MXPA00005901A - Hyperbranched polymers or dendrimers having a particular group, preparation method and compositions containing same - Google Patents

Abstract

The invention concerns a compound selected among hyperbranched polymers and dendrimers, characterised in that it comprises at least one group of formula (I). The invention also concerns a method for preparing said compounds, and their use as thickening or gelling agent, in particular in cosmetics or pharmaceutics. The invention further concerns a cosmetic or pharmaceutical composition containing, in a cosmetically or pharmaceutically acceptable medium, said compounds.

Description

HYPER-RAMIFIED OR DENDRÍMEROS POLYMERS CONTAINING A PARTICULAR GROUP, PREPARATION PROCESS, USE AND COMPOSITIONS THAT INCLUDE THEM DESCRIPTION OF THE INVENTION The present invention relates to novel compounds that can be used in cosmetics or pharmaceutical products, in particular in dermatology, and which make it possible in particular to obtain thick compositions, or even gelled compositions. Hyper-branched polymers and dendrimers are well known in the prior art. Hyper-branched polymers are molecular constructs that have a branched structure, generally around a core. Their structure generally lacks symmetry, the basic units or monomers used to construct the hyper-branched polymer can be of a diverse nature and their distribution is non-uniform. The polymer branches can be of different natures and lengths. The number of base units, or monomers, may be different depending on REF.120628 the different branch. While at the same time they are asymmetric, the hyper-branched polymers may have: an extremely branched structure, around a core; successive generations or branching layers; a layer of extreme chains. The hyperbranched polymers are generally derived from the polycondensation of one or more ABx monomers, where A and B are reactive groups capable of reacting with each other, where x is an integer greater than or equal to 2, but other processes can be considered. preparation. The hyper-branched polymers are characterized by their degree of polymerization DP = 1-b, where b is the percentage of non-terminal functionalities' in B that have not reacted with a group A. Since the condensation is not systematic, in contrast to the synthesis of the dendrimers, the degree of polymerization is less than 100%. An end group T can be reacted with the hyper-branched polymer to obtain a particular functionality on the ends of the chains. Various hyperbranched polymers can be combined together via a covalent bond or any other type of linkage, by means of their end groups. Such polymers, known as bridged polymers, fall within the definition of the hyperbranched polymers according to the present invention. Dendrimers are highly branched polymers and oligomers that have a well-defined chemical structure. As a general rule, the dendrimers comprise a core, a given number of generations of branches, or spikes, and end groups. The generations of spikes consist of structural units that are identical for the same generation of spikes and which may be identical or different for the different spike generations. The generations of spikes extend radially in a geometric progression of the nucleus. The end groups of a dendrimer from the nth generation are the extreme functional groups of the nth generation spikes or the final generation. The definition of dendrimers given above, includes molecules that contain symmetric branching; it also includes molecules containing non-symmetric branching, such as, for example, dendrimers whose spikes are lysine groups, in which the branching of a generation of spikes on the preceding generation takes place on the amin aye of the lysine, which leads to a difference in the lengths of the spikes of different branching. The dense star polymers, the starburst polymers and the rod-shaped dendrimers are included in the present definition of dendrimers. Molecules known as arboroles and cascade molecules also fall within the definition of dendrimers according to the present invention. Several dendrimers can be combined together via a covalent bond or any other type of linkage, by means of their end groups to give species known as bridged dendrimer or dendrimer aggregates. Such species are included in the definition of the dendrimers according to the present invention. The dendrimers may be in the form of a junction of molecules of the same generation, which are referred to as monodisperse junctions; these may also be in the form of junctions of different generations, known as polydispersed junctions. The definition of dendrimers according to the present invention includes the assemblies of monodisperse and polydisperse dendrimers. The French patent application FR 97/04085 in the name of the Applicant describes in particular the novel polymers selected from hyperbranched polymers and dendrimers, which comprise functional groups corresponding to the following formula: HS A C N (II) II Y wherein * Y represents an oxygen atom or an NH group, * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group selected from amino, acylamino, carboxylic acid and ester. These polymers find an application in particular in cosmetics and dermatology, as antioxidants or reducing agents. Now, the Applicant has found, surprisingly, that the said polymers can also be used to allow the preparation of the compositions, in particular cosmetic or pharmaceutical compositions, which are viscosified or thickened, or even gelled. Thus, an objective of the present invention is a compound chosen from the hyperbranched polymers and dendrimers, characterized in that it comprises at least one group of the formula: N C - A s - s A c N (I) / II II \ Y Y wherein: * Y represents an oxygen atom or an NH group, and * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group selected from: amino (-NH2), acylamino (-NH-CO-R) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms , carboxylic acid (-COOH), - ester (-COOR) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms. Another object of the invention is a process for the preparation of the above compounds, in which a polymer is oxidized, this polymer being chosen from the hyper-branched polymers and dendrimers comprising at least one group of the formula (II): HS A C N (ID Yet another object of the invention is the use of at least one compound as described above, as a thickener or gelling agent, in particular in a cosmetic or pharmaceutical composition also comprising a cosmetically or pharmaceutically acceptable medium. Yet another object of the invention is a cosmetic or pharmaceutical composition comprising, in a cosmetically or pharmaceutically acceptable medium, at least one compound as defined above.

