WO2010070233A2

WO2010070233A2 - Kit for coating keratin substances comprising a polysaccharide and a chemical crosslinking agent

Info

Publication number: WO2010070233A2
Application number: PCT/FR2009/052586
Authority: WO
Inventors: Bruno Bavouzet; Charlotte Feltin
Original assignee: L'oreal
Priority date: 2008-12-19
Filing date: 2009-12-17
Publication date: 2010-06-24
Also published as: WO2010070233A3; FR2940115B1; FR2940115A1

Abstract

The invention relates, in particular, to a kit for coating keratin substances comprising: - at least one first composition comprising a compound X; - at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together via an in situ chemical crosslinking reaction, at atmospheric pressure and ambient temperature so as to form a film, at least one of said first or second compositions comprising at least one dye, especially a pulverulent dye, in particular pigments and/or pearlescent agents, in a total content of at least 5% by weight relative to the total weight of said composition.

Description

Kit for coating keratin materials comprising a polysaccharide and a chemical crosslinking agent

The subject of the present invention is a cosmetic product, in particular a non-therapeutic make-up or care product for keratin materials comprising at least two compounds X and Y, which are capable of reacting together, at least one of the compounds being a polysaccharide.

The products according to the invention may be make-up or skincare products for keratin materials, in particular skin, lips, eyelashes, eyebrows or nails. In particular, the product according to the invention can be a foundation, a blush or an eyeshadow, a concealer, a blush, a lipstick, a lip balm, a lip gloss, a lip pencil or with eyes, a mascara, an eyeliner or a product for making up the body, for coloring the skin, or for a treatment such as a care cream, a tinted cream, or a sun product. Makeup compositions such as lipsticks and foundations are commonly used to bring an aesthetic color to the lips or to the skin, especially to the face, or to camouflage skin discolorations. These makeup products generally contain water or a hydrophilic phase, fatty substances such as waxes and / or oils, and a particulate phase generally composed of fillers and / or pigments.

These compositions, when they are applied to the skin, have the disadvantage of transferring, that is to say of being deposited at least in part, leaving traces, on certain supports with which they can be put in contact with each other. and especially a glass, a cup, a cigarette, a garment or the skin. It follows a poor persistence of the applied film, requiring regular renewal of the application of the foundation composition or lipstick. These transfer problems are all the more important that the compositions comprise a high content of pigments, which is the case when the compositions are intended to mask dyschromias, problems of damaged skin, or imperfections of relief such as wrinkles or scars. Moreover, the appearance of these unacceptable traces especially on the blouse collar can exclude some women from the use of this type of makeup.

We therefore seek cosmetic compositions called "non-transfer" which have the advantage of forming a deposit that does not transfer, at least in part, on the supports with which they are put in contact (glass, clothing, cigarette, tissue) and exhibiting good behavior over time, in particular color in the case of a makeup product. Better still, we are looking for compositions whose properties hold and non-transfer can be controlled over time, that is to say, compositions having an optimal hold during the day, and can be removed without effort at any time.

To limit the transfer of cosmetic compositions, it is known to use volatile oils. These volatile oils, when present in large quantities, make the makeup product, such as the foundation or the lipstick, uncomfortable for the user: after evaporation of the oil, the makeup deposit gives a feeling of drying and tugging.

In the field of compositions for coating eyelashes or mascaras, it is known in particular anhydrous mascaras or low water content and / or water-soluble solvents, so-called "waterproof mascaras", formulated as a dispersion of waxes in solvents non-aqueous and have good resistance to water and / or sebum.

However, the makeup film obtained after the application of these compositions is not sufficiently resistant to water, for bathing or showers for example, with tears or sweat. The mascara then tends to crumble in time: grains are deposited and unsightly marks appear around the eyes.

The object of the present invention is to provide a novel way of formulating cosmetic compositions, in particular make-up or care compositions, making it possible to obtain a film deposited on keratin materials having good non-transfer properties, good holding properties in the time, especially with water and friction, and conferring a comfortable deposit on the skin, lips, eyelashes or nails.

The inventors have discovered that it is possible to obtain such properties by using a system comprising a polysaccharide (compound X) and a crosslinking agent (compound Y) which polymerize in situ, at atmospheric pressure and at a temperature chosen according to of the system considered, so as to form a film adhering to the keratin materials without being tacky, said film may even be peelable under certain conditions. These compounds also have the advantage of being of natural origin.

Polymeric films formed in situ on keratin materials, have very good adhesion properties, resistance to water or sebum, mechanical resistance to friction, and comfort. In addition, these compositions may have "second skin" characteristics, in that the deposition on the keratin materials is obtained by an in situ reaction, directly on the skin. The resulting film adapts perfectly to the morphology of the skin. Finally, it is possible for the user to modulate the thickness of the deposit formed when it wants to camouflage irregularities of relief of the skin such as wrinkles or fine lines.

Before being applied to keratin materials, compounds X and Y may be present in the same composition or in two different compositions called first and second compositions.

In the case where the compounds X and Y are present within the same composition, they will be in conditions capable of forming a film only after application to the keratin materials.

According to a first aspect, the subject of the invention is a kit for coating keratin materials, comprising:

at least one first composition comprising a compound X; at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film.

According to a particular embodiment of the invention, the kit for coating keratin materials according to the invention comprises:

at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film, at least one of said first or second composition comprising at least one phase particle comprising fillers, pigments and / or nacres in a content of at least 5% by weight relative to the total weight of said composition. In particular, according to a particular embodiment of the invention, the kit for coating keratin materials according to the invention comprises:

at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film, at least one of said first or second composition comprising at least one material dye, especially pulverulent, and in particular pigments and / or nacres in a total content of at least 5% by weight relative to the total weight of said composition.

According to another particular embodiment, the kit for coating keratin materials according to the invention comprises:

at least one first composition comprising a compound X; at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film, and said compound X being present in a content of at least 1% by weight relative to the weight of the first composition or with respect to the total weight of the mixture of the first and the second composition.

According to one embodiment of the invention, the film obtained on keratin materials is peelable.

Preferably, the first composition comprising compound X and the second composition comprising compound Y are packaged in separate packages.

Each composition may be packaged separately in the same packaging article, for example a packaging and dispensing device being arranged to separately store the first and second compositions and comprising an adjustment member allowing a user to vary the relative proportion of the composition. less a composition in the mixture obtained, said relative proportion conditioning the properties of the mixture obtained, for example the properties of non-transfer or comfort. Alternatively, each of the first and second compositions may be packaged in a different packaging article.

According to one variant, the compound X and the compound Y are introduced in a single composition.

This is why the subject of the present invention is, according to a second aspect, a cosmetic composition for coating keratin materials comprising at least one compound X and at least one compound Y, the compound X being a polysaccharide, the said compounds X and Y reacting together by chemical in situ crosslinking reaction after application of said composition to the keratin materials at room temperature so as to form a film. According to this alternative, the film is formed after application of said composition to the keratin materials, in particular the skin, and evaporation of the continuous aqueous phase.

According to one particular embodiment, the cosmetic composition for coating keratin materials comprises (i) at least one compound X and at least one compound Y, the compound X being a polysaccharide, the said compounds X and Y reacting together by an in situ chemical crosslinking reaction after application of said composition to the keratin materials, and (ii) at least one particulate phase comprising fillers, pigments and / or nacres in a content of at least 5% by weight relative to the total weight of said composition.

According to one particular embodiment, the cosmetic composition for coating keratin materials comprises (i) at least one compound X and at least one compound Y, the compound X being a polysaccharide, the said compounds X and Y reacting together by an in situ chemical crosslinking reaction after application of said composition to the keratin materials, and (ii) at least one dyestuff, in particular pulverulent material, in particular pigments and / or nacres, in a total content of at least 5% by weight relative to the total weight of said composition.

According to another particular embodiment, the cosmetic composition for coating keratin materials comprises at least one compound X and at least one compound Y, the compound X being a polysaccharide, the said compounds X and Y reacting together by a chemical crosslinking reaction in situ after application. of said composition on the materials keratin, and said compound X being present in a content of at least 1% by weight relative to the total weight of said composition.

The subject of the invention is also, according to a third aspect, a cosmetic process for coating keratinous substances consisting of: a. mix extemporaneously:

at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, then b. to apply on said keratinous materials at least one layer of said mixture.

According to one embodiment, the cosmetic process for coating keratin materials according to the invention consists in: a. mix extemporaneously:

at least one first composition comprising a compound X; at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a particulate phase comprising fillers, pigments and / or nacres in a content of at least 5% by weight relative to the total weight of said composition, then b. to apply on said keratinous materials at least one layer of said mixture.

at least one first composition comprising a compound X; at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a dyestuff, especially pulverulent material, and in particular pigments and / or nacres in a total content of at least 5% by weight relative to the total weight of said composition, then b. to apply on said keratinous materials at least one layer of said mixture.

According to another embodiment, the cosmetic process for coating keratin materials according to the invention consists in: a. mix extemporaneously:

at least one first composition comprising a compound X; at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, and said compound X being present in the first composition in a content such that it is at least 1% by weight relative to the total weight of the mixture of the first and the second composition. then b. to apply on said keratinous materials at least one layer of said mixture.

Alternatively, compound X and compound Y are applied via at least two separate compositions, each comprising one of the compounds.

This is why the present invention also relates to a cosmetic process for coating keratin materials, the method comprising applying to said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film.

According to one embodiment, a cosmetic process for coating keratin materials according to the invention comprises the application on said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a particulate phase comprising fillers, pigments and / or nacres in a content of at least 5% by weight relative to the total weight of said composition.

According to one embodiment, a cosmetic process for coating keratin materials according to the invention comprises the application on said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a dyestuff, especially pulverulent material, and in particular pigments and / or nacres in a total content of at least 5% by weight relative to the total weight of said composition.

According to one embodiment, a cosmetic process for coating keratin materials according to the invention comprises the application on said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, and said compound X being present in the first composition in a content of at least 1% by weight relative to the total weight of said first composition.

According to this method, it is possible to apply at least one layer of the first composition comprising the compound X to the keratin materials, and then to deposit on the layer or layers of said first composition at least one layer of the second composition comprising the compound Y.

According to one variant, the process consists in applying at least one layer of the second composition comprising the compound Y to the keratin materials, and then depositing on the layer or layers of said second composition at least one layer of the first composition comprising the compound X .

It is also possible to alternately apply to the keratin materials several layers of each of the first and second compositions.

The subject of the invention is also the use of a composition or a kit as described above, for obtaining a film deposited on keratinous substances, having holding, non-transfer and / or comfort properties. improved.

Of course, each composition comprises a cosmetically acceptable medium, ie a non-toxic medium that can be applied to human keratin materials and has a pleasant appearance, odor and feel.

I. Polysaccharide (Compound X)

The polysaccharides (compound X) present in the products according to the invention can in particular be chosen from polysaccharides derived from microorganisms, polysaccharides isolated from algae and polysaccharides from higher plants, possibly modified by chemical reactions.

The polysaccharides are chosen from fructans, gellans, glucans, modified or non-modified starches (such as those derived, for example, from cereals such as wheat, corn or rice, from vegetables such as blond pea, from tubers such as potatoes or cassava), amylose, amylopectin, glycogen, dextrans, celluloses and their derivatives (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, carboxymethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans , pectic acids and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabic, Tragacanth gums, Ghatti gums, Karaya gums, locust bean gum, galactomannans such as guar gums and their nonionic (hydroxypropyl guar) and ionic derivatives, biopolysaccharide gums of microbial origin such as scleroglucan or xanthan gums, mucopolysaccharides, and especially chondroitin sulphates and mixtures thereof.

These polysaccharides may be modified chemically, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, alkylation, or by several of these modifications. The derivatives obtained can be anionic, cationic, amphoteric or nonionic.

In general, the compounds of this type which can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemicals".

Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and volume 15, pp

439-458 ", in" Polymers in Nature, by E. A. Mc GREGOR and C. T. GREENWOOD,

Editions John Wiley & Sons, Chapter 6, pp 240-328, 1980 ", in Robert L.'s book.

DAVIDSON entitled "Handbook of Water Soluble Gums and Resins" published by McGraw HiII Book Company (1980) and in Nndustrial Gums - Polysaccharides and their Derivatives,

Edited by Roy L. WHISTLER, Second Edition, Academy Edition Press Inc., the contents of these three works are fully included in this application for reference.

1. Polysaccharides made by microorganisms

xanthan

Xanthan is a heteropolysaccharide produced on an industrial scale by the aerobic fermentation of the bacterium Xanthomonas campestris. Its structure consists of a main chain of β-D-glucose linked in β (1, 4), similar to cellulose. One in two glucose molecules carries a trisaccharide side chain consisting of α-D-mannose, β-D-glucuronic acid and terminal β-D-mannose. The residue mannose is usually acetylated on carbon 6. About 30% of terminal mannose residues carry a pyruvate group bound in chelated form between carbons 4 and 6. The glucuronic acids and charged pyruvic acids are ionizable, and therefore responsible for the nature anionic xanthan (negative charge up to pH 1). The contents of the pyruvate and acetate residues vary according to the strain of bacteria, the fermentation process, the conditions after fermentation and the purification steps. These groups can be neutralized in commercial products with Na ⁺ , K ⁺ or Ca ²⁺ ions (SATIA Company, 1986). The neutralized form can be converted to an acid form by ion exchange or by dialysis of an acidic solution.

Chemical structure of the base unit of xanthan: β-Glc β-Glc

β-Man

Source: Christensen et al. (1993).

The xanthan gums have a molecular weight of between 1,000,000 and 50,000,000 and a viscosity of between 0.6 and 1.65 Pa.s for an aqueous composition containing 1% of xanthan gum (measured at 25 ^° C. under the viscometer). Brookfield, LVT type at 60 rpm).

Xanthan gum are represented for example by the products sold under the names Rhodicare by the company Rhodia Chimie, under the name SATIAXANE ™ by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industry), under the name NOVAXAN ™ the company ADM, and under the names Keltrol ^® Kelzan ^® and the CP-Kelco. pullulan

Pullulan is a polysaccharide consisting of maltotriose units, known as α (1,4) -α (1,6) -glucan. Three units of glucose in maltotriose are connected via a glycosidic linkage at α (1, 4), while the consecutive maltotriose units are connected to each other by an α (1, 6) glycosidic linkage. Pullulan is produced by fermentation from starch by the mushroom Aureobasidium pullulans.

Chemical structure of the pullulan base unit:

pullulan

Lιnear p ro γ ^y mer o ( ^y 1-6) ^r - ιnked matotrιose unites)>

The pullulan is for example produced under the reference Pullulan PF 20 by the Hayashibara group in Japan.

