WO2018213903A1

WO2018213903A1 - High spf sunscreen compositions

Info

Publication number: WO2018213903A1
Application number: PCT/BR2017/050132
Authority: WO
Inventors: Bruna Rodrigues SALOMAO; Marina Castello ESPOSITO; Angeles FONOLLA-MORENO
Original assignee: L'oreal
Priority date: 2017-05-26
Filing date: 2017-05-26
Publication date: 2018-11-29
Also published as: BR112019022772B1; BR112019022772A2

Abstract

A composition is provided that includes an emulsion having an aqueous phase and a lipophilic phase, wherein the composition includes water, a hydrophobic silica aerogel, porous microparticles of a polylactic acid-based resin, one or more organic solvents, one or more emulsifiers, one or more lipophilic materials, and one or more sunscreens. The composition can be prepared by a method including the steps of a) preparing an oil phase including the lipophilic materials, the porous microparticles of a polylactic acid-based resin, and the hydrophobic silica aerogel particles; and b) at ambient temperature and under mechanical agitation, adding to the oil phase a water phase including water and one or more emulsifiers. A method of caring for a keratin material in an animal includes applying to the keratin material an effective amount of the composition.

Description

HIGH SPF SUNSCREEN COMPOSITIONS

FIELD OF THE INVENTION

The invention relates to sunscreen compositions comprising emulsions that include porous polylactic acid particles and hydrophobic silica aerogel particles.

BACKGROUND OF THE INVENTION

Sunscreen compositions must provide good protection against the sun, a measure of which is the Sun Protection Factor (SPF) value, yet have satisfactory sensory perception, such as a smooth but not greasy feel upon application. However, this combination of properties has been difficult to achieve, particularly because many active sunscreen compounds themselves have an oily or greasy feel, and increasing their content tends to cause the final product to suffer from that effect. Therefore, compositions providing both good SPF and a non-greasy sensory effect would be a welcome advance in cosmetic sunscreen formulations.

SUMMARY OF THE INVENTION

The invention provides a composition comprising an emulsion having an aqueous phase and a lipophilic phase, wherein the composition comprises water, a hydrophobic silica aerogel, porous microparticles of a polylactic acid-based resin, one or more organic solvents, one or more emulsifiers, one or more lipophilic materials, and one or more sunscreens.

In the composition, the porous microparticles of the polylactic acid-based resin may have an enthalpy of fusion of 5 J/g or more.

In the composition, the porous microparticles of the polylactic acid-based resin may have a number average particle diameter of in a range from 1 μιη to 90 μιη.

In the composition, the porous microparticles of the polylactic acid-based resin may have a particle diameter distribution index in a range from 1 .0 to 1 .5.

In the composition, the porous microparticles of the polylactic acid-based resin may have a linseed oil absorption capacity in a range of 90 imL/g to 1000 imL/g.

In the composition, the porous microparticles of the polylactic acid-based resin may have a sphericity in a range from 80 to 100.

In the composition, the porous microparticles of the polylactic acid-based resin may be present in a range from 0.05 wt% to 1 .0 wt%.

In the composition, the hydrophobic silica aerogel may be a silica silylate. In the composition, the hydrophobic silica aerogel may have a specific surface area in a range from 500 m²/g to 1 500 m²/g as measured by BET nitrogen absorption.

In the composition, the hydrophobic silica aerogel may have a volume- average diameter in a range from 1 μιη to 1 00 μιη.

In the composition, the hydrophobic silica aerogel may be present in a range from 0.05 wt% to 0.5 wt%.

In the composition, the one or more sunscreens may be selected from the group consisting of octocrylene, butyl methoxydibenzoylmethane, oxybenzone, homosalate, ethylhexyl salicylate, ethylhexyl triazone, terephthalidene dicamphor sulfonic acid, drometrizole trisiloxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, and combinations thereof.

The composition may further comprise an active compound selected from the group consisting of disodium EDTA, triethanolamine, and tromethamine.

In the composition, the one or more lipophilic materials may comprise one or more of isononyl isononanoate, diisopropyl sebacate, stearyl alcohol, dimethicone, and caprylyl methicone.

In the composition, the one or more organic solvents may comprise one or more of ethanol, glycerol, pentylene glycol, and caprylyl glycol.

The composition may further comprise one or more aesthetic modifiers selected from the group consisting of aluminum starch octenylsuccinate, hydroxypropylmethylcellulose, xanthan gum, acrylates/Cio-C3o alkyl acrylate crosspolymers, ammonium acryloyldimethyltaurate homopolymers and ammonium acryloyldimethyltaurate/vinylpyrrolidone copolymers.

The composition may further comprise amorphous silica microspheres having an average diameter in a range from 1 μιη to 1 0 μιη.

The composition may provide an SPF of at least 30, preferably at least 50, more preferably at least 70, still more preferably at least 80, and most preferably at least 90.

In the composition, lipophilic sunscreens and the one or more lipophilic materials taken together may be present in a range from 25 wt% to 50 wt%.

The composition, if subjected to stability testing, may show essentially the same pH, viscosity profile, SEM images and photostability after 2 months' storage as just after production, for each of 4°C, room temperature, and 45°C storage conditions.

The invention also provides a method of caring for a keratin material in an animal, comprising applying to the keratin material an effective amount of the composition. The keratin material may be skin.

The invention also provides a method of preparing the composition, comprising the steps of

a) preparing an oil phase comprising the lipophilic materials, the porous microparticles of a polylactic acid-based resin, and the hydrophobic silica aerogel particles; and

b) at ambient temperature and under mechanical agitation, adding to the oil phase a water phase comprising water and one or more emulsifiers.

DETAILED DESCRIPTION OF THE INVENTION

Sunscreen compositions according to the invention are emulsions comprising hydrophobic silica aerogel particles and porous microparticles of a polylactic acid-based resin, along with one or more sunscreens, lipophilic ingredients, and water. Unless stated otherwise, all % figures herein are wt% figures expressed relative to the total weight of the composition. When multiple alternative lower and/or upper limits on a given component are recited herein, all combinations of the upper and lower limits are contemplated for that component.

Compositions according to the invention provide excellent sensorial performance as well as surprisingly high SPF values and product stability. The stability is typically such that, after 2 months' storage, the pH, viscosity profile, SEM images and photostability are essentially the same as just after production, for each of 4°C, room temperature, and 45°C storage conditions. In particular, the combination of hydrophobic silica aerogel particles and porous microparticles of a polylactic acid- based resin has been found to provide performance not seen when either of these components is omitted. The inventive compositions will now be described in terms of the types and amounts of the essential and optional ingredients used.

