COSMETIC COMPOSITION OF GEL / GEL TYPE COMPRISING A SYNTHETIC PHYLLOSILICATE

专利摘要:
The present invention relates to a composition, in particular a cosmetic makeup and / or skincare and / or nail composition, comprising: at least one aqueous phase gelled by at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; characterized in that said phases form therein a macroscopically homogeneous mixture, and in that the composition further comprises at least one synthetic phyllosilicate of molecular formula Mg3Si4O10 (OH) 2. The present invention furthermore relates to a process for the preparation of the composition and to a cosmetic process for making up and / or caring for the skin and / or the nails.
公开号:FR3028758A1
申请号:FR1558965
申请日:2015-09-23
公开日:2016-05-27
发明作者:Bouchra Bouarfa；Laurence Sebillotte-Arnaud；Veronique Ferrari
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The present invention aims to provide advantageously for the field of care and make-up of the skin and / or nails, and in particular of the skin, a new galenic which is particularly interesting with regard to its technical performance and sensory sensations. it provides the user during its application on them and in particular on the skin. By "skin" is meant the skin of the face and / or the body. By "nails" is also meant the false nails insofar as the desired cosmetic effects are very often identical. In the cosmetic field, it is common to use creams consisting of a water-in-oil emulsion (W / O), also called inverse type emulsion, comprising an aqueous phase dispersed in an oily phase. These emulsions comprising an oily continuous phase have, among other things, the advantage of forming on the surface of the skin a lipidic film which prevents the loss of transepidermal water, protects the skin from external aggression. These emulsions are particularly suitable for the care and repair of dry and dehydrated skin which they provide comfort and protection through the lipid barrier they form on the skin. However, despite their high efficiency, W / O emulsions are a minority of the galenic forms used in the cosmetic field because they pose two major problems. First of all, these emulsions have the drawback of generally lacking sensory pleasure, that is, they are oily, heavy, sticky and lack freshness due to the oily external phase. They are generally difficult to apply on the skin, penetrate with difficulty and leave on the skin a shiny and often sticky film remanent. In addition, the W / O emulsions have stability problems, making their manufacture difficult, especially when the aqueous phase is in large quantity or when the emulsion is fluid. The drops of aqueous phase then tend to aggregate and form clusters visible under the microscope. In order to remedy these drawbacks, various solutions have been envisaged. One of the solutions well known to those skilled in the art for stabilizing these W / O emulsions is to use emulsifying surfactants in an amount of up to 10% by weight relative to the total weight of the composition. Another solution is to introduce a certain amount of consistency factors, such as waxes.
[0002] However, these ingredients contribute to accentuating the cosmetic defects (tackiness, greasiness and glossiness) of the W / O emulsions and this results in the production of often compact and heavy compositions. In addition, if the emulsifier content of these emulsions is greatly increased to remedy their instability, the emulsions obtained may be irritating with regard to certain types of skin, especially sensitive skin. Finally, another constraint is that the emulsifiers must be chosen according to the polarity of the oils used within the emulsion. Consequently, their use is only compatible with a limited number of oils, which restricts the diversity of the formulations. Moreover, users are more particularly interested today in cosmetic compositions devoid of surfactants. There remains therefore a need to prepare new stable cosmetic compositions, devoid of emulsifying surfactants which are substituting for W / O emulsions, having good cosmetic properties, in particular in terms and / or of softness, and / or freshness, and / or or lightness, and / or non-sticky effect, and / or non-greasy and / or non-glossy effect. 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 a cosmetic composition for makeup and / or care of the skin and / or nails, comprising: at least one aqueous phase gelled with at least one gelling agent hydrophilic; and at least one oily phase gelled with at least one lipophilic gelling agent; Characterized in that said phases form therein a macroscopically homogeneous mixture, and in that the composition further comprises at least one synthetic phyllosilicate having the molecular formula Mg3Si4 010 (OH) 2. By virtue of its specific properties, a synthetic phyllosilicate conforming to The invention can act as a hydrophilic filler and / or gelling agent in a composition according to the invention.
[0003] Advantageously, the composition according to the present invention comprising said phyllosilicate has an infrared absorption band at 7200 cm -1 corresponding to the stretching vibration attributed to the Si-OH silanol groups at the edges of the phyllosilicate layers.
[0004] Advantageously, the composition according to the present invention comprising said phyllosilicate, is characterized by an absence of infrared absorption band at 7156 cm -1. This band 7156 cm 'corresponds to the vibration band Mg2FeOH. The composition according to the present invention comprising said phyllosilicate also preferably has an infrared absorption band at 7184 cm -1 corresponding to the stretching vibration Mg 3 OH. It should be noted that in the presence of adsorbed water, for example residual, a broad infrared absorption band is detectable, easily identifiable, for example 5500 cm -1.
[0005] According to a first variant, said synthetic phyllosilicate is used in the form of an aqueous or aqueous-alcoholic gel. According to a second variant, said synthetic phyllosilicate is used in a dry particulate form (or powder). According to a third variant, said synthetic phyllosilicate is used therein in the form of an aqueous or aqueous-alcoholic gel and in a dry particulate form (or powder). According to a preferred embodiment, said synthetic phyllosilicate is used as a hydrophilic gelling agent. According to a more preferred embodiment, said synthetic phyllosilicate in the form of an aqueous or aqueous-alcoholic gel is used as a hydrophilic gelling agent. According to an alternative embodiment, the composition according to the invention is a cosmetic or dermatological composition comprising a physiologically acceptable medium. Synthetic phyllosilicates such as those described in application WO 2008/009799 and advantageously those disclosed in patent application FR 2 977 580 are particularly suitable for the invention.
[0006] However, none of these documents WO 2008/009799 and FR 2 977 580 considers the recovery of the synthetic phyllosilicates thus obtained in compositions and in particular for purposes of cosmetic, dermatological or pharmaceutical application. 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 inventors' knowledge, this type of composition does not comprise a synthetic phyllosilicate of molecular formula Mg 3 Si 4 O 10 (OH) 2, in particular as a hydrophilic gelling agent. The compositions according to the invention are stable while providing after application a sensation of comfort, sensory pleasure, especially in terms of softness, lightness or even freshness and dullness.
[0007] In the case of skin care, another advantage of the compositions according to the invention is to allow hydration of the skin and a possible massage which allows better blood circulation. As regards the field of make-up, the compositions according to the invention may have the advantage of a better "play time" or a better hold of the make-up on the skin and / or the nails. The "play-time" of a product corresponds to the time during which the consumer can work it during its application and therefore reflects the ease of application of the product. Finally, the compositions, preferably cosmetic, according to the invention are easy to apply to the surface of the skin and / or the targeted nail. According to another of its aspects, the subject of the invention is also a process for preparing a composition, in particular a cosmetic composition, comprising at least one step of mixing - an aqueous phase gelled with at least one gelling agent; At least one oily phase gelled with at least one lipophilic gelling agent; and at least one synthetic phyllosilicate of molecular formula Mg3Si4010 (OH) 2; under conditions conducive to obtaining a macroscopically homogeneous mixture.
[0008] According to an alternative embodiment, this process may advantageously comprise a step of mixing at least two or more gelled phases. The mixing of the phases can be carried out at room temperature (between 20 ° C - 30 ° C).
[0009] However, the process of the invention may comprise a step of heating the mixture. For obvious reasons, the number of gelled aqueous phases and gelled oily phases to be considered for forming a composition according to the invention may vary for each of the two types of phase beyond two.
[0010] According to an alternative embodiment, the final formula can be manufactured without following a particular order of introduction of the various constituents and in some cases an "all-in-one" manufacture can be carried out. According to a particular embodiment, the gelled phases representative of the same type of architecture are gelled by a different gelling agent.
[0011] Multiphase formulas can thus be developed. The invention furthermore describes a process for makeup and / or care, in particular cosmetic care, of the skin and / or the nails, comprising at least one step of applying to the skin and / or the nails a composition conforming to the invention. According to yet another of its aspects, the present invention relates to a cosmetic process for making up and / or caring for the skin and / or nails, comprising at least the application to the skin and / or the nails of a composition macroscopically homogeneous obtained by extemporaneous mixing, before application or at the time of application to the skin and / or the nails, of at least one aqueous phase gelled by at least one hydrophilic gelling agent, at least one oily phase gelled with minus a lipophilic gelling agent, and at least one synthetic phyllosilicate of the molecular formula Mg3Si4010 (OH) 2 as defined hereinafter. 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. This is a droplet dispersion of one of two liquid phases in the other. The size of the droplets forming the dispersed phase of the emulsion is typically of the order of one micrometer (0.1 to 100 μm). In addition, an emulsion requires the presence of a surfactant or an emulsifier to ensure its stability over time.
[0012] In contrast, a composition according to the invention consists of a macroscopically homogeneous mixture of two immiscible gelled phases. These two phases both have a gel-like texture. This texture is reflected in particular visually by a consistent and / or creamy appearance. The term "macroscopically homogeneous mixture" means a mixture in which each of the gelled phases can not be individualized with the naked eye. More precisely, in a composition according to the invention, the gelled aqueous phase and the gelled oily phase interpenetrate and thus form a stable and consistent product. This consistency is achieved by mixing interpenetrating macro domains. These interpenetrating macro-domains are not measurable objects. Thus, at the microscope, the composition according to the invention is very different from an emulsion. A composition according to the invention can not be characterized as having a "meaning", ie an O / W or E / H direction. Thus, a composition according to the invention has a gel-like consistency. The stability of the composition is durable without surfactant. Consequently, 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 / gel-type composition, for example by introducing a coloring material either in the aqueous gelled phase or in the gelled lipophilic phase, prior to formation of the gel / gel composition. During the visual inspection, in a gel / gel composition, the coloring matter appears to be uniformly dispersed, even if the dye is present only in the gelled aqueous phase or in the gelled oily phase. In fact, if two different dyes of different colors are introduced into the oily phase and the aqueous phase respectively, before the formation of the gel / gel composition, the two colors can be observed as uniformly dispersed throughout the composition of the composition. gel / gel type. This is different from an emulsion in which, if a dye, soluble in water or soluble in oil, is introduced into the aqueous and oily phases respectively, before forming the emulsion, only the color will be observed. dye present in the outer phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282).
[0013] It is also known to distinguish a gel / gel composition from an emulsion by performing a "drop test". This test consists of demonstrating the bicontinuous nature of a gel / gel composition. Indeed, as mentioned above, the consistency of a composition is obtained thanks to the interpenetration of the aqueous and oily gelled domains. Therefore, the bi-continuous nature of a gel / gel composition can be evidenced by a simple test with hydrophilic and hydrophobic solvents respectively. This test consists in depositing, on the one hand, a drop of a hydrophilic solvent on a first sample of the tested composition, and, on the other hand, a drop of a hydrophobic solvent on a second sample of the same composition tested, and to analyze the behavior of the two drops of solvents. In the case of an O / W emulsion, the drop of hydrophilic solvent diffuses into the sample and the drop of hydrophobic solvent remains on the surface of the sample. In the case of an W / O emulsion, the drop of hydrophilic solvent remains on the surface of the sample and the drop of hydrophobic solvent diffuses throughout the sample. Finally, in the case of a gel / gel type composition (bicontinuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample.
[0014] In the case of the present invention, the test which will be preferred for distinguishing a gel / gel composition from an emulsion is a dilution test. Indeed, in a gel / gel type composition, the aqueous and oily gelled domains interpenetrate and form a consistent and stable composition, in which the behavior in water and in oil is different from the behavior of an emulsion. Therefore, the behavior upon dilution of a gel / gel composition (dual-stream system) can be compared to that of an emulsion. More specifically, the dilution test consists in putting 40 g of product and 160 g of dilution solvent (water or oil) in a suitable container. The dilution is carried out with controlled stirring to avoid any emulsification phenomenon. In particular, this is done using a planetary mixer: Speed Mixer TM DAC400FVZ. The mixer speed is set at 1500 rpm for 4 minutes. Finally, observation of the resulting sample is performed using an optical microscope at a magnification of x 100 (x 10 x 10). It can be noted that oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® marketed by Dow Corning are suitable as a diluting solvent. In the case of a gel / gel composition (bicontinuous system), when diluted in oil or water, a heterogeneous appearance is always observed. When a gel / gel composition (bicontinuous system) is diluted in water, pieces of oily gel are observed in suspension and when a gel / gel composition (bicontinuous system) is diluted in water. the oil, pieces of aqueous gel are observed in suspension.
[0015] On the contrary, during the dilution, the emulsions exhibit a different behavior. An O / W emulsion, when diluted in an aqueous solvent, gradually homogenizes without showing a heterogeneous and lumpy appearance. This same O / W emulsion, when diluted with the oil, has a heterogeneous appearance (pieces of O / W emulsion suspended in the oil). W / O emulsion, when diluted with an aqueous solvent, has a heterogeneous appearance (W / O emulsion pieces suspended in water). This same W / O emulsion, when diluted in the oil, gradually homogenizes 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 in a weight ratio ranging from 95/5 to 5/95. More preferably, the aqueous phase and the oily phase are present in a weight ratio ranging from 30/70 to 80/20. The ratio between the two gelled phases is adjusted according to the desired cosmetic properties. Thus, in the case of a make-up composition, in particular the face, it may be advantageous to promote an aqueous gelled phase / oily gelled phase weight ratio greater than 1, in particular ranging from 60/40 to 90/10, of preferably ranging from 60/40 to 80/20, and more preferably from 60/40 to 70/30. In the case of a care composition, in particular the face, it may be advantageous to promote an aqueous gelled phase / gelled phase weight ratio preferably ranging from 40/60 to 70/30. These preferred ratios are particularly advantageous for obtaining fresh and light compositions.
[0016] Advantageously, a composition according to the invention is therefore in the form of a creamy gel having a minimum stress below which it does not flow except after being subjected to external mechanical stress. As is apparent from the following a composition according to the invention can have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa. It can also advantageously have a modulus of rigidity G * of at least 400 Pa. and preferably greater than 1000 Pa. According to an advantageous variant embodiment, the gelled phases considered for forming a composition according to the invention may respectively have a threshold stress greater than 1.5 Pa, and preferably greater than 10 Pa. The characterization of the threshold stresses is performed by oscillation rheology measurements. A methodology is proposed in the exemplification chapter of this text. In general, the corresponding measurements are carried out at 25 ° C. using an imposed stress rheometer, RS600 HAAKE, equipped with a plane-plane measuring body (diameter 60 mm) provided with a anti-evaporation device (bell). For each measurement, the sample is gently placed and the measurements begin 5 minutes after the sample is placed in the gap (2 mm). The tested composition is then subjected to a ramp stress of 10 'to 103 Pa at a frequency set at 1 Hz.
[0017] A composition according to the invention may also have a certain elasticity. This elasticity is characterized by a modulus of rigidity G * which below this minimum stress threshold may be at least 400 Pa, and preferably greater than 1000 Pa. The G * value of a composition can be obtained by subjecting the composition considered at a stress ramp of 10 'to 103 Pa at a frequency set at 1 Hz.
[0018] SYNTHETIC PHYLLOSILICATE The synthetic phyllosilicate according to the invention has a crystalline structure conforming to that of a hydroxylated magnesium silicate of molecular formula Mg3Si4010 (OH) 2 belonging to the chemical family of phyllosilicates.
[0019] These phyllosilicates are generally constituted by a stack of elementary sheets of crystalline structure, the number of which varies from a few units to a few tens of units. Each elemental sheet is constituted by the association of two layers of tetrahedra, in which are positioned the silicon atoms, located on either side of a layer of octahedra in which the magnesium atoms are positioned. This group corresponds to phyllosilicates 2/1, also called T.O.T. (Tetrahedron-octahedron-tetrahedron).
[0020] As stated above, a synthetic phyllosilicate according to the invention can be obtained according to a preparation method such as that described in application WO 2008/009799 and is preferably obtained according to the technology described in application FR 2 977 580. This preparation process notably comprises a prolonged hydrothermal treatment, which makes it possible to obtain an aqueous gel of synthetic phyllosilicate. Thus, according to a first variant embodiment, the synthetic phyllosilicate can be used in the form of an aqueous or aqueous-alcoholic gel, in particular in the image of that directly obtained at the end of the synthesis process. As described in the application FR 2 977 580, the parameters which influence the synthesis and the properties of a synthetic phyllosilicate in gel form suitable for the invention are the nature of the heat treatment (200 ° C. to 900 ° C.), the pressure, the nature of the reagents and their proportions. More particularly, the duration and the temperature of the hydrothermal treatment make it possible to control the size of the particles. For example, the lower the temperature, the smaller the particles synthesized as described in the application FR 2 977 580. The size control makes it possible to bring new properties and a better control of its hydrophilic properties. hydrophobic, that is to say, amphiphilic. It should be noted, however, that the gel as obtained at the end of the synthesis process may be subjected to a possible water wash / centrifugation step, after which it is dried and milled. The synthetic phyllosilicate is then available in powder form. Thus, the synthetic phyllosilicate considered according to the invention can also be formulated as a powder in a composition according to the invention.
[0021] Analysis and structural characterization of a synthetic phyllosilicate suitable for the invention A synthetic phyllosilicate suitable for the invention can be characterized by various parameters, namely infrared absorption bands, its size, its purity, as detailed below. Under certain conditions, analyzes such as nuclear magnetic resonance, in particular with 29Si may be useful for the characterization of a synthetic phyllosilicate suitable for the invention. Similarly, thermogravimetric analysis (TGA) can be carried out for the characterization of a synthetic phyllosilicate suitable for the invention. Finally, X-ray diffraction can also be used for this purpose. Infrared 15 Method Used The apparatus used is a Nicolet 6700 FTIR spectrometer with Fourier transform, equipped with an integrating sphere, with an InGaA detector and a CaF 2 separator and resolution of 12 cm -1, more preferably 8 cm -1 and more preferably 4 cm '. In other words, the values of the absorption bands given in this description are to be considered to be more or less 6 cm 2 and more preferably more or less 4 cm 2 and still more preferably 2 cm 3. The near-infrared recordings of the 7184 cm 'elongation region were decomposed by Pseudo-Voigts using the Fityk software (Wojdyr, 2010).
[0022] In order to visualize the absorption spectrum in a composition comprising at least one aqueous part, such as an emulsion, it is recommended to heat this composition to a temperature corresponding to a temperature greater than or equal to 100 ° C. (for example 120 ° C. C) and less than or equal to 500 ° C (for example 400 ° C) in order to eliminate the adsorbed water part and possibly some or all of the organic compound (s) present (s) ) in the composition. Generally to confirm an infrared absorption band, those skilled in the art carry out stretching enlargements, in particular, the latter may for example make such enlargements to plus or minus 200 cm-1 on either side. a suspected infrared absorption band. A natural talc is a mineral species composed of doubly hydroxylated magnesium silicate of formula Mg3Si4010 (OH) 2, which may contain traces of nickel, iron, aluminum, calcium or sodium. Natural talc has an infrared spectrum having a typical, fine and intense absorption band of 7184 cm-1 corresponding to the stretching vibration Mg 3 OH. Natural talc generally has magnesium and silicon substituting elements in the crystal structure which require the appearance of at least one additional infrared absorption band, particularly that corresponding to the 7156 cm elongation vibration. 1 attributable to 2 v Mg 2 FeOH. The spectrum of the synthetic phyllosilicate suitable for the invention differs from a natural talc by an infrared absorption band of 7200 cm -1 corresponding to the stretching vibration attributed to the Si-OH silanol groups at the edges of the phyllosilicate layers. . To confirm this infrared absorption band, a person skilled in the art can carry out an enlargement of stretching and in particular in the area of 7400 cm-1 7000 cm-1, and more particularly in the area of 7300 cm-1 - 7100 cm-1. Preferably, the synthetic phyllosilicate spectrum is also characterized by an absence of an infrared absorption band of 7156 cm -1. This 7156 cm-1 band corresponds to the vibration band of Mg2FeOH. Preferably, the spectrum of synthetic phyllosilicate is also characterized by the infrared absorption band of 7184 cm -1 common to natural talc. It should be noted that in the presence of adsorbed water, for example residual, a broad infrared absorption band is detectable, easily identifiable, for example 5500cm-1. Advantageously, the composition according to the present invention comprising said phyllosilicate has an infrared absorption band at 7200 cm -1 corresponding to the stretching vibration attributed to the Si-OH silanol groups at the edges of the layers of the phyllosilicate.
[0023] Advantageously, the composition according to the present invention comprising said phyllosilicate, is characterized by an absence of an infrared absorption band of 7156 cm-1. This 7156 cm-1 band corresponds to the vibration band of Mg2FeOH. The composition according to the present invention comprising said phyllosilicate also preferably has an infrared absorption band at 7184 cm-1 corresponding to the stretching vibration Mg 3 OH. In a composition according to the invention, it should be noted that in the presence of adsorbed water, for example residual, a broad infrared absorption band is detectable, easily identifiable, for example 5500cm-1.
[0024] Size Method Used In order to perform the particle size analysis of synthetic phyllosilicates suitable for the invention, photon correlation spectroscopy was used. This analytical technique provides access to particle size based on the principle of dynamic light scattering. This device measures, over time, the intensity of the light scattered by the particles at a given angle θ and the scattered rays are then processed by the Padé-Laplace algorithm. This technique, non-destructive, requires a dissolution of the particles.
[0025] The particle size measurement obtained by this technique corresponds to the value of the hydrodynamic diameter of the particle, that is to say that it comprises both the size of the particle but also the thickness of the hydration layer. The analyzes were carried out using a VASCO-2 granulometer from Cordouan. In order to obtain statistical information as to the particle distribution, the NanoQTM software was used in multi-acquisition mode with the Padé-Laplace algorithm. Thus, a synthetic phyllosilicate suitable for the invention, when in the form of aqueous or aqueous-alcoholic gel, advantageously has an average size ranging from 300 nm to 500 nm.
[0026] By contrast, a synthetic phyllosilicate when it is used in the form of a powder, like that obtained by dehydration of an aqueous gel, as defined above, may have an average size ranging from a few microns to several hundred microns, preferably ranging from 5 to 100 microns, or may be in the form of porous micron or plurimicron aggregates composed of said particles. These characteristics are advantageous vis-à-vis a natural talc, one of the constraints is the uncontrolled dimension of its particles.
[0027] Purity The synthetic phyllosilicate according to the invention has a degree of purity of at least 99.90%, preferably at least 99.99%. It is thus advantageously free of impurities or undesirable compounds including asbestos such as asbestos (serpentine), chlorite, carbonates, heavy metals, iron sulphides, etc., which are generally associated. with natural talc and / or incorporated into the structure of natural talc. NMR (Nuclear Magnetic Resonance) Methods Used The NMR spectra of silicon 29 (29Si) were recorded on a BRUKER Avance 400 spectrometer (9.4 T). The reference for chemical shifts is tetramethylsilane (TMS). The samples were placed in 4 mm zirconia rotors. The rotation speed around the magic angle (MAS) has been set to 8kHz. The experiments were carried out at room temperature of 21 ° C. The 295i spectra were obtained either by direct polarization (rotation of 30 °) with a recycling time of 60 s or by cross polarization (CP) between 1H and 295i (recycling time of 5 s and contact time of 3 ms). In silicon NMR (295i), natural talc has a single peak at -97 ppm.
[0028] In silicon NMR (295i), unlike natural talc, the spectrum of the synthetic phyllosilicate according to the invention reveals two peaks: one at -95 ppm and the other at -97 ppm, and without need for particle size fractionation to less than 500nm.
[0029] ATG (Thermogravimetric Analysis) Method Used The recordings were made using a Perkin Elmer Diamonds thermobalance.
