WO2016102398A1

WO2016102398A1 - Aqueous composition comprising a 4-(heterocycloalkyl)-benzene-1,3-diol compound, a polymer and a glycol

Info

Publication number: WO2016102398A1
Application number: PCT/EP2015/080645
Authority: WO
Inventors: Marie-Lise CHIRON; Véronique Chevalier
Original assignee: L'oreal
Priority date: 2014-12-22
Filing date: 2015-12-18
Publication date: 2016-06-30
Also published as: FR3030249B1; FR3030249A1

Abstract

The invention relates to a composition comprising: at least one 4-(heterocycloalkyl)-benzene-1,3-diol compound; at least one anionic or non-ionic polymer; at least one glycol; and water. The invention also relates to the use of the composition for making-up, caring for and/or cleaning keratin materials, in particular the skin.

Description

An aqueous composition comprising a 4- (heterocycloalkyl) -benzene-1,3-diol compound, a polymer and a glycol

The subject of the present invention is a composition, preferably a cosmetic composition, comprising a 4- (heterocycloalkyl) -benzene-1,3-diol compound, a polymer and at least one glycol.

The 4- (heterocycloalkyl) -benzene-1,3-diol derivatives are compounds used for the treatment of cutaneous signs of aging and more particularly as a depigmenting agent for keratin materials.

However, these compounds which are in solid form at room temperature and have a high melting point (> 210 ° C) are difficult to solubilize. They are notably poorly soluble in water and glycerine.

However, it is necessary that these compounds be formulated in a solubilized form, and in particular at a high content, such as greater than or equal to 0.20% by weight, in order to make the most of their activity and it is also preferable that their solubilization is maintained over time to avoid any recrystallization phenomenon during the storage of compositions comprising such compounds.

In fact the solubilized forms lead to a better bioavailability in the skin than crystallized forms whose crystal size is poorly controlled.

For the purposes of this application, the term "bioavailability" refers to the molecular penetration of the active agent into the living layers of the skin and in particular of the epidermis. It will be sought that the penetrated concentration is as high as possible, so as to increase the rate of asset reaching the living layers of the skin.

By "solubilized form" is meant a dispersion of the derivatives according to the invention in a liquid, in the free molecular state, in particular in uncomplexed form. No crystallization of 4- (heterocycloalkyl) -benzene-1,3-diol derivatives is visible to the naked eye or in cross-polarized light microscopy.

Compositions containing a high level of glycols provide a tacky and greasy feel of the skin. It is therefore sought to increase the solubility of these active ingredients but using limited quantities of solvents which reduce the cosmetic properties of the compositions.

The object of the present invention is precisely to propose a novel galenic formulation of the 4- (heterocycloalkyl) -benzene-1,3-diol compounds making it possible to overcome of the abovementioned disadvantages, and therefore to incorporate these compounds in a solubilized form and durable over time, these compounds being in particular present at a high content (such as a content greater than or equal to 0.20% by weight relative to the weight total of the composition). This new galenic formulation of the compounds 4- (heterocycloalkyl) -benzene-1,3-diol makes it possible in particular to improve the efficacy of the active ingredient for the treatment of keratin materials such as the skin. The compositions according to the invention make it possible to use lower amounts of glycols.

The inventors have in fact unexpectedly discovered that the combination of at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound with at least one glycol and at least one nonionic or anionic polymer makes it possible to solubilize this compound while avoiding recrystallization, especially after storage for at least 1 week, or even 1 month, 2 months or more at room temperature (25 ° C) and / or at 4 ° C and / or 45 ° C . More specifically, the subject of the invention is a composition, in particular a cosmetic composition, comprising;

at least one nonionic or anionic polymer;

at least one glycol;

- some water,

at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound of formula (I);

as defined below.

The present invention also relates to a process for preparing such a composition comprising the following steps:

1) preparing a solution A by mixing at least one nonionic or anionic polymer and water, and

2) preparing a solution B by mixing at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound in at least one glycol, and

3) mixing solutions A and B

Preferably step 1) of said process is the preparation of a solution A by mixing at least one polymer according to the invention and water by simply contacting with stirring (for example magnetic stirring) at room temperature. ambient temperature (20-25 ° C). Preferably step 2) of said process is the preparation of a solution B by the mixture of at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound in at least one glycol by heating, in particular by heating at a temperature of 40-60 ° C, preferably at about 50 ° C, for about 10 minutes with stirring (eg magnetic). Preferably step 3) of said process is the mixture of solutions A and B by pouring solution A on solution B at room temperature.