Polylactic acid (PLA) microparticles

The compositions of the invention comprise porous microparticles of a polylactic acid-based resin, sometimes referred to herein as "polylactic acid microparticles" or "PLA microparticles." The amount of PLA microparticles present in the compositions will typically be at least 0.02%, or at least 0.05, 0.10, or 0.12%. It will typically be at most 1 .0%, or at most 0.7, 0.5, 0.3, or 0.2%.

Suitable PLA microparticles are described in U.S. Pat. No. 9,017,812, incorporated herein by reference, and can be prepared by the methods disclosed there. The PLA microparticles may have an enthalpy of fusion of 5 J/g or more, preferably 10 J/g or more, more preferably 20 J/g or more, and most preferably 30 J/g or more. Further, the upper limit is preferably 100 J/g or less, although it is not limited in particular. Enthalpy of fusion refers to a value calculated from a peak area, which shows heat capacity of fusion at approximately 160°C, in a differential scanning calorimetry (DSC) where a temperature is raised to 200°C with the temperature rise of 20°C per minute.

Enthalpy of fusion can be adjusted by controlling the co-polymerization ratio (L/D) between L-lactic acid and D-lactic acid which constitute the polylactic acid- based resin. When the L/D ratio is 95/5 or more, enthalpy of fusion becomes 5 J/g or more and the polylactic acid-based resin becomes crystalline. It is preferred that the co-polymerization ratio of L-lactic acid is high because higher ratios facilitate crystallization. L/D is more preferably 97/3 or more, and most preferably 98/2 or more. L/D is 100/0 or less. Because optical isomers such as L and D have molecular structures that are mirror images of each other and physical properties are not different, enthalpy of fusion remains unchanged when the above-described L/D is substituted with D/L and consequently suitable resins include ones in which L/D is substituted with D/L.

Further, the polylactic acid-based resin may contain copolymerization ingredients other than lactic acid. The other copolymerization ingredient units can be, for example, a multivalent carboxylic acid, a polyhydric alcohol, a hydroxycarboxylic acid or a lactone. Exemplary multivalent carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5- sodium sulfoisophthalic acid and 5-tetrabutyl phosphonium sulfoisophthalic acid. Exemplary polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1 ,4- cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, an aromatic polyhydric alcohol produced by an addition reaction of ethylene oxide to a bisphenol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Exemplary hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6- hydroxycaproic acid and hydroxybenzoic acid. Exemplary lactones include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- butyrolactone, γ-butyrolactone, pivalolactone and δ-valerolactone. The volume content of the other copolymerization units is preferably 30 mol % or less, more preferably 20 mol % or less, further more preferably 10 mol % or less, most preferably 5 mol % or less, relative to the total monomer units of the polylactic acid-based resin as 100 mol%.

Although molecular mass and molecular mass distribution of the polylactic acid-based resin are not limited in particular, the lower limit of weight average molecular mass of the polylactic acid-based resin is preferably 10,000 or more, more preferably 50,000 or more, further more preferably 100,000 or more, most preferably 200,000 or more. Further, although not limited in particular, the upper limit of weight average molecular mass is preferably 1 ,000,000 or less. The weight average molecular mass referred to herein is weight average molecular mass in terms of polymethyl methacrylate (PMMA), measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

The PLA microparticles may have a number average particle diameter of 90 μιη or less, preferably 50 μιη or less, more preferably 30 μιη or less. This improves smoothness. Further, in uses such as cosmetics, because coagulation of particles tends to occur when the number average particle diameter is too small, the lower limit of the number average particle diameter is generally 1 μιη or more, preferably more than 1 μιη, more preferably 2 μιη or more, most preferably 3 μιη or more.

The particle diameter distribution index is preferably 2 or less in order to improve flow of the particles and impart a smoother touch. The upper limit of the particle diameter distribution index is preferably 1 .5 or less, more preferably 1 .3 or less, most preferably 1 .2 or less. Further, the lower limit is 1 in theory.

The above-described number average particle diameter of polylactic acid-based resin microparticles having porous shapes can be calculated by measuring diameters of 100 random particles in a scanning electron microscope image and computing the arithmetic average thereof. If a shape of a particle in the SEM image is not a perfect circle, for example, an ellipse, the maximum diameter of the particle is used as its diameter. To measure the particle diameter precisely, the measurement is carried out with a magnification of at least 1000 times or more, preferably with a magnification of 5000 times or more.

The particle diameter distribution index is calculated on the basis of the conversion equations described below, using measurements of the particle diameters obtained by measurement described above:

On ~ Ri /n

1=4

PD! ^~ Dv/Dn

wherein Ri: particle diameter of single particle, n: the number of measurements (=100), Dn: number average particle diameter, Dv: volume average particle diameter, PDI: particle diameter distribution index.

Although the actual amount of pores in a porous microparticle of polylactic acid-based resin is difficult to measure directly, it is possible to use linseed oil absorption capacity as an indirect index, which is defined in pigment test methods such as Japan Industrial Standards (Refined Linseed Oil Method, JIS K 5101 ).

In particular, in the uses such as cosmetics and paints, higher linseed oil capability is preferable, and the lower limit of linseed oil capability is preferably 90 mL/100 g or more, more preferably 100 mL/100 g or more, further more preferably 120 mL/100 g or more, particularly preferably 150 mL/100 g or more, remarkably preferably 200 mL/100 g or more, most preferably 300 mL/100 g or more. The upper limit of linseed oil absorption capability is preferably 1000 mL/1 00 g or less.

Further, it is preferred that the above-described porous microparticles of polylactic acid-based resin have enthalpy of fusion of 5 J/g or more. Higher enthalpy of fusion brings higher crystallization tendency and, as a result, heat resistance and durability tend to become high. The lower limit of enthalpy of fusion is preferably 10 J/g or more, more preferably 20 J/g or more, further more preferably 30 J/g or more. Further, the upper limit is preferably 100 J/g or less. Enthalpy of fusion can be calculated from an area of peak showing thermal capacity of fusion at approximately 160°C in Differential Scanning calorimetry (DSC) in which a temperature is raised to 200°C with a temperature rise of 20°C per minute. Sphericity of the above-described porous microparticles of polylactic acid-based resin is preferably 80 or more, more preferably 85 or more, further more preferably 90 or more, particularly preferably 92 or more, most preferably 95 or more. Further, in theory, the upper limit is 100. When sphericity is within the above-described range, it becomes possible to achieve an improvement in quality such as slidability. The sphericity is calculated by observing particles by a scanning electron microscope, measuring both the longest diameters and the shortest diameters of 30 random particles and subsequently substituting the measurements into the equation described below:

wherein S: Sphericity, n: the number of measurements (=30), Ds: the shortest diameter of single particle, DL: the longest diameter of single particle.