Yet another object is the use of at least one polymer chosen from the hyperbranched polymers and dendrimers comprising at least one group of the formula (II), for the preparation of a composition comprising at least one compound as defined above. . The prior art describes a number of common gelling agents or thickeners, which can be used to modify the viscosity of the compositions, in particular cosmetics. Mention may thus be made of the extracts of algae such as agar-agar, carrageenans and alginates; gums; seed extracts, plant exudates or exudates of microorganisms, and cellulose derivatives; fruit extracts such as pectins; gelling agents of animal origin such as gelatin, caseinates or synthetic gelling polymers, soluble in water, such as crosslinked polyacrylic acids. However, these gelling agents have certain drawbacks. Specifically, common gelling agents give gels or thick media as soon as they are introduced into said medium. These in this way must necessarily be introduced into the medium before it is applied to the intended support. Now, it has been found that by using the compounds according to the invention or a composition that includes them, it is possible to form the gel when desired, and in particular in if for example after the composition has been applied to the support In this way, it is possible to form the gel before it has been packed, and thus have available a gelled composition ready to be applied. In this case, the compounds according to the invention are used as common gelling agents. However, it is also possible to prepare a composition which is not gelled because it is not oxidized, to be packaged in this form and to carry out oxidation, and thus gelation, only when the composition is applied to the support, example by oxidation outdoors. This can be advantageous in particular in the case of hair care applications, such as styling gels or hair coloring compositions.

Thus, the invention provides a system for gelling the composition before, during or after it has been applied to the support. Another advantage of the invention lies in the fact that, in certain cases, it may be necessary to separately store two liquid solutions that need to be mixed together, at the time of application, and the viscosity of the resulting mixture needs to be increased before the application. This is the case in particular for certain hair coloring products. The compounds according to the invention allow these requirements to be satisfied. The compounds which are the subject of the invention are thus chosen from the hyperbranched polymers and dendrimers, and comprise at least one group of the formula (I): \ / wherein: * Y represents O or NH, * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group chosen from: amino (-NH2) optionally in the form of a salt or an inorganic or organic acid, acylane (-NH-COR) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group from 1 to 10 carbon atoms, carboxylic acid (-COOH), -ester (-C00R) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms. Preferably, the compound according to the invention is chosen from the hyperbranched polymers, and in particular from polyethylene imine, which comprises at least one group of the formula (I). Preferably, Y represents an oxygen atom. Preferably, the heteroatoms are chosen from oxygen and nitrogen (O and N). Preferably, A is a methyl, ethylene, propylene, methylpropylene, ethylpropylene, tetramethylene, pentamethylene, hexamethylene, phenylene or phenyldiyl group.

