falling within a range of 1 to 30 µm, preferably 5 to 25 µm, more preferably 5 to 20 µm and even more preferably 5 to 15 µm.

Silica airgel particle sizes can be measured by static light scattering using a commercial particle size analyzer such as Malvern's MasterSizer 2000 machine. The data is processed based on Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an “ effective ” particle diameter. According to an advantageous embodiment, the hydrophobic silica airgel particles which can be used in the present invention have a specific surface area per unit mass (S _M ) lying in a range of 600 to 800 m ² /g and a size expressed as the volume average diameter (D[0.5]) ranging from 5 to 20 µm and even more preferably from 5 to 15 µm.

The silica airgel particles that can be used in the present invention can advantageously have a tapped density ρ in the range of 0.02 g/cm ³ to 0.10 g/cm ³ , preferably from 0.03 g/cm ³ to 0.08 g/cm ³ and preferably from 0.05 g/cm ³ to 0.08 g/cm ³ .

According to a preferred embodiment, the hydrophobic silica airgel particles which can be used in the present invention have a specific surface area per unit volume S _V lying in a range from 5 to 60 m ² /cm ³ , preferably from 10 to 50 m ² /cm ³ and more preferably from 15 to 40 m ² /cm ³ . The specific surface per unit volume is given by the relationship: S _V = S _M x ρ, where ρ is the density after settlement, expressed in g/cm ³ , and S _M is the specific surface per unit mass, expressed in m ² /g, as defined above.

Preferably, the hydrophobic silica airgel particles which can be used according to the invention have an oil absorption capacity, measured at the wet point, lying in a range from 5 to 18 ml/g, preferably from 6 to 15 ml/g and more preferably 8 to 12 ml/g. The absorption capacity measured at the wet point, noted Wp, corresponds to the quantity of oil which must be added to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the “wet point” method or the method for determining the oil uptake of a powder described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below: a quantity m = 2 g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added drop by drop. After adding 4 to 5 drops of oil to the powder, mixing is carried out using a spatula, and the addition of oil is continued until conglomerates of oil and powder are formed. From this moment, the oil is added drop by drop and the mixture is then triturated with the spatula. The addition of oil is stopped when a creamy and firm paste is obtained. This paste must be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil uptake corresponds to the Vs/m ratio.

The aerogels which can be used according to the present invention are hydrophobic silica aerogels, preferably silyl silica (INCI name: silica silylate). The term "hydrophobic silica" is understood as meaning any silica whose surface is treated with silylation agents, for example with halogenated silanes, such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes, such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl Si—Rn groups, for example trimethylsilyl groups.

The hydrophobic silica can be present in a concentration of about 0.25%, 0.5% or 1% to about 1.5%, 2%, 3% or 5% by weight.

POLYHYDRIC ALCOHOL

In accordance with certain embodiments of the present invention, the compositions may include at least one polyhydric alcohol compound. The polyhydric alcohol compound can be selected from the group consisting of glycerin, glycols, polyglycerin, esters of polyhydric alcohols, and mixtures thereof.

Suitable glycols include those which are liquid at room temperature. The glycol can contain from 2 to 12 carbon atoms, such as from 2 to 10 carbon atoms such as, for example, glycerine, propylene glycol, butylene glycol, propane diol, hexylene glycol, polyglycerin, dipropylene glycol and diethylene glycol. In certain other embodiments, the polyhydric alcohol compound includes glycerin, propylene glycol, butylene glycol, propane diol, hexylene glycol, polyglycerin, and combinations thereof. In certain other embodiments, the polyhydric alcohol is glycerin.

Suitable polyhydric alcohol esters include liquid esters of C1-C26 polyhydric alcohols, saturated or unsaturated, linear or branched. The total number of carbon atoms of the esters may be greater than or equal to 8, such as greater than or equal to 10, such as greater than or equal to 12 and such as less than 50, including all ranges and subranges between these such as from 8 to 50, from 10 to 40, from 12 to 30, from 8 to 25, from 10 to 50, etc. Specific examples of suitable polyhydric alcohol esters include, but are not limited to, esters of dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols. The polyhydric alcohol ester can be a glyceryl ester such as, for example, glyceryl triglycolate, glyceryl tricitrate, glyceryl trilactate, glyceryl trilactate, glyceryl tributanoate, glyceryl triheptanoate, trioctanoate glyceryl, etc.