One suitable commercial PLA microparticle is sold by Toray Industries Inc. under the name Toraypearl® PLA (Example value of isononyl isononanoate oil uptake is 465.9 ml_/100g).

Hydrophobic silica aerogel particles

The amount of hydrophobic silica aerogel present in the compositions will typically be at least 0.005%, or at least 0.01 , 0.05, or 0.10%. It will typically be at most 0.70%, or at most 0.5, 0.3, or 0.2%.

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 liquid medium and then dried, usually by extraction of a supercritical fluid, the one most commonly used being supercritical CO2. This type of drying makes it possible to avoid shrinkage of the pores and of the material. The sol-gel process and the various drying processes are described in detail in Brinker CJ., and Scherer G.W., Sol-Gel Science: New York: Academic Press, 1990.

The hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size expressed as the mean volume diameter (D[0.5]), ranging from 1 to 30 μιη, preferably from 5 to 25 μιη, better still from 5 to 20 μιη and even better still from 5 to 15 μιη. The specific surface area per unit of mass may be determined via the BET (Brunauer-Emmett-Teller) nitrogen absorption method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The size of the silica aerogel particles may be measured by static light scattering using a commercial granulometer such as the MasterSizer 2000 machine from Malvern. The data are processed on the basis of the 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. This theory is especially described in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

According to one advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of mass (SM) ranging from 600 to 800 m²/g and a size expressed as the mean volume diameter (D[0.5]) ranging from 5 to 20 μιη and better still from 5 to 15 μιη.

The silica aerogel particles used in the present invention may advantageously have a tamped density r) ranging from 0.04 g/cm³ to 0.10 g/cm³ and preferably from 0.05 g/cm³ to 0.08 g/cm³.

In the context of the present invention, this density, known as the tamped density, may be assessed according to the following protocol:

40 g of powder are poured into a measuring cylinder; the measuring cylinder is then placed on a Stav 2003 machine from Stampf Volumeter; the measuring cylinder is then subjected to a series of 2500 packing motions (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); the final volume Vf of packed powder is then measured directly on the measuring cylinder. The tamped density is determined by the ratio m/Vf, in this instance 40/Vf (Vf being expressed in cm³ and m in g).

According to one embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface area per unit of volume Sv ranging from 5 to 60 m²/cm³, preferably from 10 to 50 m²/cm³ and better still from 15 to 40 m²/cm³.

The specific surface area per unit of volume is given by the relationship: Sv = SM.r where r is the tamped density expressed in g/cm³ and SM is the specific surface area per unit of mass expressed in m²/g, as defined above.

Preferably, the hydrophobic silica aerogel particles according to the invention have an oil-absorbing capacity, measured at the wet point, ranging from 5 to 18 imL/g, preferably from 6 to 15 imL/g and better still from 8 to 12 imL/g.

The oil-absorbing capacity measured at the wet point, noted Wp, corresponds to the amount of water that needs to be added to 100 g of particle 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 amount of oil adsorbed onto the available surface of the powder and/or absorbed by the powder by measuring the wet point, described below:

An amount m=2g of powder is placed on a glass plate, and the oil (isononyl isononanoate) is then added dropwise. After addition of 4 to 5 drops of oil to the powder, mixing is performed using a spatula, and addition of oil is continued until a conglomerate of oil and powder has formed. At this point, the oil is added one drop at a time and the mixture is then triturated with the spatula. The addition of oil is stopped when a firm, smooth 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 imL) of oil used is then noted. The oil uptake corresponds to the ratio Vs/m.

The aerogels used according to the present invention are hydrophobic silica aerogels, preferably of silylated silica (INCI name: silica silylate).

The term "hydrophobic silica" means any silica whose surface is treated with silylating agents, for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.

As regards the preparation of hydrophobic silica aerogels particles that have been surface-modified by silylation, reference may be made to document US 7 470 725.

Use will be made in particular of hydrophobic silica aerogels particles surface-modified with trimethylsilyl groups.

As hydrophobic silica aerogels that may be used in the invention, examples that may be mentioned include the aerogel sold under the name VM-2260 (INCI name: Silica silylate), by the company Dow Corning, the particles of which have a mean size of about 1000 μιη and a specific surface area per unit of mass ranging from 600 to 800 m²/g.

Mention may also be made of the aerogels sold by the company Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova Aerogel MT 1 100 and Enova Aerogel MT 1200.

Use will be made more particularly of the aerogel sold under the name VM-2270 (INCI name: Silica silylate), by the company Dow Corning, the particles of which have a mean size ranging from 5-15 μιη and a specific surface area per unit of mass ranging from 600 to 800 m²/g. It has an oil absorption capability of 1090 mL/100 g based on isononyl isononanoate.

Sunscreens

Sunscreens typically constitute at least 10% of the compositions of the invention, or at least 15, 20, or 25%. They typically constitute at most 50% of the compositions, or at most 45, 40, or 35%.

Suitable sunscreens may be lipophilic or hydrophilic. They may be organic or inorganic. Examples of suitable sunscreens include octocrylene, oxybenzone, benzophenones, homosalate, and ethylhexyl salicylate, triazines, dibenzoyl methane derivatives, for example butyl methoxydibenzoylmethane (avobenzone), and combinations thereof. Other examples include ethylhexyl triazone, terephthalylidene dicamphor sulfonic acid, drometrizole trisiloxane, bis- ethylhexyloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutyl phenol, and titanium dioxide. Compositions according to the invention typically provide an SPF of at least 30, preferably at least 50, more preferably at least 70, still more preferably at least 80, and most preferably at least 90.

Lipophilic materials

As used herein, the term "lipophilic material" means any water-immiscible cosmetic or dermatological organic compound, other than sunscreens, that may be completely dissolved in molecular form in a liquid fatty phase, or that may be dissolved in colloidal form (for example, in micellar form) in a liquid fatty phase. Lipophilic materials in total typically constitute at least 0.5% of the composition, or at least 1 , 3, 5, or 7%. They typically constitute at most 25%, or at most 20, 15, 12, or 10%.

Lipophilic materials and lipophilic sunscreens, taken together, typically constitute at least 10% of the composition, or at least 15, 20 or 25%. They typically constitute at most 90%, or at most 80, 70, 60, or 50%. The lipophilic materials, combined with any lipophilic sunscreens present, may form a lipophilic, fatty, or oily phase. That phase may be dispersed (O/W emulsion) or continuous (W/O emulsion).