[0030] For each analysis, about 20 mg of sample was needed. During the analysis, the sample is subjected to a temperature rise ranging from 30 ° C to 1200 ° C with a step of 10 ° C.min-1 under a flow of 100 ml.min-1 of air . Thermogravimetric analysis of a synthetic phyllosilicate according to the invention shows a lower thermal stability (around 800 ° C.) than that of natural talc and is characterized by four losses of mass unlike natural talc which does not has only one, around 900 ° C. To establish these losses of masses it is useful to refer to the article Angela Dumas, François Martin, Christophe Le Roux, Pierre Micoud, Sabine Petit, Eric Ferrage, Jocelyne Brendle, Olivier Grauby, Greenhill-Hooper Mike "Phyllosilicates synthesis: a NMR and FTIR spectroscopies. Example of synthetic talc "(Phys Chem Minerals, published February 27, 2013). X-Ray Diffraction Method Used The X-ray diffractogram analysis, in particular using the material and method used for the X-ray diffraction analyzes, is detailed in the application FR 2 977 580.
[0031] Preferably, since the X-ray diffraction is only on solids, to visualize the absorption spectrum in a composition comprising at least one aqueous portion, such as an emulsion, it is recommended to heat this composition. at a temperature corresponding to a temperature greater than or equal to 100 ° C (for example 120 ° C) and less than or equal to 500 ° C (for example 400 ° C) in order to eliminate the adsorbed water portion and, if appropriate, part or all of the organic compound (s) present in the composition.
[0032] The X-ray diffractogram of the synthetic phyllosilicate suitable for the invention has the same positions of the diffraction lines as those of the natural talc, with the exception of one line. Indeed, the natural talc has a diffraction line at 9.36 while the synthetic phylosilicate according to the invention has a diffraction line greater than 9.4 Å, and up to 9.8 Å. It should be noted that a synthetic phyllosilicate according to the invention is devoid of interfoliary cations. Indeed, this feature is demonstrated by the absence of an X-ray diffraction line located at a distance of between 12.00 A and 18.00 Å, usually revealing a swelling phase having interfoliary spaces in which interfoliary cations and possible water molecules. A synthetic phyllosilicate suitable for the invention may be present in an amount ranging from 0.01% to 20% by weight, preferably ranging from 0.1% to 15% by weight, more preferably ranging from 0.1% to 11% by weight. % by weight, still more preferably from 0.5% to 11% by weight, more preferably from 0.5% to 7% by weight, more preferably from 1% to 6% by weight, and even more preferably from 2% to % to 5% by weight relative to the total weight of the composition. It is understood that when a synthetic phyllosilicate according to the invention is in gel form, the "% by weight" means "% by weight of dry matter" or "% by weight of active material".
[0033] According to an alternative embodiment, when a synthetic phyllosilicate which is suitable for the invention is in the form of an aqueous or aqueous-alcoholic gel, it may constitute part but also totally the aqueous phase of the composition containing it. According to a particular embodiment, a synthetic phyllosilicate which is suitable for the invention in the form of an aqueous gel constitutes the aqueous phase of a composition according to the invention, that is to say that the aqueous phase of the composition is exclusively consisting of this gel. According to a preferred embodiment, a synthetic phyllosilicate that is suitable for the invention is present in an amount ranging from 0.5 to 20% by weight of active material, preferably from 1% to 15% by weight, and even more preferably ranging from from 2% to 10% by weight, based on the total weight of the aqueous phase.
[0034] As stated above, a synthetic phyllosilicate that is suitable for the invention can act as a hydrophilic gelling agent and / or as a filler in a composition according to the invention.
[0035] HYDROPHILIC GELIFIFIERS The compositions according to the invention comprise at least one aqueous phase gelled by at least one hydrophilic gelling agent. As described above, a synthetic phyllosilicate suitable for the invention can act as a hydrophilic gelling agent. Nevertheless, a composition according to the invention may comprise, as hydrophilic gelling agents in the gelled aqueous phase, other components such as those defined below. Thus, according to one particular embodiment, a composition according to the invention contains, as hydrophilic gelling agent, at least one synthetic phyllosilicate that is suitable for the invention. In this particular embodiment, the synthetic phyllosilicate suitable for the invention can also act as a filler.
[0036] According to another particular embodiment, a composition according to the invention contains, as hydrophilic gelling agents, at least one synthetic phyllosilicate that is suitable for the invention and at least one additional hydrophilic gelling agent, different from a synthetic phyllosilicate that is suitable for the invention. In this particular embodiment, the synthetic phyllosilicate suitable for the invention can also act as a filler. According to another particular embodiment, a composition according to the invention contains, as hydrophilic gelling agent, at least one hydrophilic gelling agent, other than a synthetic phyllosilicate that is suitable for the invention. In this particular embodiment, a synthetic phyllosilicate suitable for the invention is however necessarily present within the composition and then plays the role of charge. The term "hydrophilic gelling agent" in the sense of the present invention, a compound capable of gelling the aqueous phase of the compositions according to the invention. The gelling agent is hydrophilic and is therefore present in the aqueous phase of the composition.
[0037] The gelling agent may be water-soluble or water-dispersible. As specified above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent.
[0038] The hydrophilic gelling agent is chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, mixed silicates and pyrogenic silicas, and mixtures thereof.
[0039] I. Natural or Naturally Polymeric Gelling Agents Polymeric hydrophilic gelling agents suitable for the invention may be natural or of natural origin. For the purposes of the invention, the expression "of natural origin" means polymeric gelling agents obtained by modifying natural polymeric gelling agents.
[0040] These gelling agents may be particulate or non-particulate. More specifically, these gelling agents fall within the category of polysaccharides. In general, the polysaccharides can be distinguished into several categories. Thus the polysaccharides suitable for the invention may be homopolysaccharides such as fructans, glucans, galactans and mannans or heteropolysaccharides like hemicellulose. Similarly, they may be linear polysaccharides like pullulan or branched in the image of gum arabic and amylopectin, or mixed in the image of starch.
[0041] More particularly, the polysaccharides suitable for the invention can be distinguished according to whether they are starchy or non-starchy. Amylaceous Polysaccharides Representative of this category may be particularly mentioned, native starches, modified starches and particulate starches. Native starches The starches which can be used in the present invention are more particularly macromolecules in the form of polymers consisting of elementary units which are anhydroglucose (dextrose) units, linked by α (1,4) bonds, of chemical formula (C61-11005). not. The number of these units and their assembly make it possible to distinguish amylose, a molecule formed from about 600 to 1000 molecules of linearly chain-linked glucose, and amylopectin, a branched polymer around every 25 glucose residues (a (1, The total chain can make between 10,000 and 100,000 glucose residues Starch is described in particular in "KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd edition, volume 21, pages 492-507, Wiley Interscience, 1983". The relative proportions of amylose and amylopectin, as well as their degree of polymerization, vary according to the botanical origin of the starches.On average, a native starch sample consists of approximately 25% amylose and 75% amylopectin.
[0042] Sometimes, there is presence of phytoglycogen (between 0% and 20% starch), an analogue of amylopectin but branched every 10 to 15 glucose residues. The starch can be in the form of semi-crystalline granules: amylopectin is organized in sheets, amylose forms a less well-organized amorphous zone between the different layers.
[0043] The amylose is organized into a right helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, more easily if it is in the form of amylopectin. Indeed, helical formation does not promote the accessibility of starch to enzymes. The starches are generally in the form of a white powder insoluble in cold water, the size of the elementary particles is from 3 to 100 microns. By treating it with hot water, we obtain the poisoning. It is used in the industry for its thickener and gelling properties. The starch molecules used in the present invention may have as botanical origin cereals or tubers. Thus, the starches are for example selected from starches of maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, pea. The native starches are represented, for example, by the products sold under the names C * Amilogel ™, Cargill Ge1 ™, C * Ge1 ™, Cargill Gum ™, Dry Ge1 ™, C * Pharm Ge1 ™ by the company Cargill, under the name Amidon de Mais 30 by Roquette. and under the name Tapioca Pure by the company National Starch.
[0044] Modified starches The modified starches used in the composition of the invention may be modified by one or more of the following reactions: pre-gelatinization, degradation (acid hydrolysis, oxidation, dextrinisation), 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 giving rise to very rapid retrogression during 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 the introduction of carboxyl groups into the starch molecule (mainly oxidation of the group C6 hydroxyl); 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 bonded together (for example with glyceryl and / or phosphate groups); Alkaline esterification for the grafting of functional groups, in particular C 1 -C 6 acyl (acetyl), C 1 -C 6 hydroxyalkyl (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic. In particular, it is possible to obtain, by means of crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-O-PO- (OX) 2 type), diamidon phosphates (of the Am-O-PO- (OX) -O- type). Am) or even triamidon (of the type Am-O-PO- (O-Am) 2) or mixtures thereof. X denotes in particular alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonium salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1,2-propanediol, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline.
[0045] The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate. According to the invention, it is also possible to use amphoteric starches, these amphoteric starches contain one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites, preferably they are bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type and preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type. The amphoteric starches are in particular chosen from the compounds of the following formulas: ## STR2 ## CH-CH-COOM R 'R (I) COOM R 1 I CH-CH-COOM St Embedded image in which: ## STR2 ## wherein: ## STR5 ## wherein: ## STR5 ## wherein: ## STR5 ## wherein a starch molecule; R, which may be identical or different, represents a hydrogen atom or a methyl radical; R ', which may be identical or different, represents a hydrogen atom, a methyl radical or a -COOH group; n is an integer equal to 2 or 3; M, identical or different, denotes a hydrogen atom, an alkali metal or alkaline earth metal such as Na, K, Li, NH 4, a quaternary ammonium or an organic amine; "represents a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms. These compounds are described in particular in US Pat. Nos. 5,455,340 and 4,017,460. The starch molecules can be derived from all plant sources of starch such as, in particular, maize, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above. The modified starches are represented for example by the products sold under the names C * Tex-Instant (pre-gelatinized adipate), C * StabiTex-Instant 20 (pre-gelatinized phosphate), C * PolarTex-Instant (pre-gelatinized hydroxypropyl) , C * Set (acid hydrolysis, oxidation), C * size (oxidation), C * BatterCrisp (oxidation), C * DrySet (dextrinisation), C * TexTM (acetylated diamidon adipate), C * PolarTexTM (hydroxypropylated diamidon phosphate) ), C * StabiTexTM (diamidon phosphate, acetylated diamidon phosphate) by the company Cargill, diamidon phosphates or compounds rich in diamidon phosphate, such as the product sold under the references PREJEL VA-70-T AGGL (phosphate hydroxypropylated manioc diamidon gelatinized) or PREJEL TK1 (gelatinized manioc diamidon phosphate) or PREJEL 200 (gelatinized acetylated manioc diamidon phosphate) by the company AVEBE or STRUCTURE ZEA by NATIONAL STARCH (cornstarch phosphate gelatinis e).
[0046] As examples of oxidized starches, use will be made in particular those marketed under the name C * size of the company Cargill.
[0047] The native or modified starches described above may advantageously be used in a proportion of 0.1% to 8% by weight of dry matter, and preferably about 1% by weight, relative to the total weight of the product. the aqueous phase.
[0048] Particle starches In particular, particulate starches may be mentioned: starches grafted with an acrylic polymer (homopolymer or copolymer) and especially with sodium polyacrylate, for example those sold under the name Sanfresh ST-100 ™ by the company Sanyo Chemical Industries or Makimousse 25, Makimousse 12 by the company Daito Kasei (INCI name Sodium Polyacrylate Starch); hydrolysed starches grafted with an acrylic polymer (homopolymer or copolymer) and especially acryloacrylamide / sodium acrylate copolymer, for instance 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.
[0049] Especially noteworthy are the (C 1 -C 4) carboxyalkyl starches, hereinafter referred to as "carboxyalkyl starch". These compounds are obtained by grafting carboxyalkyl groups on one or more alcohol functions of the starch, in particular by reaction of starch and sodium monochloroacetate in an alkaline medium. The carboxyalkyl groups are generally attached through an ether function, more particularly to carbon 1. The degree of carboxyalkyl substitution of the (C 1 -C 4) carboxyalkyl of starch is preferably from 0.1 to 1, and more particularly from 0.15 to 0.5. The degree of substitution is defined according to the present invention as the average number of hydroxyl groups substituted by an ester or ether group per monosaccharide unit of the polysaccharide.
[0050] The carboxyalkyl starches are advantageously used in the form of salts and especially of alkali metal or alkaline earth metal salts such as Na, K, Li, NH 4, a quaternary ammonium or an organic amine such as mono, di or triethanolamine.
[0051] The (C 1 -C 4) carboxyalkyl starches are advantageously in the context of the present invention carboxymethyl starches. The carboxymethyl starches preferably comprise units of the following formula: ## STR2 ## in which X, whether or not covalently linked to the carboxylic unit, denotes a hydrogen atom, an alkali metal or alkaline earth metal, such as Na, K, Li or N, 14, a quaternary ammonium or an organic amine such as for example such as mono, di or triethanolamine. Preferably, X denotes a Nat cation. The carboxyalkyl starches which can be used according to the present invention are preferably non-pregelatinized carboxyalkyl starches. The carboxyalkyl starches which can be used according to the present invention are preferably cross-linked carboxyalkyl starches, partially or totally. In general, a cross-linked carboxyalkyl starch has, as opposed to a non-crosslinked carboxyalkyl starch, an increased, controllable and increased stability viscosity. The crosslinking thus makes it possible to reduce the syneresis phenomena and to increase the resistance of the gel to shearing effects. The carboxyalkyl starches considered according to the invention are more particularly potato carboxyalkyl starches. Thus, the carboxyalkyl starches which can be used according to the present invention are preferably sodium salts of carboxyalkyl starch, in particular a sodium salt of potato carboxymethyl starch sold, for example, under the name PRIMOJEL® by the company DMV International or GLYCOLYS® and GLYCOLYS® LV by the Roquette Company. According to a particular mode, use will be made of potato carboxymethyl starches sold in particular under the name GLYCOLYS® by the Roquette Company.
[0052] As stated above, the starch-containing carboxyalkyl (C 1 -C 4) particles are present in the compositions according to the invention in an inflated and unexploded form. This swelling may be characterized by a swelling power Q which may advantageously be from 10 to 30 ml / g, preferably from 15 to 25 ml (volume of absorbed liquid) / g of dry particulate material. Thus, the size of the swollen carboxyalkyl starch particles used according to the present invention generally varies from 25 to 300 μm. For example, PRIMOJEL® gel at 10% by weight of potato carboxyalkyl starch and sodium salt in water contains more than 80% of swollen particles of this starch having a diameter greater than 50 microns, and more particularly greater than 100 microns. According to a preferred embodiment of the invention, these particles are used for the preparation of the compositions according to the invention, in this swollen particulate state. To do this, these particles are advantageously used in the form of an aqueous gel either prepared beforehand or already commercially available. The gels considered according to the invention are advantageously translucent. For example, a carboxymethyl starch gel such as PRIMOJEL® which is at a concentration of 10% by weight can be adjusted to the required concentration before being used to prepare the expected cosmetic composition. Such a particulate starch can be used in a proportion of 0.1% to 5% by weight of dry matter relative to the total weight of the aqueous phase, preferably between 0.5% and 2.5% by weight, and in particular at about 1.5% by weight, based on the total weight of the aqueous phase. Non-starch polysaccharides In general, the non-starch polysaccharides may be chosen from polysaccharides prepared by microorganisms; polysaccharides isolated from algae, polysaccharides from higher plants, such as homogeneous polysaccharides, in particular celluloses and its derivatives or fructans, heterogeneous polysaccharides such as gums arabic, galactomannans, glucomannans, pectins, and their derivatives; and their mixtures. In particular, the polysaccharides may be chosen from fructans, gellanes, glucans, amylose, amylopectin, glycogen, pullulan, dextrans, celluloses and their derivatives, in particular methylcelluloses, hydroxyalkylcelluloses and ethylhydroxyethylcelluloses. and carboxymethylcelluloses, mannans, xylans, lignins, arabans, galactans, galacturonans, alginate compounds, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, and the like. pectic acids and pectins, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabic, Tragacanth gums, Ghatti gums, Karaya gums, locust bean gum, galactomannan such as guar gums. and their nonionic derivatives, in particular hydroxypropyl guar, and ionic, biopolysaccharide gums of microbial origin, and especially scleroglucan or xanthan gums, mucopolysaccharides, and especially chondroitin sulphates and mixtures thereof.
[0053] These polysaccharides can be modified chemically, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, amidation, alkylation, or by several of these modifications. The derivatives obtained can be anionic, cationic, amphoteric or non-ionic. Advantageously, the polysaccharides may be chosen from carrageenans, in particular kappa-carrageenan, gellan gum, agar-agar, xanthan gum, and alginate-based compounds, in particular alginate. sodium, saroglucan gum, guar gum, inulin, pullulan, and mixtures thereof.
[0054] In general, the compounds of this type which can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and Vol. 15, pp 439-458 ", in" Polymers in Nature, by EA Mc GREGOR and CT GREENWOOD, John Wiley & Sons Editions, Chapter 6, pp 240-328, 1980 ", in 25 by Robert L. DAVIDSON entitled "Handbook of Water Soluble Gums and Resins" edited by Mc Graw Hill Book Company (1980) and in the Industrial Gums "Polysaccharides and their Derivatives", Edited by Roy L. WHISTLER, Second Edition, Edition Academic Press Inc. " Such a gelling agent may be used in a proportion of 0.1% to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1 to 6% by weight, preferably from 0, 5% and 2.5% by weight, in particular about 1%, or about 1.5% by weight relative to the total weight of the aqueous phase.
[0055] More specifically, these polysaccharides suitable for the invention can be distinguished according to whether they are derived from microorganisms, algae or higher plants, and are detailed below.
[0056] Polysaccharides Produced by Xanthan Microorganisms 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 β3 (1,4) -linked β-D-glucoses, similar to cellulose. One out of every two glucose molecules carries a trisaccharide side chain composed of a-D-mannose, a P-D-glucuronic acid and a terminal P-D-mannose. The internal mannose residue is generally acetylated on the carbon 6. About 30% of the end mannose residues carry a pyruvate group bound in chelated form between the carbons 4 and 6. The glucuronic acids and the charged pyruvic acids are ionizable, and therefore responsible. the anionic nature of xanthan (negative charge up to pH 1). The contents of the pyruvate and acetate residues vary according to the strain of bacteria, the fermentation process, the conditions after fermentation and the purification steps. These groups can be neutralized in commercial products with Na +, K + or Ca 'ions (SATIA Company, 1986). The neutralized form can be converted to acid form by ion exchange or by dialysis of an acidic solution. The xanthan gums have a molecular weight of between 1,000,000 and 50,000,000 and a viscosity of between 0.6 and 1.65 Pa.s for an aqueous composition containing 1% of xanthan gum (measured at 25 ° C. using a viscometer). Brookfield, LVT type at 60 rpm).
[0057] The xanthan gums are represented for example by the products sold under the names Rhodicare by the company Rhodia Chimie, under the name Satiaxanetm by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industry), under the name NOVAXANTM by ADM, and under the names Kelzan® and Keltrol® by CP-Kelco.
[0058] Pullulan Pullulan is a polysaccharide consisting of maltotriose units, known as a (1,4) -a (1,6) -glucan. Three units of glucose in maltotriose are connected by a glycosidic linkage to a (1,4), while the consecutive maltotriose units are connected to each other via a glycosidic linkage to a (1,6). The pullulan is for example produced under the reference Pullulan PF 20 by the Hayashibara group in Japan. Dextran and Dextran Sulfate Dextran is a neutral, biologically inert, charged group-free polysaccharide prepared by fermentation of beet sugar containing only hydroxyl groups. It is possible to obtain from the native dextran by hydrolysis and purification, dextran fractions of different molecular weights. Dextran may in particular be in the form of dextran sulfate. Dextran is represented, for example, by the products sold under the name Dextran or Dextran T by the company Pharmacosmos, under the name Dextran 40 powder or Dextran 70 powder by the company Meito Sangyo Co. Dextran sulphate is marketed by the company PK Chemical A / S under the name Dextran sulphate. Succinoglycan Succinoglycan is an extracellular polymer produced by bacterial fermentation, of high molecular weight and consisting of repeated units of octasaccharides (repetition of 8 sugars). Succinoglycans are, for example, sold under the name Rheozan by Rhodia. Scleroglucan Scleroglucan is a nonionic branched homopolysaccharide consisting of 30 P-D glucan units. The molecules consist of a main linear chain consisting of D-glucose units linked by P (1,3) bonds and of which one in three is linked to a lateral D-glucose unit via a p (1,6) bond.
[0059] A more complete description of scleroglucans and their preparation can be found in US 3,301,848. Scleroglucan is for example sold under the name AMIGEL by the company ALBAN MULLER, or under the name ACTIGUMTM CS by the company 5 Cargill. Gellan gum Gellan gum is an anionic linear heteropolyoside based on 4 -oseose oligoside units (tetra-oside). D-glucose, L-rhamnose and D-glucuronic acid in 2: 1: 1 ratios are present in the gellan gum as monomeric elements. It is for example sold under the name KELCOGEL CG LA by the company CP KELCO.
[0060] Polysaccharides Isolated from Galactan Algae The polysaccharide according to the invention may 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 Gigartinacae, Hypneaceae, Furcellariaceae and Polyideaceae. They are generally obtained by hot aqueous extraction from natural strains of said algae. These linear polymers, formed by disaccharide units, are composed of two D-galactopyranose units alternately linked by α (1,3) and 13 (1,4) bonds. These are highly sulphated polysaccharides (20-50%) and the α-D-galactopyranosyl residues may be in the form of 3,6-anhydro. 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, iotacarraghenans which have two ester-sulfate groups and lambda carrageenans which have three ester sulfate groups.
[0061] The carrageenans consist essentially of potassium, sodium, magnesium, triethanolamine and / or calcium salts and polysaccharide sulfate esters. Carrageenans are marketed by Seppic under the name Solagum®, by Gelymar under the name Carragel®, Carralact® and Carrasol® by Cargill under the trade names SATIAGELTM and SATIAGUMTm. CP-Kelco company under the name GENULACTA®, GENUGEL® and GENUVI SC 0 Agaract galactans are galactose polysaccharides contained in the cell wall of some of these species of red algae (rhodophyceae). They are formed of a polymer group whose base skeleton is a chain f3 (1,3) Dgalactopyranose and a (1,4) L 3-6 anhydrogalactose, these units repeating regularly and alternately. Differences within the agar family are due to the presence or absence of methylated or carboxyethylated solvated groups. These hybrid structures are generally present in variable percentage, depending on the species of algae and the season of harvest. Agar-agar is a mixture of polysaccharides (agarose and agaropectin) of high molecular weight, between 40,000 and 300,000 g.mo1-1. It is obtained by making algae extraction juices, usually by autoclaving, and treating these juices which comprise about 2% agar-agar, in order to extract it. The agar is for example produced by the group B & V Agar Producers, under the name Gold Agar, Agarite and Grand Agar by the company Hispanagar, and under the names Agar-Agar, QSA (Quick Soluble Agar), and Puragar by the company Setexam .
[0062] Furcellarane Furcellaran is obtained commercially from red algae Furcellaria fasztigiata. Furcellarane is for example produced by the company East-Agar. Alginate Compound For the purposes of the invention, the term "alginate-based compound" means alginic acid, alginic acid derivatives and alginic acid salts (alginates) or derivatives thereof. .
[0063] Preferably, the alginate compound is water soluble. Alginic acid, a natural substance derived from brown algae or certain bacteria, is a polyuronic acid composed of 2 uronic acids linked by (1,4) glycosidic linkages: PD-manuronic acid (M) and acid aL -glucuronic (G).
[0064] The alginic acid is capable of forming water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, substituted amine and substituted ammonium cations such as methylamine, ethanolamine, diethanolamine, triethanolamine. These alginates are water-soluble in aqueous medium at a pH of 4 but dissociate in alginic acid at a pH below 4.
[0065] This (s) compound (s) based on alginate is (are) capable (s) to crosslink in the presence of at least one crosslinking agent, by formation of ionic bonds between the (s) said (s) compound (s) based on alginate and said (s) agent (s) crosslinking. The formation of multiple crosslinks between several molecules of the said alginate-based compound (s) causes the formation of a water-insoluble gel.
[0066] Alginate-based compounds having a weight average molecular weight of from 10,000 to 1,000,000, preferably from 15,000 to 500,000, and preferably from 20,000 to 250,000, are preferably used. In a preferred embodiment, the alginate compound is alginic acid and / or a salt thereof.