In particular, the present invention relates to a process for preparing such a composition comprising the following steps:

1) preparation of a solution A by mixing at least one polymer according to the invention and water, in particular by simple contact with stirring (for example magnetic stirring) at room temperature (20-25 ° C. ), and

2) preparing a solution B by mixing at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound in at least one glycol, preferably by heating, in particular by heating to a temperature of 40- 60 ° C, preferably at about 50 ° C, for about 10 minutes with stirring (eg magnetic); then

3) mixing solutions A and B, preferably by pouring solution A on solution B at room temperature.

Steps 1 and 2 of said method can be implemented in any order.

The 4- (heterocycloalkyl) -benzene-1,3-diol compounds according to the invention have the following general formula (I):

in which

R1, R2, R3, R4, which may be identical or different, represent:

- a hydrogen

a C1-C4 alkyl radical

a hydroxymethyl, a hydroxyethyl,

a C1-C4 alkoxycarbonyl,

a C1-C4 alkoxy,

- a hydroxyl

or

R1 and R2 are interconnected and form a carbon ring with 5 or 6 carbon atoms with the carbon atom to which they are bonded and R3 and R4, identical or different, represent: - a hydrogen

a C1-C4 alkyl radical

or R1 and R4 are connected together and form a chain - (CH2) ₂ - or - (CH2) ₃ - and R2 and R3, which may be identical or different, represent:

- a hydrogen

a C1-C4 alkyl radical X represents an oxygen atom, or a sulfur atom.

Y represents a hydrogen, a chlorine atom or a fluorine atom.

m can take the values 1 or 2 and n can take the values 0 or 1 and when n = 0, then m = 1 or 2, and when n = 1, then m = 1. as well as the salts of the compounds of general formula (I), and their isomeric and enantiomeric forms.

Among the salts of the compounds of general formula (I), there may be mentioned preferably salts with an organic base or with an inorganic base.

Suitable inorganic bases are, for example, potassium hydroxide, sodium hydroxide or calcium hydroxide.

Suitable organic bases are, for example, morpholine, piperazine, arginine, lysine. The compounds of general formula (I) may also exist in the form of hydrates or solvates.

Suitable solvents for forming solvates are, for example, alcohols such as ethanol or iso-propanol. According to the present invention, the term C1-C4 alkyl denotes a saturated hydrocarbon chain, linear or branched, comprising from 1 to 4 carbon atoms.

According to the present invention, C1-C4 alkyloxycarbonyl denotes a carboxy radical substituted with an alkyl radical containing from 1 to 4 carbon atoms.

According to the present invention, C1-C4 alkoxy denotes an oxygen atom substituted by a linear or branched saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms. According to the present invention, the isomers are the cis and trans forms relating to the substituents on the heterocycloalkyl at the 4-position of benzene-1,3-diol.

According to the present invention, the compounds of general formula (I) that are particularly preferred are those for which:

R1 represents a hydrogen, a C1-C4 alkyl radical or a hydroxymethyl radical,

R2 represents a hydrogen,

R3 represents a hydrogen,

R4 represents a hydrogen,

X represents an oxygen atom

Y represents a hydrogen or a fluorine atom

m = 1 and n = 1, as well as the salts of these compounds of general formula (I), and their isomeric and enantiomeric forms.

Among the compounds of formula (I) falling within the scope of the present invention, mention may be made in particular of the following:

I: 4- (tetrahydro-pyran-4-yl) -benzene-1,3-diol

2: 4- (tetrahydro-thiopyran-4-yl) -benzene-1,3-diol

3: 4- (cis-2,6-Dimethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

4: trans-4- (2-methyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

5: cis-4- (2-methyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

6: trans-4- (2-Ethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

7: cis-4- (2-Ethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

8: trans-4- (2-Hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

9: 4- (2,2,6,6-tetramethyltetrahydro-pyran-4-yl) benzene-1,3-diol

10: 4- (tetrahydro-furan-3-yl) -benzene-1,3-diol

I: 4- (tetrahydro-thiophen-3-yl) -benzene-1,3-diol

12: 4- (6-Oxa-spiro [4.5] dec-9-yl) -benzene-1,3-diol

13: 4-Chloro-6- (tetrahydro-pyran-4-yl) -benzene-1,3-diol

14: 4-Fluoro-6- (tetrahydro-pyran-4-yl) -benzene-1,3-diol

15: 4- (2,2-Diethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

16: 4- (tetrahydro-pyran-3-yl) -benzene-1,3-diol

17: trans-4- (5-Hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

18: cis-4- (5-Hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

19: trans-4-Fluoro-6- (5-hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

20: cis-4-Fluoro-6- (5-hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

21: trans-4-Fluoro-6- (2-hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol 22: cis-4-Fluoro-6- (2-hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

23: cis-4- (8-Oxa-bicyclo [3.2.1] oct-3-yl) -benzene-1,3-diol

24: trans-4- (8-Oxa-bicyclo [3.2.1] oct-3-yl) -benzene-1,3-diol

25: 4-Fluoro-6- (tetrahydro-thiopyran-4-yl) -benzene-1,3-diol

These compounds can be prepared according to the procedures described in the application WO2010063773.