Advantageously, A represents a radical corresponding to one of the following formulas (a) to (d): (a) -CHR ^ CHR -'- CHR3- (b) -CHR ^ -CHR ^ -CHR '3-CHR'4 - (c) (d) - (CHR '' rl) - (CHR '' '2) -CH (C02H) -NH-in which * R1, R2, R-, R'1, R'2, R'3 and R '4, R' '' and R '' '2, which may be identical or different, represent: a hydrogen atom; a linear, branched or cyclic, saturated or unsaturated alkyl radical of 1 to 6 carbon atoms; an amino radical (-NH2); a carboxylic acid radical (-COOH); an alkylamino radical of 1 to 10 carbon atoms; an acylamino radical of 1 to 10 carbon atoms; * R "1, R" 2, R "3 and R" 4, which may be identical or different, represent: a hydrogen atom; a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 carbon atoms, the arrows indicating the positions of the substitutions; * k is an integer, preferably 0 or 1. Preferably, A is chosen from the following groups: -CH2-CH (C02H) -NH-; - (CH2) 2- (CH3CONH) CH-; - (CH2) 3- and -CH2-CH (NH-CO-CH3) -. The compounds according to the invention can be obtained in particular by the oxidation of the polymers described in the patent application FR 97/04085, the content of which is incorporated by reference herein, and which are chosen from the polymers hyper-branches and dendrimers, comprising functional groups corresponding to formula (II): HS A C N (II) II Y wherein: * Y represents 0 or NH, * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group chosen from amino, acylamino, carboxylic acid and ester. Oxidation can be carried out by any known means, for example in air or using a common oxidizing agent such as hydrogen peroxide. The oxidation step allows the formation of disulfide, intramolecular and intermolecular bridges, starting with the thiol functional groups, according to the following scheme: The formation of the disulphide bridges causes a "pseudo-crosslinking" of the initial compounds A, which is reflected, depending on the experimental conditions, on the thickening / gelling of the medium, due to the formation of the compounds B. A gel comprising the compounds B is thus directly obtained. The oxidation step is preferably carried out in the presence of water, for example in aqueous or aqueous-alcoholic medium. It is thus possible to obtain gels which can be, preferably, aqueous gels or aqueous-alcoholic gels containing only water or an alcohol / water mixture, for example ethanol / water, one or more compounds B according to the invention and optionally Initial A compounds that have not reacted, when the oxidation is only partially carried out. In addition, it has been found that it is possible to incorporate water-soluble or water-insoluble additives into the aqueous or aqueous-alcoholic medium while at the same time retaining the possibility of obtaining a composition of suitable viscosity. Among the additives that may be incorporated, mention may be made of water-soluble dyes such as fluorescein; cosmetic active agents or pharmaceuticals soluble in water; water-insoluble products having optical properties such as phosphorescence or fluorescence; pigments; fillers; sun filters; cosmetic active agents or pharmaceuticals insoluble in water. It has further been found that the solid additives, the pigment particles or fillers, for example, were completely dispersed homogeneously in the gel; When the viscosity of the mixture is sufficient, decantation or release of said particles is not observed. It is known that the properties of the gels obtained depends on the oxidation conditions, in particular on the concentration of the initial thiol-containing polymer, the number of thiol functional groups in the thiol-containing polymer, the molar mass of the polymer and the pH of the aqueous / aqueous-alcoholic medium before oxidation. Thus, for example, for a poly (ethylene imine) of a given molar mass (molar mass before the grafting of thiol functional groups), with identical thiol grafts, it has been found that the higher the number of grafts, The compounds will mostly gel at low concentration and at a more acidic pH. A thickened solution or a gel is thus obtained, which may preferably have a viscosity of between 10"2 and 107 Pa.s, in particular between 10 and 107 Pa.s and, for example, between 104 and 106 Pa.s. and which can be used, in its native form, as a cosmetic or pharmaceutical composition, or incorporated within a composition, in particular a cosmetic or pharmaceutical composition, depending on the oxidation conditions, it is possible that the completely oxidized mixture remains liquid with a very small increase in viscosity (disulfides are soluble in water at low concentration.) In this case, the medium can be concentrated until a very viscous or thick or gelled solution is obtained, depending on the use considered. It is possible to extract all or part of the water present in said gel, for example by vacuum drying.The dried product obtained in this way, which is generally hygroscopic, once again gives a g when it is put back into water under suitable conditions. When solid additives, for example such as pigment particles are added to the medium before the oxidation step, and when the gel obtained is dried, it was found that, when the dried product is rehydrated by the addition of water and / or alcohol, it is it again obtains a gel having the initial characteristics, in particular without any "release" of the solid particles being observed. When the gel comprising the compounds according to the invention is intended to be used in a cosmetic or pharmaceutical composition, the composition further comprises a cosmetically or pharmaceutically acceptable medium. The aforementioned cosmetic or pharmaceutical composition can be in any form that is suitable for topical application, in particular in the form of aqueous or aqueous-alcoholic gels; in the form of water-in-oil, oil-in-water or multiple emulsions, of more or less thick liquid consistency, such as milk or cream; sprays or spray foams; bars or tubes; solutions or liquid dispersions. A person skilled in the art knows how to prepare these compositions according to the usual methods, based on his general knowledge. In particular, these compositions may contain adjuvants usually used in the cosmetic or pharmaceutical fields, such as oils, waxes or other common fatty substances; surfactants; humectants; emollients; sun filters; hydrophilic or lipophilic agents such as ceramides; free radical scavengers; polymers; proteins; bactericides; kidnapping agents; antidandruff agents; antioxidants; conservative agents; alkalizing or acidifying agents; fragrances; fillers; colorants; active cosmetic or pharmaceutical agents. The amounts of these various adjuvants are those conventionally used in the fields under consideration and can be readily determined by a person skilled in the art. It goes without saying that a person skilled in the art will be careful in selecting this or these optional additional adjuvants, and / or the amount thereof, such that the advantageous properties of the composition according to the invention are not, or are not substantially affected adversely by the considered addition. The compositions according to the invention are, for example, lotions, milks or creams for skin care or hair care; creams, lotions or makeup removing milks; makeup bases; lotions, milks or creams against the sun or after exposure to the sun; lotions, milks or creams for artificial tanning; creams or foams for shaving; aftershave lotions; body hygiene compositions such as bars or deodorant creams; shampoos; hair products to maintain hair style or to shape hair such as styling gels; hair coloring products; lipsticks; lick them or eyeliners which may be for treatment purposes; varnishes for nails or products for the care of the nails. The invention is illustrated in more detail in the following examples. Examples 1 to 8 describe the preparation of the starting compounds of the formula (II). Examples 9 to 16 describe the preparation of the gels according to the invention. The gels obtained were characterized by macroscopic and microscopic observation under polarized light and by X-ray diffraction. The results of these analyzes were, respectively, the isotropic behavior and the absence of crystals.

Example 1: The polyethyleneimine branched polymer of average molecular weight PM = 2000 containing 4 functional SH groups on average per unit 4. 33 ml of β-thiobutyrolactone (for example 50 mmol, 4 molar equivalents calculated in relation to the monomer) are added, at room temperature, to 50 grams of a 50% aqueous solution of polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (within about 30 minutes). After stirring for 4 hours, no more is detected-thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after the revelation with sodium nitroprusside. It is thus observed that some of the initial primary amine functional groups are in the form of -NH-CO- (CH2) 3-SH. This aqueous phase is diluted with water to 100 ml. The active material content of this aqueous phase is 30.11 g / 100 ml, for example 0.5 mol «liter of thiol and 0.125 M of thiol-containing polymer. The pH is 10.3. The molar mass of the synthesized product is: 2408.64 g * mol ":.

Example 2: The polyethyleneimine branched polymer of average molecular weight PM = 2000 containing 10 SH functional groups on average per unit 6. 5 ml of β-thiobutyrolactone (for example 10 molar equivalents calculated in relation to the monomer) are added, at room temperature, to 30 grams of a 50% aqueous solution of polyethyleneimine of average molecular weight MW = 2000, sold by the BASF company under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (within about 30 minutes). After stirring for 24 hours, no more is detected-thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after the revelation with sodium nitroprusside. This aqueous phase is diluted with water to 100 ml.