According to certain embodiments, the at least one polyhydric alcohol compound is present in the compositions of the present invention in an amount greater than about 3% by weight, such as greater than about 5% by weight. According to certain embodiments of the invention, the concentration of polyhydric alcohol compound is from about 3%, 5%, 8%, 10% or 12% to about 12%, 15%, 20%, 30%, 40% or 50%, with all weights being based on the weight of the composition.

C2-C4 monoalcohol

According to certain embodiments of the invention, the gel compositions of the present invention may include a C2-C4 monoalcohol such as ethanol or isopropanol. The concentration of C2-C4 monoalcohol can range from about 0.5%, 1%, or 2% to about 3%, 4%, 5%, or 10%.

Other fillers and pigments

According to the present invention, the gel compositions of the present invention may include other fillers and pigments (other than hydrophobic silica) which may be suspended in the gel composition.

The pigments which can be used according to the present invention can be chosen from white, colored, inorganic, organic, polymeric and non-polymeric pigments. Representative examples of mineral pigments include titanium dioxide, 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, barium, strontium, calcium and aluminum lakes.

According to certain embodiments, the other fillers and pigments are chosen from those comprising iron oxide, titanium dioxide and mica.

The other fillers and pigments useful in the compositions of the present invention may or may not be surface treated. For embodiments wherein the other filler or pigment is surface treated with a hydrophobic treatment, the concentrations of such hydrophobically treated fillers and pigments may be less than about 0.5%, such as less than about 0.1% by weight.

For other fillers and pigments that are not treated with a hydrophobic surface treatment, their collective concentration by weight in the gel compositions of the present invention may range from about 1%, 2%, 3% or 5% to about 5%, 10% or 20% by weight.

Aqueous phase

The gel compositions of the present invention also contain water. The water is preferably present in an amount of about 30%, 35%, 40% or 50% to about 50%, 60%, 70%, 80% or 90% by weight, with all weights being based on the total weight of the composition.

Fatty compounds

According to certain embodiments of the present invention, the compositions can include at least one fatty compound (fatty substance). However, in certain other embodiments, it is desirable that the composition be substantially free of such fatty compounds.

Fatty substances include oil(s) and/or wax(es). An "oil" means any non-aqueous medium that is liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg). A "wax" for the purposes of this disclosure is a lipophilic fatty compound which is solid at room temperature (25°C) and transitions from solid to liquid state reversibly, having a melting temperature of more than 30°C and, for example, more than 45°C, which can be as high as 150°C, a hardness of more than 0.5 MPa at room temperature, and an anisotropic crystal organization in the solid state. By bringing the wax to its melting temperature, it is possible to use wax(es) by themselves as carriers and/or it is possible to make the wax(es) wax(es) miscible with oils to form a microscopically homogeneous mixture.

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 certain embodiments, the compositions of the present invention preferably comprise one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having a viscosity at room temperature of less than or equal to 6 cSt and having from 2 to 7 silicon atoms, these silicones being optionally substituted by alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils which may 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 such as octyltrimethicone, hexyltrimethicone, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, cyclotetradimethylsiloxane or cyclopentasiloxane D4 or D5, and others.

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 WO03/042221, the contents of which are incorporated herein by reference. In one embodiment, the volatile linear silicone oil is decamethyltetrasiloxane. In another embodiment, the decamethyltetrasiloxane is further combined with another solvent which is more volatile than the decamethyltetrasiloxane.