The compound 4- (tetrahydro-pyran-4-yl) -benzene-1,3-diol is particularly preferred.

compound 1

The compound of formula (I) may be present in the composition according to the invention, in a content ranging from 0.001% to 10% by weight, relative to the total weight of the composition, more particularly in a content ranging from 0.05 % to 5% by weight, and preferably ranging from 0.1% to 2% by weight, and preferably ranging from 0.2% to 1.5% by weight.

The composition according to the invention comprises at least one nonionic or anionic polymer.

The nonionic or anionic polymer or polymers according to the invention are especially chosen from:

homopolymers and copolymers of vinylpyrrolidone,

polyvinyl alcohols,

celluloses, preferably hydroxyalkyl (C 1 -C 4) celluloses and hydroxyalkyl (C 1 -C 4) alkyl (C 1 -C 4) celluloses,

homopolymers and copolymers of at least one monomer containing a sulphonic group (polymers containing sulphonic groups),

- and their mixtures.

Among the homopolymers that may be mentioned polyvinylpyrrolidones (PVP) of different molecular weights, the weight average molecular weight of said homopolymer being measured by diffraction of light.

More particularly, the polyvinylpyrrolidones (PVP) are chosen from polyvinylpyrrolidones having a weight average molecular weight ranging from 2000 Daltons to 3000000 Daltons, more particularly having a weight average molecular weight ranging from 30000 Daltons to 2000000 Daltons, preferably having a molecular weight. average in weight ranging from 40000 Daltons to 1500000 Daltons. In a preferred embodiment of the invention, said homopolymer (s) and copolymer (s) of vinylpyrrolidone present in the composition is chosen from polyvinylpyrrolidone having a weight average molecular weight ranging from 40000 Daltons to 80000 Daltons, and polyvinylpyrrolidone having a weight average molecular weight of from 900000 Daltons to 1500000 Daltons.

By way of example, a polyvinylpyrrolidone according to the invention is available under the trade name PVP K 30L® from the company ISP.

By way of example, a polyvinylpyrrolidone according to the invention is available under the trade name PVP K 90® from the ISP company (ASHLAND.

In the composition of the invention, any type of vinylpyrrolidone copolymer can be used. The term "copolymer" as used herein refers to polymers resulting from the polymerization of vinylpyrrolidone with a single type of monomer, as those resulting from the polymerization of vinylpyrrolidone with several kinds of monomers, and for example with two kinds of monomers leading to the production of of terpolymer.

Among the copolymers, mention may be made of polyvinylpyrrolidone / vinyl acetate copolymers (PVPA A), polyvinylpyrrolidone / butene copolymers; polyvinylpyrrolidone / decene, polyvinylpyrrolidone / hexadecene, polyvinylpyrrolidone / (meth) acrylic acid / C8-C20 alkyl methacrylate including lauryl, polyvinylpyrrolidone / vinyl acetate / itaconic acid, polyvinylpyrrolidone / vinyl acetate / vinyl propionate.

In a particular embodiment according to the invention, the homo- and copolymers are chosen from polyvinylpyrrolidones (PVP) and vinylpyrrolidone / vinyl acetate copolymers (PVPA / A).

These copolymers are commercially available, for example under the trademark LUVISKOL® (PVP and PVPA / A) from BASF and under the names PVP-K or PVPA / A from ISP.

The polyvinyl alcohols (PVA) are chosen in particular from PVA having a weight average molecular weight ranging from 10,000 Daltons to 200,000 Daltons, more particularly having a weight average molecular weight ranging from 100,000 Daltons to 200,000 Daltons.

The polyvinyl alcohols according to the invention can have polymers of different degrees of hydrolysis and / or different viscosities. In particular, polyvinyl alcohol having a degree of hydrolysis varying from 74 to 99% and / or having a viscosity ranging from 2.6 to 67 cps (2.6 to 67 mPa.s) can be used. As polyvinyl alcohol, mention may be made for example the product available under the trade name CELVOL 205 PV ALCOHOL® from Sekisui Specialty Chemicals.

