WO2018148933A1

WO2018148933A1 - Cosmetic mask and process

Info

Publication number: WO2018148933A1
Application number: PCT/CN2017/073942
Authority: WO
Inventors: Kun Yu
Original assignee: L'oreal
Priority date: 2017-02-17
Filing date: 2017-02-17
Publication date: 2018-08-23
Also published as: CN110234310B; CN110234310A

Abstract

A cosmetic mask for topical application which comprises a water-insoluble substrate and a composition which comprises in an aqueous phase a) at least one polyol; and b) at least one diethanolammonium derivative of formula (I), wherein all numbers and groups are as defined in the specification. The cosmetic mask provides long-term hydration benefit to the skin.

Description

COSMETIC MASK AND PROCESS

TECHNICAL FIELD

The present invention relates to a cosmetic mask for topical application which comprises a water-insoluble substrate and a composition. Further， the present invention relates to the corresponding non-therapeutic cosmetic process involving use of same cosmetic mask.

BACKGROUND ART

A sheet which is formed by a substrate sheet such as a non-woven fabric sheet impregnated with a lotion or the like has be used for cosmetic treatments of the skin， in particular the face. Such masks for cosmetic treatment are disclosed， for example in the patent application WO 02/062132.

It is also known to use actives in the cosmetic products for treating or caring for the skin， such as hydration， whitening， anti-aging， pore minimizing， freshness， smoothness， softness， and so on. Among which， skin conditioning effect， such as hydration， is always an interest to consumers around the world. Cosmetic masks impregnated with lotion containing skin conditioning agents are suitable for applying on the skin to provide especially skin hydration effect. Answering to this demand， various cosmetic masks have been developed.

However， the up-to-date cosmetic masks are still to be improved especially in terms of long-term hydration effect. Specifically， with the up-to-date cosmetic masks， repeated application in a short time interval has to be done if one intends for a long-term (e.g. 6 hours) hydration feeling on the skin， which is unfavourable.

AIMS OF THE INVENTION

Therefore， it is necessary to provide cosmetic masks， which are capable， upon application， of providing long-term hydration effect to the skin.

The cosmetic mask according to the present invention especially makes it possible to give the keratin material， preferably the skin， long-term hydration feeling after application， i.e. the hydration effect persists for several hours after the application of the cosmetic mask， even if the keratin materials， such as the skin， are no longer in contact with the cosmetic mask according to the present invention.

DISCLOSURE OF INVENTION

Surprisingly， the inventors have discovered that a specific combination comprising a) at least one polyol and b) at least one diethanolammonium derivative of formula (I) below can meet the abovementioned requirement as to the long-term hydration effect.

In the formula (I) ，

R₁ and R₂ independently denote：

(i) a linear or branched C₁-C₁₂ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ； said radical being optionally substituted with a group -COR； or

(ii) an aralkyl radical C_mH_2mAr such that m denotes an integer ranging from 1 to 6 and Ar denotes an aryl radical optionally substituted with a group -COR；

R denotes a group -OR’ or -NR’ R” where R’ and R” independently denote hydrogen or a linear or branched C₁-C₆ alkyl radical which is saturated or unsaturated with an ethylenic double bond；

n is equal to 0 or 1；

the electrical neutrality of said compounds being provided by an organic or inorganic external anion X^- (n＝l) or internally (n＝0) when a single COOH radical is present and forms a CO₂ ^-radical；

it being understood that when R₁ denotes a methyl radical and R₂ denotes a methyl radical substituted with a -COOH group， then n＝1.

The inventors further discovered that the specific combination provides the long-term hydration effect to the most significant extent in a cosmetic mask use， as compared with other cosmetic use like toner， lotion or cream.

The other subject of the present invention is a non-therapeutic cosmetic process for caring for the keratin materials， preferably the skin， and more preferably the facial skin， comprising the step of applying on the keratin material the cosmetic mask of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Throughout the description， including the claims， the term ″comprising a″ should be understood as being synonymous with ″comprising at least one″ ， unless otherwise mentioned. Moreover， the expression ″at least one″ used in the present description is equivalent to the expression ″one or more″ .

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 ... ″ . Further， the terms ″between... and... ″ and ″ranging from... to... ″ should be understood as being inclusive of the limits， unless otherwise specified.

Preferably， the “keratin material” according to the present invention is the skin. By “skin” ， we intend all the body skin. Still preferably， the keratin material is the face， or neck， especially the facial skin.

By “topical application” ， it meant that the composition is applied or spread onto the surface of the keratin material， such as the skin.

The present invention relates to a cosmetic mask for caring for keratin materials， which comprises a water-insoluble substrate and a composition which comprises in an aqueous phase a) at least one polyol； and b) at least one diethanolammonium derivative.

The present cosmetic mask provides long-term hydration benefit to the skin. The hydration feeling can persist for several hours after the application of the cosmetic mask， for example 6 hours.

Water insoluble substrate

According to the present invention， the cosmetic mask comprises a water insoluble substrate. For the purpose of the invention， the term “water insoluble” means that the substrate is not dissolvable in water， nor does it breaks apart upon immersion in water.

The material of the substrate according to the present invention is not limited， and therefore any material can be used for preparing. Two or more materials may be used. Typically， the material may be a woven or non-woven fabric made of natural fibers such as cotton， pulp， bamboo and cellulose fibers， semi-natural fibers such as viscose rayon fibers and synthetic fibers such as polyester fibers， polyethylene terephthalate fibers， polyethylene fibers， and polypropylene fibers. Two or more selected from the above fibers may be used in combination.

Alternatively， the material may be a film or sheet made from at least one selected from synthetic polymers such as polyethylenes and polyvinylalcohols， semi-synthetic polymers such as bio-celluloses and alginates， and natural polymers such as polysaccharides (e.g.， carageenan and xanthan gum) ， mucopolysaccharides (e.g.， hyaluronic acid and sodium hyaluronate) ， polypeptides (e.g.， γ-polyglutamic acid) and proteins (e.g.， gelatin and collagen) . The film or sheet may be in the form of a gel or a jelly which may be transparent， translucent or opaque. Two or more selected from the above substances may be used in combination.

