FR3045337A1

FR3045337A1 - GEL / GEL TYPE COMPOSITION BASED ON HYDROPHOBIC COATED PIGMENTS, A PARTICULAR GLYCOL COMPOUND AND AT LEAST ONE POLAR OIL

Info

Publication number: FR3045337A1
Application number: FR1562601A
Authority: FR
Inventors: Elodie Valverde
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2015-12-17
Filing date: 2015-12-17
Publication date: 2017-06-23
Anticipated expiration: 2035-12-17
Also published as: FR3045337B1

Abstract

La présente invention concerne une composition, notamment comprenant un milieu physiologiquement acceptable, notamment de revêtement des matières kératiniques, plus particulièrement de maquillage et/ou de soin des matières kératiniques, telles que la peau, contenant : - au moins une phase aqueuse gélifiée par au moins un agent gélifiant hydrophile ; et - au moins une phase huileuse gélifiée par au moins un agent gélifiant lipophile et comprenant au moins une huile polaire ; lesdites phases y formant un mélange macroscopiquement homogène et ladite composition comprenant en outre : i) au moins un pigment traité hydrophobe ; et ii) au moins un composé de formule suivante (1) : CH3- [CH2CH2]m- [COO]n - CH2-CH(OH)CH2OH (1) dans laquelle - m étant compris entre 2 et 4 - n étant égal à 0 ou 1.The present invention relates to a composition, in particular comprising a physiologically acceptable medium, in particular for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as the skin, containing: at least one aqueous phase gelled with minus a hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil; said phases forming a macroscopically homogeneous mixture therein and said composition further comprising: i) at least one hydrophobic treated pigment; and ii) at least one compound of the following formula (1): CH3- [CH2CH2] m- [COO] n -CH2-CH (OH) CH2OH (1) in which - m being between 2 and 4 - n being equal at 0 or 1.

Description

Gel / gel composition based on hydrophobic coated pigments, a particular glycol compound and at least one polar oil

The present invention aims to provide for the field of skincare and / or makeup keratin materials, especially the skin and / or lips, and in particular the skin, and keratinous fibers, including eyebrows, a new galenic all particularly interesting in view of its technical performance and sensory sensations that it provides to the user during its application on them and in particular on your skin.

By "keratin materials" is meant in particular the skin, the lips, the eyebrows and / or the eyelashes, in particular the skin and / or the eyebrows, and preferably the skin.

Cosmetic compositions, for example foundation, are commonly used to bring an aesthetic color to the skin, but also to camouflage, and / or to unify the imperfections of the relief of the skin such as wrinkles and / or fine lines and / or or scars. In this regard, many formulations, solid or fluid, anhydrous or not, have so far been developed.

To date, there are multiphase compositions that are interesting with regard to the makeup properties that they confer, in particular mattness and coverage and holding makeup.

Compositions, called gel-gel, have already been proposed in the cosmetics field and are particularly interesting as alternatives to emulsions which tend to give an important sensation of fat, and stickiness, a lack of freshness and a lack of lightness for the skin. obtained textures. This type of formulation combines a gelled aqueous phase with a gelled oily phase. Thus, gel / gel formulations are described in Almeida et al, Pharmaceutical Development and Technology, 2008, 13: 487, Tables 1 and 2, page 488; WO 99/65455; PI 0405758-9; WO 99/62497; JP 2005-112834 and WO 2008/081175, FR2984736, FR3002444, FR3004343, WO14 / 128680, WO14 / 128678. However, these formulations are not fully satisfactory. Indeed, the use of particulate materials such as hydrophobic treated pigments at high levels in the fat phase of the gel / gel compositions tends to increase the viscosity of said fat phase. A large difference in viscosity between the gel of the aqueous phase and the gel of the fatty phase tends to lead to macroscopically inhomogeneous gel / gel type compositions: the highly concentrated pigmented oily gel disperses in macro-domains which are then visible to the naked eye and gives an unsightly appearance to the product. These macroscopic heterogeneities can lead to a deterioration of the sensory feeling on application (ie: freshness, lightness, emollience, comfort, coverage of imperfections) as well as a loss of stability of the composition over time.

There is therefore still a need to find new formulations of the gel-gel type which confer good makeup properties such as mattness, good coverage, good sensory properties such as freshness and lightness on application as well as good held in time without the disadvantages mentioned above.

The Applicant has surprisingly discovered that this objective could be achieved with a composition, in particular comprising a physiologically acceptable medium, in particular for coating keratin materials, more particularly for making up and / or caring for keratin materials, such as the skin, containing at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil; said phases forming a macroscopically homogeneous mixture therein and said composition further comprising: i) at least one hydrophobic coated pigment; and ii) at least one glycol compound of the following formula (1):

CH 3 - [CH 2 CH 2] m - [COO] n - CH 2 -CH (OH) CH 2 OH (1) in which - m being between 2 and 4 - n being equal to 0 or 1.

This discovery is the basis of the invention.

Thus, according to one of its aspects, the present invention relates to a composition, in particular comprising a physiologically acceptable medium, in particular for coating keratin materials, more particularly for makeup and / or care of keratin materials, such as the skin, containing at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil; said phases forming a macroscopically homogeneous mixture therein and said composition further comprising: i) at least one hydrophobic coated pigment; and ii) at least one glycol compound of the following formula (1):

CH3 - [CH2CH2] m - [COO] n - CH2 - CH (OH) CH2OH (1) in which the m - m being between 2 and 4 - n being equal to O or 1. The invention also relates to a coating process for keratin materials, more particularly makeup and / or care of keratin materials, such as the skin, characterized in that it comprises the application to keratin materials of a composition as defined above

The present invention also relates to a method for preparing a composition as defined above, comprising at least one step of mixing: the gelled aqueous phase with at least one hydrophilic gelling agent; and - the oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil under conditions conducive to obtaining a macroscopically homogeneous mixture; said composition further comprising at least one hydrophobic coated pigment and at least one compound of formula (1).

According to a particular embodiment, said method comprises a step of mixing at least three gelled phases or more.

According to another particular embodiment, the mixture of the gelled phases as described above is carried out at room temperature. Definitions

In the context of the present invention, the term "keratinous material" is understood to mean the skin (body, face, eye contour), the lips, the eyelashes and the eyebrows. More particularly, the term "keratinous material" is understood to mean the skin.

By "physiologically acceptable" is meant compatible with the skin and / or its integuments, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness), likely to divert the consumer from the skin. use this composition.

GEL GEL

First of all, it is important to note that a composition according to the invention of the gel-gel type is different from an emulsion.

An emulsion generally consists of an oily liquid phase and an aqueous liquid phase. It is a dispersion of droplets of one of the two liquid phases in the other. The size of the droplets forming the dispersed phase of the emulsion is typically of the order of one micrometer (0.1 to 100 μm). In addition, an emulsion requires the presence of a surfactant or an emulsifier to ensure its stability over time. In contrast, a composition according to the invention consists of a macroscopically homogeneous mixture of two immiscible gelled phases. These two phases both have a gel-like texture. This texture is reflected in particular visually by a consistent and / or creamy appearance.

The term "macroscopically homogeneous mixture" means a mixture in which each of the gelled phases can not be individualized with the naked eye.

More precisely, in a composition according to the invention, the gelled aqueous phase and the gelled oily phase interpenetrate and thus form a stable and consistent product. This consistency is achieved by mixing interpenetrated macrodomains. These interpenetrating macro-domains are not measurable objects. Thus, under the microscope, the composition according to the invention is very different from an emulsion. A composition according to the invention can not be characterized as having a "sense", ie an O / W or E / H direction.

Thus, a composition according to the invention has a gel-like consistency. The stability of the composition is durable without surfactant. Therefore, a particular cosmetic composition according to the invention does not require surfactant or silicone emulsifier to ensure its stability over time.

It is known from the state of the art to observe the intrinsic nature of a mixture of aqueous and oily gels in a gel-gel type composition, for example, by introducing a coloring material either in the aqueous gelled phase or in the gelled lipophilic phase, before the formation of the gel-gel composition. In the visual inspection, in a gel-gel composition, the coloring matter appears to be uniformly dispersed, even if the dye is present only in the gelled aqueous phase or in the gelled oily phase. Indeed, if two different dyes of different colors are introduced respectively into the oily phase and into the aqueous phase, before the formation of the gel-gel type composition, the two colors can be observed as uniformly dispersed throughout the composition of type gel-gel. This is different from an emulsion in which, if a water-soluble or oil-soluble dye is introduced into the aqueous and oily phases, respectively, before forming the emulsion, only the color of the dye will be observed. present in the outer phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282).

It is also known to distinguish a gel-gel type composition from an emulsion by performing a "drop test". This test consists of demonstrating the bi-continuous nature of a gel-gel composition. Indeed, as mentioned above, the consistency of a composition is obtained thanks to the interpenetration of the aqueous and oily gelled domains. Therefore, the bi-continuous nature of a gel-gel composition can be evidenced by a simple test with hydrophilic and hydrophobic solvents respectively. This test consists in depositing, on the one hand, a drop of a hydrophilic solvent on a first sample of the tested composition, and, on the other hand, a drop of a hydrophobic solvent on a second sample of the same composition tested, and to analyze the behavior of the two drops of solvents. In the case of an O / W emulsion, the drop of hydrophilic solvent diffuses into the sample and the drop of hydrophobic solvent remains on the surface of the sample. In the case of an W / O emulsion, the drop of hydrophilic solvent remains on the surface of the sample and the drop of hydrophobic solvent diffuses throughout the sample. Finally, in the case of a gel-gel type composition (b-continuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample.

In the case of the present invention, the test that will be preferred for distinguishing a gel-gel composition from an emulsion is a dilution test. Indeed, in a gel-gel type composition, the aqueous and oily gelled domains interpenetrate and form a consistent and stable composition, in which the behavior in water and in oil is different from the behavior of an emulsion. Therefore, the behavior during a dilution of a gel-gel type composition (bi-continuous system) can be compared to that of an emulsion.

More specifically, the dilution test consists in putting 40 g of product and 160 g of dilution solvent (water or oil) in a 500 ml plastic beaker. The dilution is carried out with controlled stirring to avoid any emulsification phenomenon. In particular, this is done using a planetary mixer: Speed Mixer TM DAC400FVZ®. The mixer speed is set at 1500 rpm for 4 minutes. Finally, observation of the resulting sample is performed using an optical microscope at a magnification of x 100 (x10x10). It may be noted that oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® marketed by Dow Corning are suitable as a diluting solvent in the same way as one of the oils contained in the composition.

In the case of a gel-gel type composition (bicontinuous system), when it is diluted in oil or in water, a heterogeneous appearance is always observed. When a gel-gel composition (bicontinuous system) is diluted in water, pieces of oily gel are observed in suspension and when a gel-gel composition (bicontinuous system) is diluted in water. the oil, pieces of aqueous gel are observed in suspension.

On the contrary, during the dilution, the emulsions exhibit a different behavior. An O / W emulsion, when diluted in an aqueous solvent, gradually reduces without having a heterogeneous and lumpy appearance. This same O / W emulsion, when diluted with the oil, has a heterogeneous appearance (pieces of O / W emulsion suspended in the oil). W / O emulsion, when diluted with an aqueous solvent, has a heterogeneous appearance (W / O emulsion pieces suspended in water). This same W / O emulsion, when diluted in the oil, gradually reduces without presenting a heterogeneous and lumpy appearance.

According to the present invention, the aqueous gelled phase and the gelled oily phase forming a composition according to the invention are present in a weight ratio ranging from 95/5 to 5/95. More preferably, the aqueous phase and the oily phase are present in a weight ratio ranging from 30/70 to 80/20.

The ratio between the two gelled phases is adjusted according to the desired cosmetic properties.

Thus, in the case of a make-up composition, in particular the face, it will be advantageous to promote an aqueous gelled phase / oily gelled phase weight ratio greater than 1, in particular ranging from 60/40 to 90/10, preferably varying. from 60/40 to 80/20, preferentially from 60/40 to 70/30 and even more preferably to promote an aqueous gelled phase / glycerized glycerol weight ratio of 60/40 or 70/30.

These preferred ratios are particularly advantageous for obtaining fresh and light compositions.

Advantageously, a composition according to the invention can therefore be in the form of a creamy gel having a minimum stress below which it does not flow unless subjected to external mechanical stress.

As is apparent from the following a composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa.

It can also advantageously have a modulus of rigidity G * of at least 400 Pa, and preferably greater than 1000 Pa.

According to an advantageous variant embodiment, the gelled phases considered for forming a composition according to the invention may respectively have a threshold stress greater than 1.5 Pa, and preferably greater than 10 Pa.

The characterization of the threshold stresses is performed by oscillation rheology measurements. A methodology is proposed in the exemplification chapter of this text. In general, the corresponding measurements are carried out at 25 ° C. using an imposed stress rheometer, RS600 HAAKE®, equipped with a plane-plane measurement body (diameter 60 mm) provided with a anti-evaporation device (bell). For each measurement, the sample is gently placed and the measurements begin 5 minutes after the sample is placed in the gap (2 mm). The tested composition is then subjected to a stress ramp of 10 -2 to 10 3 Pa at a frequency set at 1 Hz.

A composition according to the invention may also have a certain elasticity. This elasticity is characterized by a modulus of rigidity G * which below this minimum stress threshold may be at least 400 Pa, and preferably greater than 1000 Pa. The G * value of a composition can be obtained by subjecting the composition considered at a ramp stress of 10'2 to 103 Pa at a frequency set at 1 Hz.

HYDROPHILIC GELIFIER

The term "hydrophilic gelling agent" in the sense of the present invention, a compound capable of gelling the aqueous phase of the compositions according to the invention.

The gelling agent is hydrophilic and is therefore present in the aqueous phase of the composition. t

The gelling agent may be water-soluble or water-dispersible.

As specified above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent. The hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, mixed silicates and pyrogenic silicas, and mixtures thereof.

Preferably, the hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents. I. Natural or naturally occurring polymeric gelling agents

Polymeric hydrophilic gelling agents that are suitable for the invention may be natural or of natural origin.

For the purposes of the invention, the expression "of natural origin" means polymeric gelling agents obtained by modifying natural polymeric gelling agents.

These gelling agents may be particulate or non-particulate.

More specifically, these gelling agents fall within the category of polysaccharides. In general, the polysaccharides can be distinguished into several categories.

Thus, the polysaccharides that are suitable for the invention may be homopolysaccharides such as fructans, glucans, galactans and mannans or heteropolysaccharides such as hemicellulose.

Similarly, they may be linear polysaccharides like pullulan or branched in the image of gum arabic and amylopectin, or mixed in the image of starch.

More particularly, the polysaccharides that are suitable for the invention can be distinguished according to whether they are starchy or not. THE. Amylaceous Polysaccharides Representative of this category may be particularly mentioned, native starches, modified starches and particulate starches.

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 anhydroglucose (dextrose) units, linked by α (1, 4) linkages, of chemical formula (CeHioOsIn the number of these units. and their assembly makes it possible to distinguish between amylose, a molecule formed of about 600 to 1000 molecules of linearly-linked glucose, and amylopectin, a branched polymer about every 25 glucose residues (α-linkage). between 10,000 and 100,000 glucose residues Starch is described in particular in "KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd edition, Volume 21, pages 492-507, Wiley Interscience, 1983".

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 molecules used in the present invention may have as botanical origin cereals or tubers. Thus, the starches are for example chosen from starches 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 ™, Dry Gel ™, C * Pharm Gel ™ by the company Cargill, under the name Amidon de mais by Roquette, and under the name Tapioca Pure by the company National Starch. ♦

Modified starches

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

More particularly, these reactions can be carried out as follows: pre-gelatinization by bursting the starch granules (for example drying and cooking in a drying drum); - acid hydrolysis resulting in a very rapid retrogressive 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 C6 hydroxyl); dextrinisation in an acid medium at high temperature (hydrolysis then repolymerization); crosslinking by 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 acyl in CrC6 (acetyl), hydroxyalkyl in C1-C6 (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.

In particular, it is possible to obtain, by means of crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-0-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, 3-aminopropanediol-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.

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 bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type, 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:

(I)

(II)

(III)

(IV) wherein: - St-0 represents a starch molecule; R, identical or different, represents a hydrogen atom or a methyl radical; R ', which may be 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 metal or alkalinoteræux such as Na, K, Li, NH4, 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 US Pat. Nos. 5,455,340 and 4,017,460.

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-Instant® (pre-gelatinized adipate), C * StabiTex-Instant® (pre-gelatinized phosphate), C * PolarTex-Inactive (pre-gelatinized hydroxypropyl) ), C * Set (acid hydrolysis, oxidation), C * size (oxidation), * BatterCrisp® (oxidation), C * DrySet® (dextrinization), C * TexTM (acetylated diamidon adipate), C * PolarTexTM® ( hydroxypropylated diamidon phosphate), C * StabiTexTM® (diamidon phosphate, acetylated diamidon phosphate) by Cargill, diamidon phosphates or compounds rich in diamidon phosphate, such as the product proposed under the references PREJEL VA-70- T AGGL® (gelatinized hydroxypropylated manioc diamidon phosphate) or PREJEL TK1® (gelatinized manioc diamidon phosphate) or PREJEL 200® (gelatinized acetylated manioc diamidon phosphate) by the company AVEBE or STRUCTURE ZEA® by NATIONAL STARCH (phosphate of diamidon of m gelatinized). As examples of oxidized starches, use will be especially those marketed under the name C * size® Cargill company.

The native or modified starches described above may advantageously be used in a proportion of 0.1 to 8% by weight of dry matter, and preferably of approximately 1% by weight, relative to the total weight of the aqueous phase. .

Particulate starches In particular, particulate starches may be mentioned: starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular with sodium polyacrylate, for example those sold under the name Sanfresh ST-100 ™ by the company Sanyo Chemical Industries or Makimousse 25®, Makimousse 12® by the company Daito Kasei (INCI name Sodium Polyacrylate Starch); hydrolyzed starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular acryloacrylamide / sodium acrylate copolymer, for instance those marketed under the names Water Lock A-240®, A-180®, B-204®, D -223®, A-100®, C-200®, D-223®, by Grain Processing (INCI name: Starch / acrylamide / sodium acrylate copolymer); polymers based on starch, gum and cellulose derivative, such as that containing starch and sodium carboxymethylcellulose, such as, for example, that sold under the name Lysorb 220® by the company Lysac.