The content of active material of this aqueous phase is 22.66 g / 100 ml, for example 0.75 mol * liter_1 of thiol and 0.075 M of thiol-containing polymer. The pH is 9.6. The molar mass of the synthesized product is: 3021.6 g «mol_1.

Example 3: Branched polyethyleneimine polymer of average molecular weight MW = 10,000 containing 50 SH functional groups on average per unit 11. 30 grams of 99% polyethyleneimine of average molecular weight MW = 10,000, sold by the company Polysciences are diluted with 11.30 ml of water, followed by the addition of 4.9 ml of β-thiobutyrolactone (for example 50 molar equivalents calculated in relation to the monomer ), at room temperature, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (in approximately 30 minutes). After stirring for 20 hours, no longer detected -thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after the revelation with sodium nitroprusside.

The molecular mass of the synthesized product is 15.108 gßmol "1. This aqueous phase is diluted with water up to 100 ml and the pH is adjusted to 6.7 by the addition of aqueous hydrochloric acid solution, obtaining in this way a homogeneous aqueous solution. it contains 13.67 g / 100 ml of thiol-containing polymer, for example, 0.452 mol / liter.

EXAMPLE 4 Branched polyethyleneimine polymer of average molecular weight MW = 10,000 containing 20 SH functional groups on average per unit . 15 grams of 99% polyethyleneimine of MW = 10,000 average molecular weight sold by the company Polysciences are diluted with 10.15 ml of water, followed by the addition at room temperature of 1.76 ml of β-thiobutyrolactone (for example 20 molar equivalents calculated in relation to to the monomer) under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (within approximately 30 minutes). After stirring for 20 hours, no longer detected -thiobutyrolactone in the medium.

An aqueous polyethyleneimine solution containing thiol with a molar mass of 12,043.2 containing on average 20 SH functional groups per polymer chain is thus obtained. This solution is diluted with water to 100 ml (formation of a stable emulsion) and the pH is adjusted to 6 by the addition of aqueous hydrochloric acid solution. A homogeneous aqueous solution is thus obtained which contains 10.51 g / ml of thiol-containing polymer, for example 0.174 mol / liter.

Example 5: Branched polyethyleneimine polymer of average molecular weight MW = 25,000 containing 50 SH functional groups on average per unit 12. 28 g of water are added, at room temperature, to 12.28 grams of 56% aqueous solution of polyethyleneimine of average molecular weight MW = 25,000, sold by the company BASF under the name Lupasol HF, followed, when the medium became homogeneous , by 1.2 ml of? -thiobutyrolactone (for example 50 molar equivalents calculated in relation to the monomer) under inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (within about 30 minutes). After stirring for 24 hours, no longer detected -thiobutyrolactone in the medium. An aqueous solution of the polyethyleneimine containing thiol of molecular mass of 30,108 which contains on average 50 SH functional groups per polymer chain is obtained in this way. 19.60 g of this solution are diluted with water to 25 ml. An aqueous solution containing 25 g / 100 ml of thiol-containing polymer is thus obtained, for example 0.415 mol / liter of thiol and 8.30 mmol / liter of thiol-containing polymer. The pH of this solution is 10.65.

Example 6: Branched polyethyleneimine polymer of average molecular weight MW = 25,000 containing 125 SH functional groups on average per unit 22. 43 g of water and then 5.44 ml of β-thiobutyrolactone (for example 125 molar equivalents calculated relative to the monomer) are added, at room temperature, to 22.43 grams of a 56% aqueous solution of polyethyleneimine of average molecular weight MW = 25,000 , sold by the company BASF under the name Lupasol HF, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (within about 30 minutes). After stirring for 24 hours, no longer detected -thiobutyrolactone in the medium. An aqueous polyethyleneimine solution containing thiol of molecular mass 37,770, which contains on average 125 SH functional groups per polymer chain, is obtained in this way. 32,080 g of this solution are diluted with water to 50 ml. An aqueous solution containing 25 g / 100 ml of thiol-containing polymer, for example 0.827 mol / liter of thiol and 6.619 mmol / liter of thiol-containing polymer is obtained in this way. The pH of this solution is 9.96.

Example 7: Preparation of the thiol-containing dendrimer: starburst dendrimer (PAMAM) with a generation 1 ethylene diamine core containing 8 SH functional groups on the surface 1. 35 ml of β-thiobutyrolactone (for example, one equivalent calculated in relation to all the primary amine functional groups) is added to 5 grams of an aqueous solution containing 55.7 g / 100 g of starburst dendrimer (PAMAM) with a Generation 1 ethylene diamine core (8 NH2 functional groups on the surface) diluted with 5 ml of water, under an inert atmosphere at room temperature. The medium, which is heterogeneous in the addition, quickly becomes homogeneous after 1 hour. After stirring for 48 hours, only traces of the γ-thiobutyrolactone are detected in the medium. The mixture is washed three times with 10 ml of diethyl ether (the ether is added to the medium, which is stirred for 10 minutes and then allowed to stand and the ether phase is then separated). Nitrogen is bubbled into the aqueous phase obtained in this way to remove all traces of ether. The aqueous solution obtained in this way is analyzed by NMR. In this way it is shown that all the initial primary amine functional groups are in the form of -NH-CO- (CH2) 3-SH. The content of active material of this aqueous phase is 37.76 g / 100 g, for example 134.42 meq SH / 100 g, pH = 8.8. The dendrimer obtained in this way (molar mass 2247.16) is used in aqueous solution without further modification.