The substrate can be made into a wide variety of shapes and forms such as flat pads， thick pads， thin sheets of irregular thickness， depending on the desired use and characteristic of the mask. The substrate is typically designed to fit the area of the skin to which topical application is desired. For example， when the mask is applied to the face， the substrate is designed to correspond to the shape of the face avoiding the eye， nostril， and mouth areas， as necessary. Non-limiting examples of the substrates useful in the present invention are described， for example， in the patent application WO 02/062132， or EP 2489286A.

Composition

The present invention comprises， in addition to the substrate， a composition. The composition impregnates， coats， or is otherwise in contact with the water insoluble substrate.

Preferably， the weight ratio of the water insoluble substrate and the composition ranges from 1∶3 to 1∶30. More preferably， the weight ratio of the water insoluble substrate and the composition ranges from 1∶10 to 1∶25.

In the patent application， unless specifically mentioned otherwise， the contents are expressed on a weight basis relative to the total weight of the composition.

The composition of the present invention comprises in an aqueous phase at least a) at least one polyol； and b) at least one diethanolammonium derivative.

Polyol

The compositions of the present invention comprise at least one polyol， which is essential for the long-term hydration effect.

For the purposes of the present invention， the term “polyol” should be understood as meaning any organic molecule comprising at least two free hydroxyl groups.

Preferably， a polyol in accordance with the present invention is present in liquid form at room temperature.

A polyol that is suitable for use in the invention may be a compound of linear or branched， saturated or unsaturated alkyl type， bearing at least two -OH functions， especially two or three -OH functions.

The polyols that are advantageous according to the present invention are compounds of the following formula (A) ， such as glycerol， propylene glycol， butylene glycol， pentylene glycol or hexylene glycol.

wherein Ra denote a linear or branched C₂-C₂₀ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ， preferably a linear or branched C₂-C₁₀ alkyl radical or a linear or branched C₂-C₄ alkyl radical， and a denotes an integer ranging from 2 to 4， preferably an integer ranging from 2 to 3.

According to one particular embodiment， for improved long-term hydration effect， the compositions of the invention comprise at least glycerol as the polyol.

According to one particular embodiment， for improved long-term hydration effect， the compositions of the invention comprise the combination of a glycol and glycerol. As the glycol， the compound of formual (A) wherein a denotes 2 can be exemplified. Herein， the weight ratio of glycerol to the glycol may be from 1∶10 to 10∶1， preferentially from 1∶5 to 5∶1， and even more preferentially from 1∶2 to 1∶1.

A composition of the invention may comprise at least 10％by weight， preferably at least 15％by weight and better still from 15％to 45％by weight of the at least one polyol relative to the total weight of the composition.

Diethanolammonium derivatives

The compositions of the present invention comprise at least one diethanolammonium derivative， which is essential for the long-term hydration effect.

The diethanolammonium derivatives in accordance with the present invention correspond to formula (I) below， and also include the optical isomers and/or geometrical isomers thereof：

in which：

R₁ and R₂ independently denote：

(ii) an aralkyl radical C_mH_2mAr such that m denotes an integer ranging from 1 to 6 and Ar denotes an aryl radical such as phenyl， naphthyl， furyl or indolyl， optionally substituted with a group-COR；

R denotes a group-OR’ or-NR’ R” where R’ and R” independently denote hydrogen or a linear or branched C₁-C₆ alkyl radical which is saturated or unsaturated with one or more ethylenic double bonds；

n is equal to 0 or 1；

the electrical neutrality of said compounds being provided by an organic or inorganic external anion X- (n＝1) or in the form of an internal salt (n＝0) when a single COOH radical is present and forms a CO₂ ^-radical (presence of a single COR radical with R＝ OR’ and R’ ＝ H， namely of a single CO₂H radical in CO₂ ^-form where the anion X-is non existent) ；

it being understood that when R₁ denotes a methyl radical and R₂ denotes a methyl radical substituted with a-COOH group， then n ＝ 1.

Advantageously， the anion X^-is chosen such that the compound of formula (I) is physiologically acceptable.

In a particular embodiment， the diethanolammonium derivatives according to the invention correspond to the formula (I) as mentioned above in which R₁ and R₂ independently denote：

(i) a linear or branched C₁-C₁₂ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ； said radical being optionally substituted with a group-COR； or

(ii) an aralkyl radical C_mH_2mAr such that m denotes an integer ranging from 1 to 6 and Ar denotes an aryl radical chosen among phenyl， naphthyl， or furyl， optionally substituted with a group-COR； and more particularly the aryl radical group is phenyl optionally substituted with a group-COR.

For the purposes of the invention， the term ″physiologically acceptable compound″ is intended to denote any compound of formula (I) or (II) or (III) that is suitable for the topical administration of a composition in which it is present.

A physiologically acceptable compound of formula (I) or (II) or (III) is preferentially a compound of formula (I) or (II) or (III) that has no unpleasant odour or appearance and that is entirely compatible with the topical administration route. In the present case in which the composition is intended for topical administration， i.e. by application to the surface of the keratin material under consideration， such a compound is considered in particular to be physiologically acceptable when it does not cause any discomfort， such as stinging or tautness that is unacceptable to the user.

X^-denotes an organic or mineral anion.

The term ″organic anion X^-″ means the anionic forms of organic compounds bearing one or more acid functions (in particular carboxylic acid or sulfonic acid) such as the anionic forms of amino acids (carboxylates such as aspartate) ， or methanesulfonate， para-toluenesulfonate， camphorsulfonate， tartrate， citrate， acetate， levulinate or methosulfate.