Examples of suitable lipophilic materials include fatty substances that are liquid at room temperature (oils), fatty substances that are solid at room temperature (waxes), fatty substances that are semi-solid at room temperature, such as pasty fatty substances or butters, and mixtures thereof.

The lipophilic material may include one or more oils.

Here, "oil" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 immHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile.

The oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.

The oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.

As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

As examples of animal oils, mention may be made of, for example, squalene and squalane.

As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C1-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.

Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols, and esters of monocarboxylic, dicarboxylic, or tricarboxylic acids and of non-sugar C4- C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols may also be used.

Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di- n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2- ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non- conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate, and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate. More particularly, use is made of monoesters and diesters and especially sucrose, glucose, or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates.

An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2- ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate), and glyceryl tri(caprate/caprylate/linolenate).

As examples of silicone oils, mention may be made of, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, dimethicone, caprylyl methicone and the like; and mixtures thereof.

Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils may also be organomodified. The organomodified silicones that can be used in accordance with the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile. When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 71 58 by Union Carbide, Silbione® 70045 V5 by Rhodia, and dodecamethylcyclohexasiloxane sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 31 09 sold by the company Union Carbide, of formula:

I— D" - D' D" - D'— I

Chi ' ' CH₃

I I

with D" : — Si - O— _{and with} D' : - Si - O—

CH₃ C₈H₁₇

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1 , 1 '-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane; and

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x 1 0 ⁶ m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C.

Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, in a non- limiting manner, of the following commercial products: the Silbione^® oils of the 47 and 70 047 series or the Mirasil^® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

the oils of the Mirasil^® series sold by the company Rhodia;

the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm²/s; and

the Viscasil^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.

The phenyl silicone oil may be chosen from the phenyl silicones of the followin formula:

in which

Ri to R10, independently of each other, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon-based radicals, preferably C1-C12 hydrocarbon-based radicals, and more preferably C1-C6 hydrocarbon-based radicals, in particular methyl, ethyl, propyl, or butyl radicals, and

m, n, p, and q are, independently of each other, integers of 0 to 900 inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100 inclusive,

with the proviso that the sum n+m+q is other than 0.

Examples that may be mentioned include the products sold under the following names:

the Silbione® oils of the 70 641 series from Rhodia;

the oils of the Rhodorsil® 70 633 and 763 series from Rhodia; the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning; the silicones of the PK series from Bayer, such as the product

PK20;

certain oils of the SF series from General Electric, such as SF 1023, SF 1 154, SF 1250, and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (Ri to Rio are methyl; p, q, and n = 0; m=1 in the above formula) is preferable.

The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.

Hydrocarbon oils may be chosen from:

linear or branched, optionally cyclic, C6-C16 lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane, and isodecane; and

linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam®, and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.

The term "fatty" in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C12-C20 alkyl and C12-C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group. As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

It is preferable that the fatty alcohol be a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated C6-C30 alcohols, preferably straight or branched, saturated C6-C30 alcohols, and more preferably straight or branched, saturated C12-C20 alcohols.

The term "saturated fatty alcohol" here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C6-C30 fatty alcohols. Among the linear or branched, saturated C6-C30 fatty alcohols, linear or branched, saturated C12-C20 fatty alcohols may preferably be used. Any linear or branched, saturated C16-C20 fatty alcohols may be more preferably used. Branched C16-C20 fatty alcohols may be even more preferably used.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from cetyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.

It is preferable that the oil be chosen from hydrocarbon oils, ester oils, silicone oils, and mixtures thereof.

Organic solvents

Compositions of the invention may include one or more organic solvents. If present, they will, in total, typically constitute at least 1 % of the composition, or at least 2, 3, 4, 5, or 6%. They will typically constitute at most 20%, or at most 15 or 10%.

Suitable solvents may include water-soluble solvents. Specific exemplary solvents include ethanol, glycerol (glycerin), 1 ,3-propanediol, propylene glycol, butylene glycol, pentylene glycol, and caprylyl glycol. Emulsifiers

The composition according to the present invention comprises at least one emulsifier. If two or more emulsifiers are used, they may be the same or different.

The amount of the emulsifier(s) may be 20% by weight or less, preferably 1 5% by weight or less, and more preferably 1 0% by weight or less, relative to the total weight of the composition according to the present invention, with the proviso that the amount of the emulsifier(s) is not zero. The amount of the emulsifier(s) may be 0.01 % by weight or more, preferably 0.05% by weight or more, and more preferably from 0.1 % by weight or more, relative to the total weight of the composition.

Thus, the amount of the emulsifier(s) in the composition according to the present invention may range from 0.01 % to 20% by weight, preferably from 0.05% to 1 5% by weight, and more preferably from 0.1 % to 1 0% by weight, relative to the total weight of the composition. Typically, at least 1 % will be present, or at least 2 or 3%. Typically, at most 7% or 5% will be present.

The types of the emulsifier are not limited. Thus, for example, amphiphilic powder(s) may be used as the emulsifier. In this case, the composition according to the present invention may be in the form of a Pickering emulsion.

It is preferable that the emulsifier be selected from surfactants.

Thus, the composition according to the present invention may include at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactant may be used.

The surfactant used in the present invention may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants, preferably from nonionic surfactants.

Anionic Surfactants

The composition according to the present invention may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

It is preferable that the anionic surfactant be selected from the group consisting of (C6-C3o)alkyl sulfates, (C6-C3o)alkyl ether sulfates, (C6-C3o)alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; {Ce- C3o)alkylsulfonates, (C6-C3o)alkylamide sulfonates, (C6-C3o)alkylaryl sulfonates, a- olefin sulfonates, paraffin sulfonates; (C6-C3o)alkyl phosphates; (C6-C3o)alkyl sulfosuccinates, (C6-C3o)alkyl ether sulfosuccinates, (C6-C3o)alkylamide sulfosuccinates; (C6-C3o)alkyl sulfoacetates; (C6-C24)acyl sarcosinates; (C6-C24)acyl glutamates; (C6-C3o)alkylpolyglycoside carboxylic ethers; (C6-C3o)alkylpolyglycoside sulfosuccinates; (C6-C3o)alkyl sulfosuccinamates; (C6-C24)acyl isethionates; Ν-(Οβ- C24)acyl taurates; C6-C30 fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (Cs-C2o)acyl lactylates; (C6-C3o)alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C6-C3o)alkyl ether carboxylic acid salts; polyoxyalkylenated (C6-C3o)alkylaryl ether carboxylic acid salts; and polyoxyalkylenated {Ce- C3o)alkylamido ether carboxylic acid salts; and corresponding acid forms.