The celluloses that can be used according to the invention are for example chosen from

hydroxypropyl methylcelluloses sold especially under the names METHOCEL F4M STANDARD or METHOCEL K 15M by the company DOW CHEMICAL;

methylcelluloses, for example sold under the name TYLOSE MH 200 KG4 by CLARIANT;

the hydroxyethylcelluloses for example sold under the name NATROSOL 250 HHR by the company ASHLAND

hydroxypropylcelluloses for example sold under the name "KLUCEL H" by the company ASHLAND;

the hydroxyethyl methylcelluloses for example sold under the name "TYLOSE MH 300" by the company HOECHST

According to the invention, the polymers containing sulphonic groups are homo or copolymers that can be obtained from at least one ethylenically unsaturated monomer containing a sulphonic group, which can be in free form or partially or totally neutralized.

Preferably, the polymers in accordance with the invention may be partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organic base such as mono-, di- or tri-ethanolamine, aminomethylpropanediol, N methyl glucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds. They are usually neutralized. The term "neutralized" in the present invention means polymers that are totally or substantially completely neutralized, that is to say neutralized to at least 90%. The polymers used in the composition of the invention generally have a number-average molecular weight ranging from 1000 to 20,000,000 g / mol, preferably from 20,000 to 5,000,000 and even more preferably from 100,000 to 1,500,000. g / mol.

These polymers according to the invention may be crosslinked or non-crosslinked.

The monomers containing sulphonic groups of the polymer used in the composition of the invention are chosen in particular from vinylsulphonic acid, styrenesulphonic acid, (meth) acrylamido (C 1 -C ₂₂ ) alkylsulphonic acids, N- (dC) acids. ₂₂ ) alkyl- (meth) acrylamido (C 1 -C ₂₂ ) alkylsulfonic acid such as undecyl-acrylamido-methane- sulfonic acid, as well as their partially or totally neutralized forms, and their mixtures.

According to a preferred embodiment of the invention, the monomers containing a sulphonic group are chosen from (meth) acrylamido (Ci-C ₂ 2) alkylsulphonic acids, such as, for example, acrylamido-methanesulfonic acid and acrylamido acid. ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butane sulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulphonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or completely neutralized forms, and their mixtures.

More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms are used.

When the polymers are crosslinked, the crosslinking agents may be chosen from the olefinically-polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization.

According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

The homopolymer of monomers containing sulfonic groups may be crosslinked with one or more crosslinking agents.

These homopolymers are generally crosslinked and neutralized.

As polymers with sulfonic groups, mention may be made in particular of the crosslinked and neutralized homopolymer of 2-acrylamido-2-methylpropanesulphonic acid, marketed by the company Clariant under the trademark "Hostacerin® AMPS" (CTFA name: ammonium polyacryldimethyltauramide).

The nonionic or anionic polymer (s) may be present at a content ranging from 0.01% to 15% by weight, preferably ranging from 0.1% to 10% by weight, relative to the total weight of the composition. According to a particular embodiment, the celluloses and the polymers of monomers containing a sulfonic group may be present in a content ranging from 0.01% to 5% by weight, preferably ranging from 0.1% to 2%. by weight, more preferably from 0.2% to 1% by weight, relative to the total weight of the composition.

Particularly advantageously, the PVP polymer (s) and polyvinyl alcohol (s) can be present in a content ranging from 0.1% to 10% by weight, preferably ranging from 1% to 5% by weight. , relative to the total weight of the composition. According to a preferred embodiment, the mass ratio of the said polymer / compound of formula (I) present in the composition according to the invention is preferably from 0.1 to 15, for example ranging from 1 to 10.

The composition according to the present invention comprises at least one glycol.

By glycol according to the invention is meant a hydrocarbon chain comprising at least 2 carbon atoms, preferably 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, preferably having 2 to 10 carbon atoms, and preferably having from 2 to 6 carbon atoms, and bearing two hydroxyl groups. The glycols used in the present invention may have a weight average molecular weight less than or equal to 1000, preferably between 60 and 500.

The glycol may be a natural or synthetic glycol. The glycol may have a linear, branched or cyclic structure.

The glycol may be chosen from diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 1,3-propanediol, 1,5-pentanediol and polyethylene glycols, especially having 5 to 50 ethylene oxide groups, and mixtures thereof.

More particularly, the glycol may be chosen from the group consisting of dipropylene glycol, propylene glycol, propanediol-1, 3, butylene glycol, and their mixture, and more particularly dipropylene glycol. The said glycol (s) may be present in a content ranging from 0.50% to 50% by weight, relative to the total weight of the composition, preferably ranging from 3% to 30% by weight. % by weight, and preferably ranging from 5% to 20% by weight, relative to the total weight of the composition. According to the invention, the composition according to the present invention comprises water.