Dextran and dextran sulfate

Dextran is a neutral polysaccharide without charged group, biologically inert, prepared by fermentation of beet sugar containing only hydroxyl groups. It is synthesized from sucrose by fermentation in the presence of certain lactic acid bacteria, the most common being Leuconostoc mesenteroides and Streptococcus mutans. This connected polysaccharide consists of a succession of glucose molecules forming a chain of variable lengths. The main chain consists of glucose molecules linked together by glycosidic bonds in α (1, 6), and the branches are connected to the main chain by glycosidic bonds in α (1, 3) (and in some cases, in α (1, 2) and α (1, 4)).

Chemical structure of dextran:

It is possible to obtain from the native dextran by hydrolysis and purification, dextran fractions of different molecular weights. Dextran may in particular be in the form of dextran sulfate.

Dextran is represented, for example, by the products sold under the name Dextran or Dextran T by the company Pharmacosmos, under the name Dextran 40 powder or Dextran 70 powder by the company Meito Sangyo Co. Dextran sulphate is marketed by the company PK Chemical A / S under the name Dextran sulphate.

succinoglycane

Succinoglycan is an extracellular polymer produced by bacterial fermentation, of high molecular weight and consisting of repeated units of octasaccharides (repetition of 8 sugars). These units are synthesized in the membranes of the microorganism related to isoprenoid lipids. The main chain contains 3 glucoses and 1 galactose, and the side chain contains 4 glucoses. The sugars are linked together by glycoside bonds β (1, 4) and β (1, 3). The pyruvate substituent is attached to the last glucose of the side chain, however, the succinate can be linked to one of the other 2 glucoses of the same side chain. In addition, the basic unit of said succinoglycans may contain residues of other organic acids, such as pyruvile or acetyl residues, as well as other sugars such as glucuronic acid and / or mannose. The molar ratios between glucose and such organic acid residues are generally between (5 to 8) / (0.01 to 2). The molar ratios between said other sugars and glucose are generally between (0 to 1) / (5 to 8).

The succinoglycans can be obtained by microbial fermentation, for example by fermentation of a medium containing at least one carbon source, by means of a microorganism which preferably belongs to the genus Arthrobacter, such as Arthrobacter Stabilis, to the genus Agrobacterium, such as Agrobacterium tumefaciens, Agrobacterium radiobacter, or Agrobacterium rhizogenes, to the genus Rhizobium, to the genus Alcaligenes, such as Alcaligenes faecalis. The fermentation media comprising the carbon source and the methods of fermentation are extensively described in the literature.

Succinoglycan is an anionic polysaccharide which has the particularity of having a helix-pelot transition, induced by a temperature change. This conformational transition is very cooperative, leading to a significant change in the rigidity of the polymer.

Succinoglycans are, for example, sold under the name Rheozan by Rhodia.

scleroglucan

Scleroglucan is a branched, nonionic homopolysaccharide composed of β-D glucan units. The molecules consist of a main linear chain formed of D-glucose linked by β (1, 3) linkages and of which one in three is linked to a lateral D-glucose unit via a β bond (1, 6).

Chemical structure of scleroglucans:

These polysaccharides are obtained by fermentation of a medium based on sugar and mineral salts, under the action of a Sclerotium-type microorganism, such as Sclerotium glucanium and Sclerotium rolfsii. A more complete description of scleroglucans and their preparation can be found in US 3,301,848.

Scleroglucan is for example sold under the name AMIGEL by ALBAN MULLER, or under the name ACTIGUM ™ CS by Cargill.

2. Polysaccharides isolated from algae Compounds based on alginic acid

By "alginic acid-based compound" is meant in particular alginic acid, alginic acid derivatives and alginic acid salts (alginates) or derivatives thereof. Preferably, the alginic acid-based compound is water soluble.

Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of 2 uronic acids linked by (1, 4) glycosidic linkages: β-D-Manuronic acid (M) and α-L-glucuronic acid (G), having the following chemical structures:

β-D-mannuronate

α-L-glucuronate

The alginic acid is capable of forming water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, lower amine and substituted ammonium cations such as methylamine, ethanolamine, diethanolamine, triethanolamine. These alginates are water-soluble in aqueous medium at pH = 4 but dissociate in alginic acid at a pH below 4.

These alginates are capable of crosslinking with each other in the presence of complexing agents, by formation of ionic bonds between said complexing agents and the negatively charged group of the residue G. The formation of multiple crosslinks between several alginate molecules results in the formation of a matrix forming a gel insoluble in water. Alginic acid-based compounds having a weight average molecular weight of from 10,000 to 1,000,000, preferably from 15,000 to 500,000 and most preferably from 20,000 to 250,000, are preferably used.

According to a preferred embodiment, the alginic acid-based compound is a sodium or potassium alginate.

The alginates and derivatives are represented for example by the products sold under the names SATIALGINE ™, CECALGUM ™ or ALGOGEL ™ by the company Cargill products, under the name Protanal ™ by the company FMC Biopolymer, under the name GRINDSTED ^® Alginate by the company Danisco under the name KIMICA ALGIN KIMICA by the company, and under the name ^® and Manucol Manugel ^® by ISP.

Galactannes

The compound X of the composition according to the invention may be a galactan, especially chosen from agar or carrageenans.

Carrageenans are anionic polysaccharides constituting the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinacae, Hypneaceae, Furcellariaceae and Polyideaceae. they are generally obtained by hot aqueous extraction from natural strains of said algae. These linear polymers, formed by disaccharide units, are composed of two D-galactopyranose units alternately linked by α (1, 3) and β (1, 4) linkages. They are highly sulphated polysaccharides (20-50%) and the α-D-galactopyranosyl residues can be in 3,6-anhydro form. Depending on the number and the position of ester-sulfate groups on the repeating disaccharide of the molecule, there are several types of carrageenans namely: kappa-carrageenans which have an ester-sulfate group, iota-carrageenans which have two ester groups sulphate and lambda-carrageenans which have three ester-sulphate groups.

The carrageenans have in particular the following chemical structures:

Kappa Iota

lambda

Carrageenans consist essentially of potassium, sodium, magnesium, triethanolamine and / or calcium salts and sulfate esters of polysaccharides.

The physico-chemical properties and uses of these polysaccharides as gelling agents rely on their ability to establish conformational platelet-helix transitions as a function of the thermal and ionic environment [Kloareg et al. Oceanography and Marine Biology - An Annual Review 26: 259-315 (1988)].

Carrageenans are especially sold by Seppic under the name Solagum ^®, the Gelymar under the name of Carragel ^®, Carralact ^® and Carrasol ^® by Cargill, under the names SATIAGEL ™ and satiagum ™, and CP-Kelco under the name GENULACTA ^® , GENUGEL ^® and GENUVISCO ^® .

Galactans Agar type are galactose polysaccharides contained in the cell wall of some of these species of red algae (rhodophycea). They are formed of a polymer group whose base skeleton is a chain β (1,3) D-galactopyranose and α (1,4) L 3-6 anhydrogalactose, these units repeating regularly and alternately. Differences within the agar family are due to the presence or absence of methylated or carboxyethylated solvated groups. These structures Hybrids are generally present as a variable percentage, depending on the species of algae and the season of harvest.

The agar is a mixture of polysaccharides (agarose and agaropectin) of high molecular weight, between 40,000 and 300,000 g. mol ^"1. It is obtained by manufacturing algae extraction juice, usually by autoclaving, and treating these juices which include about 2% of agar to extract it.

The agar is for example produced by the group B & V Agar Producers, under the name GoId Agar, Agarite and Grand Agar by the company Hispanagar, and under the names Agar-Agar, QSA (Quick Soluble Agar), and Puragar by the company Setexam .

furcellarane

Furcellaran is obtained commercially from red algae Furœllaria fasztigiata, mainly found in the northern seas of Europe. Its structure is very close to that of carrageenans. Furcellarane is for example produced by the company East-Agar.

3. Polysaccharides of higher plants

We distinguish between homogeneous polysaccharides (a single species of dares) and heterogeneous compounds of several types of dares.

Homogeneous polysaccharides

1. Glucosans

The compound X present in the composition according to the invention may be a glucosane, in particular chosen from native or modified starches, dextrins and derivatives, celluloses and derivatives or fructans.

Native starches

The starches which can be used in the present invention are more particularly macromolecules in the form of polymers consisting of elementary units which are hydroglucose (dextrose) units, linked by α (1, 4) bonds, of chemical formula

(C ₆ H ₁₀ Os) _n - The number of these motifs and their assembly make it possible to distinguish amylose, a molecule formed from about 600 to 1000 linearly chain-linked glucose molecules, and amylopectin, a branched polymer around every 25 glucose residues (α (1, 6) linkage.) The total chain can make between 10,000 and 100,000 residues. glucoses. starch is described in particular in "Kirk-Othmer ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, ^3rd edition, volume 21, p.492-507, Wiley Interscience, 1983".

Chemical structure of starch: Dextrose

amyloidosis

amylopectin

CH _» OH CH.OH

/ /

O

-

The relative proportions of amylose and amylopectin, as well as their degree of polymerization, vary according to the botanical origin of the starches. On average, a sample of native starch consists of about 25% amylose and 75% amylopectin. Sometimes, there is presence of phytoglycogen (between 0 and 20% of the starch), an analogue of amylopectin but branched every 10 to 15 glucose residues.

The starch can be in the form of semi-crystalline granules: amylopectin is organized in sheets, amylose forms a less well-organized amorphous zone between the different layers.

Amyloidosis is organized into a right helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, more easily if it is in the form of amylopectin. Indeed, helical formation does not promote the accessibility of starch to enzymes.

The starches are generally in the form of a white powder insoluble in cold water, the size of the elementary particles ranges from 3 to 100 microns. By treating it with hot water, we obtain the poisoning. It is used in the industry for its thickener and gelling properties.

The starch or amylose molecules used in the present invention may have as botanical origin cereals or tubers. Thus, the starches or amyloses are for example chosen from starches or amyloses of maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, pea.

The native starches are represented for example by the products sold under the names C ^* Amilogel ™, Cargill Gel ™, C ^* Gel ™, Cargill Gum ™, DryGel ™, C ^* Pharm Gel ™ by the company Cargill, under the name Starch of but by the company Roquette, and under the name Tapioca Pure by the company National Starch.

Modified starches

The starches used in the composition of the invention may be modified by one or more of the following reactions: pregelatinization, degradation (acid hydrolysis, oxidation, dextrinization), substitution (esterification, etherification), crosslinking (esterification), bleaching.

More particularly, these reactions can be carried out as follows: - pregelatinization by bursting the starch granules (for example drying and cooking in a drying drum),

acid hydrolysis giving rise to very rapid retrogression on cooling,

- oxidation with strong oxidants (alkaline medium, in the presence of sodium hypochlorite NaOCI for example) leading to the depolymerization of the starch molecule and the introduction of carboxyl groups in the starch molecule (mainly oxidation of the group C ₆ hydroxyl,

dextrinisation in an acid medium at high temperature (hydrolysis then repolymerization),

crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules which will thus be bonded together (for example with glyceryl and / or phosphate groups)

alkaline esterification for the grafting of functional groups, in particular C ₆ acyl (acetyl), hydroxyalkyl C ₆ (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.

In particular, it is possible to obtain, by crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-O-PO- (OX) _{2 type} ), diamidon phosphates (of the Am-O-PO- (OX) -O-Am type). ) or even triamidon (of the type Am-O-PO- (O-Am) ₂ ) or their mixtures.

X denotes in particular alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonium salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, amino-3-propanediol-1,2, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline.

The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.

Other oxidized starches are described later in the description.

According to the invention, it is also possible to use amphoteric starches, these amphoteric starches contain one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites; preferably they are linked to the same reactive site. Anionic groups can be of carboxylic type, phosphate or sulfate and preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type. The amphoteric starches are in particular chosen from compounds of the following formulas:

R 'R

CH-CH-COOM

/

St-O - (CH ₂ ) - N,

CH-CH-COOM

R 'R

(I)

COOM R

CH CH-COOM

St-O - (CH ₂ ) -N

\

R "

(H)

R 's / R "

N St-O-CH ₂ CH-COOM, _{| NOT )}

R 's / R "

N St-O-CH - CH ₂ -COOM, _{| V)}

formulas in which:

St-O represents a starch molecule, R, identical or different, represents a hydrogen atom or a methyl radical,

R ', identical or different, represents a hydrogen atom, a methyl radical or a -COOH group, n is an integer equal to 2 or 3,

M, identical or different, denotes a hydrogen atom, an alkali or alkaline earth metal such as Na, K, Li, NH _4, a quaternary ammonium or an organic amine,

R "represents a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms. These compounds are described in particular in US Pat. Nos. 5,455,340 and 4,017,460, which are incorporated by reference.

The starch molecules can be derived from all plant sources of starch, such as in particular corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above.

The modified starches are represented for example by the products sold under the names C ^* Tex-lnstant (pre-gelatinized adipate), C ^* StabiTex-lnstant (pre-gelatinized phosphate), C ^* PolarTex-Inactive (pre-gelatinized hydroxypropyl), C ^* Set (acid hydrolysis , oxidation), C ^* size (oxidation), C ^* BatterCrisp (oxidation), C ^* DrySet (dextrinization),

C ^* Tex ™ (acetylated diamidon adipate), C ^* PolarTex ™ (hydroxypropylated diamidon phosphate), C ^* StabiTex ™ (diamidon phosphate, acetylated diamidon phosphate) by Cargill, diamidon phosphates or rich compounds in diamidon phosphate as the product proposed under the references PREJEL VA-70-T

AGGL (hydroxypropylated manioc phosphate phosphate gelatinized) or PREJEL TK1

(Gelatinized cassava dihydrogen phosphate) or PREJEL 200 (gelatinized acetylated manioc diamidon phosphate) by the company AVEBE or STRUCTURE ZEA by NATIONAL STARCH (gelatinized cornstarch).

As examples of oxidized starches, use will be made in particular those marketed under the name C ^* size of the company Cargill.

(Cyclo) dextrin and derivatives

Cyclodextrins are a family of cyclic oligosaccharides composed of α (1, 4) -linked glucopyranose subunits. These natural products resulting from the degradation of starch by the bacterium Bacillus macerans, were discovered in 1891 by Villiers. Three families are mainly used or studied the α-, β- and γ-cyclodextrins according to which are formed of 6, 7 or 8 subunits (families of several tens of subunits were synthesized for research purposes).

The empirical formula of β-cyclodextrin is C42H70O35, so its molar mass is 1,134.98 g. mol ^"1 , its CAS number is 7585-39-9 The cyclodextrins are in particular oligosaccharides of formula:

in which x may be a number equal to 4 (which corresponds to α-cyclodextrin), to 5 (β-cyclodextrin) or to 6 (γ-cyclodextrin).