Example 8: Poly (ethylene imine) branched polymer of average molecular weight of 2000 containing 11.09 SH functional groups on average per unit 12 ml of? -thiobutyrolactone (for example 11. 09 equivalents calculated in relation to the monomer) are added, at room temperature, to 50 grams of a 50% aqueous solution of poly (ethyleneimine) of molecular weight equal to 2000, sold by BASF under the trade name Lupasol G35, under inert atmosphere at room temperature (slightly exothermic addition). The medium, which is heterogeneous after the addition, quickly becomes homogeneous (within about 30 minutes). After stirring for 16 hours, the reaction is complete (no more is detected -thiobutyrolactone in the medium, and the aqueous phase gives a positive reaction after the revelation with the sodium nitroprusside). Thus, it is shown that some of the initial amine functional groups are in the form -N-CO- (CH2) 3-SH. This aqueous phase can be diluted with water up to 100 ml.

The content of active material of this aqueous phase is 39.16 g / 100 ml, for example 1386 mol * liter_1 of thiol and the pH of 10.15. The polymer obtained in this way can be used in aqueous solution without further modification. The average molar mass of the synthesized product is: 3132.95 g * mol-1.

Example 9: Preparation of aqueous gels from polyethyleneimine containing thiol, according to Example 1 a) Gel is aqueous "simpl is" Starting with the solution containing 30.11 g / 100 ml prepared in Example 1, various solutions are prepared by dilution with water and / or acidification with aqueous solution of hydrochloric acid. Its characteristics are as follows: A few milliliters of solutions 1 and 2 are oxidized with the theoretical amount of added 6% aqueous hydrogen peroxide solution (eg 0.5 times the number of thiol functional groups to be oxidized to disulfide), with vigorous stirring. Solutions 1 and 2 lead instantaneously to clear, transparent, clear gels. b) Gel is for those who have a phosphorescent inorganic filter.

Starting with the solution 1 prepared above, several samples containing zinc sulphide doped with copper sold under the name Green are prepared according to the following table.

LBY 2330 (RN = [68611-70-l]): The% pigment is calculated by the weight relative to the weight of the thiol-containing polymer. The samples are vortexed and then treated with ultrasound, after which a few milliliters of solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added (for example 0.5 times the number of thiol functional groups that they will be oxidized to disulfide) with vigorous agitation (in vortex). Under these conditions, solutions 3, 4 and 5 lead instantaneously to very pale yellow gels, clearly hard, which are phosphorescent throughout the mass of the gel. The phosphorescence is proportionally more intense the greater the amount of pigment. All the pigment particles are evenly distributed in the mass of the gel.

Example 10: Preparation of aqueous gels starting with thiol-containing poly (ethyleneimine) according to Example 2 a) Gel is aqueous "simpl is" Starting with the solution containing 22.66 g / 100 ml prepared in Example 2, various solutions are prepared by dilution with water and / or acidification with aqueous solution of hydrochloric acid. Its characteristics are as follows: A few milliliters of solutions 6 to 10 are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous stirring. Solutions 6 to 10 lead instantaneously to the gels. Solutions 6 and 7 lead to opaque white gels. Gels 8, 9 and 10 are clear, colorless and transparent. The aqueous solutions 6 to 10 can be diluted with water according to the indications in the following table: A few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide, added with vigorous stirring. The solution 11 leads instantaneously to a relatively non-opaque, whitish gel. Solutions 13 and 14 lead to transparent, colorless, clear gels. Solutions 12 and 15 lead to slightly viscous, clear, colorless, clear gels. The gel obtained with solution 14a has a viscosity coefficient associated with the permanent flow obtained by the flow experiments at equilibrium, of 5 x 105 Pa.s. For comparative purposes, solution 14a, which is not oxidized but diluted with a volume of water equal to the volume of the added oxidation agent to form the gel, has a viscosity coefficient associated with the permanent flow obtained by the equilibrium flow experiments. , 1.2 x 10"3 Pa. s. b) Gel is a chemical that contains a phosphorous inorganic component. Starting with solutions 8 and 10 prepared above, various samples are prepared containing zinc sulphide doped with copper, sold under the name Green LBY 2330, according to the next table: The samples are agitated by whirling and then ultrasonic stirring, after which a few milliliters of solution is oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide, added with vigorous stirring. Solutions 16, 17 and 18 instantly lead to very pale yellow gels that are clearly hard, which are phosphorescent throughout the mass of the gel. The phosphorescence is proportionally more intense the greater the amount of pigment. All the pigment particles are evenly distributed in the mass of the gel. Solutions 19, 20 and 21 lead to gels after 30 seconds to 2 minutes; the medium is thus kept under vigorous agitation alternating with ultrasound treatment until it has gelled. Very pale yellow gels which are clearly hard and which are phosphorescent throughout the mass of the gel are obtained.All the pigment particles are evenly distributed in the mass of the gel. c) Gel is aqueous - to the cools. Starting with the solution containing 22.66 g / 100 ml of thiol-containing polymer prepared according to Example 2, a solution containing 19.536 g / 100 ml of thiol-containing polymer is prepared pH 8.97, by acidification with 4 N hydrochloric acid aqueous solution. 0.5 ml of absolute ethanol is added to 1 ml of this aqueous solution. The oxidation is carried out with 180 μl (microliters) of 1.8 M aqueous hydrogen peroxide solution. The corresponding aqueous-alcoholic gel is obtained instantaneously.