The amount of water is not limited, and may range from 50% to 99% by weight, preferably from 55% to 95% by weight, and more preferably from 70% to 90% by weight, based on weight. total of the composition.

According to a particular embodiment of the invention, the composition according to the present invention further comprises at least one C2-C4 monoalcohol.

C2-C4 monoalcohols comprise a hydroxy group and 2 to 4 carbon atoms. Ethanol, propanol, isopropanol, butanol-1, isobutanol and mixtures thereof can be used. The C2-C4 monoalcohol is preferably ethanol.

The concentration of C2-C4 monoalcohol can range from 0.1% to 30% by weight, preferably from 0.5% to 15% by weight, relative to the total weight of the composition.

The compositions used according to the invention may comprise a physiologically acceptable medium, that is to say a medium which is suitable for the topical administration of a composition, that is to say compatible with the keratinous substances of the present invention. human beings such as the skin, the scalp, the hair, the nails.

According to the invention a physiologically acceptable medium is preferably a cosmetically acceptable medium, that is to say without odor, or unpleasant appearance, and which is perfectly compatible with the topical route of administration. The term "keratin materials" according to the invention is understood to mean the skin, the body, the face and / or the contour of the eyes, the lips, the nails, the mucous membranes, the eyelashes, the eyebrows, the hairs, the scalp and / or the hair, or any other skin area of the body. More particularly, the keratin materials according to the invention are the scalp, the hair, and / or the skin.

Preferably, the keratin materials according to the invention are the scalp and / or the hair.

Preferably the keratin materials according to the invention is the skin.

By "skin" is meant all of the skin of the body, and preferably, the skin of the face, décolleté, neck, arms and forearms, or even more preferably, the skin of the skin. face, including forehead, nose, cheeks, chin, eye area.

As specified below, the compound of formula (I) is advantageously present in the compositions according to the invention in a solubilized form. By way of example, the composition according to the invention may be intended to be administered topically, that is to say by surface application of the keratin material in question, such as the skin under consideration. The composition of the invention may be a cosmetic composition (either intended for cosmetic use) or dermatological. Preferably, according to the invention, the composition is a cosmetic composition and even more preferentially a cosmetic composition for topical application.

The term "cosmetic composition" is understood to mean a substance or a preparation intended to be brought into contact with the various superficial parts of the human body, in particular the epidermis, the hair and hair systems, the nails, the lips and the oral mucosa, in particular view, exclusively or mainly, to clean, embellish, perfume, change the appearance, protect, maintain or repair body odors.

The compositions according to the invention may be in the form of aqueous solutions, hydroalcoholic solutions, oil-in-water (O / W) or water-in-oil (W / O) or multiple (triple: E / W) emulsions. H / E or H / E / H), aqueous gels. These compositions are prepared according to the usual methods.

The composition may comprise at least one oil. As usable oils, there may be mentioned for example:

hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn or soybean oils, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, castor oil, avocado, triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names "Miglyol 810", "812" and "818" by Dynamit Nobel, jojoba oil, shea butter oil;

esters and synthetic ethers, in particular of fatty acids, such as the oils of formulas R 1 COOR 2 and R 10 R 2 in which R 1 represents the residue of a fatty acid comprising from 8 to 29 carbon atoms, and R 2 represents a hydrocarbon-based chain , branched or unbranched, containing from 3 to 30 carbon atoms, for example purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, stearate of octyl-2-dodecyl, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate; heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythrityl tetraisostearate;

linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam oil;

fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol;

silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl-dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes;

- their mixtures.

The term "hydrocarbon-based oil" in the list of oils mentioned above, any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and / or alcohol groups. The composition according to the invention may comprise solid bodies at ambient temperature (25 ° C.), for example fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid and palmitic acid. and oleic acid; waxes such as lanolin, beeswax, carnauba or candelilla wax, paraffin waxes, microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, Fischer waxes, Tropsch.

These fatty substances may be chosen in a varied manner by those skilled in the art in order to prepare a composition having the desired properties, for example of consistency or textures. According to a particular embodiment of the invention, the composition according to the invention is a water-in-oil (W / O) or oil-in-water (O / W) emulsion. The proportion of the oily phase of the emulsion may range from 1% to 80% by weight, and preferably from 5% to 50% by weight relative to the total weight of the composition. The emulsions generally contain at least one emulsifier, especially chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture, and optionally a co-emulsifier. The emulsifiers are suitably selected according to the emulsion to be obtained (W / O or O / W). The emulsifier and the co-emulsifier are generally present in the composition, in a proportion ranging from 0.3 to 30% by weight, and preferably from 0.5 to 20% by weight relative to the total weight of the composition.