In an embodiment when ″organic anion X^-″ denotes an anionic form of organic compounds bearing one or more carboxylic acid functions， it is chosen among compounds of formula A or B or C as defined below：

wherein，

Ra₁ means a hydrogen atom or an a linear or branched alkyl radical C₁-C₁₈，

Ra₂ means a hydrogen atom or an a linear or branched alkyl radical C₁-C₁₈ or an a linear or branched alkylcarbonyl radical C₁-C₁₈，

Ra₁ and Ra₂ can together form a five to eight membered ring with the N atom bearing them，

Ra₂ and Ra₃ can together form a five membered ring of formula A1 or A2 with the N atom bearing them.

Ra₃ is chosen among the radical described below

Preferentially

Ra₁ means a hydrogen atom，

Ra₂ means a hydrogen atom or an a linear or branched alkyl radical C₁-C₈ or an a linear or branched alkylcarbonyl radical C₁-C₈，

Ra₃ is chosen among the radical described below

R_b1 means a linear or branched alkyl radical C₁-C₆ preferably C₁-C₄ substituted by at least one OH radical preferably one OH radical or an saturated heterocycle of 5 to 8 membered ring containing one atom of N， S， O and substituted by at least one OH radical preferably one OH radical.

Preferentially，

R_b1 means a linear or branched alkyl radical C₁-C₄ substituted by one OH radical or a pyrrolidine containing substituted by one OH radical.

More preferably，

R_b1 is chosen among -CH₂OH， -CH (OH) Me，

R_c1 means a linear or branched alkyl radical C₁-C₁₈ or a linear or branched alkyl carbonyl C_1-18，

Preferentially， R_c1 fits with compounds described in FR3012960 (as the anionic part) and FR2581542.

More preferably， R_c1 is corresponding to the 2 compounds described below

When X^-denotes an anionic form of organic compounds bearing one or more carboxylic acid functions it could also be chosen among anionic forms of compounds described in either FR2835525 or FR2810033.

In this embodiment， preferred X^-are described below：

Preferentially when X^-denotes an anionic form of organic compounds bearing one or more carboxylic acid functions， they are chosen among compounds of formula B.

In another embodiment， the term ″mineral anion X^-″ means， for example， halides， in particular chloride， bromide or iodide， sulfates， phosphates， hydrogen phosphates， dihydrogen phosphates， carbonate or hydrogen carbonate.

Preferably， X^-is an anion chosen from halides， in particular chloride， bromide or iodide， sulfates， phosphates， hydrogen phosphates， dihydrogen phosphates， carbonate， hydrogen carbonate， methanesulfonate， para-toluenesulfonate， camphorsulfonate， tartrate， citrate， acetate， levulinate or aspartate.

X^-denotes more preferentially an inorganic anion and even more preferentially a halide， in particular bromide， iodide or chloride， levulinate or else a methosulfate anion.

Most particularly， X^-is an anion chosen from halides， in particular chloride， bromide or iodide.

As examples of compounds of formula (I) ， mention may be made of the following compounds：

where X^- denotes an organic or inorganic anion as previously indicated.

In particular， the compounds of formula (I) are chosen from the following compounds (1) to (24) and most particularly compounds (2) ， (3) ， (13) and (14) ， and even more preferentially compound (2) ：

According to a preferred variant of the invention， the compounds of formula (I) are such that R₁ and R₂ independently denote a linear or branched C₁-C₈ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ， and which is optionally substituted with a group -COR where R has the same meaning as indicated previously.

According to this variant， the compounds that will even more particularly be chosen are those for which R₁ and R₂ independently denote a linear or branched， saturated C₁-C₈ alkyl radical which is optionally substituted with a group -COR where R denotes a radical chosen from -OR’and -NR’R”， with R’and R” independently denoting hydrogen or a linear or branched， saturated C₁-C₆ alkyl radical.

According to this variant， the compounds of formula (I) particularly preferably denote compounds (a) ， (b) ， (d) and (f) described previously and even more preferentially compounds (1) ， (2) ， (3) ， (4) ， (5) ， (7) ， (8) ， (10) and (11) described previously.

The diethanolammonium derivatives in accordance with the invention may be obtained by quaternization of the corresponding amine in the presence of an excess of alkyl halide. Moreover， certain ethanolammonium derivatives that form the subject of the present invention are commercially available. For example， compound (1) is available from the supplier Acros Organics (France) under the reference 402530250.

In the case of the symmetrical compounds of formula (I) ， i.e. in which the radicals R₁ and R₂ are identical， N， N-diethanolamine， dissolved in an organic solvent (such as methanol， ethanol， tetrahydrofuran， N， N-dimethylformamide， etc. ) is treated with an excess of alkyl halide R₁-X in which R₁ and X have the same meanings indicated previously in formula (I) ， at a temperature ranging from 0 to 150℃ for 1 to 24 hours according to the reaction scheme below：

In the case of the asymmetrical compounds of formula (I) ， i.e. in which the radicals R₁ and R₂ are different， N， N-diethanolamine， dissolved in an organic solvent (such as methanol， ethanol， tetrahydrofuran， N， N-dimethylformamide， etc. ) is treated with one equivalent of alkyl halide R1-X in which R₁ and X have the same meanings indicated previously in formula (I) ， at a temperature ranging from 0 to 150℃ for 1 to 24 hours.

The product resulting from this first alkylation is then dissolved in an organic solvent (such as methanol， ethanol， tetrahydrofuran， N， N-dimethylformamide， etc. ) and treated with an excess of alkyl halide R₂-X in which R₂ and X have the same meanings indicated previously in formula (I) ， at a temperature ranging from 0 to 150℃ for 1 to 24 hours.

In the case where R₁ is methyl， the intermediate N-methyl-N， N-diethanolamine is commercially available (for example Acros Organics France) and it can be used directly in the second step.

The at least one diethanolammonium derivative is preferably present in amounts ranging from 0.01％to 10％by weight， preferentially from 0.02％to 9％and even more particularly from 0.1％to 8％by weight， in particular from 1％to 7％by weight and more particularly from 2％to 6％by weight relative to the total weight of the composition.

According to one particular embodiment， for improved long-term hydration effect， the weight ratio of the at least one diethanolammonium derivative to the at least one polyol is from 3∶1 to 1∶15， preferentially from 2∶1 to 1∶10， and even more preferentially from 1∶1 to 1∶6.

