FR3067937A1 - GEL-GEL COMPOSITION COMPRISING A CRYSTALLINE STATE WAX. - Google Patents

Abstract

The present invention relates to a composition, in particular a cosmetic composition, in particular a makeup and / or care composition for keratin materials, comprising: at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one gelled oily phase comprising at least one oil chosen from apolar hydrocarbon oils, non-phenylated silicone apolar oils, esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C2-C8 dicarboxylic acid and a C2-C8 alcohol, and mixtures thereof; said oily phase being gelled by at least one crystalline wax selected from vegetable waxes and behenic acid and glycerol esters; said phases forming a macroscopically homogeneous mixture therein. The invention also relates to a cosmetic process comprising at least one step of applying a composition as defined above.

Description

The present invention aims to propose for the field of care and hygiene of keratin materials, in particular of the skin and / or the lips, and in particular of the skin, a new galenics which is particularly advantageous with regard to its technical performance and sensory feelings it provides to the user when applied to them, in particular to the skin.

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

Cosmetic compositions are commonly used to camouflage and / or unify imperfections in the relief of the skin such as pores, wrinkles and / or fine lines and / or scars. In this regard, many formulations, solid or fluid, anhydrous or not, have to date been developed.

When these compositions are more particularly intended to blur the visibility of the relief of the skin, the formulator implements therein diffusing or blurring charges. However, the corresponding compositions, currently available, are not entirely satisfactory, in particular in terms of blurring performance.

In order to obtain a satisfactory degree of blurring, it is often necessary to introduce a large quantity of blurring charges into the composition. However, this level of blurring charges can lead to destabilization of said composition and lead to cosmetic properties not in accordance with user expectations, in particular the formation of fluff during the application of the product and / or after drying and / or penetration of the product into the skin.

This defect is prohibitive for the user, because the application is not homogeneous or pleasant given this fluffy effect on the application or during the elimination of the product. In addition, it gives an impression of "dirty" on the skin.

In order to overcome this problem and have a comfortable treatment with a blurring effect, alternative anhydrous dosage forms are currently offered on the cosmetic market.

However, these formulations have the drawbacks linked to the presence of high levels of fatty phase in the composition, namely the procuring of shiny skin and / or the sensation of oily and / or sticky skin.

Another alternative is the use of cross-linked silicones. This type of raw material makes it possible to combine mat effect and soft-focus. However, they have the disadvantage of being characterized by an uncomfortable greasy and warm touch, with a "mask" effect.

It therefore remains difficult for those skilled in the art to develop homogeneous compositions capable of providing an immediate visual result on the skin with a feeling of lightness and comfort on application, and a "light" effect on the skin, this expected immediate result is preferably good coverage of colon imperfections and / or relief imperfections.

There therefore remains a need for cosmetic compositions which make it possible to mask the imperfections of the skin, while having good cosmetic properties, in particular in terms of optical and sensory effects.

The present invention aims precisely to meet this need.

Thus, according to one of its aspects, the present invention relates to a composition, in particular cosmetic, in particular for making up and / or caring for keratin materials, comprising:

- at least one aqueous phase gelled with at least one hydrophilic gelling agent; and

at least one gelled oily phase comprising at least one oil chosen from non-polar hydrocarbon oils, non-phenylated silicone non-polar oils, esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C2-Cg dicarboxylic acid and a C2-Cg alcohol, and mixtures thereof;

said oily phase being gelled with at least one wax in the crystalline state chosen from waxes of plant origin and esters of behenic acid and of glycerol; said phases forming therein a macroscopically homogeneous mixture.

By "in the crystalline state" is meant the fact that the wax or waxes are in the form of crystals in the composition according to the invention.

Against all expectations, the inventors have found that the combination of a wax and a specific oil makes it possible to improve the optical and sensory performance of a composition having a gel-gel architecture.

As can be seen from the examples given below, the compositions according to the invention exhibit better sensorality as well as better soft-focus optical effect.

Indeed, the presence of a specific oil advantageously allows the crystallization of the wax (es). The waxy crystals thus formed allow in particular to gel the oily phase without requiring the presence of another oily gelling agent.

Advantageously, these crystals also make it possible to provide a surface roughness and a covering of the microreliefs which makes it possible to increase the refraction of the light, thus bringing an improved soft-focus effect.

Compositions, called gel-gel, are already proposed in the cosmetic field. 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. However, to the knowledge of the inventors, this type of composition does not at present make it possible to conceal and smooth out imperfections in relief without altering the other expected cosmetic performances.

As stated above, the inventors have found that the addition of a specific wax and oil in a gel-gel type composition makes it possible to obtain a composition combining optical and sensory performance. In particular, a composition according to the invention makes it possible to mask the imperfections and to provide a luminous complexion, while having good sensory properties.

Another subject of the invention is, according to another of its aspects, a cosmetic process for making up and / or caring for keratin materials, in particular the skin and / or the lips, comprising at least one step of application to said said keratin materials of a composition according to the invention.

COSMETIC COMPOSITION

First of all, it is important to note that a composition according to the invention 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 from 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 a 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.

Conversely, 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 cannot be individualized with the naked eye.

More specifically, 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 the interpenetrating macro-domains. These interpenetrated 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 also not be characterized as having a "sense", ie an O / W or W / O sense.

Thus, a composition according to the invention has a gel-like consistency. The stability of the composition is durable without surfactant. Consequently, a composition, in particular a cosmetic composition, according to the invention does not require a surfactant or a 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-type composition, for example, by introducing a coloring matter either in the aqueous gelled phase or in the lipophilic gelled phase, before the gel-type composition is formed. Upon visual inspection, in a gel-like 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 distinct colors are introduced respectively in the oily phase and in the aqueous phase, before the formation of the gel-type composition, the two colors can be observed as uniformly dispersed throughout the gel-type composition. This is different from an emulsion in which, if a dye, soluble in water or soluble in oil, is introduced respectively in the aqueous and oily phases, before forming the emulsion, only the color of the dye will be observed. present in the external phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282).

It is also known to distinguish a gel-like composition from an emulsion by performing a "gout test". This test consists in demonstrating the bi-continuous nature of a gel-type composition. In fact, as mentioned previously, the consistency of a composition is obtained by the interpenetration of the aqueous and oily gelled domains. Consequently, the bi-continuous nature of a gel-type composition can be demonstrated 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 composition tested, and on the other hand, a drop of a hydrophobic solvent on a second sample of the same composition tested, and 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 a 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-type composition (bi-continuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample.

In the case of the present invention, the test which will be favored for distinguishing a gel-type composition from an emulsion is a dilution test. In fact, in a 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. Consequently, the behavior during dilution of a gel-type composition (bi-continuous system) can be compared to that of an emulsion.

More specifically, the dilution test consists of 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 motion mixer: Speed Mixer TM DAC400FVZ. The speed of the mixer is set at 1500 rpm for 4 minutes. Finally, the observation of the resulting sample is carried out using an optical microscope at a magnification of x 100 (xlOxlO). It can be noted that the oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® sold by Dow Corning are suitable as dilution solvent in the same way as one of the oils contained in the composition.

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

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

According to the present invention, the aqueous gelled phase and the oily gelled phase forming a composition according to the invention are present therein in an aqueous phase / oily phase weight ratio varying from 95/5 to 5/95. More preferably, the aqueous phase and the oily phase are present in a weight ratio aqueous phase / oily phase varying from 50/50 to 90/10.

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

Thus, in the case of a makeup composition, in particular of the face, it will be advantageous to favor a weight ratio aqueous gelled phase / oily gelled phase greater than 1, in particular varying from 55/45 to 90/10, preferably varying from 60/40 to 85/15.

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 it has been subjected to an external mechanical stress.

As follows from what follows, 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 stiffness modulus G * at least equal to 400 Pa, and preferably greater than 1000 Pa.

According to an advantageous alternative embodiment, the gelled phases considered to form 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 carried out by rheology measurements in oscillation. A methodology is proposed in the exemplification chapter of this text.

Generally, the corresponding measurements are carried out at 25 ° C. using an imposed constraint rheometer, RS600 HAAKE, equipped with a plane-plane measuring body (diameter 60 mm) provided with a device. anti-evaporation (bell). For each measurement, the sample is gently placed and the measurements begin 5 minutes after the sample is placed in the air gap (2 mm). The composition tested is then subjected to a stress ramp of 10 ′ ² to 10 ³ Pa at a frequency fixed at 1 Hz.

A composition according to the invention can also have a certain elasticity. This elasticity can be characterized by a modulus of rigidity G * which under this threshold of minimum stress can be at least equal to 400 Pa, and preferably greater than 1000 Pa. The G * value of a composition can be obtained by subjecting the composition considered at a stress ramp of 10 ′ ² to 10 ³ Pa at a frequency fixed at 1 Hz.

Lipophilic gelling agent: Wax

As indicated above, the oily phase of a composition according to the invention is gelled with at least one wax in the crystalline state chosen from waxes of plant origin and esters of behenic acid and of glycerol.

By “wax” within the meaning of the present invention, is meant a lipophilic compound, solid at room temperature (25 ° C.), with reversible solid / liquid state change, having a melting temperature greater than or equal to 30 ° C., and up to 120 ° C. In particular, the waxes have a melting point above 30 ° C, and better still above 45 ° C.

Within the meaning of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (differential scanning calorimetry or DSC) as described in standard ISO 1 1357-3; 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 5 mg sample of wax placed in a crucible is subjected to a first temperature rise ranging from - 20 ° C to 100 ° C, at the heating rate of 10 ° C / minute, then is cooled from 100 ° C to - 20 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise ranging from - 20 ° C to 100 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the wax sample is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of the temperature.

According to the invention, the wax or waxes in the crystalline state are chosen from waxes of plant origin and esters of behenic acid and of glycerol.

As a wax of vegetable origin, it is possible to advantageously use the waxes chosen from beeswax, in particular that which is marketed under the name WHITE BEESWAX SP 453P by the company STRAHL & PITSCH or even CERABEIL LOR by the company B AERLOCHER , buckwheat wax such as that sold by the company CODIF, camauba wax, candellila wax, in particular the commercial reference CANDELILLA WAX SP 75 G from the company STRAHL & PITSCH, hydrogenated jojoba wax, sumac wax, the waxes obtained by hydrogenation of esterified olive oil with C12 to Cis chain fatty alcohols sold by the company SOPHIM in the Phytowax range (12L44, 14L48, 16L55 and 18L57), bran wax rice, cetyl, stearyl and behenic alcohols, laurel wax, or Ouricury wax.

As an ester of behenic acid and of glycerol, mention may in particular be made of mixtures of esters of behenic acid and of glycerol, for example the mixture of glyceryl dibehenate, tribehenin, glyceryl behenate, in particular that sold by the company Gattefossé under the reference COMPRITOL 888 CG ATO (mixture at 53% glyceryl dibehenate, 30% tribehenin, 17% glyceryl behenate).

According to a preferred embodiment, a composition according to the invention comprises from 0.5% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, of waxes in the crystalline state chosen from waxes of vegetable origin and behenic acid and glycerol esters relative to the total weight of the composition.

Preferably, the wax in the crystalline state is chosen from hydrogenated jojoba wax and mixtures of esters of behenic acid and of glycerol.

More preferably, it is a mixture of glyceryl dibehenate, tribehenin, glyceryl behenate.

According to a particularly preferred embodiment, a composition according to the invention comprises from 0.5% to 15% by weight, preferably from 1% to 10% by weight, and more preferably from 2% to 8% by weight, d 'A mixture of glyceryl dibehenate, tribehenin, glyceryl behenate, relative to the total weight of the composition.