Particularly suitable are the (C 1 -C 4) carboxyalkyl starches, hereinafter referred to as "carboxyalkyl starch". These compounds are obtained by grafting carboxyalkyl groups on one or more alcohol functions of the starch, in particular by reaction of starch and sodium monochloroacetate in an alkaline medium. (

The carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1. The degree of substitution in the carboxyalkyl unit of the (C1-C4) carboxyalkyl of starch is preferably from 0.1 to 1 , and more particularly from 0.15 to 0.5. The degree of substitution is defined according to the present invention as the average number of hydroxyl groups substituted by an ester or ether group per monosaccharide unit of the polysaccharide.

The carboxyalkyl starches are advantageously used in the form of salts and in particular of alkali metal or alkaline earth metal salts such as Na, K, Li, NH 4, of a quaternary ammonium or of an organic amine such as mono, di or triethanolamine. . The (C1-C4) carboxyalkyl starches are advantageously in the context of the present invention carboxymethyl starches. The carboxymethyl starches preferably comprise units of the following formula:

in which X, covalently bonded or not to the carboxylic unit, denotes a hydrogen atom, an alkali metal or alkaline earth metal such as Na, K, Li, NH 4, a quaternary ammonium or an organic amine such as, for example, such as mono, di or triethanolamine.

Preferably, X denotes an Na + cation. The carboxyalkyl starches which can be used according to the present invention are preferably non-pregelatinized carboxyalkyl starches. The carboxyalkyl starches which may be used according to the present invention are preferably partially or completely crosslinked carboxyalkyl starches.In general, a crosslinked carboxyalkyl starch has, in contrast to an uncrosslinked carboxyalkyl starch, an increased viscosity which is controllable and of increased stability. thus to reduce the phenomena of syneresis and to increase the resistance of the gel to shearing effects.

The carboxyalkyl starches considered according to the invention are more particularly potato carboxyalkyl starches. Thus, the carboxyalkyl starches which can be used according to the present invention are preferably sodium salts of carboxyalkyl starch, in particular a sodium salt of potato carboxymethyl starch sold, for example, under the name PRIMOJEL® by the company DMV International or GLYCOLYS® and GLYCOLYS® LV by the Roquette Company.

According to a particular mode, use will be made of potato carboxymethyl starches sold in particular under the name GLYCOLYS® by the Roquette Company. As stated above, the starch-containing carboxyalkyl (C 1 -C 4) particles are present in the compositions according to the invention in an inflated and unexploded form. This swelling may be characterized by a swelling power Q which may advantageously be between 10 and 30 ml / g, preferably between 15 and 25 ml (volume of absorbed liquid) / g of dry particulate material.

Thus, the size of the swollen carboxyalkyl starch particles implemented according to the present invention generally ranges from 25 to 300 μm. For example, PRIMOJEL® gel containing 10% by weight of potato carboxyalkyl starch and sodium salt in water, contains more than 80% of swollen particles of this starch having a diameter greater than 50 microns, and more particularly greater than 50 microns. at 100 microns.

According to a preferred embodiment of the invention, these particles are used for the preparation of the compositions according to the invention, in this swollen particulate state. To do this, these particles are advantageously used in the form of an aqueous gel either prepared beforehand or already commercially available. The gels considered according to the invention are advantageously translucent.

For example, a carboxymethyl starch gel such as PRIMOJEL® which is at a concentration of 10% by weight can be adjusted to the required concentration before being used to prepare the expected composition.

Such a particulate starch may be used in a proportion of from 0.1 to 5% by weight of dry matter relative to the total weight of the aqueous phase, preferably from 0.5 to 2.5% by weight, and in particular at a rate of about 1.5% by weight, relative to the total weight of the aqueous phase. 4

According to one variant embodiment, the hydrophilic gelling agent is non-starchy. IB non-starch polysaccharides In a general manner, the non-starch polysaccharides may be chosen from polysaccharides prepared by microorganisms; polysaccharides isolated from algae, polysaccharides from higher plants, such as homogeneous polysaccharides, in particular celluloses and its derivatives or fructans, heterogeneous polysaccharides such as gums arabic, galactomannans, glucomannans, pectins, and their derivatives ; and their mixtures.

In particular, the polysaccharides may be chosen from fructans, gellanes, glucans, amylose, amylopectin, glycogen, pullulan, dextrans, celluloses and their derivatives, in particular methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, and carboxymethylcelluloses, mannans, xylans, lignins, arabans, galactans, galacturonans, alginate compounds, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, acids pectics and pectins, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabic, tragacanth gums, ghatti gums, karaya gums, locust bean gum, galactomannan such as guar gums and their derivatives ionic, in particular hydroxypropyl guar, and ionic, biopolysaccharide gums of microbial origin, in particular the 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.

Advantageously, the polysaccharides may be chosen from carrageenans, in particular kappa-carrageenan, gellan gum, agar-agar, xanthan gum, and alginate-based compounds, in particular alginate. sodium, saroglucan gum, guar gum, inulin, pullulan, and mixtures thereof. In general, the compounds of this type that can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and Vol. 15, pp 439-458 ", in" Polymers in Nature, by EA Mc GREGOR and CT GREENWOOD, Editions John Wiley & Sons, Chapter 6, pp. 240-328, 1980 ", in Robert L. DAVIDSON's book" Handbook of Water Soluble Gums and Resins "published by Mc Graw Hill Book Company (1980) and in the Industrial Gums" Polysaccharides and their Derivatives, Edited by Roy L. WHISTLER, Second Edition, Edition Academie Press Inc. ".

Such a gelling agent may be used in a proportion of 0.1 to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1 to 6% by weight, preferably from 0.5 to 2.5% by weight, in particular about 1%, or about 1.5% by weight relative to the total weight of the aqueous phase.

More specifically, these polysaccharides suitable for the invention can be distinguished according to whether they are derived from microorganisms, algae or higher plants, and are detailed below.

Polysaccharides elaborated by microanisms

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-linked glucose βη 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 internal mannose residue is generally acetylated on the carbon 6. About 30% of the terminal mannose residues carry a pyruvate group bound in chelated form between the carbons 4 and 6. The glucuronic acids and the charged pyruvic acids are ionizable, and therefore responsible for the anionic nature of 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 Ca2 + ions (SATIA Company, 1986). The neutralized form can be converted to an acid form by ion exchange or by dialysis of an acidic solution.

The xanthan gums have a molecular weight of between 1000000 and 50000000 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. on a Brookfield viscometer, type LVT). at 60 rpm).

Xanthan gums 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. ™ by the company ADM, and under the names Kelzan® and Keltrol® by the company CP-Kelco.

pullulan

Pullulan is a polysaccharide consisting of maltotriose units, known as a (1,4) -a (1,6) -glucan. Three units of glucose in maltotriose are connected by a glycosidic linkage to a (1,4), while the consecutive maltotriose units are connected to each other by a glycosidic linkage to a (1,6).

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

Dextran and dextran sulphate

Dextran is a neutral polysaccharide without charged group, biologically inert, prepared by fermentation of beet sugar containing only hydroxyl groups.

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.

Succinoalvcane

Succinoglycan is an extracellular polymer produced by bacterial fermentation, of high molecular weight and consisting of repeated units of octasaccharides (repetition of 8 sugars). Succinoglycans are, for example, sold under the name Rheozan® by the company Rhodia.

Scléroalucane

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 (1,6) bond.

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 the company ALBAN MULLER, or under the name ACTIGUM ™ CS by Cargill.

Gum of aellane

Gellan gum is an anionic linear heteropolyoside based on oligoside units composed of 4 atoms (fetra-ostef). D-glucose, L-rhamnose and D-glucuronic acid in proportions 2: 1: 1 are present in the gellan gum as monomeric elements.

It is for example sold under the name KELCOGEL CG LA® by the company CP KELCO.

Polysaccharides isolated from Galactannes algae

The polysaccharide 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 B (1,4) bonds. These are highly sulphated polysaccharides (20-50%) and the α-D-galactopyranosyl residues can be in 3,6-anhydro form. Depending on the number and position of ester-sulphate groups on the repeating disaccharide of the molecule, there are several types of carrageenans namely: kappa-carrageenans which have an ester-sulphate group, iota-carrageenans which have two ester groups sulphate and lambda-carrageenans which have three ester-sulphate groups.

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

The carrageenans are marketed by the company Seppic under the name Solagum®, by the company Gelymar under the name Carragel®, Carralact®, and Carrasol® by the company Cargill under the names SATIAGEL ™ and SATIAGUM ™, and by 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 β (1,3) D-galactopyranose and a (1,4) L 3-6 anhydrogalactose chain, 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 hybrid structures are generally present as a variable percentage, depending on the species of algae and the season of harvest. Agar-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 producing algae extraction juices, usually by autoclaving, and treating these juices which include about 2% agar-agar, in order to extract it. The agar is for example produced by Group B & V Agar Producers, under the name Gold 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 Furcellaria fasztigiata. Furcellarane is for example produced by the company East-Agar.

Alginate-based compound

For the purposes of the invention, the term "alginate-based compound" means alginic acid, alginic acid derivatives and alginic acid salts (alginates) or derivatives thereof.

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

This (s) compound (s) based on alginate is (are) capable (s) to crosslink in the presence of at least one crosslinking agent, by formation of ionic bonds between the (s) said (s) compound ( s) based on alginate and said crosslinking agent (s). The formation of multiple crosslinks between several molecules of the said alginate-based compound (s) causes the formation of a water-insoluble gel.

Alginate-based compounds having a weight average molecular weight of from 10,000 to 1,000,000, preferably from 15,000 to 500,000, and more preferably from 20,000 to 250,000, are preferably used.

According to a preferred embodiment, the alginate-based compound is alginic acid and / or a salt thereof.

Advantageously, the alginate compound is an alginate salt, and preferably sodium alginate.

The alginate-based compound may be chemically modified, 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.

The alginate-based compounds that are suitable for the invention can be represented, for example, by the products sold under the names KELCOSOL®, SATIALGINE ™, CECALGUM ™ or ALGOGEL ™ by the company Cargill products, under the name Protanal ™ by the company FMC Biopolymer Company, under the name GRINDSTED® Alginate by the company Danisco, under the name KIMICA ALGIN® by the company KIMICA, and under the names Manucol® and Manugel® by the company ISP.

Polysaccharides of higher plants

This category of polysaccharides can be divided into homogeneous polysaccharides (a single species of oses) and heterogeneous compounds of several types of oses. a) Homogeneous polysaccharides and their derivatives

The polysaccharide according to the invention may be chosen from celluloses and derivatives or fructans.

Cellulose and derivatives

The polysaccharide 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, nitrate, cellulose, nitrocellulose) . The invention may also contain a cellulosic associative polymer. Cellulosic compound is understood to mean, according to the invention, any polysaccharide compound having in its structure linear chains of anhydroglucopyranose (AGU) residues united by β (1,4) glycosidic linkages. The repeating 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:

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, there may be mentioned alkylcelluloses such as methylcelluloses and hexylcelluloses; hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxyalkyl-alkylcellulose celluloses such as hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses and hydroxybutyl-methylcelluloses.

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 cross-linked quaternized hydroxyethylcelluloses, or

The quaternizer may be especially glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. Another cationic cellulose ether that may be mentioned is hydroxyethylcellulose hydroxypropyltrimethylammonium.

The quaternized cellulose derivatives are, in particular: quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof; quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof.

Jr

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

Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200®, QUATRISOFT® LM-X 529-18-A®, QUATRISOFT LM-X 529-18B® (C12alkyl) and QUATRISOFT LM-X 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (C-β alkyl) marketed by the company CRODA.

Among the cellulose derivatives, mention may also be made of: - celluloses modified with groups comprising at least one fatty chain, for example hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl groups, especially C8-C22 groups; arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS® (C16 alkyl) sold by AQUALON, and - celluloses modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM-1500 ® (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol.

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.

The celluloses and derivatives are represented for example by the products sold under the names Avicel® (microcrystalline cellulose, MCC) by the company FMC Biopolymers, under the name Cekol® (carboxymethylcellulose) by the company Noviant (CP-Kelco), under the name Akucell AF. (sodium carboxymethylcellulose) by the company Akzo Nobel, under the name MethocelTM (cellulose ethers) and Ethoce ITM® (ethylcellulose) by the company DOW, under the names Aqualon® (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel® (methylcellulose), BlanoseTM (carboxymethylcellulose), Culminai® (methylcellulose, hydroxypropyl methylcellulose), Klucel® (hydroxypropylcellulose), Polysuii® (cetyl hydroxyethylcellulose) and Natrosol® CS (hydroxyethylcellulose) by Hercules Aqualon. '

fructans

The polysaccharide according to the invention may in particular be a fructosan selected from among inulin and its derivatives (especially dicarboxy and carboxymethyl inulines).

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. 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 for the most part linked by β (2,1) linkages. Β 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, that is to say having sequences β (2,6) and β (2,1). 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 artichoke, preferably from chicory.

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. 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 the company Sensus. b) Heterogeneous polysaccharides and their derivatives

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

Gum arabic "

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.

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

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 in a (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.

Galactomannans have the following chemical structure:

"<* 3: Beautiful Locust (GU) MM): Guargum m »2: Ter gum

guar

Guar gum is characterized by a ratio of mannose: galacitosis 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.

The unmodified nonionic guar gums are, for example, the products sold under the name Vidogum GH®, Vidogum G® and Vidocrem® by the company Unipektin and under the name Jaguar® by the company Rhodia, under the name Meypro® Guar by the company Danisco company, under the name VISCOGUI \ il ™ by the company Cargill, and under the name Supercol® guar gum by the company Aqualon.

The hydrolyzed nonionic guar gums that can be used according to the invention are for example represented by the products sold under the name Meyprodor® by Danisco.

The modified nonionic guar gums which can be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups, among which, by way of example, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups may be mentioned.

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 the company Rhodia, or under the name N-Hance® HP (hydroxypropyl guar) by AQUALON.

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.

For the purposes of the present invention, the term "cationic galactomannan gum" generally means any galactomannan gum containing cationic groups and / or ionizable groups in cationic groups.

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 103 and 3 × 10 6.

The cationic galactomannan gums that can be used according to the present invention are, for example, gums comprising cationic trialkyl (C 1 -C 4) ammonium groups. Preferably, from 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, the cationic galactomannan gum is preferably a guar gum comprising hydroxypropyltrimethylammonium groups, that is to say a guar gum modified for example with 2,3-epoxypropyltrimethylammonium chloride.

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. trade names of 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.

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 seed (Ceratonia siliqua).

The unmodified carob gum that can be used in this invention is sold, for example, under the trademark Viscogum ™ by the company Cargill, under the name Vidogum L by the company Unipektin, under the name Grinsted® LBG by the company 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 that can be used in the context of this invention is sold, for example, under the name Vidogum SP® by the company Unipektin.

Glucomannans (koniac gum)

Glucomannan is a high molecular weight polysaccharide (500 000 <Glucomannan <2,000,000), consisting of units of D-mannose and D-glucose with branching every 50 or 60 units. 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.

The products that can be used according to the invention are for example sold under the name Propol® and Rheolex® by the company Shimizu.

LM and HM pectins, and derivatives

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. Uronic acid molecules have carboxyl functions. This function gives pectins the ability to exchange ions when they are in COO 'form. Bivalent ions (especially calcium) 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 -COOCH3 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 an -NH 2 group.

The pectins are sold 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

Among the other polysaccharides that may be used according to the invention, mention may also be made of chitin (Poly N-acetyl-D-glucosamine, β (1,4) -2-acetamido-2-deoxy-D-glucose), chitosan and derivatives (chitosan-beta-glycerophosphate, carboxymethylchitine, etc.) as those sold by France-Chitine; Glycosaminoglycans (GAG) such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, and preferably hyaluronic acid; xylans (or arabinoxylans) and derivatives. k

Arabinoxylans are polymers of xylose and arabinose, all grouped under the name "pentosans".

The xylans consist of a main chain of β (1,4) -linked D-xylose units on which three substituents are found (Rouau & Thibault, 1987): acid units, α-L units -arabinofuranose, side chains may contain arabinose, xylose, galactose and glucuronic acid.

According to this variant, the polysaccharide is preferably hyaluronic acid, or one of its salts such as sodium salt (sodium hyaluronate). II. Synthetic polymeric gelling agents

For the purposes of the invention, the term synthetic means that the polymer is neither naturally existing nor derived from a polymer of natural origin.

The synthetic polymeric hydrophilic gelling agent according to the invention may be particulate or non-particulate.

For the purposes of the invention, the term "particulate" means that the polymer is in the form of particles, preferably spherical.

As is apparent from the following, the polymeric hydrophilic gelling agent is advantageously chosen from crosslinked acrylic homopolymers or copolymers; associative polymers, in particular associative polymers of the polyurethane type; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropane sulfonic acid, crosslinked and / or neutralized; carboxyvinyl polymers, modified or otherwise, and mixtures thereof, in particular as defined below. II.A. Particulate synthetic polymeric gelling agents

They are preferably chosen from crosslinked polymers.

It may in particular be crosslinked homopolymers or acrylic copolymers, preferably partially neutralized or neutralized, which are in particulate form.

According to one embodiment, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates. Preferably, it has, in the dry or non-hydrated state, an average size of less than or equal to 100 μm, preferably less than or equal to 50 μm. The average particle size corresponds to the mean diameter by mass (D50) measured by laser particle size distribution or other equivalent method known to those skilled in the art.

Thus, preferably, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates, preferably in the form of particles having a mean size (or average diameter) less than or equal to 100 microns, more preferably in the form of particles. spherical. By way of example of crosslinked sodium polyacrylates, mention may be made of those sold under the names Octacare X100®, X110® and RM 100® by the company Avecia, those sold under the names Flocare GB300® and Flosorb 500® by the company SNF. those marketed under the names Luquasorb 1003®, Luquasorb 1010®, Luquasorb 1280® and Luquasorb 1110® by the company BASF, those sold under the names Water Lock G400® and G430® (INCI name: Acrylamide / Sodium acrylate copolymer) by the Grain Processing Company.

Cross-linked polyacrylate microspheres such as, for example, those marketed under the name AQUAKEEP® 10 SH NF proposed by the company Sumitomo Seika may also be mentioned.

Such gelling agents may be used in a proportion of from 0.1 to 5% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.5 to 2% by weight, and in particular at the rate of about 0.8 to 1.7% by weight relative to the total weight of the aqueous phase. ll.b. Non-particulate synthetic polymeric gelling agents

This family of gelling agents can be detailed in the following sub-families: 1. Associative polymers, 2. Polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized, and 3. The carboxyvinyl polymers modified or not. ll.b. 1 Associative polymers

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

Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly from those whose hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly by a vinyl carboxylic acid and very particularly with an acrylic acid, a methacrylic acid or their mixtures, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (I): CH 2 = C (R ') CH 2 O Bn R (I) in which R 'denotes H or CH3, B denotes the ethyleneoxy radical, n is nil or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals; , comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms.