Example 11: Preparation of aqueous gels starting with thiol-containing poly (ethyleneimine) according to Example 3 Starting with the solution containing 13.67 g / 100 ml prepared according to Example 3, an aqueous gel is prepared by oxidation with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide). A clear, colorless, clear gel is obtained.

Example 12: Preparation of aqueous gels from polyethyleneimine containing thiol according to Example 4 Starting with the solution containing 10.51 g / 100 ml prepared according to Example 4, an aqueous gel is prepared by oxidation with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide). A clear, colorless, transparent gel is obtained 1 to 2 minutes after the addition of the oxidizing agent.

Example 13: Preparation of aqueous gels starting with the thiol-containing poly (ethyleneimine) according to Example 5 a) Gel is watery "simpl es' Starting with the solution containing 25 g / 100 ml prepared in Example 5, various solutions are prepared by dilution with water and / or acidification with aqueous ochloric acid solution. The features are as follows: A few milliliters of solution are oxidized with the theoretical amount of 6% aqueous solution of ogen peroxide added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide). Solutions 25 to 28 lead to clear, colorless, clear gels: instantaneously for Examples 25 and 26, after 30 seconds for Example 27 and after approximately 2 minutes for Example 28 for which the gel obtained is still viscous. The aqueous solutions 24, 25, 26 and 27 can be diluted with water according to the indications of the following table: A few milliliters of solution are oxidized with the theoretical amount of the 6% aqueous solution of ogen peroxide added with vigorous stirring. Solutions 29 and 30 lead instantaneously to clear, colorless, clear gels that are slightly viscous. Solutions 31 and 32 lead, after 30 seconds to 1 minute, clear, colorless, clear gels, which are slightly viscous. b) Gel is aqueous that contains solid products that are insolubl in the medium. Beginning with solutions 26, 27 and 28 prepared above, several samples are prepared according to the following table, which contain: product A: phosphorescent pigment (zinc sulphide doped with copper sold under the name Green LBY 2330) product B: blue pigment (Ultra arine Blue, Cl 77007) product C: yellow pigment (FD &C Yellow No. 5 Aluminum Lake, Cl 19140 : 1) - product D: water-insoluble red pigment (D &C Red No. 36, Cl 12085) product E: water-insoluble fluorescent product (trans, trans-1,4-bis [2- (3, 4, 5- trimethoxyphenyl) vinyl] -benzene). pH of the solution before the solution with 1/2 volume of water The samples are shaken by whirling and ultrasound, after which a few milliliters of solution are oxidized with the theoretical amount of 6% aqueous solution of ogen peroxide, added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide). Solutions 33 to 37 lead instantaneously to colored gels or gels having specific optical properties as indicated below: solution 33: very pale yellow, almost colorless gel, which is phosphorescent throughout its mass. All the pigment particles are uniformly distributed in the mass of the gel. - solution 34: blue gel of intense brightness. All the pigment particles are uniformly distributed in the mass of the gel. Solution 35: intense bright yellow gel. All the pigment particles are uniformly distributed in the mass of the gel. Solution 36: intense bright red gel. All the pigment particles are uniformly distributed in the mass of the gel. solution 37: green-yellow "fluo-type" gel, which is transparent and fluorescent in the blue region under UV radiation at 365 nm. All the particles of product E are uniformly distributed in the mass of the gel. Fluorescence throughout the mass of the gel. c) Aqueous gels that contain sunspots in water Starting with solutions 26, 27 and 28 prepared above, several samples are prepared, according to the following table, which contains: dye F = fluorescein, sodium salt ( Yellow Acid 73, Color Index 45350) dye G = Rhodamine b (RN = [81-88-9]) - dye H = Orange G (Orange Acid 10, Color Index 16230) pH of the solution before dilution with 1/2 volume of the aqueous solution of the dye pH of the solution before dilution with 1/5 volume of the aqueous solution of the dye The samples are vortexed and sonicated, after which a few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous stirring (for example 0.5 times the number of functional groups thiol that will be oxidized to disulfide). Solutions 38 to 41 lead instantaneously to colored gels as indicated below. Solution 38: intense bright fluorescent yellow gel. solution 39: intense fuchsia pink gel, solution 40: slightly pale orange gel. - solution 41: very pale yellow gel.