According to certain embodiments of the present invention, the composition preferably comprises one or more volatile silicone-free oils which can be chosen from volatile hydrocarbon oils, volatile esters and volatile ethers. Examples of such silicone-free volatile oils include, but are not limited to, volatile oils of hydrocarbons having 8 to 16 carbon atoms and mixtures thereof and in particular branched C ₈ to C ₁₆ alkanes such as isoalkanes C ₈ to C ₁₆ (also known as isoparaffins), isohexadecane, isododecane, isodecane, and for example, the oils sold under the brand names of Isopar or Permethyl. Preferably, the silicone-free volatile oils have a flash point of at least 40°C.

Non-limiting examples of volatile oils without silicone are for example: isododecane, isohexadecane, Isopar L (C ₁₁ -C ₁₃ isoparaffin), Isopar H (C ₁₁ -C ₁₂ isoparaffin) and others.

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

According to certain embodiments of the present invention, the composition 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: vegetable oils based on hydrocarbons having a high content of triglycerides consisting of esters of glycerol fatty acids, the fatty acids of which may have variable chain lengths, these chains possibly being linear or branched, and saturated or unsaturated; these oils are especially wheat germ oil, corn oil, sunflower oil, shea oil, castor oil, sweet almond oil, macadamia oil, apricot oil, soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy seed oil, pumpkin oil, sesame oil, pumpkin seed oil, avocado oil, hazelnut oil, grape seed oil, black currant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, bancoul oil, passion fruit oil or musk rose; or caprylic/capric acid triglycerides.

According to certain embodiments of the present invention, the compositions of the present invention further comprise at least one wax. Suitable examples of waxes which can be used in accordance with the present disclosure include those generally used in the field of cosmetics: they include those of natural origin, such as beeswax, carnauba wax, candelilla wax , ouricury wax, Japan wax, cork fiber wax or sugar cane wax, rice middling wax, rice wax, Montan wax, paraffin wax, wax of lignite or a microcrystalline wax, ceresin or ozokerite, and hydrogenated oils such as hydrogenated castor oil or jojoba oil; synthetic waxes such as polyethylene waxes obtained from the polymerization or copolymerization of ethylene, and Fischer-Tropsch waxes, or fatty acid esters, such as octacosanyl stearate, glycerides which are waxy at 30°C, for example at 45°C.

According to certain embodiments of the present invention, the compositions of the present invention further include at least one silicone wax. Examples of suitable silicone waxes include, but are not limited to, silicone waxes such as alkyl- or alkoxydimethicones having an alkyl or alkoxy chain in the range of 10 to 45 carbon atoms, poly (di)methylsiloxane 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% by mole of siloxy units corresponding to 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 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 content of which is incorporated herein by reference, with a particular example being C30-C45 alkyldimethylsilylpolypropylsilsesquioxane; and mixtures thereof.

According to certain embodiments of the present invention, the compositions of the present invention further include at least one long chain alcohol wax. Preferably, the at least one long chain alcohol wax has an average carbon chain length between about 20 and about 60 carbon atoms, most preferably between about 30 and about 50 carbon atoms. Suitable examples of long chain alcohol waxes include, but are not limited to, alcohol waxes commercially available from Baker Hughes under the trade name Performacol such as, for example, Performacol 350, 425 and 550. Most preferably, the long chain alcohol wax has a melting temperature range of about 93°C to about 105°C.

According to preferred embodiments, the compositions of the present invention contain less than 2% wax and less than 2% oil.

According to preferred embodiments, the compositions of the present invention contain less than 1% wax and/or less than 1% oil.

According to preferred embodiments, the compositions of the present invention contain less than 0.5% wax and/or less than 0.5% oil.

According to preferred embodiments, the compositions of the present invention do not contain wax and/or oil.

According to certain other embodiments, the compositions of the present invention include up to about 2% volatile oil and less than about 1% non-volatile waxes and oils.