Many derivatives can be obtained from natural cyclodextrins: the hydroxyl groups of the glucopyranose units can be amino, esterified or etherified. The synthesis of these derivatives is often intended to improve solubility. Among the most studied cyclodextrins are β-cyclodextrin (BCD, natural), hydroxypropyl-β-cyclodextrin (HPCD) and methyl-β-cyclodextrin (MCD).

It may especially be used a beta-cyclodextrin sold by Wacker under the name CAVAMAX W7 and a gamma-cyclodextrin sold by the company Wacker under the name CAVAMAX W8.

The cyclodextrin derivatives are, for example, methyl cyclodextrins, such as methyl-beta-cyclodextrin sold by the company Wacker under the name CAVASOL W7.

Cellulose and derivatives

The compound X according to the invention may also be a cellulose or a derivative thereof in particular ethers or cellulose esters (eg methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate, nitrocellulose) .

The invention may also contain a cellulosic associative polymer. According to the invention, the term "cellulosic compound" is intended to mean any polysaccharide compound having in its structure linear chains of anhydroglucopyranose (AGU) residues linked by glycosidic β (1, 4) linkages. The repetition pattern is the cellobiose dimer. The AGUs are in chair conformation and have 3 hydroxyl functions: 2 secondary alcohols (in position 2 and 3) and a primary alcohol (in position 6). The polymers thus formed combine with each other by intermolecular links of the hydrogen bonding type, thus conferring a fibrillar structure on the cellulose (approximately 1500 molecules per fiber).

The degree of polymerization differs enormously depending on the origin of the cellulose; its value can vary from a few hundred to a few tens of thousands.

Cellulose has the following chemical structure:

CellûBiôfδ

A, f

J

The hydroxyl groups of the cellulose may partially or totally react with different chemical reagents to give cellulose derivatives having their own properties. The cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Among these derivatives, there are cellulose ethers, cellulose esters and cellulose ether esters.

Among the nonionic cellulose ethers, mention may be made of alkylcelluloses such as methylcelluloses and ethylcelluloses; hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxyalkyl-alkylcellulose celluloses such as hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses and hydroxybutylmethylcelluloses.

Among the anionic cellulose ethers, mention may be made of carboxyalkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses and carboxymethylhydroxyethylcelluloses and their sodium salts.

Among the cationic cellulose ethers, mention may be made of quaternized hydroxyethylcelluloses which may or may not be crosslinked. The quaternizer may especially be glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. Another cationic cellulose ether that may be mentioned is hydroxyethylcellulose hydroxypropyltrimethylammonium. Among the cellulose esters, there are the inorganic esters of cellulose (cellulose nitrates, sulphates, or phosphates, etc.), the organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetatetrimellitates). ) and mixed organic / inorganic cellulose esters such as cellulose acetate-butyrate sulphates and cellulose acetate propionates. Among the cellulose ether esters, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulphates.

The cellulosic compounds of the invention may be chosen from unsubstituted celluloses and substituted celluloses.

Celluloses and derivatives are exemplified by the products sold under the names Avicel ^® (microcrystalline cellulose, MCC) by FMC Biopolymers, under the name Cekol (carboxymethylcellulose) by the company Noviant (CP-Kelco), under the name Akucell AF (carboxymethylcellulose sodium) by Akzo Nobel under the name Methocel ™ (cellulose ethers) and Ethocel ™ (ethylcellulose) by Dow under the names Aqualon ^® (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel ^® (methylcellulose) Blanose ™ (carboxymethylcellulose), Culminai ^® (methylcellulose, hydroxypropyl methylcellulose), Klucel ^® (hydroxypropylcellulose), Polysurf ^® (cetyl hydroxyethyl cellulose) and Natrosol ^® CS (hydroxyethylcellulose) from Hercules Aqualon.

2. Fructosanes

The compound X present in the composition according to the invention may especially be a fructosan selected from among inulin and its derivatives (especially dicarboxy and carboxymethyl inulins).

Fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with a plurality of different saccharide residues of fructose. The fructans can be linear or branched. The fructans can be products obtained directly from a plant or microbial source or products whose chain length has been modified (increased or reduced) by fractionation, synthesis or hydrolysis in particular enzymatic. The fructans generally have a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60. There are 3 groups of fructans. The first group corresponds to products whose fructose units are mostly linked by β (2,1) linkages. These are essentially linear fructans such as inulin.

The second group also corresponds to linear fructoses but the fructose units are essentially linked by β (2,6) bonds. These products are levanes. The third group corresponds to mixed fructans, ie having β (2,6) and β (2,1) chains. These are essentially branched fructans than graminans.

The preferred fructans in the compositions according to the invention are inulins. Inulin can be obtained for example from chicory, dahlia or Jerusalem artichokes. Preferably, the inulin used in the composition according to the invention is obtained for example from chicory.

The polysaccharides, in particular inulins, used in the compositions according to the invention can be hydrophobically modified. In particular, they are obtained by grafting hydrophobic chains onto the hydrophilic backbone of the fructan.

The hydrophobic chains capable of being grafted onto the main chain of the fructan can in particular be linear or branched hydrocarbon chains, saturated or unsaturated, having from 1 to 50 carbon atoms, such as the alkyl, arylalkyl, alkylaryl or alkylene groups; divalent cycloaliphatic groups or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may in particular comprise one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea, and / or sulphonamide functions, such as especially methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene.

In particular, the polysaccharide, especially inulin, has a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60, and a degree of substitution of less than 2 on the basis of a fructose unit.

According to a preferred embodiment, the hydrophobic chains have at least one alkyl carbamate group of formula R-NH-CO- in which R is an alkyl group having from 1 to 22 carbon atoms.

According to a more preferred embodiment, the hydrophobic chains are lauryl carbamate groups. The inulin used for this invention is represented, for example, by the products sold under the name Beneo ™ inulin by the company Orafti, and under the name

Frutafit® by Sensus. By way of nonlimiting illustration, hydrophobic modified inulins that can be used in the compositions according to the invention include stearoyl inulin such as those sold under the names Lifidrem Inst by Engelhard and Rheopearl INS by Ciba; palmitoyl inulin; undecylenoyl inulin such as those sold under the names Lifidrem INUK and

Lifidrem INUM by the company Engelhard; and inulin lauryl carbamate such as that sold under the name INUTEC SP1 by the company Orafti.

Heterogeneous polysaccharides:

gums

The polysaccharides that may be used according to the invention may be gums, for example cassia, karaya, konjac, tragacanth, acacia or arabic gum.

Gum arabic Gum arabic, of which the gum of Senegal (Acacia seyal, family Leguminosae) is the main variety, consists of a exudate of descending sap solidified, amalgamated naturally or by incision, on the trunk and at the foot of trees, of the family of acacias.

Gum arabic is a highly branched acidic polysaccharide which is in the form of mixtures of potassium, magnesium and calcium salts. The monomeric elements of the free acid (arabic acid) are D-galactose, L-arabinose, L-rhamnose and D-glucuronic acid. It is assumed that gum arabic consists of at least two polysaccharide fractions of different structures. The higher molecular weight fraction contains a modest amount of amino acids but is critical for its properties. The indicated average molecular mass oscillates between

200 and 300 kDa.

Gum arabic is commercially available in the form of powder or unmilled crystals more or less round, yellow to white to yellowish brown in color. The outer surface of the crystals is matte and cracked and their breaks are glassy; they are also often crossed by fine cracks. The gum is bland and odorless. It is soluble in water, insoluble in alcohol. Gum arabic is characterized by three main fractions, an arabinogalactan (AG) fraction with a very small protein fraction, representing 88% of the gum and having a molecular weight of 250 000 Da, an arabinogalactan-protein complex (AGP) having a high molecular weight (1, 5.10 ⁶ ) - protein complex (AGP) representing about 10% by weight of the gum, and a glycoprotein (G1) with a molecular weight of 200,000 Da, component 1, 2% of the gum. The carbohydrate blocks (AG) are linked together by a main polypeptide chain. The carbohydrate blocks consist of a β-linked (1, 3) -linked galactopyranose skeleton, with numerous branches bound to galactopyranose residues in β (1, 6) and containing arabinofuranose, arabinopyranose (Ara), rhamnopyranose (Rha) sugars. ), glucuronic acids (GIcA) and 4-O-methylglucoronic acid. Gum arabic can be precipitated in the presence of trivalent cations and by salts such as silicates, borates and mercuric nitrate.

The gum arabic used for this invention is represented, for example, by the products sold under the name Eficacia ™ by the company Colloides Naturels International, by the product sold under the name Gum Arabia Quick Gum Type 8074 by the company Max Haenelt, by the product sold under the name Arabian Gum Powder 396D sold by Alland & Robert, by the product sold under the name Ticamulsion B-2001 by the company TIC Gums.

Tragacanth

Gum tragacanth, also known as tragacanth or dragon gum, is an exudate obtained from the dried mucilaginous sap of about twenty species of plants of the genus Astracantha (formerly Astragalus) originating in south-eastern Europe and Southwest Asia.

This gum is a complex mixture of several polysaccharides. The two main fractions are tragacanthin (60-70%) and bassorine, also called "tragacanthic acid" (30-40%). In contact with water, tragacanthin dissolves to form a colloidal hydrosol, while the insoluble bassorine swells to form a gel. By using a small amount of water, an adhesive paste is obtained.

The constituent sugar residues of this arabinogalactan are 75% of L-arabinose, 12% of D-galactose, 3% of D-galacturonic acid methyl ester and L-rhamnose. The tragacanthic acid is water-soluble and consists of a (1,4) -linked α-D-galactopyranosyluronic acid backbone with short branches such as β-linked residues D-xylopyranose (1). 3), D-xylopyropyranosyl-1,2-α-1-dimers. β-linked fucopyranose (1, 3), and β-linked D-xylopyranose-1, 2-d-galactopyranose dimers (1, 3).

The constituent sugars of gum tragacanth are therefore in relative proportions 43% of D-galacturonic acid, 40% of D-xylose, 10% of L-fucose and 4% of D-galactose. The average molecular mass of tragacanthic acid is of the order of 840 000 Da.

Karaya gum

Karaya gum is a partially acetylated, high molecular weight polysaccharide, exuded by trees of the species Sterculia (Urens and Setigera), is one of the least water-soluble natural gums. It swells to give a viscous colloidal dispersion.

Karaya gum is a strongly acetylated acid polysaccharide, with a backbone consisting of alternating α-D-galacturonopyranosyluronic acid (1, 4) -related units and α-L-rhamnopyranosyl (1,2) -linked residues. Groups of β-D-galactopyranosyl and D-glucuronopyranosyluronic acid are connected to the oxygens (02 and 03) of the galacturonic acid residues, while half of the rhamnose residues are bound (in 04) to β-residues. D-galactopyranosyl at (1, 4). The molecule also has 13% by weight of acetyl groups. Karaya gum is poorly soluble in water, however, it swells easily in cold water to occupy several times its original volume, especially at small particle size (<200 mesh), giving a dispersion that appears homogeneous

The karaya gum used for this invention is represented for example by the products sold under the names Gum Karaya Powder by the company Alland & Robert.

Galactomannans (guar, carob, fenugreek, tara gum) and derivatives (phosphated guar, hydroxypropyl guar, ..):

Galactomannans are nonionic polysaccharides extracted from the albumen of leguminous seeds of which they constitute the reserve carbohydrate.

Galactomannans are macromolecules consisting of a main chain of β (1, 4) -linked D-mannopyranose units, bearing lateral branches consisting of a single unit D-galactopyranose linked at α (1, 6) to the chain main. The different galactomannans are distinguished on the one hand by the proportion of α-D-galactopyranose units present in the polymer, and on the other hand by significant differences in terms of distribution of galactose units along the mannose chain.

The mannose / galactose ratio (M / G) is of the order of 2 for guar gum, 3 for tara gum and 4 for locust bean gum. The guar molecule thus has on average twice as many branches as the carob. However, within the same sample, this ratio may vary depending on the fractions. Knowledge of the M / G ratio is one way of characterizing the sample although it does not inform the statistical distribution of galactosyl residues on the main chain.

Galactomannans have the following chemical structure:

m ≈ 3; toeust bcam gwm m ≈ 3; T & T mistletoe

Tara gum is characterized by a more statistically random distribution of lateral chains while carob is characterized by a non-statistically random and non-regular distribution, with alternating unsubstituted blocks of intermediate length (smooth regions) and branched blocks (regions hairy). Guar flour has very few smooth regions, with very regular distribution of side chains of galactose.

As for cellulose, the galactomannans that can be used according to the invention contain primary and secondary hydroxyl groups, which, in principle, can be derived and substituted. At the industrial level, only hydroxyalkyl derivatives, carboxymethyl and cationic derivatives, as well as partially depolymerized grades, are commercially available.

The hydroxyalkyl derivatives which can be used according to the invention are obtained for example by treating galactomannans with ethylene or with propylene oxide in an alkaline medium. These derivatives differ from the raw material in their faster hydration kinetics and better solubility.

The products that can be used according to the invention can also be carboxymethyl derivatives. These derivatives are obtained by "etherification" of a certain portion of the hydroxyl groups with hydrochloric acid or sodium chloroacetate. Unlike carboxymethylcelluloses, which are soluble only from degrees of substitution of 0.7 to 1.0, galactomannans (if not already soluble before chemical modification) become completely soluble at a degree of substitution of less than 0.05.

The products that can be used according to the invention can also be cationic derivatives. Cationic derivatives are obtained by treating galactomannans with suitable organic amines such as 2-hydroxy-3-chloropropyltrimethylammonium chloride or its reaction product, 2,3-epoxypropyltrimethylammonium chloride, which is formed in an alkaline medium.

Finally, the products that can be used according to the invention can be partially depolymerized galactomannans, thus having reduced viscosities. These depolymerizations are obtained by acid hydrolysis, oxidation, or enzymatic degradation.

guar

Guar gum is characterized by a mannose: galactose ratio of the order of 2: 1. The galactose group is regularly distributed along the mannose chain.

The guar gums that may be used according to the invention may be nonionic, cationic or anionic.

According to the invention, chemically modified or unmodified nonionic guar gums can be used.

Non unmodified nonionic guar gums are for example the products sold under the name VIDOGUM GH VIDOGUM G and Vidocrem by Unipektin company and under the name Jaguar by Rhodia under the name Meypro ^® Guar by the company Danisco under the name VISCOGUM ™ by the company Cargill, and under the name Supercol ^® guar gum by the company Aqualon. The nonionic guar gums hydrolyzed used according to the invention are for example represented by the products sold under the name Meyprodor ^® by the company Danisco.

The modified nonionic guar gums which can be used according to the invention are preferably modified with dC ₆ hydroxyalkyl groups.