Aqueous phase

The composition according to the invention comprises an aqueous phase.

The aqueous phase comprises water.

The aqueous phase may also comprise water-miscible organic solvents other than polyols mentioned hereinbefore (at room temperature： 25℃) ， for instance monoalcohols containing from 2 to 6 carbon atoms， such as ethanol or isopropanol； glycol ethers (especially containing from 3 to 16 carbon atoms) such as mono-， di-or tripropylene glycol (C₁-C₄) alkyl ethers， mono-， di-or triethylene glycol (C₁-C₄) alkyl ethers， and mixtures thereof.

The aqueous phase may also comprise any water-soluble or water-dispersible compound that is compatible with an aqueous phase， such as film-forming polymers， preservatives or surfactants such as EDTA， and mixtures thereof.

In particular， a composition of the invention may comprise the aqueous phase in a content ranging from 10％to 99.9％by weight， especially from 50％to 99.9％and more particularly from 70％to 99.9％by weight relative to the total weight of the composition.

According to a preferred embodiment， water is present in an amount ranging from 20％to 90％by weight， preferably 30％to 85％by weight， relative to the total weight of the composition.

Hydrophilic gelling agents

The composition according to the present invention may comprise at least one hydrophilic gelling agent.

For the purposes of the present invention， the term ″hydrophilic gelling agent″ means a compound that is capable of gelling the aqueous phase of the compositions according to the present invention.

The gelling agent that may be used according to the present invention may especially be characterized by its capacity to form in water， beyond a certain concentration C*， a gel characterized by oscillatory rheology (μ ＝ 1 Hz) by a flow threshold τc at least equal to 10 Pa. This concentration C*may vary widely according to the nature of the gelling polymer under consideration.

The gelling agent may be present in the composition in an amount that is sufficient to adjust the stiffness modulus G* (1 Hz， 25℃) of the composition to a value greater than or equal to 10 000 Pa and especially ranging from 10 000 Pa to 100 000 Pa.

The method for measuring these parameters of the composition is described， for example， in patent application EP 1 534 218 in the paragraph entitled ″rheological characterization″ .

It is understood that the alkali metal， alkaline-earth metal or transition metal salts， such as zinc stearate， zinc myristate or magnesium stearate are not considered within the meaning of the present invention as hydrophilic gelling agents. Specifically， such compounds serve first and foremost as fillers.

Thickening fillers

Thickening fillers may fulfil this function as aqueous-phase gelling agents. Such fillers preferably comprise a clay that is capable of swelling in water and/or hollow mineral or organic microspheres.

The clay present in the composition according to the present invention is clay that is capable of swelling in water； this clay swells in water and forms after hydration a colloidal dispersion.

Clays are products that are already well known per se， which are described， for example， in the publication Minéralogie des argiles [Mineralogy of Clays] ， S. Caillère， S. Hénin， M. Rautureau， 2nd Edition 1982， Masson.

Clays are silicates containing a cation advantageously chosen from calcium， magnesium， aluminium， sodium， potassium and lithium cations， and mixtures thereof.

Examples of such products that may be mentioned include clays of the smectite family such as montmorillonites， hectorites， bentonites， beidellites and saponites， and also of the vermiculite， stevensite and chlorite families.

These clays may be of natural or synthetic origin. Clays that are cosmetically compatible and acceptable with the skin are preferably used.

According to one particularly preferred embodiment of the present invention， the clay used， that is capable of swelling in water， is chosen from montmorillonites， hectorites， bentonites， beidellite and saponites， and more particularly hectorites and bentonites.

As clays that are capable of swelling in water which may be used according to the present invention， mention may be made of synthetic hectorites (also known as laponites) ， for instance the products sold by the company Laporte under the name Laponite XLG， Laponite RD and Laponite RDS (these products are sodium magnesium silicates and in particular sodium lithium magnesium silicates) ； bentonites， for instance the product sold under the name Bentone HC by the company Rheox； magnesium aluminium silicates， especially hydrated， for instance the product sold by the Vanderbilt Company under the name Veegum Ultra， or calcium silicates and especially the product in synthetic form sold by the company under the name Micro-cel C.

The clay may be present in the composition in a content ranging from 0.5％to 5％by weight and better still from 1％to 3％by weight relative to the total weight of the composition.

Polymeric hydrophilic thickeners

More particularly， this gelling agent may be chosen from the following polymeric thickeners：

- acrylic or methacrylic acid homopolymers or copolymers or salts and esters thereof and in particular the products sold under the names Versicol F or Versicol K by the company Allied Colloid， Ultrahold 8 by the company Ciba-Geigy， and polyacrylic acids of Synthalen K type， and salts， especially sodium salts， of polyacrylic acids (corresponding to the INCI name sodium acrylate copolymer) and more particularly a crosslinked sodium polyacrylate (corresponding to the INCI name sodium acrylate copolymer (and) caprylic/capric triglycerides) sold under the name Luvigel EM by the company，

- -copolymers of acrylic acid and of acrylamide sold in the form of the sodium salt thereof under the names Reten by the company Hercules， the sodium polymethacrylate sold under the name Darvan No. 7 by the company Vanderbilt， and the sodium salts of polyhydroxycarboxylic acids sold under the name Hydagen F by the company Henkel，

- - polyacrylic acid/alkyl acrylate copolymers， preferably modified or unmodified carboxyvinyl polymers； the copolymers most particularly preferred according to the present invention are acrylate/C₁₀-C₃₀-alkylacrylate copolymers (INCI name： Acrylates/C_10-30 Alkyl acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR1， Pemulen TR2， Carbopol 1382 and Carbopol ETD 2020， and even more preferentially Pemulen TR-2；

- AMPS (polyacrylamidomethylpropanesulfonic acid partially neutralized with aqueous ammonia and highly crosslinked) sold by the company Clariant，

- -AMPS/acrylamide copolymers such as the products Sepigel or Simulgel sold by the company SEPPIC， especially a copolymer of INCI name Polyacrylamide (and) C13-14 Isoparaffin (and) Laureth-7.