Additional additives

The composition of the invention may also include any additive usually used in the field under consideration. For example, dispersants such as poly(12-hydroxystearic acid), antioxidants, essential oils, sunscreens, preservatives, fragrances, fillers such as cellulose fibers, neutralizing agents, cosmetic and dermatological active agents such as, for example, emollients, moisturizers, vitamins, essential fatty acids, surfactants, silicone elastomers, thickening agents, gelling agents, particles, pasty compounds, viscosity-increasing agents may be added. A non-exhaustive list of such ingredients may be found in U.S. Patent Application Publication No. 2004/0170586, the entire contents of which are incorporated herein by reference. The person skilled in the art will take care to choose the optional additional additives and/or the quantity thereof in such a way that the advantageous properties of the composition according to the invention are not, or are not substantially, adversely affected. by the proposed addition.

These substances can be variably chosen by the person skilled in the art in order to prepare a composition which has the desired properties, for example, a consistency or a texture.

These additives can be present in the composition in a proportion of 0% to 70% (such as from 0.01% to 70%) relative to the total weight of the composition and in addition such as from 0.1% to 50% (if applicable), including all ranges and sub-ranges between them.

Of course, the composition of the invention must be cosmetically or dermatologically acceptable, that is, it must contain a non-toxic physiologically acceptable medium and must be capable of being applied to the keratinous materials of human beings such as, for example, the lips, skin or eyebrows.

According to preferred embodiments, the compositions of the present invention contain less than 1.5% surfactant. By “surfactant”, is meant a compound having hydrophilic and hydrophobic parts and which, when it is present in water in a concentration of 0.5%, is capable of reducing the surface tension of water at temperature and ambient pressure to less than about 60 mN/m, such as less than about 50 mN/m.

According to preferred embodiments, the compositions of the present invention contain less than 1.0%, such as less than 0.5% surfactant.

According to certain other embodiments, the gel compositions of the present invention include 20%-90% water, 3-40% polyhydric alcohol, 0.75%-2% sulfonic acid acrylic monomer copolymer , 1.75% to 4% film-forming polymers selected from film-forming acrylic polymer, film-forming urethane polymer, and combinations thereof, and 0.5% to 2% hydrophobic silica.

According to preferred embodiments of the present invention, methods for treating, caring for and/or making up a keratinous material by applying compositions of the present invention to the keratinous material in an amount sufficient to treat, care for and/or or make up the keratinous material are provided. Preferably, the "makeup" of the keratinous material includes the application of at least one coloring agent to the keratinous material in an amount sufficient to provide color to the keratinous material.

According to still other preferred embodiments, methods of enhancing the appearance of keratinous material by applying compositions of the present invention to the keratinous material in an amount sufficient to enhance the appearance of the keratinous material are provided.

In accordance with the preceding preferred embodiments, the compositions of the present invention are applied topically to the desired area of the keratinous material in an amount sufficient to treat, heal and/or make up the keratinous material, to cover or mask defects associated with the keratinous material. , or to enhance the appearance of the keratinous material. The compositions can be applied to the desired area as needed, preferably once daily, and then preferably allowed to dry before subjecting them to contact such as with clothing or other objects. Preferably, the composition is allowed to dry for about 4 minutes or less, more preferably for about 2 minutes or less.

Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and the like, 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 set forth in the following specification and appended claims are approximations which may vary depending on the properties desired to be achieved by the present invention. Despite the fact that the ranges and numerical parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are given as accurately as possible. Any numerical value, however, 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 the scope as a result. Percentages are given on a weight basis.

Example 1 –

The following are examples of compositions compatible with the embodiments of the invention described herein:

Ingredient E1 E2 E3 Water 75-90 20-40 75-90 Copolymer formed from sulfonic acid acrylic monomer 0.75-2.5 0.75-2.5 0.75-2.5 Film-forming acrylic polymer 1.5-2.0 1.5-2.0 1.5-2.0 Film-forming urethane polymer 1.25-2.0 1.25-2.0 1.25-2.0 hydrophobic silica 1.0-1.5 1.0-1.5 1.0-1.5 Polyhydric alcohol compound 3-10 30-40 3-10 Additional pigments or fillers 0 10-15 2-5 C2-C4 monoalcohol 0 2-5 2-5 volatile oil < 0.5 < 1 < 0.5 Surfactants and emulsifiers < 1 < 1.5 < 1