Among the hydroxyalkyl groups, there may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the state of the art and may for example be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum so as to obtain a gum of guar modified with hydroxypropyl groups.

The level of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably varies from 0.4 to 1.2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names Jaguar HP 60, Jaguar HP 105 and Jaguar HP 120 (hydroxypropyl guar), by Rhodia, or under the name N-Hance ^® HP (hydroxypropyl guar) by the company Aqualon.

The compositions according to the invention may also comprise a cationic galactomannan gum. Preferably the galactomannan gum is a cationic guar gum.

The cationic galactomannan gums preferably have a cationic charge density less than or equal to 1.5 meq / g and more particularly between 0.1 and 1 meq./g. The charge density can be determined according to the Kjeldahl method. It generally corresponds to a pH of the order of 3 to 9.

In general terms, within the meaning of the present invention, the term "cationic galactomannan gum" means any galactomannan gum containing cationic groups and / or ionizable groups in cationic groups. The preferred cationic groups are chosen from those comprising primary, secondary, tertiary and / or quaternary amine groups.

The cationic galactomannan gums used generally have a weight average molecular weight of between about 500 and 5 × 10 ⁶ , and preferably between about 10 ³ and ³ × 10 ⁶ .

The cationic galactomannan gums that can be used according to the present invention are, for example, gums comprising trialkyl (d-C ₄ ) ammonium cationic groups. Preferably, 2 to 30% by number of the hydroxyl functions of these gums carry trialkylammonium cationic groups.

Among these trialkylammonium groups, there may be mentioned very particularly trimethylammonium and triethylammonium groups.

Even more preferentially, these groups represent from 5 to 20% by weight of the total weight of the modified galactomannan gum.

According to the invention, a guar gum comprising hydroxypropyltrimethylammonium groups, that is to say a gum modified for example by 2,3-epoxypropyltrimethylammonium chloride, is preferably used.

Example of a cationic guar structure:

These galactomannan gums, in particular guar gums modified with cationic groups, are products that are already known per se and are described, for example, in US Pat. Nos. 3,589,578 and 4,031,307. Such products are sold in particular under the US Pat. tradenames Jaguar EXCEL, Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 (guar hydroxypropyltrimonium chloride) by Rhodia under the name Amilan ^® Guar (guar hydroxypropyltrimonium chloride) by Degussa and under the name N-Hance ^® 3000 (Guar Hydroxypropyltrimonium Chloride) by Aqualon.

According to the invention, the cationic galactomannan gum may represent from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, and still more preferably from 0.01% to 3% by weight, of the total weight of the composition.

The anionic guar gums that may be used according to the invention are polymers containing groups derived from carboxylic, sulfonic, sulphene, phosphoric, phosphonic acid or pyruvic acid. Preferably the anionic group is a carboxylic acid group. The anionic group may also be in the form of an acid salt, especially a salt of sodium, calcium, lithium or potassium.

The anionic guar gums that can be used according to the invention are preferably carboxymethyl guar derivatives (carboxymethyl guar or carboxymethyl hydroxypropyl guar).

Carob

Locust bean gum is extracted from carob tree seeds (Ceratonia siliqua), which is an evergreen tree native to Syria and Asia Minor but grown throughout the Mediterranean coast.

Galactose sugars are also not evenly distributed along the chain, but tend to be grouped together in blocks. The chains have an irregular structure with "smooth" zones and alternately substituted zones. Locust bean gum useful in this invention can be chemically modified with the same chemical modifications as previously described for guar gum.

The gum unmodified carob used in this invention is sold for example under the name Viscogum ™ by Cargill under the name VIDOGUM L by Unipektin company, under the name Grinsted ^® LBG by Danisco.

The chemically modified carob gums which can be used in this invention can be represented, for example, by the cationic carob sold under the name Catinal CLB (carob Hydroxypropyltrimonium Chloride) by the company Toho.

TARA rubber

The tara gum for use in this invention can be chemically modified with the same chemical modifications as previously described for guar gum.

The Tara gum that can be used in the context of this invention is sold, for example, under the name Vidogum SP by the company Unipektin.

Glucomannans (konjac gum):

Glucomannan is a high molecular weight polysaccharide (500,000 <Mgucomannan <2,000,000), composed of D-mannose units and D-glucose with a branch every 50 or 60 units or so. It is found in wood but it is also the main constituent of Konjac gum. Konjac (Amorphophallus konjac) is a plant of the family Araceae.

Chemical structure of konjac gum: The products used according to the invention are for example sold under the name ^® and Propol Rheolex ^® by the company Shimizu.

LM and HM pectins, and derivatives

Pectins, or more broadly pectic substances, are polysaccharides, attached to carbohydrates. These are substances of exclusively vegetable origin. Pectin is present in large quantities in some algae, in pips and zests of gooseberry, apple, quince, lemon. The pectins are extracted from the raw material by solubilization in hot acid medium and then by precipitation in alcohol. The precipitate is then washed with a sodium hydroxide solution to obtain the desired pH. Pectins are polymers of acidic polysaccharides. The pectins are linear polymers of α-D-galacturonic acid (at least 65%) bonded in position 1 and 4, with a certain proportion of carboxylic groups esterified with a methanol group. About 20% of the sugars constituting the pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, D-xylose). The residues of L-rhamnose are found in all the pectins, integrated in the main chain in positions 1, 2. They are at the origin of the nonlinear character of the main chain (cf chemical structure). Their molecular weight is of the order of 10 ⁵ g / mol.

Chemical structure (polygalacturonic acid):

Uronic acid molecules have carboxyl functions. This function gives pectins the ability to exchange ions when they are in COO form. ^" Bivalent ions (calcium in particular) have the ability to form ionic bridges between two carboxyl groups of two different pectin molecules. In the natural state, a certain proportion of the carboxylic groups are esterified with a methanol group. The degree of natural esterification of a pectin can vary between 70 (apple, lemon) and 10% (strawberry) depending on the source used. From pectins of high degree of esterification, it is possible to hydrolyze the -COOCH ₃ groups, in order to obtain weakly esterified pectins. Depending on the proportion of methylated monomers or not, the chain is therefore more or less acidic. HM pectins (High methoxy) having a degree of esterification greater than 50% and LM (Low Methoxy) pectins having a degree of esterification of less than 50% are thus defined. In the case of amidated pectins, the -OCH ₃ group is substituted with a -NH ₂ group.

The degree of esterification influences the gelation properties of the HM pectins. The ester group is less hydrophilic than the acidic group, and therefore HM pectin (with a high degree of esterification) gels at a higher temperature than LM pectin (with a low degree of esterification). The difference is reflected in terms of fast, medium and slow gelation.

The pectins are marketed by the company Cargill under the name Unipectine ™, by the company CP-Kelco under the name GENU, by Danisco under the name GRINSTED Pectin.

Other Polysaccharides:

Chitin, chitosan and derivatives

Among the polysaccharides that may be used according to the invention, mention may also be made of polysaccharides originating from the animal kingdom. This is for example the case of chitin, chitosan and derivatives (chitosan-beta-glycerophosphate, carboxymethylchitine, etc.).

Chitin is an amino sugar, polysaccharide, made of acetylglucosamine (N-acetyl-D-glucose-2-amino) groups linked together by a β-type bond (1, 4). It is this type of bond that links the glucose groups in the cellulose molecule.

The chemical name of the molecule is PoIy N-acetyl-D-glucosamine, β (1, 4) -2-Acetamido

2-deoxy-D-glucose.

Chitin is one of the constituents of the cuticle of insects, spiders and crustaceans, so it has a protective role. Associated with calcium carbonate, it becomes rigid and then forms the exoskeleton of crustaceans and all shelled animals such as snails. Chitosan is a polysaccharide composed of the random distribution of β (1,4) linked D-glucosamine (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit). It is produced by chemical (alkaline) or enzymatic deacetylation of chitin, the component of the exoskeleton of arthropods (crustaceans) or the endoskeleton of cephalopods (calamari ...) or the wall of fungi. This raw material is demineralized by treatment with hydrochloric acid, then deproteinized in the presence of sodium hydroxide or potassium hydroxide and finally discolored with an oxidizing agent.

Chemical structure of chitosan:

The degree of acetylation (DA) is the percentage of acetylated units relative to the number of total units, it can be determined by infrared spectrometry with

Fourier (IR-TF) or by titration with a strong base. The border between chitosan and chitin corresponds to a DA of 50%: on the other hand, the compound is called chitosan, beyond, chitin.

Chitosan is soluble in acidic medium unlike chitin which is insoluble. It is important to distinguish between the degree of acetylation (DA) and the degree of deacetylation (DD). One being the opposite of the other, that is to say that chitosan having a

DD 85%, has 15% of acetyl groups and 85% of amino groups on its chains.

Chitin is a particularly effective moisturizing agent. Its advantage is twofold: it brings water and prevents dehydration. In addition, the great advantage of chitin and its derivatives is the persistence of this moisturizing power over time. Finally, chitosan forms on the surface of the skin a protective and tensor film, able to fix other active ingredients for the skin. Thus other moisturizing agents, sunscreens, organic acids or other active ingredients may be associated with chitin derivatives. Chitin would promote their effects. The products that can be used according to the invention are, for example, those sold by France-Chitine.

Glycosaminoglycans (GAG)

Hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate or heparin and heparan sulfate may be mentioned in particular.

The polysaccharides that may be used according to the invention are also represented by glycosaminoglycans or glycosaminoglycans (GAGs). These polysaccharides have long been referred to as "acidic mucopolysaccharides" because of their high water retention capacity ("muco"), their carbohydrate nature ("polysaccharides") and their acidity from their multiples. negative charges ("acids"). It is indeed sulphated linear (unbranched) chains composed of the repetition of a basic diholoside always containing a hexosamine (glucosamine (GIcN) or galactosamine (GaIN)) and another monosaccharide (glucuronic acid (GIcA), iduronic acid (IdoA), galactose (GaI)). Glucosamine is either N-sulfated (GIcNS) or N-acetylated (GIcNac). Galactosamine is always N-acetylated (GaINac).

They form important connective tissue components and account for about 30 percent of organic matter.

GAG chains can be covalently linked to a protein to form proteoglycans.

GAGs include chondroitin sulfate (elastic cartilage, hyaline cartilage, bone, dermis, cornea), dermatan sulfate (dermis, tendon, ligament, fibrous cartilage), keratan sulfate (cartilage, cornea), heparin / heparan sulfate ( liver, lung, aorta), and hyaluronic acid.

On the one hand, we distinguish simple polymers which only have GIcA residues along their chain (hyaluronic acid, chondroitin sulfate) and, on the other hand, copolymers comprising both residues of GIcA and IdoA (heparin). heparan sulfate and dermatan sulfate). There are also glucosaminoglycans of structure [UA-GlcN] n and galactosaminoglycans of structure [UA-GalN] n. Hyaluronic acid (from the Greek hyalos = vitreous + uronic because it was first isolated from the vitreous humor and has a high level of uronic acid) is a glycosaminoglycan distributed widely among the connective tissues, epithelial and nervous. It is found, for example, in vitreous humor and synovial fluid. It is one of the main components of the extracellular matrix. It contributes significantly to the proliferation and migration of cells. He may be involved in the progression of certain malignant tumors.

It is associated with a protein fraction to form a mucoprotein. Hyaluronic acid is a polymer of disaccharides, themselves composed of D-glucuronic acid and DN-acetylglucosamine, linked to each other by alternating glycoside bonds β (1, 4) and β (1, 3). The polymers of this repeating unit can have a size between 10 ² and 10 ⁴ kDa in vivo.

Chemical structure of hyaluronic acid:

Hyaluronic acid is energy stable, partly because of the stereochemical aspects of the disaccharides that make it up.

Hyaluronic acid is made up of about 50000 dissachable units, it is about the size of a bacterium and has a gel appearance.

Hyaluronic acid is mainly obtained, industrially, by two different processes: extraction of rooster ridges (after grinding, chemical treatment and purification), or bacterial fermentation (the hyaluronic acid filaments are synthesized by genetically modified bacteria) .

Sodium hyaluronate is the sodium salt of hyaluronic acid. Chondroitin sulfate, or chondroitin sulfate, is a glycosaminoglycan found in connective tissue.

Chondroitin sulfate is a component of the cartilage matrix. Its function is to maintain osmotic pressure by absorbing water and helping to moisturize cartilage. It also contributes to the flexibility and elasticity of the bone. More importantly, it acts as a chondroprotective agent protecting the cartilage against enzymatic reactions and free radical damage (including nitric oxide released by chondrocytes). The basic unit of chondroitin sulfate is glucuronic acid β (1, 3) N-acetyl galactosamine 6 sulfate. Each unit is connected to the next by a link β (1, 4). Chondroitin sulfate varies in its composition depending on the animal species even if the basic structure is mainly unchanged.

Chemical structure of chondroitin sulfate:

Heparin is a molecule that is part of the glycosaminoglycans (GAG).

It is formed of the dimer L-iduronic acid-2-O-sulfate (α (1,4) D-glucosamine-N-sulfate, 6-O-sulphate α (1,4) Chemical structure of heparin:

According to a preferred embodiment, hyaluronic acid will be used.

Xylans (or arabinoxylans) and derivatives The flour contains fragments of the primary walls of the starchy albumen of wheat; they belong essentially to a family of polysaccharides: arabinoxylans. These are polymers of xylose and arabinose, all grouped under the name "pentosans". The wheat grain arabinoxylan is composed of residues of β-D-xylopyranose (Rodionova et al., 1992). Xylans consist of a main chain of β-linked (1, 4) -D-xylose units on which three substitutes are found (Rouau & Thibault, 1987): acidic units, α-L- arabinofuranose, side chains that may contain arabinose, xylose, galactose and glucuronic acid. Arabinoxylan generally consists of 1500-5000 residues of α-L-arabinofuranose and D-xylopyranose (Chaplin, 2004). The presence of arabinose side chains reduces the interaction between chains because of their hydrophilic and flexible furanose conformation (Chaplin, 2004).

Non-cationic oxidized polysaccharides

According to a particular embodiment of the invention, the compound X is a non-cationic oxidized polysaccharide of formula (I) and / or their salts of organic or inorganic carboxylic acids:

P- (CHO) _m (COOH) _n (I) in which:

P represents a polysaccharide chain consisting of monosaccharides comprising 5 carbon atoms or more than 5 carbon atoms, preferably 6 or more carbon atoms and more particularly 6 carbon atoms. "M + n is greater than or equal to 1, m is such that the degree of substitution of the polysaccharide by one or more aldehyde groups (DS (CHO)) is in the range of from 0.001 to 2, preferably from 0.005 to 1.5, n is such as the degree of the substitution of the polysaccharide with one or more carboxyl groups (DS (COOH)) is in the range from 0 to 3, preferably from 0.001 to 2.7. By degree of substitution DS (CHO) or DS (COOH) polysaccharides according to the invention means the ratio between the number of oxidized carbons in an aldehyde or carboxyl group for all repeating units and the number of elemental monosaccharides (even open by pre-oxidation) constituting the polysaccharide.