Oil

As indicated previously, the gelled oily phase of a composition according to the invention comprises at least one oil chosen from non-polar hydrocarbon oils, non-phenylated silicone non-polar oils, esters of isononanoic acid, dialkyl carbonates, triglycerides fatty acid, diesters of a dicarboxylic acid, _C2-C8 alcohol and a C 2 -C _8, and mixtures thereof.

The term “oil” means any fatty substance in liquid form at room temperature at atmospheric pressure.

By “apolar oil” within the meaning of the present invention, is meant an oil whose solubility parameter at 25 ° C., _{a a} , is equal to 0 (J / cm ³ ) ^{/ 2} .

The definition and calculation of the solubility parameters in the HANSEN three-dimensional solubility space are described in the article by C. M. HANSEN: The three dimensionnai solubility parameters J. Paint Technol. 39, 105 (1967).

According to this Hansen space:

- ô _D characterizes the dispersion forces of LONDON resulting from the formation of dipoles induced during molecular shocks;

- δ _ρ characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles;

- ô _h characterizes the specific interaction forces (such as hydrogen, acid / base, donor / acceptor, etc.); and

- ô _a is determined by the equation: ô _a = (ô _p ² + ôh ² ) ' ^{/ 2} .

The parameters ô _p , ôh, ô _D and ô _a are expressed in (J / cm ³ ) ^{/ 2} .

According to a particular embodiment, a composition according to the invention comprises from 0.5% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, oil (s) chosen from apolar hydrocarbon oils, non-phenylated silicone apolar oils, isononanoic acid esters, dialkyl carbonates, fatty acid triglycerides, diesters of a C2 dicarboxylic acid -C ₈ and a C2-C ₈ alcohol, and mixtures thereof, relative to the total weight of the composition.

According to another particular embodiment, a composition according to the invention comprises from 0.01% to 30% by weight, in particular from 0.05% to 20% by weight, in particular from 0.1% to 15% by weight oil (s) chosen from esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C ₂ -C ₈ dicarboxylic acid and of an alcohol C2-C ₈ , and mixtures thereof.

Apolar hydrocarbon oil

An oil according to the invention may in particular be an apolar hydrocarbon oil.

Preferably, the non-volatile nonpolar hydrocarbon-based oil is free of oxygen atom.

Preferably, the non-volatile nonpolar hydrocarbon-based oil can be chosen from linear or branched hydrocarbons, of mineral or synthetic origin. In particular, it can be chosen from:

paraffin oil or its derivatives, petrolatum oil, naphthalene oil, polybutylenes, in particular INDOPOL H-100 (of molar mass or MW = 965 g / mol), INDOPOL H-300 (MW = 1340 g / mol), INDOPOL H-1500 (MW = 2160 g / mol) sold or manufactured by the company AMOCO,

- polyisobutenes and hydrogenated polyisobutenes, in particular Parléam® marketed by the company NIPPON OIL FATS, PANALANE H-300 E marketed or manufactured by the company AMOCO (MW = 1340 g / mol), VISEAL 20000 marketed or manufactured by the company SYNTEAL (MW = 6000 g / mol), REWOPAL PIB 1000 marketed or manufactured by WITCO (MW = 1000 g / mol), decene / butene copolymers, polybutene / polyisobutene copolymers, in particular Indopol L-14 , the hydrogenated polydecenes and the polydecenes, in particular PURESYN 10 (MW = 723 g / mol), PURESYN 150 (MW = 9200 g / mol) marketed or manufactured by the company MOBIL CHEMICALS,

- and their mixtures.

Preferably, the oil according to the invention is a hydrogenated polyisobutene.

Non-phenylated silicone apolar oil

An oil according to the invention can also be chosen from non-phenylated silicone apolar oils.

The non-phenylated non-volatile silicone oil can in particular be chosen from non-volatile polydimethylsiloxanes (PDMS), and PDMS comprising pendant alkyl or alkoxy groups and / or at the ends of the silicone chain, groups each having from 2 to 24 carbon atoms .

Preferably, the oil according to the invention is a non-volatile polydimethylsiloxane.

Isononanoic acid esters

An oil according to the invention can also be chosen from esters of isononanoic acid.

Such esters can in particular be chosen from isononyl isononanoate, octyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, isostearyl isononanoate, oleyl erucate and their mixtures.

Preferably, the oil according to the invention is isononyl isononanoate.

Dialkyl carbonates

An oil according to the invention can also be chosen from dialkyl carbonates.

In particular, such an oil is chosen from C4C12 dialkyl carbonates, and preferably is dicaprylyl carbonate, for example the product sold under the name "Cetiol CC" by the company Cognis.

Preferably, the oil according to the invention is dicaprylyl carbonate.

Triglycerides of fatty acids

An oil according to the invention can also be chosen from fatty acid triglycerides.

Among the triglycerides of fatty acids (liquid at room temperature), there may be mentioned in particular those of fatty acids having from 7 to 40 carbon atoms, in particular the triglycerides of heptanoic or octanoic acids or jojoba oil. In particular, mention may be made of saturated triglycerides such as caprylic / capric triglyceride, glyceryl triheptanoate, glycerol trioctanoate, and Cig-36 acid triglycerides such as those sold under the reference DUB TGI 24 sold by Stearineries Dubois.

Preferably, the oil according to the invention is caprylic / capric triglyceride.

Diester of a C? -Cs dicarboxylic acid and a C? -Cs alcohol

An oil according to the invention can also be chosen from the diesters of a C2-C8 dicarboxylic acid and of a C2-C8 alcohol, optionally hydroxylated.

In particular, mention may be made of diisopropyl adipate, 2-diethyl hexyl adipate, dibutyl adipate, or diisostearyl adipate.

Preferably, the oil according to the invention is diisopropyl adipate.

Preferably, the oil according to the invention is chosen from hydrogenated polyisobutenes, non-volatile polydimethylsiloxanes, isononyl isononanoate, dicaprylyl carbonate, caprylic / capric triglyceride, diisopropyl adipate, and mixtures thereof.

According to a preferred embodiment, the oil according to the invention is chosen from non-polar hydrocarbon oils, non-phenylated silicone non-polar oils, and their mixtures.

More preferably, the oil according to the invention is chosen from hydrogenated polyisobutenes, non-volatile polydimethylsiloxanes, and their mixtures.

According to a preferred embodiment, the gelled oily phase of a composition according to the invention comprises at least two oils chosen from apolar hydrocarbon oils, non-phenylated silicone apolar oils, esters of isononanoic acid, dialkyl carbonates , fatty acid triglycerides, diesters of a C2-C8 dicarboxylic acid and a C2-C8 alcohol, and mixtures thereof.

HYDROPHILIC GEL

“Hydrophilic gelling agent” is understood to mean, within the meaning 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.

The gelling agent can 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 can be chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, mixed silicates and fumed silicas, and mixtures thereof.

Preferably, the hydrophilic gelling agent can be chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, and mixtures thereof.

More preferably, the hydrophilic gelling agent can be chosen from synthetic polymeric gelling agents.

I. Natural or natural polymeric gelling agents

The hydrophilic polymeric gelling agents which are suitable for the invention may be natural or of natural origin.

Within the meaning of the invention, the expression “of natural origin” is intended to denote the polymeric gelling agents obtained by modification of the natural polymeric gelling agents.

These gelling agents can be particulate or non-particulate.

More specifically, these gelling agents come under the category of polysaccharides.

Generally speaking, polysaccharides can be distinguished into several categories.

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

Similarly, they can be linear polysaccharides like Pullulan or branched like Arabian Gum and Amylopectin, or mixed like Starch.

More particularly, the polysaccharides suitable for the invention can be distinguished according to whether they are starchy or not.

THE. Starchy polysaccharides

As a representative of this category may be mentioned very particularly, 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 bonds a (1,4), of chemical formula (C6HioOsjn. The number of these units and their assembly make it possible to distinguish amylose, a molecule formed from approximately 600 to 1000 molecules of glucose chained linearly, and amylopectin, a branched polymer all approximately 25 glucose residues (bond a (1, 6). The total chain can make between 10,000 and 100,000 glucose residues.

The 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 depending on the botanical origin of the starches. On average, a native starch sample consists of approximately 25% amylose and 75% amylopectin.

Sometimes there is the presence of phytoglycogen (between 0% and 20% of starch), an analog of amylopectin but branched every 10 to 15 glucose residues.

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

The amyloidosis is organized in a straight helix with six glucoses per revolution. It dissociates into assimilable glucose under the action of enzymes, amylases, all the more easily if it is in the form of amylopectin. Indeed, the helical formation does not favor 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 of which ranges from 3 to 100 microns.

By treating it with hot water, we get the poison. It is used in the industry for its thickening and gelling properties.

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

Native starches are represented for example by the products sold under the names C * AmilogelTM, Cargill GelTM, C * GelTM, Cargill GumTM, DryGelTM, C * Pharm GelTM by the company Cargill, under the name Amidon de mais by the company Roquette, and under the name Tapioca Pure by the company National Starch.

Modified starches

The modified starches used in the composition of the invention can 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 causing very rapid retrogradation on cooling;

- oxidation by strong oxidants (alkaline medium, in the presence of sodium hypochlorite NaOCl for example) leading to the depolymerization of the starch molecule and to the introduction of carboxyl groups in the starch molecule (mainly oxidation of the group hydroxylated in C6);

- dextrinization 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 linked together (for example with glyceryl and / or phosphate groups);

- esterification in an alkaline medium for the grafting of functional groups, in particular acyl in Ci-Cô (acetyl), hydroxyalkylés in Ci-Cô (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinique.

It is possible in particular to obtain, by crosslinking with phosphorus-containing compounds, mono-starch phosphates (of the Am-0-P0- (0X) 2 type), diamidon phosphates (of the Am-O-PO- (OX) -O-Am type ) or even triamidon (of the Am-0-P0- (O-Am) _{2 type} ) or their mixtures.

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

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

According to the invention, amphoteric starches can also be used, these amphoteric starches contain one or more anionic groups and one or more cationic groups. The anionic and cationic groups can be linked to the same reactive site of the starch molecule or to different reactive sites, preferably they are linked to the same reactive site. The anionic groups can be of the carboxylic, phosphate or sulphate type and preferably carboxylic. The cationic groups can be of primary, secondary, tertiary or quaternary amine type.

The amphoteric starches are especially chosen from the compounds of the following formulas:

(Π) (ΙΠ)

R 'R

CH —CH-COOM

Z

St-O- (CH ₂ ) -N _x

CH —CH-COOM

R 'R

COOM R

CH-CH-COOM

Z

St-O- (CH ₂ ) -N

R

R 'R \ X

NI ₅ St-O —CH ₂ -CH-COOM

R 'R s /

NOT

St-O —CH — CH — COOM in which:

- St-O represents a starch molecule;

- R, identical or different, represents a hydrogen atom or a methyl radical;

- R ’, identical or different, represents a hydrogen atom, a methyl radical or a -COOH group;

- n is an integer equal to 2 or 3;

- M, identical or different, denotes a hydrogen atom, an alkali or alkaline earth metal such as Na, K, Li, NH ₄ , a quaternary ammonium or an organic amine;

- R represents a hydrogen atom or an alkyl radical having from 1 to 18 carbon atoms.

These compounds are described in particular in US patents 5,455,340 and US 4,017,460.

The starch molecules can come from all vegetable sources of starch such as corn, potato, oats, rice, tapioca, (IV) sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above.

