WO2021132045A1

WO2021132045A1 - Anhydrous composition for topical delivery of active ingredients

Info

Publication number: WO2021132045A1
Application number: PCT/JP2020/047308
Authority: WO
Inventors: Rohit Jain; Yuanyuan Sun; Nathalie Monteiro VARELA; Gaurav Agarwal; Ritesh Sinha
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2019-12-24
Filing date: 2020-12-11
Publication date: 2021-07-01
Anticipated expiration: 2022-06-24
Also published as: JP2021104934A

Abstract

The present invention relates to an anhydrous composition for keratinous substances, such as skin, comprising: (a) at least one oil, (b) at least one organic lipophilic gelling agent, and (c) at least one water soluble particle. The present invention also relates to a cosmetic process for a keratin substance such as skin, comprising the steps of: applying onto the keratin substance the anhydrous composition according to the present invention, and contacting an aqueous composition comprising water with the applied anhydrous composition. The composition and the cosmetic process according to the present invention are very useful for topical delivery of active ingredients for keratinous substances, such as skin.

Description

DESCRIPTION

TITLE OF INVENTION

ANHYDROUS COMPOSITION FOR TOPICAL DELIVERY OF ACTIVE INGREDIENTS

TECHNICAL FIELD

The present invention relates to a cosmetic composition, in particular an anhydrous cosmetic composition for a topical delivery of active ingredients.

BACKGROUND ART

Active delivery through skin is one of the important unmet needs in the cosmetic field. In order to satisfy this need, use of compositions comprising particles has been proposed. To date, some prior art documents relating to compositions comprising water soluble particles have been published.

For example, US 6,531,433 B1 discloses a non-aqueous personal scrubbing composition comprising (a) at least one water-soluble carbohydrate having a mean particle size diameter from about 100 microns to about 2000 microns in an amount from about 10 to about 90 weight percent of the total composition, wherein the at least one water-soluble carbohydrate is a monosaccharide, or a disaccharide, and (b) non-aqueous media in an amount from about 10 to about 90 weight percent of the total composition.

Also, JP-T-2018-530621 discloses a non-aqueous cosmetic composition comprising 0.01 wt% to 15 wt% of angulated water-soluble scrub particles containing a polypeptide and having a particle size of 0.01 mm to 2 mm.

Also, WO 2018/104428 A1 discloses an anhydrous, in particular cosmetic, composition comprising, in an oily fatty phase, at least: a) a C3-C10 diol, b) hydrophobic silica aerogel particles, c) exfoliating particles in an amount ranging from 10% to 50% by weight with respect to the total weight of the composition, said composition exhibiting, at a temperature of 25°C, a viscosity of between 10 and 20 Pa.s.

However, there is still a need to improve a topical delivery property of active ingredients in cosmetic compositions.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide an anhydrous composition for keratin substances, such as skin, which can provide an improved penetration property of the cosmetic active ingredients.

The above objective of the present invention can be achieved by an anhydrous composition comprising:

(a) at least one oil,

(b) at least one organic lipophilic gelling agent, and

(c) at least one water soluble particle. The (b) organic lipophilic gelling agent may be selected from tyrenic block copolymers, semi-crystalline polymers, a glutamide-based compounds, polyamides, and mixtures thereof, and preferably is polyamides.

The (c) water soluble particle may have an average primary particle size of 10 pm or more, preferably 30 pm or more, more preferably 50 pm or more, and even more preferably 100 pm or more, and in particular 200 pm or more, and of 1 mm or less, preferably 800 pm or less, and more preferably 600 pm or less, and even more preferably 500 pm or less.

The (c) water soluble particle may comprise polysaccharide particles, monosaccharide particles, amino acids particles, sugar alcohol particles, or ascorbic acid particles, and a mixture thereof.

The amount of the (a) oil may be 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more, and is 99% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, and even more preferably 85% by weight or less, relative to the total weight of the anhydrous composition.

The amount of the (b) organic lipophilic gelling agent is 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and even more preferably 4% by weight or more, and is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 7% by weight or less, relative to the total weight of the anhydrous composition.

The amount of the (c) water soluble particle may be 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.5% by weight or more, and may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less, relative to the total weight of the anhydrous composition.

The anhydrous composition may have 10 ¹ Pa or more of a linear viscoelastic regions of a storage modulus (G’) profile and a loss modulus (G”) in a log scale and more than 4% strain of a crossover point of G’ and G”, measured with a rheometer using 40mm cone plate at 25°C and 1 Hz of frequency.

The anhydrous composition may further comprise at least one alcohol, preferably having Hansen solubility parameters of 5_H (a hydrogen-bonding component) being less than 30 and dc (a volume-dependent combined parameter: dc = (6D² + dr²)^1/2) being less than 25 at 25 °C.

The amount of the alcohol may be 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and may be 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the anhydrous composition.

The present invention also relates to a cosmetic process for a keratin substance such as skin, comprising the steps of: applying onto the keratin substance the anhydrous composition according to the present invention, and contacting an aqueous composition comprising water with the applied anhydrous composition.

The aqueous composition may comprise at least one active ingredient for a keratinous substance, such as skin, preferably selected from skin-whitening active ingredients, antiaging active ingredients, anti wrinkle active agents, or antioxidant active ingredients.

The amount of the active ingredient may be 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, and may be 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, and even more preferably 5% by weight or less, relative to the total weight of the aqueous composition.

The amount of water may be 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more, and may be 90% by weight or less, preferably 80% by weight or less, more preferably 75% by weight or less, and even more preferably 60% by weight or less, relative to the total weight of the aqueous composition.

The aqueous composition may be applied to the applied anhydrous composition in a form of a wet sheet mask, a mist, spray, or by a topical application.

BRIEF DESCRIPTION OF DRAWINGS

[Fig. 1] Figure 1 shows a result of a viscoelasticity measurement on the composition according to Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have surprisingly found out that an anhydrous composition comprising at least one water soluble particle and at least one lipophilic gelling agents can improve the penetration property of the active ingredients. In addition, the inventors have surprisingly found out a new cosmetic process for topical active delivery using the anhydrous composition above, and thus completed the present invention.

Thus, the anhydrous composition for keratin substance, such as skin, according to the present invention comprises:

(a) at least one oil,

(b) at least one organic lipophilic gelling agent, and

(c) at least one water soluble particle.

Hereafter, the composition according to the present invention will be described in a detailed manner.

[Composition]

The composition according to the present invention can be a cosmetic composition, in particular a cosmetic anhydrous composition for keratin substances. The keratinous substances can include skin, for example, of the face, neck and body. Preferably, the composition according to the present invention is a skin care composition. The composition according to the present invention may take various forms, such as, a solution, a gel, a lotion, a serum, a suspension, a dispersion, a fluid, a milk, a paste, a cream, or the like. Since the composition also includes the oil and the organic lipophilic gelling agent, the composition is preferably in the form of a gel, i.e. oil gel.

The term “gel” here includes a thick liquids which can be a Newtonian fluid or a non-Newtonian fluid. The Newtonian fluid means a fluid which does not change its viscosity with the change in flow condition. The gel also includes a shear thinning gel.