The CHO and COOH groups can be obtained during the oxidation of certain carbon atoms, for example in the C2, C3 or C6 position, of a saccharide unit with 6 carbon atoms. Preferably, the oxidation can be C 2 and C 3, more particularly from 0.01% to 75% by number, and preferably from 0.1% to 50% by number of the cycles which may have been opened;

The polysaccharide chain, represented by P, is preferably chosen from: fructans or fructosans, in particular inulin and graminane - glucans, in particular starch, carboxymethyl starch, pectin, amylopectin, amylose, cellulose and its alkyl, hydroxyalkyl or carboxyalkyl derivatives, such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose; curdlane, dextran, pullulan; galactans, in particular agar-agar and carrageenans - hemicelluloses, in particular arabans, xylans, hexosans and polyuronides, mannan, guar, alginates, xanthanes and pentosans

The oxidation can be carried out according to a process known in the art, for example according to the process described in patent FR 2842200 or FR 2854161 or in the article "Hydrophobic films from maize bran hemicelluloses" by E. Fredon et al., Carbohydrate Polymers 49, 2002, pp. 1-12, Industrial Crops and Products 7, 1997, pp. 45-52. These oxidation processes are simple to implement, effective, do not generate toxic byproducts or difficult to eliminate.

These processes make it possible to prepare a modified polysaccharide by conversion of hydroxymethyl groups (CH 2 OH) to carboxylic acid groups (COOH) or aldehyde groups (CHO).

Among these oxidation processes, one of the preferred ones is that described in application FR2842200. In this process, a glucose unit polysaccharide is subjected to the action of a peroxide, preferably hydrogen peroxide and in the presence of a phthalocyanine-metal catalyst complex. In a particular embodiment, a tetrasulfophthalocyanine, designated FePcS, is used as the catalyst.

More preferably, the polysaccharide chain P is obtained by oxidation of cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, carboxymethyl starch, amylose, inulin, guar, xanthan, carrageenan, dextran or scleroglucan.

In particular, it will be an amylose of maize, a potato starch, a starch of wheat or rice,

The non-cationic oxidized polysaccharide according to the invention is generally present in the composition in an amount ranging from 0.05 to 99% by weight relative to the total weight of the composition, preferably from 0.1 to 30% by weight, and better from 1 to 20% by weight relative to the total weight of the composition.

According to a particular embodiment, the compound X is a polysaccharide prepared by microorganisms selected from xanthan, pullulan, dextran and dextran sulfate, succinoglycan, scleroglucan and their mixture.

According to another embodiment, the compound X is a polysaccharide isolated from the algae chosen from galactans, furcellaran and their mixture.

In another embodiment, the compound X is a polysaccharide of higher plants selected from homogeneous polysaccharides consisting of a single species of oste and heterogeneous polysaccharides composed of several types of oste.

According to one particular embodiment, the compound X is a homogeneous polysaccharide chosen from glucosans, fructosans and their mixture.

According to one variant, the compound X is a glucosane chosen from native starches, modified starches, (cyclo) dextrin and its derivatives, cellulose and its derivatives.

According to another variant, the compound X is a fructan selected from inulin and its derivatives such as in particular dicarboxy and carboxymethyl inulin. According to a particular embodiment, the compound X is a heterogeneous polysaccharide chosen from gums, galactomannans and their derivatives, LM and HM pectins and their derivatives, chitin, chitosan and their derivatives, glycosaminoglycans, xylans (poly C-5 ) and their derivatives.

In particular, compound X is a gum chosen from cassia gums, acacia gum or gum arabic, karaya gum, konjac gum, gum tragacanth, and their mixture.

In another embodiment, the compound X is a galactomannan chosen from guar, carob, fenugreek, tara gum and their derivatives from phosphated guar, hydroxypropyl guar and their mixture.

According to yet another embodiment, the compound X is a polysaccharide chosen from chitin, chitosan and derivatives, glycosaminoglycan, xylan and their mixture.

In a particular embodiment, the compound X is a glycosaminoglycan selected from hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate or heparin and heparan sulfate.

According to a particular embodiment, the compound X is a glucosane, in particular a modified starch, and in particular an oxidized starch.

According to another particular embodiment, the compound X is a galactomanane, in particular a locust bean gum.

According to another particular embodiment, the compound X is a glycosaminoglycan, in particular hyaluronic acid.

According to one particular embodiment of the invention, the compound X is an oxidized non-cationic polysaccharide of formula (I) as described above, in particular an oxidized starch. In particular, it will be an oxidized starch, in particular an amylose of corn, a potato starch, a wheat starch or a rice starch, obtained according to the process described in the patent application FR 2842200. The polysaccharide (s) (X) may be present in the composition according to the invention in a content ranging from 0.1 to 40% by weight, relative to the total weight of the composition, preferably from 1 to 40% by weight, more preferably 1 to 20% by weight, and more preferably 1 to 10% by weight.

According to a particular embodiment, the polysaccharide (s) (X) will be present in the first composition in a content of at least 1% by weight relative to the total weight of said composition, in particular for the variants' single composition comprising X and Y and successive application of the first comprising X and the second composition comprising Y 'according to the invention

According to another embodiment, the polysaccharide (s) (X) will be present in the first composition in a content such that it will be at least 1% by weight relative to the total weight of the mixture of the first and second composition, in particular for the extemporaneous mixing variant of the first composition comprising X and of the second composition comprising Y 'before application.

II. The crosslinking agent (compound Y)

The crosslinking agent (compound Y) according to the invention is a compound capable of reacting with the polysaccharide X by chemical crosslinking, that is to say by forming a covalent bond between the polysaccharide and the crosslinking agent.

The crosslinking agent Y may belong to the group of aldehydes, anhydrous acids, isocyanates, thioisocyanates, azides, azolides, carboimides, epoxides, esters, glycidyl ethers, halogens, imidazoles, imidates, succinimides, succinimidyl esters, and mixtures thereof.

By way of non-limiting example, the following crosslinking agents may be mentioned as examples:

The esters of adipic acid of formula R- (CH ₂ VR with R = COOCOCH ₃ ,

Epichlorohydrin, ethylene glycol diglycidyl ether,

Benzoquinone,

Maleic anhydride Idéhyde glutaraldehyde of formula OHC- (CH ₂ ) ₃ -CHO,

Formaldehyde,

1- (3-Dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC),

Polyethers such as polyethylene oxide (PEO), polysaccharides distinct from those chosen as agent X in the first composition

Proteins, modified or not, such as gelatin, caseins,

Sugars such as sucrose,

The bases, acids or diacids of compounds of plant origin such as mucic acid,

Amino acids such as lysine, (di-amino for example) or its didisocyanate, poly-lysines (Al and Ep),

Phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate, and mixtures thereof.

According to one particular embodiment, the crosslinking agent Y is distinct from the xanthan gum.

According to a preferred embodiment, the crosslinking agent Y is chosen from: polyethers such as polyethylene oxide (PEO),

The polysaccharides distinct from those chosen as agent X in the first composition, proteins, modified or not, such as gelatin, caseins,

1- (3-Dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC). Phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.

Examples of gelatin include gelatin marketed by the company under the GELATINA Gelatina reference ^® gelatin, or Rousselot Rousselot PS of society. The crosslinking agent (Y) may be present in the composition according to the invention in a content ranging from 0.5% to 95% by weight relative to the total weight of the second composition, preferably from 1% to 90%. and better from 2% to 50%.

In particular, the preferred pairs of polysaccharide (X) and crosslinking agent (Y) are chosen from:

Carboxymethylcellulose with polyethers such as polyethylene oxide (PEO), - chitosan with modified or unmodified polysaccharides, such as oxidized starch, galactomananes (guar, carob) with epichlorohydrin, starches with adipate (R- (CH ₂ VR with R = COOCOCH ₃ ) in an alkaline medium, starches with phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate,

Carboxymethylcellulose with phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate, modified starches, in particular oxidized starches, with gelatin or collagen

Hyaluronic acid with modified starches, especially oxidized starches

Hyaluronic acid with 1- (3-dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC), - carboxymethylcellulose with 1- (3-dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC)

More preferably, the pairs will be chosen from:

Carboxymethylcellulose with polyethers such as polyethylene oxide (PEO), chitosan with modified or unmodified polysaccharides, such as oxidized starch,

Modified starches, in particular oxidized starches, with gelatin or collagen

Hyaluronic acid with modified starches, especially oxidized starches

Hyaluronic acid with 1- (3-dimethylaminopropyl) -3-ethylcarbodimide In the case where the compound (s) X and / or Y are in gelled form at ambient temperature, a heating step may be necessary to fluidify them before mixing.

Aqueous phase

According to one particular embodiment, at least one of the first or second compositions according to the invention comprises an aqueous phase.

In particular, the composition (s) according to the invention comprises (nen) t water. The water may be floral water such as cornflower water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or thermal water.

The composition (s) according to the invention may also comprise water-miscible organic solvents (at room temperature - 25 ^° C.), for example monoalcohols having from 2 to 6 carbon atoms, such as ethanol, isopropanol; the polyols having in particular 2 to 20 carbon atoms, preferably having 2 to 10 carbon atoms, and preferably having 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as the mono, di or tri propylene glycol (C 1 -C 4) alkyl ethers, the mono (C 1 -C 4) alkyl ethers, di- or triethylene glycol, and mixtures thereof.

The liquid fraction of the aqueous phase comprises in particular water and organic solvents miscible with water.

Preferably, the aqueous phase may be present in the composition according to the invention in a content ranging from 20% to 99% by weight, relative to the total weight of the composition, preferably ranging from 30% to 80% by weight. and preferably ranging from 40% to 60% by weight.

Hydrophilic gelling agent The composition (s) according to the invention may comprise a hydrophilic gelling agent distinct from the polysaccharides described above.

Of course, those skilled in the art will take care to choose a gelling agent that will not interact with the polysaccharide and / or the complexing agent already present in the composition.

The hydrophilic gelling agents that can be used in the compositions according to the invention can be chosen from: homo or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the names VERSICOL F ^® or VERSICOL K ^® by the company ALLIED COLLOID, UTRAHOLD 8 ^® by CIBA-GEIGY, polyacrylic acids of SYNTHALEN K type,

- copolymers of acrylic acid and of acrylamide sold in the form of their sodium salt under the names Reten ^® by the company Hercules, the sodium polymethacrylate sold under the name Darvan 7 ^® by the company Vanderbilt, salts sodium hydroxide of polyhydroxycarboxylic acids sold under the name HYDAGEN F ^® by Henkel,

polyacrylic acid / alkyl acrylate copolymers of the PEMULEN type; AMPS (polyacrylamidomethyl propanesulfonic acid partially neutralized with ammonia and highly crosslinked) marketed by the company CLARIANT,

- copolymers AMPS / acrylamide type Sepigel ^® or SIMULGEL ^® marketed by SEPPIC, and

polyoxyethylenated AMPS / alkyl methacrylate copolymers (crosslinked or otherwise), proteins such as proteins of plant origin such as wheat or soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates;

cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, as well as the quaternized derivatives of cellulose;

polymers of natural origin, which may be modified, such as: arabic gums, guar gum, xanthan derivatives, karaya gum, locust bean gum, alginates and carrageenans (the alginates being preferably used in the presence of salts such as calcium chloride), glycoaminoglycans, hyaluronic acid and its derivatives, shellac resin, sandarac gum, dammars, elemis, copals, muccopolysaccharides such as chondroitin sulfate,

acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;

vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and of malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;

deoxyribonucleic acid;

unmodified clays, in particular montmorillonites, hectorites, smectites, bentones and laponites, and mixtures thereof.

Some of these water-soluble gelling agents may also act as film-forming polymers.

The water-soluble gelling polymer may be present in the composition according to the invention in a solids content ranging from 0.01% to 30% by weight, relative to the total weight of the composition, preferably from 0.05% to 20% by weight. % by weight, and more preferably from 0.1% to 10% by weight.

Fatty phase

The composition (s) according to the invention may comprise a fatty phase comprising an oily phase.

By oily phase is meant all the oils present in the composition.

The oily phase may comprise at least one oil chosen from volatile oils, non-volatile oils and their mixture.

According to a preferred embodiment, the composition according to the invention may comprise at least one non-volatile oil.

By "non-volatile oil" is meant an oil remaining on the skin at room temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 0.13 Pa (0.01 mm Hg) at ambient temperature ( 25 ° C). These non-volatile oils may be hydrocarbon oils, in particular of animal or vegetable origin, silicone oils, or mixtures thereof. The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and / or phosphorus atoms.

The non-volatile oils may in particular be chosen from fluorinated hydrocarbon oils which may be fluorinated and / or non-volatile silicone oils.

As non-volatile hydrocarbon oil, mention may notably be made of:

- hydrocarbon oils of animal origin,

hydrocarbon oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , the latter being linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or triglycerides of caprylic / capric acids such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810 ^®, 812 ^® and 818 ^® by Dynamit Nobel,

synthetic ethers having from 10 to 40 carbon atoms;

linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof,

synthetic esters such as oils of formula R ₁ COOR ₂ in which R 1 represents the residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, in particular a branched hydrocarbon chain, containing from 1 to 40 carbon atoms with the proviso that R 1 + R ₂ is> 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C _1-2 benzoate benzoates ₅ , hexyl laurate, diisopropyl adipate, isononyl isononanoate, isodecyl neopentanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl-dodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters,

at room temperature liquids with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol or 2-butyloctanol, and 2- undecylpentadecanol,

higher fatty acids such as oleic acid, linoleic acid, linolenic acid and mixtures thereof.

The non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising pendant alkyl or alkoxy groups and / or silicone chain ends, groups each having from 2 to 24 atoms. carbon, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and mixtures thereof.

The non-volatile oils may be present in the composition according to the invention in a content ranging from 1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 3% to 50% by weight, preferably ranging from from 5% to 35% by weight, and more preferably from 10% to 30% by weight.

The composition according to the invention may further comprise at least one volatile oil.

For the purposes of the invention, the term "volatile oil" means any oil capable of evaporating on contact with the skin at ambient temperature and atmospheric pressure. The volatile oils of the invention are volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 0.13 Pa to 40,000 Pa (0.001 to 300 mm). Hg) and preferably ranging from 1.3 to 1300 Pa (0.01 to 10 mmHg). The volatile oil may be chosen from volatile hydrocarbon oils, volatile silicone oils, volatile fluoro oils, and mixtures thereof.