[0067] Advantageously, the alginate compound is an alginate salt, and preferably sodium alginate. The alginate-based compound may be chemically modified, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, alkylation, or several of these modifications. The derivatives obtained can be anionic, cationic, amphoteric or nonionic. The alginate compounds suitable for the invention can be represented, for example, by the products sold under the names Kelcsol, Satigaline, 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 3028758 32 by the company KIMICA, and under the names Manucol and Manugel by the company ISP. This class of polysaccharides can be divided into homogeneous polysaccharides (a single species of oses) and heterogeneous compounds composed of several types of monosaccharides. a) Homogeneous polysaccharides and their derivatives The polysaccharide according to the invention may be chosen from celluloses and derivatives or fructans. Cellulose and derivatives The polysaccharide according to the invention may also be a cellulose or one of its derivatives in particular ethers or cellulose esters (eg methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylpropylcellulose, cellulose acetate, cellulose nitrate nitrocellulose). The invention may also contain a cellulosic associative polymer. According to the invention, the term "cellulosic compound" is intended to mean any polysaccharide compound having in its structure linear chains of anhydroglucopyranose (AGU) residues united by glycoside bonds f3 (1,4). The repetition pattern is the cellobiose dimer. The AGUs are in chair conformation and have 3 hydroxyl functions: 2 secondary alcohols (in position 2 and 3) and a primary alcohol (in position 6).
[0068] The polymers thus formed combine with each other by intermolecular links of the hydrogen bonding type, thus conferring a fibrillar structure on the cellulose (about 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.
[0069] The cellulose has the following chemical structure: The hydroxyl groups of the cellulose may react partially or totally with different chemical reagents to give cellulose derivatives having their own properties. The cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Among these derivatives, there are cellulose ethers, cellulose esters and cellulose ether esters. Among the nonionic cellulose ethers, mention may be made of alkylcelluloses such as methylcelluloses and ethylcelluloses; hydroxyalkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed hydroxyalkyl-alkylcellulose celluloses such as hydroxypropylmethylcelluloses, hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses and hydroxybutyl-methylcelluloses. Among the anionic cellulose ethers, there may be carboxyalkylcelluloses and their salts. By way of example, there may be carboxymethylcelluloses, carboxymethylmethylcelluloses and carboxymethylhydroxyethylcelluloses and their sodium salts. Among the cationic cellulose ethers, mention may be made of quaternized hydroxyethylcelluloses which may or may not be crosslinked.
[0070] The quaternizer may be especially glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. Another cationic cellulose ether that may be mentioned is hydroxyethylcellulosehydroxypropyltrimethylammonium. The quaternized cellulose derivatives are, in particular: quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof ; they can be cited as the quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12alkyl) and QUATRISOFT LM-X. 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA. Among the cellulose derivatives, mention may also be made of: - celluloses modified with groups comprising at least one fatty chain, for example hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl groups, especially C 8- C22, arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS (C16 alkyl) sold by AQUALON, and - celluloses modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM- 1500 (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol. Among the cellulose esters, there are the inorganic esters of cellulose (cellulose nitrates, sulphates or phosphates, etc.), the organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetate butyrates, acetate propionates or acetatetrimellitates). .) and mixed organic / inorganic cellulose esters such as cellulose acetate-butyrate sulphates and cellulose acetate propionates. Among the cellulose ether esters, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulphates. The cellulosic compounds of the invention may be selected from unsubstituted celluloses and substituted celluloses. The celluloses and derivatives are represented for example by the products sold under the names Avicel® (microcrystalline cellulose, MCC) by the company FMC 3028758 Biopolymers, under the name Cekol (carboxymethylcellulose) by the company Noviant (CP-Kelco), under the name Akucell AF (sodium carboxymethylcellulose) by the company Akzo Nobel, under the name MethocelTM (cellulose ethers) and EthocelTM (ethylcellulose) by the company DOW, under the names Aqualon® 5 (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel® (methylcellulose), BlanoseTM (carboxymethylcellulose), Culminai® (methylcellulose, hydroxypropyl methylcellulose), Klucel® (hydroxypropylcellulose), Polyaryl (cetyl hydroxyethylcellulose) and Natrosol® CS (hydroxyethylcellulose) by Hercules Aqualon.
[0071] Fructosans The polysaccharide according to the invention may in particular be a fructosan selected from among inulin and its derivatives (in particular dicarboxy and carboxymethyl inulines). The fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with a plurality of different saccharide residues of fructose. The fructans can be linear or branched. The fructans can be products obtained directly from a plant or microbial source or products whose chain length has been modified (increased or reduced) by fractionation, synthesis or hydrolysis, in particular enzymatic. The fructans generally have a degree of polymerization of from 2 to about 1000, and preferably from 2 to about 60. There are 3 groups of fructans. The first group corresponds to products whose fructose units are mostly linked by bonds (3 (2,1). These are essentially linear fructans than inulin.
[0072] The second group also corresponds to linear fructoses but the fructose units are essentially linked by (3) (2,6) linkages.These products are levans.The third group corresponds to mixed fructans, that is to say having (3 (2,6) and (3 (2,1) These are essentially branched fructans than the graminans.
[0073] The preferred fructans in the compositions according to the invention are inulins. Inulin can be obtained for example from chicory, dahlia or Jerusalem artichoke, preferably from chicory. In particular, the polysaccharide, especially inulin, has a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60, and a degree of substitution of less than 2 based on a fructose unit. The inulin used for this invention is represented, for example, by the products sold under the name Beneo ™ Inulin by the company Orafti and under the name Frutafit® by the company Sensus. B) Heterogeneous Polysaccharides and Their Derivatives The polysaccharides that may be used according to the invention may be gums, for example cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum or arabic gum.
[0074] Gum arabic Gum arabic is a highly branched acidic polysaccharide which is in the form of mixtures of potassium, magnesium and calcium salts. The monomeric elements of the free acid (arabic acid) are D-galactose, L-arabinose, L-rhamnose and D-glucuronic acid. Galactomannans (guar, carob, fenugreek, tara gum) and derivatives (phosphated guar, hydroxypropyl guar ...) Galactomannans are nonionic polysaccharides extracted from the albumen of 25 legume seeds of which they constitute the reserve carbohydrate. Galactomannans are macromolecules consisting of a main chain of F3 (1,4) -linked D-mannopyranose units, bearing lateral branches consisting of a single unit D-galactopyranose linked in a (1,6) to the chain main. The different galactomannans are distinguished on the one hand by the proportion of α-D-galactopyranose units present in the polymer, and on the other hand by significant differences in terms of distribution of the galactose units along the mannose chain.
[0075] The ratio mannose / galactose (M / G) is of the order of 2 for guar gum, 3 for tara gum and 4 for locust bean gum. The galactomannans have the following chemical structure: L: 11. () 1-1 L sr :: 1 r: rn - = 2: Te 5 Guar Guar gum is characterized by a mannose: galactose ratio of about 2 1. The galactose group is regularly distributed along the mannose chain. The guar gums that may be used according to the invention may be nonionic, cationic or anionic. According to the invention, non-ionic guar gums which are chemically modified or unmodified can be used. The unmodified nonionic guar gums are, for example, the products sold under the name Vidogum GH, Vidogum G and Vidocrem by the company Unipektin and under the name Jaguar by the company Rhodia, under the name Meypro® Guar by the company Danisco, under the name the name VISCOGUMTM by the company Cargill, and under the name Supercol® guar gum by the company Aqualon. The hydrolyzed nonionic guar gums that can be used according to the invention are for example represented by the products sold under the name Meyprodor® by Danisco. The modified nonionic guar gums which may be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups, among which, by way of example, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups may be mentioned. Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names Jaguar HP 60, Jaguar HP 105 and Jaguar HP 120 (hydroxypropyl guar), by Rhodia, or under the name N-Hance HP (hydroxypropyl guar) by AQUALON. The cationic galactomannan gums preferably have a cationic charge density less than or equal to 1.5 meq / g and more particularly between 0.1 and 1 meq / g. The charge density can be determined according to the Kjeldahl method. It generally corresponds to a pH of the order of 3 to 9. In general, for the purposes of the present invention, the term "cationic galactomannan gum" means any galactomannan gum containing cationic groups and / or ionizable groups. in cationic groups.
[0076] The preferred cationic groups are selected from those having primary, secondary, tertiary and / or quaternary amine groups. The cationic galactomannan gums used generally have a weight average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6.
[0077] The cationic galactomannan gums which can be used according to the present invention are, for example, gums comprising trialkyl (C 1 -C 4) ammonium cationic groups. Preferably, 2% to 30% by number of the hydroxyl functions of these gums carry cationic trialkylammonium groups. Among these trialkylammonium groups, trimethylammonium and triethylammonium groups may be mentioned in particular. Even more preferentially, these groups represent from 5% to 20% by weight of the total weight of the modified galactomannan gum. According to the invention, the cationic galactomannan gum is preferably a guar gum comprising hydroxypropyltrimethylammonium groups, that is to say a guar gum modified, for example, with 2,3-epoxypropyltrimethylammonium chloride. These galactomannan gums, in particular guar gums modified with cationic groups, are products already known in themselves and are for example described in patents US Pat. Nos. 3,589,578 and 4,031,307. Such products are sold in particular under the trade names of Jaguar EXCEL, Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 (Guar Hydroxypropyltrimonium Chloride) by the company Rhodia, under the name Amilan® Guar (Guar Hydroxypropyltrimonium 3028758 39 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 containing groups derived from carboxylic, sulfonic, sulfenic, phosphoric, phosphonic acid or pyruvic acid. Preferably, the anionic group is a carboxylic acid group. The anionic group may also be in the form of an acid salt, especially a salt of sodium, calcium, lithium or potassium. The anionic guar gums which can be used according to the invention are preferably carboxymethyl guar derivatives (carboxymethyl guar or carboxymethyl hydroxypropyl guar). Carob The carob gum is extracted from carob seeds (Ceratonia siliqua). The unmodified carob gum that can be used in this invention is sold for example under the trademark ViscogumTM by the company Cargill, under the name Vidogum L by the company Unipektin, under the name Grinsted® LBG by the company Danisco. The chemically modified carob gums which can be used in this invention can be represented, for example, by the cationic carob sold under the name Catinal CLB (carob Hydroxypropyltrimonium Chloride) by the company Toho. TARA gum The Tara gum which can be used in the context of this invention is sold for example under the name Vidogum SP by the company Unipektin. Glucomannans (konj ac gum) Glucomannan is a high molecular weight polysaccharide (500,000 <Mglucomannan <2,000,000), composed of D-mannose units and D-glucose with a branch every 50 or 60 units about. It is found in wood but it is also the main constituent of Konjac gum. Konjac (Amorphophallus konjac) is a plant of the family Araceae.
[0078] The products that can be used according to the invention are for example sold under the name Propol® and Rheolex® by the company Shimizu. Pectins LM and HM, and Derivatives Pectins are linear polymers of α-D-galacturonic acid (at least 65%) linked at the 1- and 4-positions, with a certain proportion of carboxylic groups esterified with a methanol group. About 20% of the sugars constituting the pectin molecule are neutral sugars (L-rhamnose, D-glucose, D-galactose, L-arabinose, D-xylose). The residues of L-rhamnose are found in all the pectins, integrated in the main chain in positions 1,2. Uronic acid molecules have carboxyl functions. This function gives the pectins the ability to exchange ions when they are in C00- form. Bivalent ions (especially calcium) have the ability to form ionic bridges between two carboxyl groups of two different pectin molecules.
[0079] In the natural state, a certain proportion of the carboxylic groups are esterified with a methanol group. The degree of natural esterification of a pectin can vary between 70% (apple, lemon) and 10% (strawberry) depending on the source used. From pectins of high degree of esterification, it is possible to hydrolyze the -COOCH 3 groups, in order to obtain weakly esterified pectins. Depending on the proportion of methyl or non-methyl monomers, the chain is therefore more or less acidic. HM pectins (High methoxy) having a degree of esterification greater than 50% and LM (Low Methoxy) pectins having a degree of esterification of less than 50% are thus defined. In the case of amidated pectins, the -OCH3 group is substituted with a -NH2 group.
[0080] The pectins are in particular sold by 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 that may be used according to the invention, mention may also be made of chitin (Poly N-acetyl-D-glucosamine, (3 (1,4) -2-acetamido-2-deoxy-Dglucose), chitosan and derivatives (chitosan-beta-glycerophosphate, carboxymethylchitine, 3028758 41 etc.), such as those sold by France-Chitin, Glycosaminoglycans (GAG) such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, and preferably hyaluronic acid, xylans (or arabinoxylans) and derivatives The arabinoxylans are polymers of xylose and arabinose, all grouped under the name "pentosans." The xylans consist of a main chain of α-1,4-linked D-xylose units on which there are three substituents (Rouau & Thibault, 1987): acid units, α-arabinofuranose units, side chains which may contain arabinose, xylose, galactose and glucuronic acid.
[0081] II. Synthetic Polymeric Gelling Agents A hydrophilic gelling agent may be at least one synthetic polymeric gelling agent chosen from crosslinked acrylic homopolymers or copolymers; associative polymers, in particular associative polymers of the polyurethane type; polyacrylamides and crosslinked and / or neutralized 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers; carboxyvinyl polymers, modified or otherwise, and mixtures thereof. For the purposes of the invention, the term synthetic means that the polymer is neither naturally existing nor derived from a polymer of natural origin.
[0082] The synthetic polymeric hydrophilic gelling agent according to the invention may be particulate or non-particulate. For the purposes of the invention, the term "particulate" means that the polymer is in the form of particles, preferably spherical.
[0083] II.A particulate synthetic polymeric gelling agents They are preferably selected from crosslinked polymers. It may in particular be crosslinked homopolymers or acrylic copolymers, preferably partially neutralized or neutralized, which are in particulate form.
[0084] According to one embodiment, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates. Preferably, it has, in the dry or non-hydrated state, an average size of less than or equal to 100 μm, preferably less than or equal to 50 μm. The average particle size corresponds to the mean diameter by mass (D50) measured by laser particle size distribution or other equivalent method known to those skilled in the art. Thus, preferably, the particulate gelling agent according to the present invention is selected from cross-linked 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 spherical particles. By way of example of crosslinked sodium polyacrylates, mention may be made of those sold under the names Octacare X100, X110 and RM100 by the company Avecia, those sold under the names Flocare GB300 and Flosorb 500 by the company SNF, those marketed under the names the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1110 by the company BASF, those sold under the names Water Lock G400 and G430 (INCI name: Acrylamide / Sodium acrylate copolymer) by the company Grain Processing.
[0085] Cross-linked polyacrylate microspheres such as, for example, those marketed under the name AQUAKEEP® 10 SH NF proposed by the company Sumitomo Seika can also be mentioned. Such gelling agents may be used in a proportion of 0.1% to 5% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.5 to 2% by weight, and in particular with from about 0.8% to 1.7% by weight relative to the total weight of the aqueous phase. MB Non-particulate synthetic polymeric gelling agents This family of gelling agents can be detailed in the following sub-families: 1. associative polymers, 2. polyacrylamides and cross-linked 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers and / or neutralized and, 3. carboxyvinyl polymers modified or not. 1. Associative Polymers For the purposes of the present invention, the term "associative polymer" means any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers according to the present invention may be anionic, cationic, nonionic or amphoteric. Associative Anionic Polymers Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly from those whose hydrophilic unit consists of an ethylenic unsaturated anionic monomer. , more particularly with a vinyl carboxylic acid and more particularly with an acrylic acid, a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (I): CH 2 = C (R) Wherein R 'denotes H or CH 3, B denotes the ethyleneoxy radical, n denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl radicals, arylalkyl, aryl, alkylaryl, cycloalkyl, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms. Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP 0 216 479. Among the associative anionic polymers, mention may also be made of terpolymers of maleic anhydride / α-olefin. C30-C38 / alkyl maleate such as the maleic anhydride copolymer / C30-C38 α-olefin / isopropyl maleate sold under the name Performa V 1608 by the company NEWPHASE TECHNOLOGIES. Among the anionic associative polymers, according to a preferred embodiment, the copolymers comprising, among their monomers, an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester may be used. Preferably, these compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester and a C 1 -C 4 alcohol ester, as an example of this type of compound. ACULYN 22® sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer (comprising 20 OE units) or ACULYN 28 (methacrylic acid / acrylate terpolymer). ethylen / behenyl methacrylate oxyethylene (250E) As associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of acidic type Olefinic unsaturated carboxylic acid, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C 10 -C 30) alkyl ester type. By way of example, mention may be made of the anionic polymers described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949. Associated anionic polymers that may also be mentioned are anionic terpolymers. The anionic terpolymer used according to the invention is a linear or branched and / or crosslinked terpolymer of at least one monomer (1) bearing an acid function in free form, partially or totally salified with a chosen nonionic monomer (2). from among NN, dimethylacrylamide and 2-hydroxyethyl acrylate and at least one polyoxyethylenated alkyl (3) acrylate monomer of the following formula (I): ## STR2 ## wherein R 1 represents a hydrogen atom, R represents a linear or branched C2-C8 alkyl radical and n represents a number ranging from 1 to 10. "Connected polymer" denotes a nonlinear polymer which has pendant chains so as to obtain, when this polymer is applied, solution in water, a high state of entanglement leading to viscosities, very low speed gradient. The term "crosslinked polymer" denotes a non-linear polymer which is in the form of a three-dimensional network which is insoluble in water but swellable with water and which leads to the production of a chemical gel. (1) is in particular the sulfonic acid, phosphonic acid function, said functions being in free form, partially or totally salified.
[0086] The monomer (1) may be chosen from styrene sulfonic acid, ethylsulfonic acid or 2-methyl-2 [(1-oxo-2-propenyl] amino] 1-propanesulfonic acid (also called Acryloyldimethyltaurate) in the form of It is present in the anionic terpolymer, preferably in molar proportions of between 5% and 95% by mole and more particularly between 10% and 90% by mole, and the monomer (1) will be more particularly present. 2-methyl-24 (1-oxo-2-propenyl] amino] 1-propanesulfonic acid 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 salt of sodium or potassium, an ammonium salt, an aminoalcohol salt such as a monoethanolamine salt or an amino acid salt such as a salt of lysine.The monomer (2) is preferably present in the anionic terpolymer in pro molar portions of between 4.9% and 90% molar and more particularly between 9.5% and 85% molar and even more particularly between 19.5% and 75% molar. In the formula (I), as an example of linear C8-C16 alkyl radical, mention may be made of octyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl. In the formula (I), as an example of a C8-C16 branched alkyl radical, mention may be made of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2hexyldecyl, 420 methylpentyl, 5-methylhexyl and 6-methylheptyl. 15-methylpentadecyl, 16-methylheptadecyl, 2-hexyloctyl. According to one particular form of the invention, in formula (I), R denotes a C 12 -C 16 alkyl radical.
[0087] According to one particular form of the invention, in formula (I), n ranges from 3 to 5. Tetraethoxylated lauryl acrylate will more particularly be used as monomer of formula (I). The monomer (3) of formula (I) is preferably present in the anionic terpolymer in molar proportions of between 0.1% and 10% by mole and more particularly between 0.5% and 5% by mole.
[0088] According to one particular embodiment of the invention, the anionic terpolymer is crosslinked and / or connected by a diethylenic or polyethylenic compound in the proportion expressed relative to the total amount of monomers used, from 0.005% to 1% molar and preferably from 0.01% to 0.5% by mole and more particularly from 0.01% to 0.25% by mole. The crosslinking agent and / or the branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxoacetic acid or a salt thereof, such as sodium diallyloxyacetate, tetraallyloxyethane, ethylene glycol diacrylate, diallyl urea, triallyl amine, trimethylol propanetriacrylate, methylenebis (acrylamide) or mixtures thereof. The anionic terpolymer may contain additives such as complexing agents, transfer agents, chain-limiting agents. More particularly, an anionic terpolymer of 2-methyl-2 - [(1-oxo-2-propenyl] amino] 1-propanesulfonic acid partially or totally salified in the form of ammonium salt, N, N-dimethylacrylamide will be used more particularly. and of lauryl acrylate tetraethoxylated and crosslinked with trimethylolpropanetriacrylate, INCI name Polyacrylate Crosspolymer-6 such as the product sold under the trade name SEPIMAX ZEN® by the company SEPPIC.
[0089] Cationic Associative Polymers As cationic associative polymers, mention may be made of polyacrylates containing amine side groups. The polyacrylates with amino side groups, quaternized or otherwise, have, for example, hydrophobic groups of the steareth type (polyoxyethylenated stearyl alcohol (20)). Examples of aminated side chain polyacrylates include polymers 8781-121B or 9492-103 from the company National Starch. Nonionic Associative Polymers The nonionic associative polymers may be chosen from: copolymers of vinylpyrrolidone and fatty-chain hydrophobic monomers; Copolymers of methacrylates or of C 1 -C 6 alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain; copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer; associative polyurethanes. The associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic sequences of a most often polyoxyethylenated nature (the polyurethanes may then be called polyurethane polyethers) and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic chains. In particular, these polymers comprise at least two hydrocarbon-based lipophilic chains having from C6 to C30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block. The associative polyurethanes can be sequenced in the form of triblock or multiblock. The hydrophobic sequences can therefore be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These polymers may also be graft or star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1,000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic blocks, hence the origin of the name. According to a preferred embodiment, a nonionic associative polymer of the polyurethane type is used as a gelling agent. As examples of fatty-chain nonionic polyurethane polyethers for use 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 ELEMENTIS or else with Rheolates 208, 204 or 212, as well as Acrysol® RM 184 or Acrysol® RM 2020. Mention may also be made of the C12 alkyl chain product ELFACOS® T210. C14 and the product C18-18 alkyl chain (C18-18) alkylated ELFACOS® T212 (AKG-14 Palmeth-60 Hexyl Dicarbamate) from AKZO. The product DW 1206B® from Rohm & Haas containing a C20 alkyl chain and a urethane linkage, proposed at 20% solids content in water, may also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of RHEOLATE® 255, RHEOLATE® 278 and RHEOLATE® 244 sold by the company ELEMENTIS. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas. The associative polyurethanes that can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380-389 (1993). More particularly still, according to the invention, it is also possible to use an associative polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate. Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names ACULYN® 46, ACULYN® 44 and ACULYN 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, of stearyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%), ACULYN® 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexyl isocyanate) (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, in particular in water or in an aqueous-alcoholic medium. By way of example, such polymers may be mentioned, SER AD FX1010, SER AD FX1035 and SER AD 1070 from ELEMENTIS, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the 3028758. 49 company ELEMENTIS. It is also possible to use Aculyn® 44, Aculyn® 46, DW 1206F and DW 1206J products, as well as Acrysol® RM 184 from the company Rohm & Haas, or even Borchi Gel LW 44 from the company BORCHERS, and their mixtures.