- -polyoxyethylenated AMPS/alkyl methacrylate copolymers (crosslinked or non-crosslinked) of the type such as Aristoflex HMS sold by the company Clariant，

- and mixtures thereof.

Other examples of polymeric thickeners that may be mentioned include：

- -anionic， cationic， amphoteric or nonionic chitin or chitosan polymers；

- -cellulose polymers， other than alkylcellulose， chosen from hydroxyethylcellulose， hydroxypropylcellulose， hydroxymethylcellulose， ethylhydroxyethylcellulose and carboxymethylcellulose， and also quaternized cellulose derivatives；

- vinyl polymers， for instance polyvinylpyrrolidones， copolymers of methyl vinyl ether and of malic anhydride， the copolymer of vinyl acetate and of crotonic acid， copolymers of vinylpyrrolidone and of vinyl acetate； copolymers of vinylpyrrolidone and of caprolactam； polyvinyl alcohol；

- -optionally modified polymers of natural origin， such as：

galactomannans and derivatives thereof， such as konjac gum， gellan gum， locust bean gum， fenugreek gum， karaya gum， gum tragacanth， gum arabic， acacia gum， guar gum， hydroxypropyl guar， hydroxypropyl guar modified with sodium methylcarboxylate groups (Jaguar XC97-1， Rhodia) ， hydroxypropyltrimethylammonium guar chloride， and xanthan derivatives；

- alginates and carrageenans；

- glycoaminoglycans， hyaluronic acid and derivatives thereof；

- deoxyribonucleic acid；

- -mucopolysaccharides such as hyaluronic acid and chondroitin sulfates， and mixtures thereof.

According to one particularly preferred embodiment， the gelling agent is chosen from associative polymers.

For the purposes of the present invention， the term ″associative polymer″ means any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers in accordance with the present invention may be anionic， cationic， nonionic or amphoteric.

Associative anionic polymers

Among the associative anionic polymers that may be mentioned are those comprising at least one hydrophilic unit， and at least one fatty-chain allyl ether unit， more particularly those whose hydrophilic unit is formed by an unsaturated ethylenic anionic monomer， advantageously by a vinylcarboxylic acid and most particularly by an acrylic acid or a methacrylic acid or mixtures thereof， and whose fatty-chain allyl ether unit corresponds to the monomer of formula (I) below：

CH₂ ＝ C (R’ ) CH₂O B_n R (I)

in which R’ denotes H or CH₃， B denotes an ethylenoxy radical， n is 0 or denotes an integer ranging from 1 to 100， and R denotes a hydrocarbon-based radical chosen from alkyl， arylalkyl， aryl， alkylaryl and cycloalkyl radicals containing from 8 to 30 carbon atoms， preferably 10 to 24 and even more particularly from 12 to 18 carbon atoms.

Anionic amphiphilic polymers of this type are described and prepared， according to an emulsion polymerization process， in patent EP-0 216 479.

Among the associative anionic polymers that may also be mentioned are maleic anhydride/C₃₀-C₃₈ α-olefin/alkyl maleate terpolymers， such as the product (maleic anhydride/C₃₀-C₃₈ α-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608 by the company Newphase Technologies.

Among the associative anionic polymers， it is possible， according to one preferred embodiment， to use copolymers comprising among their monomers an α， β-monoethylenically unsaturated carboxylic acid and an ester of an α， β-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Preferentially， these compounds also comprise as monomer an ester of an α， β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄ alcohol.

Examples of compounds of this type that may be mentioned include Aculyn

sold by the company &Haas， which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate (comprising 20 OE units) terpolymer or Aculyn 28 (methacrylic acid/ethyl acrylate/oxyethylenated behenyl methacrylate (25 OE) terpolymer) .

Associative anionic polymers that may also be mentioned include anionic polymers comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type， and at least one hydrophobic unit exclusively of (C-₁₀-C₃₀) alkyl ester of unsaturated carboxylic acid type. Examples that may be mentioned include the anionic polymers described and prepared according to patents US-3 915 921 and 4 509 949.

Cationic associative polymers

Cationic associative polymers that may be mentioned include quaternized cellulose derivatives and polyacrylates bearing amine side groups.

The quaternized cellulose derivatives are， in particular：

- quaternized celluloses modified with groups comprising at least one fatty chain， such as alkyl， arylalkyl or alkylaryl groups comprising at least 8 carbon atoms， or mixtures thereof，

- quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain， such as alkyl， arylalkyl or alkylaryl groups containing at least 8 carbon atoms， or mixtures thereof.

The polyacrylates bearing quaternized or non-quaternized amine side groups contain， for example， hydrophobic groups of the type such as steareth-20 (polyoxyethylenated (20) stearyl alcohol) .

The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl， benzyl， naphthyl or anthryl groups.

Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃₀ fatty chains that may be indicated include the products Quatrisoft LM 200， Quatrisoft LM-X 529-18-A， Quatrisoft LM-X 529-18B (C₁₂ alkyl) and Quatrisoft LM-X 529-8 (C₁₈ alkyl) sold by the company Amerchol and the products Crodacel QM， Crodacel QL (C₁₂ alkyl) and Crodacel QS (C₁₈ alkyl) sold by the company Croda.

Examples of polyacrylates bearing amino side chains that may be mentioned are the polymers 8781-121B or 9492-103 from the company National Starch.

Nonionic associative polymers

The nonionic associative polymers may be chosen from：

-celluloses modified with groups comprising at least one fatty chain， for instance hydroxyethylcelluloses modified with groups comprising at least one fatty chain， such as alkyl groups， especially of C₈-C₂₂， arylalkyl and alkylaryl groups， such as Natrosol Plus Grade 330 CS (C₁₆ alkyls) sold by the company Aqualon，

-celluloses modified with alkylphenyl polyalkylene glycol ether groups， such as the product Amercell Polymer HM-1500 (nonylphenyl polyethylene glycol (15) ether) sold by the company Amerchol，

- -guars such as hydroxypropyl guar， modified with groups comprising at least one fatty chain such as an alkyl chain，

- -copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers，

-copolymers of C₁-C₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain，

-copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain， for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer，

-associative polyurethanes.

Associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic blocks usually of polyoxyethylene nature (polyurethanes may also be referred to as polyurethane polyethers) ， and hydrophobic blocks that may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.

In particular， these polymers comprise at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms， separated by a hydrophilic block， the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular， it is possible for one or more pendent chains to be envisaged. In addition， the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

Associative polyurethanes may be block polymers， in triblock or multiblock form. The hydrophobic blocks may thus be at each end of the chain (for example： triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example： multiblock copolymer) . These polymers may also be graft polymers or star polymers. Preferably， the associative polyurethanes are triblock copolymers in which the hydrophilic block is a polyoxyethylene chain comprising from 50 to 1000 oxyethylene groups. In general， associative polyurethanes comprise a urethane bond between the hydrophilic blocks， whence arises the name.

According to one preferred embodiment， a nonionic associative polymer of polyurethane polyether type is used as gelling agent.

By way of example of polyurethane polyethers that may not be used in the present invention， mention may be made of the polymer C₁₆-OE₁₂₀-C₁₆ from the company Servo Delden (under the name SER AD FX1100， which is a molecule containing a urethane function and having a weight-average molecular weight of 1300) ， OE being an oxyethylene unit.

Rheolate 205 bearing a urea function， sold by the company Rheox， or Rheolate 208 or 204， or alternatively Rheolate FX 1100 by Elementis of INCI name Steareth-100/PEG-136/HDI， may also be used as associative polyurethane polymer. These associative polyurethanes are sold in pure form. The product DW 1206B from

&Haas containing a C₂₀ alkyl chain and a urethane bond， sold at a solids content of 20％in water， may also be used.

It is also possible to use solutions or dispersions of these polymers， in particular in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned include SER AD FX1010， SER AD FX1035 and SER AD 1070 from the company Servo Delden， and Rheolate 255， Rheolate 278 and Rheolate 244 sold by the company Rheox. It is also possible to use the products Aculyn 46， DW 1206F and DW 1206J， and also Acrysol RM 184 or Acrysol 44 from the company

&Haas， or alternatively Borchigel LW 44 from the company Borchers， and mixtures thereof.

According to one preferred embodiment， the hydrophilic gelling agent is chosen from：

-optionally modified hydroxypropyl guar， in particular hydroxypropyl guar modified with sodium methylcarboxylate groups (Jaguar XC97-1， Rhodia) or hydroxypropyltrimethylammonium guar chloride，

-vinyl polymers， such as polyvinyl alcohol，

-anionic associative polymers derived from (meth) acrylic acid， such as the non-crosslinked copolymer obtained from methacrylic acid and steareth-20 methacrylate， sold under the name Aculyn 22 by

&Haas，

-nonionic associative polymers of polyurethane polyether type， such as Steareth-100/PEG-136/HDI Copolymer sold under the name Rheolate FX 1100 by Elementis.

&Haas，

Amphoteric associative polymers

Among the associative amphoteric polymers of the present invention， mention may be made of crosslinked or non-crosslinked， branched or unbranched amphoteric polymers， which may be obtained by copolymerization

1) of at least one monomer of formula (IVa) or (IVb) ：

in which R₄ and R₅， which may be identical or different， represent a hydrogen atom or a methyl radical，

R₆， R₇ and R₈， which may be identical or different， represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms，

Z represents a group NH or an oxygen atom，

n is an integer from 2 to 5，

A^- denotes an anion derived from a mineral or organic acid， such as a methosulfate anion or a halide such as chloride or bromide.

in which R₉ and R₁₀， which may be identical or different， represent a hydrogen atom or a methyl radical；

Z₁ represents a group OH or a group NHC (CH₃) ₂CH₂SO₃H；

3) of at least one monomer of formula (VI) ：

in which R₉ and R₁₀， which may be identical or different， represent a hydrogen atom or a methyl radical， X denotes an oxygen or nitrogen atom and R₁₁ denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms；

4) optionally at least one crosslinking or branching agent； at least one of the monomers of formula (IVa) ， (IVb) or (VI) comprising at least one fatty chain containing from 8 to 30 carbon atoms and the said compounds of the monomers of formulae (IVa) ， (IVb) ， (V) and (VI) possibly being quaternized， for example with a C₁-C₄ alkyl halide or a C₁-C₄ dialkyl sulfate.

The monomers of formulae (IVa) and (IVb) of the present invention are preferably chosen from the group formed by：

- dimethylaminoethyl methacrylate， dimethylaminoethyl acrylate，

- dimethylaminopropyl methacrylate， dimethylaminopropyl acrylate，

- dimethylaminopropylmethacrylamide or dimethylaminopropylacrylamide， optionally quaternized， for example with a C₁-C₄ alkyl halide or a C₁-C₄ dialkyl sulfate.

More particularly， the monomer of formula (IVa) is chosen from acrylamidopropyltrimethylammonium chlorideand methacrylamidopropyltrimethylammonium chloride.

The compounds of formula (V) of the present invention are preferably chosen from the group formed by acrylic acid， methacrylic acid， crotonic acid， 2-methylcrotonic acid， 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-methylpropanesulfonic acid. More particularly， the monomer of formula (V) is acrylic acid.

The monomers of formula (VI) of the present invention are preferably chosen from the group formed by C₁₂-C₂₂ and more particularly C₁₆-C₁₈ alkyl acrylates or methacrylates.

The crosslinking or branching agent is preferably chosen from N， N′-methylenebisacrylamide， triallylmethylammonium chloride， allyl methacrylate， n-methylolacrylamide， polyethylene glycol dimethacrylates， ethylene glycol dimethacrylate， diethylene glycoldimethacrylate， 1， 6-hexanediol dimethacrylate and allyl sucrose.