In one preferred embodiment of the present invention, the composition is a gel having a non-Newtonian viscosity. In another preferred embodiment of the present invention, the composition is shear thinning. The non-Newtonian shear thinning material changes state from a gel to a liquid in the presence of an applied shear stress, and changes back to a gel in the absence of the applied shear stress. A shear thinning material by definition is one in which when an applied shear stress is increased, the material's viscosity decreases in a nonlinear way.

The gel composition according to the present invention can be defined with its rheological characteristics. The inventors of the present invention surprisingly found out that gel composition having 10 ¹ Pa or more of a linear viscoelastic regions of a storage modulus (G’) profile and a loss modulus (G”) and more than 4% strain of a crossover point of G’ and G” profile is ideal for the purpose of the present invention. This is because such a gel composition can exhibit a preferable shear thinning property so that the gel transforms into almost water-like thin viscous state in mild shear conditions which enables the water soluble particles to be dispersed homogenously in the composition, and as soon as the shear is removed, the gel retains its original thick viscosity without a lot of increase of viscosity, i.e. without a lot of hysteresis. Also, the gel composition can gives a plumpy texture which is consumer’s preference. Furthermore, this property can provide a stability and a long shelve life with the composition so that the water soluble particles in the composition do not precipitate for a long period.

Regarding the hysteresis, for the gel composition according to the present invention, change in final viscosity values in all the shear conditions can be less than 10% compared to the initial viscosity values.

The “crossover point” of the amplitude sweep, which can be also called as a “dumping point”, is a point where the storage modulus (G’) and the loss modulus (G”) have the same value.

This point is also known as a transition point of a sol-gel state.

Preferably, the gel composition according to the present invention has 8% strain or more of the crossover point, and more preferably 12% or more of the crossover point. In the embodiments of the present invention, the crossover point of the present invention is 100% strain or less, and preferably 50% strain or less, and even more preferably 30% strain or less.

The linear viscoelastic region is a region where values G’ or G” are constant at low strain (%). The gel composition preferably have 0 Pa or more of the linear viscoelastic regions of G’ and G” in a log scale. In the embodiments of the present invention, the gel composition may have 10⁴ Pa or less of the linear viscoelastic region, preferably 10³ Pa or more of the linear viscoelastic region in a log scale. The linear viscoelastic region can be measured in the same way as the crossover point. The modulus of the linear viscoelastic region and the crossover point can be measured, for example, by plotting G’ and G” values of a gel sample as a function of strain (%) in an amplitude sweep of shear stress at a constant frequency. In the present invention, the crossover point can be measured using a rheometer with 40 mm cone plate and following conditions:

Set gap: 30 pm Temperature: 25 °C Strain(%) : 0.01 - 1000 %

Frequency: lHz

In addition, the gel composition according to the present invention can show very low hysteresis. The hysteresis here means a difference of an initial viscosity and a final viscosity after a shear force is applied. For example, the hysteresis can be measured by applying a cycle shear force while measuring a viscosity. Because the gel composition according to the present invention can exhibit the very low hysteresis, the gel composition can possess a characteristic like a shape memory gel.

The composition according to the present invention can be transparent or translucent, which is a consumer’s preference. This is because particles may not precipitate and suspend in the composition due to the gel property of the composition. This means that the anhydrous composition according to the present invention can show an improved stability since the particles in the composition does not precipitate and maintains its form for a long time. The transparency of the composition can be determined by measuring the turbidity with, for example, a turbidimeter (2100Q portable, Hach Company). Preferably, the composition has a turbidity of more than 0, preferably more than 10, and less than 200, preferably less than 150.

The term “anhydrous composition” here means a composition which is anhydrous, or comprises less than 3% by weight, less than 1% by weight, or less than 0.1% by of water relative total weight of the composition.

The anhydrous composition according to the present invention comprises (a) at least one oil, (b) at least one organic lipophilic gelling agent, and (c) at least one water soluble particle.

The ingredients in the composition will be described in a detailed manner below.

(Oil)

The anhydrous composition according to the present invention comprises (a) at least one oil. Two or more (a) oils may be used in combination. Thus, a single type of oil or a combination of different types of oils may be used.

As used herein, the expression “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 mmHg). These oil(s) may be volatile or non-volatile, preferably non-volatile.

The (a) 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. It is preferable that the (a) oil be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, and hydrocarbon oils, and mixtures thereof.

As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, com 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 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), pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, capryl caprylic triglycerides, 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 octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.

Preferably, the oil phase of the present invention does not include any silicone oil. In other words, the (a) oil of the present invention may be selected from non-silicone oil.

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, isoeicosane, and decene/butene copolymer; and mixtures thereof.

It may be preferable that the (a) oil is chosen from non-polar hydrocarbon oils which are in the form of a liquid at a room temperature.

The amount of the (a) oil(s) may be 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more, and may 99% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, and even more preferably 85% by weight or less, relative to the total weight of the anhydrous composition.

(Organic Lipophilic Gelling Agent)

The anhydrous composition according to the present invention comprises (b) at least one organic lipophilic gelling agent. Two or more (b) organic lipophilic gelling agents may be used in combination. Thus, a single type of an organic lipophilic gelling agent or a combination of different types of organic lipophilic gelling agents may be used.

The term “lipophilic” here means substances which are soluble in oils at a concentration of at least 1 % by weight relative to the total weight of the oils at room temperature (25°C) and atmosphere pressure (10⁵ Pa).

The term “gelling agent” here means substances which are capable of thickening or gelling oils.

The (b) organic lipophilic gelling agent used in the present invention can be selected from styrenic block copolymers, semi-crystalline polymers, a glutamide-based compounds, polyamides, and mixtures thereof.

The styrenic block copolymers are hydrocarbon-based block copolymers. The styrenic block copolymers is obtained from at least one styrene monomer and at least one olefin. The olefin may especially be an elastomeric ethylenically unsaturated monomer. Examples of olefins that may be mentioned include ethylenic carbide monomers, especially containing one or two ethylenic unsaturations and containing from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene, isoprene or pentadiene. Advantageously, the styrenic block copolymer is an amorphous block copolymer of styrene and of olefin.

Block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene or a mixture thereof are especially preferred. According to one preferred embodiment, the styrenic block copolymer is hydrogenated to reduce the residual ethylenic unsaturations after the polymerization of the monomers.

According to one preferred embodiment, the styrenic block copolymer comprises at least one diblock copolymer, which is preferably hydrogenated, preferably chosen from styreneethylene/propylene copolymers, styrene-ethylene butadiene copolymers and styreneethylene/butylene copolymers. The diblock polymers are especially sold under the name Kraton® GI 701 E by the company Kraton Polymers.

According to another preferred embodiment, the the styrenic block copolymer comprises at least one triblock copolymer, which is preferably hydrogenated, preferably chosen from styreneethylene/propylene-styrene copolymers, styrene-ethylene/butadiene-styrene copolymers, styrene-isoprene-styrene copolymers and styrene-butadiene-styrene copolymers. Triblock polymers are especially sold under the names Kraton® G1650, Kraton® G1652, Kraton®G1657, Kraton® DI 101, Kraton® DI 102 and Kraton® DI 160 by the company Kraton Polymers.

The term “semi-crystalline polymers here means polymers comprising a crystallizable portion, pendent chain or block in the backbone, and an amorphous portion in the backbone and exhibiting a first-order reversible phase change temperature, in particular a melting point (solid-liquid transition). When the crystallizable portion is a block of the polymer backbone, this crystallizable block has a chemical nature different from that of the amorphous blocks; in this case, the semi-crystalline polymer is a block polymer, for example of the diblock, triblock or multiblock type.