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

Among the associative anionic polymers, mention may also be made of terpolymers of maleic anhydride / C 3 -C 8 α-olefin / alkali metal aldehyde such as the maleic anhydride / C 3 -C 8 α-olefin copolymer / isopropyl maleate product sold under the name Performa V 1608 by the company Newphase Technologies.

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

Preferably, these compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester and a C 1 -C 4 alcohol ester. By way of example of this type of compound, mention may be made of Aculyn 22® sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer (comprising 20 EO units) or Aculyn 28® (terpolymer of methacrylic acid / ethyl acrylate / behenyl methacrylate oxyethylene (250E).

As associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type. By way of example, mention may be made of the anionic polymers described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949.

As associative anionic polymers, mention may also be made of anionic terpolymers.

The anionic terpolymer used according to the invention is a linear or branched and / or crosslinked terpolymer of at least one monomer (1) bearing an acid function in free form, partially or totally salified with a chosen nonionic monomer (2). from NN, dimethylacrylamide and 2-hydroxyethyl acrylate and at least one polyoxyethylene alkyl acrylate monomer (3) of the following formula (I):

(I) wherein R1 represents a hydrogen atom, R represents a linear or branched C2-C8 alkyl radical and n represents a number ranging from 1 to 10.

By "connected polymer" is meant a nonlinear polymer which has pendant chains so as to obtain, when this polymer is dissolved in water, a high state of entanglement leading to viscosities at low speed gradient. very important.

The term "crosslinked polymer" denotes a non-linear polymer in the form of a three-dimensional network which is insoluble in water but swellable with water and leads to the production of a chemical gel.

The acid function of the monomer (1) is in particular the sulphonic acid, phosphonic acid function, said functions being in free form, partially or totally salified.

The monomer (1) can be chosen from styrene sulphonic acid, ethylsulphonic acid or 2-methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulphonic acid (also called Acryloyldimethyltaurate) in the form of free, partially or totally salified It is present in the anionic terpolymer preferably in molar proportions of between 5 and 95 mol% and more particularly between 10 and 90 mol%, the monomer (1) will be more particularly 2- methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulfonic acid in free form, partially or totally salified.

The acid function in partially or fully salified form will preferably be an alkali metal salt such as a sodium or potassium salt, an ammonium salt, an aminoalcohol salt such as a monoethanolamine salt or a salt thereof. amino acid such as a salt of lysine.

The monomer (2) is preferably present in the anionic terpolymer in molar proportions ranging from 4.9 to 90 mol% and more particularly from 9.5 to 85 mol% and even more particularly from 19.5 to 75 mol%.

In the formula (I), as an example of a linear C8-C16 alkyl radical, there may be mentioned dodecyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl.

In the formula (I), as an example of a C8-C16 branched alkyl radical, mention may be made of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 4-methylpentyl and 5-methylhexyl. 6-methylheptyl, 15-methylpentadecyl, 16-methylheptadecyl, 2-hexyloctyl.

According to one particular form of the invention, in formula (I), R denotes a C12-C16 alkyl radical.

According to one particular form of the invention, in the formula (I), n varies from 3 to 5.

Tetraethoxylated lauryl acrylate will be used more particularly as monomer of formula (I).

The monomer (3) of formula (I) is preferably present in the anionic terpolymer in molar proportions ranging from 0.1 to 10 mol% and more particularly from 0.5 to 5 mol%.

According to one particular embodiment of the invention, the anionic terpolymer is crosslinked and / or connected by a diethylenic or polyethylenic compound in the proportion expressed relative to the total amount of monomers employed, from 0.005 to 1 mol% and preferably from 0.01 to 0.5 mol% and more particularly 0.01 to 0.25 mol%. The crosslinking agent and / or the branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxoacetic acid or a salt thereof, such as sodium diallyloxyacetate, tetraallyloxyethane, ethylene glycol diacrylate, diallyl urea, triallyl amine, trimethylol propanetriacrylate, methylenebis (acrylamide) or mixtures thereof.

The anionic terpolymer may contain additives such as complexing agents, transfer agents, chain-limiting agents.

More particularly, an anionic terpolymer of 2-methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulphonic acid partially or totally salified in the form of ammonium salt, N, N-dimethylacrylamide and of lauryl acrylate tetraethoxylated and crosslinked with trimethylol propanetriacrylate, INCI Polyacrylate Crosspolymer-6 name such as the product-sold under the trade name Sepimax Zen® by the company Seppic.

Association-Associative Polymers

As cationic associative polymers, mention may be made of polyacrylates with amino side groups.

The polyacrylates with amino side groups, quaternized or otherwise, have, for example, hydrophobic groups of the Steareth type (polyoxyethylenated stearyl alcohol (20)).

Examples of aminated side chain polyacrylates include polymers 8781-121B or 9492-103 from National Starch.

Nonionic associative polymers

The nonionic associative polymers may be chosen from: copolymers of vinylpyrrolidone and hydrophobic fatty-chain monomers; copolymers of methacrylates or of C1-C6 alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain; copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer; associative polyurethanes.

The associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic sequences most often of polyoxyethylenated nature (the polyurethanes may then be called polyurethane polyethers) and hydrophobic sequences which may be aliphatic chains alone and / or or cycloaliphatic and / or aromatic chains.

In particular, these polymers comprise at least two hydrocarbon-based lipophilic chains having from C6 to C30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The associative polyurethanes can be sequenced in the form of triblock or multiblock. The hydrophobic sequences may therefore be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These polymers may also be graft or star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name.

According to a preferred embodiment, a nonionic associative polymer of the polyurethane type is used as a gelling agent. As examples of fatty-chain nonionic polyurethane polyethers that can be used in the invention, it is also possible to use Rheolate® FX 1100 (Steareth-100 / PEG 136 / HDI (hexamethyl diisocyanate) copolymer), Rheolate® 205 to urea function sold by Elementis or the Rheolates® 208, 204 or 212, as well as Acrysoi® RM 184 or Acrysol® RM 2020.

Mention may also be made of the product Elfacos® T210 with a C12-C14 alkyl chain and the product Elfacos® T212 with a C16-18 alkyl chain (PPG-14 Palmeth-60 Hexyl Dicarbamate) from Akzo.

The product DW 1206B® from Rohm & Haas C20 alkyl chain and urethane bond, proposed at 20% dry matter in water, can also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Elementis. It is also possible to use the product DW 1206F and DW 1206J proposed by Rohm & Haas.

The associative polyurethanes that can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen, Colloid Polym. Sci., 271, 380-389 (1993).

More particularly still, according to the invention, it is also possible to use an associative polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by Rohm & Haas under the names Aculyn® 46 and Aculyn® 44. Aculyn 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis (4-cyclohexyl) isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%), and Γ Aculyn® 44 is a polyethylene glycol polycondensate with 150 or 180 moles of ethylene, decyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI), 35% by weight in a mixture of propylene glycol (39%) and water (26%).

It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of SER AD FX1010®, SER AD FX1035® and SER AD 107® from Elementis, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold. by Elementis. Aculyn® 44, Aculyn® 46, DW 1206F® and DW 1206J® can also be used, as well as Acrysol® RM 184 from Rohm & Haas, or the Borchi Gel LW 44® from Borchers, and their mixtures.

Amphoteric associative polymers

Among the associative amphoteric polymers of the invention, mention may be made of the amphoteric polymers, crosslinked or non-crosslinked, branched or non-branched, which may be obtained by the copolymerization of: 1) at least one monomer of formula (IVa) or (IVb): ί

(IVa) (IVb) in which R4 and R5, which may be identical or different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 atoms of carbon ; Z represents an NH group or an oxygen atom; n is an integer of 2 to 5; A 'is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide; 2) at least one monomer of formula (V):

(V) wherein Rg and R10, identical or different, represent a hydrogen atom or a methyl radical; Z1 represents an OH group or an NHC (CH3) 2CH2SO3H group; 3) at least one monomer of formula (VI):

(VI) in which R 8 and K 10, which are identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R 11 denotes a linear or branched alkyl radical having from 1 to 30 atoms of carbon ; 4) optionally at least one crosslinking agent or branching agent; at least one of the monomers of formula (IVa), (IVb) or (VI) comprising at least one fatty chain having from 8 to 30 carbon atoms and said compounds of the monomers of formula (IVa), (IVb), ( V) and (VI) may be quaternized, for example, with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. t

The monomers of formula (IVa) and (IVb) of the present invention are preferably chosen from the group consisting of: dimethylaminoethylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylmethacrylate, diethylaminoethylacrylate, dimethylaminopropylmethacrylate, dimethylaminopropylacrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, optionally quaternized for example with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate.

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

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

The monomers of formula (VI) of the present invention are preferably chosen from the group consisting of C12-C22 and more particularly C16-C18 alkyl acrylates or methacrylate. The crosslinking or branching agent is preferably chosen from N, N'-methylenebisacrylamide, triallylmethylammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylate and dimethacrylate. ethylene glycol, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose.

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

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

The weight average molecular weights of amphoteric associative polymers have a weight average molecular weight of greater than 500, preferably ranging from 10,000 to 10,000,000, and even more preferably from 100,000 to 800,000.

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

Preferably, the molar ratio between the compound (s) of formula (IVa) or (IVb) and the compound (s) of formula (V) varies from 20:80 to 95: 5, and more preferably from 25:75 to 75: 25.

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

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

According to a preferred embodiment, the associative polymer is chosen from nonionic associative polymers and more particularly from associative polyurethanes, such as Steareth-100 / PEG-136 / HDI Copolymer sold under the name Rheolate FX 1100® by Elementis.

Such an associative polymer is advantageously used in a proportion of 0.1 to 8% by weight of dry matter and preferably of 0.5 to 4% by weight relative to the total weight of the aqueous phase. II. B. 2 Polvacrylamides and polymers and copolymers of 2-acrvlamido-2-methylpropane sulphonyl acid

The polymers used which are suitable as aqueous gelling agents for the invention may be homopolymers or copolymers, crosslinked or non-crosslinked, comprising at least the 2-acrylamido-2-methylpropanesulphonic acid monomer (AMPS®), in partially or totally neutralized form. by a mineral base other than ammonia such as soda or potash.

They are preferably neutralized completely or substantially completely neutralized, that is to say neutralized to at least 90%.

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

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

Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, di (meth) acrylate and the like. ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane diallyl ether, allyl meth) acrylate, the allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and the allylic esters of the derivatives of phosphoric acid and / or vinylphosphonic acid; , or mixtures of these compounds.

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

The AMPS® polymers that are suitable for the invention are water-soluble or water-dispersible. They are in this case: either "homopolymers" comprising only AMPS® monomers and, if they are crosslinked, one or more crosslinking agents as defined above; or copolymers obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above. When said copolymers comprise hydrophobic ethylenically unsaturated monomers, the latter do not comprise a fatty chain and are preferably present in small amounts.

For the purposes of the present invention, the term "fatty chain" means any hydrocarbon chain comprising at least 7 carbon atoms.

By "water-soluble or water-dispersible" is meant polymers which, introduced into an aqueous phase at 25 ° C., at a mass concentration equal to 1%, make it possible to obtain a solution that is macroscopically homogeneous and transparent, that is to say having a maximum transmittance value of the light, at a wavelength equal to 500 nm, through a sample 1 cm thick, at least 60%, preferably at least 70%.

The "homopolymers" according to the invention are preferably crosslinked and neutralized, and they can be obtained according to the preparation process comprising the following steps: (a) the monomer such as AMPS in free form is dispersed or dissolved in a solution of t-butanol or water and tert-butanol; (b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more inorganic or organic bases, preferably ammonia NH 3, in an amount making it possible to obtain a degree of neutralization of the sulfonic acid functions of the polymer; ranging from 90 to 100%; (c) adding to the solution or dispersion obtained in (b), the crosslinking monomer (s); (d) conventional radical polymerization is carried out in the presence of free radical initiators at a temperature of from 10 to 150 ° C; the precipitating polymer in the tert-butanol solution or dispersion.

The water-soluble or water-dispersible copolymers of AMPS® according to the invention contain water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof.

The water-soluble comonomers may be ionic or nonionic.

Among the water-soluble ionic comonomers, there may be mentioned, for example, the following compounds and their salts: (meth) acrylic acid, styrene sulphonic acid, vinylsulfonic acid and (meth) allylsulphonic acid, vinyl phophonic acid, maleic acid, itaconic acid, crotonic acid, the water-soluble vinyl monomers of formula (A) below: (A)

wherein: - Ri is selected from H, -CH3, -C2H5 or-C3H7; - Xi is chosen from: - alkyl oxides of -OR2 type where R2 is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms, substituted by at least one sulfonic group (-SO3 ' and / or sulfate (-SO4) and / or phosphate (-PO4H2-).

Among the nonionic water-soluble comonomers that may be mentioned for example: (meth) acrylamide, N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methyl-N- vinylformamide, maleic anhydride, vinylamine, N-vinyllactams containing a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam, vinyl alcohol of the formula CH 2 = CHOH, - the water-soluble vinyl monomers of the following formula (B): (8) in which:

R3 is chosen from H, -CH3, -C2H5 or -C3H7; X 2 is chosen from alkyl oxides of the -OR 4 type in which R 4 is a linear or branched, saturated or unsaturated hydrocarbon-based radical containing from 1 to 6 carbons, optionally substituted with a halogen atom (iodine, bromine, chlorine; fluorine); a hydroxy group (-OH); ether.

Examples include glycidyl (meth) acrylate, hydroxyethyl methacrylate, and ethylene glycol, diethylene glycol or polyalkylene glycol (meth) acrylates.

Among the hydrophobic comonomers without fatty chain, there may be mentioned, for example: styrene and its derivatives such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene; vinyl acetate of formula CH2 = CH-OCOCH3; Vinyl ethers of formula CH2 = CHOR in which R is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbons; acrylonitrile; caprolactone; vinyl chloride and vinylidene chloride; silicone derivatives, leading after polymerization to silicone polymers such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides; the hydrophobic vinyl monomers of formula (C) below:

(C) wherein: R4 is selected from H, -CH3, -C2H5 or -C3H7; X 3 is chosen from: alkyl oxides of the type -OR 5 where R 5 is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms.

Examples include methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate and isobornyl acrylate, and 2-hexyl ethyl acrylate.

The water-soluble or water-dispersible AMPS® polymers of the invention preferably have a molar mass ranging from 50000 to 10000000 g / mol, preferably from 80000 to 8000000 g / mol, and even more preferably from 100 000 to 7000000 g / mol. mole.

As water-soluble or water-dispersible homopolymers of AMPS® that are suitable for the invention, mention may be made, for example, of cross-linked or non-crosslinked polymers of sodium acrylamido-2-methyl propane sulphonate such as that used in the commercial product Simulgel 800® (CTFA name : Sodium polyacryloyldimethyltaurate), crosslinked polymers of ammonium acrylamido-2-methyl propane sulfonate (INCI name: Ammonium polyacryldimethyltauramide) such as those described in patent EP0815928B1 and such as the product sold under the trade name Hostacerin AM PS® by the company Clariant.

As hydrosoluble or water-dispersible copolymers of AMPS in accordance with the invention, mention may be made, for example, of: crosslinked acrylamide / sodium acrylamido-2-methyl propane sulfonate copolymers such as that used in the commercial product SEPIGEL 305® (CTFA name: Polyacrylamide / C13-C14 Isoparaffin / Laureth-7) or that used in the commercial product sold under the name Simulgel 600® (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate / lsohexadecane / Polysorbate-80) by the company Seppic; copolymers of AMPS® and of vinylpyrrolidone or of vinylformamide, such as that used in the commercial product sold under the name Aristoflex AVC® by the company Clariant (CTFA name: Ammonium Acryloyldimethyltaurate / VP Copolymer) but neutralized with sodium hydroxide or potash; copolymers of AMPS® and of sodium acrylate, for example the AMPS® / sodium acrylate copolymer such as that used in the commercial product sold under the name Simulgel EG® by the company Seppic or under the trade name Sepinov EM® (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyltoluene copolymer); copolymers of AMPS® and of hydroxyethyl acrylate, for example the AMPS® / hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or as the product sold under the name Copolymer Acrylamido-2-methylpropane Sodium sulfonate / Hydroxyethylacrylate as the commercial product Sepinov EMT 10® (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl taurate copolymer).

Preferred hydrosoluble or hydrodispersible copolymers of AMPS® according to the invention include copolymers of AMPS® and hydroxyethyl acrylate. In general, an aqueous phase according to the invention may comprise from 0.1 to 8% by weight of dry matter, preferably from 0.2 to 5% by weight and more preferably from 0.7 to 5% by weight. of polyacrylamide (s) and / or polymer (s) and copolymer (s) of 2-acrylamido-2-methylpropanesulfonic acid, crosslinked and / or neutralized (s) relative to its total weight. II. B. 3 Modified or unmodified carboxyvinyl polymers

The modified or unmodified carboxyvinyl polymers may be copolymers resulting from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or their esters, with at least one ethylenically unsaturated monomer (b). having a hydrophobic group.

By "copolymers" is meant both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers such as terpolymers obtained from three kinds of monomers.

Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. "Hydrophobic group or unit" means a saturated or unsaturated, linear or branched hydrocarbon-based radical comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Preferably, these copolymers are chosen from copolymers resulting from the polymerization: of at least one monomer of formula (1) below:

(1) wherein R 1 is H or CH 3 or C 2 H 5, that is, acrylic acid, methacrylic acid or ethacrylic acid monomers, and - at least one C 10 -C 30 alkyl ester monomer ) unsaturated carboxylic acid corresponding to the following monomer of formula (2): t

(2) in which, R2 denotes H or CH3 or C2H5 (that is to say, acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denoting an alkyl radical; C10-C30, and preferably C12-C22.

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

According to a preferred embodiment, these polymers are crosslinked.

Among this type of copolymers, more particularly polymers derived from the polymerization of a monomer mixture comprising: - essentially acrylic acid; - an ester of formula (2) described above and in which R2 designates H or CH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, and - a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene , (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among this type of copolymer, use will more particularly be made of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) ) and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above. ►

Among the above polymers, acrylate / Cio-C3o-alkylacrylate copolymers (INCI name: Acrylates / C 10-30 Alkyl acrylate crosspolymer), such as the products sold by Lubrizol under the US Pat. trade names Pemulen TR-1®, Pemulen TR-2®, Carbopol 1382®, Carbopol EDT 2020®, Carbopol Ultrez 20® Polymer and even more preferentially Pemulen TR-2®.