According to a preferred embodiment, the volatile oil is chosen from hydrocarbon oils.

The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and / or phosphorus atoms.

Volatile hydrocarbon oils may be chosen from hydrocarbon oils having from 8 to 16 carbon atoms, and especially branched alkanes, C ₈ -C ₆ isoalkanes C ₈ -C ₆ of petroleum origin (also known as isoparaffins), isododecane (also called 2,2,4,4,6-pentamethylheptane), isohexadecane, and for example the oils sold under the trade names Isopars ^® or Permethyls ^® .

As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, in particular those having a viscosity <5 centistokes (5 × 10 ^-6 m ² / s), and having in particular from 2 to 10 silicon atoms, preferably 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms, For example, the volatile silicone oil that may be used in the invention may be mentioned octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethylisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

The volatile fluorinated oil does not usually have a flash point.

As fluorinated volatile oil, mention may be made of nonafluoroethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane and dodecafluoropentane, and mixtures thereof.

The volatile oil may be present in the composition according to the invention in a content ranging from 1% to 40% by weight, relative to the total weight of the composition, preferably ranging from 3% to 30% by weight, preferably ranging from from 5% to 20% by weight, and more preferably from 5% to 10% by weight. The oily phase of the composition (s) according to the invention may be present in a total content ranging from 1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 3% to 50%. by weight, preferably ranging from 5% to 35% by weight, and more preferably ranging from 10% to 30% by weight.

Structuring agent

The composition (s) according to the invention may comprise at least one structuring agent of liquid fatty phase chosen from waxes, pasty fatty substances, semi-crystalline polymers, lipophilic gelling agents and mixtures thereof.

waxes

The composition (s) according to the invention may comprise at least one wax.

For the purposes of the present invention, the term "wax" is intended to mean a lipophilic fatty compound which is solid at room temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 10 ⁵ Pa), with a solid / liquid state change. reversible, having in particular a melting point greater than or equal to 30 ^° C., in particular greater than or equal to 45 ° C., and up to 250 ^° C., in particular up to 230 ^° C., and in particular up to 120 ^° C.

By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by restoring the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixed.

The melting point values correspond, according to the invention, to the melting peak measured using a differential scanning calorimeter (DS C), for example the calorimeter sold under the name DSC 30 by the company METLER, with a rise in temperature of 5 or 10 ⁰ C per minute.

The waxes, within the meaning of the invention, may be those used generally in the cosmetic or dermatological fields. They can in particular be hydrocarbon, silicone and / or fluorinated, optionally comprising ester or hydroxyl functions. They can also be of natural or synthetic origin.

By way of illustration and not limitation of these waxes, mention may be made in particular of: - beeswax, lanolin wax, and insect waxes from China; rice wax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax, sugar cane wax, japanese wax and sumach wax; montan wax, microcrystalline waxes, paraffin waxes, ozokerites, ceresin wax, lignite wax, polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, esters of fatty acids and the concrete glycerides at 40 ^° C. and especially at more than 45 ^° C.,

the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains, especially hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil,

silicone waxes or fluorinated waxes, and mixtures thereof

The wax (es) may be present in the composition (s) according to the invention in a content ranging from 1 to 15% by weight, relative to the total weight of the composition, preferably from 2 to 12% by weight, and more preferably from 4 to 9% by weight.

Pasty fat

The composition (s) according to the invention may comprise at least pasty fatty substance.

Pasty fatty substance is understood to mean a lipophilic fatty compound containing, at a temperature of 23 ° C., a liquid fraction and a solid fraction. Said pasty compound preferably has a hardness at 20 ⁰ C ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.

The hardness is measured according to a method of penetration of a probe in a sample of compound and in particular using a texture analyzer (for example the

TA-XT2i from Rhéo) equipped with a stainless steel cylinder 2 mm in diameter. The hardness measurement is carried out at 20 ^° C. in the center of 5 samples. The cylinder is introduced into each sample at a pre-speed of 1 mm / s and then at a measurement speed of 0.1 mm / s, the penetration depth being 0.3 mm. The measured value of the hardness is that of the maximum peak.

The liquid fraction of the pasty compound measured at 23 ° C. preferably represents 9 to 97% by weight of the compound. This liquid fraction at 23 ° C is preferably between 15 and

85%, more preferably between 40 and 85% by weight. The liquid fraction by weight of pasty compound at 23 ° C is equal to the ratio of the enthalpy of fusion consumed at 23 ° C on the heat of fusion of the pasty compound.

The heat of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in crystalline solid form. The pasty compound is said to be in a liquid state when all of its mass is in liquid form. The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a rise in temperature of 5 or 10 ⁰ C per minute, according to the standard ISO 11357-3: 1999. The enthalpy of fusion of the pasty compound is the amount of energy required to pass the compound from the solid state to the liquid state. It is expressed in J / g. The heat of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23 ° C consisting of a liquid fraction and a solid fraction.

The liquid fraction of the pasty compound measured at 32 ° C is preferably 30 to 100% by weight of the compound, preferably 80 to 100%, more preferably 90 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32 ° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 ° C.

The liquid fraction of the pasty compound measured at 32 ° C. is equal to the ratio of the enthalpy of fusion consumed at 32 ° C. to the heat of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C.

Paste bodies are generally hydrocarbon compounds such as lanolines and their derivatives or PDMSs.

Lipophilic gelling agents

The composition (s) according to the invention may comprise at least one lipophilic gelling agent.

The gelling agents that may be used in the compositions according to the invention may be organic or inorganic, polymeric or molecular lipophilic gelling agents.

As the mineral lipophilic gelling agent, the optionally modified clays may be mentioned as hectorites modified with a fatty acid ammonium chloride C ₁ 0 -C _22, such as hectorite modified by chloride distearyl di-methyl ammonium such as, for example, that marketed under the name of Bentone 38V ^® by the company ELEMENTIS. It is also possible to mention fumed silica optionally treated hydrophobic surface whose particle size is less than 1 micron. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups can be:

trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are named "Silica Silylate" according to the CTFA (6 ^th edition, 1995). They are for example marketed under the references Aerosil R812 ^® by Degussa, Cab-O-Sil TS-530 ^® by the company Cabot;

dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl Silylate" according to the CTFA (6 ^th edition, 1995). They are for example marketed under the references Aerosil R972 ^® , and Aerosil R974 ^® by the company DEGUSSA, CAB-O-SIL TS-610 ^® and CAB-O-SIL TS-720 ^® by CABOT.

The hydrophobic fumed silica has in particular a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm.

The polymeric organic lipophilic gelling agents are, for example elastomeric organopolysiloxanes partially or totally crosslinked, three-dimensional structure, such as those sold under the names KSG6 ^®, KSG 16 ^® and KSG 18 ^® by the company Shin-Etsu, Trefil E-505C ^® and Trefil E-506C ^® by DOW-CORNING, Gransil SR-CYC ^® , SR DMF10 ^® , SR-DC556 ^® , SR 5CYC gel ^® , SR DMF 10 gel ^® and SR DC 556 gel ^® by the company GRANT INDUSTRIES, SF 1204 ^® and JK 113 ^® by the company GENERAL ELECTRIC; ethyl cellulose such as that sold under the name Ethocel ^® by Dow Chemical; polycondensates of polyamide type resulting from the condensation between (oc) at least one acid selected from dicarboxylic acids comprising at least 32 carbon atoms such as dimeric fatty acids and (β) an alkylene diamine and in particular ethylene diamine, wherein the polyamide polymer comprises at least one group terminal carboxylic acid esterified or amidated with at least one monohydric alcohol or a monoamino comprising from 12 to 30 linear and saturated carbon atoms, and in particular ethylene diamine / stearyl dilinoleate copolymers such as the one sold under the name Uniclear 100 VG ^® by the company ARIZONA CHEMICAL; silicone polyamides of the polyorganosiloxane type, such as those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680, for example those sold under the reference Dow Corning 2-8179 and Dow Corning 2-8178 Gellant by Dow Corning; galactomannans comprising from one to six, particularly two to four hydroxyl groups per saccharide, substituted with a saturated alkyl chain or not, such as guar gum alkylated with alkyl chains to C _6, and in particular C 1 to C ₃ and mixtures thereof. Block copolymers of "diblock", "triblock" or "radial" of the polystyrene / polyisoprene or polystyrene / polybutadiene type such as those marketed under the name Luvitol HSB ^® by the company BASF, of the polystyrene / copoly (ethylene-propylene) such as those marketed under the trademark Kraton ^® by the company Shell Chemical Co., or the polystyrene / copoly (ethylene-butylene), triblock and radial copolymers of the mixtures (star) in isododecane such as those sold by the PENRECO company under the name Versagel ^® such as the mixture of butylene / ethylene / styrene triblock copolymer and star copolymer ethylene / propylene / styrene in isododecane (Versagel M 5960).

Among the gelling agents that may be used in the compositions according to the invention, mention may also be esters of dextrin fatty acid, such as dextrin palmitates, especially such as those sold under the names Rheopearl TL ^® or Rheopearl KL ^® by the company CHIBA FLOUR.

The structuring agent of the oily phase may be present in the composition (s) according to the invention in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, preferably in a content ranging from 0.5% to 7% by weight.

The composition (s) according to the invention may comprise a fatty phase formed of the oils and structuring agents described above, present in a content ranging from 5 to 50% by weight relative to the total weight of the composition. preferably from 10 to 40% by weight, and more preferably from 15 to 30% by weight. Film-forming polymer

At least one of the compositions according to the invention may comprise a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.

The film-forming polymer may be present in a solids content (or active materials) ranging from 0.1% to 30% by weight relative to the total weight of each composition, preferably from 0.5% to 20% by weight. and better from 1% to 15% by weight.

Among the film-forming polymers that may be used in the compositions of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. By radical-forming film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates).

The radical-type film-forming polymers may in particular be polymers, or copolymers, vinylic polymers, in particular acrylic polymers. The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers.

As monomer bearing an acid group, it is possible to use α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid. The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 1 -C ₃₀ alkyl, preferably C ₁ -C ₂₀ aryl, (meth) acrylates, in particular C ₆ -C ₁₀ aryl, hydroxyalkyl (meth) acrylates, in particular C ₂ -C ₆ hydroxyalkyl.

Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate. Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and methacrylate of 2-hydroxypropyl acrylate. hydroxypropyl.

Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

Amides of the acidic monomers include, for example, (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular C ₂ -C ₁₂ alkyls. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide.

The vinyl film-forming polymers can also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.

Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. Styrene monomers include styrene and alpha-methyl styrene.

Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

The polyurethanes may be chosen from anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, poly-urethanes-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and their polyurethanes. mixtures.

The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.

The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-acid. -dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, acid 1, 3- cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These acid monomers The dicarboxylic acid can be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen.

The diol may be chosen from aliphatic, alicyclic and aromatic diols. A diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol and 4-butanediol is preferably used. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane. The polyester amides can be obtained in a similar manner to the polyesters by polycondensation of diacids with diamines or amino alcohols. As the diamine, there can be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As aminoalcohol, monoethanolamine can be used. The polyester may further comprise at least one monomer bearing at least one -SO ₃ M group, with M representing a hydrogen atom, an ammonium ion NH ₄ ⁺ or a metal ion, such as for example an ion Na ⁺ , Li ⁺ , K +, Mg ²⁺ , Ca ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ . In particular, it is possible to use a bifunctional aromatic monomer comprising such a group -SO ₃ M.

The aromatic nucleus of the bifunctional aromatic monomer additionally bearing a -SO ₃ M group as described above may be chosen for example from benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl and methylenediphenyl nuclei. An example of a bifunctional aromatic monomer also bearing an -SO ₃ M group is sulfoisophthalic acid, sulfoterephthalic acid, sulphophthalic acid and 4-sulphonaphthalene-2,7-dicarboxylic acid. It is preferred to use copolymers based on isophthalate / sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid.

The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammars, elemis, copals, cellulosic polymers, and mixtures thereof.

According to a first embodiment of the invention, the film-forming polymer may be a water-soluble polymer and may be present in an aqueous phase of the first and / or second composition; the polymer is solubilized in the aqueous phase of the composition.

According to another variant, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents such as those described above (it is said that the film-forming polymer is a polymer fat-soluble). Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil, the oils may be chosen from the oils mentioned above.

As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group). These copolymers may be crosslinked using crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. divinyl.

Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinylether , vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate of vinyl vinyl / allyl acetate, 2,2-dimethyl-2 vinyl octanoate / vinyl laurate, 2,2-dimethyl-2-allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, dimethyl allyl propionate / stearate vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% of tetraal lyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate cross-linked with 0 2% divinyl benzene.

Liposoluble film-forming polymers that may also be mentioned include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen from copolymers of vinyl polycrystearate, vinyl polystearate crosslinked with divinylbenzene, diallyl ether or diallyl phthalate, copolymers of poly (meth) acrylate stearyl, vinyl polylaurate, lauryl poly (meth) acrylate, these poly (meth) acrylates can be crosslinked using dimethacrylate of the ethylene glycol or tetraethylene glycol. The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

Mention may also be made of liposoluble homopolymers, and in particular those resulting from the rhomopolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 2 to 24 carbon atoms.

As examples of liposoluble homopolymers, there may be mentioned in particular: vinyl polylaurate and lauryl poly (meth) acrylates, these poly (meth) acrylates being capable of being crosslinked by means of ethylene glycol dimethacrylate or tetraethylene glycol . According to an advantageous embodiment, the first and / or second composition of the process according to the invention comprises at least one film-forming polymer polyvinyl acetate.

Liposoluble film-forming polymers that can be used in the invention also include polyalkylenes and especially copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated, for example ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still of C3 to C20 alkene. By way of example of a copolymer of VP which may be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, polyvinylpyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid, VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate. Mention may also be made of silicone resins, generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers. The nomenclature of the silicone resins is known under the name of "MDTQ", the resin being described according to the different siloxane monomeric units that it comprises, each of the letters "MDTQ" characterizing a type of unit. As examples of commercially available polymethylsilsesquioxane resins, mention may be made of those sold: by the company Wacker under the reference Resin MK such as Belsil PMS MK: by the company SHIN-ETSU under the references KR-220L. As siloxysilicate resins, mention may be made of trimethylsiloxysilicate (TMS) resins such as those sold under the reference SR1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of timethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name "KF-7312J" by the company Shin-Etsu, "DC 749", "DC 593" by the company Dow Corning.

Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by Dow Corning under the reference BIO-PSA and described in document US Pat. No. 5,162,410. or the silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and a diorganosiloxane as described in document WO 2004/073626.

It is also possible to use polyorganosiloxane-type silicone polyamides such as those described in documents US-A-5 874 069, US-A-5,919,441, US-A-6,051, 216 and

U.S.-A-5,981,680.