For the W / O emulsions, examples of emulsifiers that may be mentioned include dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C" by the company Dow Corning, and the alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the name "Dow Corning 5200 Formulation Aid" by the company Dow Corning and Cetyl dimethicone copolyol sold under the name "Abil EM 90®" by the company Goldschmidt.

For O / W emulsions, mention may be made, for example, as emulsifiers, of nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated fatty acid esters (oxyethylenated and / or oxypropylenated); oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; and mixtures thereof such as the mixture of glyceryl stearate and PEG-100 stearate.

The composition may be an aqueous gel, and in particular comprise conventional aqueous gelling agents.

In a known manner, the composition according to the invention may also contain adjuvants which are customary in the cosmetic or dermatological field, such as gelling agents, thickeners, film-forming polymers, preservatives, perfumes, fillers, UV filters, bactericidal agents, odor absorbers, dyestuffs, plant extracts, vitamins, polyols such as glycerin, sugars such as sorbitol, cosmetic and dermatological active ingredients, and salts. The amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.001 to 20% of the total weight of the composition.

The composition preferably comprises glycerin.

Advantageously, the composition according to the invention has a pH ranging from 3 to 7. Preferably, the pH of the composition ranges from 4 to 6. More particularly, the subject of the invention is also a process for the cosmetic treatment of skincare, makeup, and / or cleaning of keratinous substances, in particular the skin, comprising the application on said keratin materials, in particular the skin, of a composition according to the invention as described above.

Said method of cosmetic treatment of care, makeup, and / or cleansing of the skin is non-therapeutic.

The subject of the invention is also a cosmetic process for the depigmentation, lightening and / or bleaching of keratin materials, in particular human skin, hair or hair, comprising the application to said keratin materials of a composition according to the invention. invention as described above.

The subject of the invention is also a cosmetic process for preventing and / or treating cutaneous signs of aging, comprising at least one step of topical application to keratin materials, such as the skin, of a composition according to the invention as previously described.

The cutaneous signs of the aging to be prevented and / or treated in the cosmetic process according to the invention may be chosen from the lines and wrinkles, and / or to fight against the skin withered, soft and / or thinned. The invention also relates to the cosmetic use of a composition according to the invention as defined above, for the care, makeup and / or cleaning of keratin materials.

In another embodiment, the invention relates to a cosmetic treatment method for the care, makeup, and / or cleaning of keratinous substances, in particular the skin, comprising the administration, topically, to an individual, of a composition as defined above.

The expressions "between ... and ..." and "from ... to ...", or "at least ..", or "at least .." must be understood as inclusive, unless the opposite is specified.

The following examples of compositions according to the invention are given by way of illustration and without limitation. The compounds are indicated in chemical name or INCI name. The contents of the ingredients are expressed in percentage by weight.

Example 1: Evaluation of the stability of formulations Method of preparation :

The polymer (homopolymer of vinylpyrrolidone (PVP)) is mixed in the water simply by contacting with magnetic stirring at room temperature. The solution of compound 1 in dipropylene glycol is then prepared by heating at about 50 ° C for about 10 minutes with magnetic stirring. The polymer solution is poured into the water at room temperature.

Evaluation Protocol:

The stability of the obtained preparation stored at 4 ° C. and at room temperature after 24 hours is evaluated by a macroscopic examination with the eye (observation or not of a cloudiness or a deposit) and by observation under a microscope under a light. polarized (presence or absence of crystals) and after 2 months of storage.

The following results were obtained with different associations evaluated:

The same results were obtained by replacing PVPK30L (weight average molecular weight ranging from 40000 Daltons to 80000 Daltons) with PVP K90 (weight average molecular weight ranging from 900000 Daltons to 1500000 Daltons).

It has thus been found that, unexpectedly, the compositions 1A, 1B, and 1C in accordance with the invention are stable at room temperature and at 4 ° C., and show no recrystallization of compound 1, this resorcinol derivative is so very well solubilized in these particular associations.

Examples 2 to 5

Composition in% MA 2 3 4 5 Compound 1: 4- 1 1 1 1

(Tetrahydro-pyran-4-yl) benzene-1,3-diol

Dipropylene glycol 23 23 23 23

Phenoxyethanol 0.8 0.8 0.8 0.8

Polyvinyl alcohol 7

(SELVOL 540 SM from

SEKISUI SPECIALTY

Chemicals)

Hydroxypropyl methyl - 0,4 - - cellulose

(METHOCEL E 4 M

PREMIUM from DOW

Chemical)

Hydroxyethylcellulose 0.4 (NATROSOL 250 HHR

CS of ASHLAND)