Apart from the crystallizable chains or blocks, the blocks of the polymers are amorphous.

The term “crystallizable chain or block” here means a chain or block which, if it were alone, would change from the amorphous state to the crystalline state reversibly, according to whether the temperature is above or below the melting point.

According to a specific embodiment of the invention, the semi-crystalline polymer is chosen from homopolymers obtained by polymerization of at least one monomer having a crystallizable chain, chosen from C14-C24 alkyl (meth)acrylates, C11-C15 perfluoroalkyl (meth)acrylates, N-(C_M to C24 alkyl)(meth)acrylamides with or without fluorine atom, vinyl esters having C_M to C24 alkyl or perfluoroalkyl chains, vinyl ethers having C_M to C24 alkyl or perfluoroalkyl chains, C_M to C24 a-olefms or para-alkylstyrenes with a C_M to C24 alkyl group, and from the copolymers of these monomers obtained by copolymerization of these monomers with a hydrophilic monomer, preferably other than methacrylic acid, such as, for example, N-vinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate or acrylic acid. Such copolymers can, for example, be copolymers of C_M-C24-alkyl acrylate,

C_M-C₂₄-alkyl methacrylate, C_M-C₂₄-alkylacrylamide or C_M-C₂₄-alkylmethacrylamide with N-vinylpyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate or acrylic acid, or their mixtures.

The semi-crystalline polymers of the composition of the invention can be non-crosslinked or partially crosslinked. Preferably, the semi-crystalline polymers of the composition according to the invention are non-crosslinked.

According to a specific embodiment of the invention, the semi-crystalline polymer is a homopolymer resulting from the polymerization of a monomer having a crystallizable chain chosen from C_M-C24 alkyl acrylates and C_M-C24 alkyl methacrylates. Mention may in particular be made of those sold under the name Intelimer® by Landec, described in the brochure Intelimer® Polymers, Landec IP22. These polymers are in the solid form at ambient temperature. They carry crystallizable side chains and correspond to saturated C_M-C24 alkyl acrylate or methacrylate homopolymers. Mention may more particularly be made of the stearyl acrylate homopolymer (Intelimer IPA-13.1) (INCI name: Poly CIO-30 alkyl acrylate) or the behenyl acrylate homopolymer (Intelimer IPA-13.6) (INCI name: Poly Cl 0-30 alkyl acrylate).

The glutamide-based compounds of the present invention are known to comprise a type of organic gelling agents. Preferably, the glutamide-based compounds of the present invention are non-polymeric.

Preferably, the glutamide-based compounds are non-polymeric and are chosen from: a low molecular weight dialkyl N-acylglutamide bearing a linear alkyl chain, chosen especially from di(C2-C6)alkyl N-acylglutamides in which the acyl group comprises a linear C8 to C22 alkyl chain, preferably such as lauroylglutamic acid dibutylamide (or dibutyl lauroyl glutamide), and/or a low molecular weight dialkyl N-acylglutamide bearing a branched alkyl chain, chosen especially from di(C2-C6)alkyl N-acylglutamides in which the acyl group comprises a branched Cg to C22 alkyl chain, preferably such as N-2-ethylhexanoylglutamic acid dibutylamide (or dibutyl ethylhexanoyl glutamide), and mixtures thereof.

Preferably, among the non-polymeric glutamide-based compounds that may be used are combinations of at least one low molecular weight dialkyl N-acylglutamide bearing a linear alkyl chain, chosen especially from (C2-C6)dialkyl N-acylglutamides in which the acyl group comprises a linear C8 to C22 alkyl chain such as lauroylglutamic acid dibutylamide (dibutyl lauroyl glutamide), with at least one low molecular weight dialkyl Nacylglutamide bearing a branched alkyl chain, chosen especially from (C2-C6)dialkyl Nacylglutamides in which the acyl group comprises a branched C8 to C22 alkyl chain such as N-2-ethylhexanoyl glutamic acid dibutylamide (dibutyl ethylhexanoyl glutamide) and preferably with a solvent that is capable of forming hydrogen bonds with these two glutamide-based compounds.

In preferred embodiments, the glutamide-based compound suitable for use in the present invention is Dibutyl Lauroyl Glutamide, known by the tradename GP-1 and sold by the company Ajinomoto.

For the purposes of the invention, the term "polyamide" means a compound containing at least two repeating amide units, preferably at least three repeating amide units and better still ten repeating amide units. In particular, the (b) organic lipophilic gelling agent of the present invention comprises at least one polyamide. The inventors of the present invention surprisingly found out that the use of the polyamides as the organic lipophilic gelling agent can impart very preferable viscoelasticity to the composition according to the present invention. The polyamides of the present invention can be polyamide polycondensates. The term "polycondensate" refers in terms of the invention to a polymer obtained through polycondensation namely by chemical reaction between monomers that have different functional groups chosen in particular from among the acid, alcohol and amine functions. The lipophilic polyamide polycondensates can in particular be chosen from among the polyamide polymers comprising a) polymeric backbone that has hydrocarbon repetition patterns provided with at least one non-pendant amide pattern, and possibly b) at least one pendant fatty chain comprising from 6 to 120 carbon atoms, preferably from 8 to 120 carbon atoms, and more preferably from 12 to 70 carbon atoms, and/or at least one terminal fatty chain that may be functionalized, comprising at least 4 carbon atoms and being linked to these hydrocarbon patterns.

The term "functionalized chains" in terms of the invention refers to an alkyl chain comprising one or several functional group or reagents in particular chosen from among the amides, hydroxyl, ether, oxyalkylene or polyoxyalkylene groups, halogen, of which the fluorinated or perfluorinated groups, ester, siloxane, polysiloxane. Furthermore, the hydrogen atoms of one or several fatty chains can be substituted at least partially with fluorine atoms.

The term "hydrocarbon repetition patterns" in terms of the invention refers to a pattern comprising from 2 to 80 carbon atoms, and preferably from 2 to 60 carbon atoms, carrying hydrogen atoms and possibly oxygen atoms, which can be linear, branched or cyclic, saturated or unsaturated. These patterns further comprise at least one amide group advantageously non-pendant and found in the polymeric backbone.

Advantageously, the pendant chains are directly linked to at least one of the atoms of nitrogen of the polymeric backbone.

The lipophilic polyamide polycondensate can comprise between the hydrocarbon patterns silicone patterns or oxyalkylene patterns in C2-C3.

Furthermore, the lipophilic polyamide polycondensate of the composition of the invention advantageously comprises from 40 to 98% of the fatty chains with respect to the total number of amide patterns and fatty chains and more preferably from 50 to 95%.

Preferably, the pendant fatty chains are linked to at least one of the atoms of nitrogen of the amide patterns of the polymer. In particular, the fatty chains of this polyamide represent from 40 to 98% of the total number of amide patterns and of the fatty chains, and more preferably from 50 to 95%.

Advantageously, the lipophilic polyamide polycondensate has a mean molecular weight by weight less than 100,000 (in particular ranging from 1000 a 100000), in particular less than 50,000 (in particular ranging from 1000 to 50,000), and more particularly ranging from 1000 to 30,000, preferably from 2000 to 20,000, and more preferably from 2000 to 10,000.