These silicone polymers may belong to the following two families: polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and / or polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.

According to one embodiment of the invention, the film-forming polymer is a film-forming linear ethylenic block polymer, which preferably comprises at least a first block and at least a second block having different glass transition temperatures (Tg), said first and second sequences being interconnected by an intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. Advantageously, the first and second sequences and the block polymer are incompatible with each other.

Such polymers are described for example in EP 1411069 or

WO04 / 028488.

The film-forming polymer may also be present in the first and / or second composition in the form of particles in dispersion in an aqueous phase or in a non-aqueous solvent phase, generally known as latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

Aqueous dispersions of film-forming polymer may be used include the acrylic dispersions sold under the names Neocryl XK-90 ^®, ^® Neocryl A-1070, Neocryl A-1090 ^®, Neocryl BT-62 ^®, Neocryl A-1079 and Neocryl ^® A- 523 ^® by the company AVECIA- Neoresins, Dow Latex 432 ^® by the company Dow Chemical, Daitosol 5000 AD ^® or Daitosol 5000 SJ ^® by the company Daito Kasey Kogyo; Syntran 5760 ^® by the company Interpolymer Allianz OPT by the company Rohm & Haas, aqueous dispersions of acrylic or styrene / acrylic polymers sold under the trade name Joncryl ^® by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the denominations Neorez R-981 ^® and Neorez R-974 ^® by the company AVECIA-NEORESINS, Avalure UR-405 ^® , Avalure UR-410 ^® , Avalure UR-425 ^® , Avalure UR-450 ^® , Sancure 875 ^® , Sancure 861 ^® , Sancure 878 ^® and Sancure 2060 ^® by the company GOODRICH, Impranil 85 ^® by the company BAYER, Aquamere H-1511 ^® by the company HYDROMER; sulphopolyesters sold under the brand name Eastman AQ ^® by Eastman Chemical Products, vinyl dispersions, Mexomere PAM ^® from Chimex, and mixtures thereof.

Examples of non-aqueous dispersions of film-forming polymer include the acrylic dispersions in isododecane, Mexomer PAP ^® from the company Chimex, particle dispersions of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid fatty phase , the ethylenic polymer being advantageously dispersed in the absence of additional stabilizer at the surface of the particles as described in particular in WO 04/055081.

The compositions according to the invention may comprise a plasticizer promoting the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from all compounds known to those skilled in the art as being capable of performing the desired function.

COLORING MATERIALS

A composition according to the invention may comprise at least one dyestuff, in a total content of at least 5% by weight relative to the total weight of said composition.

A cosmetic composition in accordance with the invention may advantageously incorporate at least one dyestuff chosen from organic dyestuffs or inorganic, in particular of the type of pigments or pearlescent agents conventionally used in cosmetic, liposoluble or water-soluble compositions, of materials with specific optical effect, and their mixtures.

Advantageously, a composition of the invention may comprise at least one pulverulent dyestuff in a content of at least 5% by weight relative to the total weight of said composition, in particular chosen from pigments, nacres, effect materials optical, and their mixtures.

In particular, the composition comprises at least pigments and / or nacres in a content of at least 5% by weight relative to the total weight of said composition.

Pulverulent dyestuffs

At least one of the first or second compositions according to the invention comprises a colored powder phase comprising pigments, and / or pearlescent agents.

According to one particular embodiment, this colored pulverulent phase represents at least 5% by weight relative to the total weight of said composition.

The term "pigments" should be understood to _mean inorganic or organic particles, which are insoluble in the liquid organic phase, intended to color and / or opacify the composition.

The pigments may be inorganic or organic pigments. As pigments, it is possible to use metal oxides such as iron oxides (in particular those of yellow, red, brown or black color), titanium dioxides, cerium oxide, zirconium oxide and chromium oxide. ; manganese violet, blue ultramarine, prussian blue, ultramarine blue, ferric blue, and mixtures thereof. It is preferable to use pigments of iron oxides or of titanium dioxide.

The pigments can be treated with a hydrophobic agent to make them compatible with the organic phase of the composition. The hydrophobic treatment agent may be chosen from silicones such as methicones, dimethicones and perfluoroalkylsilanes; fatty acids such as stearic acid; metal soaps such as aluminum dimyristate, hydrogenated tallow glutamate aluminum salt, perfluoroalkyl phosphates, perfluoroalkyl silanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides, polyorganosiloxanes comprising groups perfluoroalkyl perfluoropolyethers, amino acids; N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, and mixtures thereof. The N-acyl amino acids may comprise an acyl group having from 8 to 22 carbon atoms, for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid can be for example lysine, glutamic acid, alanine

The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.

Hydrophobic treated pigments are described in particular in application EP-A-1086683.

The pigments are present in the composition according to the invention in a content ranging from 1% to 30% by weight, relative to the total weight of the composition, preferably ranging from 5% to 20% by weight.

In addition to the pigments, the colored particulate phase of the invention may comprise nacres.

By "nacres", it is necessary to understand iridescent particles, in particular produced by certain shellfish in their shell or else synthesized, insoluble in the medium of the composition.

The nacres may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with, for example, ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

The nacres may be present in each of the compositions according to the invention in a content ranging from 0.5% to 30% by weight, relative to the total weight of the composition, preferably ranging from 1% to 20% by weight, and preferably ranging from 2% to 10% by weight. The cosmetic composition according to the invention may also contain at least one material with a specific optical effect.

This effect is different from a simple conventional hue effect, i.e. unified and stabilized as produced by conventional dyestuffs, such as, for example, monochromatic pigments. For the purposes of the invention, "stabilized" means devoid of effect of color variability with the angle of observation or in response to a change in temperature.

For example, this material may be chosen from particles with a metallic sheen, goniochromatic coloring agents, diffractive pigments, thermochromic agents, optical brighteners, and especially interferential fibers. Of course, these different materials can be combined to provide the simultaneous manifestation of two effects, or even a new effect according to the invention.

The particles with a metallic sheen that can be used in the invention are in particular chosen from: particles of at least one metal and / or at least one metal derivative, the particles comprising an organic or inorganic substrate, monomatiere or multimaterial, coated with at least partially by at least one metal-reflecting layer comprising at least one metal and / or at least one metal derivative, and - mixtures of said particles.

Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te. Se and their mixtures or alloys. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (e.g., bronzes and brasses) are preferred metals. "Metal derivatives" means compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides.

Illustrative of these particles include aluminum particles, such as those sold under the names Starbrite 1200 EAC ^® by Siberline and METALURE® ^® by the company Eckart. Mention may also be made of copper metal powders or mixtures of alloys, such as the references 2844 sold by the company Radium Bronze, metallic pigments, such as aluminum or bronze, such as those sold under the trade names ROTOSAFE 700 ECKART company, the silica-coated aluminum particles marketed under the name VISIONAIRE BRIGHT SILVER by the company ECKART and the metal alloy particles, such as bronze powders (alloy copper and zinc) coated with silica marketed under the name of Visionaire Bright Natural GoId from Eckart. It may also be particles comprising a glass substrate such as those sold by the company NIPPON SHEET GLASS under the names MICROGLASS METASHINE.

The goniochromatic coloring agent may be selected from, for example, interfering multilayer structures and liquid crystal coloring agents.

Examples of symmetrical interferential multilayer structures that can be used in compositions produced in accordance with the invention are, for example, the following structures: Al / SiO ₂ / Al / SiO ₂ / Al, pigments having this structure being marketed by the company DUPONT DE NEMOURS; Cr / MgF ₂ / AI / MgF ₂ / Cr, pigments having this structure being marketed under the name CHROMAFLAIR by the company FLEX; MoS ₂ / SiO ₂ / Al / SiO ₂ / MoS ₂ ; Fe ₂ O ₃ ZSiO ₂ ZAIZSiO ₂ ZFe ₂ O ₃ , and Fe ₂ O ₃ ZSiO ₂ ZFe ₂ O ₃ ZSiO ₂ ZFe ₂ O ₃ , pigments having these structures being sold under the name SICOPEARL by the company BASF; MoS ₂ ZSiO ₂ Zmica-oxide ZSiO ₂ ZMoS ₂ ; Fe ₂ O ₃ ZSiO ₂ Zmica-oxide ZSiO ₂ ZFe ₂ O ₃ ; TiO ₂ ZSiO ₂ ZTiO ₂ and TiO ₂ ZAl ₂ O ₃ ZTiO ₂ ; SnOZTiO ₂ ZSiO ₂ ZTiO ₂ ZSnO; Fe ₂ O ₃ ZSiO ₂ ZFe ₂ O ₃ ;

Sn0ZmicaZTi0 ₂ ZSi0 ₂ ZTi0 ₂ ZmicaZSn0, pigments having these structures being marketed under the name XIRONA by MERCK (Darmstadt). By way of example, these pigments may be the pigments with a silica structure, titanium oxide, tin oxide sold under the name Xirona Magic by the company Merck, pigments with a silica structure, and brown iron oxide sold under the name Xerona Indian Summer by the company Merck. and the pigments with a silica structureZincoxideZmicaZoxide of tin sold under the name XIRONA CARRIBEAN BLUE by the company MERCK. Mention may also be made of the INFINITE COLORS pigments from SHISEIDO. Depending on the thickness and nature of the different layers, different effects are obtained. Thus, with the Fe ₂ O ₃ ZSiO ₂ ZAIZ SiO ₂ ZFe ₂ O _{3 structure,} gold-green to gray-red is passed for SiO ₂ layers of 320 to 350 nm; from red to golden for SiO ₂ layers of 380 to 400 nm; from violet to green for SiO ₂ layers from 410 to 420 nm; from copper to red for SiO ₂ layers from 430 to 440 nm.

Mention may be made, by way of example of pigments with a polymeric multilayer structure, those marketed by the company 3M under the name COLOR GLITTER.

As liquid crystal goniochromatic particles, can be used, for example, those sold by the company Chenix and those sold under the name Helicone® ^® HC by Wacker. The optical effect materials may be present in each of the compositions according to the invention in a content ranging from 0.1% to 15% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 10% by weight. % by weight, and preferably ranging from 1% to 5% by weight.

Other coloring matters

The composition according to the invention may further comprise at least one hydro or liposoluble dye.

By "fat-soluble dyes", it is necessary to include generally organic compounds that are soluble in fats such as oils.

By "water-soluble dyes" it is necessary to include generally organic compounds soluble in water or water-miscible solvents.

The fat-soluble dyes are, for example, Sudan Red, D & C Red No. 17, D & C Green No. 6, β-Carotene, Soybean Oil, Sudan Brown, D & C Yellow No. 11, Purple D & C. No. 2, D & C orange No. 5, yellow quinoline, annatto, bromoacids.

The synthetic or natural water-soluble dyes are, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beet), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, riboflavin.

CHARGESIn addition to the dyestuffs described above, the composition according to the invention may comprise fillers.

By fillers, it is necessary to include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured.

The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Talc, mica, silica, kaolin, polyamide (Nylon®) powders, poly-β-alanine powders, polyethylene powders, polymethyl methacrylates, polyurethane powders such as the hexamethylene diisocyanate and trimethylol hexyl lactone copolymer powder sold under the names PLASTIC POWDER D-400 by the company TOSHIKI, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine, starch, boron nitride, polyvinylidene chloride / acrylonitrile copolymers, copolymers of acrylic acid, silicone resin powders, in particular silsesquioxane powders (silicone resin powders, in particular described in patent EP 293795, Toshiba Tospearls®, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate , magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres, glass or ceramic microcapsules, metal arrays derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate; barium sulphate and their mixtures.

The fillers may be present in each of the compositions according to the invention in a total content ranging from 0.05% to 40% by weight, relative to the total weight of the composition, preferably ranging from 1% to 25% by weight. and preferably ranging from 5% to 15% by weight.

The pulverulent phase may be present in the composition according to the invention in a content ranging from 1 to 40% by weight, relative to the total weight of the composition, preferably from 5 to 40% by weight. According to a particular embodiment, the pulverulent phase represents at least 5% by weight relative to the total weight of said composition. The compositions according to the invention may also comprise a cosmetic additive such as surfactants, antioxidants, preservatives, perfumes, bactericidal or antiperspirant active agents, neutralizers, emollients, moisturizers, vitamins and filters in particular solar.

Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the corresponding composition according to the invention are not, or not substantially, impaired by the contemplated addition, in particular so as not to interfere with the reaction between compounds X and Y. galenic

The composition (s) according to the invention may be independently in the form of a suspension, a dispersion, a solution, a gel, an emulsion, in particular an oil-in-water (O / W) emulsion, a wax-in water-in-oil (W / O), or multiple (W / O / E or polyol / H / E or H / E / H), in the form of cream, foam, dispersion of vesicles including ionic lipids or not, lotion biphasic or multiphase, powder, paste, including soft dough.

According to a preferred embodiment, the compositions according to the invention have an aqueous continuous phase, and may preferably be in the form of an emulsion, in particular an oil-in-water (O / W) emulsion, a wax-in-water emulsion, or multiple (W / O / E or polyol / H / E), or aqueous solution.

According to a more preferred embodiment, the compositions according to the invention may be in the form of an emulsion, in particular an oil-in-water emulsion (O / W).

The compositions comprising compounds X and Y can in particular be in liquid, solid or pasty form. It may in particular act stick, powders, gels or liquids.

According to a particular embodiment, the kit according to the invention may comprise: a first composition in pulverulent form associated with a second liquid composition; or a first liquid composition or gel associated with a second liquid composition, or a first liquid composition or gel associated with a second powder composition, or a first solid composition such as a stick associated with a second liquid composition, or first liquid composition or gel associated with a second composition sprayed with a spray.

According to another preferred embodiment, when the second composition of the kit comprises the crosslinking agent Y, it may be in a sprayed form, in particular by a spray. The method according to the invention can be advantageously used for the makeup of the skin, lips, eyelashes and / or nails depending on the nature of the ingredients used. In particular, the compositions of the process according to the invention can be independently present in the form of a solid foundation, a stick or a lipstick paste, a concealer product, or an eye or eye contour. liner, mascara, eye shadow, body make-up product or a skin coloring product.

According to one embodiment, the first and second compositions are lipstick compositions.

According to another embodiment, the first and second compositions are compositions for coating eyelashes or eyebrows and more particularly mascaras.

According to another preferred embodiment, the first and second compositions are compositions for coating the skin of the body or of the face, more particularly makeup compositions for the skin of the body or of the face, such as, for example, foundations or makeup compositions of the body.

Those skilled in the art may choose the appropriate dosage form, as well as its method of preparation, on the basis of its general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support, and on the other hand, the intended application for each composition.

According to one particular embodiment, at least one of the two compositions of the kit according to the invention comprises an aqueous phase comprising water.