[0090] Amphoteric Associative Polymers Among the associative amphoteric polymers of the invention, mention may be made of the amphoteric polymers, crosslinked or non-crosslinked, branched or non-branched, which may be obtained by the copolymerization of: 1) at least one monomer of formula (IVa) or (IVb): wherein R4 and R5, which are the same or different from R4 to R4, are selected from R4 to R6 (R11) different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, 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 of 2 to 5; A- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide; 2) at least one monomer of formula (V): wherein R 9 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical; Z1 is OH or NHC (CH3) 2CH2SO3H; 3) at least one monomer of formula (VI): embedded image in which R 9 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R 11 denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms; 4) optionally at least one crosslinking agent or branching agent; at least one of the monomers of formula (IVa), (IVb) or (VI) comprising at least one fatty chain having from 8 to 30 carbon atoms and said compounds of the monomers of formula (IVa), (IVb), ( V) and (VI) may be quaternized, for example, with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. The monomers of formula (IVa) and (IVb) of the present invention are preferably chosen from the group consisting of: dimethylaminoethylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylmethacrylate, diethylaminoethylacrylate, dimethylaminopropylmethacrylate, dimethylaminopropylacrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, optionally quaternized for example with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. More particularly, the monomer of formula (IVa) is selected from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride. The compounds of formula (V) of the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-methylcrotonic acid, 2- acrylamido-2-methylpropanesulphonic acid and 2-methacrylamido-2-methylpropanesulphonic acid. More particularly, the monomer of formula (V) is acrylic acid. The monomers of formula (VI) of the present invention are preferably chosen from the group consisting of C12-C22 alkyl acrylates or methacrylates, and more particularly C16-C18 alkyl acrylates or methacrylates. (VI) The crosslinking or branching agent is preferably selected from N, N'-methylene bis-acrylamide, triallyl methyl ammonium chloride, allyl methacrylate, n-methylolacrylamide, dimethacrylate, and the like. polyethylene glycols, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose. The polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C1-C4 alkyl acrylates or methacrylates. The ratio of the number of cationic charges / anionic charges in these amphoteric polymers is preferably equal to about 1. The weight average molecular weights of the associative amphoteric polymers have a weight average molecular weight of greater than 500, preferably of between 10,000. and 10,000,000 and even more preferably between 100,000 and 800,000. Preferably, the associative amphoteric polymers of the invention contain from 1% to 99% of moles, more preferably from 20% to 95% of moles and even more preferably of 25%. at 75% moles of compound (s) of formula (IVa) or (IVb). They also preferably contain from 1% to 80% by moles, more preferably from 5% to 80% by moles and even more preferably from 25% to 75% by moles of compound (s) of formula (V). The content of compound (s) of formula (VI) is preferably between 0.1% and 70% by moles, more preferably between 1% to 50% by moles and even more preferably between 1% and 10% by moles. . The crosslinking or branching agent when present is preferably between 0.0001% and 1% moles and more preferably between 0.0001% and 0.1% moles. Preferably, the molar ratio between the compound (s) of formulas (IVa) or (IVb) and the compound (s) of formula (V) ranges from 20:80 to 95: 5 and more preferably from 25:75 to 75: 25. The associative amphoteric polymers according to the invention are for example described in the patent application WO 98/44012. The amphoteric polymers that are particularly preferred according to the invention are chosen from acrylic acid / acrylamidopropyl trimethylammonium chloride / stearyl methacrylate copolymers.
[0091] 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. .
[0092] Such an associative polymer is advantageously used in a proportion of from 0.1% to 8% by weight of dry matter and preferably from approximately 3% by weight relative to the total weight of the aqueous phase. 2. The polyacrylamides and the polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized The polymers used as aqueous gelling agent for the invention may be homopolymers or copolymers, crosslinked or not crosslinked agents comprising at least the 2-acrylamido-2-methylpropanesulphonic acid monomer (AMPS®), in form partially or completely neutralized with a mineral base other than ammonia such as sodium hydroxide or potassium hydroxide. They are preferably neutralized completely or substantially completely neutralized, that is to say neutralized to at least 90%. These AMPS® polymers according to the invention may be crosslinked or non-crosslinked.
[0093] When the polymers are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for the crosslinking of the polymers obtained by radical polymerization. Examples of crosslinking agents which may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, di (meth) acrylate and the like. ethylene glycol or tetraethylene glycol, trimethylolpropane triacrylate, methylenebisacrylamide, methylene-bis-methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane diallylether, (meth) acrylate allyl, allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and allylic esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures of these compounds.
[0094] According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The degree of crosslinking generally ranges from 0.01% to 10% by moles and more particularly from 0.2% to 2% by moles relative to the polymer.
[0095] The AMPS® polymers suitable for the invention are water-soluble or water-dispersible. They are in this case: either "homopolymers" containing 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 comprise hydrophobic ethylenically unsaturated monomers, the latter do not comprise a fatty chain and are preferably present in small amounts.
[0096] For the purposes of the present invention, the term "fatty chain" means any hydrocarbon chain containing at least 7 carbon atoms. By "water-soluble or water-dispersible" is meant polymers which, introduced in an aqueous phase at 25 ° C., at a mass concentration equal to 1%, make it possible to obtain a macroscopically homogeneous and transparent solution. have a maximum transmittance value of light, at a wavelength of 500 nm, through a sample 1 cm thick, at least 60%, preferably at least 70%. The "homopolymers" according to the invention are preferably crosslinked and neutralized, and they can be obtained according to the preparation process comprising the following steps: (a) the monomer such as VAMPS in free form is dispersed or dissolved in a solution tert-butanol or water and tert-butanol; (b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more inorganic or organic bases, preferably ammonia NH 3, in an amount which makes it possible to obtain a degree of neutralization of the sulphonic acid functions of the polymer ranging from 90 to 100%; (C) adding to the solution or dispersion obtained in (b), the crosslinking monomer (s); (d) conventional radical polymerization is carried out in the presence of free radical initiators at a temperature of from 10 to 150 ° C; the precipitating polymer in the tert-butanol solution or dispersion. The water-soluble or water-dispersible copolymers of AMPS® according to the invention contain water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof. The water-soluble comonomers may be ionic or nonionic.
[0097] Examples of ionic water-soluble comonomers include 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: ## STR2 ## in which: - Ri is chosen from H, -CH3, -C2H5 or -C3H7, - Xi is chosen from: - alkyl oxides of -OR2 type where R2 is a hydrocarbon radical, linear or branched, saturated or unsaturated , having from 1 to 6 carbon atoms, substituted with at least one sulfonic group (-SO3-) and / or sulfate (-SO4-) and / or phosphate (-PO4H2-). Among the nonionic water-soluble comonomers that may be mentioned for example: (meth) acrylamide, N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methyl N-vinylformamide, maleic anhydride, vinylamine, N-vinyllactams containing a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and Nvinylcaprolactam, the vinyl alcohol of formula CH 2 = CHOH, the water-soluble vinyl monomers of formula (B) below: I-12C R 3 CO 10 X 2 in which: R 3 is chosen from H, -CH 3, -C 2 H 5 or -C 3 E 17; X 2 is chosen from: - alkyl oxides of the type -OR 4 where R 4 is a linear or branched, saturated or unsaturated hydrocarbon radical containing from 1 to 6 carbons, optionally substituted with a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether. Examples include glycidyl (meth) acrylate, hydroxyethyl methacrylate, and ethylene glycol, diethylene glycol or polyalkylene glycol (meth) acrylates. Among the hydrophobic comonomers without fatty chain, there may be mentioned for example: styrene and its derivatives such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene; vinyl acetate of formula CH2 = CH-OCOCH3; vinyl ethers of formula CH2 = CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons; - acrylonitrile; Caprolactone; (B) 3028758 56 - 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 2 C = R 4 CO (C) X 3 in which: R 4 is chosen from H, -CH 3, -C 2 H 5 or -C 3 F 17; - X3 is chosen from: - alkyl oxides of -0R5 type where R5 is a hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms. Examples include methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate and isobornyl acrylate, and 2-hexyl ethyl acrylate.
[0098] The water-soluble or water-dispersible AMPS polymers of the invention preferably have a molar mass of 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 20 suitable for the invention, mention may be made, for example, of cross-linked or non-crosslinked polymers of 2-acrylamido-2-methylpropane sulphonate of sodium such as that used in the commercial product SIMULGEL 800 ( CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of ammonium 2-acrylamido-2-methylpropane sulfonate acid (INCI name: AMMONIUM POLYACRYLDIMEHYLTAURAMIDE) than those described in patent EP0815928B1 and such as the product sold under the name commercial HOSTACERIN AMPS® by the company Clariant. As water-soluble or water-dispersible copolymers of AMPS in accordance with the invention, mention may be made, for example, of: crosslinked acrylamide / sodium acrylamido-2-methyl propane sulfonate copolymers such as that used in the commercial product SEPIGEL 305 (CTFA name: Or the one used in the commercial product sold under the name Simulgel 600 (CTFA name: ACRYLAMIDE / SODIUM ACRYLOYLDIMETHYLTAURATE / ISOHEXADECANE / POLYSORBATE-80) by the company SEPPIC; Copolymers of AMPS® and of vinylpyrrolidone or of vinylformamide, such as that used in the commercial product sold under the name ARISTOFLEX AVC® by the company CLAMANT (CTFA name: AMMONIUM ACRYLOYLDIMETHYLTAURATE / VP COPOLYMER) but neutralized with sodium hydroxide or potash; Copolymers of AMPS® and of sodium acrylate, 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 under (CTFA name: HYDROXYETHYL ACRYLATE / SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER); Copolymers of AMPS® and of hydroxyethyl acrylate, such as, for example, the AMPS® / hydroxyethyl acrylate copolymer, such as that used in the commercial product sold under the name SIMULGEL NS® by the company SEPPIC (CTFA name: HYDROXYETHYL ACRYLATE / SODIUM ACRYLOYLDIMETHYLTAURATE COPOLYMER (AND) SQUALANE (AND) POLYSORBATE 60 or the product sold under the name COPOLYMER ACRYLAMIDO-2-METHYL PROPANE SULPHONATE SULFONATE / HYDROXYETHYLACRYLATE as the commercial product SEPINOV EMT 10 (INCI name: HYDROXYETHYL ACRYLATE / SODIUM ACRYLOYLDIMETHYL TAURATE In general, an aqueous phase according to the invention may comprise from 0.1% to 8% by weight of dry matter, preferably from 0.2% to 5% by weight and more preferably from 0% to 10% by weight. From 7% to 2.5% by weight of polyacrylamide (s) and / or polymer (s) and copolymer (s) of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized by relative to its total weight 3. Modified or Unmodified Carboxyvinyl Polymers The modified or unmodified carboxyvinyl polymers may be copolymers resulting from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or their esters. with at least one ethylenically unsaturated monomer (b) having a hydrophobic group. The term "copolymers" means both copolymers obtained from two kinds of monomers and those obtained from more than two kinds of monomers such as terpolymers obtained from three kinds of monomers. Their chemical structure more particularly comprises at least one hydrophilic unit and at least one hydrophobic unit. Hydrophobic group or unit means a hydrocarbon radical, 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 copolymers resulting from the polymerization of: at least one monomer of formula (1) below: CH 2 C-C-OH II (1) in which, R 1 denotes H or CH 3 or C 2 H 5 , ie monomers of acrylic acid, methacrylic acid or ethacrylic acid, and of at least one unsaturated carboxylic acid alkyl ester (C 10 -C 30) monomer corresponding to the monomer of formula (2) ) wherein R2 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units); R3 denotes a C1-C30 alkyl radical, and preferably a C1-C22 alkyl radical. The alkyl esters (C 10 -C 30) of unsaturated carboxylic acids are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, acrylate and the like. 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. (2) Among this type of copolymer, polymers derived from the polymerization of a monomer mixture comprising: - essentially acrylic acid; - an ester of formula (2) described above, and wherein R2 is H or CH3, R3 is an alkyl radical having 12 to 22 carbon atoms, and (iii) a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among this type of copolymer, use will more particularly be made of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit). ), and 0% to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of alkyl acrylate C 10 -C 30 (hydrophobic unit), and 0.1% to 0.6% by weight of crosslinking polymerizable monomer as previously described. Among said polymers above, acrylate / Cio-C30-alkyl acrylate copolymers (INCI name: Acrylates / Cio-3o Alkyl acrylate crosspolymer), such as the products sold by Lubrizol under the names, are particularly preferred according to the present invention. PEMULEN TR-1, PEMULEN TR-2, CARBOPOL 1382, CARBOPOL EDT 2020, CARBOPOL ULTREZ POLYMER and even more preferably PEMULEN TR-2. Among the modified or unmodified carboxyvinyl polymers, mention may also be made of sodium polyacrylates such as those sold under the name Cosmedia 25 SP® containing 90% dry matter and 10% water, or Cosmedia SPL® in inverse emulsion containing about 60 % of dry matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by Cognis. Partially neutralized sodium polyacrylates which are in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by the company BASF, may also be mentioned.
[0099] The modified or unmodified carboxyvinyl polymers may also be chosen from crosslinked (meth) acrylic acid homopolymers. By "(meth) acrylic" within the meaning of the present application, the term "acrylic or methacrylic".
[0100] By way of example, mention may be made of those sold by LUBRIZOL under the names Carbopol, 910, 934, 940, 941, 934, 980, 981, 2984, 5984, CARBOPOL ULTREZ POLYMER, or by 3V-SIGMA under the names Synthalen® K, Synthalen® L, or Synthalen® M.
[0101] Among the carboxyvinyl polymers modified or not, there may be mentioned Carbopol (CTFA name: carbomer) and Pemulen (CTFA name: Acrylates / C10-30 alkyl acrylate crosspolymer) marketed by Lubrizol. The carboxyvinyl polymers, modified or not, may be present in a proportion of from 0.1% to 5% by weight of dry matter relative to the weight of the aqueous phase, in particular from 0.3% to 1% by weight, of preferably about 1% by weight based on the weight of the aqueous phase. Advantageously, the hydrophilic gelling agent is at least one synthetic polymeric gelling agent chosen from crosslinked acrylic homopolymers or copolymers; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid, crosslinked and / or neutralized; carboxyvinyl polymers, modified or otherwise, and mixtures thereof. More particularly, it is at least one 2-acrylamido-2-methylpropanesulphonic acid polymer or copolymer, an associative polyurethane and / or a crosslinked sodium polyacrylate.
[0102] III. Other hydrophilic gelling agents These gelling agents are more particularly chosen from mixed silicates and pyrogenic silicas.
[0103] III.A Mixed Silicate For the purposes of the present invention, mixed silicate is understood to mean all silicates of natural or synthetic origin containing several (two or more) types of cations chosen from alkali metals (for example Na, Li, K) or alkaline earth (eg Be, Mg, Ca), transition metals and aluminum. These mixed silicates are different from a synthetic phyllosilicate that is suitable for the invention. According to a particular embodiment, the mixed silicate or silicates are in the form of solid particles containing at least 10% by weight of at least one silicate relative to the total weight of the particles. In the remainder of the present disclosure, these particles are referred to as "silicate particles". Preferably, the silicate particles contain less than 1% by weight of aluminum relative to the total weight of the particles. Even more preferably, they contain from 0% to 1% by weight of aluminum based on the total weight of the particles. Preferably, the silicate particles contain at least 50% by weight of silicate, more preferably at least 70% by weight relative to the total weight of the particles. Particles containing at least 90% by weight of silicates, based on the total weight of the particles, are particularly preferred. In particular, it is a silicate or a mixture of silicates of alkali or alkaline earth metals, aluminum or iron. Preferably, it is sodium silicate, magnesium and / or litium. To guarantee good cosmetic properties, these silicates are generally in 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 may be of any shape, for example the shape of spheres, flakes, needles, platelets, disks, leaflets, or totally random shapes. Preferably, the silicate particles are in the form of disks or sheets. Also, the term "average size" of the particles means the average size in number of the largest dimension (length) that can be measured between two diametrically opposed points of an individual particle. The size can be determined, for example, by transmission electron microscopy, or from the measurement of the specific surface area by the BET method, or by means of a laser granulometer.
[0104] When the particles in the form of disks 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 oxides of metals or metalloids, obtained for example by thermal melting of its various constituents. When the particles further comprise such a metal oxide or metalloid, it is preferably selected from silicon oxide, boron or aluminum. The mixed silicates that are suitable for the invention may be chosen for example from montmorillonites, hectorites, bentonites, beidellite, saponites. According to a preferred embodiment of the invention, the mixed silicates used are more particularly chosen from hectorites and bentonites, and even better from laponites. A family of silicates particularly preferred in the compositions of the present invention is that of laponites. Lapponites are magnesium, sodium, and optionally lithium silicates having a layered structure similar to that of montmorillonites. Lapponite is the synthetic form of the natural mineral called "hectorite". The synthetic origin of this family of silicates presents a considerable advantage over the natural form because it allows a good control of the composition of the product. In addition, laponites have the advantage of having a particle size well below that of natural hectorite and bentonite. As laponites, there may be mentioned in particular the products sold under the following names: Laponite® XLS, Laponite® XLG, Laponite® RD, Laponite® RDS, LAPONITE® XL21 (these products are sodium and magnesium silicates and sodium silicates , lithium and magnesium) by Rockwood Additives 25 Limited. Such gelling agents may be used in a proportion of 0.1% to 8% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1% to 5% by weight, and in particular from 0% to 5% to 3% by weight relative to the total weight of the aqueous phase.
[0105] III.B Hydrophilic pyrogenic silica The pyrogenic silicas according to the present invention are hydrophilic.
[0106] The pyrogenic hydrophilic silicas are obtained by continuous flame pyrolysis at 1000 ° C. of silicon tetrachloride (SiC14) in the presence of hydrogen and oxygen. Among the fumed silicas of hydrophilic nature which can be used according to the present invention, mention may be made in particular of those sold by Degussa or Evonik 5 Degussa under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or by the company CABOT under the name Carbosil H5. Such hydrophilic additional gelling agents may be used in amounts of 0.1% to 10% by weight of dry matter relative to the total weight of the aqueous phase, in particular from 0.1% to 5% by weight, and in particular from 0.5% to 3% by weight based on the total weight of the aqueous phase. LIPOPHILIC GELIFIFIERS The term "lipophilic gelling agent" within the meaning of the present invention, a compound capable of gelling the oily phase of the compositions according to the invention.
[0107] The gelling agent is lipophilic and therefore present in the oily phase of the composition. The gelling agent is liposoluble or lipodispersible. As is apparent from the following, the lipophilic gelling agent is advantageously chosen from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, hydrocarbon-based block copolymers, and their derivatives. mixtures. I. Particulate Gelling Agents The particulate gelling agent used in the composition according to the invention is in the form of particles, preferably spherical. As representative of the lipophilic particulate gelling agents that are suitable for the invention, polar, polar and apolar waxes, modified clays, silicas such as pyrogenic silicas and hydrophobic silica aerogels may be particularly mentioned.
[0108] Waxes The term "wax" as used in the context of the present invention generally means a lipophilic compound, solid at room temperature (25 ° C), with a reversible solid / liquid state change, having melting point greater than or equal to 30 ° C up to 200 ° C and especially up to 120 ° C. For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in the ISO 11357-3 standard; 1999. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments. The measurement protocol is as follows: A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise from -20 ° C. to 100 ° C. at a heating rate of 10 ° C./minute. , then cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / min and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 5 ° C. ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the wax sample is measured as a function of temperature. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature. The waxes that may be used in the compositions according to the invention are chosen from waxes which are solid at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof. The waxes, within the meaning of the invention, may be those used generally in the cosmetic or dermatological fields. They may in particular be polar or apolar, silicone hydrocarbon and / or fluorinated, optionally having ester or hydroxyl functions. They can also be of natural or synthetic origin. a) Apolar waxes For the purposes of the present invention, the term "apolar wax" is intended to mean a wax whose solubility parameter at 25 ° C. as defined below, Ô, is equal to 0 (J / cm 3). / 4.
[0109] 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 dimensionna" solubdiC parameters "J. Paint Technol. 39, 105 (1967). According to this Hansen space: 5 - ôt, characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular shocks; δp characterizes the Debye interaction forces between permanent dipoles as well as the Keesom interaction forces between induced dipoles and permanent dipoles; - Off, characterizes the specific interaction forces (hydrogen bond type, acid / base, donor / acceptor, etc.); - δa is determined by the equation: δa = ((1p2 151h2) 1/4 .The parameters ôp, ôn, ôD and δa are expressed in (J / cm3) 1/4 The apolar waxes are in particular the hydrocarbon waxes consisting solely of carbon and hydrogen atoms and free from heteroatoms such as N, O, Si and P. Apolar waxes are selected from microcrystalline waxes, paraffin waxes, ozokerite, polyethylene waxes Ozokerite Wax SP 1020 P may be mentioned as ozokerite. As microcrystalline waxes which may be used, mention may be made of Multiwax W 445 sold by the company Sonneborn, Microwax HW® and Base Wax 30540 ° marketed by the company. Paramelt and Cerewax® No. 3 sold by the company Baerlocher As microwaxes which can be used in the compositions according to the invention as apolar wax, mention may in particular be made of polyethylene microwires such as those sold on the market. or the names Micropoly 200®, 220®, 220L® and 2505® by the company Micro Powders. As polyethylene wax, mention may be made of Performalene 500-L Polyethylene and Performalene 400 Polyethylene marketed by New Phase Technologies, Asensa® SC 211 sold by Honeywell. B) Polar wax For the purposes of the present invention, the term "polar wax" is intended to mean a wax whose solubility parameter at 25 ° C. a is different from 0 (J / cm 3) 1/4. In particular, "polar wax" means a wax whose chemical structure is formed essentially or even consisting of carbon and hydrogen atoms, and comprising at least one highly electronegative heteroatom such as an atom of oxygen, nitrogen, silicon or phosphorus. The polar waxes may especially be hydrocarbon, fluorinated or silicone.
[0110] Preferentially, the polar waxes may be hydrocarbon-based. By "hydrocarbon wax" is meant a wax formed essentially, or even constituted, of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon atom or fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.
[0111] By "ester wax" is meant according to the invention a wax comprising at least one ester function. By "alcohol wax" is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group. In particular, ester waxes may be used: ester waxes such as those chosen from: i) waxes of formula R 1 COOR 2 in which R 1 and R 2 represent linear, branched or cyclic aliphatic chains whose number of atoms varies from 10 to 50, which may contain a heteroatom such as O, N or P and whose melting point temperature varies from 25 to 120 ° C. Ii) di- (trimethylol-1,1,1 propane) tetrastearate, sold under the name Hest 2T-4S® by the company Heterene. iii) diester waxes of a dicarboxylic acid of general formula R3 - (- OCOR4-COO-R5), in which R3 and R5 are identical or different, preferably identical, and represent a C4-C30 alkyl group (alkyl group comprising from 4 to 30 carbon atoms) and R4 represents a linear C4-C3i aliphatic group (alkyl group comprising from 4 to 30 carbon atoms) linear branched which may or may not contain one or more unsaturation (s), and preferably linear and unsaturated. Iv) We may also mention the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched, C8-C32 fatty chains, for example such as hydrogenated jojoba oil, sunflower oil hydrogenated, hydrogenated castor oil, hydrogenated coconut oil, and waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol. v) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylene lanolin wax, rice bran wax, Ouricury wax , Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, laurel wax, wax hydrogenated Jojoba, sunflower wax, lemon wax, olive wax, berry wax. According to another embodiment, the polar wax may be an alcohol wax. By "alcohol wax" is meant according to the invention a wax comprising at least one alcohol function, that is to say comprising at least one free hydroxyl (OH) group. As alcohol wax, there may be mentioned, for example, the C30-5o Alcohols Performacol® 550 Alcohol wax marketed by New Phase Technologie, stearyl alcohol, cetyl alcohol. It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably at a low melting point. By "silicone wax" is meant an oil comprising at least one silicon atom, and in particular comprising Si-O groups. Among the commercial silicone waxes of this type, mention may be made in particular of those sold under the names Abilwax 9800, 9801 or 9810 (Goldschmidt), KF910 and KF7002 (Shin Etsu), or 176-1118-3 and 176-11481 (General Electric ). The silicone waxes that may be used may also be alkyl or alkoxydimethicones, as well as (C 20 -C 60) alkyl dimethicones, in particular (C 30 -C 45) alkyl dimethicones, such as the silicone wax sold under the name SF-1642 by the company GE-Bayer. Silicones or C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane under the name SW-8005® C30 Resin Wax sold by the company Dow Corning.
[0112] In the context of the present invention, mention may be made, as particularly advantageous waxes, of polyethylene waxes, jojoba wax, candelilla wax and silicone waxes, in particular candelilla wax.
[0113] They may be present in the oily phase in a proportion of 0.5% to 30% by weight relative to the weight of the oily phase, for example between 5% and 20% of the oily phase, and more particularly of 2% at 15% by weight relative to the weight of the oily phase.
[0114] Modified clays The composition according to the invention may comprise at least one lipophilic clay. The clays can be natural or synthetic and are rendered lipophilic by treatment with an alkylammonium salt such as a C 10 -C 22 ammonium chloride, for example di-stearyl dimethyl ammonium chloride. They may be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.
[0115] Preferably, they are selected from hectorites. Preferably, the lipophilic clays used are hectorites modified with a C 10 -C 22 ammonium chloride, such as hectorite modified with distearyl dimethyl ammonium chloride such as, for example, that sold under the name Bentone 38V® by Elementis or bentone gel in isododecane sold under the name Bentone Gel ISD V® (Isododecane 87% / Disteardimonium Hectorite 10% / Propylene carbonate 3%) by Elementis. Lipophilic clay may in particular be present in a content ranging from 0.1% to 15% by weight, in particular from 0.5% to 10%, more particularly from 1% to 10% by weight relative to the total weight. oily phase.