The lipophilic polyamide polycondensate is not soluble in water or has a solubility of less than lg/L or 0.1 g/L in water, in particular at 25 °C and an atmosphere pressure. In particular, it does not comprise an ionic group.

As preferred lipophilic polyamide polycondensates that can be used in the invention, mention can be made of polyamides branched by pendant fatty chains and/or terminal fatty chains having from 6 to 120 carbon atoms and more particularly from 8 to 120 and in particular from 12 to 68 carbon atoms, with each terminal fatty chain being linked to the polyamide backbone by at least one bond group L. The bond group L can be chosen from among the ester, ether, amine, urea, urethane, thioester, thioether, thiurea, thiourethane groups. Preferably, these polymers comprise a fatty chain at each end of the polyamide backbone.

These polymers are preferably polymers resulting from a polycondensation between a carboxylic diacid having at least 32 carbon atoms (that has in particular from 32 to 44 carbon atoms) with an amine chosen from among diamines that have at least 2 carbon atoms (in particular from 2 to 36 carbon atoms) and triamines having at least 2 carbon atoms (in particular from 2 to 36 carbon atoms). The diacide is preferably a dimer coming from ethylene unsaturation fatty acid having at least 16 carbon atoms, preferably from 16 to 24 carbon atoms, such as oleic, linoleic or linolenic acid. The diamine is preferably diamine ethylene, diamine hexylene, diamine hexamethylene. The triamine is for example triamine ethylene. For polymers comprising one or 2 terminal carboxylic acid groups, it is advantageous to esterify them with a monoalcohol that has at least 4 carbon atoms, preferably from 10 to 36 carbon atoms and more preferably from 12 to 24 and even more preferably from 16 to 24, for example 18 carbon atoms.

The lipophilic polyamide polycondensate of the composition according to the invention can be in particular chosen from among the polymers having the following formula (A):

wherein: n is an integer varying from 1. to 30,

R'i represents at each occurrence independently a fatty chain and is chosen from among an alkyl or alcenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms;

R'2 represents at each occurrence independently a divalent hydrocarbon chain comprising from 1 to 52 carbon atoms;

Rh represents at each occurrence independently a divalent hydrocarbon group, saturated or unsaturated, cyclic or acyclic, possibly substituted and/or possibly interrupted by one or several heteroatoms preferably chosen from among oxygen and nitrogen comprising at least one carbon atoms, in particular RT represents a linear or branched alkylene chain (Ci-Cs); preferably linear alkylene (C1-C6) such as ethylene;

R'4 represents at each occurrence independently: a hydrogen atom, one alkyl group by comprising from 1 to 10 carbon atoms, or a direct link with at least one group chosen from among R'3 and another R'4 in such a way that when said group is another R’₄ ,the nitrogen atom to which are linked both R'3 and R'4 is part of a heterocyclic structure defined by R'4-N-R'3, with the condition that at least 50% of the R'4 represent a hydrogen atom, and L represents a bond group chosen preferably from among an ester or ether or amine or urea or urethane or thioester or thioether or thiurea or thiourethane group, possible substituted by at least one group R'i such as defined hereinabove.

According to an embodiment, these polymers are chosen from among the polymers having formula (A) wherein the bond group L represents an ester group ester -C(0)-0- or -O-C(O)-.

These polymers are more specially those described in the US-A-5783657 from Union Camp.

Each one of these polymers satisfies in particular the following formula (B):

wherein:

- m designates an integer of an amid group such that the number of the ester group represents from 10% to 50% of the total number of ester and amide groups;

- Ri represents at each occurrence independently an alkyl or alcenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms;

- R2 represents at each occurrence independently a C4 to C42 hydrocarbon group with the condition that 50% of the groups R2 represent a C30 to C42 hydrocarbon group;

- R3 represents at each occurrence independently a divalent hydrocarbon group, saturated or unsaturated, cyclic or acyclic, possibly substituted and/or possibly interrupted by one or several heteroatoms preferably chosen from among oxygen and nitrogen comprising at least one carbon atoms, in particular R3 represents a linear or branched alkylene. chain (Ci-Cs); preferably linear alkylene (C1-C6) such as ethylene; and

- R4 represents at each occurrence independently a hydrogen atom, a Ci to C10 alkyl group or a direct link to R3 or to another R4 in such a way that the nitrogen atom to which are linked both R3 and R4 is a part of a heterocyclic structure defined by R4-N-R3, with at least 50% of the R4 representing a hydrogen atom.

In the particular case of the formula (B), the terminal fatty chains possibly functionalized in terms of the invention are terminal chains linked to the last nitrogen atom, of the polyamide backbone.

In particular, the ester groups of the formula (B), which are part of the terminal and/or pendant fatty chains in terms of the invention, represent from 15 to 40% of the total number of ester and amide groups and in particular from 20 to 35%.

In addition, m advantageously represents an integer ranging from 1 to 5 and more particular greater than 2. Preferably, Ri is a C12 to C22 alkyl group and preferably Ci6 to C22. Advantageously, R2 can be a divalent, saturated or unsaturated, cyclic or acyclic hydrocarbon group in particular R2 represents a linear or branched (C10-C42) alkylene chain. Preferably, 50% at least and more preferably at least 75% of the radicals R2 are groups having 30 to 42 carbon atoms. The other R2 are hydrocarbon groups in C4 to C19 and even in C4 to C12.

Preferably, R3 represents a C2 to C36 hydrocarbon group or polyoxyalkylene group and R4 represents a hydrogen atom. Preferably, R3 represents a C2 to C12 hydrocarbon group.

The hydrocarbon groups can be linear, cyclic or branched, saturated or unsaturated groups. Moreover, the alkyl and alkylene groups can be linear or branched, saturated or not, groups.

In general, the polymers of the formula (B) have the form of mixtures of polymers, with these mixtures furthermore able to contain a synthesis product that corresponds to a compound of formula (B) where n is equal to 0, i.e. a diester.

According to a particularly preferred form of the invention, a mixture of copolymers of a C36 diacid condensed on diamine ethylene will be used; the terminal ester groups result from the esterification of the terminations of remaining acid by the cetylic, stearylic alcohol or mixtures thereof (also called cetylstearylic) (INCI name: Ethylenediamine/Stearyl Dimer Dilinoleate Copolymer). Its mean molar mass by weight is preferably 6000, further preferentially 4000. These mixtures are in particular sold by ARIZONA CHEMICAL under the trade names UNICLEAR 80 and UNICLEAR 100 VG respectively in the form of a at 80% (in active material) in a mineral oil and at 100% (in active material). These mixtures are also sold by CRODA under the trade name OLEOCRAFT LP-IO-PA-(MV) respectively at 99.7% (in active material) with a preservative. They have a softening point from 88°C to 94°C.

In terms of polyamide polycondensates that satisfy the general formula (A), mention can also be made of polymers comprising at least one terminal fatty chain linked to the polymeric backbone by at least one tertiary amid bond group (also called amide terminated polyamide or ATPA). For more information on these polymers, reference can be made to document US 6503522.

