WO2019227275A1

WO2019227275A1 - Composition in the form of shape-memory gelly cream

Info

Publication number: WO2019227275A1
Application number: PCT/CN2018/088649
Authority: WO
Inventors: Yirui ZHU; Yangdong CHEN; Ruijun Chen
Original assignee: L'oreal; Yirui ZHU
Priority date: 2018-05-28
Filing date: 2018-05-28
Publication date: 2019-12-05
Also published as: CN112654343B; CN112654343A

Abstract

A composition comprising: (a) at least one associative polymeric thickener chosen from the group consisting of polyurethane/polyethers comprising in their chain at least one polyoxyethylenated hydrophilic block and at least one hydrophobic block containing at least one sequence chosen from aliphatic sequences, cycloaliphatic sequences, and aromatic sequences; (b) at least one surfactant chosen from the polyoxyalkylene alkyl ether carboxylic acids or salts thereof having the formula {RO-(AO) _n-A'-COO} _mM; (c) at least one hydrophilic gelling agent chosen from the optionally modified carboxyvinyl polymers; (d) hyaluronic acid or salt thereof; and (e) at least one oil; said composition being in the form of oil dispersed in a gel phase.

Description

COMPOSITION IN THE FORM OF SHAPE-MEMORY GELLY CREAM

The present invention concerns a composition in the form of a shape-memory gelly cream. The present invention also concerns cosmetic compositions that are useful for personal skin care.

The development of formulations dedicated to caring for and/or making up the skin and/or lips, is permanent. Said formulations have to show satisfactory properties in terms of sensory feeling after application.

It is therefore desirable to provide compositions that present excellent application and sensory characteristics.

It is also desirable to provide compositions not only with an aesthetically appealing attribute upon application, but also which advantageously remain in place on the keratinous surface to which it is applied so that it does not drip or run.

The aim of the present invention is to provide a composition with an improved sensory effect, especially concerning the slimy feeling, the stickiness and the penetration feeling.

The aim of the present invention is also to provide a composition with a suitable viscosity in the form of a gelly cream.

The aim of the present invention is also to provide a stable composition in the form of a gelly cream and having a shape-memory effect.

Therefore, the present invention relates to a composition, preferably a cosmetic composition, comprising:

(a) at least one associative polymeric thickener chosen from the group consisting of polyurethane/polyethers comprising in their chain at least one polyoxyethylenated hydrophilic block and at least one hydrophobic block containing at least one sequence chosen from aliphatic sequences, cycloaliphatic sequences, and aromatic sequences;

(b) at least one surfactant chosen from the polyoxyalkylene alkyl ether carboxylic acids or salts thereof, having the following formula (1) :

{RO- (AO) _n-A'-COO} _m’ M

wherein:

- R is a hydrocarbon group having from 4 to 30 carbon atoms,

- AO is an alkyleneoxy group having from 2 to 4 carbon atoms,

- n is an average addition mole number of AO and is greater than 5,

- A' is an alkylene group having from 1 to 3 carbon atoms,

- M is a cation or is a hydrogen atom, and

- m’ is a valence of M;

(c) at least one hydrophilic gelling agent chosen from the optionally modified carboxyvinyl polymers;

(d) hyaluronic acid or a salt thereof; and

(e) at least one oil;

said composition being in the form of oil dispersed in a gel phase.

The composition of the invention has a shape-memory effect. In other words, this composition is a non-flowable composition. As used herein, the term “non-flowable” means when external forces are applied to the composition, memory shape transformation starts and upon application to the surface of treated keratinous tissue, the composition stays put and does not drip.

According to an embodiment, the cosmetic composition is a clear, flowable semi-solid, and converts to a non-flowable semi-solid upon rubbing. As used herein, the term “flowable” means the composition behaves like honey and has thick viscosity and slower flow response when pouring from a container.

According to an embodiment, the composition of the invention has a viscosity measured at 25℃ of at least 15 UD, such viscosity being measured with M3 stirrer.

In that which follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "of between" and "ranging from ... to ..." .

Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more" .

Throughout the instant application, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones. As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of” ) .

Associative polymeric thickener (a)

The composition of the invention comprises at least one associative polymeric thickener (a) as defined above. It may also comprise a mixture of several associative polymeric thickeners (a) as defined above.

Two or more (a) associative thickeners may be used in combination. Thus, a single type of associative thickener or a combination of different types of associative thickener may be used.

As used herein, the expression "associative thickener" means an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, for example, at least one C ₈-C ₃₀ fatty chain and at least one hydrophilic unit.

Preferably, the associative polyurethane thickener used in the present invention is nonionic. In particular, said associative polyurethane thickener is chosen from the nonionic polyurethane-polyethers. The nonionic polyurethane-polyethers may have both at least one hydrophilic moiety and at least one hydrophobic moiety. More particularly, said polymers may contain in their chain both hydrophilic sequences most often of a polyoxyethylenated nature and hydrophobic sequences which may be aliphatic linkages alone and/or cycloaliphatic and/or aromatic linkages.

Preferably, these polyether-polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, preferably from 6 to 20, separated by a hydrophilic sequence, it being possible for the hydrocarbon chains to be pendent chains or chains at the end of a hydrophilic sequence. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.