[0116] Silicas The oily phase of a composition according to the invention may also comprise, as gelling agent, fumed silica or silica airgel particles. A) Pyrogenic Silica Particularly suitable for the invention, the hydrophobic treated silica treated surface. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by Cabot. Dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by Degussa, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by Cabot. The fumed silicas may be present in a composition according to the present invention at a content of between 0.1% and 40% by weight, more particularly between 1% and 15% by weight and even more particularly between 2% and 10%. % by weight, based on the total weight of the oily phase. B) Hydrophobic silica aerogels The oily phase of a composition according to the invention may also comprise, as gelling agent, at least silica aerogel particles. Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air. They are generally synthesized by sol-gel process in a liquid medium and then usually dried by extraction of a supercritical fluid, the most commonly used being supercritical CO2. This type of drying avoids the contraction of the pores and the material. The sol-gel process and the various dryings are described in detail in Brinker CJ, and Scherer GW, Sol-Gel Science: New York: Academic Press, 1990. The hydrophobic silica airgel particles used in the present invention exhibit a specific surface per unit mass (SM) ranging from 500 to 1500 3028758 m 2 / g, preferably from 600 to 1200 m 2 / g and better still from 600 to 800 m 2 / g, and a size expressed as mean diameter by volume (D [0.5]) ranging from 1 to 1500 μm, more preferably from 1 to 1000 μm, preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, more preferably from 5 to 20 μm. lm and even better better from 5 to 15 iam.
[0117] According to one embodiment, the hydrophobic silica airgel particles used in the present invention have a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 30 μm, preferably from 5 to 25 μm. pm, better from 5 to 20 iam and even better from 5 to 15 iam. The specific surface area per unit mass can be determined by the nitrogen absorption method called the BET method (Brunauer-Emmet-Teller) described in "The Journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (Appendix D). The BET surface area corresponds to the total specific surface area of the particles under consideration. The silica airgel particle sizes can be measured by static light scattering using a MasterSizer 2000 commercial particle size analyzer from Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" diameter of particles. This theory is described in particular in Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. According to an advantageous embodiment, the aerogels particles of hydrophobic silica used in the present invention have a specific surface per unit mass (SM) ranging from 600 to 800 m2 / g. The silica airgel particles used in the present invention may advantageously have a packed density p ranging from 0.02 g / cm 3 to 0.10 g / cm 3, preferably from 0.03 g / cm 3 to 0.08 g / cm3, in particular ranging from 0.05 g / cm3 to 0.08 g / cm3. In the context of the present invention, this density can be assessed according to the following protocol, called the packed density: 40 g of powder are poured into a graduated test tube; then the specimen is placed on the STF 2003 machine from Stampf Volumeter; the test piece is then subjected to a series of 2500 settlements (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio m / Vf, in this case 40 / Vf (Vf being expressed in cm 'and m in g). According to a preferred embodiment, the hydrophobic silica airgel particles used in the present invention have a specific surface area per volume unit SV ranging from 5 to 60 m 2 / cm 3, preferably 10 to 50 m 2 / cm 3 and better from 15 to 40 m2 / cm3. The specific surface area per unit volume is given by the relation: Sv = SM x p; where p is the packed density expressed in g / cm 3 and SM is the specific surface area per unit of mass, expressed in m 2 / g, as defined above.
[0118] Preferably, the hydrophobic silica airgel particles according to the invention have an oil absorption capacity measured at Wet Point ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and better still 8 to 12 ml / g. The absorption capacity measured at Wet Point, and denoted Wp, corresponds to the amount of oil which must be added to 100 g of particles in order to obtain a homogeneous paste. It is measured according to the so-called Wet Point method or method for determining the setting of powder oil described in standard NF T 30-022. It corresponds to the amount of oil adsorbed on the available surface of the powder and / or absorbed by the powder by Wet Point measurement, described below: A quantity m = 2 g of powder is placed on a glass plate then the oil (isononyl isononanoate) is added dropwise. After addition of 4 to 5 drops of oil in the powder, mixing is carried out with a spatula and oil is added until the formation of oil and powder conglomerates. From this moment, the oil is added one drop at a time and then triturated with the spatula.
[0119] The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracks or lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil intake corresponds to the ratio Vs / m. The aerogels used according to the present invention are aerogels of hydrophobic silica, preferably of silylated silica (INCI name: silica silylate). "Hydrophobic silica" means any silica whose surface is treated with silylating agents, for example with halogenated silanes such as alkyl chlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes. in order to functionalize the OH groups by Si-Rn silyl groups, for example trimethylsilyl groups. With respect to the preparation of hydrophobic silica airgel particles surface-modified by silylation, reference can be made to US Pat. No. 7,470,725. Hydrophobic silica airgel particles that are surface-modified with trimethylsilyl groups, preferably INCI Silica silylate, will preferably be used. Examples of hydrophobic silica aerogels that may be used in the invention include, for example, the airgel marketed under the name VM-2260 or VM-2270 (INCI name: Silica silylate), by the company Dow Corning, of which the particles have an average size of about 1000 microns and a specific surface area per unit mass of 600 to 800 m 2 / g. The aerogels marketed by Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, ENOVA Aerogel MT 1100 and ENOVA Aerogel MT 1200 may also be mentioned. The airgel marketed under the name VM2270 will preferably be used. (INCI name Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5-15 microns and a specific surface area per unit mass ranging from 600 to 800 m2 / g. Preferably, the particles of hydrophobic silica aerogels are present in the composition according to the invention in a dry matter content ranging from 0.1% to 8% by weight, preferably from 0.2% to 5% by weight. weight, preferably from 0.2% to 3% by weight relative to the total weight of the oily phase.
[0120] II. Organopolysiloxane Elastomer The organopolysiloxane elastomer, which can be used as a lipophilic gelling agent, has the advantage of giving the composition according to the invention good application properties. It provides a very soft and matifying after application, particularly advantageous for application on the skin. It can also allow an effective filling of the hollows present on the keratin materials.
[0121] By "organopolysiloxane elastomer" or "silicone elastomer" is meant a flexible, deformable organopolysiloxane having viscoelastic properties and especially the consistency of a sponge or a soft sphere. Its modulus of elasticity is such that this material resists deformation and has a limited capacity for extension 5 and contraction. This material is able to recover its original shape after stretching. It is more particularly a crosslinked organopolysiloxane elastomer. Thus, the organopolysiloxane elastomer can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and diorganopolysiloxane having silicon-bonded ethylenically unsaturated groups, especially in the presence of platinum catalyst; or by condensation-crosslinking dehydrogenation reaction between a hydroxyl-terminated diorganopolysiloxane and a diorganopolysiloxane containing at least one silicon-bonded hydrogen, especially in the presence of an organotin; or by crosslinking condensation reaction of a hydroxyl-terminated diorganopolysiloxane and a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of organoperoxide catalyst; or by crosslinking of organopolysiloxane by high energy radiation such as gamma rays, ultraviolet rays, electron beam. Preferably, the organopolysiloxane elastomer is obtained by addition reaction crosslinking (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) diorganopolysiloxane having at least two ethylenically unsaturated groups bonded to a silicon. silicon, especially in the presence (C) of platinum catalyst, as for example described in application EP-A-295886.
[0122] In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst. Compound (A) is the base reagent for the formation of elastomeric organopolysiloxane and the crosslinking is carried out by the addition reaction of the compound (A) with the compound (B) in the presence of the catalyst (C).
[0123] The compound (A) is in particular an organopolysiloxane having at least two hydrogen atoms bonded to separate silicon atoms in each molecule. The compound (A) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure.
[0124] The compound (A) may have a viscosity at 25 ° C ranging from 1 to 50,000 centistokes, especially to be well miscible with the compound (B). The organic groups bonded to the silicon atoms of the compound (A) can be alkyl groups such as methyl, ethyl, propyl, butyl, octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. Compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogenosiloxane copolymers and cyclic dimethylsiloxane-methylhydrogensiloxane copolymers. The compound (B) is advantageously a diorganopolysiloxane having at least two lower alkenyl groups (for example C2-C4); the lower alkenyl group may be chosen from vinyl, allyl and propenyl groups. These lower alkenyl groups may be located at any position of the organopolysiloxane molecule but are preferably located at the ends of the organopolysiloxane molecule. The organopolysiloxane (B) may have a branched chain, straight chain, cyclic or network structure but the linear chain structure is preferred. The compound (B) may have a viscosity ranging from the liquid state to the gum state. Preferably, the compound (B) has a viscosity of at least 100 centistokes at 25 ° C. In addition to the aforementioned alkenyl groups, the other organic groups bonded to the silicon atoms in the compound (B) may be alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group.
[0125] The organopolysiloxanes (B) may be chosen from methylvinylpolysiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylpolysiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers, and dimethylvinylsiloxy-dimethylvinylsiloxy copolymers. trimethylsiloxy-terminated methylvinylsiloxane, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxanemethylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) -polysiloxane, and terminally-terminated dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymers; dimethylvinylsiloxy. In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst. Advantageously, the sum of the number of ethylenic groups per molecule of the compound (B) and the number of hydrogen atoms bonded to silicon atoms per molecule of the compound (A) is at least 5. It is advantageous that the compound (A) is added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in the compound (A) and the total amount of all the ethylenically unsaturated groups in the compound (B) is in the range of 1.5: 1 to 20: 1. The compound (C) is the catalyst of the crosslinking reaction, and is in particular chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acidketone complexes, platinum black, and platinum supported .
[0126] The catalyst (C) is preferably added from 0.1 to 1000 parts by weight, more preferably from 1 to 100 parts by weight, as a clean platinum metal per 1000 parts by weight of the total amount of the compounds (A) and (B). The elastomer is advantageously a non-emulsifying elastomer. The term "non-emulsifying" defines organopolysiloxane elastomers not containing a hydrophilic chain, and in particular not containing polyoxyalkylene (especially polyoxyethylene or polyoxypropylene) units or polyglyceryl units. Thus, according to a particular embodiment of the invention, the composition comprises an organopolysiloxane elastomer devoid of polyoxyalkylene units and a polyglyceryl unit. In particular, the silicone elastomer used in the present invention is selected from Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name ). The organopolysiloxane elastomer particles may be transported in the form of a gel consisting of an elastomeric organopolysiloxane included in at least one hydrocarbon oil and / or a silicone oil. In these gels, the organopolysiloxane particles are often non-spherical particles. Non-emulsifying elastomers are described in EP 242 219, EP 285 886, EP 765 656 and JP-A-61-194009. The silicone elastomer is generally in the form of a gel, a paste or a powder, but advantageously in the form of a gel in which the silicone elastomer is dispersed in a linear silicone oil ( dimethicone) or cyclic (eg cyclopentasiloxane), advantageously in a linear silicone oil. As non-emulsifying elastomers, those sold under the names "KSG-6", "KSG-15", "KSG-16", "KSG-18", "KSG-41", "KSG-42" can more particularly be used. KSG-43, KSG-44, by Shin Etsu, DC9040, DC9041, Dow Corning, SFE 839 by General Electric. According to one particular embodiment, a silicone elastomer gel dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenylmethicone, phenyldimethicone, phenyltrimethicone, and cyclomethicone, is used. preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C. ranging from 1 to 500 cst at 25 ° C., optionally modified with aliphatic groups, optionally fluorinated, or with functional groups such as hydroxyl groups, thiols and / or amines.
[0127] In particular, mention may be made of the following INCI name compounds: Dimethicone / Vinyl Dimethicone Crosspolymer, such as USG-105 and USG107A from Shin Etsu; "DC9506" and "DC9701" from Dow Corning, 3028758 77 - Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as "KSG-6" and "KSG-16" from Shin Etsu; Dimethicone / Vinyl Dimethicone Crosspolymer (and) Cyclopentasiloxane, such as "KSG-15"; 5 - Cyclopentasiloxane (and) Dimethicone Crosspolymer, such as "DC9040", "DC9045" and "DC5930" from Dow Corning; Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041" from Dow Corning; Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning (a mixture of polydimethylsiloxane cross-linked with hexadiene / polydimethyl siloxane (2 cSt)); - C4-24 Alkyl Dimethicone / DivinylDimethicone Crosspolymer, such as NuLastic Silk MA by the company Alzo.
[0128] As examples of silicone elastomers dispersed in a linear silicone oil which can advantageously be used according to the invention, mention may be made in particular of the following references: Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as "KSG-6" and " KSG-16 "from Shin Etsu; Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041" from Dow Corning; and Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning (Hexadiene / Polydimethylsiloxane crosslinked polydimethylsiloxane (2 cSt)).
[0129] According to one preferred embodiment, the composition according to the invention comprises at least one crosslinked silicone elastomer of INCI name "dimethicone crosspolymer" or "dimethicone (and) dimethicone crosspolymer", with a dimethicone having a viscosity ranging from 1 to 100 cst. in particular from 1 to 10 cc at 25 ° C, such as the mixture of hexadiene / polydimethylsiloxane crosslinked polydimethylsiloxane (5cst) sold under the name DC 9041 by the company Dow Corning or the mixture of 3028758 78 Polydimethylsiloxane crosslinked with Hexadiene / Polydimethylsiloxane (2cst) sold under the name El-9240® by Dow Corning. According to a particularly preferred embodiment, the composition according to the invention comprises at least one crosslinked silicone elastomer of the INCI name "dimethicone (and) dimethicone crosspolymer", preferably with a dimethicone of viscosity ranging from 1 to 100 cSt, in particular from 1 to 10 cst at 25 ° C, such as the mixture of polydimethylsiloxane crosslinked with hexadiene / polydimethylsiloxane (5cst) sold under the name DC 9041 by Dow Corning. The organopolysiloxane elastomer particles may also be used in the form of a powder, in particular mention may be made of the powders sold under the names "Dow Corning 9505 Powder" and "Dow Corning 9506 Powder" by the company Dow Corning. These powders have the following properties: for INCI name: dimethicone / vinyl dimethicone crosspolymer. The organopolysiloxane powder may also be coated with silsesquioxane resin as described, for example, in US Patent 5,538,793. Such elastomer powders are sold under the names "KSP-100", "KSP-101", "KSP102", "KSP-103", "KSP-104", "KSP-105" by the company Shin Etsu, INCI: vinyl dimethicone / methicone silsesquioxane Crosspolymer. Examples of organopolysiloxane powders coated with silsesquioxane resin that can advantageously be used according to the invention include, for example, the reference "KSP-100" from Shin Etsu. According to a particularly preferred embodiment, the composition according to the invention comprises at least one crosslinked silicone elastomer of INCI name: vinyl dimethicone / methicone silsesquioxane Crosspolymer, as oily gelling agent and / or blooming filler. As preferred lipophilic gelling agent of the organopolysiloxane elastomer type, there may be mentioned in particular cross-linked organopolysiloxane elastomers chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone 30 Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), and in particular Dimethicone Crosspolymer (INCI name).
[0130] The organopolysiloxane elastomer may be present in a composition of the present invention at a content of between 0.2% and 10% by weight of active (dry) material, in particular between 0.2% and 5% by weight. % by weight, based on the total weight of the oily phase.
[0131] III. Semi-crystalline polymers The composition according to the invention may comprise at least one semicrystalline polymer. Preferably, the semi-crystalline polymer has an organic structure, and a melting temperature greater than or equal to 30 ° C.
[0132] For the purposes of the invention, the term "semicrystalline polymer" means polymers comprising a crystallizable part and an amorphous part and having a first-order reversible phase change temperature, in particular melting (solid-liquid transition). ). The crystallizable portion is either a side chain (or pendant chain) or a sequence in the backbone.
[0133] When the crystallizable portion of the semi-crystalline polymer is a sequence of the polymeric backbone, this crystallizable block is of a different chemical nature from that of the amorphous sequences; in this case, the semicrystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable portion is a chain pendant to the backbone, the semi-crystalline polymer may be a homopolymer or a copolymer. The melting temperature of the semi-crystalline polymer is preferably less than 150 ° C. The melting temperature of the semi-crystalline polymer is preferably greater than or equal to 30 ° C and less than 100 ° C. More preferably, the melt temperature of the semicrystalline polymer is greater than or equal to 30 ° C and less than 70 ° C. The semi-crystalline polymer (s) according to the invention used are solids at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg), whose melting temperature is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by Mettler, with a temperature increase of 5%. or 10 ° C per minute (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).
[0134] The semi-crystalline polymer (s) according to the invention preferably have a melting point higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the nails. According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, in particular at least 1% by weight, at a temperature above their melting temperature. Apart from the crystallizable chains or blocks, the sequences of the polymers are amorphous. For the purposes of the invention, the term "chain or crystallizable block" means a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state. reversibly, depending on whether it is above or below the melting temperature. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one of the repeating units of the polymer. Preferably, the polymer backbone of the semi-crystalline polymers is soluble in the fatty phase at a temperature above their melting point. Preferably, the crystallizable sequences or chains of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. Crystallizable side-chain semi-crystalline polymers are homo- or co-polymers. The semicrystalline polymers of the invention having crystallizable blocks are block copolymers or multiblock copolymers. They can be obtained by reactive (or ethylenic) double bond monomer polymerization or by polycondensation. When the polymers of the invention are crystallizable side chain polymers, the latter are advantageously in random or statistical form.
[0135] Preferably, the semi-crystalline polymers of the invention are of synthetic origin. According to a preferred embodiment, the semi-crystalline polymer is chosen from: homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing hydrophobic side chain (s) crystallizable (s) ( s), - polymers carrying in the backbone at least one crystallizable block, polyester-type polycondensates, aliphatic or aromatic or aliphatic / aromatic, - copolymers of ethylene and propylene prepared by metallocene catalysis, and - acrylate / silicone copolymers.
[0136] The semicrystalline polymers that may be used in the invention may be chosen in particular from: - block copolymers of controlled crystallization polyolefins, the monomers of which are described in EP 0 951 897, - polycondensates, and in particular of polyester, aliphatic or aromatic or aliphatic / aromatic, - copolymers of ethylene and propylene prepared by metallocene catalysis, - homo- or co-polymers carrying at least one crystallizable side chain and homo- or co-polymers bearing in the skeleton at least a crystallizable block, such as those described in US Pat. No. 5,156,911, such as the (Cio-C30) alkyl polyacrylates corresponding to Intelimer® from Landec, described in the brochure "Intelimer® Polymers", Landec IP22 (Rev. 4-97 ) and for example the product Intelimer® IPA 13-1 from Landec, which is a stearyl polyacrylate with a molecular weight of about 145,000 and whose at melting point 49 ° C., the homo- or co-polymers bearing at least one crystallizable side chain, in particular with fluorinated group (s), as described in document WO 01/19333, acrylate / silicone copolymers, such as copolymers of acrylic acid and polydimethylsiloxane grafted stearyl acrylate, polydimethylsiloxane grafted stearyl methacrylate copolymers, and polydimethylsiloxane grafted stearyl methacrylate and acrylic acid copolymers, copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. Mention may in particular be made of the copolymers sold by the company SHIN-ETSU under the names KP-561 (CTFA name: acrylates / dimethicone), KP-541 (CTFA name: acrylates / dimethicone and isopropyl alcohol), KP-545 (CTFA name acrylates / dimethicone and cyclopentasiloxane), and mixtures thereof. Preferably, the amount of semicrystalline polymer (s), preferably selected from semicrystalline crystallizable side chain polymers, is from 0.1% to 30% by weight of dry matter relative to the total weight. the oily phase, for example from 0.5% to 25% by weight, better still from 5% to 20%, or from 5% to 12% by weight, relative to the total weight of the oily phase.
[0137] IV. Dextrin Esters The composition according to the invention may comprise, as lipophilic gelling agent, at least one dextrin ester. In particular, the composition preferably comprises at least one ester of dextrin and fatty acid, preferably C12 to C24, in particular C14 to C18, or mixtures thereof. Preferably, the dextrin ester is a C12-C18, in particular C14-C18, fatty acid dextrin ester. Preferably, the dextrin ester is selected from dextrin myristate and / or dextrin palmitate, and mixtures thereof.
[0138] According to one particular embodiment, the dextrin ester is dextrin myristate, such as the one marketed under the name Rheopearl MKL-2 by Chiba Flour Milling. According to a preferred embodiment, the dextrin ester is dextrin palmitate. This may for example be chosen from those sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling. In a particularly preferred manner, the oily phase of a composition according to the invention may comprise from 0.1% to 30% by weight of ester (s) of dextrin, preferably from 2% to 25% and preferably from 7% to 5% to 17% by weight, based on the total weight of the oily phase. In a particularly preferred manner, the composition according to the invention may comprise between 0.1% and 10% by weight of dextrin palmitate, preferably between 0.5% and 5% by weight relative to the total weight of the oily phase. Dextrin palmitate may in particular be that sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling.
[0139] V. Hydrogen-Bonded Polymers As a representative of the hydrogen-bonded polymers that are suitable for the invention, polyamides and in particular hydrocarbon polyamides and silicone polyamides can be particularly mentioned.
[0140] Polyamides The oily phase of a composition according to the invention may comprise at least one polyamide chosen from hydrocarbon polyamides, silicone polyamides, and mixtures thereof.
[0141] Preferably, the total content of polyamide (s) is between 0.1% and 30% by weight, expressed in dry matter, preferably between 0.1% and 20% by weight, preferably between 0.5% by weight. and 10% by weight, based on the total weight of the oily phase. For the purposes of the invention, the term "polyamide" means a compound having at least 2 amide repeating units, preferably at least 3 amide repeating units and more preferably 10 amide repeating units. a) Hydrocarbon Polyamide The term "hydrocarbon-based polyamide" is intended to mean a polyamide formed essentially or even consisting of carbon and hydrogen atoms, and optionally of oxygen and nitrogen atoms, and not containing any silicon atom or fluorine atom. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. For the purposes of the invention, the term "functionalized chain" means an alkyl chain comprising one or more functional groups or reactive groups chosen in particular from hydroxyl, ether, esters, oxyalkylene or polyoxyalkylene groups.
[0142] Advantageously, this polyamide of the composition according to the invention has a weight average molecular weight of less than 100,000 g / mol, especially ranging from 1000 to 100,000 g / mol, in particular less than 50,000 g / mol, in particular ranging from 1,000. at 50 000 g / mol, and more particularly ranging from 1000 to 30 000 g / mol, preferably from 2000 to 20 000 g / mol, and better still from 2000 to 10 000 g / mol.
[0143] This polyamide is insoluble in water, especially at 25 ° C. According to a first embodiment of the invention, the polyamide used is a polyamide of formula (I): ## STR2 ## in which X represents a group -N (R 1) 2, or a group -OR 'in which R1 is a linear or branched C8 to C22 alkyl radical, which may be identical to or different from each other, R2 is a C28-C42 diacid dimer residue, R3 is a radical ethylene diamine, n is from 2 to 5; and their mixtures. According to a particular embodiment, the polyamide used is an amide-terminated polyamide of formula (Ia): ## STR2 ## in which X represents a group -N (R 1) 2, in which R 1 is linear or branched C8 to C22 alkyl radical, which may be the same or different from each other, R2 is a C28-C42 diacid dimer residue, R3 is an ethylene diamine radical, n is 2 to 5; and their mixtures.