According to one particular embodiment of the invention, said aqueous phase comprises water-miscible organic solvents chosen from monoalcohols having from 2 to 6 carbon atoms; the polyols having in particular from 2 to 20 carbon atoms, preferably having from 2 to 10 carbon atoms, and preferably having from 2 to 6 carbon atoms; glycol ethers having in particular from 3 to 16 carbon atoms; the (C 1 -C 4) alkyl ethers of mono-, di- or triethylene glycol, and mixtures thereof. According to one particular embodiment of the invention, said aqueous phase is present in the composition according to the invention in a content ranging from 20% to 99% by weight, relative to the total weight of the composition, preferably ranging from 30% to 80% by weight. % by weight, and preferably ranging from 40% to 60% by weight.

According to another particular embodiment of the invention, at least one of the two compositions of the kit comprises a hydrophilic gelling agent distinct from the polysaccharides (X).

In particular, the hydrophilic gelling agent is chosen from: homo- or copolymers of acrylic or methacrylic acids or their salts and esters, polyacrylic acids, copolymers of acrylic acid and acrylamide, sodium polymethacrylate, salts of polyhydroxycarboxylic acids, polyacrylic acid / alkyl acrylate copolymers, AMPS (partially neutralized with ammonia and highly crosslinked polyacrylamidomethyl propane sulfonic acid), AMPS / acrylamide copolymers, and AMPS / methacrylate copolymers of polyoxyethylenated alkyl (crosslinked or otherwise), proteins such as proteins of plant origin such as wheat proteins, soya; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates; cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and quaternized cellulose derivatives; polymers of natural origin, which may be modified, such as: gum arabic, guar gum, xanthan derivatives, karaya gum, locust bean gum, alginates and carrageenans (the alginates being used preferably in presence of salts such as calcium chloride), glycoaminoglycans, hyaluronic acid and its derivatives, shellac resin, sandarac gum, dammars, elemis, copals, muccopolysaccharides such as chondroitin sulfate, polymers or acrylic copolymers, vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol; deoxyribonucleic acid; mucopolysaccharides such as chondroitin sulphate, unmodified clays and especially montmorillonites, hectorites, smectites, bentones, laponites, and mixtures thereof.

Preferably, the water-soluble gelling polymer is present in the composition in a solids content ranging from 0.01% to 30% by weight, relative to the total weight of the composition, preferably from 0.05% to 20% by weight. weight, and more preferably from 0.1% to 10% by weight.

According to a particular embodiment of the invention, at least one of the two compositions of the kit according to the invention comprises a fatty phase comprising an oily phase.

In a preferred embodiment, the oily fatty phase comprises a non-volatile oil.

In particular, the non-volatile oil (s) are chosen from hydrocarbon-based oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths. various C ₄ to C ₂₄ , the latter may be linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or triglycerides of caprylic / capric acids such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810 ^®, 812 ^® and 818 ^® by Dynamit Nobel, and mixtures thereof.

In particular, the volatile oil (s) are chosen from volatile hydrocarbon oils, volatile silicone oils, volatile fluorinated oils, and mixtures thereof. According to one embodiment, the oil phase comprises at least one volatile oil chosen from hydrocarbon oils having from 8 to 16 carbon atoms, and especially branched alkanes, C ₈ -C ₆ isoalkanes C ₈ -C ₆ d petroleum origin such as isododecane, isohexadecane; volatile silicones, for example volatile linear or cyclic silicone oils, chosen from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane and octamethyltrisiloxane; decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

According to one particular embodiment, said oily phase is present in a total content ranging from 1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 3% to 50% by weight, preferably ranging from 5% by weight. at 35% by weight, and more preferably from 10% to 30% by weight.

According to a particular embodiment of the invention, at least one of the two compositions of the kit according to the invention comprises at least one wax.

In particular, the wax is chosen from:

- beeswax, lanolin wax, and insect waxes from China; rice wax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax, sugar cane wax, japanese wax and sumach wax; montan wax, microcrystalline waxes, paraffin waxes, ozokerites, ceresin wax, lignite wax, polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, esters of fatty acids and the concrete glycerides at 40 ^° C. and especially at more than 55 ^° C., the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C ₈ -C ₃₂ fatty chains, especially jojoba oil hydrogenated, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, silicone waxes or fluorinated waxes, and mixtures thereof

In particular, the wax is present in a content ranging from 1 to 15% by weight, relative to the total weight of the composition, preferably from 2 to 12% by weight, and more preferably from 4 to 9% by weight. The invention is further illustrated by the examples described hereinafter. Unless otherwise indicated, the quantities indicated are expressed as a percentage by mass.

EXAMPLES

EXAMPLE 1 Composition of O / W Complexion

Preparation of Oxidized Polysaccharides Three non-cationic oxidized polysaccharides, respectively an amylose of oxidized corn, and two oxidized potato starches, were synthesized by oxidation of the corresponding non-oxidized polysaccharides in water in the presence of hydrogen peroxide and iron tetrasulfophthalocyanine catalyst at 58 ° C. Such an oxidation method is described in Application FR-A-2842200, by way of example as in Example 2.

Compound 1: Amylose of oxidized maize obtained by oxidation of maize amylose (Hylon VII) supplied by National Starch & Chemical. Compound 1 has a carbonyl content of 0.95 mmol / g and a carboxyl content of 2.63 mmol / g.

Compound 2: oxidized potato starch obtained by oxidation to potato starch provided by Roquette (case no .: 9005-25-8). Compound 2 has a carbonyl content of 1.08 mmol / g and a carboxyl content of 1.4 mmol / g.

Compound 3: oxidized potato starch obtained by oxidation to potato starch supplied by Roquette (case no .: 9005-25-8). Compound 3 has a carbonyl content of 0.99 mmol / g and a carboxyl content of 1.1 mmol / g.

The gelatin is first solubilized hot (90 ^° C.) in distilled water (phase A1). The mixture is then placed in a water bath at 50 ^° C., and the A2 phase is added. In parallel, the oily phase B is also brought to 50 ^° C. It is added progressively in the phase (A1 + A2) to carry out the emulsion. When the emulsion obtained is homogeneous, phase C is added with stirring for 30 seconds. The composition is then applied.

The resulting film is virtually dry after 6-7 minutes. The resulting film is cohesive, easily peelable, flexible and elastic. To the touch, the film is soft.

Other compositions have been made in which compound 1 is replaced respectively by compound 2 or compound 3 (oxidized potato starches). The resulting film is cohesive and peelable.

Example 2: Foundation Kit

Composition A: Gelatin 4%

Beeswax 10% iron oxide black 0.05% iron oxide red 0.34% iron oxide yellow 1, 03% Ultramarine blue 0.23% Preservatives 0.45% Simethicone (anti-foam) 0.13% Cetyl potassium phosphate (Rock Amphisol K) 4% Water Qs 100

Composition B Oxidized starch 3% Preservatives q Water qs 100

This composition is packaged in an aerosol / fogger.

A layer of the composition A is then applied to the skin of the face and then the composition B is sprayed on the assembly using the aerosol

The film formed on the face by chemical crosslinking of the gelatin with the oxidized starch has a good resistance to water.

This film can be removed easily by peeling by pulling with your fingers.

Example 3: Foundation Kit

Composition A:

WATER DESIONIZED 81, 2

AMYLOSE OF OXIDE CORN

A1 (compound 1 as described in Example 1) 2

BENZYL ALCOHOL 0.8

GLYCEROL 5

DESIONIZED WATER 6

YELLOW IRON OXIDE (Cl:

77492) 0.87

A2 RED IRON OXIDE (Cl:

77491) 0.4

BLACK IRON OXIDE (CI:

77499) 0.1 1

TITANIUM OXIDE (ANATASE 3.62 NOT PROCESSED) (CI: 77891)

Preparatory mode

The constituents of the phase A2 are mixed and then the pigment paste is milled with the three-roll mill (3 passages). In phase A1 at 25 ° C., benzyl alcohol is introduced, followed by polysaccharide (oxidized starch) with vigorous stirring (Rayneri, deflocculating blade, 700 rpm). The complete solubilization of the polysaccharide is awaited before the introduction of the pigment paste A2. Stir for 10 minutes at 700 rpm.

Composition B: Hyaluronic acid 3% Preservatives 0.2% Water qs 100

Embossing the films (spread on a glass plate at 37 ° C.):

A composition of composition A and another 50/50 mixture of compositions A and B is applied to a glass plate at 37 ° C with the minimum thickness to wet the glass well.

The characteristics of the film are observed on the one hand and the properties of non-transfer (on a tissue) and the properties of resistance to water and / or sebum, respectively. The results of these observations are indicated in the table below:

Observations of the films

These results show that the implementation of a composition comprising a polysaccharide (oxidized starch) associated with a composition comprising a chemical crosslinking agent (hyaluronic acid) makes it possible to obtain both a cohesive, peelable, non-tacky film with very good non-transfer properties and improved resistance to water and sebum.

Claims

A kit for coating keratin materials comprising: at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film, at least one of said first or second composition comprising at least one material dye, especially pulverulent, in particular pigments and / or nacres, in a total content of at least 5% by weight relative to the total weight of said composition.

2. Kit for coating keratin materials comprising: at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure and ambient temperature so as to form a film, and and said compound X being present in a content of at least 1 % by weight in the first composition or in a content such that it is at least 1% by weight relative to the total weight of the mixture of the first and the second composition.

3. Coating kit according to one of the preceding claims, characterized in that the compound X is selected from polysaccharides from microorganisms, polysaccharides isolated from algae, polysaccharides of higher plants, and their mixture.

4. coating kit according to the preceding claim, characterized in that: - the polysaccharides produced by microorganisms are selected from xanthan, pullulan, dextran and dextran sulfate, succinoglycan, scleroglucan and mixtures thereof; the polysaccharides isolated from the algae are chosen from galactans, furcellaran and their mixture; the polysaccharides of the higher plants are chosen from among the homogeneous polysaccharides consisting of a single species of oste, such as glucosans, in particular native starches, modified starches, cyclo (cyclo) dextrin and its derivatives, cellulose and its derivatives; fructans, in particular inulin and its derivatives such as in particular dicarboxy and carboxymethyl inulin, and their mixture; and ob) heterogeneous polysaccharides composed of several types of odds, such as gums, in particular cassia gums, acacia gum or gum arabic, karaya gum, konjac gum, gum tragacanth, and their mixture; galactomannans and their derivatives, in particular guar, carob, fenugreek, tara gum and their derivatives among phosphated guar, hydroxypropyl guar and their mixture; LM and HM pectins and their derivatives; chitin, chitosan and their derivatives; glycosaminoglycans, in particular hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate or heparin and heparan sulfate; xylans (poly C-5) and their derivatives.

5. coating kit according to any one of the preceding claims, characterized in that the crosslinking agent Y is chosen from aldehydes, anhydrous acids, isocyanates, thioisocyanates, azides, azolides, carboimides, epoxides, esters, glycidyl ethers, halogens, imidazoles, imidates, succinimides, succinimidyl esters, and mixtures thereof.

6. coating kit according to the preceding claim, characterized in that the crosslinking agent Y is chosen from:

The esters of adipic acid of formula R- (CH ₂ VR with R = COOCOCH ₃ , epichlorohydrin,

Ethylene glycol diglycidyl ether,

Benzoquinone,

Maleic anhydride

Idéhyde glutaraldehyde of formula OHC- (CH ₂ ) ₃ -CHO, formaldehyde,

1- (3-Dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC),

Polyethers such as polyethylene oxide (PEO),

The polysaccharides, distinct from those chosen as agent X in the first composition, proteins, modified or not, such as gelatin, caseins,

Sugars such as sucrose,

The basics, Acids or diacids of compounds of plant origin such as mucic acid, amino acids such as lysine (for example, di-amino) or its didisocyanate, poly-lysines (Al and Ep),

Coating kit according to one of the preceding claims, characterized in that the polysaccharide (X) and crosslinking agent (Y) pair is chosen from:

Carboxymethylcellulose with polyethers such as polyethylene oxide

(PEO), chitosan with modified or unmodified polysaccharides, such as oxidized starch, galactomanane (guar, carob) with epichlorohydrin, starches with adipate (R- (CH ₂ VR with R = COOCOCH ₃ ) in alkaline medium,

Starches with phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate,

Carboxymethylcellulose with phosphorus compounds, such as, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate,

Modified starches, in particular oxidized starches, with gelatin or collagen

Hyaluronic acid with modified starches, especially oxidized starches

Hyaluronic acid with 1 - (3-dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC),

Carboxymethylcellulose with 1 - (3-dimethylaminopropyl) -3-ethylcarbodimide hydrochloride (EDC).

30

8. Coating kit according to one of the preceding claims, characterized in that the compound X represents from 1 to 40% by weight, relative to the total weight of the composition, preferably from 1 to 20% by weight, and better from 1 to 10% by weight.

The coating kit according to one of the preceding claims, characterized in that the crosslinking agent (Y) is present in a content of from 0.5% to 95% by weight relative to the total weight of the second composition, preferably from 1% to 90% and better still from 2% to 50%.

10. Kit according to any one of the preceding claims, characterized in that the first and / or second compositions are packaged separately in the same packaging article.

1. A cosmetic composition for coating keratin materials comprising at least one compound X and at least one compound Y, the compounds X and Y being as defined in any one of the preceding claims and the compound X being present in said composition. a content of at least 1% by weight relative to the total weight of said composition, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film.

12. Cosmetic process for coating keratinous substances consisting of: a. mix extemporaneously:

at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a dyestuff, especially pulverulent material, in particular pigments and / or nacres in a total content of at least 5% by weight relative to the total weight of said composition, then b. to apply on said keratinous materials at least one layer of said mixture.

13. Cosmetic process for coating keratin materials, comprising: a. mix extemporaneously:

at least one first composition comprising a compound X;

at least one second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, and said compound X being present in the first composition in a content such that it is at least 1% by weight relative to the total weight of the mixture of the first and the second composition then b. to apply on said keratinous materials at least one layer of said mixture.

14. A cosmetic process for coating keratin materials comprising the application to said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, at least one of said first or second composition comprising at least a dyestuff, especially pulverulent material, in particular pigments and / or nacres in a total content of at least 5% by weight relative to the total weight of said composition.

15. A cosmetic process for coating keratin materials, comprising the application to said keratin materials: a. at least one layer of a first composition comprising a compound X; b. at least one layer of a second composition comprising a compound Y; the compound X being a polysaccharide, said compounds X and Y reacting together by chemical crosslinking reaction in situ, at atmospheric pressure (and ambient temperature) so as to form a film, and said compound X being present in the first composition in a content at least 1% by weight relative to the total weight of said first composition.