The polyether-polyurethanes may be polyblocks, in particular in triblock form. The hydrophobic sequences may be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (polyblock copolymers for example) . These same polymers may also be in the form of graft units or may be star-shaped.

Therefore, the associative polyurethane thickeners can increase viscosity or consistency of the composition according to the present invention. Thus, after application of the composition according to the present invention, it can recover the original elasticity of the composition quickly.

The nonionic polyether-polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name.

By extension, those whose hydrophilic sequences are linked by other chemical bonds to the hydrophobic sequences are also included among the nonionic polyether-polyurethanes containing a hydrophobic chain.

By way of examples of nonionic polyether-polyurethanes containing a hydrophobic chain which can be used in the present invention, it is also possible to use

205 containing a urea functional group sold by the company RHEOX or else the

208, 204 or 212, as well as Acrysol RM

There may also be mentioned the product ELFACOS

containing a C ₁₂-C ₁₄ alkyl chain and the product ELFACOS

containing a C ₁₈ alkyl chain from AKZO.

The product DW

from ROHM &HAAS containing a C ₂₀ alkyl chain and with a urethane bond, sold at 20%dry matter content in water, may also be used.

It is also possible to use solutions or dispersions of these polymers in particular in water or in an aqueous-alcoholic medium. By way of examples of such polymers, there may be mentioned

255,

278 and

244 sold by the company RHEOX. It is also possible to use the product DW 1206F and DW 1206J provided by the company ROHM &HAAS.

The above-described polyether-polyurethanes which can be used can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen-Colloid Polym. Sci 271, 380-389 (1993) .

As the above-described polyether-polyurethanes, mention may be made of polyurethane-polyethers comprising in their chain at least one polyoxyethylenated hydrophilic block and at least one of hydrophobic blocks containing at least one sequence chosen from aliphatic sequences, cycloaliphatic sequences, and aromatic sequences.

It may be preferable that the polyurethane-polyethers comprise at least two hydrocarbon-based lipophilic chains having from 8 to 30 carbon atoms, separated by a hydrophilic block, and wherein the hydrocarbon-based chains are chosen from pendent chains and chains at the end of the hydrophilic block.

According to a specific form of the present invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) a polyoxyethylenated stearyl alcohol comprising 100 mol of ethylene oxide, and (iii) a diisocyanate.

Such polyurethane/polyethers are sold especially by the company Elementis under the name Rheolate FX

and Rheoluxe

which is a polycondensate of polyethylene glycol containing 136 mol of ethylene oxide, of stearyl alcohol polyoxyethylenated with 100 mol of ethylene oxide and of hexamethylene diisocyanate (HDI) with a weight-average molecular weight of 40000 (INCI name: PEG-136/Steareth-100/HDI Copolymer) .

According to another specific form of the present invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane/polyethers are sold in particular by the company Rohm &Haas under the names Aculyn

and Aculyn

Aculyn

having the INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer, is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis (4-cyclohexyl isocyanate) (SMDI) at 15%by weight in a matrix of maltodextrin (4%) and water (81%) (INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer) .

Aculyn

(PEG-150/Decyl Alcohol/SMDI Copolymer) is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis (4-cyclohexyl isocyanate) (SMDI) at 35%by weight in a mixture of propylene glycol (39%) and water (26%) (INCI name: PEG-150/Decyl Alcohol/SMDI Copolymer) .

As the associative polymeric thickener (a) , it may be preferable to use a compound represented by the following formula (2) :

R ¹- { (O-R ²) _k-OCONH-R ³ [-NHCOO- (R ⁴-O) _n-R ⁵] _h} _m (2)

wherein R ¹ represents a hydrocarbon group, R ² and R ⁴ independently represent alkylene groups having 2 to 4 carbon atoms, which alkylene groups may be identical or different from each other, or a phenylethylene group, R ³ represents a hydrocarbon group, which may optionally have a urethane bond, R ⁵ represents a branched chain or secondary hydrocarbon group, m represents a number of at least 2, h represents a number of at least 1, k represents a number within the range of 1 to 500, and n represents a number within the range of 1 to 200.

The hydrophobically modified polyurethane that is represented by the general formula (2) shown above is obtained by, for example, reacting at least one polyether polyol that is represented by the formula R ¹- [ (O-R ²) _k-OH] _m, at least one polyisocyanate that is represented by the formula R ³- (NCO) _h+1, and at least one polymonoalcohol that is represented by the formula HO- (R ⁴-O) _n-R ⁵.

In such cases, R ¹ to R ⁵ in the general formula (2) are determined by the compounds R ¹- [ (O-R ²) _k-OH] _m, R ³- (NCO) _h+1 and HO- (R ⁴-O) _n-R ⁵. The loading ratios among the three compounds are not limited particularly and should preferably be such that the ratio of the isocyanate group derived from the polyisocyanate to the hydroxyl group derived from the polyether polyol and the polyether monoalcohol is selected within the range of NCO/OH of between 0.8: 1 and 1.4: 1.

The polyether polyol compound that is represented by the formula R ¹- [ (O-R ²) _k-OH] _m and that may be used preferably for obtaining the associative thickener represented by the general formula (2) may be obtained from addition polymerization of an m-hydric polyol with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or epichlorohydrin, or with styrene oxide, and the like.