[0144] The oily phase of a composition according to the invention may additionally comprise, in this case, at least one additional polyamide of formula (Ib) X represents a group -OR 'in which R1 is a linear or branched C8 to C22, preferably C16 to C22, alkyl radical which may be the same or different from each other; R2 is a diacid dimer residue; at C28-C42, R3 is an ethylene diamine radical, n is between 2 and 5, such as the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100 or Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG, whose INCI name is "ethylenediamine / stearyl dimer dilinoleate copolymer". B) Silicone Polyamide Silicone polyamides are preferably solid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). The silicone polyamides may preferentially be polymers comprising at least one unit of formula (III) or (IV): -R 4 SiO x YO 1 -R 4 -NH x Si-X N 1 -1. or in which: R 4, R 5, R 6 and R 7, which may be identical or different, represent a group chosen from: linear or branched or cyclic hydrocarbon groups containing from 1 to 40 carbon atoms, saturated or unsaturated, which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, which may be substituted in part or totally by fluorine atoms, C 6 to C 10 aryl groups, optionally substituted by a or more C 1 -C 4 alkyl groups, - the polyorganosiloxane chains containing or not containing one or more oxygen, sulfur and / or nitrogen atoms, - the X, identical or different, represent an alkylene di-yl group, linear or branched C1 to C8, which may contain in its chain one or more oxygen and / or nitrogen atoms, - Y is a divalent alkylene group, linear or branched, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, in C 1 to C 50, which may be 3028758 have one or more oxygen, sulfur and / or nitrogen atoms, and / or substitute one of the following atoms or groups of atoms: fluorine, hydroxy, C3 to C8 cycloalkyl, C1 to C8 alkyl C 40, C 5 -C 10 aryl, phenyl optionally substituted with 1 to 3 C 1 -C 3 alkyl, C 1 -C 3 hydroxyalkyl and C 1 -C 6 alkylamino, or Y represents a group of the formula: R 8 T wherein T represents a trivalent or tetravalent hydrocarbon group, linear or branched, saturated or unsaturated, C3 to C24 optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents an atom trivalent chosen from N, P and Al, and - R8 represents a linear or branched C1-C50 alkyl group, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulfonamide that can be bound or not to another chain of the polymer, n is an integer ranging from 2 to 500, preferably from 2 to 200 and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and better still from 6 to 200. According to one particular embodiment, the silicone polyamide comprises at least one unit of formula (III) in which m ranges from 50 to 200, in particular from 75 to 150, and preferably from 100 to 100, preferably still R4, R5, R6 and R7 independently represent a linear or branched C1-C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group in the formula (III). By way of example of a silicone polymer which may be used, mention may be made of one of the silicone polyamides obtained according to Examples 1 to 3 of US Pat. No. 5,981,680. Mention may be made of the compounds marketed by Dow Corning under the name DC 2-8179 (DP 100) and DC 2-8178 (DP 15) whose INCI name is "Nylon-611 / dimethicone copolymers", that is, say nylon-611 / dimethicone copolymers. The silicone polymers and / or copolymers advantageously have a solid state transition temperature in the liquid state of from 45 ° C to 190 ° C. Preferably, they have a solid state transition temperature in the liquid state of from 70 ° C to 130 ° C and more preferably from 80 ° C to 105 ° C.
[0145] Preferably, the total content of polyamide (s) and / or silicone polyamide (s) is between 0.5% and 25% by weight of dry matter, in particular from 2% to 20% by weight. preferably between 2% and 12% by weight, based on the total weight of the oily phase. Advantageously, the hydrogen bonded polymer is selected from ethylene diamine / stearyl dimer dilinoleate copolymer and nylon 611 / dimethicone copolymers. According to an advantageous variant, a composition according to the invention comprises a lipophilic gelling agent chosen from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers and mixtures thereof, and in particular at least one organopolysiloxane elastomer. As a representative of lipophilic gelling agents, mention may also be made of other polymeric gelling agents which are the hydrocarbon-based block copolymers also known as block copolymers. EXAMPLES OF COPOLYMER HYDROCARBON SEQUENCE The polymeric gellant is capable of thickening or gelling the hydrocarbon phase of the composition. By "amorphous polymer" is meant a polymer that does not have a crystalline form. The polymeric gelling agent is preferably also film-forming, that is to say that it is capable of forming a film when it is applied to the skin and / or the nails.
[0146] The hydrocarbon-based block copolymer may in particular be a diblock, triblock, multiblock, radial or star copolymer, or mixtures thereof.
[0147] Such hydrocarbon block copolymers are described in the application US-A-2002/005562 and in US-A-5 221 534. The copolymer may have at least one block whose glass transition temperature is preferably lower. at 20 ° C, preferably less than or equal to 50 ° C, preferably less than or equal to -20 ° C, more preferably less than or equal to -40 ° C. The glass transition temperature of said block may be between -150 ° C. and 20 ° C., in particular between -100 ° C. and 0 ° C. The hydrocarbon block copolymer present in the composition according to the invention is an amorphous copolymer formed by polymerization of an olefin. The olefin may in particular be an ethylenically unsaturated elastomeric monomer. As an example of an olefin, mention may be made of ethylenic carbide monomers, especially having one or two ethylenic unsaturations, having from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene, isoprene or pentadiene. .
[0148] Advantageously, the hydrocarbon-based block copolymer is an amorphous block copolymer of styrene and olefin. Particularly preferred are block copolymers comprising at least one styrene block and at least one block comprising units selected from butadiene, ethylene, propylene, butylene, isoprene or a mixture thereof.
[0149] According to a preferred embodiment, the hydrocarbon block copolymer is hydrogenated to reduce residual ethylenic unsaturations after polymerization of the monomers. In particular, the hydrocarbon-based block copolymer is a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C 3 -C 4 alkylene blocks.
[0150] According to a preferred embodiment, the composition according to the invention comprises at least one diblock copolymer, preferably hydrogenated, preferably chosen from styrene-ethylene / propylene copolymers, styrene / butadiene copolymers, styrene-styrene copolymers and the like. ethylene / butylene. Diblock polymers are in particular sold under the name Kraton® G1701E by Kraton Polymers. According to another preferred embodiment, the composition according to the invention comprises at least one triblock copolymer, preferably hydrogenated, preferably chosen from styrene-ethylene / propylene-styrene copolymers, styrene-ethylene / butadiene-styrene copolymers. styrene-isoprene-styrene copolymers, styrene-butadiene-styrene copolymers. Triblock polymers are sold in particular under the names Kraton® G1650, Kraton® D1101, Kraton® D1102 and Kraton® D1160 by Kraton Polymers. According to one embodiment of the present invention, the hydrocarbon block copolymer is a styrene-ethylene / butylene-styrene triblock copolymer. According to a preferred embodiment of the invention, use may especially be made of a mixture of a triblock styrene-butylene / ethylene-styrene copolymer and a diblock styrene-ethylene / butylene copolymer, in particular those sold under the name Kraton®. G1657M by Kraton Polymers. According to another preferred embodiment, the composition according to the invention comprises a mixture of styrene-butylene / ethylene-styrene triblock hydrogenated copolymer and ethylene-propylene-styrene hydrogenated star polymer, such a mixture possibly being in isododecane. or in another oil. Such mixtures are for example sold by PENRECO under the trade names VERSAGEL® M5960 and VERSAGEL® M5670. Advantageously, a diblock copolymer such as those described above, in particular a diblock copolymer of styrene-ethylene / propylene, or a mixture of diblock and triblock, as described above, is used as polymeric gelling agent. Thus, according to a preferred embodiment, a composition according to the invention comprises, as lipophilic gelling agent, at least one hydrocarbon-based block copolymer, preferably a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C 3 -C 4 alkylene blocks, still more preferably chosen from: a diblock copolymer, preferably hydrogenated, such as a styrene-ethylene / propylene copolymer, a styrene-ethylene / butadiene copolymer; a triblock copolymer, preferably hydrogenated, such as a styrene / propylene-styrene copolymer, a styrene-ethylene / butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a styrene-butadiene-styrene copolymer; A mixture of styrene-butylene / ethylene-styrene triblock hydrogenated copolymer and hydrogenated ethylene-propylene-styrene star polymer; and 3028758 - their mixtures. The hydrocarbon block copolymer (or the mixture of hydrocarbon block copolymers) may be present in a content ranging from 0.1% to 15% by weight, preferably ranging from 0.1% to 10% by weight, more preferably ranging from From 0.5% to 5% by weight, more preferably from 1% to 5% by weight, and still more preferably from 1% to 3% by weight, relative to the total weight of the composition. ADDITIVES TO LIPOPHILIC GELIFIFIERS The above-mentioned lipophilic gelling agents present in the gelled oily phase may be combined with any type of lipophilic polymer such as, for example, film-forming pseudoblocks such as an acrylic acid / isobutyl acrylate / isobornyl acrylate copolymer marketed under the name MEXOMERE PAS by the company CHIMEX described in the application FR2 995 785.
[0151] These lipophilic polymers, when present in the compositions according to the invention, are present in a content ranging from 0.1% to 20% by weight, preferably ranging from 0.5% to 15% by weight, more preferably ranging from from 1% to 10% by weight, better still from 2% to 9% by weight, relative to the total weight of the composition.
[0152] 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 that is 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 that can be used in the composition of the invention may also be volatile. Among the water-soluble solvents that can be used in the composition according to the invention, there may be mentioned lower monoalcohols having from 1 to 30 carbon atoms, such as ethanol and isopropanol, glycols having from 2 to 8 atoms. carbon such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C3 and C4 ketones and C2-C4 aldehydes.
[0153] The aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 5% to 95%, better still from 30% to 80% by weight, preferably from 40% to 80% by weight. 75% by weight, relative to the total weight of said composition.
[0154] According to another variant embodiment, the aqueous phase of a composition according to the invention may comprise at least one C2-C32 polyol. By "polyol" is meant for the purposes of the present invention, any organic molecule comprising at least two free hydroxyl groups. Preferably, a polyol according to the present invention is present in liquid form at room temperature. A polyol that is suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing at least two -OH functions on the alkyl chain, in particular at least three -OH functions, and more particularly at minus four functions -OH.
[0155] The polyols which are particularly suitable for the formulation of a composition according to the present invention are those having in particular 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms. Advantageously, the polyol can be, for example, chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols, such as oligomers of glycerol such as diglycerol, polyethylene glycols, and mixtures thereof. According to a preferred embodiment of the invention, said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof. According to one particular embodiment, the composition of the invention may comprise at least propylene glycol. According to another particular embodiment, the composition of the invention may comprise at least glycerol.
[0156] The aqueous phase may be composed of a synthetic phyllosilicate suitable for the invention in gel form, alone or in combination with other gelling agents.
[0157] According to one particular embodiment, a synthetic phyllosilicate that is suitable for the invention may be used in the form of an aqueous or aqueous-alcoholic gel. When the gel is aqueous, it can then constitute all or part of the aqueous phase. According to one particular embodiment, a synthetic phyllosilicate that is suitable for the invention in the form of an aqueous gel constitutes the aqueous phase of a composition according to the invention, that is to say that the aqueous phase of the composition is exclusively consisting of this gel. OIL PHASE For the purposes of the invention, an oily phase comprises at least one oil. The term "oil" means any fatty substance in liquid form at ambient temperature at atmospheric pressure. An oily phase suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon oils, silicone oils, fluorinated or otherwise, or mixtures thereof. The oils may be volatile or non-volatile. They can be of animal, vegetable, mineral or synthetic origin. According to one variant embodiment, the oils of plant 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.
[0158] The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms. The oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acidic radicals.
[0159] By "volatile oil" is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at ambient temperature and atmospheric pressure, especially having a vapor pressure ranging from 0.13 Pa to 40,000 Pa ( 101 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); mm Hg). Volatile oils Volatile oils can be hydrocarbon or silicone. Among the volatile hydrocarbon oils having from 8 to 16 carbon atoms, mention may be made especially of C 8 -C 16 branched alkanes, for example C 8 -C 16 isoalkanes (also known as isoparaffins), isododecane, isodecane and the like. isohexadecane and for example the oils sold under the trade names of Isopars or permetyls, branched C8-C16 esters such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isohexadecane. It is also possible to mention 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 (Cii) and of n-tridecane (C13) obtained in Examples 1 and 2 of the application WO 2008/155059 from Cognis, and mixtures thereof. Silicone volatile oils that may be mentioned include linear silicone volatile oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane. Cyclic silicone volatile oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
[0160] Non-volatile oils Non-volatile oils may, in particular, be chosen from hydrocarbon oils, fluorinated oils and / or non-volatile silicone oils. Non-volatile hydrocarbon oils that may especially be mentioned include: - hydrocarbon-based oils of animal origin, - hydrocarbon-based oils of vegetable origin, synthetic ethers having from 10 to 40 carbon atoms, such as dicapryl ether, - synthetic esters, such as the oils of formula RiCOOR 2, in which R 1 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, a branched chain containing from 1 to 40 atoms carbon, with the proviso that R 1 + R 2 is 10. The esters may be, in particular, chosen from alcohol and fatty acid esters, for example, cetostearyl octanoate, esters of isopropyl alcohol, such as such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, such as lactate. isostearyl, the hydroxystearate Examples include octyl alcohol, ricinoleates of alcohols or polyalcohols, hexyl laurate, neopentanoic acid esters, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, and the like. isononyl isononanoate, isotridecyl isononanoate, - polyol esters and pentaerythritol esters, such as dipentaerythritol tetrahydroxystearate / tetraisostearate, - branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, C12-C22 higher fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof, non-phenyl silicone oils, for example caprylyl methycone, and phenyl silicone oils, for example phenyl trimethicones, phenyl dimethicones, phenyl trimethylsil oxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone of lower viscosity or equal to 100 cSt, trimethylpentaphenyltrisiloxane, and mixtures thereof; as well as the mixtures of these different oils. Preferably, a composition according to the invention comprises volatile and / or nonvolatile silicone oils.
[0161] A composition according to the invention may comprise from 5% to 95% by weight, more preferably from 5% to 40% by weight, preferably from 7% to 35% 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. Advantageously, a composition according to the invention may comprise one or more filler (s), other than a synthetic phyllosilicate that is suitable for the invention, conventionally used in skincare and / or makeup compositions. These ancillary charges are colorless or solid white particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Of mineral or organic nature, natural or synthetic, they make it possible to confer on the composition containing them softness, dullness and uniformity in makeup. In particular, such additional charges may 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% by weight. , 5% and 5% by weight, based on the total weight of the composition. According to one embodiment of the invention, a composition may comprise at least solid particles such as pigments and / or additional charges. Advantageously, a composition according to the invention may comprise from 0.01% to 25% by weight, especially from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably 5% by weight. at 15% by weight of charges, relative to the total weight of the composition.
[0162] In the case of a care composition, a composition according to the invention may comprise from 0.001% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 0.5% to 10% by weight. % by weight and preferably from 0.5% to 5% by weight of charges, relative to the total weight of the composition.
[0163] DISPERSANT AGENT Advantageously, a composition according to the invention may further comprise a dispersing agent. Such a dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them. According to a particular embodiment, a dispersing agent according to the invention is a surfactant. According to a particular variant embodiment, a composition according to the invention comprises less than 1% by weight of surfactant relative to the total weight of the composition, or even is devoid of surfactant. ACTIVE For a particular care application, a composition according to the invention may comprise at least one moisturizing agent (also called humectant).
[0164] This hydrating agent may be any aqueous active classically used in the cosmetic field. Preferably, the moisturizing agent is sodium hyaluronate and / or glycerin, preferably sodium hyaluronate. According to a preferred embodiment, the composition according to the invention comprises sodium hyaluronate in the gelled aqueous phase, the latter thus playing the dual role of moisturizing agent and hydrophilic gelling agent. The moisturizing agent (s) may be present in the composition in a content ranging from 0.1% to 15% by weight, especially from 0.5% to 10% by weight, or even from 1% to 6% by weight, relative to to the total weight of said composition.
[0165] Other active agents which may be used in the composition of the invention include, for example, vitamins, sunscreens and mixtures thereof. Preferably, a composition according to the invention comprises at least one active ingredient. It falls within the routine operations of those skilled in the art to adjust the nature and the quantity of the additives present in the compositions in accordance with the invention. so that the desired cosmetic properties thereof are not affected.
[0166] According to one embodiment, a composition of the invention may advantageously be in the form of a composition for the care of the skin of the body or of the face, in particular the face, or nails. According to another embodiment, a composition of the invention may advantageously be in the form of a makeup base composition for makeup of the skin and / or nails. According to another embodiment, a composition of the invention may advantageously be in the form of a foundation. According to one embodiment, a composition of the invention may advantageously be in the form of a makeup composition for the skin and in particular the face. It can be an eyeshadow or a blush. Such compositions are especially prepared according to the general knowledge of those skilled in the art. Throughout the description, including the claims, the phrase "comprising one" should be understood as being synonymous with "having at least one", unless the contrary is specified. Expressions "between ... and ..." and "from ... to ..." must be understood as inclusive terms unless otherwise specified.
[0167] The invention is further illustrated by the examples and figures presented below. Unless otherwise indicated, the quantities indicated are expressed as a percentage by mass. METHODOLOGY FOR OSCILLATION DYNAMIC RHEOLOGY MEASUREMENTS These are harmonic rheological measurements that measure the elastic modulus.
[0168] The measurements are carried out using a Haake RS600 rheometer on a product at rest, at 25 ° C. with a plane plane geometry. The diameter of the mobile is 0 60 mm and the air gap is 2 mm. Measurements in the harmonic regime make it possible to characterize the viscoelastic properties of the products. The technique involves subjecting a material to sinusoidally varying stress over time and measuring the response of the material to that stress. In a domain where the behavior is linear viscoelastic (zone where the deformation is proportional to the stress), the stress (T) and the deformation (y) are two sinusoidal functions of the time which are written in the following way: t) = To sin ((DO y (t) = yo sin (wt + δ) where: To represents the maximum amplitude of the stress (Pa), yo represents the maximum amplitude of the deformation (-); = 2IN represents the pulsation (rad.s-1) with N representing the frequency (Hz), and represents the phase shift of the stress with respect to the deformation (rad) Thus, the two functions have the same angular frequency but they are phase shifted by an angle δ, depending on the phase shift S between T (t) and y (t), the behavior of the system can be understood: - If S = 0, the material is purely elastic - If S = II / 2, the material is purely viscous (Newtonian fluid), and - If 0 <S <II / 2, the material is viscoelastic. al, the stress and the deformation are written in complex form: T * (t) = 'ro eiwt 25 y * (t) = yo e (iwt +8) A complex modulus of rigidity, representing the overall resistance of the material to the 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 '= (To / yo) cos S; and 3028758 99 G "is the viscous loss or modulus module that characterizes the energy dissipated by internal friction during a cycle, G" = (ro / yo) sin δ. The parameter adopted is the modulus of average stiffness G * measured at the plateau measured at a frequency of 1 Hz.
[0169] EXAMPLES Example 1 Preparation of a synthetic phyllosilicate in the form of an aqueous gel suitable for the invention A synthetic phyllosilicate in the form of an aqueous gel suitable for the invention is prepared according to the technology described in Example 1 of the application FR No. 2,977,580, page 21, line 26 to page 22, line 29. Thus, the formation of the hydrogel was carried out without a drying and lyophilization step. The compositions according to the invention illustrated in the following examples comprise a synthetic phyllosilicate according to the invention as obtained in this example 1. EXAMPLE 2: Gel-gel Composition Comprising a Synthetic Phyllosilicate Which Is Suitable for the Invention in Gel Form The synthetic phyllosilicate suitable for the invention and used in the following composition was prepared according to Example 1.
[0170] 3028758 Phase INGREDIENTS% by weight Al DIBLOC COPOLYMER BASED on 20.00% of the gel (ie STYRENE and 3.00% ai *) of ETHYLENE / PROPYLENE sold under the name KRATON® G1701 EU by the company Kraton Polymers; dispersed at 15% at 85 ° C. in isohexadecane ACRYLIC ACIDIC ACRYLIC COPOLYMER / ISOBUTYL ACRYLATE / ISOBORNYL ACRYLATE 50% in isododecane sold under the name MEXOMERE® PAS by the company Chimex 15.00 (ie 7.50% *) A2 ISODODECANE 13.49 A3 SYNTHETIC PHYLLOSILICATE (gel) at 11% 2.00% ma * B Moisturizing active ingredient (SODIUM HYALURONATE sold under the name Hyactive® 120 by the company CONTRIPO) 1.00 Preservative qs WATER qs% m.wt.% by weight of active ingredient Procedure: 1-Disperse and homogenize at 85 ° C the kraton particles in isohexadecane and allow to cool to room temperature (20-30 ° C). A clear gel with 15% active material is obtained. To 20% Kraton gel, add and homogenize the MEXOMERE PAS with stirring with Rayneri stirrer. 3-Disperse Na hyaluronate in water. Add the phyllosilicate as an aqueous or hydroalcoholic gel. Homogenize until a homogeneous and smooth aqueous gel is obtained at room temperature (20-30 ° C). Add preservatives if needed. 4- Disperse the aqueous gel obtained in 2, the oily gel obtained in 1 at room temperature (20-30 ° C). A homogeneous formula is obtained.
[0171] The composition is stable after 1 year at room temperature (25 ° C), is easy to apply to the skin and provides sensory pleasure in terms of softness, freshness and comfort after application. In addition, the composition leaves a soft film on the skin. This formula has matt qualities (gloss meter measurement: brightness of 1%) and coverage after application. PROTOCOLS OF MEASUREMENTS 1- Measurement of the mattness / gloss 20 Protocol for measuring the mattness of a composition The brightness of a deposit resulting from the application of a composition can be commonly measured according to various methods, such as that using a Byk Micro Gloss glossmeter 20 ° / 60 ° / 85 °.
[0172] 25 Principle of measurement using this Brillancemeter The device illuminates the sample to be analyzed according to a certain incidence and measures the intensity of the specular reflection. The intensity of the reflected light depends on the material and the angle of illumination. For non-ferrous materials (paint, plastic), the reflected light intensity increases with the illumination angle. The remainder of the incident light penetrates into the material and according to the hue of the color, it is either partially absorbed or diffused. The measurement results of the reflectometer are not based on the amount of incident light but on a black and polished glass standard of defined refractive index.
[0173] The measurement is normalized to an internal standard and reduced to 100: For this standard, the measured value is set to 100 units of gloss (calibration). The closer the measured value is to 100, the more brilliant the sample. The unit of measurement is the Gloss Unit (UB). The angle of illumination used greatly influences the value of the reflectometer. To be able to differentiate between very bright and dull surfaces, standardization has defined 3 geometries, or 3 measurement domains.
[0174] Test Protocol a- On a LENETA brand contrast card and FORM 1A PENOPAC reference card, spread a 30 μm thick layer of the composition whose medium gloss is to be evaluated, using an automatic spreader. The layer covers the white background and the black background of the map. B. Allow to dry for 24 hours at 37 ° C. c- Measure the gloss at 20 °, 60 ° and 85 ° on the white matt absorbent base (3 measurements) using a BYK GARDNER Brilliance Meter and microTRI-GLO SS reference. The measured UB values obtained for the different compositions tested should then be compared. The lower the measured value, the more the deposit is dull. Results The composition illustrated in Example 2 according to the invention has a measured value in UB of less than 10, and therefore this composition forms a dull film. 25 2-TEST coverage: measure of transparency. The measuring device used is: Haze-gard (BYK-Gardner). Test protocol a-Spread on a transparent plastic film (Byk), a 25.4 μm thick layer of the test composition, using an automatic spreader, b- Allow to dry for 1 hour at room temperature (20 ° C-25 ° C), 3028758 103 c-Measure transparency using Haze-gard (average 3 measurements). Haze is the diffuse transmitted light / total transmitted light. The results are expressed in percentages. The higher the Haze value, the higher the coverage. The composition illustrated in Example 2 according to the invention forms a very covering film, which can hide the imperfections of the skin. Example 3: FOUNDATION FOUNDATION, compositions 3 to 5 The compositions 3 and 5 are not in accordance with the invention. The composition 4 is in accordance with the invention and comprises a synthetic phyllosilicate that is suitable for the invention in the form of an aqueous gel. The gel / gel compositions were prepared at room temperature (20-25 ° C) by weighing all raw materials in a beaker and then vigorously stirring with rayneri until the mixture became homogeneous.
[0175] Chemical Names Composition 3 (excluding Composition 4 (according to the invention) the invention) (excluding the invention) DESIONIZED WATER Qsp100 Qs 100 Qs 100 MICROBIOLOGICALLY CLEAN GLYCERIN 5.28 5.28 5.28 COPOLYMER 2.40 2.40 3,17 SODIUM ACRYLAMIDO-2-METHYL PROPANE SULFONATE / HYDROXYETHYLACRYLATE AS POWDER SEPINOV EMT 100 SEPPIC PHENOXY-2 ETHANOL 0.78 0.78 0.78 SYNTHETIC PHYLLOSILICATE GEL 11.0% IN WATER - 18.00 ( or - 2.00% ai *) Natural talc (LUZENAC® - - 2.00 PHARMA M) POLY DIMETHYLSILOXANE (VISCOSITY: 5 CST) 8.00 8.00 8.00 DOW CORNING TORAY SH200 C FLUID SCSO MIXTURE OF 14, 0 14.00 14.00 POLYDIMETHYLSILOXANE RETICULATED BY HEXADIENE / POLY DIMETHYLSILOXANE SCST (DOW CORNINGO 9041 SILICONE ELASTOMER BLEND PIGMENTS NAI 18.00 18.00 18.00 VISCOSITY 25 ° C 64 poises 123 poises 64 poises% ai *: percentage by weight of active material 3028758 A comparative mattness test was carried out according to the method described in Example 2 above. The synthetic phyllosilicate composition according to the invention is the most matte and the rest after 1 hour of drying. 5