Modified starches are represented, for example, by the products sold under the names C * Tex-Instant (pre-gelatinized adipate), C * StabiTex-Instant (pregelatinized phosphate), C * PolarTex-Instant (pre-gelatinized hydroxypropylated), C * Set (acid hydrolysis, oxidation), C * size (oxidation), C * BatterCrisp (oxidation), C * DrySet (dextrinization), C * TexTM (acetylated diamidon adipate), C * PolarTexTM (hydroxypropylated diamidon phosphate), C * StabiTexTM (diamidon phosphate, acetylated diamidon phosphate) by the company Cargill, by diamidon phosphates or compounds rich in diamidon phosphate such as the product offered under the references PREJEL VA-70-T AGGL (cassava diamidon phosphate gelatinized hydroxypropylated) or PREJEL TK1 (gelatinized cassava diamidon phosphate) or PREJEL 200 (acetylated gelatinized cassava diamidon phosphate) by the company AVEBE or STRUCTURE ZEA from NATIONAL STARCH (gelatinized corn diamidon phosphate).

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

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

Particulate starches

As particular starches may be mentioned in particular:

- starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular with sodium polyacrylate, such as for example those sold under the name Sanfresh ST-100MC 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 the acryloacrylamide / sodium acrylate copolymer, such as for example those sold under the names Water Lock A-240, A-180,

B-204, D-223, A-100, C-200, D-223, by the company 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.

Mention may in particular be made of starch (C1-C4) carboxyalkyls, also referred to below as "carboxyalkyl starch". These compounds are obtained by grafting carboxyalkyl groups onto 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 fixed via an ether function, more particularly on carbon 1. The degree of substitution in carboxyalkyl unit of carboxyalkyl in (C1-C4) starch preferably ranges 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 being 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 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) starch carboxyalkyls are advantageously in the context of the present invention carboxymethyl starches. The carboxymethyl friend donations preferably comprise units of the following formula:

-O

OH OH in which X, which may or may not covalently bind to the carboxylic unit, denotes a hydrogen atom, an alkali 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 a Na ⁺ cation. The carboxyalkyl starches which can be used according to the present invention are preferably the non-pre-gelatinized carboxyalkyl starches. The carboxyalkyl starches which can be used according to the present invention are preferably partially or totally crosslinked carboxyalkyl starches.

In general, a cross-linked carboxyalkyl starch has, in contrast to a non-cross-linked carboxyalkyl starch, an increased, controllable viscosity and increased stability. Crosslinking thus makes it possible to reduce the phenomena of syneresis and to increase the resistance of the gel to the effects of shearing.

The carboxyalkyl starches considered according to the invention are more particularly carboxyalkyl starches of potatoes. 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 carboxymethyl starch of potato sold in particular 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 the potato carboxymethyl friend sold in particular under the name GLYCOLYS® by the company Roquette. As previously specified, the carboxyalkyl (Ci-C4) particles of starch are present in the compositions according to the invention in a swollen and unexploded form. This swelling can be characterized by a swelling power Q which can advantageously be between 10 and 30 ml / g, preferably between 15 and 25 ml (volume of liquid absorbed) / g of dry particulate material.

Thus, the size of the swollen particles of carboxyalkyl starch used according to the present invention generally varies from 25 to 300 μm. For example, PRIMO JEL® gel at 10% by weight of carboxyalkyl potato 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 100 microns.

According to a preferred variant 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 can be used in an amount of 0.1% to 5% by weight in dry matter relative to the total weight of the aqueous phase, preferably between 0.5% and

2.5% by weight, and in particular at a rate of approximately 1.5% by weight, relative to the total weight of the aqueous phase.

According to an alternative embodiment, the hydrophilic gelling agent is non-starchy.

I.B. Non-starch polysaccharides

In general, the non-starch polysaccharides can be chosen from the polysaccharides produced by microorganisms; polysaccharides isolated from algae, polysaccharides from higher plants, such as homogeneous polysaccharides, in particular celluloses and its derivatives or fructosans, heterogeneous polysaccharides such as gum arabic, galactomannans, glucomannans, pectins, and their derivatives ; and their mixtures.

In particular, the polysaccharides can be chosen from fructans, gellans, 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, arabic gums, Tragacanth gums, Ghatti gums, Karaya gums, carob gums, galactomannans such as guar gums and their non-derivatives ionic, in particular hydroxypropyl guar, and ionic, gums of biopolysaccharides of microbial origin, in part regular scleroglucan or xanthan gums, mucopolysaccharides, and in particular chondroitin sulfate and their mixtures.

These polysaccharides can be modified chemically, in particular by urea or urethane groups, or by hydrolysis, oxidation, esterification, etherification, sulfation, phosphating, amination, amidation, alkylation, or by several of these modifications.

The derivatives obtained can be anionic, cationic, amphoteric or nonionic.

Advantageously, the polysaccharides can be chosen from carrageenans, in particular kappa-carraghenane, gellan gum, agar-agar, xanthan gum, alginate-based compounds, in particular alginate of sodium, sceroglucan gum, guar gum, inulin, pullulan, and mixtures thereof.

Preferably, the polysacccharide can be xanthan gum.

In general, the compounds of this type, which can be used in the present invention, are chosen from those which are especially described in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, volume 3, pp. 896-900, and volume 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 the book by Robert L. DAVIDSON entitled “Handbook of Water soluble gums and resins” published by Mc Graw Hill Book Company (1980) and in the industrial Gums “Polysaccharides and their Dérivatives, Published by Roy L. WHISTLER, Second Edition, Edition Academie Press Inc . ”.

Such a gelling agent can be used at a rate of 0.1% to 8% by weight in dry matter relative to the total weight of the aqueous phase, in particular from 0.1% to 6% by weight, preferably between 0, 5% and 2.5% by weight, in particular at a rate of approximately 1%, or alternatively at a rate of approximately 1.5% by weight relative to the total weight of the aqueous phase.

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

Polysaccharides produced by microorganisms

xanthan

Xanthan is a heteropolysaccharide produced on an industrial scale by the aerobic fermentation of the bacterium Xanthomonas campestris. Its structure consists of a main chain of β-D-glucoses linked in β (1,4), similar to cellulose. One in two glucose molecules carries a trisaccharide side chain composed of an α-D-mannose, a β-D-glucuronic acid and a terminal β-D-mannose. The internal mannose residue is generally acetylated on carbon 6. About 30% of the terminal mannose residues carry a pyruvate group hey in chelated form between 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 until pH equal to 1). The content of pyruvate and acetate residues varies according to the strain of bacteria, the fermentation process, the conditions after fermentation and the purification steps. These groups can be neutralized in commercial products with Na ⁺ , K ⁺ or Ca ²⁺ ions (Société S ΑΤΙΑ, 1986). The neutralized form can be converted to the acid form by ion exchange or by dialysis of an acid solution.

Xanthan gums have a molecular weight between 1,000,000 and 50,000,000 and a viscosity between 0.6 and 1.65 Pa.s for an aqueous composition containing 1% xanthan gum (measured at 25 ° C using a viscometer Brookfield, LVT type at 60 revolutions per minute).

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.

Advantageously, a composition according to the invention comprises a xanthan gum.

The xanthan gum (s) can be used at a rate of 0.01% to 5% by weight in dry matter relative to the total weight of the composition, in particular from 0.05% to 2% by weight, preferably between 0.05% and 1% by weight, in particular between 0.1% and 0.2% by weight, relative to the total weight of the composition.

pullulan

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

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

Dextran and dextran sulfate

Dextran is a neutral polysaccharide without a 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, fractions of dextran of different molecular weights. Dextran can 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. The dextran sulfate is marketed by the company PK Chemical A / S under the name Dextran sulphate.

succinoglycane

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

scleroglucan

Scleroglucan is a branched non-ionic homopolysaccharide, consisting of β-D glucan units. The molecules consist of a main linear chain formed by D-glucose units linked by β (1,3) bonds and one in three of which is linked to a lateral D-glucose unit by a β (1,6) link.

A more complete description of scleroglucans and their preparation can be found in document 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 the company Cargill.

Gellan gum

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

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

Polysaccharides isolated from algae

Galactannes

The polysaccharide according to the invention can be a galactan in particular chosen from agar or carrageenans.

Carrageenans are anionic polysaccharides constituting the cell walls of various red algae (Rhodophyceae) belonging to the families of 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 Dgalactopyranose units linked alternately by a (1,3) and β (1,4) bonds. These are highly sulfated polysaccharides (20-50%) and the α-D-galactopyranosyl residues can be in the 3,6-anhydro form. Depending on the number and position of ester-sulfate groups on the repeating disaccharide of the molecule, there are several types of carrageenans, namely: kappa-carrageenans which have an ester-sulfate group, iotacarraghenanes which have two ester-sulfate groups and lambda-carrageenans which have three ester-sulfate groups.

Carrageenans are mainly composed of potassium, sodium, magnesium, triethanolamine and / or calcium salts and esters of polysaccharide sulfates.

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

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

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 manufacturing seaweed extraction juices, generally by autoclaving, and by treating these juices which comprise approximately 2% agar, in order to extract the latter.

The agar is for example produced by the B&V Agar Producers group, 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

Furcellarane is obtained commercially from red algae Furcellaria fasztigiata. Furcellarane is for example produced by the company Est-Agar.

Alginate compound

By "alginate-based compound" is meant within the meaning of the invention, alginic acid, alginic acid derivatives and alginic acid salts (alginates) or of said derivatives.

Preferably, the alginate-based compound is water-soluble.

Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of 2 uronic acids linked by glycosidic links (l, 4): β-D-manuronic acid (M) and α-L-glucuronic acid (G).

Alginic acid is able to form water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, substituted amine and lower ammonium cations such as methylamine, ethanolamine, diethanolamine, triethanolamine. These alginates are water-soluble in an aqueous medium at a pH equal to 4 but dissociate into alginic acid at a pH below 4.

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

Use is preferably made of alginate-based compounds having a weight average molecular weight ranging from 10,000 to 1,000,000, preferably from 15,000 to 500,000, and better still from 20,000 to 250,000.

According to a preferred embodiment, the alginate-based compound is alginic acid and / or one of its salts.

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

The alginate-based compound can be modified chemically, in particular by urea or urethane groups, or by the reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, d amidation, alkylation, or by several of these modifications.

The derivatives obtained can be anionic, cationic, amphoteric or non-ionic.

The alginate-based compounds which 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, 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 ose) and heterogeneous composed of several types of ose.

a) Homogeneous polysaccharides and their derivatives

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

Cellulose and derivatives

The polysaccharide according to the invention may also be a cellulose or one of its derivatives, in particular cellulose ethers or esters (eg methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate, nitrocellulose).

The invention may also contain an associative cellulosic polymer. By cellulosic compound is meant according to the invention any polysaccharide compound having in its structure linear sequences of anhydroglucopyranose residues (AGU) united by β (1,4) glycosidic bonds. The repeating motif is the cellobiose dimer. 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 associate with each other by intermolecular bonds of the hydrogen bond 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:

Cdtofetose

VS

AT

K J

Y

Reducing end

OH ‘GH

AHhydfssgÎueopyranôse .OH 'G-'

HO - g

OH

OH

Reducing end

The hydroxyl groups of the cellulose can react partially or totally with different chemical reagents to give cellulose derivatives having their own properties. The cellulose derivatives can be anionic, cationic, amphoteric or non-ionic. Among these derivatives, a distinction is made between cellulose ethers, cellulose esters and cellulose ether esters.