The polyols should preferably be di-to octa-hydric polyols. Examples of the di-to octa-hydric polyols include dihydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopenthyl glycol; trihydric alcohols, such as glycerol, trioxy isobutane, 1, 2, 3-butanetriol, 1, 2, 3-pentanetriol, 2-methyl-1, 2, 3-propanetriol, 2-methyl-2, 3, 4-butanetriol, 2-ethyl-1, 2, 3-butanetriol, 2, 3, 4-pentanetriol, 2, 3, 4-hexanetriol, 4-propyl-3, 4, 5-heptanetriol, 2, 4-dimethyl-2, 3, 4-pentanetriol, pentamethylglycerol, pentaglycerol, 1, 2, 4-butanetriol, 1, 2, 4-pentanetriol, trimethylolethane, and trimethylolpropane; tetrahydric alcohols, such as pentaerythritol, 1, 2, 3, 4-pentanetetrol, 2, 3, 4, 5-hexanetetrol, 1, 2, 4, 5-pentanetetrol, and 1, 3, 4, 5-hexanetetrol; pentahydric alcohols, such as adonitol, arabitol, and xylitol; hexahydric alcohols, such as dipentaerythritol, sorbitol, mannitol, and iditol; and octahydric alcohols, such as sucrose.

Also, R ² is determined by the alkylene oxide, styrene oxide, or the like, which is subjected to the addition. Particularly, for availability and excellent effects, an alkylene oxide having 2 to 4 carbon atoms, or styrene oxide is preferable.

The alkylene oxide, styrene oxide, or the like, to be subjected to the addition may be subjected to single polymerization, or random polymerization or block polymerization of at least two members. The procedure for the addition may be a conventional procedure. Also, the polymerization degree k may be selected within the range of 0 to 1,000, preferably within the range of 1 to 500, and more preferably within the range of 10 to 200. Further, the ratio of the ethylene group occupying R ² should preferably be within the range of 50 to 100 mass %with respect to the total quantity of R ². In such cases, the associative thickener appropriate for the purposes of the present invention is obtained.

Furthermore, the molecular weight of the polyether polyol compound that is represented by the formula R ¹- [ (O-R ²) _k-OH] _m should preferably be selected within the range of 500 to 100,000, and should more preferably be selected within the range of 1,000 to 50,000.

The polyisocyanate that is represented by the formula R ³- (NCO) _h+1 and that may be used preferably for obtaining the hydrophobically modified polyether urethane represented by the general formula (2) employed in accordance with the present invention is not limited particularly in so far as the polyisocyanate has at least two isocyanate groups in the molecule. Examples of the polyisocyanates include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl diisocyanate, phenylmethane diisocyanate, phenylmethane triisocyanate, and phenylmethane tetraisocyanate.

Also, it is possible to employ dimers and trimers (isocyanurate bonds) of the above-enumerated polyisocyanates. Further, it is possible to employ biuret obtained by a reaction with an amine.

Furthermore, it is possible to employ a polyisocyanate having a urethane bond obtained by a reaction of the aforesaid polyisocyanate compound and a polyol. As the polyol, di-to octa-hydric polyols are preferable, and the above-enumerated polyols are preferable. In cases where a tri-or higher-hydric polyisocyanate is used as the polyisocyanate that is represented by the formula R ³- (NCO) _n+1, it is preferable to employ the aforesaid polyisocyanate having the urethane bond.

The polyether monoalcohol that is represented by the formula HO- (R ⁴-O) _n-R ⁵ and that may be used preferably for obtaining the hydrophobically modified polyether urethane represented by the general formula (2) employed in accordance with the present invention is not limited particularly in so far as the polyether monoalcohol is a polyether of a straight chain, branched chain, or secondary monohydric alcohol. The polyether monoalcohol may be obtained by addition polymerization of the straight chain, branched chain, or secondary monohydric alcohol with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or epichlorohydrin, or with styrene oxide, and the like.

The compound represented by the general formula (2) may be produced by, for example, heating at a temperature of 80℃ to 90℃ for 1 to 3 hours and thereby causing a reaction to occur in the same manner as that in the ordinary reaction of a polyether and an isocyanate.

As the compound represented by the general formula (2) , polyethyleneglycol-240/decyltetradeceth-20/hexamethylene diisocyanate copolymer is preferable. The polyethyleneglycol-240/decyltetradeceth-20/hexamethylene diisocyanate copolymer is referred to also as PEG-240/HDI copolymer bis-decyltetradeceth-20 ether.

According to the present invention, it is preferable that the associative polyurethane thickener be selected from Steareth-100/PEG-136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX 1100, PEG-240/HDI Copolymer Bis-decyltetradeceth-20 ether sold by the company Asahi Denka under the name of Adekanol GT-700, and mixtures thereof.

The amount of the (a) associative thickener in the composition according to the present invention may be less than 5%by weight relative to the total weight of said composition.

The amount of the (a) associative thickener in the composition according to the present invention may be from 0.01 to 10%by weight, preferably from 0.1 to 5%by weight, relative to the total weight of the composition.

Surfactant (b)

The composition of the invention comprises at least one surfactant (b) as defined above. It may also comprise a mixture of several surfactants (b) as defined above.