Among the modified or unmodified carboxyvinyl polymers, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia SP® containing 90% of dry matter and 10% of water, or Cosmedia SPL® in inverse emulsion containing approximately 60% of dry matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by Cognis. ^

Mention may also be made of partially neutralized sodium polyacrylates in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by the company BASF.

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

By "(meth) acrylic" within the meaning of the present application, the term "acrylic or methacrylic". By way of example, mention may be made of those sold by Lubrizol under the names Carbopol, 910, 934, 940, 941, 934, 980, 981, 2984, 5984, Carbopol Ultrez Polymer, or by 3V-Sigma under the name Synthalen® K, Synthalen® L, or Synthalen® M.

Among the modified or unmodified carboxyvinyl polymers, there may be mentioned in particular Carbopol® (CTFA name: carbomer) and Pemulen® (CTFA name: Acrylates / Cio-3o alkyl acrylate crosspolymer) marketed by Lubrizol.

The carboxyvinyl polymers, modified or not, may be present in a proportion of 0.1 to 5% by weight of dry matter relative to the weight of the aqueous phase, in particular of 0.3 to 1% by weight, preferably of 0 to 4 to 1% based on the weight of the aqueous phase.

Advantageously, a composition according to the invention comprises a synthetic polymeric hydrophilic gelling agent chosen from polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid.

According to a preferred variant, the synthetic polymeric hydrophilic gelling agent is a crosslinked sodium polyacrylate or, preferably, a copolymer of 2-acrylamido-2-methylpropanesulphonic acid and hydroxyethyl acrylate.

According to another preferred variant, the synthetic polymeric hydrophilic gelling agent is at least one ammonium 2-acrylamido-2-methylpropane sulfonate acid polymer. III. Other hydrophilic gelling agents

These gelling agents are more particularly chosen from mixed silicates and pyrogenic silicas. III.A. Mixed silicate

For the purposes of the present invention, mixed silicate is understood to mean all silicates of natural or synthetic origin containing several (two or more) types of cations chosen from alkali metals (for example Na, Li, K) or alkaline earth metals ( for example Be, Mg, Ca), transition metals and aluminum.

According to a particular embodiment, the mixed silicate or silicates are in the form of solid particles containing at least 10% by weight of at least one silicate relative to the total weight of the particles. In the remainder of the present disclosure, these particles are referred to as "silicate particles".

Preferably, the silicate particles contain less than 1% by weight of aluminum relative to the total weight of the particles. Even more preferably, they contain from 0 to 1% by weight of aluminum relative to the total weight of the particles.

Preferably, the silicate particles contain at least 50% by weight of silicate, more preferably at least 70% by weight relative to the total weight of the particles. Particles containing at least 90% by weight of silicates, based on the total weight of the particles, are particularly preferred.

In particular, it is a silicate or a mixture of silicates of alkali or alkaline earth metals, aluminum or iron.

Preferably, it is sodium silicate, magnesium and / or litium.

To guarantee good cosmetic properties; these silicates are generally in a finely divided form, and in particular in the form of particles having an average size ranging from 2 nm to 1 μm (from 2 to 1000 nm), and preferably from 5 to 600 nm, and even more preferentially from 20 to 250 nm.

The silicate particles may have any shape, for example the shape of spheres, flakes, needles, platelets, disks, sheets, or totally random forms. Preferably, the silicate particles are in the form of disks or sheets. there

Also, the term "average size" of the particles means the average size in number of the largest dimension (length) that can be measured between two diametrically opposed points of an individual particle. The size can be determined for example by transmission electron microscopy, or from the measurement of the specific surface area by the BET method, or by means of a laser granulometer. *

When the particles in the form of disks or sheets, they generally have a thickness ranging from about 0.5 to 5 nm.

The silicate particles may consist of an alloy with oxides of metals or metalloids, obtained for example by thermal melting of its various constituents. When the particles further comprise such a metal oxide or metalloid, it is preferably selected from silicon oxide, boron or aluminum.

According to one particular embodiment of the invention, the silicates are phyllosilicates, namely silicates having a structure in which the SiO 4 tetrahedra are organized into sheets between which the metal cations are enclosed.

The mixed silicates that are suitable for the invention may be chosen for example from montmorillonites, hectorites, bentonites, beidellite, saponites. According to a preferred embodiment of the invention, the mixed silicates used are more particularly chosen from hectorites and bentonites, and even better from laponites.

A family of silicates particularly preferred in the compositions of the present invention is that of laponites. Laponites are silicates of magnesium, sodium and possibly lithium, having a layered structure similar to that of montmorillonites. Lapponite is the synthetic form of the natural mineral called "hectorite". The synthetic origin of this family of silicates presents a considerable advantage over the natural form because it allows a good control of the composition of the product. In addition, laponites have the advantage of having a much smaller particle size than natural hectorite and bentonite.

As laponites, there may be mentioned in particular the products sold under the following names: Laponite® XLS, Laponite® XLG, Laponite® RD, Laponite® RDS, LAPONITE® XL21 (these products are sodium and magnesium silicates and sodium silicates , lithium and magnesium) by Rockwood Additives Limited.

Such gelling agents may be used in a proportion of from 0.1 to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1 to 5% by weight, and in particular from 0.5% by weight. at 3% by weight relative to the total weight of the aqueous phase. III.B. Hydrophilic Dvroaénée Silica

The fumed silicas according to the present invention are hydrophilic.

The pyrogenic hydrophilic silicas are obtained by pyrolysis in continuous flame at 1000 ° C. of silicon tetrachloride (SiCl) in the presence of hydrogen and oxygen. Among the hydrophilic silicas of hydrophilic nature that can be used according to the present invention, mention may be made in particular of those sold by the company Degussa or Evonik Degussa under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or by CABOT under the name Carbosil H5® name.

Such gelling agents may be used in a proportion of 0.1 to 10% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1 to 5% by weight, and in particular from 0.5% by weight. at 3% by weight relative to the total weight of the aqueous phase.

GELIFYING LIPOPHILE

For the purposes of the present invention, the term "lipophilic gelling agent" is intended to mean a compound capable of gelling the oily phase of the compositions according to the invention.

The gelling agent is therefore lipophilic present in the oily phase of the composition.

The gelling agent is liposoluble or lipodispersible.

As is apparent from the following, the lipophilic gelling agent is advantageously chosen from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, and mixtures thereof. I. Particulate gelling agents

The particulate gelling agent used in the composition according to the invention is in the form of particles, preferably spherical. As a representative of the lipophilic particulate gelling agents that are suitable for the invention, polar, polar and apolar waxes, modified clays, silicas such as pyrogenic silicas and hydrophobic silica aerogels may be particularly mentioned.

Waxes

By "wax" considered in the context of the present invention is generally meant a lipophilic compound, solid at room temperature (25 C), reversible solid state / liquid change, having a melting point greater than or equal to at 30 ° C up to 200 ° C and in particular up to 120 ° C.

For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3; 1999. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments.

The measurement protocol is as follows:

A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise ranging from -20 ° C. to 100 ° C., at a heating rate of 10 ° C./min, then is cooled from 100 ° C. to -20 ° C. ° C at a cooling rate of 10C / minute and finally subjected to a second temperature rise from -20 ° C to 100 C at a heating rate of 5 C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the wax sample as a function of temperature is measured. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The waxes that may be used in the compositions according to the invention are chosen from waxes, solid, at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof.

The waxes, within the meaning of the invention, may be those used generally in the cosmetic or dermatological fields. They may in particular be polar or apolar, silicone hydrocarbonaceous and / or fluorinated, optionally having ester or hydroxyl functions. They can also be of natural or synthetic origin. a) Apolar waxes

By "apolar wax", within the meaning of the present invention, is meant a wax whose solubility parameter at 25 ° C as defined below, 0a is equal to 0 (J / cm3) 1/2.

The definition of the solubility parameters in Hansen's three-dimensional solubility space is described in the article by CM Hansen: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967).

According to this Hansen space: - δd characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular shocks; - δρ characterizes the Debye interaction forces between permanent dipoles as well as the Keesom interaction forces between induced dipoles and permanent dipoles; - oh characterizes the forces of specific interactions (type hydrogen bonds, acid / base, donor / acceptor, etc.): - oa is determined by the equation:

The parameters δρ, ôh, δd and δa are expressed in (J / cm3) / 2.

Solubility parameters are calculated with HSPiP v4.1 software.

The apolar waxes are in particular hydrocarbon waxes consisting solely of carbon and hydrogen atoms and free of heteroatoms such as N, O, Si and P.

The apolar waxes are chosen from microcrystalline waxes, paraffin waxes, ozokerite, polyethylene waxes, and mixtures thereof.

As ozokerite mention may be made of Ozokerite Wax SP 1020 P®.

Microcrystalline waxes that may be used include Multiwax W 445® sold by Sonneborn, Microwax HW® and Base Wax 30540® sold by Paramelt, and Cerewax® No. 3 sold by Baerlocher.

As microwaxes that can be used in the compositions according to the invention as apolar wax, there may be mentioned in particular polyethylene microwires such as those sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders.

As polyethylene wax, mention may be made of Performalene 500-L Polyethylene® and Performalene 400 Polyethylene® sold by New Phase Technologies, Asensa® SC 211 sold by the company Honeywell. b) Polar wax

For the purposes of the present invention, the term "polar wax" is intended to mean a wax whose solubility parameter at 25 ° C. is different from 0 (J / cm 3) / 2.

In particular, "polar wax" is understood to mean a wax whose chemical structure is formed essentially or even consisting of carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an oxygen atom. , nitrogen, silicon or phosphorus.

The polar waxes may especially be hydrocarbon, fluorinated or silicone.

Preferably, the polar waxes may be hydrocarbon-based.

By "hydrocarbon wax" is meant a wax formed essentially, or even constituted, of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon atom or fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. i

By "ester wax" is meant according to the invention a wax comprising at least one ester function. By "alcohol wax" is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group.

In particular, the ester waxes used may be: ester waxes such as those chosen from: i) waxes of formula R 1 COROR 2 in which R 1 and R 2 represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 10 at 50, which may contain a heteroatom such as O, N or P and whose melting point temperature varies from 25 to 120 C. ii) di- (1,1,1-trimethylolpropane) tetrastearate, sold under the designation of Hest 2T-4S® by the company Heterene. iii) diester waxes of a dicarboxylic acid of general formula R3 - (- OCO-R4-COO-R5), in which R3 and R5 are identical or different, preferably identical, and represent a C4-C30 alkyl group ( alkyl comprising from 4 to 30 carbon atoms) and R4 represents a C4-C30 aliphatic group (linear or branched alkyl group comprising 4 to 30 carbon atoms) which may or may not contain one or more unsaturations, and preferably linear and unsaturated. iv) We may also mention the waxes obtained by catalytic hydrogenation of animal or vegetable oils having C8-C32 linear or branched fatty chains, for example such as hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, and waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol. v) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylene lanolin wax, rice bran wax, Ouricury wax , Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax, wax Hydrogenated Jojoba, sunflower wax, lemon wax, olive wax, berry wax.

According to another embodiment, the polar wax may be an alcohol wax. By "alcohol wax" is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group. As alcohol wax, mention may be made, for example, of the wax C30-50 Alcohols Performacol® 550 Alcohol marketed by New Phase Technologie, stearyl alcohol and cetyl alcohol.

It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably at a low melting point.

By "silicone wax" is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups.

Among the commercial silicone waxes of this type, mention may be made in particular of those sold under the names Abilwax 9800®, 9801® or 9810® (Goldschmidt), KF910® and KF7002® (Shin Etsu), or 176-1118-3® and 176-11481® (General Electric).

The silicone waxes which may be used may also be alkyl or alkoxydimethicones, as well as (C 2 -C 6) alkyl dimethicones, in particular (C 3 -C 4) alkyl dimethicones, for instance the silicone wax sold under the name SF-1642® by the company GE-Bayer. Silicones or C30-C45 Alkyldimethylsilyl Polypropylsilsesquioxane under the name SW-8005® G30 Resin Wax® marketed by Dow Corning.

In the context of the present invention, mention may be made, as particularly advantageous waxes, of polyethylene waxes, jojoba wax, candelilla wax and silicone waxes, in particular candelilla wax.

They may be present in the oily phase in a proportion of 0.5 to 30% by weight relative to the weight of the oily phase, for example from 5 to 20% of the oily phase, and more particularly from 2 to 15% by weight. by weight relative to the weight of the oily phase.

Modified clays

The composition according to the invention may comprise at least one lipophilic clay.

The clays can be natural or synthetic and are rendered lipophilic by treatment with an alkylammonium salt such as a C 10 -C 22 ammonium chloride, for example di-stearyl dimethyl ammonium chloride.

They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

Preferably, they are chosen from hectorites.

Preferably, the lipophilic clays used are hectorites modified with a C10 to C22 ammonium chloride, such as hectorite modified with di-stearyl dimethyl ammonium chloride such as, for example, that marketed under the name of Bentone 38V® by Elementis or the bentone gel in isododecane sold under the name Bentone Gel ISD V® (Isododecane 87% / Disteardimonium Hectorite 10% / Propylene carbonate 3%) by Elementis.

Lipophilic clay may especially be present in a content ranging from 0.1 to 15% by weight, in particular from 0.5 to 10%, more particularly from 1 to 10% by weight relative to the total weight of the phase. oily.

Silicas

The oily phase of a composition according to the invention may also comprise, as gelling agent, fumed silica or silica airgel particles. <a) Pyrogenic silica

Particularly suitable for the invention, the hydrophobic treated silica treated surface. 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 may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by 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 (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by Degussa, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by Cabot.

The fumed silicas may be present in a composition according to the present invention at a content ranging from 0.1 to 40% by weight, more particularly from 1 to 15% by weight and even more particularly from 2 to 10% by weight. , based on the total weight of the oily phase. b) Hydrophobic silica aeroqels

The oily phase of a composition according to the invention may also comprise, as gelling agent, at least silica aerogel particles.

Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.

They are generally synthesized by sol-gel process in a liquid medium and then usually dried by extraction of a supercritical fluid, the most commonly used being supercritical CO2. This type of drying avoids the contraction of the pores and the material. The sol-gel process and the various dryings are described in detail in Brinker CJ, and Scherer GW, Sol-Gel Science: New York: Academic Press, 1990.

The hydrophobic silica airgel particles used in the present invention have a surface area per unit mass (SM) of from 500 to 1500 m 2 / g, preferably from 600 to 1200 m 2 / g and more preferably from 600 to 800 m 2 / g. g, and a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 1500 μm, better still from 1 to 1000 μm, preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably 5 to 25 μm, more preferably 5 to 20 μm and more preferably 5 to 15 μm.

According to one embodiment, the hydrophobic silica airgel particles used in the present invention have a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 30 μm, preferably from 5 to 25 μm. better from 5 to 20 μm and even better from 5 to 15 μm.

The specific surface area per unit mass can be determined by the nitrogen absorption method called the BET method (Brunauer - Emmet - Teller) described in "The Journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (Appendix D). The BET surface area corresponds to the total specific surface area of the particles under consideration.

The silica airgel particle sizes can be measured by static light scattering using a MasterSizer 2000 commercial particle size analyzer from Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" diameter of particles. This theory is particularly described in Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the hydrophobic silica aerogel particles used in the present invention have a specific surface per unit mass (SM) ranging from 600 to 800 m 2 / g.

The silica airgel particles used in the present invention may advantageously have a packed density p ranging from 0.02 to 0.10 g / cm3, preferably from 0.03 to 0.08 g / cm3, in particular ranging from 0.05 to 0.08 g / cm.

In the context of the present invention, this density can be evaluated according to the following protocol, referred to as packed density:

40 g of powder are poured into a graduated cylinder; then the specimen is placed on the STAV 2003 machine from Stampf Volumeter; the test piece is then subjected to a series of 2500 settlements (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio m / Vf, in this case 40 / Vf (Vf being expressed in cm3 and m in g).

According to a preferred embodiment, the hydrophobic silica airgel particles used in the present invention have a specific surface area per volume unit SV ranging from 5 to 60 m 2 / cm 3, preferably from 10 to 50 m 2 / cm 3 and better still 15 to 40 m2 / cm3.

The specific surface area per unit volume is given by the relation:

Sv = SM xp; where p is the is packed density expressed in g / cm3 and SM is the specific surface per unit mass expressed in m2 / g, as defined above. ,

Preferably, the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity measured at Wet Point ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and better still from 8 to 18 ml / g. at 12 ml / g.

The absorption capacity measured at Wet Point, and denoted by Wp, corresponds to the amount of oil that must be added to 100 g of particles in order to obtain a homogeneous paste.

It is measured according to the so-called Wet Point method or method for determining the setting of powder oil described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and / or absorbed by the powder by measuring the Wet Point, described below:

An amount m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added dropwise. After addition of 4 to 5 drops of oil in the powder, mixing is carried out with a spatula and oil is added until the formation of oil and powder conglomerates. From this moment, the oil is added one drop at a time and then triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracks or lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil intake corresponds to the ratio Vs / m.

The aerogels used according to the present invention are aerogels of hydrophobic silica, preferably of silylated silica (INCI name: silica silylate).

By "hydrophobic silica" is meant any silica whose surface is treated with silylating agents, for example by halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, in order to functionalize the OH groups by Si-Rn silyl groups, for example trimethylsilyl groups.

Concerning the preparation of hydrophobic silica airgel particles surface-modified by silylation, reference can be made to US Pat. No. 7,470,725.

Hydrophobic silica airgel particles that are surface-modified with trimethylsilyl groups, preferably INCI Silica silylate, will preferably be used. Examples of hydrophobic silica aerogels that can be used in the invention include, for example, the airgel marketed under the name VM-2260® or VM-2270® (INCI name: Silica silylate), by the company Dow Corning, whose particles have an average size of about 1000 microns and a specific surface area per unit mass of 600 to 800 m 2 / g.

The aerogels marketed by Cabot under the Aerogel TLD 201®, Aerogel OGD 201®, Aerogel TLD 203®, ENOVA® Aerogel MT 1100® and ENOVA Aerogel MT 1200® standards can also be mentioned.

The airgel marketed under the name VM-2270® (INCI name Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5 to 15 microns and a specific surface per unit mass ranging from from 600 to 800 m2 / g.

Such an airgel advantageously makes it possible to promote the resistance of the deposit to sebum and sweat.