In at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form.

It is more preferable that the anionic surfactant be selected from salts of (C6-C3o)alkyl sulfate, (C6-C3o)alkyl ether sulfates or polyoxyalkylenated (C6-C3o)alkyl ether carboxylic acid salified or not.

Amphoteric Surfactants

The composition according to the present invention may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

The amphoteric or zwitterionic surfactants can be, for example (non- limiting list), amine derivatives such as aliphatic secondary or tertiary amine, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain including 8 to 22 carbon atoms and containing at least one water- solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate, or phosphonate).

The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoaminecarboxylated derivatives.

It is preferable that the amphoteric surfactant be selected from betaine- type surfactants.

The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and alkylamidoalkylsulfobetaines, in particular, (Cs- C24)alkylbetaines, (C8-C24)alkylamido(Ci-C8)alkylbetaines, sulphobetaines, and (Cs- C24)alkylamido(Ci-C8)alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are chosen from (Cs-C24)alkylbetaines, (Cs- C24)alkylamido(Ci -C8)alkylsulphobetaines, sulphobetaines, and phosphobetaines.

Non-limiting examples that may be mentioned include the compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine, oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or as mixtures.

The betaine-type amphoteric surfactant is preferably an alkylbetaine and an alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

Among the amidoaminecarboxylated derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781 ,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and Amphocarboxypropionates, with the respective structures:

Ri-CONHCH2CH2-N⁺(R2)(R3)(CH₂COO-) M⁺ X^" (B1 ) in which:

Ri denotes an alkyl radical of an acid R1-COOH present in hydrolyzed coconut oil, a heptyl, nonyl, or undecyl radical,

R2 denotes a beta-hydroxyethyl group,

R3 denotes a carboxymethyl group,

M⁺ denotes a cationic ion derived from alkaline metals such as sodium; ammonium ion; or an ion derived from an organic amine;

X^" denotes an organic or inorganic anionic ion such as halides, acetates, phosphates, nitrates, alkyl(Ci -C4)sulfates, alkyl(Ci-C4)- or alkyl(Ci-C4)aryl-sulfonates, particularly methylsulfate and ethylsulfate; or M⁺ and X^" are not present;

Ri'-CONHCH₂CH2-N(B)(C) (B2)

in which:

Ri' denotes an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, such as a C7, C9, C11 , or C13 alkyl radical, a Ci 7 alkyl radical and its iso-form, or an unsaturated C17 radical,

B represents -CH2CH2OX', C represents

with z=1 or 2,

X' denotes a -CH2-COOH group, -CH₂-COOZ\ -CH2CH2-COOH, - CH2CH2-COOZ', or a hydrogen atom, and

Y' denotes -COOH, -COOZ', -CH2-CHOH-SO3Z', -CH2-CHOH-SO3H radical, or a -CH₂-CH(OH)-SO3-Z' radical,

wherein Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ion derived from an organic amine, or an ammonium ion;

and

Ra"-NH-CH(Y")-(CH2)n-C(O)-NH-(CH2)n'-N(Rd)(Re) (B'2) in which:

Y" denotes -C(O)OH, -C(0)OZ", -CH₂-CH(OH)-SO₃H or -CH₂-CH(OH)- SO3-Z", wherein Z" denotes a cationic ion derived from alkaline metal or alkaline-earth metals such as sodium, an ion derived from organic amine or an ammonium ion;

Rd and Re denote a C1-C4 alkyl or C1-C4 hydroxyalkyl radical;

Ra- denotes a C10-C30 group alkyl or alkenyl group from an acid, and n and n' independently denote an integer from 1 to 3.

It is preferable that the amphoteric surfactant with formula B1 and B2 be selected from (Cs-C24)-alkyl amphomonoacetates, (Cs-C24)alkyl amphodiacetates, (Cs- C24)alkyl amphomonopropionates, and (Cs-C24)alkyl amphodipropionates

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium Caprylamphodipropionate, Lauroamphodipropionic acid, and Cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M concentrate by the company Rhodia Chimie.

Among compounds of formula (B'2) mention may be made of sodium diethylaminopropyl cocoaspartamide (CTFA) marketed by CHIMEX under the denomination CHIMEXANE HB.

Cationic Surfactants The composition according to the present invention may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

The cationic surfactant may be selected from the group consisting of optionally polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:

those of general formula (B3) below:

\ /

/ \

1½ ¾

(B3)

wherein

Ri , R2, R3, and FU, which may be identical or different, are chosen from linear and branched aliphatic radicals including from 1 to 30 carbon atoms and optionally including heteroatoms such as oxygen, nitrogen, sulfur, and halogens. The aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide, (Ci2-C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkylacetate, and hydroxyalkyi radicals; and aromatic radicals such as aryl and alkylaryl; and X^" is chosen from halides, phosphates, acetates, lactates, (C2-C6) alkyl sulfates, and alkyl- or alkylaryl-sulfonates;

quaternary ammonium salts of imidazoline, for instance those of formula

(B4) below:

(B4)

wherein:

R5 is chosen from alkenyl and alkyl radicals including from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;

R6 is chosen from hydrogen, C1-C4 alkyl radicals, and alkenyl and alkyl radicals including from 8 to 30 carbon atoms; R7 is chosen from C1 -C4 alkyl radicals;

Rs is chosen from hydrogen and C1 -C4 alkyl radicals; and

X^" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R5 and R6 are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals including from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R7 is methyl, and Rs is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG and W75HPG by the company Witco;

Di or tri quaternary ammonium salts of formula (B5):

wherein:

R9 is chosen from aliphatic radicals including from 16 to 30 carbon atoms;

R10 is chosen from hydrogen or alkyl radicals including from 1 to 4 carbon atoms or a group -(CH2)3 ( Ri6a) ( Ri 7a) ( Ri8a)N⁺X--;

R11 , R12, R13, Ri 4, Ri 6a, Ri 7a, and Risa, which may be identical or different, are chosen from hydrogen and alkyl radicals including from 1 to 4 carbon atoms; and

X^" is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates.