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

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

Among the cationic cellulose ethers, mention may be made of cross-linked or non-crosslinked quaternized hydroxyethylcelluloses.

The quaternizing agent can in particular be glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. As another cationic cellulose ether, mention may be made of hydroxyethylcellulosehydroxypropyltrimethylammonium.

The quaternized cellulose derivatives are, in particular:

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

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

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

As examples of C ₈ -C ₃₀ fatty chain quaternized alkyl hydroxyethylcelluloses, the products QUATRISOFT LM 200, QUATRISOFT LM-X 52918-A, QUATRISOFT LM-X 529-18B (C _i2 alkyl) and QUATRISOFT LM- X 529-8 (Cis alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C ₁ alkyl) and CRODACEL QS (C ₈ alkyl) marketed by the company CRODA.

Among the cellulose derivatives, mention may also be made of:

- celluloses modified by groups comprising at least one fatty chain such as for example hydroxyethylcelluloses modified by groups comprising at least one fatty chain such as alkyl groups, in particular C ₈ -C ₂₂ , arylalkyl, alkylaryl groups, such as NATROSOL PLUS GRADE 330 CS (Ciô alkyls) sold by the company AQUALON, and

- celluloses modified with polyalkylene glycol alkyl phenol ether 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 inorganic cellulose esters (nitrates, sulfates, or cellulose phosphates, etc.), organic cellulose esters (monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates or acetate trimellitates, etc.). ) and mixed organic / inorganic cellulose esters such as acetate butyratesulfates and cellulose acetate propionatesulfates. Among the cellulose ether esters, mention may be made of hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

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

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 Akzo Nobel, under the name MethocelTM (cellulose ethers) and EthocelTM (ethylcellulose) by DOW, under the names Aqualon® (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel® (methylcellulose), BlanoseTM ( carboxymethylcellulose), Culminai® (Methylcellulose, hydroxypropyl methylcellulose), Klucel® (hydroxypropylcellulose), Polysurf® (cetyl hydroxyethylcellulose) and Natrosol® CS (hydroxyethylcellulose) by the company Hercules Aqualon.

fructans

The polysaccharide according to the invention may in particular be a fructosan chosen from inulin and its derivatives (in particular dicarboxy and carboxymethyl inulins).

Fructans or fructans are oligosaccharides or polysaccharides comprising a chain of anhydrofructose units possibly associated with one or more saccharide residues different from fructose. Fructans can be linear or branched. 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 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 P (2, 1) bonds. These are essentially linear fructans such as inulins.

The second group also corresponds to linear fructoses but the fructose units are essentially linked by β (2,6) bonds. These products are levans.

The third group corresponds to mixed fructans, that is to say having sequences β (2.6) and β (2.1). They are essentially branched fructans such as 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, in particular of inulin, has a degree of polymerization from 2 to approximately 1000 and preferably from 2 to approximately 60, and a degree of substitution less than 2 based on a fructose unit.

The inulin used for this invention is represented for example by the products sold under the name BeneoTM inulin by the company Orafti, and under the name Frutafit® by the company Sensus.

b) Heterogeneous polysaccharides and their derivatives

The polysaccharides which can be used according to the invention can be gums such as, for example, cassia, karaya, konjac, tragacanth, tara, acacia or arabic gum.

Gum arabic

Gum arabic is a strongly 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 (phosphate guar, hydroxypropylguar ...)

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

Galactomannans are macromolecules consisting of a main chain of D-mannopyranose units opened in β (1,4), carrying lateral branches consisting of a single D-galactopyranose unit opened in a (1,6) 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 around 2 for guar gum, 3 for tara gum and 4 for locust bean gum.

Galactomannans have the following chemical structure:

m "3; Locust tare pure ”! !. Gear (> i; re m = 2; Tara gum

guar

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

The guar gums which can be used according to the invention can be nonionic, cationic or anionic. According to the invention, chemically modified or unmodified nonionic guar gums can be used.

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, under the name VISCOGUMTM by the company Cargill, and under the name Supercol® guar gum by the company Aqualon.

Hydrolysed nonionic guar gums which can be used according to the invention are for example represented by the products sold under the name Meyprodor® by the company Danisco.

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

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 the company 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 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.

Generally, for the purposes of the present invention, the term “cationic galactomannan gum” means any galactomannan gum containing cationic groups and / or groups which can be ionized into cationic groups.

The preferred cationic groups are chosen from those comprising primary, secondary, tertiary and / or quaternary amine groups.

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

The cationic galactomannan gums which can be used according to the present invention are, for example, gums comprising cationic trialkyl (C1-C4) ammonium groups. Preferably, 2% to 30% by number of the hydroxyl functions of these gums carries trialkylammonium cationic groups.

Among these trialkylammonium groups, mention may very particularly be made of trimethylammonium and triethylammonium groups.

Even more preferably, 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 hydroxypropyl trimethylammonium groups, that is to say a guar gum modified for example by 2,3-epoxypropyl trimethylammonium chloride.

These galactomannan gums, in particular guar gums modified with cationic groups, are products already known in themselves and are for example described in patents ETS 3,589,578 and ETS 4,031,307. Such products are also sold in particular under trade names of Jaguar EXCEL, Jaguar 03 S, Jaguar C 15, Jaguar C 17 and Jaguar 062 (Guar Hydroxypropyltrimonium Chloride) by the company Rhodia, under the name Amilan® Guar (Guar Hydroxypropyltrimonium Chloride) by the company Degussa, and under the name N-Hance® 3000 (Guar Hydroxypropyltrimonium Chloride) by the company Aqualon.

The anionic guar gums which can be used according to the invention are polymers comprising groups derived from carboxylic, sulfonic, sulfenic, phosphoric, phosphonic or pyruvic acid. Preferably, the anionic group is a carboxylic acid group. The anionic group can also be in the form of an acid salt, in particular a sodium, calcium, lithium or potassium salt.

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

Carob

Carob gum is extracted from carob seeds (Ceratonia siliqua).

The unmodified locust bean gum usable in this invention is sold for example under the name 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 locust bean gums which can be used in this invention can be represented for example by the cationic locust beans sold under the name Catinal CLB (locust bean Hydroxypropyltrimonium Chloride) by the company Toho.

TARA gum

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

Glucomannans (konjac gum)

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

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

IM and HM pectins, and derivatives

Pectins are linear polymers of α-D-galacturonic acid (at least 65%) linked 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 pectins, integrated into the main chain in positions 1,2.

Uronic acid molecules have carboxyl functions. This function gives pectins the ability to exchange ions, when these are in COO 'form. Bivalent ions (calcium in particular) have the capacity 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 by 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 with a high degree of esterification, it is possible to hydrolyze the -COOCH3 groups, in order to obtain low esterified pectins. Depending on the proportion of monomers, methylated or not, the chain is therefore more or less acidic. HM (High methoxy) pectins, having a degree of esterification greater than 50%, and LM pectins (Low Methoxy), having a degree of esterification less than 50%, are thus defined.

In the case of amidated pectins, the group -OCH3 is substituted by a group -NH ₂ .

Pectins are sold in particular by the company Cargill under the name UnipectineTM, by the company CP-Kelco under the name GENU, by Danisco under the name GRINSTED Pectin.

Other Polysaccharides

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

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

The xylans consist of a main chain of D-xylose units linked in β (1,4) and on which there are three substituents (Rouau & Thibault, 1987): acid units, α-L- units arabinofuranose, side chains which 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 the sodium salt (sodium hyaluronate).

II. Synthetic polymeric gelling agents

Within the meaning of the invention, the term synthetic signifies that the polymer is neither naturally existing nor does it derive from a polymer of natural origin.

The synthetic polymeric hydrophilic gelling agent considered according to the invention may or may not be particulate.

Within the meaning of the invention, the term particulate means that the polymer is in the form of particles, preferably spherical.

As is clear from what follows, the polymeric hydrophilic gelling agent is advantageously chosen from crosslinked acrylic homopolymers or co-polymers; associative polymers, in particular associative polymers of polyurethane type; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropane sulfonic acid, crosslinked and / or neutralized; carboxyvinyl polymers, modified or not, and mixtures thereof, in particular as defined below.

According to a preferred embodiment, the hydrophilic gelling agent is chosen from synthetic polymeric gelling agents, and preferably from associative polymers, polyacrylamides, polymers and copolymers of 2-acrylamido-2-methylpropane sulfonic acid and carboxyvinyl polymers, and more preferably among the polymers and copolymers of 2-acrylamido-2-methylpropane sulfonic acid.

More preferably, the hydrophilic gelling agent is chosen from crosslinked or non-crosslinked polymers of sodium acrylamide-2-methyl propane sulfonate.

II.A. Particulate synthetic polymeric gelling agents

They are preferably chosen from crosslinked polymers.

They may especially be cross-linked acrylic homopolymers or co-polymers, 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 less than or equal to 100 μm, preferably less than or equal to 50 μm. The average particle size corresponds to the mass average diameter (D50) measured by laser granulometry 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 an average 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 marketed under the names Octacare XI00, XI10 and RMI00 by the company Avecia, those marketed 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 BASF, those marketed under the names Water Lock G400 and G430 (INCI name: Acrylamide / Sodium acrylate copolymer) by Grain Processing.

Mention may also be made of crosslinked polyacrylate microspheres such as, for example, those sold under the name AQUAKEEP® 10 SH NF offered by the company Sumitomo Seika.

Such gelling agents can be used at a rate of 0.1% to 5% by weight in dry matter relative to the total weight of the aqueous phase, in particular from 0.5% to 2% by weight, and in particular at a rate from about 0.8% to 1.7% by weight relative to the total weight of the aqueous phase.

II. B. Non-particulate synthetic polymeric gelling agents

This family of gelling agent can be detailed in the following sub-families:

1. Associative polymers,

2. Polyacrylamides and polymers and copolymers of 2- acrylamido-2 methylpropane sulfonic acid, crosslinked and / or neutralized, and

3. Modified or unmodified vinyl carboxy polymers.

II.B.l Associative polymers

By “associative polymer” within the meaning of the present invention, is meant any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers in accordance with the present invention can 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 allyl ether unit with a fatty chain, more particularly from those whose hydrophilic unit is constituted by an anionic ethylenically unsaturated monomer, more particularly by a vinyl carboxylic acid and very particularly with an acrylic acid, a methacrylic acid or mixtures thereof, and the fatty chain allyl ether unit of which corresponds to the monomer of formula (I) below:

CH ₂ = C (R ') CH ₂ OB _n R (I) in which R' denotes H or CH ₃ , B denotes the ethyleneoxy radical, n is zero 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 still 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 / a C ± o-CWalkyl maleate such as the maleic anhydride / a-olefin C ₃ oC ₃ 8 / maleate copolymer product. isopropyl sold under the name Performa V 1608 by the company Newphase Technologies.

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

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

As an example of this type of compound, mention may be made of TAculyn 22® sold by the company Rohm and Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer (comprising 20 EO units) or Aculyn 28® (methacrylic acid / ethyl acrylate / behenyl oxyethylene methacrylate (25OE) terpolymer.

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

As associative anionic polymers, anionic terpolymers can also be mentioned.

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

R1

(I) in which RI 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 "branched polymer" is meant a non-linear polymer which has pendant chains so as to obtain, when this polymer is dissolved in water, a strong state of entanglement leading to viscosities, at low speed gradient very important.

By "crosslinked polymer" is meant a non-linear polymer in the state of a three-dimensional network insoluble in water but swellable with water and leading to the production of a chemical gel.