Preferably, the particles of hydrophobic silica aerogels are present in the composition according to the invention in a dry matter content ranging from 0.1 to 8% by weight, preferably from 0.2 to 5% by weight. preferably from 0.2 to 1.5% by weight relative to the total weight of the oily phase. II. Oranopolysiloxane Elastomer The organopolysiloxane elastomer, which can be used as a lipophilic gelling agent, has the advantage of giving the composition according to the invention good application properties. It provides a very soft and matifying after application, especially advantageous for application on the skin. It can also allow an effective filling of the hollows present on the keratin materials.

By "organopolysiloxane elastomer" or "silicone elastomer" is meant a flexible, deformable organopolysiloxane having viscoelastic properties and especially the consistency of a sponge or a flexible sphere. Its modulus of elasticity is such that this material resists deformation and has a limited capacity for extension and contraction. This material is able to recover its original shape after stretching.

It is more particularly a crosslinked organopolysiloxane elastomer.

Thus, the organopolysiloxane elastomer can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and diorganopolysiloxane having silicon-bonded ethylenically unsaturated groups, especially in the presence of platinum catalyst; or by condensation-crosslinking dehydrogenation reaction between a hydroxyl-terminated diorganopolysiloxane and a diorganopolysiloxane containing at least one silicon-bonded hydrogen, especially in the presence of an organotin; or by crosslinking condensation reaction of a hydroxyl-terminated diorganopolysiloxane and a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of organoperoxide catalyst; or by crosslinking of organopolysiloxane by high energy radiation such as gamma rays, ultraviolet rays, electron beam.

Preferably, the organopolysiloxane elastomer is obtained by addition reaction crosslinking (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) diorganopolysiloxane having at least two silicon-bonded ethylenic unsaturation groups. , especially in the presence (C) of platinum catalyst, as for example described in the application EP-A-295886. '

In particular, the organopolysiloxane elastomer can be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst.

The compound (A) is the basic reagent for the formation of organopolysiloxane elastomer and the crosslinking is carried out by addition reaction of the compound (A) with the compound (B) in the presence of the catalyst (C).

The compound (A) is in particular an organopolysiloxane having at least two hydrogen atoms bonded to distinct silicon atoms in each molecule.

The compound (A) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure.

The compound (A) may have a viscosity at 25 ° C ranging from 1 to 50000 centistokes, in particular to be well miscible with the compound (B).

The organic groups bonded to the silicon atoms of the compound (A) can be alkyl groups such as methyl, ethyl, propyl, butyl, octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group.

The compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogenosiloxane copolymers, and dimethylsiloxane-methylhydrogensiloxane cyclic copolymers.

The compound (B) is advantageously a diorganopolysiloxane having at least two lower alkenyl groups (for example C2-C4); the lower alkenyl group may be chosen from vinyl, allyl and propenyl groups. These lower alkenyl groups may be located at any position of the organopolysiloxane molecule but are preferably located at the ends of the organopolysiloxane molecule. The organopolysiloxane (B) may have a branched chain, straight chain, cyclic or network structure but the linear chain structure is preferred. The compound (B) can have a viscosity ranging from the liquid state to the gum state. Preferably, the compound (B) has a viscosity of at least 100 centistokes at 25 ° C.

In addition to the aforementioned alkenyl groups, the other organic groups bonded to the silicon atoms in the compound (B) may be alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group.

The organopolysiloxane (B) can be chosen from methylvinylpolysiloxanes, the methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes comprising dimethylvinylsiloxy endings, dimethylsiloxane-methylphenylsiloxane dimethylvinylsiloxy end groups, copolymers terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane dimethylsiloxane copolymers, dimethylsiloxane-methylvinylsiloxane trimethylsiloxy termini, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) -polysiloxane, and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymers .

In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst.

Advantageously, the sum of the number of ethylenic groups per molecule of the compound (B) and the number of hydrogen atoms bonded to silicon atoms per molecule of the compound (A) is at least 5.

It is advantageous that the compound (A) is added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in the compound (A) and the total amount of all the groups to Ethylenic unsaturation in the compound (B) is in the range of 1.5: 1 to 20: 1.

Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and platinum. on support.

The catalyst (C) is preferably added from 0.1 to 1000 parts by weight, more preferably from 1 to 100 parts by weight, as clean platinum metal per 1000 parts by weight of the total amount of the compounds (A) and ( B). The elastomer is advantageously a non-emulsifying elastomer.

V

The term "non-emulsifying" defines organopolysiloxane elastomers that do not contain a hydrophilic chain, and in particular that do not contain polyoxyalkylene (especially polyoxyethylene or polyoxypropylene) units or polyglyceryl units. Thus, according to one particular embodiment of the invention, the composition comprises an organopolysiloxane elastomer devoid of polyoxyalkylene units and a polyglyceryl unit.

In particular, the silicone elastomer used in the present invention is selected from Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name) .

The organopolysiloxane elastomer particles may be conveyed in the form of a gel consisting of an elastomeric organopolysiloxane included in at least one hydrocarbon oil and / or a silicone oil. In these gels, the organopolysiloxane particles are often non-spherical particles.

Non-emulsifying elastomers are described in EP 242 219, EP 285 886, EP 765 656 and JP-A-61-194009. The silicone elastomer is generally in the form of a gel, a paste or a powder, but advantageously in the form of a gel in which the silicone elastomer is dispersed in a linear silicone oil (dimethicone ) or cyclic (eg cyclopentasiloxane), advantageously in a linear silicone oil.

As non-emulsifying elastomers, those sold under the names "KSG-6®", "KSG-15®", "KSG-16®", "KSG-18®", "KSG-41®", can be used more particularly. "KSG-42®", "KSG-43®", "KSG-44®", by Shin Etsu, "DC9040®", "DC9041®", by Dow Corning Corporation, "SFE 839®" by General Electric company.

According to one particular embodiment, a silicone elastomer gel dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenylmethicone, phenyldimethicone, phenyltrimethicone and cyclomethicone, is used. preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C. ranging from 1 to 500 ° C. at 25 ° C., optionally modified with aliphatic groups, optionally fluorinated, or with functional groups such as groups hydroxyls, thiols and / or amines. *

Mention may in particular be made of the following INCI name compounds: Dimethicone / Vinyl Dimethicone Crosspolymer, such as USG-105® and USG-107A® from Shin Etsu; "DC9506®" and "DC9701®" from Dow Corning, - Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as "KSG-6®" and "KSG-16®" from Shin Etsu; t-Dimethicone / Vinyl Dimethicone Crosspolymer (and) Cyclopentasiloxane, such as "KSG-15®"; - Cyclopentasiloxane (and) Dimethicone Crosspolymer, such as "DC9040®", "DC9045®" and "DC5930®" from Dow Corning; Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041®" from Dow Corning; Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning (a mixture of polydimethylsiloxane cross-linked with hexadiene / polydimethyl siloxane (2 cSt)); - C4-24 Alkyl Dimethicone / DivinyIDimethicone Crosspolymer, such as NuLastic Silk MA® by the company Alzo.

As examples of silicone elastomers dispersed in a linear silicone oil that can advantageously be used according to the invention, mention may be made in particular of the following references:

Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as "KSG-6®" and "KSG-16®" from Shin Etsu;

Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041®" from Dow Corning; and Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning.

The organopolysiloxane elastomer particles may also be used in the form of a powder, in particular mention may be made of the powders sold under the names "Dow Corning 9505 Powder" and "Dow Corning 9506 Powder®" by the company Dow Corning. These powders have the following properties: for INCI name: dimethicone / vinyl dimethicone crosspolymer.

The organopolysiloxane powder may also be coated with silsesquioxane resin, as described, for example, in US Pat. No. 5,538,793. Such elastomer powders are sold under the names "KSP-100®", "KSP-101®", "KSP-102®", "KSP-103®", "KSP-104®", "KSP-105 ® by the company Shin Etsu, and are INCI name: vinyl dimethicone / methicone silsesquioxane Crosspolymer.

Examples of organopolysiloxane powders coated with silsesquioxane resin that can advantageously be used according to the invention include, in particular, the reference "KSP-100®" from Shin Etsu. As preferred lipophilic gelling agent of the organopolysiloxane elastomer type, there may be mentioned in particular cross-linked organopolysiloxane elastomers chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer ( INCI name), DimethiconeA / Inyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), and in particular Dimethicone Crosspolymer (INCI name). The organopolysiloxane elastomer may be present in a composition of the present invention at a content ranging from 0.1 to 35% by weight of dry matter, especially from 1 to 20% and more particularly from 2 to 10% by weight. weight, relative to the total weight of the composition. III. Semi-crystalline polymers

The composition according to the invention may comprise at least one semi-crystalline polymer. Preferably, the semi-crystalline polymer has an organic structure, and a melting temperature greater than or equal to 30 ° C.

For the purposes of the invention, the term "semi-crystalline polymer" is intended to mean polymers comprising a crystallizable part and an amorphous part and having a first-order reversible phase change temperature, in particular melting (solid-liquid transition). . The crystallizable portion is either a side chain (or pendant chain) or a sequence in the backbone.

When the crystallizable portion of the semi-crystalline polymer is a sequence of the polymer backbone, this crystallizable block is of a different chemical nature from that of the amorphous sequences; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable portion is a chain pendant to the backbone, the semi-crystalline polymer may be a homopolymer or a copolymer.

The melting temperature of the semi-crystalline polymer is preferably less than 150 ° C.

The melting temperature of the semi-crystalline polymer is preferably greater than or equal to 30 ° C and less than 100 ° C. More preferably, the melting temperature of the semi-crystalline polymer is greater than or equal to 30 ° C and less than 70 ° C.

The semicrystalline polymer (s) according to the invention used are solids at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg), the melting point of which is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the Mettler company, with a temperature rise of 5 or 10 C per minute (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).

The semi-crystalline polymer (s) according to the invention preferably have a melting point higher than the temperature of the keratinous support intended to receive said composition, in particular the skin, the lips or the eyebrows.

According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, especially at least 1% by weight, at a temperature above their melting point. Apart from the crystallizable sequences chains, the sequences of the polymers are amorphous

By "chain or crystallizable block" is meant, in the sense of the invention, a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state, reversibly, depending on whether it is above or below below the melting temperature. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one, of the repeating units of the polymer.

Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the fatty phase at a temperature above their melting point.

Preferably, the crystallizable sequences or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. Crystallizable side-chain semi-crystalline polymers are homo- or co-polymers. The semicrystalline polymers of the invention with crystallizable sequences are copolymers, sequenced or multiblocked.

They can be obtained by reactive (or ethylenic) double bond monomer polymerization or by polycondensation. When the polymers of the invention are crystallizable side chain polymers, the latter are advantageously in random or statistical form.

Preferably, the semi-crystalline polymers of the invention are of synthetic origin.

According to a preferred embodiment, the semi-crystalline polymer is chosen from: homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing hydrophobic side chain (s) crystallizable (s) ), polymers carrying in the backbone at least one crystallizable block, polycondensates of polyester, aliphatic or aromatic or aliphatic / aromatic type, metallocene-catalyzed copolymers of ethylene and propylene, and acrylate / copolymers. silicone.

The semicrystalline polymers that may be used in the invention may be chosen in particular from: - block copolymers of controlled crystallization polyolefins, the monomers of which are described in EP 0 951 897, - polycondensates, and in particular of polyester, aliphatic or aromatic or aliphatic / aromatic, copolymers of ethylene and propylene prepared by metallocene catalysis, homopolymers or copolymers bearing at least one crystallizable side chain and homo- or co-polymers carrying in the skeleton at least one crystallizable sequence, such as those described in US Pat. No. 5,156,911, such as the (CiO-C3o) alkyl polyacrylates corresponding to Intelimer® from Landec, described in the brochure "Intelimer® Polymers", Landec IP22® (Rev. 4-97) and for example the product Intelimer® IPA 13-1® from Landec, which is a stearyl polyacrylate with a molecular weight of about 145,000 and whose melting temperature is equal to 49 ° C, homopolymers or copolymers bearing at least one crystallizable side chain, in particular with a fluoro group (s), as described in document WO 01/19333, acrylate / silicone copolymers, such as copolymers of acrylic acid and polydimethylsiloxane grafted stearyl acrylate, polydimethylsiloxane grafted stearyl methacrylate copolymers, polydimethylsiloxane grafted stearyl methacrylate and acrylic acid copolymers, copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Mention may in particular be made of the copolymers sold by the company SHIN-ETSU under the names KP-561® (CTFA name: acrylates / dimethicone), KP-541® (CTFA name: acrylates / dimethicone and isopropyl alcohol), KP-545® (CTFA name: acrylates / dimethicone and cyclopentasiloxane), and mixtures thereof.

Preferably, the amount of semicrystalline polymer (s), preferably chosen from semi-crystalline crystallizable side chain polymers, represents from 0.1 to 30% by weight of dry matter relative to the total weight of the phase. oily, for example from 0.5 to 25% by weight, better still from 5 to 20%, or from 5 to 12% by weight, relative to the total weight of the oily phase. IV. Esters of dextrin

The composition according to the invention may comprise, as lipophilic gelling agent, at least one dextrin ester.

In particular, the composition preferably comprises at least one ester of dextrin and fatty acid, preferably C 12 to C 24, in particular C 14 to C 18, or mixtures thereof.

Preferably, the dextrin ester is a C12-C18, especially C14-C18, fatty acid dextrin ester.

Preferably, the dextrin ester is selected from dextrin myristate and / or dextrin palmitate, and mixtures thereof.

According to a particular embodiment, the dextrin ester is dextrin myristate, such as that sold especially under the name Rheopearl MKL-2® by Chiba Flour Milling.

According to a preferred embodiment, the dextrin ester is dextrin palmitate. This may for example be chosen from those sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling.

In a particularly preferred manner, the oily phase of a composition according to the invention may comprise from 0.1 to 30% by weight of dextrin ester (s), preferably from 2 to 25% and preferably from 7.5 to to 17% by weight, based on the total weight of the oily phase. .

In a particularly preferred manner, the composition according to the invention comprises from 0.1 to 10% by weight of dextrin palmitate, preferably from 0.5 to 5% by weight relative to the total weight of the oily phase. Dextrin palmitate may in particular be that marketed under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling. V. Hydrogen-Bonded Polymers As a representative of the hydrogen-bonded polymers that are suitable for the invention, polyamides and in particular hydrocarbon polyamides and silicone polyamides may be particularly mentioned.

Polyamides

The oily phase of a composition according to the invention may comprise at least one polyamide chosen from hydrocarbon polyamides, silicone polyamides, and mixtures thereof.

Preferably, the total content of polyamide (s) ranges from 0.1 to 30% by weight, expressed as dry matter, preferably from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight. , based on the total weight of the oily phase.

For the purposes of the invention, the term "polyamide" means a compound having at least 2 amide repeating units, preferably at least 3 amide repeating units and more preferably 10 amide repeating units. a) Hydrocarbon polyamide

By "hydrocarbon-based polyamide" is meant a polyamide formed essentially or even consisting of carbon and hydrogen atoms, and optionally of oxygen, nitrogen, and not containing a silicon atom or fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

For the purposes of the invention, the term "functionalized chain" means an alkyl chain comprising one or more functional groups or reactive groups chosen in particular from hydroxyl, ether, esters, oxyalkylene or polyoxyalkylene groups. Advantageously, this polyamide of the composition according to the invention has a weight average molecular weight of less than 100 000 g / mol, in particular ranging from 1000 to 100000 g / mol, in particular less than 50 000 g / mol, in particular ranging from 1000 to 50 000. g / mol, and more particularly ranging from 1000 to 30000 g / mol, preferably from 2000 to 20000 g / mol, and better still from 2000 to 10000 g / mol.

This polyamide is insoluble in water, especially at 25 ° C.

According to a first embodiment of the invention, the polyamide used is a polyamide of formula (I) (:

Wherein X is -N (R1) 2 or -OR1 wherein R1 is a linear or branched C6-C22 alkyl radical, which may be the same or different from each other, R2 is a residue; of C 28 -C 42 diacid dimer, R 3 is an ethylene diamine radical, n is 2 to 5; and their mixtures.

According to one particular embodiment, the polyamide used is an amide-terminated polyamide of formula (Ia):

Wherein X represents a group -ΝΝ) 2 in which R₁ is a linear or branched C en to C₂₂ alkyl radical, which may be the same or different from each other, R₂ is a C 28 diacid dimer residue. -C42, R3 is an ethylene diamine radical, n is between 2 and 5; and their mixtures.

The oily phase of a composition according to the invention may furthermore additionally comprise, in this case, at least one additional polyamide of formula (ib):

Qb) in which X represents a group -OR1 in which R1 is a linear or branched C8 to C22, preferably C16 to C22, alkyl radical which may be identical to or different from each other, R2 is a residue of C 28 -C 42 diacid dimer, R 3 is an ethylene diamine radical, n is between 2 and 5, such as the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100 or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG, whose INCI name is "ethylenediamine / stearyl dimer dilinoleate copolymer". bl Silicone polyamide.

The silicone polyamides are preferably solids at room temperature (25 ° C.) and atmospheric pressure (760 mmHg).

The silicone polyamides may preferentially be polymers comprising at least one unit of formula (III) or (IV):

or in which:

R4, R5, R6 and R7, which are identical or different, represent a group chosen from: linear or branched or cyclic hydrocarbon groups, C 1 to C 40, saturated or unsaturated, which may contain in their chain one or more atoms of oxygen, sulfur and / or nitrogen, and which may be substituted in part or totally by fluorine atoms, C6-C10 aryl groups, optionally substituted with one or more C1-C4 alkyl groups, polyorganosiloxane chains. whether or not containing one or more oxygen, sulfur and / or nitrogen atoms, the X, which are identical or different, represent a linear or branched C 1 -C 30 alkylene di-yl group which may contain in its chain a or a plurality of oxygen and / or nitrogen atoms, Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, C1 to C50, group which may comprise one or more oxygen atoms , sulfur and / o nitrogen, and / or substitute one of the following atoms or groups of atoms: fluorine, hydroxy, C3-C8 cycloalkyl, C1-C40 alkyl, C5-C5 aryl, phenyl optionally substituted with 1 to 3 C 1 -C 3 alkyl, C 1 -C 3 hydroxyalkyl and C 1 -C 6 alkyl, or Y is a group of the formula

in which - T represents a trivalent or tetravalent hydrocarbon group, linear or branched, saturated or unsaturated, C3 to C24 optionally substituted with a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al, and - R8 represents a linear or branched C1-C50 alkyl group, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or or sulfonamide which may or may not be bound to another chain of the polymer, n is an integer ranging from 2 to 500, preferably from 2 to 200 and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200.

According to one particular embodiment, the silicone polyamide comprises at least one unit of formula (III) in which m ranges from 50 to 200, in particular from 75 to 150, and preferably of the order of 100.