Example 14: Preparation of aqueous gels starting with thiol-containing poly (ethyleneimine) according to Example 6 a) Gel is aqueous "simpl is" Starting with the solution containing 25 g / 100 ml prepared in Example 6, various solutions are prepared by dilution with water and / or acidification with aqueous solution of hydrochloric acid. Its characteristics are as follows: A few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are to be oxidized to disulfide). Solutions 43 to 46 lead to clear, colorless, clear gels: instantaneously for Examples 42 and 43, after about 10 seconds for Example 44, after 30 seconds at 1 minute for Example 45 and after about 5 minutes for Example 46. Oxidation of solution 42 leads to a whitish, slightly opaque gel. The aqueous solutions 42 to 45 can be diluted with water according to the following indications: A few milliliters of the solution are oxidized with the theoretical amount of aqueous solution to the 6% of hydrogen peroxide added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are to be oxidized to disulfide). Solutions 48 to 50a lead to transparent, colorless, clear gels: after a few seconds for Example 50a; after about 1 minute for Examples 48 and 49, and after 5 minutes for Example 50. After oxidation, solution 47 becomes viscous in 10 to 20 seconds. The viscous mixture obtained with solution 47 has a viscosity coefficient associated with the permanent flow obtained by equilibrium flow experiments, 4.5 x 10"2 Pa.s. For comparative purposes, solution 47 is not oxidized but diluted with a volume of water equal to the volume of oxidizing agent added to thicken it, has a viscosity coefficient associated with the permanent flow obtained by the experiments of flow at equilibrium, of 1.9 x 10"3 Pa.s. The gel obtained with the solution 50a has a viscosity coefficient associated with the permanent flow obtained by equilibrium flow experiments of approximately 2 x 105 Pa.s. b) Gel is for those that continue with solid products that are insolubles in the medium. Beginning with the solutions 42, 43, 44, 45 and 46 prepared above, several samples are prepared, which contain: - product A: phosphorescent pigment (zinc sulphide doped with copper sold under the name Green LBY 2330) product I: blue pigment (FD &C Blue No. 1 Aluminum Lake, color index 42090: 2) product J: green pigment ( Chromium Hydroxide Green, Color Index 77289) product K: red pigment (D &C Red No. 7 Calcium Lake) product E: water insoluble fluorescent product (trans, trans-1, 4-bis [2- (3,4,5-trimethoxyphenyl) vinyl] -benzene). * pH of the solution before dilution with 1 volume of water ** pH of the solution before dilution with 1/5 volume of water The samples are shaken by whirling and ultrasound, after which a few milliliters of solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide, added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide).

Solutions 51 to 55 lead instantaneously to colored gels or to gels having specific optical properties, as indicated below: solution 51: deep blue gel. All the pigment particles are uniformly distributed in the mass of the gel. Solution 52: intense green gel. All the pigment particles are uniformly distributed in the mass of the gel. solution 53: intense red gel All the pigment particles are uniformly distributed in the mass of the gel. solution 54: green-yellow "fluo-type" gel, which is transparent and fluorescent in the blue region under UV irradiation at 365 nm. All the pigment particles are uniformly distributed in the mass of the gel. There is fluorescence throughout the mass of the gel. - solution 55: very pale yellow, almost colorless gel which is phosphorescent throughout its mass. All the pigment particles are uniformly distributed in the mass of the gel. c) Gel is water-based and contains col orant is sun in water. Beginning with solutions 42, 43, 44, 45 and 46 prepared above, several samples are prepared, containing: dye F = fluorescein, sodium salt (Acid Yellow 73, Color Index 45350) Dye G = Rhodamine B (RN = [81-88-9]) Dye H = Orange G (Orange Acid 10, Color Index 16230) * pH of the solution before dilution with 1 volume of the aqueous solution of the dye ** pH of the solution before dilution with 1/2 volume of the aqueous solution of the dye *** pH of the solution before dilution with 1/5 volume of the aqueous solution of the dye The samples are shaken by whirling and ultrasound, after which a few milliliters of solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide, added with vigorous stirring (for example 0.5 times the number of thiol functional groups that are going to be oxidized to disulfide). Solutions 56 to 60 lead to colored gels as indicated below: solution 56: intense fuchsia pink gel. Solution 57: intense yellow fluorescent gel. Solution 58: intense fuchsia pink gel. Solution 59: intense yellow fluorescent gel. Solution 60: pale orange gel.

Example 15: Preparation of aqueous gels starting with the thiol-containing dendrimer according to Example 7 Starting with the solution containing 37.76 g / 100 g prepared according to Example 7, various solutions are prepared by dilution with water and / or acidification with aqueous hydrochloric acid solution. Its characteristics are as follows: before dilution with water A few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous (vortex) agitation (for example 0.5 times the number of thiol functional groups to be oxidized to disulfide). Solutions 61 and 62 lead to opaque white gels that are very hard (snapshots for Example 61, after a few seconds for Example 62). Solution 64 leads to an opaque white gel after a few minutes. Solution 63 leads, after a few minutes, to a clear, colorless, clear, clearly rigid gel.

Example 16: Preparation of aqueous gels starting with polyethyleneimine containing thiol according to Example 8 a) Gel is watery "simpl is" Beginning with the solution containing 39. 16 g / 100 ml prepared in Example 8, various solutions are prepared by dilution with water and / or acidification with an aqueous solution of hydrochloric acid. Its characteristics are as follows: A few milliliters of solutions 65 to 68 are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous agitation (in vortex) for example 0.5 times the number of thiol functional groups that are to be oxidized to disulfide . Solution 65 leads instantaneously to a transparent gel, colorless, clear. Solutions 66, 67 and 68 lead to colorless, clear, clear gels after the respective times of 5 to 10 seconds, 10 to 20 seconds and a few minutes. The gel obtained with solution 67 has a viscosity coefficient associated with the permanent flow obtained by flow experiments at equilibrium, 3.5 x 104 Pa.s. For comparative purposes, the non-oxidized solution 67, but diluted with a volume of water equal to the volume of the oxidation agent added to form the gel, has a viscosity of 2 x 10"3 Pa.s. Solutions 65 to 67 may be diluted with water according to the indications of the following table: A few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous agitation (in vortex). Solution 69 leads instantaneously to a clear, colorless, clear gel. Solutions 70 to 80 lead to transparent, clear, clear gels at times ranging from a few seconds to a few minutes. b) Gel is acuosos -alcoholic "simpl es" Solutions 66 and 67 can be diluted with absolute ethanol according to the indications in the following table: A few milliliters of the solution are oxidized with the theoretical amount of 6% aqueous solution of hydrogen peroxide added with vigorous agitation (in vortex). Under these conditions, solutions 81 and 82 lead to transparent, colorless, clear gels, which are similar in appearance, respectively, to the gels obtained with aqueous solutions 74 and 78.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (18)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A compound chosen from dendrimers and hyperbranched polymers, characterized in that it comprises at least one group of the formula: wherein: * Y represents an oxygen atom or an NH group, and * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group selected from: amino (-NH2), acylamino (-NH-CO-R) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms; carbon, carboxylic acid (-COOH), -ester (-C00R) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms.