According to a particularly preferred form of the invention, use will be made more particularly of a copolymer of hydrogenated linoleic diacide, ethylenediamine, di(C14-C18)alkylamine(s) (INCI name: Ethylenediamide/Hydrogenated Dimer Dilinoleate Copolymer Bis-Di-C14-Cl 8 Alkyl Amide). This copolymer is in particular sold under the trade name SYLVACLEAR A200V by ARIZONA CHEMICAL.

According to another embodiment, the polyamide having formula (A) can also be a poly(ester-amide) with ester ends (ester-terminated poly(ester-amide) or ETPEA), as for example those for which the preparation is described in document US 6552160.

According to a particularly preferred form of the invention, use will be made more particularly of a copolymer of hydrogenated linoleic diacide, ethylenediamine, neopentylglycol and stearylic alcohol (INCI name: Bis-Stearyl Ethylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleate Copolymer). This copolymer is in particular sold under the trade name SYLVACLEAR C75 V by ARIZONA CHEMICAL.

As polyamide polycondensates that can be used in the invention, further mention can be made of those that contain at least one terminal fatty chain linked to the polymeric backbone by at least one ether or polyether bond group (it is then referred to as ether terminated poly(ether)amide). Such polymers are described for example in the document US 6399713.

The polyamides in accordance with the invention advantageously have a softening temperature greater than 65°C and are able to range up to 190°C. Preferably, it has a softening temperature ranging from 70 to 130°C and more preferably from 80 to 105°C. The polyamide is in particular a non- waxy polymer.

As polyamide polycondensates that can be used in the invention, mention can also be made of polyamide resins resulting from the condensing of a aliphatic di-carboxylic acid and of a diamine (including the compounds that have more than 2 carbonyl groups and 2 amine groups), with the carbonyl and amine groups of adjacent unitary patterns being condensed by an amide bond. These polyamide resins are in particular those marketed under the brand Versamid by General Mills, Inc. and Henkel Corp. (Versamid 930, 744 or 1655) or by Olin Mathieson Chemical Corp., under the brand Onamid in particular Onamid S or C. These resins have a mean molar mass by weight ranging from 6000 to 9000. For more information on these polyamides, reference can be made to documents US 3645705 and US 3148125. More specifically, Versamid 930 or 744 are used.

Polyamides sold by Arizona Chemical under references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) can also be used and the product sold under the , reference Macromelt 6212 by Henkel. For more information on these polyamides, reference can be made to document US 5500209.

It is also possible to use resins of polyamides coming from vegetables such as those described in patents US 5783657 and US 5998570.

Preferably, the lipophilic polyamide polycondensate is a copolymer of a C36 diacid condensed on diamine ethylene; the terminal ester groups result from the esterification of the terminations of remaining acid by the cetylic, stearylic alcohol or mixtures thereof.

The amount of the (b) organic lipophilic gelling agent(s) may be 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and even more preferably 4% by weight or more, and may 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 7% by weight or less, relative to the total weight of the anhydrous composition.

(Water Soluble Particle) The anhydrous composition according to the present invention comprises at least one (c) water soluble particle. Two or more (c) water soluble particles may be used in combination. Thus, a single type of a water soluble particle or a combination of different types of water soluble particles may be used.

The term “water soluble” here means substances having a solubility of at least lg/L, preferably at least lOg/L, and more preferably at least 100/L, in water at room temperature (25°C) and atmosphere pressure (10⁵ Pa).

Preferably, the (c) water soluble particles are insoluble in oil, i.e. have a solubility of less than 1 g/L, preferably of less than 0.1 g/L in oils.

The water soluble particles may be of any shape: platelet-shaped, spherical, oblong, or multangular, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.).

In one preferred embodiment of the present invention, the (c) water soluble particles of the present invention can function as a water soluble scrub particle. The (c) water soluble particle as a scrub particle can physically disrupt keratinous substances, such as skin, in particular the stratum comeum. In this embodiment, the water soluble particles can be formed in the forms of hard, sharply edged and rough surface particles. The sharply edged particles of the present invention may be formed in a polypyramid form. Further, the edged scrub particles may be microneedles which are formed in the form of a tetrahedral or pyramid shaped microstructure. In addition, each face of the microneedles may be flat, may include roughness, or may be hollow. The sharp edges or rough surface can lead to the alteration of the Stratum Comeum structure. This functional particle later can be dissolved by contacting the particles with water. After the particles are dissolved, the active ingredients can be efficiently penetrated into the skin.

In specific embodiments of the present invention, the water soluble particles may have an aspect ratio of at least 1.1, preferably at least 1.2, and more preferably at least 1.5, even more preferably at least 2, and in particular at least 2.5. In other embodiments of the present invention, the water soluble particles may have an aspect ratio of 2 or less, preferably 1.5 or less, and more preferably 1.2 or less. The aspect ratio can be measured by common technology in the art, for example, image analysis using an electron microscope.

In other specific embodiments of the present invention, the water soluble particles may have an average circularity determined by an image analysis method of 0.95 or less, preferably 0.9 or less, and more preferably 0.85 or less, and even more preferably 0.8 or less. In other embodiments of the present invention, the water soluble particles an average circularity determined by an image analysis method of 0.7 or more, preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.9 or more.

The "average circularity" may be determined by an image analysis method. In particular, the "average circularity" may be an arithmetic mean of circularity obtained by image analysis of a scanning electron microscope (SEM) image of no less than 2000 particles observed at a magnification of 1000 by secondary electron detection using a scanning electron microscope (SEM). The "circularity" of each particle is a value determined by the following formula:

C = 4p8 / L² wherein C represents a circularity, S represents an area (projected area) of the particle in the image, and L represents a length of a periphery (perimeter) of the particle in the image. When the average circularity approaches 1 , the shape of each of the particles becomes more spherical.

The water soluble particles may have an average primary particle size of 10 qm or more, preferably 30 pm or more, more preferably 50 pm or more, and even more preferably 100 pm or more, and in particular 200 pm or more. The average primary particle size of the water soluble particles may be 1 mm or less, preferably 800 pm or less, and more preferably 600 pm or less, and even more preferably 500 pm or less.

The term “average primary particle size” used herein represents a volume-average size mean diameter which is given by the statistical particle size distribution to half of the population, referred to as D50. For example, the volume-average size mean diameter can be measured by a laser diffraction particle size distribution analyzer, such as Mastersizer 2000 by Malvern Corp. The substances of the (c) water soluble particles of the present invention are not particularly limited as long as they dissolve by contacting an aqueous component, such as water.

However, in the cosmetic process according to the present invention, an aqueous composition is applied after the composition according to the present invention is applied on keratinous substances, and the (c) water soluble particles are dissolved and penetrated into the keratinous substances, such as skin. Therefore, preferably, the (c) water soluble particles are composed of cosmetically benefit ingredients for keratinous substances, such as skin.

Accordingly, the water soluble particles can composed of polysaccharide particles, monosaccharide particles, amino acids particles, sugar alcohol particles, or ascorbic acid particles, and a mixture thereof. The polysaccharide may include disaccharides, such as sucrose, lactose, maltose, and trisaccharides such as raffmose, and mucopolysaccharides, such as hyaluronic acid, chondroitin sulfate, and heparin. The monosaccharide may include pentose, hexose, and heptose, such as glucose, dextrose, galactose, mannose, and glucuronic acid. The sugar alcohols may include sorbitol and glucamines. The ascorbic acids may include vitamin C.