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

The monomer (1) can be chosen from styrenesulfonic acid, ethylsulfonic acid or 2-methyl-2 - [(l-oxo-2-propenyl] amino] 1-propanesulfonic acid (also called Acryloyldimethyltaurate) 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 the acid 2-methyl-2 - [(l-oxo-2-propenyl] amino] 1propanesulfonic in free form, partially or fully 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 amino alcohol salt such as a monoethanolamine salt or else a salt of amino acid such as a lysine salt.

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

In formula (I), as an example of a linear C ₈ -C ₆ alkyl radical, there may be mentioned octyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl.

In formula (I), as an example of a C ₈ -C 6 branched alkyl radical, mention may be made of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 4methylpentyl, 5-methylhexyl, 6 -methylheptyl, 15-methylpentadecyl,

16-methylheptadecyl, 2-hexyloctyl.

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

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

Use will more particularly be made, as monomer of formula (I), of tetraethoxylated lauryl acrylate.

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

According to a particular embodiment of the invention, the anionic terpolymer is crosslinked and / or branched with a diethylene or polyethylene compound in the proportion expressed relative to the total amount of monomers used, from 0.005% to 1 mol% and preferably from 0.01% to 0.5 mol% and more particularly from 0.01% to 0.25% molar.

The crosslinking agent and / or the branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxoacetic acid or one of its salts, such as sodium diallyloxyacetate, tetraallyloxyethane, ethylene glycol diacrylate, diallyl urea, triallyl amine, trimethylol propanetriacrylate, methylenebis- (acrylamide) or their mixtures.

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

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

Cationic associative polymers

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

Polyacrylates with amino side groups, quaternized or not, have, for example, hydrophobic groups of the steareth 20 type (polyoxyethylenated stearyl alcohol (20)).

As examples of polyacrylates containing amino side chains, mention may be made of polymers 8781-121B or 9492-103 from the company National Starch.

Non-ionic associative polymers

The nonionic associative polymers can be chosen from:

- copolymers of vinyl pyrrolidone and hydrophobic fatty chain monomers;

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

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

- associative polyurethanes.

Associative polyurethanes are nonionic block copolymers comprising in the chain, both hydrophilic blocks of a nature most often polyoxyethylenated (the polyurethanes can then be called polyether polyurethanes) and hydrophobic sequences which can be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.

In particular, these polymers comprise at least two lipophilic hydrocarbon chains, having from Ce to C30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains can be pendant chains or chains at the end of hydrophilic block. In particular, it is possible that one or more hanging 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 a triblock or multiblock. The hydrophobic blocks can therefore be at each end of the chain (for example: triblock copolymer with hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These polymers can also be in grafts or in a star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In general, associative polyurethanes have a urethane bond between hydrophilic sequences, hence the origin of the name.

According to a preferred embodiment, a non-ionic polyurethane type associative polymer is used as the gelling agent.

As examples of non-ionic polyether polyurethanes with a fatty chain which 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 with urea function sold by the company Elementis or the Rhéolates® 208, 204 or 212, as well as Acrysol® 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 C12-alkyl chain (PPG-14 Palmeth-60 Hexyl Dicarbamate) from Akzo.

The product DW 1206B® from Rohm & Haas with a C20 alkyl chain and a urethane bond, available 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 alcoholic medium. By way of example of such polymers, mention may be made of Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Elementis. One can also use the product DW 1206F and the DW 1206J offered by the company Rohm & Haas.

The associative polyurethanes which 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 capable of being obtained 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 the company 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), 15% by weight in a matrix of maltodextrin (4%) and water (81%), and Aculyn® 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), at 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 alcoholic medium. By way of example of such polymers, mention may be made of SER AD FX1010, SER AD FX1035 and SER AD 1070 of the company Elementis, Rhéolate® 255, Rhéolate® 278 and Rhéolate® 244 sold by the company Elementis . It is also possible to use the products Aculyn® 44, Aculyn® 46, DW 1206F and DW 1206J, as well as Acrysol® RM 184 from Rohm & Haas, or even 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 amphoteric polymers, crosslinked or noncrosslinked, branched or not branched, capable of being obtained by copolymerization:

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

^R s ^A I ^R 4- g = T “θ - ^Z - ( ^C n ^H 2n) -NR _? (| Va) ^R 5 ^{0 R} 0 _z ^R 6 ^R - θ = T θ - ^z - (θπΗ _2η ) -N _χ (IVb)

R O r

7 in which:

- R4 and R5, identical or different, represent a hydrogen atom or a methyl radical;

- R6, R7 and Rg, identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms;

- Z represents an NH group or an oxygen atom;

- n is an integer from 2 to 5;

- A 'is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide;

2) at least one monomer of formula (V):

R - 0 = 0 ^ -00-2. (V)

H ^{10 1} in which R9 and Rio, identical or different, represent a hydrogen atom or a methyl radical and Ζχ represents an OH group or an NHC group (CH3) ₂ CH ₂ SO3H;

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

R —C = CR ₁₀ -COXR ₁₁ (VI) in which R9 and Rio, identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and Rn denotes an alkyl radical linear or branched having from 1 to 30 carbon atoms;

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

The monomers of formula (IVa) and (IVb) of the present invention are preferably chosen from the group consisting of:

- dimethylaminoethylmethacrylate, dimethylaminoethylacrylate,

- diethylaminoethyl methacrylate, diethylaminoethylacrylate,

- dimethylaminopropylmethacrylate, dimethylaminopropylacrylate,

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

More particularly, the monomer of formula (IVa) is chosen from acrylamide-propyl trimethyl ammonium chloride and methacrylamidopropyl trimethyl ammonium chloride.

The compounds of formula (V) of the present invention are preferably chosen from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-methyl crotonic acid, 2- acid. acrylamido-2-methylpropane sulfonic and 2methacrylamido-2-methylpropane sulfonic 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 Cw-Cis alkyl acrylates or methacrylate.

The crosslinking or branching agent is preferably chosen from N, N'methylene bis-acrylamide, triallyl methyl ammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylate, dimethacrylate d 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 approximately 1.

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

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% of moles, more preferably from 5% to 80% of moles and even more preferably from 25% to 75% of moles of compound (s) of formula (V). The content of compound (s) of formula (VI) is preferably between 0.1% and 70% of moles, more preferably between 1% to 50% of moles and even more preferably between 1% and 10% of moles. The crosslinking or branching agent when it is present is preferably between 0.0001% and 1% of moles and even more preferably between 0.0001% and 0.1% of moles.

Preferably, the molar ratio between the compound (s) of formulas (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 patent application WO 98/44012.

The amphoteric polymers which are particularly preferred according to the invention are chosen from copolymers of acrylic acid / acrylamide propyl trimethyl ammonium chloride / stearyl methacrylate.

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

Such an associative polymer is advantageously used in an amount of 0.1% to 8% by weight in dry matter and preferably between 0.5% and 4% by weight relative to the total weight of the aqueous phase.

II.B.2 Polyacrylamides and polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid

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

They are preferably completely or almost completely neutralized, i.e. at least 90% neutralized.

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

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

Mention may be made, for example, as crosslinking agents, of divinylbenzene, diallyl ether, dipropylene glycol-diallylether, polyglycol-diallyl ethers, triethylene glycol-divinyl ether, hydroquinone-diallyl ether, di (meth) acrylate. ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallylcyanurate, diallylmaleate, tetraallylethylenediamine, tetra-allylethyl-ethanol-trimlylethyl-ethanol meth) allyl acrylate, allyl ethers of alcohols from the sugar series, or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as allyl esters of 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 crosslinking rate generally ranges from 0.01% to 10% by mole and more particularly from 0.2% to 2% by mole relative to the polymer.

The AMPS® polymers suitable for the invention are water-soluble or water-dispersible. They are in this case:

- or "homopolymers" comprising only AMPS monomers and, if they are crosslinked, one or more crosslinking agents such as those 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 contain hydrophobic ethylenically unsaturated monomers, the latter do not contain a fatty chain and are preferably present in small amounts.

“Fat chain” is understood to mean, within the meaning of the present invention, any hydrocarbon chain containing 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%, allow a macroscopically homogeneous and transparent solution to be obtained, that is to say having a maximum light transmittance value, 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) dispersing or dissolving the monomer such as AMPS in free form in a solution of tert-butanol or of water and of tert-butanol;

(b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more mineral or organic bases, preferably ammonia NH ₃ , in an amount making it possible to obtain a rate of neutralization of the sulfonic acid functions of the polymer ranging from 90% to 100%;

(c) adding the crosslinking monomer (s) to the solution or dispersion obtained in (b);

(d) a conventional radical polymerization is carried out in the presence of free radical initiators at a temperature ranging from 10 ° C to 150 ° C; the polymer precipitating in the solution or dispersion based on tert-butanol.

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

The water-soluble co-monomers can be ionic or non-ionic.

Among the ionic water-soluble comonomers, mention may be made, for example, of the following compounds and their salts:

- (meth) acrylic acid,

- styrene sulfonic acid,

- vinylsulfonic acid and (meth) allylsulfonic acid,

- vinyl phophonic acid,

- maleic acid,

- itaconic acid,

- crotonic acid,

- the water-soluble vinyl monomers of formula (A) below:

H, C = CR, éo WX _1: in which:

- Ri is chosen from H, -CH ₃ , -C2H5 or -C3H7;

- Xi is chosen from alkyl oxides of type -OR2 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 co-monomers, there 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 comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,

- vinyl alcohol of formula CH ₂ = CHOH,

- the water-soluble vinyl monomers of formula (B) below:

H, C — CR, eo '

I ^X 2 in which:

- R3 is chosen from H, -CH ₃ , -C2H5 or -C3H7;

- X2 is chosen from alkyl oxides of type -OR4 where R4 is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, optionally substituted by a halogen atom (iodine, bromine, chlorine , fluorine); a hydroxy group (-OH); ether.

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

Among the hydrophobic comonomers without a fatty chain, there may be mentioned for example:

- styrene and its derivatives such as 4-butylstyrene, alpha methylstyrene and vinyltoluene;

- vinyl acetate of formula CH ₂ = CH-OCOCH ₃ ;

- vinyl ethers of formula CH ₂ = CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, 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:

H, C = CR

I ⁴ (C)

CO '’

I x ₃ in which:

- R4 is chosen from H, -CH ₃ , -C2H5 or -C ₃ H ₇ ;

- X ₃ is chosen from alkyl oxides of type -OR5 where R5 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 isobomyl acrylate and the like. 2-hexyl ethyl acrylate.

The water-soluble or water-dispersible AMPS® polymers of the invention preferably have a molar mass ranging from 50,000 g / mole to 10,000,000 g / mole, preferably from 80,000 g / mole to 8,000,000 g / mole, and even more preferably from 100,000 g / mole to 7,000,000 g / mole.

As water-soluble or water-dispersible homopolymers of AMPS suitable for the invention, mention may be made, for example, of crosslinked or non-crosslinked polymers of acrylamide-2-methyl propane sulfonate such as that used in the commercial product Simulgel 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of acrylamide-2methyl propane ammonium sulfonate (INCI name: Ammonium Polyacryldimethyltauramide) such as those described in patent EP 0 815 928 B1 and such as the product sold under the trade name Hostacerin AMPS® by the Clariant company.

Preferably, a composition according to the invention comprises an AMPS® homopolymer.

In particular, such an AMPS® homopolymer can be present in a composition according to the invention in a content of between 0.1% and 5% by weight, preferably between 0.3% and 3% by weight, and more preferably between 0.5% and 2.5% by weight, relative to the total weight of the composition.