Two or more (b) surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

As mentioned above, the surfactant (b) according to the invention is chosen from the polyoxyalkylene alkyl ether carboxylic acids or salts thereof of formula (1) as defined above. Such surfactants may also be named “alkyl ether carboxylates” .

Polyoxyalkylene alkyl ether carboxylic acid and salts thereof are compounds produced by substituting polyoxyalkylene alkyl ether with a carboxyl group at the terminal end of the ether, exhibit high degrees of foaming and emulsification, and are known as surfactants used in cosmetics, emulsifiers, solubilizers, dispersants, gelling agents, and detergent bases, for example. Properties of polyoxyalkylene alkyl ether carboxylic acid and salts thereof can be modified by changing pH. Polyoxyalkylene alkyl ether carboxylic acid and salts thereof have excellent stability against hard water, and aqueous solutions thereof are stable to various polyvalent metal ions such as aluminium ions, are gentle to the skin, and have small inhibitory effects on enzymes. Polyoxyalkylene alkyl ether carboxylic acid and salts thereof are thus expected to have various applications.

According to a preferred embodiment, in formula (1) , the number of carbon atoms in R is 4 or more, and from the viewpoints of enhancing suppression of bubbling and obtaining a high degree of emulsification of carboxylic acid or the salt thereof, is preferably 8 or more, more preferably 10 or more, and much more preferably 12 or more. On the other hand, the number of carbon atoms in R is 30 or less, and from the viewpoints of obtaining a high degree of emulsification of carboxylate or the salt thereof, is preferably 22 or less, more preferably 18 or less, and much more preferably 14 or less.

In formula (1) , the number of carbon atoms in R is 4-30, and from the viewpoints of enhancing suppression of bubbling and obtaining high degrees of foaming and emulsification of carboxylic acid or the salt thereof, is preferably 8-22, more preferably 10-18, and much more preferably 12-14. Examples of the hydrocarbon group as R include an alkyl group and an alkenyl group. R may be linear or branched, and may be a primary or secondary group.

From the viewpoints of enhancing suppression of bubbling and obtaining high degrees of foaming and emulsification of carboxylic acid or the salt thereof, R is preferably a linear or branched primary or secondary alkyl or alkenyl group, more preferably a linear primary or secondary alkyl or alkenyl group, much more preferably a linear primary alkyl or alkenyl group, and still more preferably a linear primary alkyl group.

As mentioned above, AO is an alkyleneoxy group having 2-4 carbon atoms, and from the viewpoints of versatility as a raw material and economic efficiency, is preferably an ethyleneoxy group having 2 carbon atoms, and more preferably 80%or more, by mole, of the total of AOs are ethyleneoxy groups.

In formula (1) , n is greater than 5, and from the viewpoints of enhancing suppression of bubbling and obtaining high degrees of foaming and emulsification of carboxylic acid or the salt thereof, is preferably 5-20, and more preferably 5-10.

In formula (1) , n is greater than or equal to 5 and is preferably greater than 6, even greater than 7. According to an advantageous embodiment, n is comprised between 5 and 15, and more preferably between 7 and 10. According to a preferred embodiment, in formula (1) , n is equal to 10.

In the above formula (1) , A' is an alkylene group having 1-3 carbon atoms.

Examples of M as cation include alkali metal ions, alkali earth metal ions, ammonium ions, and hydrogen ions. Examples of alkali metal ions include lithium ions, sodium ions, and potassium ions. Examples of alkali earth metal ions include magnesium ions and calcium ions. From the viewpoints of appropriate viscosity of the suspension or the solution during production and convenience of production processes, M serving as cation is more preferably alkali metal ions or hydrogen atoms. From the viewpoint of reduction of production cost, alkali metal ions are preferably sodium ions or potassium ions, and more preferably potassium ions.

According to a preferred embodiment, in formula (1) :

- R is an alkyl group comprising between 6 and 22, preferably between 10 and 18, carbon atoms,

- AO is an ethyleneoxy group,

- n is comprised between 5 and 15, preferably between 5 and 10,

- A' is a methylene group,

- M is H, and

- m’ is 1.

According to a preferred embodiment, in formula (1) :

- R is an alkyl group comprising between 10 and 18, preferably between 10 and 14, and more preferably between 10 and 12, carbon atoms,

- AO is an ethyleneoxy group,

- n is comprised between 5 and 15, preferably between 5 and 10,

- A' is a methylene group,

- M is H, and

- m’ is 1.

According to an advantageous embodiment, the amount of surfactant (b) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.

According to an embodiment, the ratio between the weight amount of the associative thickener (a) and the surfactant (b) as defined above is comprised between 1 and 10, preferably between 2 and 8, and more preferably between 3 and 7, and most preferably between 5 and 6. According to a preferred embodiment, said ratio is equal to 6.

Hydrophilic gelling agent (c)

The composition of the invention comprises at least one hydrophilic gelling agent (c) as defined above. It may also comprise a mixture of several hydrophilic gelling agents (c) as defined above.

Two or more (c) hydrophilic gelling agents may be used in combination. Thus, a single type of hydrophilic gelling agent or a combination of different types of hydrophilic gelling agents may be used.

As defined above, the hydrophilic gelling agent is chosen from the optionally modified carboxyvinyl polymers.