The amount of the (c) water soluble particle(s) may be 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.5% by weight or more, and may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less, relative to the total weight of the anhydrous composition.

(Other Ingredients) · Alcohol

The anhydrous composition according to the present invention may comprise at least one alcohol. If two or more to alcohols are used, they may be the same or different. The alcohol included in the composition according to the present invention can be characterized with Hansen solubility parameters. The Hansen solubility parameters are solubility parameters disclosed by Charles Hansen in "Hansen Solubility Parameters: A User's Handbook" by Charles M. Hansen, CRC Press (2007). Solubility parameters, as utilized herein, are calculated numerical constants which are a useful tool in predicting the behavior of a solvent material. There are three Hansen empirically- and theoretically-derived solubility parameters, a dispersion force component (5D), a polar or dipole interaction component (dr) and a hydrogen-bonding component (5H). Each of the three parameters (i.e. dispersion, polar and hydrogen bonding) represents a different characteristic of solvency, or solvent capability. ft is preferable that the alcohol has Hansen solubility parameters of 5_H (a hydrogen-bonding component) being less than 30 and dc (a volume-dependent combined parameter: dc= (do² + dr²)^1/2) being less than 25 at 25 °C.

The alcohol can be selected, for example, oleyl alcohol, dodecanol, propylene glycol, diethylene glycol and combination thereof.

The amount of the alcohol(s) may be 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and may be 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the anhydrous composition.

• Surfactants

The anhydrous composition according to the present invention may comprise at least one surfactant chosen from amphoteric, anionic, cationic, or nonionic surfactants, used alone or as a mixture.

The surfactant which can be included in the composition preferably has a low HLB value of 7.0 or less. The term HLB ("hydrophilic-lipophilic balance") is well known to those skilled in the art. If two or more surfactants are used, the HLB value is determined by the weight average of the HLB values of all the surfactants.

The examples of surfactants having a low HLB values include, but not limited to, fatty acid esters of glycol, sorbitol, and/or glycerol, such as polyglyceryl-2 stearate, polyglyceryl-2 distearate, polyglyceryl-2 isostearate, polyglyceryl-2 oleate, polyglyceryl-3 distearate, polyglyceryl-5 hexastearate, poly glyceryl- 10 pentaoleate, glyceryl stearate, sorbitan stearate, glyceryl laurate, acetylated ethylene glycol stearate, and isostearyl diglyceryl succinate.

The amount of the surfactant(s) is not limited, but may be from 0.1 to 20% by weight relative to the total weight of the anhydrous composition according to the present invention.

• Adjuvants

The anhydrous compositions according to the present invention may also contain various adjuvants conventionally used in cosmetic topical compositions, which may be selected from a physiologically acceptable medium, cationic, anionic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, peptides and derivatives thereof; protein hydrolyzates, swelling agents, penetrating agents, inorganic or organic fillers, anti-oxidants, neutralizing agents, sequestering agents, fragrances, emollients, dispersing agents, dyes and/or pigments, organic or inorganic UV filters, vitamins or provitamins, moisturizing agents, film-forming agents and/or thickeners, ceramides, preservatives, co-preservatives and opacifying agents.

The amount of the additional ingredient(s) is not limited, but may be from 0.1 to 30% by weight relative to the total weight of the anhydrous composition according to the present invention.

The composition according to the present invention can be manufactured by mixing (a) at least one oil, (b) at least one organic lipophilic gelling agent, and (c) at least one water soluble particle, and, if necessary, one or more other ingredients.

[Cosmetic Process]

The present invention also relates to a cosmetic process for keratinous substances, such as skin, comprising steps of applying the anhydrous composition according to the present invention onto the keratinous substances, and then contacting an aqueous composition comprising water with the anhydrous composition applied on the keratinous substances.

The anhydrous composition used in the first step of the process is the same as explained above. The method to apply the composition to keratin substances is not particularly limited, and any methods known in the art can be adopted. In general the composition is applied by hands.

The process according to the present invention may comprise an optional step of massaging the keratinous substance where the composition according to the present invention is applied. This step can promote the water soluble particles in the composition disrupting the surface of the keratinous substances, in particular the stratum comeum. The massaging step can be carried out for at least 1 second.

The step of contacting an aqueous composition with the anhydrous composition applied on the keratinous substances is to apply the aqueous composition to the anhydrous composition so that the water soluble particles in the anhydrous composition dissolve, and the active ingredients can be penetrated into the skin very effectively.

The aqueous composition in the process includes water. The amount of water in the aqueous composition is not particularly limited, but in general 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more, and is 90% by weight or less, preferably 80% by weight or less, more preferably 75% by weight or less, and even more preferably 60% by weight or less, relative to the total weight of the aqueous composition.

The aqueous composition can comprise other ingredients in order to meet a cosmetic purpose. For example, the aqueous composition can comprise an active ingredient for keratinous substances, such as skin, an oil, a thickener, an emulsifier, a cosmetically acceptable hydrophilic organic solvent, and adjuvants. The ingredients which can be formulated in the aqueous composition will be described below.

• Active Ingredient

The aqueous composition according to the present invention preferably comprises at least one active ingredient for keratinous substances, such as skin. Two or more active ingredient for keratinous substances may be used in combination.

The active ingredient for keratinous substances can be water soluble. More specifically, the active ingredient for keratinous substances have a solubility of at least 1 g/L, preferably at least 10 g/L in water.

The active ingredient for keratinous substances can be an organic compound having any cosmetic or dermatological effects on a keratinous substance, such as skin. In particular, the active ingredients preferably exhibit cosmetic or dermatological effects on a keratinous substance, such as skin, after they penetrate the keratinous substance, to improve skin condition. Preferably, the active ingredients are skin- whitening active ingredients, anti-aging active ingredients, anti-wrinkle active agents, or anti-oxidant active ingredients.

As the active ingredients, mention may in particular be made of Pro-Xylane (hydroxypropyl tetrahydropyrantriol), i.e. Vigna aconitifolia seed extracts such as those sold by the company Cognis under the references Vitoptine LS9529 and Vit-A-Like LS9737.

As the other active ingredients, mention may be made of, for example, ascorbic acids and derivatives thereof, extracts of plants and plant proteins and hydrolysates thereof, algal extracts and in particular of luminaria, bacterial extracts, sapogenins, a-hydroxy acids, b-hydroxy acids, such as salicylic acid, oligopeptides and pseudodipeptides and acyl derivatives thereof, hyaluronic acid and salts thereof, and mixture thereof.

The amount of the active ingredient(s) may be 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, and may be 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, and even more preferably 5% by weight or less, relative to the total weight of the aqueous composition.

• Oil

The aqueous composition according to the present invention may comprise at least one oil.

If two or more oils are used, they may be the same or different.

The oils which can be formulated into the aqueous composition can be the same as the (a) oil explained in the anhydrous composition according to the present invention as above.

In particular, the oil used in the aqueous composition may be selected from the group consisting of ester oils, silicone oils, fatty alcohols, and fatty acids.

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.

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 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, and the like; and mixtures thereof. Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS, dimethicone) 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.

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. 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.

The fatty acids that may be used in the context of the invention are more particularly chosen from saturated or unsaturated carboxylic acids containing from 6 to 30 carbon atoms and in particular from 9 to 30 carbon atoms. They are advantageously chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid. The amount of the oil(s) may range from 5 to 50% by weight, preferably from 10 to 40% by weight, and more preferably from 15 to 30% by weight, relative to the total weight of the aqueous composition.