As water-soluble or water-dispersible copolymers of AMPS in accordance with the invention, there may be mentioned for example:

- crosslinked acrylamide / acrylamido-2-methyl propane sulfonate copolymers such as that used in the commercial product SEPIGEL 305 (CTFA name: Polyacrylamide / Ci3-Ci4 Isoparaffin / Laureth-7) or that used in the commercial product sold under the name Simulgel 600 (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate / Isohexadecane / Polysorbate-80) by the company Seppic;

- the 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 (name CTFA: Ammonium Acryloyldimethyltaurate / VP Copolymer) but neutralized by soda or potash ;

- AMPS® and sodium acrylate copolymers, such as 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 Acryloyldimethyl taurate copolymer);

- the copolymers of AMPS® and of hydroxyethyl acrylate, such as for example the copolymer AMPS® / hydroxyethyl acrylate 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 marketed under the name Acrylamido-2-Methylpropane Sulfonate / Hydroxyethylacrylate copolymer as the commercial product Sepinov EMT 10 (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl taurate ).

As water-soluble or water-dispersible copolymers of preferred AMPS in accordance with the invention, mention may be made of the copolymers of AMPS® and of hydroxyethyl acrylate.

In general, a composition according to the invention can comprise from 0.1% to 8% by weight in dry matter, preferably from 0.2% to 5% by weight and more preferably from 0.7% to 3%. by weight of polyacrylamide (s) and / or polymer (s) and copolymer (s) of 2-acrylamido 2-methylpropane sulfonic acid, crosslinked (s) and / or neutralized relative to the total weight of the composition .

II.B. 3 Modified or unmodified carboxyvinyl polymers

The carboxyvinyl polymers, modified or not, may be copolymers resulting from the polymerization of at least one monomer (a) chosen from carboxylic acids containing a, b-ethylenic unsaturation or their esters, with at least one monomer (b) containing ethylenic unsaturation comprising a hydrophobic group.

The term “copolymers” means both the copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers such as the terpolymers obtained from three kinds of monomers.

Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. By hydrophobic group or unit, is meant a radical with a hydrocarbon chain, saturated or unsaturated, linear or branched, 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 the copolymers resulting from the polymerization:

- at least one monomer of formula (1) below:

CH, = C — C — OH I II ^Rl ° (1) in which Ri denotes H or CH ₃ or C2H5, that is to say monomers of acrylic acid, methacrylic acid or ethacrylic acid, and

- at least one monomer of the alkyl ester (C10-C30) type of unsaturated carboxylic acid corresponding to the monomer of formula (2) below:

CH, = C— C— OR, ² I II (2) in which R2 denotes H or CH ₃ or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units), R ₃ denoting an alkyl radical in Cio-C ₃ o, and preferably in C12-C22.

The alkyl esters (Cio-C ₃ o) of unsaturated carboxylic acids are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, acrylate dodecyl, 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, use will be made more particularly of polymers resulting from the polymerization of a mixture of monomers comprising:

- mainly acrylic acid,

an ester of formula (2) described above and in which R2 denotes H or CH ₃ , R ₃ denotes an alkyl radical having from 12 to 22 carbon atoms, and

a crosslinking agent, which is a well-known polyethylenic unsaturated copolymerizable monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among this type of copolymers, use will be made more particularly of those consisting of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Cio-C ₃ alkyl acrylate (unit hydrophobic), and 0% to 6% by weight of crosslinkable polymerizable monomer, or else those consisting of 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of alkyl acrylate in Cio-C ₃ o (hydrophobic unit), and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, very particularly preferred according to the present invention, acrylate / Cio-C ₃ o-alkylacrylate copolymers (INCI name: Acrylates / Cio ₃ o Alkyl acrylate Crosspolymer) such as the products sold by the company Lubrizol under the trade names Pemulen TR-1, Pemulen TR-2, Carbopol 1382, Carbopol EDT 2020, Carbopol Ultrez 20 Polymer and even more preferably Pemulen TR-2.

Among the carboxyvinyl polymers modified or not, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia SP® containing 90% dry matter and 10% water, or Cosmedia SPL® in reverse emulsion containing approximately 60% dry matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis.

Mention may also be made of partially neutralized sodium polyacrylates being in the form of a reverse 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 can also be chosen from crosslinked (meth) acrylic acid homopolymers.

By “(meth) acrylic” within the meaning of the present application, one understands “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 P, 980, 981, 2984, 5984, Carbopol Ultrez 10 Polymer, or by 3V-Sigma under the name Synthalen® K, Synthalen® L, or Synthalen® M.

Among the carboxyvinyl polymers modified or not, mention may in particular be made of Carbopol (CTFA name: carbomer) and Pemulen (CTFA name: Acrylates / Cio-30 akyl acrylate crosspolymer) sold by the company Lubrizol.

The carboxyvinyl polymers, modified or not, can be present in an amount of 0.1% to 5% by weight in dry matter relative to the weight of the aqueous phase, in particular from 0.3% to 1% by weight, preferably between 0.4% and 1% relative to 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-methylpropane sulfonic acid.

According to a preferred variant, the synthetic polymeric hydrophilic gelling agent is a homopolymer of AMPS®.

III. Other hydrophilic gelling agents

These gelling agents are more particularly chosen from mixed silicates and fumed silicas.

III. A. Mixed silicate

For the purposes of the present invention, the term “mixed silicate” means all the silicates of natural or synthetic origin containing several (two or more) types of cations chosen from alkali (for example Na, Li, K) or alkaline-earth metals ( e.g. Be, Mg, Ca), transition metals and aluminum.

According to a particular embodiment, the mixed silicate (s) 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 this description, these particles are designated by “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, better still at least 70% by weight relative to the total weight of the particles. Particles containing at least 90% by weight of silicates, relative to 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, of aluminum or of iron.

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

To guarantee good cosmetic properties, these silicates are generally present 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 nm to 1000 nm), and preferably from 5 nm to 600 nm, and even more preferably from 20 to 250 nm.

The silicate particles can have any shape, for example the shape of spheres, flakes, needles, platelets, discs, sheets, or totally random shapes. Preferably, the silicate particles are in the form of discs or sheets.

Also, the term “average size” of the particles is understood to mean the number-average size of the largest dimension (length) that it is possible to measure between two diametrically opposite points of an individual particle. The size can be determined for example by transmission electron microscopy, or from the measurement of the specific surface by the BET method, or even by means of a laser granulometer.

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

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

According to a particular embodiment of the invention, the silicates are phyllosilicates, namely silicates having a structure in which the S1O4 tetrahedra are organized in sheets between which the metal cations are found.

The mixed silicates suitable for the invention can 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 which is particularly preferred in the compositions of the present invention is therefore that of the laponites. Laponites are magnesium, sodium and possibly lithium silicates, having a layered structure similar to that of montmorillonites. Laponite is the synthetic form of the natural mineral called "hectorite". The synthetic origin of this family of silicates has a considerable advantage over the natural form because it allows 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, mention may in particular be made of 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 can be used in an amount of 0.1% to 8% by weight in 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% to 3% by weight relative to the total weight of the aqueous phase.

III. B. Hydrophilic fumed silica

The fumed silicas according to the present invention are hydrophilic.

Hydrophilic fumed silicas are obtained by continuous flame pyrolysis at 1000 ° C of silicon tetrachloride (S1CI4) in the presence of hydrogen and oxygen. Among the hydrophilic fumed silicas which can be used according to the present invention, mention may in particular be made of those sold by the company DEGUS SA or EVONIK DEGUS SA under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or also by the CABOT company under the name Carbosil H5.

Such gelling agents can be used at a rate of 0.1% to 10% by weight in 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% to 3% by weight relative to the total weight of the aqueous phase.

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 compound liquid 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 which can be used in the composition of the invention can also be volatile.

Among the water-soluble solvents which 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 dipropylene glycol, C3 and C ₄ 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 99%, better still from 30% to 95% by weight, preferably from 40% to 90% by weight, relative to the total weight of said composition.

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

By "polyol" should be understood, within the meaning 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 suitable for the invention may be a compound of alkyl type, linear, branched or cyclic, saturated or unsaturated, bearing on the alkyl chain at least two -OH functions, in particular at least three -OH functions, and more particularly at minus four -OH functions.

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

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

According to a particular embodiment, the composition of the invention can comprise at least dipropylene glycol.

According to another particular mode, the composition of the invention can comprise at least glycerol.

According to a preferred embodiment, the composition of the invention comprises at least one polyol, and preferably a propanediol.

Oily phase

The oily phase according to the invention can comprise at least one other oil distinct from the oils described above.

Thus, an oily phase suitable for the preparation of the compositions, in particular cosmetic compositions according to the invention, may comprise hydrocarbon oils, silicone oils, fluorinated or not, or their mixtures.

The oils may be volatile or non-volatile.

They can be of animal, vegetable, mineral or synthetic origin. According to an alternative embodiment, oils of silicone origin are preferred.

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.

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.

The term “fluorinated oil” means an oil comprising at least one fluorine atom.

"Hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms.

The oils may optionally include oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acid radicals.

By “volatile oil” is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than an hour, at ambient temperature and atmospheric pressure. Volatile oil is a volatile cosmetic compound, liquid at room temperature, in particular having a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ' ³ to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1,300 Pa (0.01 to 10 mm Hg).

Volatile oils

The volatile oils can be hydrocarbon-based, or silicone-based.

Mention may be made from volatile hydrocarbon oils having from 8 to 16 carbon atoms branched alkanes, C ₈ -Ci6 as isoalkanes (also called isoparaffins) C ₈ -Ci6, isododecane, isodecane, the 'isohexadecane and for example the oils sold under the trade names of Isopars or Permyls, branched C ₈ -C ₆ esters such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms and their mixtures, in particular from isododecane, isodecane, isohexadecane, and is in particular isohexadecane.

Mention may also be made of 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 (Cn) and ntridecane (Cn) obtained in Examples 1 and 2 of application WO 2008/155059 from the company Cognis, and their mixtures.

As volatile silicone oils, mention may be made of linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane.

As cyclic silicone volatile oils, mention may be made of hexamethylcyclotrisiloxane, octamethylcylotetrasiloxane, decamethylcyclopentasiloxane, cyclohexasiloxane and dodecamethylcyclohexasiloxane, and in particular cyclohexasiloxane.

Non-volatile oils

The non-volatile oils can, in particular, be chosen from hydrocarbon-based, fluorinated oils and / or non-volatile silicone oils.

As non-volatile hydrocarbon oil, there may be mentioned in particular:

- hydrocarbon oils of animal origin,

- hydrocarbon oils of vegetable origin, synthetic ethers having from 10 to 40 carbon atoms, such as dicapryl ether,

- hydrocarbon oils of mineral or synthetic origin, in particular paraffin oil or its derivatives, petrolatum oil, naphthalene oil, polybutylenes, hydrogenated polyisobutylenes, decene / butene copolymers, polybutene copolymers / polyisobutene, polydecenes and hydrogenated polydecenes, and mixtures thereof, and preferably hydrogenated polyisobutene;

- synthetic esters, such as oils of formula R1COOR2, in which Ri represents a residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, in particular, branched containing from 1 to 40 carbon atoms provided that Ri + R ₂ is> 10. The esters can be, in particular, chosen from alcohol and fatty acid esters, such as, for example, cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, palmitate isopropyl, ethyl palmitate, 2-ethyl-hexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, ricinoleates alcohols or polyalcohols, hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, such as isononyl isononanoate, l 'isotridecyl isononanoate,

polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetrahydroxystearate,

- fatty alcohols liquid at room temperature with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol,

- higher Ci ₂ -C ₂₂ fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof,

non-phenylated silicone oils, for example caprylyl methycone, and

- phenylated silicone oils, such as, for example, phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates or dimethethicone , trimethylpentaphenyltrisiloxane, and mixtures thereof; as well as mixtures of these different oils.