2. The compound according to claim 1, characterized in that it is chosen from the hyperbranched polymers, in particular polyethyleneimine, which comprises at least one group of the formula (I).

3. The compound according to any of the preceding claims, characterized in that Y represents an oxygen atom.

4. The compound according to any one of the preceding claims, characterized in that A is selected from (a) -CHR1-CHR-CHR3- (b) -C Rr I -CER '2 -CHR' 3-CHR '- (d) - (CHR '' r l)} - (CHR '' '2) -CH (C02H) -NH-in which * R1, R2, R3, R'1, R'2, R'3 and R'4, R' '' x and R '' '2, which may be identical or different, represent: a hydrogen atom; a linear, branched or cyclic, saturated or unsaturated alkyl radical of 1 to 6 carbon atoms; an amino radical (-NH2); a carboxylic acid radical (-COOH); an alkylamino radical of 1 to 10 carbon atoms; an acylamino radical of 1 to 10 carbon atoms; * R "1, R", R "3 and R" 4, which may be identical or different, represent: a hydrogen atom; a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 carbon atoms, the arrows indicating the positions of the substitutions; * k is an integer, preferably 0 or 1.

5. The compound according to any of the preceding claims, characterized in that A is chosen from the following groups: -CH 2 -CH (C02H) -NH-; - (CH2) 2- (CH3CONH) CH-; - (CH2) 3- and

6. A process for the preparation of the compounds according to any of the preceding claims, characterized in that a polymer is oxidized, this polymer being chosen from the dendrimers and hyper-branched polymers comprising at least one group of the formula (II): HS A C N (II) II Y wherein * Y represents an oxygen atom or an NH group, and * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms, this group optionally being interrupted with one or more heteroatoms and / or substituted with a functional group selected from: amino (-NH2), acylamino (-NH-COR) in which R represents a linear, branched or cyclic, saturated or unsaturated alkyl group of 1 to 10 carbon atoms, - acid carboxylic (-COOH), ester (-COOR) in which R represents an alkyl, linear, branched or cyclic, saturated or unsaturated group of 1 to 10 carbon atoms.

7. The process according to claim 6, characterized in that the oxidation is carried out in air or using a common oxidation agent such as hydrogen peroxide.

8. The process according to any of claims 6 and 7, characterized in that the oxidation step is carried out in the presence of water, for example in aqueous or aqueous-alcoholic medium.

9. The process according to claim 8, characterized in that the water-soluble or water-insoluble additives are incorporated in the aqueous or aqueous-alcoholic medium.

10. The process according to claim 9, characterized in that the additives are chosen from water-soluble dyes such as fluorescein; cosmetic active agents or pharmaceuticals soluble in water; water-insoluble products having optical properties such as phosphorescence or fluorescence; pigments; fillers; sun filters; cosmetic active agents or pharmaceuticals insoluble in water.

11. The use of at least one compound according to any of claims 1 to 5, as a thickening or gelling agent, in particular in a cosmetic or pharmaceutical composition also comprising a cosmetically or pharmaceutically acceptable medium.

12. A cosmetic or pharmaceutical composition, characterized in that it comprises, in a cosmetically or pharmaceutically acceptable medium, at least one compound according to any of claims 1 to 5.

13. The composition according to claim 12, characterized in that it is in the form of aqueous or aqueous-alcoholic gels; in the form of water-in-oil, oil-in-water or multiple emulsions, of more or less thick liquid consistency, such as milk or cream; sprays or spray foams; bars or tubes; solutions or liquid dispersions.

14. The composition according to any of claims 12 and 13, characterized in that it is in the form of lotions, milks or creams for skin care or hair care; creams, lotions or milks to remove makeup; makeup bases; sunscreen lotions, milks or creams or after exposure to the sun; lotions, milks or creams for artificial tanning; creams or foams for shaving; aftershave lotions; compositions for body hygiene such as bars or deodorant creams; shampoos; hair products to maintain hair style or to shape hair such as gels for styling; hair coloring products; lipsticks; lick them or eyeliners that can be for treatment purposes; nail varnishes or products for nail care.

15. The composition according to any of claims 12 to 14, characterized in that it has a viscosity of between 10 ~ 2 and 107 Pa.s, in particular between 10 and 107 Pa.s, for example between 104 and 106 Pa.s.

16. The composition according to any of claims 12 to 15, characterized in that it can be obtained by the oxidation of a composition comprising at least one polymer chosen from the dendrimers and hyper-branched polymers comprising at least one group of the formula (II ): HS A C N (ID II Y in which Y and A have the meanings defined above

17. The use of at least one polymer chosen from the dendrimers and hyperbranched polymers, comprising at least one group of the formula (II): HS A C N (II) II Y wherein Y and A have the meanings defined above, for the preparation of a composition according to any of claims 12 to 15, or of a composition comprising at least one compound according to any of claims 1 to 5.

18. The use according to claim 17, in a cosmetic or pharmaceutical composition.