• Thickener

The aqueous composition according to the present invention may comprise at least one thickener. Two or more thickeners can be combined. The thicker may be hydrophilic or lipophilic.

As the lipophilic thickener , mention can be made of lipophilic polymer thickeners, which can be chosen from carboxyvinyl polymers such as the Carbopol products (carbomers) and the Pemulen products (acrylate/C 10-C30-alkyl acrylate copolymer) or polymers having the INCI name "Poly Cl 0-30 Alkyl Acrylate", such as the Intelimer® products from Air Products, such as the product Intelimer® IPA 13-1, which is a polystearyl acrylate, or the product 30 Intelimer® IPA 13-6 which is a behenyl polymer.

As the hydrophilic thickener, mention can be made of hydrophilic nonionic polysaccharide thickener, wchih may be chosen, for example, from glucans, modified and unmodified starches (such as those derived, for example, from cereals, for instance wheat, com or rice, from vegetables, for instance yellow pea, and tubers, for instance potato or cassaya), amylose, amylopectin, glycogen, dextrans, celluloses and derivatives thereof (methylcelluloses, hydroxyalkylcelluloses, ethyl hydroxyethylcellu loses, and carboxymethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans, glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums, karaya gums, carob gums, galactomannans, such as guar gums, and nonionic derivatives thereof (e.g., hydroxypropyl guar) and xanthan gums, and mixtures thereof.

The amount of the thickener(s) may range from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, and more preferably from 0.5 to 5% by weight, relative to the total weight of the aqueous composition.

• Emulsifier

The aqueous composition according to the present invention may comprise at least one emulsifier chosen from amphoteric, anionic, cationic, or nonionic surfactants, used alone or as a mixture. Preferably, the composition comprises at least one nonionic surfactant.

Examples of nonionic surfactants usable in the compositions of the invention may include polyethoxylated fatty alcohols or polyglycerolated fatty alcohols, such as the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units (Laureth-9 to Laureth-50 as the INCI names), in particular Laureth-9; esters of polyols and of a fatty acid possessing a saturated or unsaturated chain comprising, for example, from 8 to 24 carbon atoms, and their oxyalkylenated derivatives, that is to say comprising oxyethylene and/or oxypropylene units, such as esters of glycerol and of a C8-C24 fatty acid, for example, glyceryl stearate, and their oxyalkylenated derivatives, in particular polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), for examples PEG-20 glyceryl triisostearate; polyoxyalkylenated fatty esters, such as polyoxyethylenated fatty esters, for example, 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 stearate (as the CTFA names: PEG-9 stearate to PEG-50 stearate); esters of sugar (sucrose, maltose, glucose, fructose, and/or alkylglycose) and of a C8-C24 fatty acid, for example, sucrose tristearate, and their oxyalkylenated derivatives, such asscrose tristearate; ethers of a sugar and of C8-C24 fatty alcohols, such as caprylyl/capryl glucoside; polyoxyethylene alkyl ethers; polyoxyethylene oxypropylene alkyl ethers; fatty acid alkanol amides; alkyl amine oxides; alkyl polyglycosides and silicone surfactants, such as polydimethylsiloxane containing oxyethylene groups and/or oxypropylene groups, for example, PEG- 10 dimethicone, bis-PEG/PPG-14/14 dimethicone, bis-PEG/PPG-20/20 dimethicone, and PEG/PPG-20/6 dimethicone; and polyglyceryl fatty acid ester such as polyglyceryl-6 dicaprate, polyglyceryl-6 dioleate, polyglyceryl-6 caprylate, polyglyceryl-2 oleate, and polyglyceryl-6 polyricinoleate; and mixtures thereof.

The emulsifier can also include gemini surfactants. As the gemini surfactants, mention can be made of the mixture of sodium dilauramidoglutamide lysine and of butyleneglycol (INCI name: sodium dilauramidoglutamide lysine) sold under the trade name Pellicer LB -30G by Asahi Kasei Chemicals.

The amount of the emulsifier(s) may range from 0.1 to 30% by weight, preferably from 1 to 20% by weight, and more preferably from 2 to 10% by weight, relative to the total weight of the aqueous composition.

• Cosmetically Acceptable Hydrophilic Organic Solvent

The aqueous composition according to the present invention may comprise at least one cosmetically acceptable hydrophilic organic solvent. The cosmetically acceptable hydrophilic organic solvent(s) may include, for example, substantially linear or branched lower mono-alcohols having from 1 to 8 carbon atoms, such as ethanol, propanol, butanol, isopropanol, and isobutanol; aromatic alcohols, such as benzyl alcohol and phenylethyl alcohol; polyols or polyol ethers, such as propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, glycerine, propanediol, caprylyl glycol, pentylene glycol, sorbitol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol ethers, such as propylene glycol monomethylether, diethylene glycol alkyl ethers, such as diethylene glycol monoethylether or monobutylether; polyethylene glycols, such as PEG-4, PEG-6, and PEG-8, and their derivatives, and a combination thereof.

The amount of the cosmetically acceptable hydrophilic organic solvent(s) may range from 1 to 30% by weight, preferably from 2 to 20% by weight, and more preferably from 3 to 10% by weight, relative to the total weight of the aqueous composition.

• Adjuvants

The aqueous compositions according to the present invention may also contain various adjuvants conventionally used in compositions for sun care products, which may be selected from a physiologically acceptable medium, cationic, anionic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, peptides and derivatives thereof; protein hydrolyzates, swelling agents, penetrating agents, inorganic or organic fillers, antioxidants, neutralizing agents, acidifying or basifying agents commonly used in the cosmetics field, such as sodium hydroxide, sequestering agents, such as EDTA, fragrances, emollients, dispersing agents, organic or inorganic UV filters, dyes and/or pigments, organic or inorganic UV filters, vitamins or provitamins, moisturizing agents, film-forming agents, ceramides, preservatives, such as phenoxy ethanol, methylparaben, ethylparaben, propylparaben, and chlorphenesin, co-preservatives and opacifying agents.

The amount of the additional ingredient(s) is not limited, but may be from 0.1 to 30% by weight relative to the total weight of the aqueous composition according to the present invention.

The pH of the aqueous phase of the present invention is not particularly limited. The pH of the aqueous phase may range from 3.0 to 12.0, preferably from 4.0 to 9.0. The pH of the aqueous phase of the present invention can be adjusted to the desired value using acidifying or basifying agents commonly used in the cosmetics field.

The aqueous composition according to present invention may take various forms, such as, a solution, a gel, a lotion, a serum, a suspension, a dispersion, a fluid, a milk, a paste, a cream, an emulsion (O/W or W/O form), or the like.

The aqueous composition according to present invention can be applied to the anhydrous composition according to the present invention, which has been applied on the surface of the keratinous substances, in a form of , for example, a wet sheet mask, a mist, spray, or by a topical application.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples. However, these examples should not be construed as limiting the scope of the present invention.