Example 2 – Tests

Four compositions (Ex. 4, Ex. 5, Ex. 6, and Ex. 7, each prepared in duplicate) were prepared, which were identical to each other, but with some exceptions: Composition, Ex. 4 had only 0, 72% copolymer formed from acrylic sulfonic acid monomer; Ex. 5 had only 0.2% copolymer formed from acrylic sulfonic acid monomer; Ex. 6 had no hydrophobic silica. Ex. 7 had 0.92% copolymer formed from acrylic sulfonic acid monomer and was compatible with E3 described above. All samples included iron oxide (brown) as part of the additional pigment and filler. The varying percentages of copolymer were compensated by adjusting (q.s.) the water concentrations. The samples were prepared by mixing the ingredients and were then evaluated to determine their stability.

Ex. 4 and Ex. 5 were left to equilibrate for a short period of time and showed phase instability. Ex. 6 and Ex. 7 appeared stable, so they were subjected to a more rigorous "stress test" of accelerated stability testing using a LumiSizer 651 available from LUM GmbH for stability testing. multi-wavelength accelerated during centrifugation using a 10 mm path length and an 865 nm source.

Specifically, the samples were rotated at 2000 rpm for 30 minutes at 45°C and continuously examined for extinction of emitted light along the length of the sample. The samples were further subjected to an even higher stress – 3000 rpm for 30 minutes at 45°C.

Ex. 6 and 7 were examined after centrifugation. The ex. 6 (no hydrophobic silica) separated into two distinct phases, a brown phase (presumably including colored pigments) at the bottom and a white phase at the top. The ex. 7 (including hydrophobic silica) was uniform.

The LumiSizer 651 also calculates a sedimentation velocity, where higher values indicate faster sedimentation. The sedimentation velocities for each of the two replicate tests measured by the LumiSizer for Ex. 6 and Ex. 7 are shown in the table below:

Reference Sedimentation velocity
( Repeat test 1) Sedimentation velocity
( Repeat test 2) Example 6 0.201 0.304 Example 7 < 0.001 0.013

Based on the centrifugation results and sedimentation velocities, it can be seen that the presence of the hydrophobic silica is surprisingly important in maintaining the stability of the gel compositions.

Claims (10)

Gel composition, comprising:
some water ;
a water-soluble or water-dispersible gelling agent comprising at least one copolymer formed from an acrylic sulfonic acid monomer;
a film-forming polymer selected from a film-forming acrylic polymer, a film-forming urethane polymer, and combinations thereof; And
hydrophobic silica, wherein the gel composition is substantially free of fatty compounds and wherein the concentration by weight of the at least one copolymer formed from acrylic sulfonic acid monomer in the gel composition is 0, 75% to about 5%. A gel composition according to claim 1, wherein the water-soluble or water-dispersible gelling agent comprises a copolymer of 2-acrylamido-2-methylpropane sulfonic acid and sodium acrylate, and a copolymer 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethylacrylate. A gel composition according to any preceding claim, wherein the hydrophobic silica is present in the gel composition in a concentration by weight of from about 1% to about 3%. A gel composition according to any preceding claim, wherein the water is present in the gel composition in a concentration by weight in the gel composition of from about 30% to about 90% by weight. A gel composition according to any preceding claim, further comprising at least one polyhydric alcohol compound. A gel composition according to claim 5, wherein the at least one polyhydric alcohol compound is present in a concentration by weight in the gel composition of from about 3% by weight to about 40% by weight. A gel composition according to claims 5 or 6, wherein the at least one polyhydric alcohol compound is present in a concentration by weight in the gel composition of from about 12% by weight to about 40% by weight. A gel composition according to any preceding claim, wherein the gel composition comprises from about 0.5% to about 5% of at least one C2-C4 monoalcohol. A gel composition according to any preceding claim, wherein the gel composition comprises from about 5% by weight to about 20% by weight of additional pigments or fillers. Process for treating, caring for and/or making up keratinous materials by applying the composition according to any one of the preceding claims to a user's keratinous material.