Depending on the fluidity of the composition sought, one or a plurality of thickeners and/or gelling agents, particularly hydrophilic, i.e. soluble or dispersible in water, may be incorporated in the composition. By way of hydrophilic gelling agents, mention may be made for example of optionally modified carboxyvinyl polymers, such as the products marketed under the trade names Carbopol (CTFA name: carbomer) and Pemulen (CTFA name: Acrylates/C 10-30 akyl acrylate crosspolymer) by Goodrich; polyacrylamides; 2-acrylamido 2-methylpropane sulfonic acid polymers and copolymers (AMPS) , optionally cross-linked and/or neutralized, such as poly (2-acrylamido-2-methylpropanesulfonic acid) marketed by Hoechst under the trade name "Hostacerin AMPS" (CTFA name: Ammonium Polyacryldimethyltauramide) ; cross-linked anionic acrylamide/AMPS copolymers, in the form of a W/O emulsion, such as those marketed under the name SEPIGEL 305 (C.T.F.A. name: Polyacrylamide/C13-14 Isoparaffin/Laureth-7) and under the name SIMULGEL 600 (C.T.F.A. name: Acrylamide /Sodium acryloyldimethyltaurate copolymer /Isohexadecane /Polysorbate 80) by SEPPIC; polysaccharide biopolymers such as xanthan gum, guar gum, alginates, modified celluloses; and mixtures thereof. The quantity of gelling agents is dependent on the end purpose.

According to an embodiment, the modified or unmodified carboxyvinyl polymers may be copolymers derived from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or esters thereof, with at least one ethylenically unsaturated monomer (b) comprising a hydrophobic group.

The term "copolymers" means both copolymers obtained from two types of monomer and those obtained from more than two types of monomer, such as terpolymers obtained from three types of monomer. Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. The term "hydrophobic group or unit" means a radical with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Preferably, these copolymers are chosen from copolymers derived from the polymerization:

- of at least one monomer of formula (I) below:

in which R ₁ denotes H or CH ₃ or C ₂H ₅, i.e. acrylic acid, methacrylic acid or ethacrylic acid monomers, and

- of at least one monomer of unsaturated carboxylic acid (C ₁₀-C ₃₀) alkyl ester type corresponding to the monomer of formula (II) below:

in which R ₂ denotes H or CH ₃ or C ₂H ₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units) , R ₃ denoting a C ₁₀-C ₃₀ and preferably C ₁₂-C ₂₂ alkyl radical.

The unsaturated carboxylic acid (C ₁₀-C ₃₀) alkyl esters are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate, and mixtures thereof.

According to a preferred embodiment, these polymers are crosslinked.

Among the copolymers of this type that will be used more particularly are polymers derived from the polymerization of a monomer mixture comprising:

- essentially acrylic acid,

- an ester of formula (II) described above in which R ₂ denotes H or CH ₃, R ₃ denoting an alkyl radical containing from 12 to 22 carbon atoms, and

- a crosslinking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide.

Among the copolymers of this type, use will more particularly be made of those consisting of from 95%to 60%by weight of acrylic acid (hydrophilic unit) , 4%to 40%by weight of C ₁₀-C ₃₀ alkyl acrylate (hydrophobic unit) and 0 to 6%by weight of crosslinking polymerizable monomer, or alternatively those consisting of from 98%to 96%by weight of acrylic acid (hydrophilic unit) , 1%to 4%by weight of C ₁₀-C ₃₀ alkyl acrylate (hydrophobic unit) and 0.1%to 0.6%by weight of crosslinking polymerizable monomer such as those described previously.

Among the abovementioned polymers, the ones that are most particularly preferred according to the present invention are acrylate/C ₁₀-C ₃₀-alkyI acrylate copolymers (INCI name: Acrylates/C ₁₀-C ₃₀ Alkyl acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR-1, Pemulen TR-2, Carbopol 1382, Carbopol EDT 2020 and Carbopol Ultrez 20 Polymer, and even more preferentially Pemulen TR-2.

Among the modified or unmodified carboxyvinyl polymers, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia

containing 90%solids and 10%water, or Cosmedia

as an inverse emulsion containing about 60%solids, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5) , both sold by the company Cognis.

Mention may also be made of partially neutralized sodium polyacrylates that are in the form of an inverse emulsion comprising at least one polar oil, for example the product sold under the name

EM sold by the company BASF.

The modified or unmodified carboxy vinyl polymers may also be chosen from crosslinked (meth) acrylic acid homopolymers.

For the purposes of the present patent application, the term " (meth) acrylic" means "acrylic or methacrylic" .

Examples that may be mentioned include the products sold by Lubrizol under the names Carbopol 910, 934, 940, 941, 934 P, 980, 981, 2984, 5984 and Carbopol Ultrez 10 Polymer, or by 3V-Sigma under the name

or

Among the modified or unmodified carboxyvinyl polymers, mention may be made in particular of Carbopol (INCI name: carbomer) and Pemulen (CTFA name: Acrylates/C ₁₀-C ₃₀ alkyl acrylate crosspolymer) sold by the company Lubrizol.

According to an embodiment, the amount of the hydrophilic gelling agent (c) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.

(d) Hyaluronic acid or salt thereof

As mentioned above, the composition of the invention comprises hyaluronic acid, preferably in the form of a salt.