More preferably, R4, R5, R6 and Ry independently represent a linear or branched C1-C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group in formula (III). As an example of a silicone polymer that may be used, mention may be made of one of the silicone polyamides obtained according to Examples 1 to 3 of US 5,981,680.

Mention may be made of the compounds marketed by Dow Corning under the name DC 2-8179 (DP 100) and DC 2-8178 (DP 15) whose INCI name is "Nylon-611 / dimethicone copolymers", that is, say nylon-611 / dimethicone copolymers. The silicone polymers and / or copolymers advantageously have a transition temperature of the solid state in the liquid state ranging from 45 to 190 ° C. Preferably, they have a solid state transition temperature in the liquid state of from 70 to 130 ° C and more preferably from 80 to 105 ° C.

Preferably, the total content of polyamide (s) and / or polyamide (s) silicone (s) varies from 0.5 to 25% by weight of dry matter, in particular from 2 to 20% by weight, preferably from 2 to 12% by weight, based on the total weight of the oily phase.

Advantageously, the hydrogen-bonded polymer is chosen from ethylene diamine / stearyl dimer dilinoleate copolymer and nylon-611 / dimethicone copolymers.

According to an advantageous variant, a composition according to the invention comprises a lipophilic gelling agent chosen from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, and mixtures thereof, and in particular at least one organopolysiloxane elastomer. GELIFYING SYSTEM) HYPROPHILESIS / GELIFYANTS (LIPOPHILES) As preferred synthetic polymeric hydrophilic gelling agents, mention may be made more particularly of 2-acrylamido-2-methylpropanesulphonic acid polymers, such as, for example, AMPS®, such as the acid polymer. Ammonium 2-acrylamido 2-methylpropane sulphonate sold under the trade name Hostacerin AMPS® by Clariant, and 2-acrylamido-2-methylpropanesulphonic acid copolymers and in particular AMPS® and hydroxyethyl acrylate copolyrers, as for example the AMPS® / hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydoxyethyl Acrylate / Sodfum Acryloyl Dimethyltaurate Copolymer (And) Squalane (And) Polysorbate 60 or such as the product sold under the name Copolymer Acrylamido-2-Methyl Propane Sodium Sulfonate / Hydroxyethylacrylate as the Sepinov EMT 10® commercial product (INCI name: Hydoxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer). As preferred lipophilic gelling agents, mention may be made of organopolysiloxane elastomers, preferably chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), and in particular Dimethicone Crosspolymer (INCI name) and Dimethicone (and) Dimethicone Crosspolymer (INCI name).

According to a preferred embodiment, lipophilic gelling agents that may be mentioned more particularly include silicone elastomer gels dispersed in a silicone oil and / or organopolysiloxane elastomer powders coated with silsesquioxane resin.

Thus, according to one particular embodiment, a silicone elastomer gel dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenylmethicone, phenyldimethicone, phenyltrimethicone and the cyclomethicone, preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C. ranging from 1 to 500 ° C. at 25 ° C., especially the following references: Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as KSG-6® and KSG-16® from Shin Etsu; Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041®" from Dow Corning; and

According to a particularly preferred embodiment, the composition according to the invention comprises, as lipophilic gelling agent, at least one cross-linked silicone elastomer of the INCI name "dimethicone (and) dimethicone crosspolymer", preferably with a dimethicone of viscosity ranging from 1 to 100 ° C. , in particular from 1 to 10 is at 25 ° C., such as the mixture of polydimethylsiloxane with hexadiene / polydimethyl

Siloxane (5cst) marketed under the name DC 9041 Dow Corning® and the mixture of polydimethylsiloxane by Hexadiene / Polydimethyl Siloxane (2cst) sold under the name "Dow Corning EL-9240® Silicone Elastomer Blend" by Dow Corning.

According to another particularly preferred embodiment, the composition according to the invention comprises at least one organopolysiloxane elastomer powder coated with silsesquioxane resin, INCI name: vinyl dimethicone / methicone silsesquioxane Crosspolymer, such as the reference "KSP-100®" sold by Shin Etsu. By way of nonlimiting illustration, hydrophilic gelling / gelling (s) / lipophilic gelling systems (s) that are particularly suitable for the invention may in particular be cited as the polymer (s) or copolymer (s) of acid system. 2- acrylamido 2 methylpropanesulfonic / organopolysiloxane elastomer (s).

Thus, a composition according to the invention may advantageously comprise, as hydrophilic gelling / lipophilic gelling systems, a 2-acrylamido-2-methylpropanesulphonic acid / elastomer (s) polymer system. organopolysiloxane or copolymer of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate / organopolysiloxane elastomer (s).

Preferably, a composition according to the invention may comprise, as lipophilic hydrophilic gelling / gelling system (s), a copolymer system of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate / powder. of organopolysiloxane elastomer.

AQUEOUS PHASE

The aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.

By "water-soluble solvent" is meant in the present invention a liquid compound at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25 C and atmospheric pressure).

The water-soluble solvents that can be used in the composition of the invention may also be volatile.

Among the water-soluble solvents that can be used in the composition in accordance with the invention, mention may be made in particular of lower monoalcohols having from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having from 2 to 8 carbon atoms. carbon such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dlpropylene glycol, C3 and C4 ketones and C2-C4 aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 5 to 95%, better still from 30 to 80% by weight, preferably from 40 to 75% by weight, relative to the total weight of said composition.

According to another variant embodiment, the aqueous phase of a composition according to the invention may comprise at least one C2-C32 polyol.

By "polyol" is meant for the purposes of the present invention, any organic molecule comprising at least two free hydroxyl groups.

Preferably, a polyol according to the present invention is present in liquid form at room temperature.

A polyol that is suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing at least two -OH functions on the alkyl chain, in particular at least three -OH functions, and more particularly at minus four functions -OH.

The polyols which are advantageously suitable for formulating a composition according to the present invention are those having in particular 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.

Advantageously, the polyol may be, for example, chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3 propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol and glycerol. polyglycerols, such as oligomers of glycerol such as diglycerol, polyethylene glycols, and mixtures thereof.

According to a preferred embodiment of the invention, said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof.

According to one particular embodiment, the composition of the invention may comprise at least propylene glycol.

According to another particular embodiment, the composition of the invention may comprise at least glycerol.

OIL PHASE

The composition according to the invention comprises an oily phase comprising at least one polar oil.

The term "oil" means any fatty substance in liquid form at ambient temperature at atmospheric pressure.

By "polar oil" is meant any oil having solubility parameters according to the HANSEN solubility space such as 13 <5d <22.

According to this Hansen space: - δd characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular shocks; - δρ characterizes the Debye interaction forces between permanent dipoles as well as the Keesom interaction forces between induced dipoles and permanent dipoles; - 3h characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); - δa is determined by the equation: δa = (δρ2 + δh2) / 2.

The parameters δρ, ôh, ôd and δa are expressed in (J / cm3) / 2.

Solubility parameters are calculated with HSPiP v4.1 software.

More preferentially, the oil or the polar oils in accordance with the invention will also be characterized by a 1 <oa <10. The oil or polar oils according to the invention may be of vegetable, mineral or synthetic origin.

They may be chosen from hydrocarbon oils, silicone oils, and mixtures thereof.

The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

These same oils may be volatile or non-volatile.

By "volatile oil" is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 '). 3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); mm Hg).

For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa.

The oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acidic radicals. A) Hydrocarbon polar oils

Among the hydrocarbon polar oils that can be used in the oily phase of the compositions of the invention, mention may be made of: phytostearyl esters, such as phytostearyl oleate, physostearyl isostearate and lauroyl / octyldodecyl glutamate; phytostearyl (AJINOMOTO, ELDEW PS203®), - triglycerides consisting of esters of fatty acids and of glycerol, in particular whose fatty acids may have chain lengths varying from C4 to C36, and especially from C18 to C36, these oils which may be linear or branched, saturated or unsaturated; these oils may in particular be heptanoic or octanoic triglycerides, wheat germ, sunflower seeds, grape seed oil, sesame seed (820.6 g / mol), corn, apricot, castor oil, shea butter, avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, black currant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea oil; or alternatively caprylic / capric acid triglycerides, such as those sold by Stéarineries Dubois or those sold under the names Miglyo® 810®, 812® and 818® by the company Dynamit Nobel; synthetic ethers having from 10 to 40 carbon atoms, such as dicaprylyl ether, hydrocarbon esters of formula RCOOR 'in which RCOO represents a carboxylic acid residue containing from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, such as cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, palmitate 2-ethyl-hexyl, isopropyl stearate or isostearate, isostearyl isostearate, octyl stearate, diisopropyl adipate, heptanoates, and especially isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, 4-diheptanoate and 2-hexyl ethyl palmitate, alkyl benzoate, diheptanoate polyethylene glycol, diethyl 2-propylene glycol hexanoate and mixtures thereof, C12-C15 alcohol benzoates, hexyl laurate, esters of neopentanoic acid such as isodecyl neopentanoate, isotridecyl neopentanoate, neopentanoate d isostearyl, octyl-2-dodecyl neopentanoate, esters of isononanoic acid such as isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, oleyl erucate; lauroyl isopropyl sarcosinate, diisopropyl sebaccate, isoketyl stearate, isodecyl neopentanoate, isostearyl behenate, myristyl myristate; polyesters obtained by condensation of dimer and / or trimer of unsaturated fatty acid and of diol, such as those described in patent application FR 0 853 634, such as in particular dilinoleic acid and 1,4-diol; butanediol. Mention may in particular be made of the polymer marketed by Biosynthis under the name Viscoplast 14436H® (INCI name: dilinoleic acid / butanediol copolymer), or copolymers of polyols and diacid dimers, and their esters, such as Hailuscent ISDA®. polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate, fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, 2-butyloctanol and 2-hexyl decanol, 2-undecylpentadecanol, oleic alcohol; di-alkyl carbonates, the 2 alkyl chains being identical or different, such as dicaprylyl carbonate sold under the name Cetiol CC®, by Cognis; and copolymers of vinylpyrrolidone such as the vinylpyrrolidone / 1-hexadecene copolymer, ANTARON V-216® sold or manufactured by ISP, linear fatty acid esters having a total carbon number ranging from 35 to 70, pentaerythrityl tetrapelargonate, hydroxylated esters such as polyglycerol-2 triisostearate; aromatic esters such as tridecyl trimellitate, benzoate of C 12 -C 15 alcohols, 2-phenyl ethyl ester of benzoic acid, butyl octyl salicylate, esters of fatty alcohol or branched fatty acids C24-C28 such as those described in application EP-A-0 955 039, and in particular triisoarachidyl citrate, pentaerythrityl tetraisonanoate, glyceryl triisostearate, glyceryl tri-2-tetradecanoate, pentaerythrityl tetraisostearate, polyglyceryl-2-tetraisostearate or pentaerythrityl tetradecyl-2-tetradecanoate; diol dimer and mono- or dicarboxylic acid esters and polyesters, such as diol and fatty acid esters and dimer esters; diols and dimer dicarboxylic acid, such as Lusplan DD-DA5® and Lusplan DD-DA7® marketed by the company Nippon Fine Chemical and described in the application US 2004-175338, the content of which is incorporated in the p this request by reference - and their mixtures.

According to one particular embodiment, the non-volatile hydrocarbon oil may be chosen from liquid organic lipophilic UV filters.

"Liquid organic lipophilic filter" means any organic chemical molecule capable of absorbing at least the UV radiation in the wavelength range between 280 and 400 nm; said molecule being in liquid form at room temperature (20-25 ° C) and at atmospheric pressure (760 mmHg) and capable of being miscible in an oily phase.

The organic liquid UV filters that can be used according to the invention can be chosen from: liquid lipophilic β, β-diphenylacrylate compounds-liquid lipophilic salicylate compounds-liquid lipophilic cinnamic compounds-and mixtures thereof. i) β.β-diphenylacrylate compounds

Among the lipophilic UVB filters which can be used according to the invention, mention may be made of the liquid lipophilic β, β-diphenylacrylate or α-cyano-β, β-diphenylacrylate compounds of formula (I) below:

(I) in which R 1 to R 3 can have the following meanings: R 1 and R '1, which are identical or different, represent a hydrogen atom, a straight or branched chain C 1 -C 6 alkoxy radical or an alkyl radical in C 1 -C4 straight or branched chain, - Ri and R'i being para para position; R2 represents a straight or branched chain C1-C12 alkyl radical; - R3 represents a hydrogen atom or the CN radical.

Among the straight or branched chain C1-C6 alkoxy radicals, mention may be made, for example, of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-amyloxy, isoamyloxy and neopentyloxy radicals. -hexyloxy, n-heptyloxy, n-octyloxy and 2-ethylhexyloxy.

Among the straight or branched chain C1-C4 alkyl radicals, there may be mentioned more particularly the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl radicals. For the C 1 -C 12 alkyl radicals, there may be mentioned by way of example, in addition to those mentioned above, the n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl and n-octyl radicals, 2 ethylhexyl, decyl and lauryl.

Among the compounds of general formula (I), the following compounds are more particularly preferred: 2-ethyl hexyl α-cyano-2-diphenylacrylate or octocrylene, sold in particular under the trade name "UVINUL N539®" by BASF. ethyl α-cyano-diphenylacrylate, such as Etocrylene sold in particular under the trade name Uvinul N35® by BASF, 2-ethyl hexyl β, β-diphenylacrylate, β, β-β (4'-ι-ηβίΙιοχνρΐΊβηνΙ) 3θΓνΐ3ίβ of ethyl.

Among the compounds of general formula (I), 2-cyano-3,3-diphenylacrylate of 2-ethylhexyl or octocrylene is more particularly preferred. Ii) Salicylate compounds

Among the liquid lipophilic salicylate compounds that may be used according to the invention, mention may be made of: Homosalate sold under the name Eusolex HMS® by Rona / EM Industries, Ethylhexyl Salicylate sold under the name Neo Heliopan OS® by Symrise. iifl cinnamate compounds

Among the liquid lipophilic cinnamine compounds that may be used according to the invention, mention may be made of: Ethylhexyl methoxycinnamate sold in particular under the trade name PARSOL MCX® by DSM Nutritial Products, Isopropyl methoxycinnamate, Isoamyl methoxycinnamate sold under the name commercial NEO HELIOPAN E 1000 by Symrise®,

Among the liquid lipophilic filters according to the invention, the compound Ethylhexyl methoxycinnamate will be used more particularly.

Preferably, the polar hydrocarbon oil will be ethylhexyl methoxycinnamate. B) Polar silicone oils

The polar silicone oils that can be used in the oily phase of the compositions of the invention can be chosen from certain non-phenyl silicone oils, phenyl silicone oils, and mixtures thereof.

Phenylated silicone (also called phenyl silicone oil) is understood to mean an organopolysiloxane substituted with at least one phenyl group. a) Non-phenylated silicone oils

Among the non-phenylated polar silicone oils that can be used in the oily phase of the compositions of the invention, mention may be made of cyclic silicone volatile oils having a viscosity at room temperature of less than 8 cSt and having in particular from 4 to 7 carbon atoms. silicon, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms, such as hexamethylcyclotrisiloxane, octamethelyltetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane (cyclohexasiloxane); polydimethylsiloxanes comprising aliphatic groups, in particular alkyl or alkoxy, which are pendant and / or at the end of the silicone chain; these groups each comprising from 6 to 24 carbon atoms, such as caprylyl methicone, such as the commercial product Dow Corning FZ-3196® by Dow Corning. b) Phenyl silicone oils The phenyl silicone oil may be chosen from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, trimethyl pentaphenyl trisiloxane and 2-phenylethyl trimethylsiloxysilicates. The silicone oil can meet the formula:

wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, the silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.

According to another embodiment, the silicone oil corresponds to the formula

wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five.

Mixtures of the phenyl organopolysiloxanes described above can be used.

Examples that may be mentioned are mixtures of triphenylated, tetra- or penta-phenylated organopolysiloxane.

According to another embodiment, the silicone oil corresponds to the formula

in which Me is methyl, Ph is phenyl. Such phenyl silicone is especially manufactured by Dow Corning under the reference Dow Corning 555 Cosmetic Fluid® (INCI name: trimethyl pentaphenyl trisiloxane). The Dow Corning 554 Cosmetic Fluid® reference can also be used.

According to another embodiment, the silicone oil corresponds to the formula

In which Me represents methyl, y is between 1 and 1000, and X represents -CH 2 -CH (CH 3) (Ph).

According to another embodiment, the silicone oil corresponds to the formula

in which -OR 'represents -O-SiMe3, y is between 1 and 1000 and z is between 1 and 1000. The phenyl silicone oil may be chosen from the phenyl silicones of formula (VI) below:

in which - Ri to Rio, independently of one another, are hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, C 1 -C 30, - m, n, p and q are, independently of each other, integers between 0 and 900, provided that the sum 'm + n + q' is not 0.

Preferably, the sum 'm + n + q' is between 1 and 100. Preferably, the sum 'm + n + p + q' is between 1 and 900, more preferably between 1 and 800. Preferably, q is equal to 0. The phenyl silicone oil may be chosen from the phenyl silicones of formula (VII) below: (VII)

in which: R 1 to R 6, independently of one another, are cyclic or branched linear or branched C 1 -C 30 hydrocarbon radicals, m, n and p are, independently of one another, integers between 0 and 100, provided that the sum 'n + m is between 1 and 100.

Preferably, R 1 to R 6), independently of one another, represent a saturated, linear or branched, C 1 -C 30 hydrocarbon-based radical, in particular CrCl 2, and in particular a methyl, ethyl, propyl or butyl radical.

In particular, R 1 to R 6 may be identical, and furthermore may be a methyl radical.

Preferably, one can have m = 1 or 2 or 3, and / or n = 0 and / or p = 0 or 1, in formula (VII).

It is possible to use a phenyl silicone oil of formula (VI) having a viscosity at 25 ° C. of between 5 and 1500 mnrr / s (ie 5 to 1500 ° C.), preferably having a viscosity of between 5 and 1000 mm 2 / s (either 5 to 1000 East).

As phenyl silicone oil of formula (VII), phenyltrimethicones such as DC556 from Dow Corning (22.5 cSt), Silbione 70663V30 from Rhône Poulenc (28 cSt), or diphenyldimethicones such as oils can be used in particular. Belsil, including Belsil PDM1000® (1000 East), Belsil PDM 200® (200 East) and Belsil PDM 20 (20 East) from Wacker. Values in parentheses represent viscosities at 25 ° C.