权利要求:
Claims (18)
[0001]
REVENDICATIONS1. Composition, in particular cosmetic makeup and / or care of the skin and / or nails, comprising: at least one aqueous phase gelled by at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; characterized in that said phases form therein a macroscopically homogeneous mixture, and in that the composition further comprises at least one synthetic phyllosilicate of molecular formula Mg3 Si4010 (OH) 2
[0002]
The composition of claim 1, wherein the synthetic phyllosilicate is used as a hydrophilic gelling agent.
[0003]
3. Composition according to claim 1 or 2, having an infrared absorption band of 7200 cm 'corresponding to the elongation vibration attributed to Si-OH silanol groups at the edge of the sheets of phyllosilicate.
[0004]
4. Composition according to any one of the preceding claims, characterized by an absence of an infrared absorption band of 7156 cm -1.
[0005]
5. Composition according to any one of the preceding claims, wherein said synthetic phyllosilicate is present in an amount ranging from 0.01% to 20% by weight, preferably ranging from 0.1% to 15%, more preferably ranging from From 0.1% to 11% by weight, still more preferably from 0.5% to 11% by weight, more preferably from 0.5% to 7% by weight, more preferably from 1% to 6%, and even better ranging from 2% to 5% by weight relative to the total weight of the composition.
[0006]
6. A composition according to any one of the preceding claims, wherein the synthetic phyllosilicate is in the form of an aqueous or aqueous-alcoholic gel.
[0007]
A composition according to any one of the preceding claims, wherein the synthetic phyllosilicate is in the form of an aqueous gel and constitutes the aqueous phase.
[0008]
8. Composition according to any one of the preceding claims, in which the synthetic phyllosilicate in the form of an aqueous or aqueous-alcoholic gel is present in an amount ranging from 0.5 to 20% by weight of active material, preferably from 1 to % to 15% by weight, still more preferably ranging from 2% to 10% by weight, relative to the total weight of the aqueous phase. 3028758 107
[0009]
A composition according to any one of the preceding claims, wherein said lipophilic gelling agent is selected from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, block copolymers hydrocarbon compounds, and mixtures thereof. 5
[0010]
10. Composition according to any one of the preceding claims, comprising, as lipophilic gelling agent, at least one hydrocarbon-based block copolymer, preferably a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C3-C4 alkylene blocks, even more preferentially. selected from: - a diblock copolymer, preferably hydrogenated, such as a styrene-ethylene / propylene copolymer, a styrene-ethylene / butadiene copolymer; a triblock copolymer, preferably hydrogenated, such as a styrene / propylene-styrene copolymer, a styrene-ethylene / butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a styrene-butadiene-styrene copolymer; a mixture of styrene-butylene / ethylene-styrene triblock hydrogenated copolymer and ethylene-propylene-styrene hydrogenated star polymer; and - their mixtures.
[0011]
11. Composition according to any one of the preceding claims, comprising at least one lipophilic polymer such as an acrylic acid / isobutyl acrylate / isobornyl acrylate copolymer. 20
[0012]
12. Composition according to any one of the preceding claims, comprising at least one hydrophilic gelling agent chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, mixed silicates and pyrogenic silicas, and mixtures thereof.
[0013]
13. Composition according to any one of the preceding claims, containing the aqueous and oily phases in an aqueous phase / oil phase weight ratio of 95/5 to 5/95, preferably 30/70 to 80/20.
[0014]
14. A composition according to any one of the preceding claims, wherein the composition is cosmetic or dermatological and comprises a physiologically acceptable medium. 3028758 108
[0015]
15. Composition according to any one of the preceding claims, further comprising at least one moisturizing agent, preferably sodium hyaluronate, and / or glycerin, and more preferably sodium hyaluronate.
[0016]
16. A process for preparing a composition, in particular a cosmetic composition, comprising at least one mixing step: an aqueous phase gelled with at least one hydrophilic gelling agent; at least one oily phase gelled with at least one lipophilic gelling agent; and at least one synthetic phyllosilicate of molecular formula Mg 3 SiO 10 (OH) 2 as defined in any one of Claims 1 to 8; under conditions conducive to obtaining a macroscopically homogeneous mixture.
[0017]
17. The method of claim 16, comprising a step of mixing at least two gelled phases or more. 15
[0018]
18. A cosmetic process for making up and / or caring for the skin and / or nails, comprising at least the application to the skin and / or nails of a macroscopically homogeneous composition obtained by extemporaneous mixing, before application or at the time the application to the skin and / or the nails of at least one aqueous phase gelled with at least one hydrophilic gelling agent, at least one oily phase gelled with at least one lipophilic gelling agent, and at least one a synthetic phyllosilicate of molecular formula Mg3Si4010 (OH) 2 as defined according to any one of Claims 1 to 8.