"Hyaluronic acid, " HA, also known as "hyaluronan" and "hyaluronate" , as used herein, relates to polymers of disaccharides composed of D-glucuronic acid and D-N-acetylglucosamine, linked together via alternating β-1, 4 and β-1, 3 glycosidic bonds. Hyaluronan can be 25,000 disaccharide repeats in length and range in size from 5,000 to 20,000,000 Da in vivo. The average molecular weight in human synovial fluid is 3-4 million Da. The hyaluronic acid according to the present disclosure includes salts and derivatives of hyaluronic acid, which can be crosslinked or non-crosslinked.

According to an embodiment, the hyaluronic acid or salt thereof has a weight average molecular weight of less than 100,000 Da, preferably comprised between 20,000 Da and 50,000 Da.

According to an embodiment, the hyaluronic acid or salt thereof of the composition according to the invention is a hyaluronic acid or salt thereof with a low molecular weight. According to the invention, a hyaluronic acid or salt thereof with a low molecular weight is a hyaluronic acid or salt thereof with a weight average molecular weight of less than or equal to 60,000 Da.

In particular, the hyaluronic acid or salt thereof of the composition according to the invention has a weight average molecular weight of less than or equal to 60,000 Da, preferably of less than or equal to 50,000 Da, for example varying from 10,000 Da to 60,000 Da, preferably from 15,000 Da to 50,000 Da, and more particularly from 20,000 Da to 50,000 Da.

Advantageously, the the hyaluronic acid or salt thereof of the composition according to the invention is the sodium hyaluronate of low molecular weight sold by the company Soliance under the name

According to an embodiment, the hyaluronic acid is in the form of a salt.

The salts of hyaluronic acid may be chosen from the alcaline salts such as sodium or potassium salts, or may be zinc salts, silver salts, and mixtures therof.

Preferably, the composition of the invention comprises sodium hyaluronate.

According to an embodiment, the amount of hyaluronic acid or salt thereof (d) is less than 0.3%by weight, and preferably comprised between 0.01%and 0.3%by weight, relative to the total weight of said composition.

According to an embodiment, the ratio between the total weight amount of the associative thickener (a) and of the surfactant (b) as defined above and the weight amount of hyaluronic acid or salt thereof (d) (weight of (a) + (b) /weight of (d) ) (ratio r) is comprised between 10 and 40, and preferably between 11.5 and 35.

A preferred composition according to the invention is a composition wherein:

- the ratio between the weight amount of the associative thickener (a) and the surfactant (b) as defined above is comprised between 1 and 10, preferably between 2 and 8, and more preferably between 3 and 7, and most preferably between 5 and 6; and

- the ratio between the total weight amount of the associative thickener (a) and of the surfactant (b) as defined above and the weight amount of hyaluronic acid or salt thereof (d) (weight of (a) + (b) /weight of (d) ) is comprised between 10 and 40, and preferably between 11.5 and 35.

Oil (e)

The composition of the invention may comprise one single oil or a mixture of several oils.

The oil can be volatile or non-volatile.

The term “oil” means a water-immiscible non-aqueous compound that is liquid at room temperature (25℃) and at atmospheric pressure (760 mmHg) .

The term “non-volatile oil” means an oil that remains on keratin materials at room temperature and atmospheric pressure for at least several hours and that especially has a vapour pressure of less than 10 ^-3 mmHg (0.13 Pa) . A non-volatile oil may also be defined as having an evaporation rate such that, under the conditions defined previously, the amount evaporated after 30 minutes is less than 0.07 mg/cm ².

These oils may be of plant, mineral or synthetic origin.

Preferably, said oil is chosen from hydrocarbonated, silicone or fluorinated oils.

The term “hydrocarbon-based oil” or “hydrocarbonated oil” means an oil formed essentially from, or even constituted by, carbon and hydrogen atoms, and optionally O and N atomes, and free of Si and F heteroatoms. Such oil can contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The term “silicone oil” means an oil containing at least one silicon atom, especially containing Si-O groups.

The term “fluorinated oil” means an oil containing at least one fluorine atom,

Preferably, the oil is selected from hydrocarbonated oils, preferably non-volatile.

Mention may be made, for example, of hydrocarbon-based volatile oils having from 8 to 16 carbon atoms and mixtures thereof and especially branched C8-C16 alkanes such as C8-C16 isoalkanes (also known as isoparaffins) , isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permethyl, C8-C16 branched esters such as isohexyl neopentanoate and mixtures thereof. Isododecane or isohexadecane are preferred.