Preferably, the polar oil will be selected from ethylhexyl methoxycinnamate, dodecamethylcyclohexasiloxane, caprylylmethicone, and mixtures thereof. The polar oil or oils are preferably present in the composition in concentrations ranging from 0.5 to 60% by weight, more preferably from 2 to 30% by weight relative to the total weight of the composition. The oil or the polar oils are preferably present in the composition in concentrations ranging from 2 to 95% by weight, more preferably from 5 to 80% by weight relative to the total weight of the oily phase.

Additional oils

The oily phase of the compositions of the invention may additionally contain one or more additional volatile or non-volatile oils which do not satisfy the conditions of solubility parameters according to the HANSEN solubility space, such as <5d <22. Said additional polar oils are preferably chosen from volatile or nonvolatile hydrocarbon or silicone oils.

According to one particular form of the invention, the oily phase additionally comprises at least one additional volatile hydrocarbon oil.

Among the additional volatile hydrocarbon oils, mention may be made of volatile hydrocarbon oils containing from 8 to 16 carbon atoms and branched C 6 -C 16 alkanes, such as iso-alkanes (also known as isoparaffins) with C 6 -C 6 fatty acids. isododecane, isodecane, isohexadecane and for example the oils sold under the trade names Isopars or permetyls .. - volatile linear alkanes comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms and more particularly from 11 to 13 carbon atoms, for example such as n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97® and PARAFOL 14-97®, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and 2 of Application WO 2008/155059 from Cognis, and mixtures thereof.

Among the additional nonvolatile hydrocarbon oils, mention may be made of hydrocarbon-based oils such as squalene, linear or branched hydrocarbons such as paraffin, petrolatum and naphthalene oils, hydrogenated or partially hydrogenated polyisobutene, isoeicosane, squalane, decene / butene copolymers, polybutene / polyisobutene copolymers, in particular Indopol L-14, polydecenes such as PURESYN 10®, and mixtures thereof; *

Compound of formula (1):

The compositions in accordance with the present invention comprise at least one glycol compound of formula (1) below

CH 3 - [CH 2 CH 2] m - [COO] n - CH 2 -CH (OH) -CH 2 OH (1) in which - m being between 2 and 4 - n being equal to 0 or 1.

Among the compounds of formula (1) which may be mentioned, there may be mentioned caprylyl glycol of formula CH 3 (CH 2) 4 CH 2 CH (OH) CH 2 OH (m = 2 and n = 0), such as the commercial products sold under the trade names Botanistat CG® ( Botanigenics, Inc)

Dermosoft Octiol® (Dr. Straetmans)

Hydrolite-8 109169® (Symrise) 199602 Hydrolite CG® (Symrise)

Jeecide CAP® (Jeen International Corporation)

Lexgard O (Inolex Inc.)

OriStar CPG® (Orient Stars LLC)

ParaPure® (Paradigm Science, Inc.) - glyceryl caprylate of formula CH3 (CH2) 6C00CH2CH (OH) CH20H (m = 3, n = 1) as the commercial products sold under the trade names: AEC Glyceryl Caprylate (A & E) Connock (Perfumery & Cosmetics) Ltd.)

Capmul 708G (Abitec Corporation)

CremerCOOR GC 8 (Cremer Oleo)

Dermosoft GMCY (Dr. Straetmans)

Dub 8G (Stearinerie Dubois Son)

Imwitor 308 (Cremer Oleo)

Imwitor 988 (Cremer Oleo)

Lexgard GMCY (Inolex Inc.)

OriStar GCC (Orient Stars LLC)

Sunsoft 707 (Taiyo Kagaku Company, Ltd.)

Sunsoft 700 P-2 (Taiyo Kagaku Company, Ltd.) - the glyceryl caprate of formula CH3 (CH2) 8COOCH2CH (OH) CH2OH (m = 4 and n = 1) as the commercial products sold under the trade names: AEC Glyceryl Caprate (A & E Connock (Perfumery & Cosmetics) Ltd.)

Capmul MCM C-10® (Abitec Corporation)

Dermosoft GMC® (Dr. Straetmans)

Lexgard GMC® (Inolex Inc.)

Sunsoft 760® (Taiyo Kagaku Company, Ltd.) - and mixtures thereof.

Glyceryl Caprylate / Caprate mixtures may also be mentioned, such as the commercial products sold under the trade names AEC Glyceryl Caprylate / Caprate® (A & Connock (Perfumery & Cosmetics) Ltd.) CremerCOOR GC810® (Cremer Oleo)

Dub 810 G® (Stearinerie Dubois Fils)

Caprylyl glycol, glyceryl caprylate and mixtures thereof will be used more particularly.

The compound (s) of formula (1) are present in the compositions of the invention, preferably in concentrations ranging from 0.1 to 5% by weight, and more preferably from 0.2 to 3% by weight relative to to the total weight of the composition. (

HYDROPHOBIC COATED PIGMENTS

The term "pigments" means white or colored particles, mineral or organic, insoluble in an aqueous medium, intended to color and / or opacify the composition and / or the resulting film. These pigments may be white or colored, mineral and / or organic.

By "hydrophobic coated pigment" is meant any pigment coated with at least one lipophilic or hydrophobic compound.

By "lipophilic compound" is meant any compound that is soluble or dispersible in an oily phase.

By "hydrophobic compound" is meant by any compound insoluble in water.

According to a particular embodiment, the hydrophobic modified pigments used according to the invention are chosen from inorganic pigments.

By "inorganic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, manganese violet, ultramarine blue , chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following inorganic pigments can also be used: Ta 2 O 5, Ti 3 O 5, T 2 O 3, TiO, ZrO 2 mixed with TiO 2, ZrO 2, Nb 2 O 5, CeO 2, ZnS.

The particle size of the coated pigment is strictly greater than 100 nm.

For the purposes of the invention, the "size" of a particle means its D50. The D50, or volume mean size, corresponds to the particle size defined so that 50% by volume of the particles are smaller than D50.

The average volume size can be appreciated by diffraction of light using a Malvern MasterSizer laser granulometer, said particles to be evaluated being dispersed in a liquid medium such as for example octyldodecyl neopentanoate. *

According to one embodiment, the size of the pigment particles according to the invention ranges from 100 nm to 25 μm, preferably from 200 nm to 10 μm.

In the context of the present invention, the hydrophobic modified mineral pigments are more particularly hydrophobic modified elements of iron oxide and / or titanium dioxide.

It may also be nacres and / or particles with metallic reflections.

By "nacres", it is necessary to include colored particles of any shape, iridescent or not, in particular produced by certain shellfish in their shell or else synthesized, and which exhibit a color effect by optical interference.

The nacres can be chosen from pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs.

Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.

The nacres may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection.

Advantageously, the nacres according to the invention are micas coated with titanium dioxide or iron oxide and bismuth oxychloride.

For the purposes of the present invention, the term "particles with a metallic sheen" means any compound whose nature, size, structure and surface state allows it to reflect the incident light, in particular in a non-iridescent manner.

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; particles comprising a substrate, organic or inorganic, monomaterial or multimaterial, at least partially covered 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, there may be mentioned, for example, 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 (eg bronzes and brasses) are preferred metals.

The term "metal derivatives" denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulphides.

Coating of the pigment

The composition according to the invention advantageously comprises at least one pigment coated with at least one lipophilic or hydrophobic compound. The coating may also comprise at least one additional non-lipophilic compound.

For the purposes of the invention, the "coating" of a pigment according to the invention generally refers to the total or partial surface treatment of the pigment with a surface agent, absorbed, adsorbed or grafted onto said pigment.

The surface-treated pigments may be prepared according to chemical, electronic, mechano-chemical or mechanical surface treatment techniques well known to those skilled in the art. Commercial products can also be used. The surfactant can be absorbed, adsorbed or grafted onto the pigments by solvent evaporation, chemical reaction and creation of a covalent bond.

According to one variant, the surface treatment consists of a coating of the pigments. The coating may represent from 0.1 to 20% by weight, and in particular from 0.5 to 5% by weight, of the total weight of the coated pigment. The coating may be carried out, for example, by adsorption of a liquid surface agent on the surface of the solid particles by simply stirring the particles and said surfactant, optionally while hot, prior to the incorporation of the particles into the other particles. ingredients of the makeup or care composition. The coating may be carried out for example by chemical reaction of a surfactant with the surface of the solid pigment particles and creation of a covalent bond between the surfactant and the particles. This method is described in particular in US Pat. No. 4,578,266.

The chemical surface treatment may consist in diluting the surfactant in a volatile solvent, dispersing the pigments in this mixture, and then slowly evaporating the volatile solvent, so that the surfactant is deposited on the surface pigments.

Lipophilic or hydrophobic treatment agent According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from silicone surfactants; fluorinated surfactants; fluorosilicone surfactants; metallic soaps; N-acyl amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural vegetable or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and their mixtures.

Silicone surface agent

According to a particular embodiment, the pigments may be surface-treated wholly or partially with a compound of a silicone nature.

Silicone surfactants may be chosen from organopolysiloxanes, silane derivatives, silicone-acrylate copolymers, silicone resins, and mixtures thereof.

By "organopolysiloxane compound" is meant a compound having a structure comprising an alternation of silicon atoms and oxygen atoms and comprising organic radicals bonded to the silicon atoms. /) Non-elastomeric organopolysiloxane

Non-elastomeric organopolysiloxanes that may especially be mentioned include polydimethylsiloxanes, polymethylhydrogensiloxanes and polyalkoxydimethylsiloxanes.

The alkoxy group may be represented by the radical RO- such that R represents methyl, ethyl, propyl, butyl or octyl, 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl radicals, aryl radicals such as phenyl, tolyl, xylyl, or substituted aryl radicals such as phenylethyl.

A method for surface treatment of pigments with a polymethylhydrogenosiloxane consists in dispersing the pigments in an organic solvent and then adding the silicone compound. By heating the mixture, covalent bonds are created between the silicone compound and the surface of the pigment. According to a preferred embodiment, the silicone surface agent may be a non-elastomeric organopolysiloxane, especially chosen from polydimethylsiloxanes.

According to one particular form, it is possible to use TRIETHOXYSILYLETHYL POLYDIMETHYLSILOXYETHYL DIMETHICONE as the commercial product sold under the name KF9908® by Shin Etsu. * / 7) Alkylsilanes and alkoxysilanes

Alkoxy functional silanes are especially described by Witucki in "Silane primer, Chemistry and applications of alkoxy silanes, Journal of Coatings technology, 65, 822, pages 57-60, 1993". "

Alkoxysilanes such as alkyltriethoxysilanes and alkyltrimethoxysilanes sold under the references Silquest A-137 (OSI Specialties) and Prosil 9202 (PCR) can be used for coating the pigments. The use of alkylpolysiloxanes having a reactive end group such as alkoxy, hydroxy, halogen, amino or imino is described in JP 077-196946. They are also suitable for the treatment of pigments. / '//') Polymers of silicone-acrylate

Grafted silicone-acrylic polymers having a silicone backbone as described in US Pat. Nos. 5,725,882, US 5,209,924, US 4,972,037, US 4,981,903, US 4,981,902, US 5,468,477, and US Pat. Nos. 5,219,560 and 0,888,582 may be used. Other silicone-acrylate polymers may be silicone polymers comprising in their structure the following unit of formula (I):

0) in which the radicals G 1, which are identical or different, represent hydrogen, a C 1 -C 10 alkyl radical or a phenyl radical; the radicals G2, which may be identical or different, represent a C1-C10 alkylene group; G3 represents a polymeric residue resulting from the (homo) polymerization of at least one ethylenically unsaturated anionic monomer; G4 represents a polymeric residue resulting from the (homo) polymerization of at least one hydrophobic monomer containing ethylenic unsaturation; m and n are 0 or 1; a is an integer ranging from 0 to 50; b is an integer ranging from 10 to 350, c is an integer from 0 to 50, provided that one of the parameters a and c is different from 0.

Preferably, the unit of formula (I) above has at least one, and even more preferably all, of the following characteristics: the radicals G 1 denote an alkyl radical, preferably the methyl radical; n is non-zero, and the radicals G 2 represent a divalent radical in (-63, preferably a propylene radical, G 3 represents a polymeric radical resulting from the (homo) polymerization of at least one unsaturated carboxylic acid monomer; ethylenic, preferably acrylic acid and / or methacrylic acid; G4 represents a polymeric radical resulting from the (homo) polymerization of at least one monomer of the (meth) acrylate (CrCio) type, preferably of the isobutyl or methyl (meth) acrylate type.

Examples of silicone polymers corresponding to formula (I) are, in particular, polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene-type connecting member, mixed polymeric units of the poly (meth) acrylic acid type. and of the poly (meth) acrylate type. Other examples of silicone polymers corresponding to formula (I) are, in particular, polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting member, poly (meth) acrylate type polymer units. isobutyl. iv) Silicone resins The silicone surface agent can be chosen from silicone resins.

By "resin" is meant a three-dimensional structure.

Silicone resins can be soluble or swellable in silicone oils. These resins 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 monomer units that it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter M represents the monofunctional unit of formula (CH 3) 3 SiO 1/2, the silicon atom being connected to a single oxygen atom in the polymer comprising this unit.

The letter D signifies a difunctional unit (CH3) 2SiO2 / 2 in which the silicon atom is connected to two oxygen atoms.

The letter T represents a trifunctional unit of formula (CH 2 SiO 2).

In the units M, D and T defined above, at least one of the methyl groups may be substituted by a group R other than the methyl group such as a hydrocarbon radical (in particular alkyl) having from 2 to 10 carbon atoms or a phenyl group or else a hydroxyl group.

Finally, the letter Q signifies a tetra-functional unit S104 / 2 in which the silicon atom is bonded to four hydrogen atoms, themselves linked to the remainder of the polymer.

Various resins of different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the type and number of substituted radicals, the length of the polymer chain, the degree of branching and size of the hanging chains. By way of example of these silicone resins, mention may be made of: siloxysilicates, which may be trimethylsiloxysilicate of formula [(CH 3) 3 X Si x O] (SiO 4/2) y (MQ units) in which x and y are integers ranging from 50 to 80; polysilesquioxanes of formula (CH 3 SiO 3/2) x (T units) in which x is greater than 100 and at least one of the methyl radicals may be substituted by a group R as defined above; polymethylsilsesquioxanes which are polysilsesquioxanes in which none of the methyl radicals is substituted by another group. Such polymethylsilsesquioxanes are described in US 5,246,694. 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®: polymer comprising repeating units CH3SiO3 / 2 (T units), may also comprise up to 1% by weight of (CH 3) 2 SiO 2/2 units (D units) and having an average molecular weight of about 10,000; by the company SHIN-ETSU under the references KR-220L® which are composed of T units of formula CH3S1O3 / 2 and have Si-OH end groups (silanol), under the reference KR-242A, which comprise 98% d T units and 2% of dimethyl D units and have Si-OH end groups or alternatively under the reference KR-251 comprising 88% of T units and 12% of dimethyl D units and have Si-OH end groups. .

As siloxysilicate resins, mention may be made of trimethylsiloxysilicate (TMS) resins optionally in the form of powders. Such resins are sold under the references SR1000®, E 1170-002® or SS 4230®, by the company General Electric or under the references TMS 803®, WACKER 803® and 804® by the company WACKER SILICONE CORPORATION.

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. By way of example of commercial references of pigments treated with a silicone compound, mention may be made of: the red iron oxide / dimethicone sold under the reference SA-C 338075-10® by the company Miyoshi Kasei; and

Fluoride surfactant

The pigments may be surface-treated wholly or partially with a fluorinated compound.

The fluorinated surfactants may be chosen from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, hexafluoropropylene polyoxides and polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups.

The term "perfluoroalkyl radical" is understood to mean an alkyl radical in which all the hydrogen atoms have been replaced by fluorine atoms.

Perfluoropolyethers are described in particular in the patent application EP0486135 and sold under the trade names Fomblin® by the company Montefluos.

Perfluoroalkyl phosphates are in particular described in application JP H05-86984. The perfluoroalkyl phosphate-diethanol amines marketed by Asahi Glass under the reference AsahiGuard AG530® can be used.

Among the linear perfluoroalkanes, mention may be made of perfluorocycloalkanes, perfluoro (alkylcycloalkanes), perfluoropolycycloalkanes, perfluorinated aromatic hydrocarbons (perfluoroarenes) and perfluorinated hydrocarbon compounds containing at least one heteroatom.

Among the perfluoroalkanes, there may be mentioned the series of linear alkanes such as perfluorooctane, perfluorononane or perfluorodecane.

Among the perfluorocycloalkanes and perfluoro (alkylcycloalkanes), there may be mentioned perfluorodecalin sold under the name "FLUTEC PP5 GMP®" by RHODIA, perfluoro (methyldecalin), perfluoro (C3-C5 alkylcyclohexanes) such as perfluoro (butylcyclohexane).

Among the perfluoropolycycloalkanes, mention may be made of bicyclo [3.3.1] nonane derivatives such as perfluorotrimethylbicyclo [3.3.1] nonane, derivatives of adamantane such as perfluorodimethyladamantane and perfluorinated derivatives of hydrogenated phenanthrene such as tetracosafluoro-tetradecahydrophenanthrene .

Among the perfluoroarenes, mention may be made of perfluorinated derivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1-naphthalene. By way of example of commercial references of pigments treated with a fluorinated compound, mention may be made of: yellow iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Yellow 601® by the company Daito Kasei; "The red iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Red R 516L® by the company Daito Kasei; black iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Black BL 100® by the company Daito Kasei; titanium dioxide / perfluoroalkyl phosphate sold under the reference PF 5 T1O2 CR 50® by the company Daito Kasei; yellow iron oxide / perfluoropolymethylisopropyl ether sold under the reference Iran oxide yellow BF-25-3® by the company Toshiki; DC Red 7 / perfluoropolymethylisopropyl ether sold under the reference D & C Red 7 FHC® by Cardre Inc.; and the DC Red 6 / PTFE sold under the reference T 9506® by the company Warner-Jenkinson.

Fluoro-silicone surface agent *

The pigments may be totally or partially surface-treated with a fluoro-silicone compound.

The fluoro-silicone compound may be chosen from perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialkoxysilanes.

Perfluoroalkyl silanes include LP-IT® and LP-4T® products marketed by Shin-Etsu Silicone.

The perfluoroalkyl dimethicones may be represented by the following formula: ## STR2 ## ## STR1 ##

IIII ch3 ch3 rc! H3

Wherein R represents a linear or branched divalent alkyl group having 1 to 6 carbon atoms, preferably a divalent methyl, ethyl, propyl or butyl group;

Rf represents a perfluoroalkyl radical having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms; m is selected from 0 to 150, preferably from 20 to 100; and n is chosen from 1 to 300, preferably from 1 to 100. By way of example of commercial references of pigment treated with a fluoro-silicone compound, mention may be made of titanium dioxide / fluorosilicone sold under the reference Fluorosil Titanium dioxide 100TA® by Advanced Dermaceuticals International Inc.