Crosslinked Homopolymer - - 1, 95 - Acid

acrylamidomethyl

propane sulfonic

partially neutralized

ammonia

(Hostacerin AMPS ^® from

Clariant)

Water QSP 100% QSP 100% QSP 100% QSP 100%

Stability No Step Paste Crystals Crystals Crystals crystals after 2 months after 2 months after 10 after 10 at 4 ° C and at 4 ° C and at days at 4 ° C days at 4 ° C temperature temperature and at and at ambient room temperature room temperature

EXAMPLE 6 Care Composition According to the Invention A skin care composition (oil-in-water emulsion) having the following composition was prepared:

INCI name

METHYL GLUCETH-20 3

TETRASODIUM EDTA 0.1

GLYCERYL STEARATE 1, 45

(and) PEG-100 STEARATE

(ARLACEL® 165 FL from

Uniqema)

STEARIC ACID 1 CETYL ALCOHOL 0,75

DIISOPROPYL SE BAC AT E 4,5

TOCOPHEROL 0.10

DIMETHICONE 2,5

GLYCERINE 7

CONSERVATIVE 0.5

DIPROPYLENE GLYCOL 10

WATER Qs 100

Compound 1: 4- (Tetrahydro-0.5

pyran-4-yl) -benzene-1,3-diol

XANTHAN GUM 0,1

ACRYLATES / C 10-30 ALKYL 0.2

ACRYLATE

CROSSPOLYMER

(PEMULEN TR2)

Polyvinylpyrrolidone of 3

average molecular weight

in weight of 30000 Daltons

(PVP K 30L® of the company

ISP)

ETHANOL 6

The hydrophobic compounds are heated independently of those of the hydrophilic phase at 70 ° C. The oil phase is added to the water phase with stirring and then the thickeners and the volatile compounds are added.

The composition is stable and homogeneous after storage for 1 month at 45 ° C.

This composition can be applied regularly to the skin of the face to reduce the signs of skin aging and lighten the skin.

Claims

1. Composition comprising:

a) at least one glycol;

b) at least one nonionic or anionic polymer selected from

homopolymers and copolymers of vinylpyrrolidone,

polyvinyl alcohols,

- celluloses,

homopolymers and copolymers of monomers containing a sulfonic group, and mixtures thereof.

c) water;

d) at least one 4- (heterocycloalkyl) -benzene-1,3-diol compound of the following general formula (I):

in which

R1, R2, R3, R4, identical or different, represent

a hydrogen,

a C1-C4 alkyl radical,

a hydroxymethyl, a hydroxyethyl,

a C1-C4 alkoxycarbonyl,

a C1-C4 alkoxy,

a hydroxyl,

or

R1 and R2 are interconnected and form a carbon ring with 5 or 6 carbon atoms with the carbon atom to which they are bonded and R3 and R4, identical or different, represent:

- a hydrogen

a C1-C4 alkyl radical

or

R1 and R4 are connected together and form a chain - (CH2) ₂ - or - (CH2) ₃ - and R2 and R3, which are identical or different, represent:

- a hydrogen

a C1-C4 alkyl radical X represents an oxygen atom, or a sulfur atom.

Y represents a hydrogen, a chlorine atom or a fluorine atom,

m can take the values 1 or 2 and n can take the values 0 or 1 and when n = 0, then m = 1 or 2, and when n = 1, then m = 1.

as well as the salts of the compounds of general formula (I), and their isomeric and enantiomeric forms, hydrates and solvates.

2 - Composition according to claim 1 characterized in that in the compound d) of formula (I):

R1 represents a hydrogen, a C1-C4 alkyl radical or a hydroxymethyl radical,

R2 represents a hydrogen,

R3 represents a hydrogen,

R4 represents a hydrogen,

X represents an oxygen atom

Y represents a hydrogen or a fluorine atom

- m = 1 and n = 1,

as well as the salts of these compounds and their isomeric and enantiomeric forms, hydrates and solvates.

3 - Composition according to one of claims 1 to 2 characterized in that the compound or compounds d) of formula (I) are chosen from the group consisting of:

1: 4- (tetrahydro-pyran-4-yl) benzene-1,3-diol

2: 4- (tetrahydro-thiopyran-4-yl) -benzene-1,3-diol

3: 4- (cis-2,6-Dimethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

4: trans-4- (2-methyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

5: cis-4- (2-methyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

6: trans-4- (2-Ethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

7: cis-4- (2-Ethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

8: trans-4- (2-Hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

9: 4- (2,2,6,6-tetramethyltetrahydro-pyran-4-yl) benzene-1,3-diol

10: 4- (tetrahydro-furan-3-yl) -benzene-1,3-diol

1: 4- (tetrahydro-thiophen-3-yl) -benzene-1,3-diol

12: 4- (6-Oxa-spiro [4.5] dec-9-yl) -benzene-1,3-diol

13: 4-Chloro-6- (tetrahydro-pyran-4-yl) -benzene-1,3-diol

14: 4-Fluoro-6- (tetrahydro-pyran-4-yl) -benzene-1,3-diol

15: 4- (2,2-Diethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

16: 4- (tetrahydro-pyran-3-yl) -benzene-1,3-diol

17: trans-4- (5-Hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol 18: cis-4- (5-Hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