As non-volatile oils, mention may be made of:

- hydrocarbon-based oils of mineral or synthetic origin, such as linear or branched hydrocarbons, for instance liquid paraffin or its derivatives, liquid petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam sold by the company Nippon Oil Fats, squalane of synthetic or plant origin;

- hydrocarbon-based oils of plant origin based on triglycerides made up of esters of fatty acids and of glycerol, the fatty acids of which may have varied chain lengths, it being possible for the latter to be linear or branched, and saturated or unsaturated, in particular the triglycerides of a fatty acid containing in particular from 4 to 22 carbon atoms, for instance heptanoic acid triglycerides, octanoic acid triglycerides and capric/caprylic acid triglycerides, or else hydroxylated triglycerides, such as sweet almond oil, calophyllum oil, palm oil, grape seed oil, sesame oil, arara oil, rapeseed oil, sunflower oil, cottonseed oil, apricot oil, castor oil, alfalfa oil, marrow oil, blackcurrant oil, macadamia oil, muscat rose oil, hazelnut oil, coriander oil, avocado oil, jojoba oil, olive oil, cereal (maize, wheat, barley, rye) germ oil, shea butter oil; esters of fatty acids, in particular having from 4 to 22 carbon atoms, and in particular of octanoic acid, of heptanoic acid, of lanolic acid, of oleic acid, of lauric acid or of stearic acid, such as propylene glycol dioctanoate, propylene glycol monoisostearate, polyglyceryl-2 diisostearate, neopentyl glycol diheptanoate;

- synthetic esters of formula R ₁COOR ₂ in which _R1 represents the residue of a linear or branched higher fatty acid containing from 7 to 40 carbon atoms and R ₂ represents a branched hydrocarbon-based chain containing from 3 to 40 carbon atoms, for instance purcellin oil (cetostearyl octanoate) , isononyl isononanoate, C12 to C15 alcohol benzoate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyldodecyl benzoate, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, 2-diethylhexyl succinate, diisostearyl malate, isodecyl neopentanoate, hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, glyceryl or diglyceryl triisostearate; diethylene glycol diisononanoate; pentaerythritol esters; esters of aromatic acids and of alcohols containing from 4 to 22 carbon atoms, in particular tridecyl trimellitate;

- C8-C26 higher fatty acids such as myristic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid;

- C8-C26 higher fatty alcohols such as oleyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol or octyldodecanol;

- synthetic ethers containing at least 7 carbon atoms;

- silicone oils such as linear polydimethylsiloxanes (PDMSs) that are liquid at ambient temperature, and that are optionally phenylated, such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyl-diphenyltrisiloxanes, liquid 2-phenylethyltrimethyl-siloxysilicates, optionally substituted with aliphatic and/or aromatic groups, for instance alkyl, alkoxy or phenyl groups, which are pendent and/or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms, and optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups; polysiloxanes modified with fatty acids or fatty alcohols or polyoxyalkylenes, such as dimethicone copolyols or alkyl methicone copolyols; liquid fluorosilicones;

- and mixtures thereof.

Preferably, the composition of the invention comprises at least one non-volatile oil. Preferably, said composition comprises at least one synthetic ester as defined above, such as isononyl isononanoate.

According to an embodiment, the amount of oil (e) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.

Additional ingredients

The composition of the invention may comprise at least one additive, such as fragrances, preservatives, active agents, vitamins, pH regulators and/or fillers.

A person skilled in the art can adjust the type and amount of additives present in the compositions according to the invention by means of routine operations, so that the desired cosmetic properties and stability properties for these compositions are not affected by the additives.

Methods and use

According to an embodiment, the present invention relates to a non-therapeutic method for treating a keratin material, comprising the step of applying the composition of the present invention to the keratin material.

Preferably the present invention relates to a method for caring for the skin, comprising the step of applying the composition of the present invention to the skin.

The following examples serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Compositions according to the present invention are prepared by combining the water and oil phase ingredients, in a vessel mixing the polymers to form a homogeneous phase first, and then introducing oil phase to make it disperse evenly. Add the surfactant of required amount, the pH value is adjusted to around 4.6.

The following compositions according to the invention are prepared.

Viscosity evaluation

The viscosity of each of the compositions was measured through the method attached below at room temperature (M3 stirrer) . Each composition was evaluated in accordance with the following criteria.

Viscosity of 15 UD or more: Good

Viscosity of less than 15 UD: Poor

Note: The viscosity, which is shown ‘too low’ , means the result is below the limit of detection, and cannot be read under this experimental condition.

These results show that the use of Laureth-11 carboxylic acid is preferred in comparison with the use of Laureth-5 carboxylic acid, concerning the viscosity (when comparing example 3 and comparative example 5) .

These results also show that the use of an amount of surfactant, in particular Laureth-11 carboxylic acid, of less than 0.3%is preferred in comparison with the use of an amount of 0.4%, concerning the viscosity (when comparing example 3 and example 4) .

These results also show that the use of a composition wherein the ratio r (weight of (a) + (b) /weight of (d) ) as defined above, is greater than 10 is preferred in comparison with the use of a composition wherein the ratio r is less than 10 concerning the viscosity (when comparing example 3 and example 4) .

Sensory effects

3 compositions according to the invention, examples 1 and example 2 as mentioned above, as well as example 7 (as shown in the below table) , were evaluated through corridor test in terms of slimy feeling, stickiness and penetration.

Slimy feeling

6 panelists applied each of the samples of the same amount onto the skin, and scored slimy feeling in accordance with the following criteria.

5: Completely no slimy feeling

4: Not slimy

3: Not very slimy

2: Very slimy

1: Excessively slimy

Average score of 3 or more: Good

Average score of less than 3: Poor

Stickiness

5: Completely no stickiness

4: Not sticky

3: Not very sticky

2: Very sticky

1: Excessively sticky

Average score of 3 or more: Good

Average score of less than 3: Poor

Penetration Feeling

5: Very fast penetration

4: Fast penetration

3: Not slow penetration

2: Slow penetration

1: Very slow penetration

Average score of 3 or more: Good

Average score of less than 3: Poor

	Ex. 1	Ex. 2	Ex. 7
Slimy feeling	Good	Good	Good
Stickiness	Good	Good	Good
Penetration feeling	Good	Good	Good

These results show that the compositions according to the invention have very satisfactory sensory effects, especially concerning the slimy feeling, the stickiness and the penetration feeling.