Other Lipophilic Surfactants The hydrophobic treating agent may also be selected from: (i) metal soaps such as aluminum dimyristate, and aluminum salt of hydrogenated tallow glutamate; As metal soaps, mention may be made in particular of metal fatty acid soaps having from 12 to 22 carbon atoms, and in particular those having from 12 to 18 carbon atoms.

The metal soap metal may in particular be zinc or magnesium.

As the metal soap, zinc laurate, magnesium stearate, magnesium myristate, zinc stearate, and mixtures thereof can be used. ii) fatty acids such as lauric acid, myristic acid, stearic acid, palmitic acid; iii) N-acyl amino acids or their salts which 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 amino acid can be, for example, lysine, glutamic acid or alanine.

The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts.

Thus, according to a particularly preferred embodiment, an N-acylated amino acid derivative may in particular be a glutamic acid derivative and / or a salt thereof, and more particularly a stearoyl glutamate, such as, for example, stearoyl glutamate. 'aluminum. This is for example the NAI surface treatment marketed by Miyoshi. iv) lecithin and its derivatives such as hydrogenated lecithin such as the HLC surface treatment marketed by LCW; v) triisostearyl isopropyl titanate (INCI name: isopropyl titanium triisostearate). By way of examples of pigments treated with isopropyl titanium triisostearate (ITT), mention may be made of titanium dioxides and / or ferventus oxides under the trade reference BTD-401® (Titanium Dioxide CI77891 and Isopropyl Titanium Triisostearate), BBO-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BYO-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate), and BRO-I2® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by KOBO. vi) isostearyl sebacate; (vii) natural vegetable or animal waxes or polar synthetic waxes; viii) fatty esters, in particular by jojoba esters; ix) phospholipids; and x) their mixtures. *

The waxes mentioned in the compounds mentioned above may be those generally used in the cosmetics field, as defined below.

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.

The term "polar wax" means a wax containing chemical compounds comprising at least one polar group. Polar groups are well known to those skilled in the art; it may be for example an alcohol, ester, carboxylic acid group. Polyester waxes, paraffin waxes, microcrystalline waxes, ozokerite, Fisher-Tropsch waxes are not included in the polar waxes.

In particular, the polar waxes have a mean solubility parameter δa of Hansen at 25 ° C such that δa> 0 (J / cm3) 172 and better δa> 1 (J / cm3) 172:

where δρ and 5h are respectively the polar and interaction-specific contributions to Hansen's solubility parameters.

The definition of solvents in the three-dimensional solubility space according to HANSEN is described in the article by CM HANSEN, "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967): - 5h characterizes the specific interaction forces (hydrogen bonds, acid / base, donor / acceptor, etc.); δρ characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles.

Solubility parameters are calculated with HSPiP v4.1 software.

The parameters δρ and ôh are expressed in (J / cm3) 172.

A polar wax consists in particular of molecules comprising, in addition to carbon and hydrogen atoms in their chemical structure, heteroatoms (such as O, N, P). By way of non-limiting illustration of these polar waxes, mention may be made especially of natural polar waxes, such as beeswax, lanolin wax, orange wax, lemon wax, and insect waxes. China, rice wax, Carnauba wax, Candelilla wax, Ouricury wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax, montan wax.

According to a particular embodiment, the pigments may be coated with at least one compound chosen from N-acylamino acids or their salts; isopropyl trisostearyl titanate; silicone surfactants; natural vegetable or animal waxes; hydrogenated lecithin, fatty esters; and their mixtures.

According to a more particularly preferred embodiment, the pigments may be coated with an N-acylated amino acid and / or a salt thereof, in particular with a glutamic acid derivative and / or a salt thereof, especially a stearoyl glutamate. such as aluminum stearoyl glutamate.

According to a more particularly preferred embodiment, use will be made of hydrophobic coated pigments selected from titanium dioxides and iron oxides, coated with aluminum stearoyl glutamate, for example sold under the reference NAI® by MIYOSHI KASEI.

According to a more particularly preferred embodiment, use will be made of hydrophobic coated pigments chosen from titanium dioxides and iron oxides coated with isopropyl titanium triisostearate (ITT), those sold under the trade reference BTD-401® (Titanium). Dioxide CI77891 and Isopropyl Titanium Triisostearate), BBO-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BYO-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate), and BRO-I2® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company KOBO.

The pigments coated with at least one hydrophobic compound are present in a composition of the invention, preferably in a proportion ranging from 5 to 25% by weight, relative to the total weight of the composition, more preferably ranging from 8 to 15% by weight. %.

ADDITIONAL COLORING MATERIALS

A composition according to the invention may further comprise at least one additional dyestuff and preferably at least 0.01% by weight relative to the total weight of the composition.

For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the dyestuffs considered and its adjustment is clearly within the competence of the man of the art.

A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 15% by weight. by weight of dyestuffs, relative to the total weight of said composition.

As specified above, the dyestuffs that are suitable for the invention can be water-soluble but also fat-soluble.

For the purposes of the invention, the term "water-soluble dyestuff" means any generally organic compound, natural or synthetic, soluble in an aqueous phase, or water-miscible and colorable solvents. As water-soluble dyes that are suitable for the invention, water-soluble synthetic or natural dyes, such as, 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, chlorophylline copper, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, riboflavin.

The water-soluble dyes are, for example, beet juice and caramel.

For the purposes of the invention, the term "liposoluble coloring matter" means any generally organic compound, natural or synthetic, soluble in an oily phase, or solvents miscible with a fatty substance and capable of coloring. As liposoluble dyes that are suitable for the invention, liposoluble, synthetic or natural dyes, such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11 can be mentioned. , DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow , annatto, curcumin.

It may especially be hydrophobic uncoated pigments, hydrophobic uncoated pearlescent agents and / or hydrophobic unglazed metallic reflective particles.

By "hydrophobic uncoated pigment" is meant any pigment not being coated with at least one lipophilic or hydrophobic compound.

The additional pigments may be white or colored, mineral and / or organic.

Hydrophobic non-coated mineral pigments that can be used in the invention include oxides or dioxides of titanium, zirconium or cerium, as well as oxides of zinc, iron or chromium, ferric blue, and manganese violet. ultramarine blue and chromium hydrate, and mixtures thereof.

It may also be a pigment having a structure which may for example be sericite / brown iron oxide / titanium dioxide / silica. Such a pigment is marketed for example under the reference Coverleaf NS® or JS® by the company Chemicals And Catalysts and has a contrast ratio of about 30.

It may also be pigments having a structure which may be, for example, silica microspheres type containing iron oxide. An example of a pigment having this structure is that marketed by Miyoshi under the name PC Bail PC-LL-100 P®, this pigment consisting of silica microspheres containing yellow iron oxide. "

Advantageously, the additional pigments according to the invention are iron oxides and / or titanium dioxides.

The nacres may be chosen from pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica covered with with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs.

Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride.

Among the nacres available on the market, mention may be made of the nacres Timica, Flamenco® and Duochrome® (based on mica) marketed by ENGELHARD, the nacres Timiron marketed by Merck, nacres based on mica Prestige marketed by the Eckart company and the nacres based on Sunshine synthetic mica sold by the company Sun Chemical.

Advantageously, the nacres according to the invention are micas coated with titanium dioxide or iron oxide and bismuth oxychloride. As an illustration of these additional metal-reflecting particles, mention may be made of aluminum particles, such as those sold under the names Starbrite 1200 EAC® by the company Siberline and Metalure® by the company Eckart and glass particles coated with a metal layer including those described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

EXPENSES

Advantageously, a composition according to the invention may further comprise one or more filler (s) conventionally used in skincare and / or makeup compositions.

These fillers are colorless or solid white particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition.

Of mineral or organic nature, natural or synthetic, they make it possible to confer on the composition containing them softness, dullness and uniformity in makeup. In addition, these fillers advantageously make it possible to fight against various aggressions such as sebum or sweat. As an illustration of these fillers, mention may be made of talc, mica, silica, kaolin, poly-p-alanine and polyethylene powders, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), acrylic acid copolymers, silicone resin microbeads (Toshiba Tospearls®) for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocyanate, hydroxyapatite, barium sulfate, aluminum oxides, polyurethane powders, fillers composites, hollow silica microspheres, and glass or ceramic microcapsules. Particles, which are in the form of portions of hollow spheres, as described in JP-2003 128 788 and JP-2000 191 789, may also be used.

In particular, such fillers may be present in a composition according to the invention in a content ranging from 0.01% to 25% by weight, in particular from 0.1% to 20% by weight, in particular from 1% to 10% by weight. , relative to the total weight of the composition.

ACTIVE

A composition according to the invention may comprise at least one moisturizing agent (also called humectant), in particular for a care application.

Preferably, the moisturizing agent is glycerin.

The moisturizing agent (s) may be present in the composition in a content ranging from 0.1 to 15% by weight, especially from 0.5 to 10% by weight, or even from 1 to 6% by weight, relative to the total weight. of said composition.

Other active agents which may be used in the composition of the invention include, for example, vitamins, sunscreens other than liquid organic lipophilic UV filters and mixtures thereof.

Preferably, a composition according to the invention comprises at least one active agent. It is a matter of routine practice for those skilled in the art to adjust the nature and quantity of the additives present in the compositions according to the invention, so that the desired cosmetic properties thereof are not not affected.

According to one embodiment, a composition of the invention may advantageously be in the form of a care composition of the skin and / or keratin fibers, the body or the face, in particular the face.

According to another embodiment, a composition of the invention may advantageously be in the form of a makeup composition for keratin materials, in particular the skin of the body or of the face, in particular the face.

Thus, according to a sub-mode of this embodiment, a composition of the invention may advantageously be in the form of a base composition for makeup.

A composition of the invention may advantageously be in the form of a foundation.

According to another sub mode of this embodiment, a composition of the invention may advantageously be in the form of a makeup composition of the skin and in particular the face. It can be an eyeshadow or a blush.

According to another sub mode of this embodiment, a composition of the invention may advantageously be in the form of a product for lip makeup, including a lipstick.

According to yet another sub mode of this embodiment, a composition of the invention may advantageously be in the form of a product for makeup and / or eyebrow care.

Such compositions are especially prepared according to the general knowledge of those skilled in the art.

Expressions "between ... and ..." and "from ... to ..." must be understood as inclusive terms unless otherwise specified. The invention is illustrated in more detail by the examples and figures presented hereinafter. Unless otherwise indicated, the quantities indicated are expressed as a percentage by mass. Methodology for dynamic rheology measurements in oscillation

These are harmonic rheological measurements that measure the elastic modulus.

The measurements are carried out using a Haake RS600 rheometer on a product at rest, at 25 ° C with a plane plane 60 mm and a gap of 2 mm.

The measurements in harmonic regime make it possible to characterize the viscoelastic properties of the products. The technique involves subjecting a material to a sinusoidally varying stress over time and measuring the response of the material to that stress. In a domain where the behavior is linear viscoelastic (zone where the deformation is proportional to the stress), the constraint (t) and the deformation (y) are two sinusoidal functions of the time which are written in the following way: where:

t0 represents the maximum amplitude of the stress (Pa);

Yo represents the maximum amplitude of the deformation (-); ω = 2ΠΝ represents the pulsation (rad.s'1) with N representing the frequency (Hz); and δ represents the phase shift of the stress with respect to the deformation (rad).

Thus, the two functions have the same angular frequency but they are out of phase by an angle δ. According to the phase shift δ between j (t) and Y (t), the behavior of the system can be apprehended: - If δ = 0, the material is purely elastic; - If δ = Π / 2, the material is purely viscous (Newtonian fluid); and - if 0 <δ <Π / 2, the material is viscoelastic.

In general, stress and strain are written in complex form:

A modulus of complex rigidity, representing the global resistance of the material to the deformation whether it is of elastic or viscous origin, is then defined by: Where:

G 'is the conservation modulus or elastic modulus which characterizes the energy stored and totally restored during a cycle, G' = (το / yo) cos δ; and G "is the loss modulus or viscous modulus which characterizes the energy dissipated by internal friction during a cycle, G" = (t0 / Yo) sin δ.

The parameter adopted is the modulus of average stiffness G * measured at the plateau measured at a frequency of 1 Hz.

Examples 1 to 8 of foundation gel-gel *

(*) excluding the invention

Foundation formulations 1 to 8 were prepared as described below.

The components of the phases A1 and A2 were weighed and stirred with rayneri at room temperature.

The components of phase B were weighed and stirred with rayneri at room temperature.

The components of phases B, C and D were added to phase A with vigorous stirring at room temperature.

The walls and bottom of the beaker were scraped using a sponge and the mixture was allowed to homogenize with vigorous stirring at room temperature until complete homogenization.

A gel-gel composition was formed.

The macroscopic appearance of formulas 1 to 8 was measured with the naked eye after 2 months at room temperature (25 ° C.). The results are shown in the table below.

The results showed that formulations 1 and 2 (excluding the invention) comprising a glycol compound of formula (1) (caprylyl glycol or caprylate glycol) and an oily phase comprising at least one apolar silicone oil of the linear polydimethylsiloxane type (dimethicone) had a heterogeneous macroscopic appearance after 2 months of storage at 25 ° C, unlike formulations 3 to 8 comprising a glycol compound of formula (1) (caprylyl glycol or caprylate glycol) and an oily phase comprising at least (a polar oil (cyclohexasiloxane, caprylyl methicone, ethylhexyl methocycinnamate).

The composition according to the invention can be obtained by a preparation process comprising at least one step of mixing: the gelled aqueous phase with at least one hydrophilic gelling agent; and - the oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil under conditions conducive to obtaining a macroscopically homogeneous mixture; said composition further comprising at least one hydrophobic coated pigment and at least one compound of formula (1).

According to one embodiment, the process for preparing the composition comprises a step of mixing at least three gelled phases or more.

According to a sub mode of this embodiment, the mixture is made at room temperature. \

Claims

1. Composition, especially comprising a physiologically acceptable medium, in particular for coating keratin materials, more particularly makeup and / or care of keratin materials, containing: at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil; said phases forming a macroscopically homogeneous mixture therein and said composition further comprising: i) at least one hydrophobic coated pigment; and ii) at least one glycol compound of the following formula (1): ## STR2 ## wherein equal to 0 or 1.

2. Composition according to claim 1, comprising as hydrophilic gelling agent at least one synthetic polymeric gelling agent.

3. Composition according to Claim 2, in which the synthetic polymeric hydrophilic gelling agent is chosen from 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers, and in particular is a copolymer of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate.

A composition according to any one of the preceding claims, wherein said lipophilic gelling agent is selected from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, and mixtures thereof .

5. Composition according to any one of the preceding claims, comprising, as lipophilic gelling agent, at least one organopolysiloxane elastomer, preferably chosen from Dimethicone Crosspolymer, Dimethicone (and) Dimethicone Crosspolymer, Vinyl Dimethicone Crosspolymer, Dimethicone / Vinyl Dimethicone. Crosspolymer, Dimethicone Crosspolymer-3, and especially Dimethicone Crosspolymer and Dimethicone (and) Dimethicone Crosspolymer.

6. Composition according to any one of the preceding claims, containing as a hydrophilic gelling system (s) / gelling (s) lipophilic (s), a system (s) or copolymer (s) acid 2 2-methylpropane sulfonic acid / organopolysiloxane elastomer (s).

7. Composition according to any one of the preceding claims, containing the aqueous and oily phases in an aqueous phase / oily phase weight ratio ranging from 95/5 to 5/95, preferably from 30/70 to 80/20.

A composition according to any of the preceding claims, wherein the hydrophobic coated pigments are hydrophobic coated pigments of iron oxide and / or titanium dioxide.

9. Composition according to any one of the preceding claims, wherein the hydrophobic coated pigments are coated with at least one compound chosen from N-acyl amino acids or their salts; isopropyl titanium triisostearate; silicone surfactants; natural vegetable or animal waxes; hydrogenated lecithin, fatty esters; and their mixtures.

10. Composition according to any one of the preceding claims, in which the hydrophobic coated pigments are titanium dioxides and / or coated iron oxides: an N-acylated amino acid and / or a salt thereof, more particularly by a glutamic acid derivative and / or a salt thereof, especially aluminum stearoyl glutamate; or - isopropyl titanium tri isostea spleen.

11. Composition according to any one of the preceding claims, wherein the polar oil is chosen from liquid organic lipophilic UV filters, preferably chosen from. liquid lipophilic β, β-diphenylacrylate compounds - liquid lipophilic salicylate compounds - liquid lipophilic cinnamate compounds - and their mixtures and more particularly is ethylhexyl methoxycinnamate.

12. Composition according to any one of the preceding claims, in which the polar oil is chosen from cyclic silicone volatile oils having a viscosity at room temperature of less than 8 cSt and in particular having from 4 to 7 silicon atoms, these silicones comprising optionally alkyl or alkoxy groups having from 1 to 10 carbon atoms, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane (cyclohexasiloxane); polydimethylsiloxanes comprising aliphatic groups, in particular alkyl or alkoxy, which are pendant and / or at the end of the silicone chain, in particular caprylyl methicone. i

13. Composition according to any one of claims 1 to 10, wherein the polar oil is selected from phenyl silicone oils.

14. Composition according to any one of the preceding claims, wherein the polar oil is chosen from ethylhexyl methoxycinnamate, dodecamethylcyclohexasiloxane, caprylyl methicone, and mixtures thereof.

15. A composition according to any one of the preceding claims wherein the compound of formula (1) is selected from caprylyl glycol, glyceryl caprylate, glyceryl caprylate / caprate mixtures, and mixtures thereof, and more particularly, is selected from the group consisting of caprylyl glycol, glyceryl caprylate, and mixtures thereof.

16. A process for the preparation of a composition as defined in any one of the preceding claims, comprising at least one step of mixing: the aqueous phase gelled with at least one hydrophilic gelling agent; and - the oily phase gelled with at least one lipophilic gelling agent and comprising at least one polar oil under conditions conducive to obtaining a macroscopically homogeneous mixture; said composition further comprising at least one hydrophobic coated pigment and at least one compound of formula (1).

17. The method of claim 16, comprising a step of mixing at least three gelled phases or more.

18. A method according to any one of claims 16 or 17, wherein the mixing is carried out at room temperature.

19. A cosmetic process for makeup and / or care of a keratinous material, in particular the skin and / or the lips and / or the eyebrows, and keratinous fibers, in particular the eyebrows, comprising at least one step of applying on said keratinous material a composition as defined according to any one of claims 1 to 15. a