The polymers according to the present invention may also contain other monomers such as nonionic monomers and in particular C₁-C₄ alkyl acrylates or methacrylates.

The ratio of the number of cationic charges/anionic charges in these amphoteric polymers is preferably equal to about 1.

The weight-average molecular weights of the associative amphoteric polymers represents a weight-average molecular mass of greater than 500， preferably between 10 000 and 10 000 000 and even more preferentially between 100 000 and 8 000 000.

Preferably， the associative amphoteric polymers of the present invention contain from 1 mol％to 99 mol％， more preferentially from 20 mol％to 95 mol％and even more preferentially from 25 mol％to 75 mol％of compound (s) of formula (IVa) or (IVb) . They also preferably contain from 1 mol％to 80 mol％， more preferentially from 5 mol％to 80 mol％and even more preferentially from 25 mol％to 75 mol％of compound (s) of formula (V) . The content of compound (s) of formula (VI) is preferably between 0.1 mol％and 70 mol％， more preferentially between 1 mol％and 50 mol％and even more preferentially between 1 mol％and 10 mol％. The crosslinking or branching agent， when it is present， is preferably between 0.0001 mol％and 1 mol％and even more preferentially between 0.0001 mol％and 0.1 mol％.

Preferably， the mole ratio between the compound (s) of formula (IVa) or (IVb) and the compound (s) of formula (V) ranges from 20/80 to 95/5 and more preferentially from 25/75 to 75/25.

The associative amphoteric polymers according to the present invention are described， for example， in patent application WO 98/44012.

The amphoteric polymers that are particularly preferred according to the present invention are chosen from acrylic acid/acrylamidopropyltrimethylammonium chloride/stearyl methacrylate copolymers.

- - clays；

- - optionally modified polymers of natural origin， such as xanthan gum；

- - AMPS/acrylamide copolymers such as a copolymer of INCI name Polyacrylamide (and) C 13-14 Isoparaffin Laureth-7， such as Sepigel；

- - nonionic associative polymers of polyurethane polyether type， such as a copolymer of INCI name Steareth-100/PEG-136/HDI；

and mixtures thereof.

The hydrophilic gelling agent (s) may be present in the composition according to the present invention in a solid content of greater than or equal to 0.01％by weight relative to the total weight of the composition. In particular， the hydrophilic gelling agent (s) may be present in the composition according to the present invention in a solids content ranging from 0.05％to 5％by weight and preferably from 0.1％to 3％by weight relative to the total weight of the composition.

Adjuvants

In a known manner， the composition of the invention may also contain adjuvants that are common in cosmetics and/or dermatology， such as oils， active agents， preserving agents， antioxidants， complexing agents， pH modifiers (acidic or basic) ， fragrances， fillers， bactericides， odour absorbers， colorants (pigments and dyes) ， film-forming polymers， emulsifiers such as fatty acid esters of polyethylene glycol， fatty acid esters of glycerol and fatty acid esters of sorbitan， which are optionally polyoxyethylenated， polyoxyethylenated fatty alcohols and fatty acid esters or ethers of sugars such as sucrose or glucose， and also lipid vesicles.

Needless to say， a person skilled in the art will take care to select this or these optional additional compound (s) ， and/or the amount thereof， such that the mattifying/soft focus properties of the composition according to the invention are not， or are not substantially， adversely affected by the envisaged addition.

Galenic form

The composition according to the invention may be in various forms， such as aqueous solution， dispersion or emulsion， especially such as an aqueous solution.

Method and use

The composition and the cosmetic mask of the present invention can be generally prepared according to the general knowledge of a person skilled in the art. Nevertheless， it is to be understood that a person skilled in the art can choose its method of preparation， on the basis of his/her general knowledge， taking into account the nature of the constituents used， for example， their solubility in the vehicle， and the application envisaged for the composition.

The cosmetic mask of the present invention can be used for a non-theraputic process， such as a cosmetic process or method， for caring for the keratin materials， preferably the skin， and more preferably the skin face， comprising the step of applying on the said keratin material the cosmetic mask of the present invention.

EXAMPLES

The examples that follow are aimed at illustrating the compositions and processes according to this invention， but are not in any way a limitation of the scope of the invention. All the parts and percentages in the examples are given on a weight basis and all the measurements were obtained at about 25℃， unless otherwise mentioned.

I. Preparation

The invention formulas 1 and 2， and comparative formulas 1 and 2 were prepared：

Comparative formula 1 contains a commonly used moisturizer other than the diethanolammonium derivative of the present invention；

Comparative formula 2 contains no diethanolammonium derivative of the present invention.

The invention and comparative formulas were prepared as follows：

Heating phase A to 80℃ until totally dissolved；

Mixing phase B into phase A under 80℃， homogenized until uniform；

Cooling down the mixture till 40℃；

Adding phase C to the mixture obtained above， and mixed until dissolved.

II. Evaluation of the invention and comparative formulas

The invention and comparative formulas listed above were evaluated using the following protocols.

Method for evaluating the long-term hydration effect

1. Equipment and parameter

Corneometer CM825 (COURAGE + KHAZAKA) ， Hydration value of the skin

2. Experimental design

Panel：

24 Chinese women subjects；

Age： 30-60 years old；

Dry skin on forearm with hydration value 30±15；

No skincare products 3 days before the test.

Application： Latin 6*6

Zone： forearm

3. Test procedure

1) Models wait in standard condition room (21℃， 45％RH) 30 minutes on arriving for T₀ data acquisition.

2) Randomly apply tissue mask according to the random table.

3) Tear off the tissue mask after 15 minutes and wait 1 hour in standard condition room (21℃， 45％RH) for T_1h data acquisition.

4) Models wait 5 hours in standard condition room (21℃， 45％RH) for T_6h data acquisition.

The results of the evaluation are as follow.

Item	Invention formula 1	Comparative formula 1
T_1h-T₀	28.93±16.99	20.29±10.74
T_6h-T₀	12.88±7.12	9.00±4.03

As can be seen from the results， the cosmetic mask according to the present invention provides better hydration to the skin， in particular， it provides a better long-term hydration， comparing to the comparative formula.