An example of one such diquaternary ammonium salt is FINQUAT CT-P of FINETEX (Quaternium-89) or FINQUAT CT (Quaternium-75);

and

quaternary ammonium salts including at least one ester function, such as those of formula (B6) below:

wherein: R22 is chosen from C1-C6 alkyi radicals and C1 -C6 hydroxyalkyl and dihydroxyalkyl radicals;

R23 is chosen from:

the radical below:

O

R₂₆ C linear and branched, saturated and unsaturated C1-C22 hydrocarbon- based radicals R27, and hydrogen,

R25 is chosen from:

the radical below:

O

^R28 ^C

linear and branched, saturated and unsaturated C1-C6 hydrocarbon- based radicals R29, and hydrogen,

R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C7-C21 , hydrocarbon-based radicals;

r, s, and t, which may be identical or different, are chosen from integers ranging from 2 to 6;

each of r1 and t1 , which may be identical or different, is 0 or 1 , and r2+r1 =2r and t1 +2t=2t;

y is chosen from integers ranging from 1 to 10;

x and z, which may be identical or different, are chosen from integers ranging from 0 to 10;

X^" is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R23 denotes R27, and that when z is 0, R25 denotes R29. R22 may be chosen from linear and branched alkyi radicals. In one embodiment, R22 is chosen from linear alkyi radicals. In another embodiment, R22 is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R23 is a hydrocarbon-based radical R27, it may be long and include from 12 to 22 carbon atoms, or short and include from 1 to 3 carbon atoms. When R25 is a hydrocarbon-based radical R29, it may include, for example, from 1 to 3 carbon atoms. By way of a non-limiting example, in one embodiment, R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C11 -C21 hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated C11-C21 alkyl and alkenyl radicals. In another embodiment, x and z, which may be identical or different, are 0 or 1 . In one embodiment, y is equal to 1 . In another embodiment, r, s, and t, which may be identical or different, are equal to 2 or 3, for example equal to 2. The anion X^" may be chosen from, for example, halides, such as chloride, bromide, and iodide; and C1 -C4 alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate and lactate, and any other anion that is compatible with the ammonium including an ester function, are other non-limiting examples of anions that may be used according to the present invention. In one embodiment, the anion X^" is chosen from chloride and methyl sulfate.

In another embodiment, the ammonium salts of formula (B6) may be used, wherein:

R22 is chosen from methyl and ethyl radicals,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s, and t are equal to 2;

R23 is chosen from:

the radical below:

O

^R26 C

methyl, ethyl, and C14-C22 hydrocarbon-based radicals, hydrogen;

R25 is chosen from:

the radical below:

O

^R28 ^C

and hydrogen;

R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C13-C17 hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C13-C17 alkyl and alkenyl radicals.

In one embodiment, the hydrocarbon-based radicals are linear. Non-limiting examples of compounds of formula (B6) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyethyl- dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl- methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethyl-ammonium, and mixtures thereof. In one embodiment, the acyl radicals may include from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound includes several acyl radicals, these radicals may be identical or different.

These products may be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine, or alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification may be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin; and glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by the company Cognis, Stepanquat® by the company Stepan, Noxamium® by the company Ceca, and "Rewoquat® WE 18" by the company Rewo-Goldschmidt.

Other non-limiting examples of ammonium salts that may be used in the composition according to the present invention include the ammonium salts including at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180.

The quaternary ammonium salts mentioned above that may be used in the composition according to the present invention include, but are not limited to, those corresponding to formula (I), for example tetraalkylammonium chlorides, for instance dialkyldimethylammonium and alkyltrimethylammonium chlorides in which the alkyl radical includes from about 12 to 22 carbon atoms, such as behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and benzyldimethylstearylammonium chloride; palmitylamidopropyltrimethylammonium chloride; and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk. According to one embodiment, the cationic surfactant that may be used in the composition according to the present invention is chosen from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quaternium- 83, Quaternium-87, Quaternium-22, behenylamidopropyl-2,3- dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride, and stearamidopropyldimethylamine.

Nonionic Surfactants

The composition according to the present invention may comprise at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

The nonionic surfactants are compounds well known in and of themselves (see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991 , pp. 1 16-178). Thus, they can, for example, be chosen from alcohols, alpha-diols, alkylphenols, and esters of fatty acids, these compounds being ethoxylated, propoxylated, or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non-limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; polyglycerolated fatty amides comprising, for example, from 1 .5 to 5 glycerol groups, such as from 1 .5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C6-C24)alkylpolyglycosides; N- (C6-C24)alkylglucamine derivatives; amine oxides such as (Cio-Ci4)alkylamine oxides or N-(Cio-Ci4)acylaminopropylmorpholine oxides; silicone surfactants; and mixtures thereof.

The nonionic surfactants may preferably be chosen from monooxyalkylenated, polyoxyalkylenated, monoglycerolated, or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units. Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include:

monooxyalkylenated or polyoxyalkylenated (C8-C24)alkylphenols, saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C30 alcohols,

saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C8-C30 amides,

esters of saturated or unsaturated, linear or branched, C8-C30 acids and of polyalkylene glycols,

monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C8-C30 acids, and of sorbitol,

saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated plant oils,

condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100 and most preferably between 2 and 50. According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).

Examples of polyoxyethylenated saturated fatty alcohol (or C8-C30 alcohols) that may be mentioned include the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units and more particularly those containing from 10 to 12 oxyethylene units (Laureth-10 to Laureth- 12, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 9 to 50 oxyethylene units (Beheneth-9 to Beheneth-50, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 30 oxyethylene units (Ceteareth-10 to Ceteareth-30, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 10 to 30 oxyethylene units (Ceteth-10 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 10 to 30 oxyethylene units (Steareth- 10 to Steareth-30, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 10 to 50 oxyethylene units (lsosteareth-10 to lsosteareth-50, as the CTFA names); and mixtures thereof.

Examples of polyoxyethylenated unsaturated fatty alcohol (or C8-C30 alcohols) that may be mentioned include the adducts of ethylene oxide with oleyl alcohol, especially those containing from 2 to 50 oxyethylene units and more particularly those containing from 10 to 40 oxyethylene units (Oleth-10 to Oleth-40, as the CTFA names); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C8-C40 alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C8-C40 alcohols correspond to the following formula:

RO-[CH2-CH(CH2OH)-O]m-H or RO-[CH(CH2OH)-CH₂O]m-H in which R represents a linear or branched C8-C40 and preferably C8-C30 alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1 .5 to 10.

As examples of compounds that are suitable in the context of the present invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1 .5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use a Cs/C-io alcohol containing 1 mol of glycerol, a C10/C12 alcohol containing 1 mol of glycerol, and a C12 alcohol containing 1 .5 mol of glycerol.