[Example 1 and Comparative Example 1]

Each of anhydrous compositions according to Example 1 (Ex. 1) and Comparative Example 1 (Comp. Ex. 1) were prepared by mixing ingredients listed in the following Table 1 so as to be homogeneous. The formulations are also shown in the following Table 1. Among ingredients, sucrose was obtained from the company Tereos Sucre France (product name: SUCRE SEMOULE SURFINE 250) having 250 pm of the average primary particle size. The numerical values for the amounts of the ingredients are all based on “% by weight” as active raw materials.

Table 1

[Evaluation] (Rheology Property) The viscoelastic characteristic of the anhydrous composition according to Example 1 was evaluated using a Discovery Hybrid Rheometer 2 (TA instrument) with a 40 mm parallel plate with a set gap of 30 pm at 25°C. Viscoelasticity was measured at a frequency of 1 Hz and a strain (%) variation from 0.01 to 1000%.

The hysteresis was measured in the same manner as the viscoelastic analysis above, other than applying a cycle of shear from 0.1 to 100 sec ¹ and then back from 100 to 0.1 sec ¹. For the gel composition in current invention, change in final viscosity values in all the shear conditions is less than 10% compared to the initial viscosity values.

The result of viscoelasticity is shown in Figure 1. As can be seen form Figure 1 , the crossover point of the storage modulus G’ and the loss modulus G” was 43.5 Pa modulus (Y axis) and 17.6% strain (X axis). In addition, the linear viscoelastic region of G’ showed 102 Pa and the linear viscoelastic region of G” showed 12.5 Pa.

The composition according to Example 1 showed very low level of hysteresis, i.e. change in final viscosity values in all the shear conditions was less than 10% compared to the initial viscosity values.

Accordingly, it can be said that the anhydrous composition according to Example 1 shows very preferred viscoelastic property which can provide a comfortable texture with a plumpy feel and exhibit a property like a shape memory gel. Furthermore, the anhydrous composition according to present invention can show improved stability, a shelve life, and transparency since the particles does not precipitate for a long time.

(In vitro Permeation Experiments)

The compositions according to Example 1 and Comparative Examples 1 were evaluated with regard to the property of transdermal penetration of active ingredients in accordance with a Franz-cell (static diffusion cell) test as below.

5 mg/cm² of the composition according to each of Example 1 and Comparative Examples 1 was applied onto a certain area of a surface of a full thickness porcine skin. The surface of the skin was then manually massaged with a finger covered with a finger cot for 3 minutes. The skin was dried in air for 2 minutes. 10 mg/cm² of aqueous composition was then applied on the skin surface where the anhydrous composition was applied, and the skin was massaged for 30 seconds. The formulation of the aqueous composition was listed in Table 2 below. The numerical values for the amounts of the ingredients are all based on “% by weight” as active raw materials in Table 2. The skin was then mounted onto Franz cell.

The Franz cell had an application area of 2 cm² and a cell receptor fluid was 3mL of NaCl 0.9% (w/w) solution in water. The receptor fluid was stirred during the tests. The porcine skin is located between the doner compartment and the receptor compartment with the aforementioned application area of 2 cm². The temperature of the porcine skin was maintained to 32°C. After 16 hours, the skin surface was washed with an appropriate protocol to guarantee that all chemical remaining at the skin surface was removed, the porcine skin was removed, and then Stratum Comeum was removed by 10 consecutive tape strips (DSquam®). Active ingredients (Hydroxypropyl Tetrahydropyrantriol) in the receptor fluid, epidermis, and dermis were analyzed with LC/MS/MS. For each composition, three donors in triplicate (n=9) were used.

Table 2

The mean value of the amount (mg per cm² of the skin) of the active ingredient which passed through the Stratum Comeum of the porcine skin was calculated and is shown in Table 3. Table 3

The use of the composition according to Example 1 showed superior penetration property of the active ingredients. Therefore, it can be said that the composition and the cosmetic process according to the present invention are very useful for topical delivery of active ingredients for keratinous substances, such as skin.

Claims

1. An anhydrous composition for keratinous substances, such as skin, comprising:

(a) at least one oil,

(b) at least one organic lipophilic gelling agent, and

(c) at least one water soluble particle.

2. The anhydrous composition according to Claim 1 , wherein the (b) organic lipophilic gelling agent is selected from tyrenic block copolymers, semi-crystalline polymers, a glutamide-based compounds, polyamides, and mixtures thereof, and preferably is polyamides.

3. The anhydrous composition according to Claim 1 or 2, wherein the (c) water soluble particle has an average primary particle size of 10 pm or more, preferably 30 pm or more, more preferably 50 pm or more, and even more preferably 100 pm or more, and in particular 200 pm or more, and of 1 mm or less, preferably 800 pm or less, and more preferably 600 pm or less, and even more preferably 500 pm or less.

4. The anhydrous composition according to any one of the preceding claims, wherein the (c) water soluble particle comprises polysaccharide particles, monosaccharide particles, amino acids particles, sugar alcohol particles, or ascorbic acid particles, and a mixture thereof.

5. The anhydrous composition according to any one of the preceding claims, wherein the amount of the (a) oil is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 80% by weight or more, and is 99% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, and even more preferably 85% by weight or less, relative to the total weight of the anhydrous composition.

6. The anhydrous composition according to any one of the preceding claims, wherein the amount of the (b) organic lipophilic gelling agent is 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and even more preferably 4% by weight or more, and is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 7% by weight or less, relative to the total weight of the anhydrous composition.

7. The anhydrous composition according to any one of the preceding claims, wherein the amount of the (c) water soluble particle is 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.5% by weight or more, and may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less, relative to the total weight of the anhydrous composition.

8. The anhydrous composition according to any one of the preceding claims, wherein the anhydrous composition has 10 ¹ Pa or more of a linear viscoelastic regions of a storage modulus (G’) profile and a loss modulus (G”) in a log scale and more than 4% strain of a crossover point of G’ and G”, measured with a rheometer using 40 mm cone plate at 25 °C and 1 Hz of frequency.

9. The anhydrous composition according to any one of the preceding claims, further comprising at least one alcohol, preferably having Hansen solubility parameters of 5H (a hydrogen-bonding component) being less than 30 and dc (a volume-dependent combined parameter: dc = (dϋ² + dr²)^1/2) being less than 25 at 25 °C.

10. The anhydrous composition according to Claim 9, wherein the amount of the alcohol is 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and is 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the anhydrous composition.

11. A cosmetic process for a keratin substance such as skin, comprising the steps of: applying onto the keratin substance the anhydrous composition according to any one of Claims 1 to 10, and contacting an aqueous composition comprising water with the applied anhydrous composition.

12. The process according to Claim 11 , wherein the aqueous composition comprises at least one active ingredient for a keratinous substance, such as skin, preferably selected from skin-whitening active ingredients, anti-aging active ingredients, anti-wrinkle active agents, or anti-oxidant active ingredients.

13. The process according to Claim 12, wherein the amount of the active ingredient is 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, and is 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, and even more preferably 5% by weight or less, relative to the total weight of the aqueous composition.

14. The process according to any one of Claims 11 to 13, wherein the amount of water is 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more, and is 90% by weight or less, preferably 80% by weight or less, more preferably 75% by weight or less, and even more preferably 60% by weight or less, relative to the total weight of the aqueous composition.

15. The process according to any one of Claims 11 to 14, wherein the aqueous composition is applied to the applied anhydrous composition in a form of a wet sheet mask, a mist, spray, or by a topical application.