A composition according to the invention can comprise from 5% to 95% by weight, better still from 10% to 70% by weight, preferably from 5% to 55% by weight of oil (s) relative to the total weight of said composition.

As specified above, the gelled oily phase according to the invention may have a threshold stress greater than 1.5 Pa and preferably greater than 10 Pa. This threshold stress value reflects a gel-like texture of this oily phase.

BUILDERS

loads

A composition according to the invention can also comprise at least one filler, and in particular a fuzzy effect or fuzzy effect filler.

By “fillers”, within the meaning of the present invention, it is necessary to understand the colorless or white particles, solid of all shapes, of mineral or organic, natural or synthetic nature, which are in an insoluble form and dispersed in the medium of the composition.

Of course, these fillers are used in appropriate contents and conditions so as not to be detrimental to the compositions.

The blurring charges which can be used in the composition according to the invention are in particular characterized by a refractive index of between 1.33 and 2.

They will generally comprise or consist of particles having a number average size less than or equal to 25 μm, in particular less than or equal to 20 μm, in particular less than or equal to 15 μm.

By "number-average size" is meant the dimension given by the statistical particle size distribution to half the population, called D50 measured with the Malvem-Mastersizer.

These particles can be of any shape and in particular be spherical or non-spherical.

Said filler (s) are present in whole or in part, and preferably only, in the gelled aqueous phase or are present in whole or in part, and preferably only, in the gelled oily phase. Preferably, they are present in the gelled aqueous phase.

In particular, the filler is chosen from powders of crosslinked elastomeric organopolysiloxane coated with silsesquioxane resin, powders of crosslinked elastomeric organopolysiloxane coated with hydrophilic silicone resin, polytetrafluoroethylene powders, polyurethane powders, Camauba microwires synthetic wax microwaxes, silicone resin powders, hollow hemispherical silicone particles, powders of acrylic copolymers, vinylidene / acrylonitrile / methylene methacrylate expanded microspheres, polyethylene powders, especially comprising at least one ethylene / acrylic acid, polymethyl methacrylate powders, crosslinked elastomeric organopolysiloxane powders, crosslinked elastomeric organopolysiloxane powders coated with silicone resin, starch powders, polyamide powders, silica powders and silicates, note alumina, hydrophobic airgel particles, talc of average size in number less than or equal to 3 microns, silica / TiCL composites, barium sulfate particles, boron nitride particles, silica particles surface treated with 1 to 2% mineral wax, amorphous silica microspheres, silica micro-beads, talc / TiCL / alumina / silica composite powders, silicone elastomers, spherical cellulose beads, and their mixtures.

According to a particularly advantageous embodiment of the invention, the filler is a crosslinked elastomeric organopolysiloxane powder coated with silsesquioxane resin or a crosslinked elastomeric organopolysiloxane powder coated with hydrophilic silicone resin.

Crosslinked elastomeric organopolysiloxane powder coated with hydrophilic silicone resin is generally referred to as "hydrophilic treated", that is, treated to make it hydrophilic.

Advantageously, to make the crosslinked elastomeric organopolysiloxane powder hydrophilic coated with silicone resin, the latter is subjected to a treatment aimed at associating therewith at least one cationic polymer and advantageously at least one nonionic or cationic surfactant. The cationic polymer with optionally the surfactant (s) and the crosslinked elastomeric organopolysiloxane powder can be combined by chemical bonds or by interactions in particular by van der Waals bonds.

In particular, the crosslinked elastomeric organopolysiloxane powder coated with hydrophilic treated silicone resin is combined with at least one cationic polymer, preferably a quaternary ammonium polymer, in particular a polymer of INCI name "Polyquatemium" and optionally with at least one ester. fatty acid Cg-C22 and polyoxyethylenated polyol, preferably from 2 to 20 moles of EO such as fatty acid esters Cg-Cig and polyoxyethylenated glycerol from 3 to 15 moles of EO, preferably a polyoxyethylenated Cg-Cig glycol ester, more preferably a Cg-Cig fatty acid ester and polyoxyethylenated glycerol of 5 to 10 moles of EO.

According to one embodiment, the crosslinked elastomeric organopolysiloxane powder coated with hydrophilic treated silicone resin according to the invention is combined with at least one quaternary ammonium polymer, preferably chosen from polyquatemium-6 and polyquatemium-7, preferably polyquatemium-7. Polyquatemium-6 is a poly (diallyldimethylammonium chloride). Polyquatemium 7 is a copolymer of acrylamide and diallyldimethylammonium chloride.

Advantageously, the crosslinked elastomeric organopolysiloxane powder coated with silsesquioxane resin used as a filler in the compositions according to the invention corresponds to the INCI name: vinyl dimethicone / methicone silsesquioxane Crosspolymer and in particular it is sold under the reference "KSP-100" by Shin Etsu company.

Advantageously, the crosslinked elastomeric organopolysiloxane powder coated with hydrophilic treated silicone resin, used as a filler in the compositions according to the invention corresponds to the INCI name vinyl dimethicone / methicone silsesquioxane crosspolymer treated with PEG-7 glyceryl cocoate, Polyquatemium-7 and methylsilanol triPEG-8 glyceryl cocoate and in particular it is sold under the reference "MW-SRP-100" by the company Miyoshi Kasei.

According to an alternative embodiment, a composition according to the invention can comprise from 0.2% to 40% by weight, in particular from 0.5% to 37% by weight, in particular from 2% to 15% by weight of filler ( s), and in particular of crosslinked elastomeric organopolysiloxane powder coated with silicone resin, in particular vinyl dimethicone / methicone silsesquioxane Crosspolymer, relative to the total weight of said composition.

This type of charge is particularly advantageous insofar as it allows blurring of imperfections. As indicated above, the performance of these fillers is advantageously increased by virtue of their use in a composition according to the invention.

The blurring effect is characterized by measures of Haze and transparency (TH transmission). The “Haze” corresponds to the percentage of light scattered in relation to the total transmittance according to ASTM D 1003 (Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics).

25 µm composition films are applied to 50 µm polyethylene (PE) films. The film is then measured after one hour of drying at room temperature. Finally, the film is placed in the apparatus and measurements of transparency and of Haze are carried out.

Advantageously, a composition according to the invention can comprise, in addition to one or more fillers mentioned above, one or more charge (s) conventionally used in care and / or make-up compositions.

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

Mineral or organic in nature, natural or synthetic, they give the composition containing them smoothness, mattness and uniformity to make-up.

In particular, such additional fillers can be present in a composition according to the invention in a content of between 0.5% and 10% by weight, in particular between 0.5% and 7% by weight, in particular between 0 , 5% and 5% by weight, relative to the total weight of the composition.

According to one embodiment of the invention, a composition can also comprise at least solid particles such as pigments and / or fillers.

Advantageously, a composition according to the invention can comprise from 0.01% to 45% by weight, in particular from 0.1% to 40% by weight, in particular from 1% to 35% by weight and preferably from 2% to 30% by weight of solid particles, relative to the total weight of the composition.

Coloring matters

A composition according to the invention may also comprise at least one particular or non-particulate coloring matter, water-soluble or not, and preferably at a rate of 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 clearly falls within the competence of those skilled in the art. art.

A composition according to the invention can 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 2.5% at 15% by weight of coloring matters, relative to the total weight of said composition.

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

By “water-soluble coloring matter”, within the meaning of the invention, is meant any generally organic, natural or synthetic compound, soluble in an aqueous phase or solvents miscible with water and capable of coloring.

As water-soluble dyes suitable for the invention, mention may in particular be made of synthetic or natural water-soluble 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, chlorophyllin copper, methylene blue, anthocyanins (enocianine, black carrot, hibiscus, elderberry), caramel, riboflavin.

Water-soluble colors are, for example, beet juice and caramel.

By "liposoluble coloring matter", within the meaning of the invention, is meant any generally organic, natural or synthetic compound, soluble in an oily phase or the solvents miscible with a fatty substance and capable of coloring.

As liposoluble dyes suitable for the invention, mention may in particular be made of liposoluble dyes, synthetic or natural, such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11 , DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow , annatto, curcumin.

The coloring particulate materials may be present in an amount of 0.01% to 15% by weight, relative to the total weight of the composition containing them.

It can in particular be pigments, pearlescent agents and / or particles with metallic reflections.

The term “pigments” should be understood to mean white or colored, mineral or organic particles, insoluble in an aqueous solution, intended to color and / or opacify the composition containing them.

A composition according to the invention can comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 25% by weight, and preferably from 2.5% 15% by weight of pigments, relative to the total weight of said composition.

Preferably, when the composition according to the invention is a makeup composition, it can comprise at least 2.5%, and preferably at least 10% by weight of pigments, relative to the total weight of said composition.

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

As inorganic pigments which can be used in the invention, mention may be made of titanium, zirconium or cerium oxides or dioxides, as well as zinc, iron or chromium oxides, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.

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

It can also be pigments having a structure which can be, for example, of the silica microsphere type containing iron oxide. An example of a pigment having this structure is that sold by the company Miyoshi under the reference PC Bail PC-LL100 P, this pigment being made up of silica microspheres containing yellow iron oxide.

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

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

A composition according to the invention can comprise from 0% to 15% by weight of nacres, relative to the total weight of said composition.

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 an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It can also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic coloring matters.

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, there may be mentioned the Timica, Flamenco and Duochrome nacres (on the basis of mica) marketed by the company ENGELHARD, the Timiron nacres marketed by the company Merck, the nacres on the basis of Prestige mica sold by the company Eckart and nacres based on Sunshine synthetic mica sold by Sun Chemical.

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

Advantageously, the nacres in accordance with the invention are the micas coated with titanium dioxide or iron oxide as well as bismuth oxychloride.

By “particles with a metallic reflection”, within the meaning of the present invention, is meant any compound whose nature, size, structure and surface condition allows it to reflect the incident light in particular in a non-iridescent manner.

The particles with a metallic reflection which can be used in the invention are in particular chosen from:

- particles of at least one metal and / or at least one metal derivative;

- the particles comprising a substrate, organic or inorganic, monomaterial or multimaterial, covered at least partially by at least one layer with metallic reflection comprising at least one metal and / or at least one metallic derivative; and

- mixtures of said particles.

Among the metals which 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 mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and their mixtures or alloys (e.g. bronzes and brasses) are preferred metals.

The term “metallic derivatives” denotes compounds derived from metals, in particular oxides, fluorides, chlorides and sulfides.

By way of illustration of these 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 covered with a metallic layer in particular those described in documents JP-A-09188830, JP-A-10158450, JPA-10158541, JP-A-07258460 and JP-A-05017710.

Hydrophobic treatment of coloring matter

The pulverulent dyestuffs as described above can be treated on the surface, totally or partially, with a hydrophobic agent, to make them more compatible with the oily phase of the composition of the invention, in particular so that they have good wettability with the oils. Thus, these treated pigments are well dispersed in the oily phase.

Hydrophobic treated pigments are especially described in document EP-A1086683.

The hydrophobic treatment agent can be chosen from silicones such as methicones, dimethicones, perfluoroalkylsilanes; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, the aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates; polyoxides of hexafluoropropylene; perfluoropolyethers; amino acids; Nacylated amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof.