The monoglycerolated or polyglycerolated C8-C40 fatty esters may correspond to the following formula:

RO-[CH2-CH(CH₂OR'")-0]m-R" or RO-[CH(CH₂OR'")-CH20]m-R" in which each of R', R", and R'" independently represents a hydrogen atom, or a linear or branched C8-C40 and preferably C8-C30 alkyl-CO- or alkenyl-CO- radical, with the proviso that at least one of R', R", and R'" is not a hydrogen atom, and m represents a number ranging from 1 to 30 and preferably from 1 .5 to 10.

Examples of polyoxyethylenated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA names: PEG-9 palmitate to PEG- 50 palmitate); PEG-9 to PEG-50 stearate (CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

According to one of the embodiments of the present invention, the nonionic surfactant may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units, such as glyceryl esters of a C8-C24, preferably C12-C22, fatty acid or acids, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sorbitol esters of a C8-C24, preferably C12- C22, fatty acid or acids, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sugar (sucrose, maltose, glucose, fructose, and/or alkylglycose) esters of a C8-C24, preferably C12-C22, fatty acid or acids, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugar and a C8-C24, preferably C12-C22, fatty alcohol or alcohols; and mixtures thereof.

As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di-, and/or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate, and mixtures thereof can be cited, and as polyoxyalkylenated derivatives thereof, mono-, di-, or triester of fatty acids with a polyoxyalkylenated glycerol (mono- , di-, or triester of fatty acids with a polyalkylene glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di-, and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di-, and/or tristearate) can be cited. Mixtures of these surfactants, such as for example the product containing glyceryl stearate and PEG-100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE), can also be used.

The sorbitol esters of C8-C24 fatty acids and polyoxyalkylenated derivatives thereof can be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate, and esters of fatty acids, and alkoxylated sorbitan containing for example from 20 to 100 EO, such as for example sorbitan monostearate (CTFA name: sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65), sold by the company ICI under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85), or the compounds marketed under the trade names Tween 20 or Tween 60 by Uniqema.

As esters of fatty acids and glucose or alkylglucose, glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture of oleic acid/hydroxystearic acid (CTFA name: Methyl glucose dioleate/hydroxystearate), the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can for example be cited.

As sucrose esters, saccharose palmito-stearate, saccharose stearate, and saccharose monolaurate can for example be cited.

As sugar ethers, alkylpolyglucosides can be used, and for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 1 10 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818/UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Mixtures of glycerides of alkoxylated plant oils such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides can also be cited.

The nonionic surfactant according to the present invention preferably contains alkenyl or a branched C12-C22 acyl chain such as an oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one of the embodiments of the present invention, the nonionic surfactant may be selected from copolymers of ethylene oxide and of propylene oxide, in particular copolymers of the following formula:

HO(C2H₄O)a(C3H₆O)b(C2H₄O)cH

in which a, b, and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60, and mixtures thereof. According to one of the embodiments of the present invention, the nonionic surfactant may be selected from silicone surfactants. Non-limiting mention may be made of those disclosed in documents US-A-5364633 and US-A-541 1744.

The silicone surfactant may preferably be a compound of formula (I):

in which:

Ri, R2, and R3, independently of each other, represent a C1-C6 alkyl radical or a radical -(CH2)x-(OCH2CH2)y-(OCH2CH2CH₂)z-OR4, at least one radical Ri, R2, or R3 not being an alkyl radical; R4 being a hydrogen, an alkyl radical, or an acyl radical;

A is an integer ranging from 0 to 200;

B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero;

x is an integer ranging from 1 to 6;

y is an integer ranging from 1 to 30;

z is an integer ranging from 0 to 5.

According to one preferred embodiment of the present invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6, and y is an integer ranging from 4 to 30.

As examples of silicone surfactants of formula (I), mention may be made of the compounds of formula (II):

(CH₃)₃SiO - [(CH₃)₂SiO]_A - (CH₃SiO)_B - Si(CH₃)_:

(ID

(CH₂)₂-(OCH₂CH₂)_y-OH in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 1 0, and y is an integer ranging from 10 to 20.

As examples of silicone surfactants of formula (I), mention may also be made of the compounds of formula (III):

H-(OCH2CH2)y-(CH2)3-[(CH3)2SiO]A'-(CH2)3-(OCH2CH2)y-OH

in which A' and y are integers ranging from 10 to 20. Compounds of the present invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC 7439-146, DC 2-5695, and Q4-3667. The compounds DC 5329, DC 7439-146, and DC 2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2, and y is 1 2; A is 103, B is 1 0, and y is 1 2; A is 27, B is 3, and y is 1 2.

The compound Q4-3667 is a compound of formula (III) in which A is 1 5 and y is 1 3.

Auxiliary ingredients

The compositions of the invention may also include, in the aqueous phase and/or the oily phase, any of a variety of auxiliary ingredients or additives (e.g., preservatives). Nonlimiting examples of the auxiliary ingredients include colorants, odorants, vitamins (e.g., tocopherol), chelating agents, various active agents, aesthetic modifiers, and preservatives. Nonlimiting examples of the preservatives include chlorphenesin, phenoxyethanol, and caprylyl glycol. Exemplary active agents include triethanolamine and tromethamine. The auxiliary ingredients may include amorphous silica microspheres, typically ones having an average diameter in a range from 1 μιη to 1 0 μιη.

One or more aesthetic modifiers may be included. If present, the aesthetic modifiers will in total typically constitute at least 0.5% of the composition, or at least 1 , 1 .5, 2, or 2.5%. Typically, they will constitute at most 1 0%, or at most 9, 8, 7, or 6%.

Examples of aesthetic modifiers include aluminum starch octenylsuccinate, hydroxypropylmethylcellulose, xanthan gum, acrylates/Cio-C3o alkyl acrylate crosspolymers, nylon 1 2 particles, synthetic waxes, ammonium acryloyldimethyltaurate homopolymers and ammonium acryloyldimethyltaurate/vinylpyrrolidone copolymers.

Water typically makes up the balance of the composition, and typically constitutes at least 1 0% of the composition, or at least 15, 20 or 25%. It typically constitutes at most 90%, or at most 80, 70, 60, or 50%.

Compositions according to the invention may be used in a method for caring for a keratin material in an animal, for example, a human or other mammal. Such a method comprises applying to the keratin material an amount of the composition effective to provide a desired benefit, for example, softening, detangling, coloring, or protecting against damage by sun or other insults. The keratin material may be hair, nails, and/or skin.

Making the Compositions

Compositions according to the invention may be prepared by typical emulsification methods known in the art, such as high-shear mixing.