19: trans-4-Fluoro-6- (5-hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

20: cis-4-Fluoro-6- (5-hydroxymethyl-tetrahydro-furan-3-yl) -benzene-1,3-diol

21: trans-4-Fluoro-6- (2-hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

22: cis-4-Fluoro-6- (2-hydroxymethyl-tetrahydro-pyran-4-yl) -benzene-1,3-diol

23: cis-4- (8-Oxa-bicyclo [3.2.1] oct-3-yl) -benzene-1,3-diol

24: trans-4- (8-Oxa-bicyclo [3.2.1] oct-3-yl) -benzene-1,3-diol

25: 4-Fluoro-6- (tetrahydro-thiopyran-4-yl) -benzene-1,3-diol 4 - Composition according to one of Claims 1 to 3, characterized in that the compound of formula (I) is 4- (Tetrahydro-pyran-4-yl) -benzene-1,3-diol.

5. Composition according to one of claims 1 to 4, characterized in that the compound (s) of formula (I) are present in a content ranging from 0.001% to 10% by weight, relative to the total weight of the composition, more particularly in a content ranging from 0.05% to 5% by weight, and preferably ranging from 0.1% to 2% by weight, and preferably ranging from 0.2% to 1.5% by weight.

6. Composition according to any one of the preceding claims, characterized in that (s) said glycol a) is chosen from propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol diethylene glycol, 1,3-propanediol, 1,5-pentanediol, polyethylene glycol, and a mixture thereof.

7. Composition according to any one of the preceding claims, characterized in that said glycol (s) is chosen from dipropylene glycol, propylene glycol, butylene glycol, and mixtures thereof.

8. Composition according to any one of the preceding claims, characterized in that the said glycol (s) is present (s) in a content ranging from 0.50% to 50% by weight, relative to the weight total of the composition, preferably ranging from 3% to 30% by weight, and preferably ranging from 5% to 20% by weight, relative to the total weight of the composition.

9. Composition according to any one of the preceding claims, characterized in that the polymer (s) b) are chosen from hydroxyalkyl (C1 -C4) celluloses and hydroxyalkyl (C1 -C4) alkyl (C1 -C4) celluloses.

10. Composition according to any one of the preceding claims, characterized in that the polymer (s) b) are chosen from homo- and copolymers of vinylpyrrolidone such as homopolymers of polyvinylpyrrolidones (PVP), polyvinylpyrrolidones complexed with iodine, polyvinylpyrrolidone / vinyl acetate copolymers (PVPA A), polyvinylpyrrolidone / butene; polyvinylpyrrolidone / decene, polyvinylpyrrolidone / hexadecene, polyvinylpyrrolidone / (meth) acrylic acid / C8-C20 alkyl methacrylate, polyvinylpyrrolidone / vinyl acetate / itaconic acid, polyvinylpyrrolidone / vinyl acetate / vinyl propionate.

1 1. Composition according to any one of the preceding claims, characterized in that the said polymer b) is a polymer with a sulphonic group chosen from a polymer of 2-acrylamido-2-methylpropanesulphonic acid and its salts.

12. Composition according to any one of the preceding claims, characterized in that said polymer b) is a monomer polymer containing sulfonic group selected from a crosslinked homopolymer of 2-acrylamido-2-methylpropanesulfonic acid and its salts.

13. Composition according to any one of the preceding claims, characterized in that the (or) polymers b) are present in a content ranging from 0.01% to 15% by weight, preferably from 0.1% to 10% by weight. % in weight.

14. Composition according to any one of the preceding claims, characterized in that it is in the form of a water-in-oil or oil-in-water emulsion, preferably an oil-in-water emulsion.

15. Composition according to any one of the preceding claims, characterized in that it is a cosmetic composition.

16. A process for the cosmetic treatment of keratin materials comprising the application to keratin materials, such as the skin, of a composition according to any one of the preceding claims.

17. A cosmetic process for depigmenting, lightening and / or bleaching keratinous substances, in particular human skin, hair or hair, comprising applying to said keratin materials a composition as defined according to any one of the following: Claims 1 to 15.