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BR112017010720A2|2018-02-14|

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FR3028753B1|2018-01-05|

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

US5538728A|1989-10-19|1996-07-23|Shiseido Company, Ltd.|Hydrophilic polymer-silicate mineral complex material and use thereof|

---

WO1999062497A1|1998-06-03|1999-12-09|Aiache Jean Marc|Stable gel mixture in the form of a mixture of oleogel and aqueous gel|

---

US6660277B1|1998-06-19|2003-12-09|Avon Products, Inc.|Gel matrix non-emulsion composition containing two clay gels|

---

WO2008009799A2|2006-07-17|2008-01-24|Luzenac Europe Sas|Method for preparing talcose compositions comprising synthetic mineral particles containing silicon, germanium and metal|

---

US20140205528A1|2011-07-07|2014-07-24|Universite Paul Sabatier |Process for preparing a composition comprising synthetic mineral particles and composition|

---

JPH0351651B2|1984-06-22|1991-08-07|Mizusawa Industrial Chem|

---

JPH0417162B2|1985-02-21|1992-03-25|Dow Corning Toray Silicone|

---

JPH0455611B2|1986-04-17|1992-09-03|Dow Corning Toray Silicone|

---

DE3712202C1|1987-04-10|1988-09-08|Kleinewefers Ramisch Gmbh|Process and device for gas heating of calender rolls|

---

US5219560A|1989-03-20|1993-06-15|Kobayashi Kose Co., Ltd.|Cosmetic composition|

---

US5061481A|1989-03-20|1991-10-29|Kobayashi Kose Co., Ltd.|Cosmetic composition having acryl-silicone graft copolymer|

---

US5221534A|1989-04-26|1993-06-22|Pennzoil Products Company|Health and beauty aid compositions|

---

US5156911A|1989-05-11|1992-10-20|Landec Labs Inc.|Skin-activated temperature-sensitive adhesive assemblies|

---

JP2832143B2|1993-12-28|1998-12-02|信越化学工業株式会社|Silicone fine particles and method for producing the same|

---

FR2734714B1|1995-05-30|1997-07-04|Oreal|COMPOSITION IN THE FORM OF ANHYDROUS GEL WITH FAT PHASE WITHOUT WAX, CONTAINING ORGANOMODIFIED CLAY, EXPANDED HOLLOW THERMOPLASTIC PARTICLES AND PYROGENATED SILICA|

---

DE69613647T2|1995-09-29|2002-05-08|Shiseido Co Ltd|Cosmetic preparation containing water-in-oil emulsion|

---

JPH09171154A|1995-12-19|1997-06-30|Nippon Sheet Glass Co Ltd|Image input optical system and image input device using the same|

---

DE19648798C2|1996-11-26|1998-11-19|Hoechst Ag|Process for the production of organically modified aerogels by surface modification of the aqueous gel and subsequent drying|

---

US5959019A|1997-08-22|1999-09-28|Colgate-Palmolive Company|Topical tale containing compositions|

---

DE69910880T2|1998-04-21|2004-07-15|L'oreal|A composition containing olefin copolymer with controlled crystallization for topical use|

---

US6280748B1|1998-06-12|2001-08-28|Dow Corning Toray Silicone, Ltd.|Cosmetic raw material cosmetic product and method for manufacturing cosmetic products|

---

US5981680A|1998-07-13|1999-11-09|Dow Corning Corporation|Method of making siloxane-based polyamides|

---

KR100275500B1|1998-10-28|2000-12-15|정선종|Fabrication method of integrated high voltage power institute|

---

US7101928B1|1999-09-17|2006-09-05|Landec Corporation|Polymeric thickeners for oil-containing compositions|

---

FR2820312B1|2001-02-02|2003-05-02|Oreal|PULVERULENT COMPOSITION FOR THE DECOLORATION OF HUMAN KERATINIC FIBERS|

---

JP4693330B2|2001-11-28|2011-06-01|東レ・ダウコーニング株式会社|Cosmetic raw materials, cosmetics and methods for producing cosmetics|

---

MXPA03008714A|2002-09-26|2004-09-10|Oreal|Sequenced polymers and cosmetic compositions comprising the same.|

---

WO2004055082A2|2002-12-12|2004-07-01|L'oreal|Cosmetic composition comprising a dispersion of particles of a silicone-free grafted ethylene polymer in a liquid fatty phase|

---

CA2551843A1|2004-01-06|2005-10-20|Aspen Aerogels, Inc.|Ormosil aerogels containing silicon bonded polymethacrylate|

---

WO2008155059A2|2007-06-19|2008-12-24|Cognis Ip Management Gmbh|Hydrocarbon mixtures and use thereof|

---

FR2925529B1|2007-12-19|2010-01-22|Luzenac Europ Sas|COMPOSITE MATERIAL CONSISTING OF A METALLIC MATRIX IN WHICH SYNTHETIC LAMELLAR PHYLLOSILICATE NANOPARTICLES ARE DISTRIBUTED|

---

ES2576691T3|2009-01-29|2016-07-08|L'oréal|Cosmetic composition in foam form|

---

DE102009027604A1|2009-07-10|2011-01-20|Henkel Ag & Co. Kgaa|Cosmetic compositions with suspensions of silver salts|

---

KR101061289B1|2009-11-20|2011-08-31|아모레퍼시픽|Cosmetic composition containing inorganic powder|

---

FR2969594B1|2010-12-23|2013-01-11|Univ Toulouse 3 Paul Sabatier|PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING SYNTHETIC MINERAL PARTICLES|

---

DE102011012214A1|2011-02-23|2012-08-23|Eckart Gmbh|Platelet-shaped metal oxide-containing pigment, process for its preparation and use thereof as an effect pigment and / or as a substrate for effect pigments|

---

US9717670B2|2012-04-26|2017-08-01|L'oreal|Cosmetic composition comprising mattifying fillers and a silane|

---

FR2992203B1|2012-06-21|2014-10-24|Oreal|COSMETIC COMPOSITION FOR SKIN MAKE-UP|

---

FR2992185B1|2012-06-21|2015-03-27|Oreal|MATIFYING EFFECT COMPOSITION COMPRISING HYDROPHOBIC AEROGEL PARTICLES AND SILICA PARTICLES|

---

FR2992183B1|2012-06-21|2015-04-10|Oreal|MATIFYING EFFECT COMPOSITION COMPRISING HYDROPHOBIC AEROGEL PARTICLES AND EXPANDED POLYMER PARTICLES|

---

FR3002448B1|2013-02-25|2015-04-03|Oreal|COSMETIC COMPOSITION OF GEL TYPE|

---

FR3004536B1|2013-04-15|2016-04-15|Oreal|DEVICE FOR EVALUATING A PRODUCT FROM THE APPLICATION|FR3060978B1|2016-12-27|2020-06-12|L'oreal|PICKERING EMULSION WITH IMPROVED SENSORY EFFECT|

---

FR3067934B1|2017-06-27|2019-08-09|L'oreal|GELIFIED COMPOSITION COMPRISING A DISPERSION OF SOLID AGGREGATES.|

---

CN107519027A|2017-09-01|2017-12-29|郝庆好|Dumb light elasticity eye shadow and preparation method thereof|

---

GB201718032D0|2017-11-01|2017-12-13|British American TobaccoLtd|Aerosolisable gel|

---

FR3090327B1|2018-12-20|2020-12-25|Oreal|Gelled composition comprising two hydrophilic gelling agents and solid aggregates|

法律状态:
2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |

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2017-02-24| PLFP| Fee payment|Year of fee payment: 2 |

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2017-08-10| PLFP| Fee payment|Year of fee payment: 3 |

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2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |

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2019-08-15| PLFP| Fee payment|Year of fee payment: 5 |

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2020-07-10| RX| Complete rejection|Effective date: 20200529 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1461334A|FR3028753B1|2014-11-24|2014-11-24|AQUEOUS OR HYDRO-ALCOHOLIC GEL OF SYNTHETIC PHYLLOSILICATES AS A VISCOSING AGENT, MATIFIING AND / OR HOMOGENIZING APPLICATION|

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