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

Polar additives

Advantageously, a composition according to the invention may also comprise one or more polar additive (s).

According to the present invention, the use of such a polar additive can in particular facilitate the homogenization of the dispersion in the presence of pigments.

The polar additive can be chosen from the compounds considered to be good donors or acceptors of hydrogen bonds, such as for example fatty alcohols, fatty acids, diols, esters and their mixtures.

According to one embodiment, the polar additives of the invention can be polar oils, distinct from the aforementioned oils.

According to one embodiment, the polar additives of the invention can be amphiphilic compounds, comprising a lipophilic part linked to a polar part, for example chosen from esters, branched fatty alcohols C12 to C26 such as octyldodecanol, or silicone amphiphilic compounds. The polar additives of the invention may also be agents for filtering UV-B and / or UV-A rays, the total quantity of filters possibly being between 0.01% and 10% by weight relative to the total weight of the composition.

A composition according to the invention can comprise from 0.01% to 10% by weight, in particular from 0.05% to 5% by weight, in particular from 0.05% to 2% by weight of polar additive (s) (s).

assets

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

Preferably, the hydrating agent is glycerin.

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

As other active agents which can be used in the composition of the invention, mention may, for example, be made of vitamins, sunscreens and their mixtures, and in particular vitamins such as tocopherol.

Preferably, a composition according to the invention comprises at least one active, in particular chosen from hydrating agents, preferably glycerin, vitamins, preferably tocopherol, and their mixtures.

According to a preferred embodiment, a composition according to the invention also comprises at least one active ingredient.

Preferably, the active ingredient is glycerin.

In addition, a composition according to the invention can also comprise at least one dispersing agent.

It is routine operations of a person skilled in the art to adjust the nature and the quantity of additives present in the compositions in accordance with the invention, so that the desired cosmetic properties thereof are not not affected.

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

In particular, a composition of the invention may advantageously be in the form of an anti-aging care composition for the skin of the body or of the face, in particular of the face.

According to another embodiment, a composition of the invention can advantageously be in the form of a makeup composition for the skin and / or keratin fibers, of the body or of the face, in particular of the face.

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

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

According to yet another sub-mode of this embodiment, a composition of the invention can advantageously be in the form of a lip product, in particular a lipstick.

According to yet another sub-mode of this embodiment, a composition of the invention can be in the form of an eyelash product, in particular a mascara.

According to yet another sub-mode of this embodiment, a composition of the invention can advantageously be in the form of an eyebrow product, in particular an eyebrow pencil.

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

Throughout the description, including the claims, the expression "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified.

The expressions "between ... and ...", "includes from ... to ...", "formed from ... to ...", and "ranging from ... to ..." must be understood terminals included, unless otherwise specified.

The invention is illustrated in more detail by the examples and figures presented below. Unless otherwise indicated, the quantities indicated are expressed in percentage by mass.

METHODOLOGY FOR DYNAMIC RHEOLOGY MEASUREMENTS IN

OSCILLATION

These are rheological measurements in harmonic regime which ensure the measurement of the elastic modulus.

The measurements are carried out using a Haake RS600 rheometer on a product at rest, at 25 ° C. with a mobile plane plane 0 60 mm and an air gap of 2 mm.

The harmonic measurements make it possible to characterize the viscoelastic properties of the products. The technique consists in subjecting a material to a stress which varies sinusoidally over time and in measuring the response of the material to this stress. In a domain where the behavior is linear viscoelastic (zone where the deformation is proportional to the stress), the stress (τ) and the deformation (γ) are two sinusoidal functions of time which are written as follows:

r (t) = το sin (rot) γ (ί) = γο sin (rot + δ) where:

το represents the maximum amplitude of the stress (Pa); γο 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 compared to the strain (rad).

Thus, the two functions have the same angular frequency but they are phase shifted by an angle δ. Depending on the phase shift δ between r (t) and y (t), the behavior of the system can be understood:

- If δ = 0, the material is purely elastic;

- If δ = Π / 2, the material is purely viscous (Newtonian fluid); and

- SiO <δ <Π / 2, the material is viscoelastic.

In general, the stress and the deformation are written in complex form: r * (t) = το e ^1Mt y * (t) = γο e ⁽ⁱ “ ^{t + 5)}

A complex stiffness modulus, representing the overall resistance of the material to deformation, whether of elastic or viscous origin, is then defined by:

G * = T * / y * = G ’+ iG” where:

G ’is the conservation modulus or elastic modulus which characterizes the energy stored and totally restored during a cycle, G’ = (το / γο) cos δ; and

G ”is the loss module or viscous module which characterizes the energy dissipated by internal friction during a cycle, G” = (το / γο) sin δ.

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

EXAMPLES

Example 1

Composition 1 according to the invention, and compositions 2 and 3 outside of the care invention were prepared and their cosmetic properties were evaluated.

1) Preparation of compositions 1 to 3

The compositions are prepared as described below.

Salicylic acid is dissolved in the hydrophilic phase at 75 ° C, in a homogenizer of the "COS 1000" type.

The thickeners are then added to the homogenizer, and the mixture is left to swell with stirring in a turax-type mixer with scrapers.

In a melter, capryloyl salicylic acid and glyceryl dibehenate (and) tribehenin (and) glyceryl behenate are dissolved in the lipophilic phase at a temperature of 75 ° C.

The hydrophilic and lipophilic phases are then mixed with stirring in a turax type mixer with scrapers, at a temperature of 75 ° C.

The mixture is left under stirring for 10 minutes.

Finally, the mixture is left to cool only under scrapers.

The compositions are prepared from the weight proportions detailed in the table below.

Phase compounds Composition 1 according to the invention (% by weight) Composition 2 off invention (% by weight) Composition 3 outside the invention (% by weight) Phase hydrophilic Water Qsp 100 Qsp 100 Qsp 100 Glycerin (Glicerina, Industria quimica del centra) 5.00 5.00 5.00 Propylene glycol (Propylene glycol, Lyondell) - 2.00 - Phenoxyethanol (Sepicide ld®, Seppic) 0.50 0.50 0.50 Ammonium polyacryloyldimethyltaurate (Hostacerin AMPS®, Clariant) 1.50 1.50 1.50 Sodium hydroxide (50% caustic soda, OLIN) 0.48 - 0.48 Sodium polyacrylate (Cosmedia SP®, BASF) 0.50 0.50 0.50 Salicylic acid (Salicylic acid, Alta Laboratories) 1.50 1.50 1.50 Caprylyl glycol (Dermosoft octiol®, Dr Straetmans) 0.50 0.50 0.50 Phase lipophilic Hydrogenated polyisobutene (Parléam, Nof Corporation) 4.00 - - 53% Glyceryl dibehenate, 30% tribehenin, 17% glyceryl behenate (Compritol 888 CG ATO®, Gattefosse) 4.00 3.00 4.00 Isostearyl neopentanoate (Ceraphyl 375®, ISP (Ashland) - 3.00 - Capryloyl salicylic acid (Mexoryl sab®, Chimex) 0.30 0.30 0.30 Octyldodecanol (Eutanol G®, BASF) - 5.00 - Hexyldecanol (Isofol 16®, Sasol) - - 4.00 Diisopropyl adipate (Dub dipa®, Stearinerie Dubois) 7.00 - 7.00

2) Evaluation of cosmetic properties

The determination of the soft-focus is made by measuring the Haze and the transparency, that is to say the perception of light at wide angles.

The measurements are carried out using a Hazegard on a film 50 μm thick, deposited on a PET film. 3 measurements are made after 1 hour of drying at room temperature.

The results are presented in the table below:

Composition Haze (%) Transmittance (%) 1 according to the invention 62.4 ± 0.3 91.7 ± 0.3 2 outside invention 33.6 ± 0.3 91.5 ± 0.3 3 outside invention 28.5 ± 0.3 90.7 ± 0.3

It appears from these results that the composition according to the invention has better soft-focus performance than the compositions not according to the invention.

In addition, the composition according to the invention allows a luminous deposit on the skin and has very good properties in terms of sensoriality and comfort.

Claims (15)

1. Composition, in particular cosmetic, in particular for making up and / or caring for keratin materials, comprising: - at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one gelled oily phase comprising at least one oil chosen from non-polar hydrocarbon oils, non-phenylated silicone non-polar oils, esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C2-Cg dicarboxylic acid and a C2-Cg alcohol, and mixtures thereof; said oily phase being gelled with at least one wax in the crystalline state chosen from waxes of vegetable origin and esters of behenic acid and glycerol; said phases forming therein a macroscopically homogeneous mixture. 2. Composition according to the preceding claim, comprising from 0.5% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, of waxes in the crystalline state. chosen from waxes of plant origin and behenic acid and glycerol esters relative to the total weight of the composition. 3. Composition according to any one of the preceding claims, in which the wax in the crystalline state is chosen from hydrogenated jojoba wax and mixtures of behenic acid esters and glycerol, and is preferably a glyceryl mixture. dibehenate, tribehenin, glyceryl behenate. 4. Composition according to any one of the preceding claims, comprising from 0.5% to 20% by weight, preferably from 1% to 15% by weight, and more preferably from 2% to 10% by weight, of oil. (s) chosen from apolar hydrocarbon oils, non-phenylated silicone apolar oils, esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C2- dicarboxylic acid Cg and a C2-Cg alcohol, and mixtures thereof, relative to the total weight of the composition. 5. Composition according to any one of the preceding claims, in which the oil is chosen from hydrogenated polyisobutenes, non-volatile polydimethylsiloxanes, isononyl isononanoate, dicaprylyl carbonate, caprylic / capric triglyceride, diisopropyl adipate, and their mixtures. 6. Composition according to any one of claims 1 to 4, in which the oil is chosen from non-polar hydrocarbon oils, non-phenylated silicone non-polar oils, and their mixtures. 7. Composition according to any one of the preceding claims, in which the oil is chosen from hydrogenated polyisobutenes, non-volatile polydimethylsiloxanes, and mixtures thereof. 8. Composition according to any one of claims 1 to 3, comprising from 0.01% to 30% by weight, in particular from 0.05% to 20% by weight, in particular from 0.1% to 15% by weight of oil (s) chosen from esters of isononanoic acid, dialkyl carbonates, triglycerides of fatty acids, diesters of a C2-C8 dicarboxylic acid and of a C2-C8 alcohol, and their mixtures. 9. Composition according to any one of the preceding claims, in which the hydrophilic gelling agent is chosen from synthetic polymeric gelling agents, and preferably from associative polymers, polyacrylamides, polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid , and carboxyvinyl polymers. 10. Composition according to any one of the preceding claims, in which the hydrophilic gelling agent is chosen from polymers and copolymers of 2acrylamido-2-methylpropane sulfonic acid, and preferably from crosslinked or non-crosslinked polymers of acrylamide-2-methyl propane sodium sulfonate. 11. Composition according to any one of the preceding claims, further comprising at least one polyol, and preferably a propanediol. 12. Composition according to any one of the preceding claims, in which the aqueous and oily gelled phases are present in a weight ratio aqueous phase / oily phase varying from 95/5 to 5/95, preferably varying from 50/50 to 90/10 . 13. Composition according to any one of the preceding claims, characterized in that it also comprises at least one active agent, and preferably glycerin. 14. Composition according to any one of the preceding claims, characterized in that it is a composition for caring for the skin of the body or of the face, in particular of the face. 15. Cosmetic method for making up and / or caring for keratin materials, in particular the skin and / or lips, comprising at least one step of applying to said keratin materials a composition as defined according to any one of the claims 1 to 14.