Claims

A mask for caring for keratin materials， comprising：

1) a water insoluble substrate；

2) a composition comprising in an aqueous phase：

a) at least one polyol， and

b) at least one diethanolammonium derivative of formula (I) ， and also the optical isomers and/or geometrical isomers thereof：

in which

R₁ and R₂ independently denote：

(i) a linear or branched C₁-C₁₂ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ； said radical being optionally substituted with a group -COR； or

(ii) an aralkyl radical C_mH_2mAr such that m denotes an integer ranging from 1 to 6 and Ar denotes an aryl radical optionally substituted with a group -COR；

R denotes a group -OR’ or -NR’R” where R’ and R” independently denote hydrogen or a linear or branched C₁-C₆ alkyl radical which is saturated or unsaturated with an ethylenic double bond；

n is equal to 0 or 1；

the electrical neutrality of said compounds being provided by an organic or inorganic external anion X^- (n＝l) or internally (n＝0) when a single COOH radical is present and forms a CO₂ ^- radical；

it being understood that when R₁ denotes a methyl radical and R₂ denotes a methyl radical substituted with a -COOH group， then n ＝ 1.
The mask according to Claim 1， wherein X^- is chosen from the anionic forms of organic compounds bearing one or more acid functions， such as the anionic forms of amino acids， in particular aspartate， methanesulfonate， para-toluenesulfonate， camphorsulfonate， tartrate， citrate， acetate， levulinate， or methosulfate， halides， in particular chloride， bromide or iodide， sulfates， phosphates， hydrogen phosphates， dihydrogen phosphates， carbonate or hydrogen carbonate.
The mask according to anyone of the preceding claims 1 to 2， wherein X^- is chosen from the anionic forms of organic compounds bearing one or more carboxylic acid functions such as among compounds of formula A or B or C：

wherein，

Ra₁ means a hydrogen atom or an a linear or branched alkyl radical C₁-C₁₈，

Ra₂ means a hydrogen atom or an a linear or branched alkyl radical C₁-C₁₈ or an a linear or branched alkylcarbonyl radical C₁-C₁₈，

Ra₁ and Ra₂ can together form a five to eight membered ring with the N atom bearing them，

Ra₂ and Ra₃ can together form a five membered ring of formula A1 or A2 with the N atom bearing them，

Ra₃ is chosen among the radical described below，

R_b1 means a linear or branched alkyl radical C₁-C₆ preferably C₁-C₄ substituted by at least one OH radical preferably one OH radical or an saturated heterocycle of 5 to 8 membered ring containing one atom of N， S， O and substituted by at least one OH radical preferably one OH radical，

preferentially， R_b1 means a linear or branched alkyl radical C₁-C₄ substituted by one OH radical or a pyrrolidine containing substituted by one OH radical，

more preferably， R_b1 is chosen among -CH₂OH， -CH (OH) Me and

R_c1 means a linear or branched alkyl radical C₁-C₁₈ or a linear or branched alkyl carbonyl C_1-18.
The mask according to anyone of the preceding claims 1 to 3， wherein the compound (s) of formula (I) are chosen from the following compounds：

wherein X^- has the same meaning as indicated in Claim 1.
The mask according to anyone of the preceding claims 1 to 4， wherein the compound (s) of formula (I) are chosen from the following compounds：

and more particularly chosen from the compounds (2) ， (3) ， (13) and (14) and even more particularly is compound (2) .
The mask according to anyone of the preceding claims 1 to 5， wherein the at least one diethanolammonium derivative is present in the composition in an amount ranging from 0.01％to 10％by weight， preferentially from 0.02％to 6％by weight and even more preferentially from 0.1％to 5％by weight relative to the total weight of the composition.
The mask according to anyone of the preceding claims 1 to 6， wherein the at least one polyol is a compound of formula (A) ， such as glycerol， propylene glycol， butylene glycol， pentylene glycol or hexylene glycol，

wherein Ra denote a linear or branched C₂-C₂₀ alkyl radical which is saturated or unsaturated with one or more ethylenic double bond (s) ， preferably a linear or branched C₂-C₁₀ alkyl radical or a linear or branched C₂-C₄ alkyl radical， and a denotes an integer ranging from 2 to 4， preferably an integer ranging from 2 to 3.
The mask according to anyone of the preceding claims 1 to 7， wherein the at least one polyol presents as the combination of a glycol and glycerol， wherein the weight ratio of glycerol to the glycol is from 1∶10 to 10∶1， preferentially from 1∶5 to 5∶1， and even more preferentially from 1∶2 to 1∶1.
The mask according to anyone of the preceding claims 1 to 8， wherein the at least one polyol is present in the composition in an amount of at least 10％by weight， preferably at least 15％by weight and better still from 15％to 45％by weight relative to the total weight of the composition.
The mask according to anyone of the preceding claims 1 to 9， wherein the weight ratio of the at least one diethanolammonium derivative to the at least one polyol is from 3∶1 to 1∶15， preferentially from 2∶1 to 1∶10， and even more preferentially from 1∶1 to 1∶6.
The mask according to anyone of the preceding claims 1 to 10， wherein the water insoluble substrate is at least partially made by woven or non-woven fabric made of natural fibers such as cotton， pulp， bamboo and cellulose fibers， semi-natural fibers such as viscose rayon fibers and synthetic fibers such as polyester fibers， polyethylene terephthalate fibers， polyethylene fibers， and polypropylene fibers， or a mixture thereof.
The mask according to anyone of the preceding claims 1 to 11， wherein the aqueous phase is present in the composition from 10 to 99.9％by weight， preferably from 50％to 99.9％by weight and more preferably from 70％to 99.9％by weight， relative to the total weight of the composition.
A non-therapeutic cosmetic process for caring for the keratin materials， preferably the skin， and more preferably the skin face， comprising the step of applying on the said keratin material the cosmetic mask according to anyone of the preceding claims 1 to 12.