Claims

A composition, preferably a cosmetic composition, comprising:

(a) at least one associative polymeric thickener chosen from the group consisting of polyurethane/polyethers comprising in their chain at least one polyoxyethylenated hydrophilic block and at least one hydrophobic block containing at least one sequence chosen from aliphatic sequences, cycloaliphatic sequences, and aromatic sequences;

(b) at least one surfactant chosen from the polyoxyalkylene alkyl ether carboxylic acids or salts thereof, having the following formula:

{RO- (AO) _n-A'-COO} _m’M

wherein:

- R is a hydrocarbon group having from 4 to 30 carbon atoms,

- AO is an alkyleneoxy group having from 2 to 4 carbon atoms,

- n is an average addition mole number of AO and is greater than 5,

- A' is an alkylene group having from 1 to 3 carbon atoms,

- M is a cation or is a hydrogen atom, and

- m’ is a valence of M;

(c) at least one hydrophilic gelling agent chosen from the optionally modified carboxyvinyl polymers;

(d) hyaluronic acid or a salt thereof; and

(e) at least one oil;

said composition being in the form of oil dispersed in a gel phase.
The composition of claim 1, wherein the associative polymeric thickener (a) is chosen from the group consisting of polyurethane/polyethers comprising at least two hydrocarbon-based lipophilic chains having from 8 to 30 carbon atoms, separated by a hydrophilic block, and wherein the hydrocarbon-based chains are chosen from pendent chains and chains at the end of the hydrophilic block.
The composition of claim 1 or 2, wherein the associative polymeric thickener (a) is a compound having the following formula (2) :

R ¹- { (O-R ²) _k-OCONH-R ³ [-NHCOO- (R ⁴-O) _n-R ⁵] _h} _m

wherein R ¹ represents a hydrocarbon group, R ² and R ⁴ independently represent alkylene groups having 2 to 4 carbon atoms, which alkylene groups may be identical or different from each other, or a phenylethylene group, R ³ represents a hydrocarbon group, which may optionally have a urethane bond, R ⁵ represents a branched chain or secondary hydrocarbon group, m represents a number of at least 2, h represents a number of at least 1, k represents a number within the range of 1 to 500, and n represents a number within the range of 1 to 200.
The composition of any of claims 1 to 3, wherein the amount of the associative polymeric thickener (a) is less than 5%by weight relative to the total weight of said composition.
The composition of any of claims 1 to 4, wherein the amount of the associative polymeric thickener (a) is comprised between 0.01%and 10%by weight, preferably from 0.1%to 5%by weight, relative to the total weight of said composition.
The composition of any one of claims 1 to 5, wherein, in formula (1) :

- R is an alkyl group comprising between 6 and 22, preferably between 10 and 18, carbon atoms,

- AO is an ethyleneoxy group,

- n is comprised between 5 and 15, preferably between 5 and 10,

- A' is a methylene group,

- M is H, and

- m’ is 1.
The composition of any one of claims 1 to 6, wherein, in formula (1) :

- R is an alkyl group comprising between 10 and 18, preferably between 10 and 14, and more preferably between 10 and 12, carbon atoms,

- AO is an ethyleneoxy group,

- n is comprised between 5 and 15, preferably between 5 and 10,

- A' is a methylene group,

- M is H, and

- m’ is 1.
The composition of any of claims 1 to 7, wherein the amount of surfactant (b) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.
The composition of any of claims 1 to 8, wherein the amount of the hydrophilic gelling agent (c) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.
The composition of any of claims 1 to 9, wherein the hyaluronic acid or salt thereof has a weight average molecular weight of less than 100,000 Da, preferably comprised between 20,000 Da and 50,000 Da.
The composition of any of claims 1 to 10, wherein the hyaluronic acid is in the form of a salt, preferably is sodium hyaluronate.
The composition of any of claims 1 to 11, wherein the amount of hyaluronic acid or salt thereof (d) is less than 0.3%by weight, and preferably comprised between 0.01%and 0.3%by weight, relative to the total weight of said composition.
The composition of any of claims 1 to 12, wherein the ratio between the weight amount of the associative thickener (a) and the surfactant (b) is comprised between 1 and 10, preferably between 2 and 8, and more preferably between 3 and 7, and most preferably between 5 and 6.
The composition of any of claims 1 to 13, wherein the ratio between the total weight amount of the associative thickener (a) and of the surfactant (b) and the weight amount of hyaluronic acid or salt thereof (d) is comprised between 10 and 40, and preferably between 11.5 and 35.
The composition of any of claims 1 to 14, wherein the amount of oil (e) is comprised between 0.01%and 10%by weight, preferably from 0.05%to 5%by weight, and more preferably from 0.1%to 2%by weight, relative to the total weight of said composition.
A method for caring for the skin, comprising the application to the skin of the composition of any one of claims 1 to 15.