The water phase contains water and water-soluble ingredients, for example preservative agents, emollients and hydrosoluble emulsifiers and UV filters. It may be prepared at ambient temperature with mechanical agitation, typically for about 10 to 30 minutes. The resulting phase is typically translucent.

The oil phase includes lipophilic ingredients, for example UV filters, solvents, fat-soluble emulsifiers, fatty oils, and other ingredients that are soluble or heat soluble in the oil phase. The oil phase is typically prepared in a beaker at 75°C with mechanical agitation until a translucent phase is formed, and then cooled to ambient temperature. Typically, the oil phase includes either or both of the PLA microparticles and the hydrophobic silica aerogel particles, although either or both of these may be added elsewhere when making the emulsion.

The emulsion is formed by adding the water phase to the oil phase at ambient temperature under mechanical agitation, after which agitation is continued for 15 minutes.

EXAMPLES

Table 1 shows exemplary compositions according to the invention. Composition 10 is a comparative example. The thermal spring water was sourced from La Roche-Posay.

In vivo evaluation of the UVA Protection Factor of inventive compositions 1 and 8 was performed in formulas having SPF 70 according to ISO 24442-201 1 (UVA in vivo), and the following results were obtained.

Composition 1 had an average in vivo UVA-PPD value of 27.2 (+/- 4.5), better than the expected value of 23.33.

Composition 8 had an average in vivo UVA-PPD value of 29.0 (+/- 0.4), better than the expected value of 23.33.

In vivo evaluation of Sun Protection Factor (SPF) of inventive compositions 1 and 8 was performed on five subjects according to ISO/EN 24444 (UVA in vivo), and water resistance was evaluated according to COLIPA Guidelines for Evaluating Sun Product Water Resistance (Dec 2005). For each composition, an individual Percentage Water Resistance Retention (%WRRi) value was calculated according to the formula

%WRRi = [(SPFiw-1 )^*100]/(SPFis-1 )

where SPFiw = individual wet SPF after water immersion

SPFis = individual static SPF.

The lower limit of 90% unilateral confidence interval [Mean %WRR - d] was calculated for each composition.

Composition 1 had an average SPF of 83.6, and a [Mean %WRR - d] value of 33.9%.

Composition 8 had an average SPF of 86.3, and a [Mean %WRR - d] value of 31 .4%.

Inventive composition 1 and comparative compositionI O were compared via at-home testing by twelve women for about seven days. Composition 1 was found superior with respect to higher perception of dry touch, long lasting matte effect and shine control, good spreadability texture, absence of white residue, and pleasant scent.

Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims without departing from the invention.

Claims

SET OF CLAIMS

1 . A composition comprising an emulsion having an aqueous phase and a lipophilic phase, wherein the composition comprises water, a hydrophobic silica aerogel, porous microparticles of a polylactic acid-based resin, one or more organic solvents, one or more emulsifiers, one or more lipophilic materials, and one or more sunscreens.

2. The composition according to claim 1 , wherein the porous microparticles of the polylactic acid-based resin have an enthalpy of fusion of 5 J/g or more.

3. The composition according to claim 1 or 2, wherein the porous microparticles of the polylactic acid-based resin have a number average particle diameter of in a range from 1 μιη to 90 μιη.

4. The composition according to any preceding claim, wherein the porous microparticles of the polylactic acid-based resin have a particle diameter distribution index in a range from 1 .0 to 1 .5.

5. The composition according to any preceding claim, wherein the porous microparticles of the polylactic acid-based resin have a linseed oil absorption capacity in a range of 90 imL/g to 1000 imL/g.

6. The composition according to any preceding claim, wherein the porous microparticles of the polylactic acid-based resin have a sphericity in a range from 80 to 100.

7. The composition according to any preceding claim, wherein the porous microparticles of the polylactic acid-based resin are present in a range from 0.05 wt% to 1 .0 wt%.

8. The composition according to any preceding claim, wherein the hydrophobic silica aerogel is a silica silylate.

9. The composition according to any preceding claim, wherein the hydrophobic silica aerogel has a specific surface area in a range from 500 m²/g to 1500 m²/g as measured by BET nitrogen absorption.

10. The composition according to any preceding claim, wherein the hydrophobic silica aerogel has a volume-average diameter in a range from 1 μιη to 100 μηπ.

1 1 . The composition according to any preceding claim, wherein the hydrophobic silica aerogel is present in a range from 0.05 wt% to 0.5 wt%.

1 2. The composition according to any preceding claim, wherein the one or more sunscreens are selected from the group consisting of octocrylene, butyl methoxydibenzoylmethane, oxybenzone, homosalate, ethylhexyl salicylate, ethylhexyl triazone, terephthalidene dicamphor sulfonic acid, drometrizole trisiloxane, bis- ethylhexyloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol, and combinations thereof.

1 3. The composition according to any preceding claim, further comprising an active compound selected from the group consisting of disodium EDTA, triethanolamine, and tromethamine.

14. The composition according to any preceding claim, wherein the one or more lipophilic materials comprise one or more of isononyl isononanoate, diisopropyl sebacate, stearyl alcohol, dimethicone, and caprylyl methicone.

1 5. The composition according to any preceding claim, wherein the one or more organic solvents comprise one or more of ethanol, glycerol, pentylene glycol, and caprylyl glycol.

1 6. The composition according to any preceding claim, further comprising one or more aesthetic modifiers selected from the group consisting of aluminum starch octenylsuccinate, hydroxypropylmethylcellulose, xanthan gum, acrylates/Cio-C3o alkyl acrylate crosspolymers, ammonium acryloyldimethyltaurate homopolymers and ammonium acryloyldimethyltaurate/vinylpyrrolidone copolymers.

1 7. The composition according to any preceding claim, further comprising amorphous silica microspheres having an average diameter in a range from 1 μιη to 10 μιη.

1 8. The composition according to any preceding claim, wherein the composition provides an SPF of at least 30, preferably at least 50, more preferably at least 70, still more preferably at least 80, and most preferably at least 90.

1 9. The composition according to any preceding claim, wherein lipophilic sunscreens and the one or more lipophilic materials taken together are present in a range from 25 wt% to 50 wt%.

20. The composition according to any preceding claim, wherein the composition, if subjected to stability testing, shows essentially the same pH, viscosity profile, SEM images and photostability after 2 months' storage as just after production, for each of 4°C, room temperature, and 45°C storage conditions.

21 . A method of caring for a keratin material in an animal, comprising applying to the keratin material an effective amount of the composition according to any preceding claim.

22. The method according to claim 21 , wherein the keratin material is skin.

23. A method of preparing the composition according to any one of claims 1 to 20, comprising the steps of: