GEL-TYPE COSMETIC COMPOSITION IMPROVED

专利摘要:
The present invention relates to a composition, in particular a cosmetic composition for makeup and / or care of keratinous substances, in particular skin and / or lips, and keratinous fibers, in particular the eyebrows, comprising: at least one aqueous phase gelled with minus a hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one hydrophobic film-forming polymer.
公开号:FR3025100A1
申请号:FR1458064
申请日:2014-08-28
公开日:2016-03-04
发明作者:Bouchra Bouarfa；Veronique Ferrari
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The present invention aims to provide for the field of care and / or make-up of keratinous substances, in particular of the skin and / or the lips, and in particular of the skin, and of keratinous fibers, in particular the eyebrows, a new galenic particularly interesting in view of its technical performance and sensory sensations that it provides to the user when it is applied on them and in particular on the skin. By "keratin materials" is meant in particular the skin, the lips, the eyebrows and / or the eyelashes, in particular the skin and / or the eyebrows, and preferably the skin. Cosmetic compositions, for example foundation, are commonly used to bring an aesthetic color to the skin, but also to camouflage, and / or to unify the imperfections of the relief of the skin such as wrinkles and / or fine lines and / or or scars. In this regard, many formulations, solid or fluid, anhydrous or not, have so far been developed. To date, there are multiphase compositions that are interesting in terms of the makeup properties that they confer, in particular mattness and coverage. However, the corresponding compositions currently available are not totally satisfactory. Indeed, they do not always make it possible to guarantee that the dullness is maintained over time, which tends to deteriorate during the day. Consequently, it would be advantageous to optimize the multiphasic compositions for their cosmetic uses in terms of keeping the makeup result, which maintains the mattness over time and the homogeneity of the makeup, without impairing their other performances. In fact, the users, especially having the combination to oily skin, expect from these formulations a remanence. In particular, they want these products to give them a dull effect, while avoiding having shiny skin during the day, as well as a homogeneous makeup result. Other cosmetic compositions, for example to fix the eyebrows, are also known to those skilled in the art. It is most often anhydrous architectures, especially in the form of a pencil. These pencils, which apply to the skin and eyebrows, are dedicated to redraw the eyebrows.
[0002] 3025100 2 However, these formulations have the disadvantage of coloring the skin more than the eyebrows and migrate or drool, which makes the makeup result inhomogeneous over time. Consequently, it would also be advantageous to have cosmetic compositions dedicated to the makeup of the eyebrows and capable, on the one hand, of depositing dyeing material on the surface of the eyebrows, that is to say on the keratin fiber and not on the not essentially on the skin, and secondly to guarantee a holding of this deposit satisfactory in time. The present invention aims precisely to meet these needs.
[0003] 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 keratin materials, in particular skin and / or lips, and keratinous fibers, in particular the eyebrows, comprising: - at least one aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one hydrophobic film-forming polymer. According to a preferred embodiment, a composition according to the invention comprises pigments in combination with a polar additive.
[0004] For the purposes of the invention, the term "polar additive" means a polar compound characterized by a parameter of polarity 8a equal to or greater than 3.0 (J / cm 3) 1/2. By "polarity parameter" is meant, in the sense of the invention, the average parameter 8a reflecting the polarity of a molecule: the higher the value of 8a, the higher the polarity of the molecule is high.
[0005] The average parameter 8a is defined according to the solubility parameters of Hansen 8p and 8h, according to the following relation: 8a = - / (bp2 8h2) The parameters 8p and 8h respectively characterize the Debye interaction forces between permanent dipoles and the ability of a compound to give hydrogen bonds. These parameters are defined according to the HANSEN solubility parameter space in J. Paint Technology 39, 195 (1967) "The Three Dimensional Solubility Parameter - Key to Paint Component Affinities".
[0006] Unexpectedly, and as is apparent from the examples given below, the inventors have found that the formulation of a hydrophobic film-forming polymer in a gel-gel architecture as defined above makes it possible to boost the behavior over time. dullness, and significantly improve the holding of the makeup deposit.
[0007] Moreover, these compositions make it possible to bring freshness and lightness while masking the zones of imperfections of the relief of the skin or of those without hair in the fringe of the eyebrow. Compositions, called gel-gel, are already proposed in the cosmetics 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 at the present time make it possible to guarantee all the essential properties expected in the cosmetics field, such as a pleasant texture during gripping of the product, a non-sticky deposit , comfortable and homogeneous makeup, or a stability in time of the formulation. As specified above, the inventors have found that the use of hydrophobic film-forming polymers in a multiphase composition according to the invention makes it possible to guarantee the mattness of the matt, as illustrated in the examples. Thus, a composition according to the invention has a very good behavior of dullness over time, while providing a feeling of freshness and lightness to the user. Finally, the composition is easy to apply on the surface of the targeted keratin material. Another subject of the invention, according to another of its aspects, is a process for the preparation of a composition, especially a cosmetic composition for makeup and / or care of keratin materials, in particular skin and / or lips, and keratinous fibers, in particular the eyebrows, comprising at least one mixing step: an aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; Under conditions conducive to obtaining a macroscopically homogeneous mixture; said composition further comprising at least one hydrophobic film-forming polymer.
[0008] According to an alternative embodiment, this process may advantageously comprise a step of mixing at least three or more gelled phases. 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. Advantageously, the mixing of the phases can be carried out at ambient temperature. However, the method of the invention may include, if necessary, a step of heating the mixture.
[0009] 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.
[0010] Multiphase formulas can thus be developed. According to another of its aspects, the subject of the invention is also a process for makeup and / or care, in particular cosmetic care, of a keratin material, in particular of the skin and / or the lips, and of keratinous fibers, particularly the eyebrows, comprising at least one step of applying to said keratin material a composition according to the invention. According to yet another of its aspects, the present invention relates to a cosmetic process for makeup and / or care of a keratinous material, in particular of the skin and / or the lips, and of keratinous fibers, in particular the eyebrows, comprising at least less the application on said material of a macroscopically homogeneous composition obtained by extemporaneous mixing, before application or at the time of application to said keratin material, of at least one aqueous phase gelled with at least one hydrophilic gelling agent, and at least one oily phase gelled with at least one lipophilic gelling agent; and said composition further comprising at least one hydrophobic film-forming polymer.
[0011] COSMETIC COMPOSITION First of all, it is important to note that a composition according to the invention is different from an emulsion. An emulsion generally consists of an oily liquid phase and an aqueous liquid phase. It is a dispersion of droplets of one of the two liquid phases in the other. The size of the droplets forming the dispersed phase of the emulsion is typically of the order of one micrometer (0.1 to 100 μm). In addition, an emulsion requires the presence of a surfactant or an emulsifier to ensure its stability over time.
[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. Therefore, a particularly cosmetic composition according to the invention does not require surfactant or silicone emulsifier to ensure its stability over time. It is known from the state of the art to observe the intrinsic nature of a mixture of aqueous and oily gels in a gel-type composition, for example by introducing a coloring material either in the aqueous gelled phase or in the lipophilic gelled phase, prior to formation of the gel-like composition. In visual inspection, in a gel-like composition, the coloring matter appears to be uniformly dispersed, even though the dye is present only in the gelled aqueous phase or in the gelled 3025100 6 oil phase. Indeed, if two different color-different dyes are introduced respectively into the oil phase and the aqueous phase, before the formation of the gel-type composition, the two colors can be observed as uniformly dispersed throughout the gel-like composition. This is different from an emulsion in which, if a water-soluble or oil-soluble dye is introduced into the aqueous and oily phases, respectively, before forming the emulsion, only the color of the emulsion will be observed. dye present in the outer phase (Remington: The Science and Practice of Pharmacy, 19th Edition (1995), Chapter 21, page 282). It is also known to distinguish a gel-like composition from an emulsion by performing a "drop test". This test consists in demonstrating the bi-continuous nature of a gel-type 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-like 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 at 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-type composition (bi-continuous system), the hydrophilic and hydrophobic drops diffuse throughout the sample. In the case of the present invention, the test which will be preferred for distinguishing a gel composition from an emulsion is a dilution test. Indeed, in a gel-like 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-like 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 500 ml plastic beaker. The dilution 3025100 7 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 may be noted that oils such as Parleam® and Xiameter PMX-200 Silicone Fluid 5CS® marketed by Dow Corning are suitable as a diluting solvent in the same way as one of the oils contained in the composition. In the case of a gel-like composition (bicontinuous system), when diluted in oil or water, a heterogeneous appearance is always observed. When a gel-like composition (bicontinuous system) is diluted in water, pieces of oily gel are observed in suspension and when a gel-like composition (bicontinuous system) is diluted in oil, it is observed that pieces of aqueous gel in suspension. On the contrary, during the dilution, the emulsions exhibit a different behavior. An O / W emulsion, when diluted in an aqueous solvent, gradually reduces without having a heterogeneous and lumpy appearance. This same O / W emulsion, when diluted with the oil, has a heterogeneous appearance (pieces of O / W emulsion suspended in the oil). W / O emulsion, when diluted with an aqueous solvent, has a heterogeneous appearance (W / O emulsion pieces suspended in water). This same W / O emulsion, when diluted in the oil, gradually reduces without presenting a heterogeneous and lumpy appearance. According to the present invention, the aqueous gelled phase and the gelled oily phase forming a composition according to the invention are present in a weight ratio ranging from 95/5 to 5/95. More preferably, the aqueous phase and the oily phase are present in a weight ratio ranging from 30/70 to 80/20. The ratio between the two gelled phases is adjusted according to the desired cosmetic properties. Thus, in the case of a make-up composition, in particular the face, it will be advantageous to favor an aqueous gelled phase / oily gelled phase weight ratio greater than 1, in particular ranging from 60/40 to 90/10, preferably ranging from 60/40 to 80/20, preferably 60/40 to 70/30 and even more preferably to promote an aqueous gelled phase / glycerized glycerol weight ratio of 60/40 or 70/30.
[0013] These preferred ratios are particularly advantageous for obtaining fresh and light compositions. Advantageously, a composition according to the invention can therefore be in the form of a creamy gel having a minimum stress below which it does not flow unless subjected to external mechanical stress. As is apparent from the following a composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa. It may also advantageously have a modulus of rigidity G * of at least 400 Pa, and preferably greater than 1000 Pa.
[0014] 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 carried out by means of rheology measurements in oscillation. A methodology is proposed in the chapter exemplification 15 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 device anti-evaporation (bell). For each measurement, the sample is gently set up and the measurements begin 5 minutes after the sample has been placed in the air gap (2 mm). The tested composition is then subjected to a stress ramp of 10-2 at 102 Pa at a frequency set at 1 Hz. A composition according to the invention may also have a certain elasticity. This elasticity can be characterized by a modulus of rigidity G * which below this minimum stress threshold can be at least equal to 400 Pa, and preferably greater than 1000 Pa. The G * value of a composition can be obtained by subjecting the composition considered at a stress ramp of 10-2 at 102 Pa at a frequency set at 1 Hz. HYDROPHILIC GELIFIER The term "hydrophilic gelling agent" in the sense of the present invention, a compound capable of gelling the aqueous phase of the compositions according to the invention. the invention. The gelling agent is hydrophilic and is therefore present in the aqueous phase of the composition.
[0015] The gelling agent may be water-soluble or water-dispersible. As specified above, the aqueous phase of a composition according to the invention is gelled with at least one hydrophilic gelling agent. The hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents, natural or natural polymeric gelling agents, mixed silicates and pyrogenic silicas, and mixtures thereof. Preferably, the hydrophilic gelling agent may be chosen from synthetic polymeric gelling agents.
[0016] 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.
[0017] 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.
[0018] More particularly, the polysaccharides suitable for the invention can be distinguished according to whether they are starchy or non-starchy. THE. Amylaceous Polysaccharides Representative of this category may be particularly mentioned, native starches, modified starches and particulate starches.
[0019] 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 (C6E11005). The number of these motifs 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 10 OF CHEMICAL TECHNOLOGY, 3rd edition, volume 21, pages 492-507, Wiley Interscience, 1983". The relative proportions of amylose and amylopectin, as well as their degree of polymerization, vary according to the botanical origin of the starches.On average, a sample of native starch is about 25% amylose and 75% amylopectin. Sometimes, there is presence of phytoglycogen (between 0% and 20% of the starch), an analogue of amylopectin but branched every 10 to 15 glucose residues. The starch may be in the form of semi-crystalline granules: the amylopectin is organized into sheets, the amylose forms an amorphous zone less well organized between the different layers. Amyloidosis is organized into a right helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, more easily if it is in the form of amylopectin. Indeed, helical formation does not promote the accessibility of starch to enzymes.
[0020] 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 be of botanical origin cereals or tubers. Thus, the starches are for example chosen from starches of maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, pea.
[0021] 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 Ge ™ ™ by the company Cargill, under the name Corn starch by the company. Roquette, and under the name Tapioca Pure by the company National 5 Starch. Modified starches The modified starches used in the composition of the invention may be modified by one or more of the following reactions: pre-gelatinization, degradation (acid hydrolysis, oxidation, dextrinization), substitution (esterification, etherification), crosslinking (esterification) , bleaching. More particularly, these reactions can be carried out as follows: pre-gelatinization by bursting the starch granules (eg drying and baking in a drying drum); - acid hydrolysis resulting in a very rapid retrogressive 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 C6 hydroxyl group); dextrinisation in an acid medium at high temperature (hydrolysis then repolymerization); crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules which will thus be bonded together (for example with glyceryl and / or phosphate groups); alkaline esterification for the grafting of functional groups, especially C1-C6 acyl (acetyl), hydroxyalkyl C1-C6 (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic. In particular, it is possible to obtain, by means of crosslinking with phosphorus compounds, mono-starch phosphates (of the Am-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.
[0022] In particular, X denotes alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonia salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, 3-aminopropanediol-1,2, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline. The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate. According to the invention, it is also possible to use amphoteric starches, these amphoteric starches contain one or more anionic groups and one or more cationic groups. The anionic and cationic groups may be bonded to the same reactive site of the starch molecule or to different reactive sites, preferably they are bonded to the same reactive site. The anionic groups may be of carboxylic, phosphate or sulfate type and preferably carboxylic. The cationic groups may be of primary, secondary, tertiary or quaternary amine type. The amphoteric starches are in particular chosen from 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: - St-O represents a molecule of: ## STR5 ## in which: ## STR2 ## in which: starch 5-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; integer equal to 2 or 3; 10 - 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; R "represents a hydrogen atom or an alkyl radical having 1 to 18 carbon atoms.
[0023] These compounds are in particular described in US Pat. Nos. 5,455,340 and 4,017,460. The starch molecules can be derived from all plant sources of starch such as, in particular, corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above. The modified starches are represented, for example, by the products sold under the names C * Tex-Instant (pre-gelatinized adipate), C * StabiTex-Instant (pre-gelatinized phosphate), C * PolarTex-Instant (pre-gelatinized hydroxypropyl), C * Set (acid hydrolysis, oxidation), C * size (oxidation), C * BatterCrisp (oxidation), C * DrySet 25 (dextrinisation), C * TexTM (acetylated diamidon adipate), C * PolarTexTM (hydroxypropylated diamidon phosphate) ), C * StabiTexTM (diamidon phosphate, acetylated diamidon phosphate) by Cargill, diamidon phosphates or compounds rich in diamidon phosphate, such as the product sold under the references PREJEL VA-70-T AGGL (phosphate de hydroxypropylated manioc gelatinized diamidon) or PREJEL TK1 (gelatinized manioc diamidon phosphate) or PREJEL 200 (gelatinized acetylated diamidon phosphate 3025100 14) by the company AVEBE or STRUCTURE ZEA by NATIONAL STARCH (cornstarch phosphate) gelatinized). As examples of oxidized starches, use will be made in particular those marketed under the name C * size of the company Cargill.
[0024] 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. aqueous phase.
[0025] Particle starches In particular, particulate starches may be mentioned: starches grafted with an acrylic polymer (homopolymer or copolymer) and in particular with sodium polyacrylate, for example those sold under the name Sanfresh ST-100 ™ by 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.
[0026] Particularly suitable are the (C 1 -C 4) carboxyalkyl starches, hereinafter referred to as "carboxyalkyl starch". These compounds are obtained by grafting carboxyalkyl groups on one or more alcohol functions of the starch, in particular by reaction of starch and sodium monochloroacetate in an alkaline medium. The carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1. The degree of 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 with an ester or ether group per monosaccharide unit of the polysaccharide. 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. The (C1-C4) carboxyalkyl starches are advantageously in the context of the present invention carboxymethyl starches. The carboxymethyl starches preferably comprise units of the following formula: embedded image in which X, whether or not covalently bonded to the carboxylic unit, denotes a hydrogen atom, an alkali metal or alkaline earth metal such as Na, K , Li, NH4, a quaternary ammonium or an organic amine such as for example such as mono, di or triethanolamine. Preferably, X denotes an Na + cation. The carboxyalkyl starches which can be used according to the present invention are preferably the 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.
[0027] In a particular embodiment, use will be made of potato carboxymethyl starches sold in particular under the name GLYCOLYS® by the company Roquette. 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.
[0028] This swelling may be characterized by a swelling power Q which may advantageously be between 10 and 30 ml / g, preferably between 15 and 25 ml (volume of absorbed liquid) / g of dry particulate material. Thus, the size of the swollen carboxyalkyl starch particles used according to the present invention generally varies from 25 to 300 μm. For example, 10% by weight PRIMOJEL® gel 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 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. According to one variant embodiment, the hydrophilic gelling agent is non-starchy. LB. Non-starch polysaccharides Generally, non-starch polysaccharides may be selected from polysaccharides made 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, pectic acids and pectins, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabic, tragacanth gums, ghatti gums, karaya gums, locust bean gums, galactomannans such as guar gums and their nonionic derivatives, in particular hydroxypropyl guar, and ionic, biopolysaccharide gums of microbial origin, in particular scleroglucan or xanthan gums, mucopolysaccharides, and especially chondroitin sulphates and mixtures thereof. These polysaccharides may be modified chemically, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, alkylation, or by several of these modifications.
[0029] The derivatives obtained can be anionic, cationic, amphoteric or nonionic. Advantageously, the polysaccharides may be chosen from carrageenans, in particular kappa-carrageenan, gellan gum, agar-agar, xanthan gum, and alginate-based compounds, in particular alginate. sodium, saroglucan gum, guar gum, inulin, pullulan, and mixtures thereof. In general, the compounds of this type that can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and Vol. 15, pp 439-458 ", in" Polymers in Nature, by E. A. Mc GREGOR and C. T.
[0030] 30 GREENWOOD, Editions John Wiley & Sons, Chapter 6, pp. 240-328, 1980 ", in Robert L. DAVIDSON's book" Handbook of Water Soluble Gums and Resins "edited by Mc Graw Hill Book Company (1980) and in Industrial Gums 3025100 18 "Polysaccharides and their Derivatives, Edited by Roy L. WHISTLER, Second Edition, Academic Press Publishing 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 between 0% by weight. , 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. 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.
[0031] 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 β (1,4) -linked β-D-glucoses, similar to cellulose. One out of every two glucose molecules has a trisaccharide side chain consisting of α-Mannose, β-D-glucuronic acid and terminal β-D-mannose. The internal mannose residue is generally acetylated on carbon 6. About 30% of the end mannose residues carry a pyruvate group bound in chelated form between carbons 4 and 6.
[0032] The glucuronic acids and charged pyruvic acids are ionizable and therefore responsible for the anionic nature of xanthan (negative charge up to pH 1). The contents of the pyruvate and acetate residues vary according to the strain of bacteria, the fermentation process, the conditions after fermentation and the purification steps. These groups can be neutralized in commercial products with Na +, K + or Ca2 + ions (SATIA Company, 1986). The neutralized form can be converted to an acid form by ion exchange or by dialysis of an acidic solution. The xanthan gums have a molecular weight of between 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, type 30 LVT at 60 rpm). The xanthan gums are represented for example by the products sold under the names Rhodicare by the company Rhodia Chimie, under the name 3025100 19 name SATIAXANETM by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industry), under the name NOVAXANTM by the company ADM, and under the names Kelzan® and Keltrol® by the company CP-Kelco.
[0033] 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 via 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 polysaccharide without a charged, biologically inert group 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.
[0034] Scleroglucan Scleroglucan is a nonionic branched homopolysaccharide consisting of (3-D glucan units.) The molecules consist of a linear main chain consisting of D-glucose units linked by P (1,3) bonds and one of which out of three is bound to a side D-glucose unit via a P (1,6) link.A more complete description of scleroglucans and their preparation can be found in US 3,301,848, for example, scleroglucan is sold under the name AIVIIGEL by the company ALBAN MULLER, or under the name ACTIGUMTM CS by the company Cargill Gellan gum Gellan gum is an anionic linear heteropolyoside based on units of oligoside composed of 4 Ooses (tetra-oside). Glucose, L-rhamnose and D-glucuronic acid in proportions 2: 1: 1 are present in gellan gum as monomeric elements, for example sold under the name KELCOGEL. CG LA by the company CP KELCO.
[0035] Polysaccharides isolated from algae Galactannes 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 can be in the form of 3,6-anhydro. Depending on the number and position of ester-sulphate groups on the repeating disaccharide of the molecule, there are several types of carrageenans with 3025100, namely: kappa-carrageenans which have an ester-sulphate group, iotacarraghenans which have two ester groups sulphate and lambda-carrageenans which have three ester-sulphate groups. Carrageenans consist essentially of potassium, sodium, magnesium, triethanolamine and / or calcium salts and polysaccharide sulfate esters. The carrageenans are marketed by the company Seppic under the name Solagum®, by the company Gelymar under the name Carragel®, Carralact®, and Carrasol® by the company Cargill under the names SATIAGELTM and 10 SATIAGUMTm, and by the CP-Kelco company under the name GENULACTA®, GENUGEL® and GENUVI SC Oe. Galactans Agar type are galactose polysaccharides contained in the cell wall of some of these species of red algae (rhodophycea). They are formed of a polymer group whose base skeleton is a chain f3 (1,3) D-galactopyranose and a (1,4) L 3-6 anhydrogalactose, these units repeating regularly and alternately. The differences within the agar family are due to the presence or absence of methyl or carboxyethylated solvate groups. These hybrid structures are generally present as a variable percentage, depending on the species of algae and the season of harvest.
[0036] The agar agar is a mixture of high molecular weight polysaccharides (agarose and agaropectin) of between 40,000 and 300,000 g.mol -1. It is obtained by producing algae extraction juices, usually by autoclaving, and treating these juices which include about 2% agar-agar, in order to extract it. The agar is for example produced by the B & V Agar Producers Group, under the name Gold Agar, Agarite and Grand Agar by the company Hispanagar, and under the names Agar-Agar, QSA (Quick Soluble Agar), and Puragar by the company. Setexam. Furcellarane Furcellaran is obtained commercially from red seaweed Furcellaria fasztigiata. Furcellarane is for example produced by the company East-Agar.
[0037] For the purposes of the invention, the term "alginate-based compound" means alginic acid, alginic acid derivatives and alginic acid salts (alginates) or said alginate-based compounds. derivatives.
[0038] 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). The alginic acid is capable of forming water-soluble salts (alginates) with alkali metals such as sodium, potassium, lithium, substituted amine and substituted ammonium cations such as methylamine, ethanolamine, diethanolamine, triethanolamine. These alginates are water-soluble in aqueous medium at a pH of 4 but dissociate in alginic acid at a pH below 4. This (s) compound (s) based on alginate is (are) capable (s) to crosslink in the presence At least one crosslinking agent, by formation of ionic bonds between 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. 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. Advantageously, the alginate compound is an alginate salt, and preferably sodium alginate. The alginate-based compound may be chemically modified, in particular by urea, urethane groups, or by reaction of hydrolysis, oxidation, esterification, etherification, sulfation, phosphatation, amination, amidation, alkylation, or by several of these modifications.
[0039] The derivatives obtained can be anionic, cationic, amphoteric or nonionic.
[0040] The alginate-based compounds that are suitable for the invention can be represented, for example, by the products sold under the names Kelcsol, SatalginetM, Cecalgum ™ or Algogel ™ by the company Cargill products, under the name Protanal ™ by the company FMC Biopolymer. , under the name 5 GRINDSTED® Alginate by the company Danisco, under the name KIMICA ALGIN by the company KIMICA, and under the names Manucol® and Manugel® by the company ISP. This class of polysaccharides can be divided into homogeneous polysaccharides (a single species of oses) and heterogeneous compounds 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. By cellulosic compound is meant according to the invention 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).
[0041] The polymers thus formed associate with each other by intermolecular links of the hydrogen bonding type, thus conferring a fibrillar structure on the cellulose (about 1500 molecules per fiber).
[0042] The degree of polymerization differs enormously depending on the origin of the cellulose; its value can vary from a few hundred to a few tens of thousands. Cellulose has the following chemical structure: ....................
[0043] The hydroxyl groups of the cellulose may react partially or totally with different chemical reagents to give cellulosic derivatives having their own properties. The cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Among these derivatives, there are the cellulose ethers, the cellulose esters and the 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, mention may be made of carboxyalkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses and carboxymethylhydroxyethylcelluloses and their sodium salts. Among the cationic cellulose ethers, mention may be made of quaternized hydroxyethylcelluloses which may or may not be crosslinked. The quaternizer may be especially glycidyltrimethylammonium chloride or a fatty amine such as laurylamine or stearylamine. Another cationic cellulose ether is hydroxyethylcellulose hydroxypropyltrimethylammonium. The quaternized cellulose derivatives are, in particular: quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures of these; this ; 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 celluloses or hydroxyethylcelluloses quaternized above preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
[0044] Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12 alkyl) 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, in particular with C8- 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.
[0045] Among the cellulose esters, there are the inorganic esters of cellulose (cellulose nitrates, sulphates, or phosphates, etc.), the cellulose organic 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, there may be mentioned hydroxypropyl methylcellulose phthalates and ethylcellulose sulfates.
[0046] 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 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 trade names Aqualon® (carboxymethylcellulose and sodium carboxymethylcellulose), Benecel® (methylcellulose), 10 BlanoseTM (carboxymethylcellulose), Culminai® (methylcellulose, hydroxypropyl methylcellulose), Klucel® (hydroxypropylcellulose), Polyoxy surf (cetyl hydroxyethylcellulose) and Natrosol® CS (hydroxyethylcellulose) by Hercules Aqualon.
[0047] Fructosans The polysaccharide according to the invention may especially be a fructosan selected from among inulin and its derivatives (in particular dicarboxy and carboxymethyl inulines). Fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with a number 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 like inulins.The second group also corresponds to linear fructoses but the Fructose units are essentially linked by (3 (2,6) bonds.) These products are levans.
[0048] The third group corresponds to mixed fructans, that is to say having sequences (3 (2,6) and (3 (2,1)), which are essentially branched fructans than the graminans. the compositions according to the invention are inulins.
[0049] Inulin can be obtained for example from chicory, dahlia or Jerusalem artichoke, preferably from chicory. In particular, the polysaccharide, especially inulin, has a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60, and a degree of substitution of less than 2 on the basis of a fructose unit.
[0050] 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. 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.
[0051] Galactomannans (guar, carob, fenugreek, tara gum) and derivatives (phosphated guar, hydroxypropyl guar, etc.) Galactomannans are nonionic polysaccharides extracted from the albumen of leguminous seeds of which they constitute the reserve carbohydrate. Galactomannans are macromolecules consisting of a main chain of β (1,4) -linked D-mannopyranose units carrying side branches consisting of a single α-1,6-linked D-galactopyranose unit at the main channel. The different galactomannans are distinguished on the one hand by the proportion of galactopyranose α-D-3025100 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. The mannose / galactose ratio (M / G) is of the order of 2 for guar gum, 3 for tara gum and 4 for locust bean gum.
[0052] The galactomannans have the following chemical structure: ## STR1 ## The guar gum is characterized by a mannose: galactose ratio of the order of 2: 1. The galactose group is regularly distributed along the mannose chain.
[0053] The guar gums which can be used according to the invention can be nonionic, cationic or anionic. According to the invention, chemically modified or unmodified nonionic guar gums can be used. 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 VISCOGUMTM by the company Cargill, and under the name Supercol® guar gum by the company Aqualon. The hydrolysed nonionic guar gums that may be used according to the invention are, for example, represented by the products sold under the name Meyprodor® 20 by Danisco. The modified nonionic guar gums which can be used according to the invention are preferably modified with hydroxyC 1 -C 6 groups, among which, by way of example, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups may be mentioned.
[0054] Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP 60, Jaguar HP 105 and Jaguar HP 120 (hydroxypropyl guar), by the company Rhodia, or under the name N -Hance® HP (hydroxypropyl guar) by the company AQUALON. The cationic galactomannan gums preferably have a cationic charge density less than or equal to 1.5 meq / g and more particularly between 0.1 and 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.
[0055] 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 into cationic groups. Preferred cationic groups are chosen from those comprising primary, secondary, tertiary and / or quaternary amine groups.
[0056] The cationic galactomannan gums used generally have a weight average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6. The cationic galactomannan gums that can be used according to the present invention are, for example, gums comprising cationic trialkyl (C 1 -C 4) ammonium groups. Preferably, 2% to 30% by number of the hydroxyl functions of these gums carry cationic trialkylammonium groups. Among these trialkylammonium groups, there may be mentioned very particularly trimethylammonium and triethylammonium groups. Even more preferably, these groups represent from 5% to 20% by weight of the total weight of the modified galactomannan gum. According to the invention, the cationic galactomannan gum is preferably a guar gum comprising hydroxypropyltrimethylammonium groups, that is to say a guar gum modified for example with 2,3-epoxypropyltrimethylammonium chloride.
[0057] These galactomannan gums, in particular of 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 moreover 30,25,100 sold. especially 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 Chloride) by the company Degussa, and under the name N-Hance® 3000 (Guar 5 Hydroxypropyltrimonium Chloride) by the company Aqualon. The anionic guar gums that may be used according to the invention are polymers containing groups derived from carboxylic, sulfonic, sulphene, phosphoric, phosphonic acid or pyruvic acid. Preferably, the anionic group is a carboxylic acid group. The anionic group may also be in the form of an acid salt, especially a salt of sodium, calcium, lithium or potassium. The anionic guar gums that can be used according to the invention are preferably carboxymethyl guar derivatives (carboxymethyl guar or carboxymethyl hydroxypropyl guar).
[0058] 15 Carob Locust bean gum is extracted from carob seed (Ceratonia siliqua). The unmodified carob gum that can be used in this invention is sold, for example, under the name 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.
[0059] 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.
[0060] Glucomannans (konjac gum) Glucomannan is a high molecular weight polysaccharide (500,000 <Mglucomannan <2,000,000), composed of D-mannose units and D-glucose with 3025,100 branches every 50 or 60 units approx. It is found in wood but it is also the main constituent of Konjac gum. Konjac (Amorphophallus konjac) is a plant of the family Araceae. The products which can be used according to the invention are for example sold under the name Propol® and Rheolex® by the company Shimizu. LM and HM Pectins, and Derivatives 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, Dxylose). 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. 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 may vary between 70% (apple, lemon) and 10% (strawberry) depending on the source used. From pectins of high degree of esterification, it is possible to hydrolyze the -COOCH3 groups, in order to obtain weakly esterified pectins. Depending on the proportion of methyl or non-methylated 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 an -NI-12 group. The pectins are especially marketed by Cargill under the name Unipectine ™ by the company CP-Kelco under the name GENU, by Danisco under the name GRINSTED Pectin.
[0061] 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), the chitosan and derivatives (chitosan-beta-glycerophosphate, carboxymethylchitine, 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".
[0062] Xylans consist of a main chain of P (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. According to this variant, the polysaccharide is preferably hyaluronic acid, or one of its salts, such as the sodium salt (sodium hyaluronate). II. Synthetic Polymer Gelling Agents For the purposes of the invention, the term synthetic means that the polymer is neither naturally existing nor derived from a polymer of natural origin.
[0063] The synthetic polymeric hydrophilic gelling agent according to the invention may be particulate or non-particulate. For the purposes of the invention, the term "particulate" means that the polymer is in the form of particles, preferably spherical. As is apparent from the following, the polymeric hydrophilic gelling agent is advantageously chosen from crosslinked acrylic homopolymers or copolymers; associative polymers, in particular associative polymers of the polyurethane type; polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized; carboxyvinyl polymers, modified or otherwise, and mixtures thereof, in particular as defined below.
[0064] 30 HA. Particulate synthetic polymer gelling agents They are preferably chosen from crosslinked polymers.
[0065] It may in particular be crosslinked homopolymers or acrylic copolymers, preferably partially neutralized or neutralized, which are in particulate form. According to one embodiment, the particulate gelling agent according to the present invention is chosen from crosslinked sodium polyacrylates. Preferably, it has, in the dry or non-hydrated state, an average size of less than or equal to 100 μm, preferably less than or equal to 50 μm. The average particle size corresponds to the mean diameter by mass (D50) measured by laser particle size distribution or other equivalent method known to those skilled in the art.
[0066] Thus, preferably, the particulate gelling agent according to the present invention is selected from crosslinked sodium polyacrylates, preferably in the form of particles having a mean size (or average diameter) less than or equal to 100 microns, more preferably in the form of 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 sold under the names Luquasorb 1003, Luquasorb 1010, Luquasorb 1280 and Luquasorb 1110 by BASF, those sold under the names Water Lock G400 and G430 (INCI name: Acrylamide / Sodium acrylate copolymer) by the company Grain Processing. Cross-linked polyacrylate microspheres such as, for example, those marketed under the name AQUAKEEP® 10 SH NF proposed by the company Sumitomo Seika may also be mentioned. Such gelling agents may be used in amounts of 0.1% to 5% by weight relative to the total weight of the aqueous phase, in particular from 0.5% to 2% by weight, and in particular from about 0.8% to 1.7% by weight based on the total weight of the aqueous phase. II.B. Non-particulate synthetic polymeric gelling agents This family of gelling agents can be detailed in the following subfamilies: 1. Associative polymers, 3025100 2. Polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized, and 3. Modified carboxyvinyl polymers or not.
[0067] II.B.1 Associative polymers For the purposes of the present invention, the term "associative polymer" means any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers according to the present invention may be anionic, cationic, nonionic or amphoteric.
[0068] 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 unsaturated anionic monomer. ethylenic, more particularly by a vinyl carboxylic acid and very particularly by an acrylic acid, a methacrylic acid or their mixtures, and whose fatty-chain allyl ether unit corresponds to the monomer of formula (I) below: 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, and R denotes a hydrocarbon radical chosen from alkyl and arylalkyl radicals. , aryl, alkylaryl, cycloalkyl, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms.
[0069] Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization method, in 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 / C30-C38 olefin copolymer / isopropyl maleate product sold as Performa V 1608 by Newphase Technologies. Among the associative anionic polymers, according to a preferred embodiment, copolymers comprising among their monomers an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester may be mentioned. Preferably, these compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester of C 1 -C 4 alcohol.
[0070] By way of example of this type of compound, mention may be made of Aculyn 22® sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer (comprising 20 OE units) or Aculyn 28® (terpolymer of methacrylic acid / ethyl acrylate / behenyl methacrylate oxyethylene (250E).
[0071] As associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the 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.
[0072] Associative anionic polymers also include 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) carrying a free acid function, partially or totally salified with a nonionic monomer (2). chosen from NN, dimethylacrylamide and 2-hydroxyethyl acrylate and at least one polyoxyethylenated alkyl acrylate monomer (3) of formula (I) below: (I) in which R 1 represents a hydrogen atom, R represents a linear or branched C2-C5 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 put in solution in water, a high state of entanglement leading to very high viscosities, at low velocity gradient.
[0073] By "crosslinked polymer" is meant a non-linear polymer in the form of three-dimensional network insoluble in water but swellable with water and leading to the production of a chemical gel. The acid function of the monomer (1) is especially the sulfonic acid function, phosphonic acid, said functions being in free form, partially or totally salified. The monomer (1) may be chosen from styrene sulphonic acid, ethylsulphonic acid or 2-methyl-2 [(1-oxo-2-propenyl] amino] 1-propanesulphonic acid (also called Acryloyldimethyltaurate) in free form. partially or totally salified It is present in the anionic terpolymer preferably in molar proportions of between 5% and 95% molar and more particularly between 10% and 90% molar The monomer (1) will be more particularly the acid 2-methyl-24 (1-oxo-2-propenyl] amino] 1-propanesulfonic acid in free form, partially or totally salified.
[0074] The acid function in partially or fully salified form will preferably be an alkali metal salt such as a sodium or potassium salt, an ammonium salt, an aminoalcohol salt such as a monoethanolamine salt or a salt thereof. amino acid such as a salt of lysine. The monomer (2) is preferably present in the anionic terpolymer in molar proportions of between 4.9% and 90 mol% and more preferably between 9.5% and 85 mol% 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, 2-hexyldecyl, 4-methylpentyl and 5-methylhexyl. 6-methylheptyl, 15-methylpentadecyl, 16-methylheptadecyl, 2-hexyloctyl. According to one particular form of the invention, in formula (I), R denotes a C 12 -C 16 alkyl radical.
[0075] According to one particular form of the invention, in the formula (I), n varies from 3 to 5.
[0076] More particularly, the monomer of formula (I) used will be tetraethoxylated lauryl acrylate. The monomer (3) of formula (I) is preferably present in the anionic terpolymer in molar proportions of between 0.1% and 10% mol and more preferably between 0.5% and 5% molar. According to a 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 mol% and preferably from 0.01% to 0.5% molar and more particularly from 0.01% to 0.25% molar. The crosslinking agent and / or the branching agent is preferably chosen from ethylene glycol dimethacrylate, diallyloxoacetic acid or 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. and of lauryl acrylate tetraethoxylated and crosslinked with trimethylol propanetriacrylate, INCI name Polyacrylate Crosspolymer-6 such as the product sold under the trade name Sepimax Zen® by the company Seppic.
[0077] 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 (polyoxyethylene (20) stearyl alcohol). Examples of aminated side chain polyacrylates include polymers 8781-121B or 9492-103 from National Starch.
[0078] Nonionic Associative Polymers The nonionic associative polymers may be chosen from: copolymers of vinyl pyrrolidone and of hydrophobic fatty-chain 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 containing from 50 to 1000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name. According to a preferred embodiment, a nonionic associative polymer of the polyurethane type is used as a gelling agent.
[0079] By way of examples of nonionic polyurethane polyethers with a fatty chain which can be used in the invention, it is also possible to use Rheolate® FX 1100 (Steareth-100 / PEG 136 / HDI (hexamethyl diisocyanate) copolymer), Rheolate® 205 with a urea function sold by Elementis or else Rheolates® 208, 204 or 212, as well as Acrysol® 5 RM 184 or Acrysol® RM 2020. Mention may also be made of the product Elfacos® T210 with an alkyl chain. C12-C14 and the product Elfacos® T212 C16-18 alkyl chain (PPG-14 Palmeth-60 Hexyl Dicarbamate) from Akzo. The product DW 1206B® from Rohm & Haas with a C20 alkyl chain and a urethane linkage, proposed at 20% solids content in water, can also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example of such polymers, mention may be made of Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Elementis. It is also possible to use the product DW 1206F and DW 1206J proposed by Rohm & Haas. The associative polyurethanes that can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen, Colloid Polym. Sci., 271, 380-389 (1993). Even more particularly, according to the invention, it is also possible to use an associative polyurethane that can be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide. (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate. Such polyether polyurethanes are sold in particular by Rohm & Haas under the names Aculyn® 46 and Aculyn® 44. Aculyn 46® is a polyethylene glycol polycondensate containing 150 or 180 moles of ethylene oxide. of stearyl alcohol and methylene bis (4-cyclohexyl isocyanate) (SMDI) at 15% by weight in a matrix of maltodextrin (4%) and water (81%), and Aculyn® 44 is a polyethylene glycol polycondensate containing 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%).
[0080] Solutions or dispersions of these polymers can also be used, especially in water or in a hydroalcoholic medium. By way of example of such polymers, mention may be made of SER AD FX1010, SER AD FX1035 and SER AD 1070 from Elementis, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Elementis. . It is also possible to use Aculyn® 44, Aculyn® 46, DW 1206F and DW 1206J products, as well as Acrysol® RM 184 from Rohm & Haas or Borchi Gel LW 44 from Borchers. and their mixtures. Amphoteric Associative Polymers Among the associative amphoteric polymers of the invention, mention may be made of the amphoteric, crosslinked or non-crosslinked, branched or non-branched polymers which may be obtained by the copolymerization of: 1) at least one monomer of formula Or (IVb): embedded image wherein R4 and R5, which may be identical or different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 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 represents an OH group or an NHC (CH3) 2CH2SO3H group; 3) of at least one monomer of formula (VI): wherein R 9 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes a 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 by 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 by a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate.
[0081] More particularly, the monomer of formula (IVa) is selected from acrylamidopropyl trimethyl ammonium chloride and methacrylamidopropyl trimethyl ammonium 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, acid 2, and the like. -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 selected from the group consisting of C12-C22 and more particularly C16-C18 alkyl acrylates or methacrylates. The crosslinking or branching agent is preferably chosen from N, N'-methylenebisacrylamide, triallylmethylammonium chloride, allyl methacrylate, n-methylolacrylamide and polyethylene glycol dimethacrylates. 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 from 25% to 10%. % to 75% of moles of compound (s) of formula (IVa) or (IVb). They also preferably contain from 1% to 80% by moles, more preferably from 5% to 80% by moles and even more preferably from 25% to 75% by moles of compound (s) of formula (V). The content of compound (s) of formula (VI) is preferably 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. According to a preferred embodiment, the associative polymer is chosen from nonionic associative polymers and more particularly from associative polyurethanes, such as Steareth-100 / PEG-136 / HDI Copolymer sold under the name Rheolate FX 1100 by Elementis. . Such an associative polymer is advantageously used in a proportion of from 0.1% to 8% by weight of dry matter and preferably from 0.5% to 4% by weight relative to the total weight of the aqueous phase. ILB.2 Polyacrylamides and polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid The polymers used which are suitable as aqueous gelling agents for the invention may be homopolymers or copolymers, crosslinked or non-crosslinked, comprising at least one 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 totally or substantially completely neutralized, that is to say neutralized to at least 90%. These AMPS® polymers according to the invention may be crosslinked or non-crosslinked. When the polymers are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for the crosslinking of the polymers obtained by radical polymerization. Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, di (meth) acrylate and the like. ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, the allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and the allylic esters of the phosphoric acid derivatives and / or vinylphosphonic acid, or mixtures of these compounds. According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol 3025100 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. The AMPS® polymers that are suitable for the invention are water-soluble or water-dispersible. In this case they are: either "homopolymers" comprising only AMPS monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above; or copolymers obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenically unsaturated monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above. When said copolymers comprise hydrophobic ethylenically unsaturated monomers, the latter do not comprise a fatty chain and are preferably present in small amounts. For the purposes of the present invention, the term "fatty chain" means any hydrocarbon chain comprising at least 7 carbon atoms.
[0082] By "water-soluble or water-dispersible" is meant polymers which, introduced into an aqueous phase at 25 ° C., at a mass concentration equal to 1%, make it possible to obtain a macroscopically homogeneous and transparent solution. say having a maximum light transmittance value at a wavelength of 500 nm, through a 1 cm thick sample, at least 60%, preferably at least 70%. The "homopolymers" according to the invention are preferably crosslinked and neutralized, and they can be obtained according to the preparation process comprising the following steps: (a) the monomer such as AMPS in free form is dispersed or dissolved in a solution of t-butanol or water and tert-butanol; (b) the solution or dispersion of monomer obtained in (a) is neutralized with one or more inorganic or organic bases, preferably ammonia NH 3, in an amount making it possible to obtain a degree of neutralization of the sulfonic acid functions of the polymer; ranging from 90% to 100%; (C) adding to the solution or dispersion obtained in (b), the crosslinking monomer (s); (D) conventional radical polymerization is carried out in the presence of free radical initiators at a temperature of from 10 ° C to 150 ° C; the precipitating polymer in the tert-butanol solution or dispersion. The water-soluble or water-dispersible copolymers of AMPS® according to the invention contain water-soluble ethylenically unsaturated monomers, hydrophobic monomers or mixtures thereof. The water-soluble comonomers may be ionic or nonionic. Among the water-soluble ionic comonomers, there may be mentioned, for example, the following compounds and their salts: (meth) acrylic acid, styrene sulphonic acid, vinylsulfonic acid and (meth) allylsulphonic acid vinyl phophonic acid, maleic acid, itaconic acid, crotonic acid, the water-soluble vinyl monomers of formula (A) below: HC = CR CO) (1 in which: - Ri is chosen from H, -CH3, -C2H5 or -C3I-17; - Xi is chosen from: - alkyl oxides of -0R2 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-).
[0083] Among the nonionic, water-soluble comonomers, there may be mentioned, for example: (meth) acrylamide, N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methyl N vinylylformamide, maleic anhydride, vinylamine, N-vinyllactams having 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: H 2 C = CR, & D X 2 in which: R 3 is chosen from H, -CH 3, -C 2 H 5 or -C 3 H 7; X2 is chosen from alkyl oxides of the -OR4 type in which R4 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; vinyl chloride and vinylidene chloride; - Silicone derivatives, leading after polymerization to silicone polymers such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides 30 - hydrophobic vinyl monomers of formula (C): 3025100 47 HC = CR (C) 2 4 CO 3 in which: R4 is selected from H, -CH3, -C2H5 or -C3H7; - 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.
[0084] 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 suitable for the invention, mention may be made, for example, of cross-linked or non-crosslinked polymers of sodium acrylamido-2-methyl propane sulphonate such as that used in the commercial product Simulgel 800 (CTFA name: Sodium Polyacryloyldimethyl Taurate), crosslinked polymers of ammonium acrylamido-2-methyl propane sulphonate (INCI name: Ammonium polyacryldimethyltauramide) such as those described in patent EP 0 815 20 928 B1 and such as the product sold under the trade name Hostacerin AMPS® by 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-methylpropane sulfonate copolymers such as that used in the commercial product SEPIGEL 305 (CTFA name: Polyacrylamide / C13-C14 Isoparaffin / Laureth-7) or that used in the commercial product sold under the name Simulgel 600 (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate / 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® 3025100 48 by the company Clariant (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 (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer); copolymers of AMPS® and of hydroxyethyl acrylate, such as, for example, the AMPSe / hydroxyethyl acrylate copolymer, such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate copolymer (And) Squalane (And) Polysorbate 60) or as the product sold under the name Copolymer Acrylamido2-Methylpropane Sodium sulfonate / Hydroxyethylacrylate as the commercial product Sepinov EMT 10 (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate copolymer) . Water-soluble or water-dispersible copolymers of preferred AMPS according to the invention include copolymers of AMPS® and hydroxyethyl acrylate. In general, an aqueous phase according to the invention may comprise from 0.1% to 8% by weight of dry matter, preferably from 0.2% to 5% by weight and more preferably from 0.7% to 5% by weight of polyacrylamide (s) and / or polymer (s) and copolymer (s) of 2-acrylamido-2-methylpropanesulphonic acid, crosslinked and / or neutralized relative to its total weight .
[0085] II.B.3 Modified or Unmodified Carboxyvinyl Polymers The modified or unmodified carboxyvinyl polymers may be copolymers resulting from the polymerization of at least one monomer (a) chosen from α, β-ethylenically unsaturated carboxylic acids or their esters with at least one ethylenically unsaturated monomer (b) having a hydrophobic group.
[0086] 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.
[0087] 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: ## STR2 ## in which R 1 denotes H or CH 3 or C2H5, that is to say monomers acrylic acid, methacrylic acid or ethacrylic acid, and - at least one unsaturated carboxylic acid alkyl ester (Cm-C30) monomer corresponding to the monomer of formula ( 2) wherein R 2 denotes H or CH 3 or C 2 H 5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH 3 (methacrylate units) ), R3 denotes a C10-C30 alkyl radical, and preferably C12-C22. The alkyl esters (C 10 -C 30) of unsaturated carboxylic acids are preferably chosen from lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, 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. 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 in which R2 designates H or CH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, and (2) 3025100 - a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, (meth) acrylate, allyl, 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 C10-C30 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 C10-C30 (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 / C10-30 Alkyl acrylate crosspolymer), such as the products marketed 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 SP® containing 90% of dry matter and 10% of 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. Mention may also be made of partially neutralized sodium polyacrylates in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by the company BASF.
[0088] The modified or unmodified carboxyvinyl polymers may also be selected from crosslinked (meth) acrylic acid homopolymers. By "(meth) acrylic" within the meaning of the present application, the term "acrylic or methacrylic". By way of example, mention may be made of those sold by Lubrizol under the names Carbopol, 910, 934, 940, 941, 934, 980, 981, 2984, 5984, Carbopol Ultrez Polymer, or by 3V-Sigma under Synthalen® K, Synthalen® L, or Synthalen® M.
[0089] Among the carboxyvinyl polymers that may or may not be modified, Carbopol (CTFA name: carbomer) and Pemulen (CTFA name: Acrylates / Cio-3oalkyl acrylate crosspolymer) marketed by Lubrizol may be mentioned in particular. The carboxyvinyl polymers, modified or not, may be present in a proportion of 0.1% to 5% by weight of dry matter relative to the weight of the aqueous phase, in particular of 0.3% to 1% by weight, of preferably between 0.4% and 1% relative to the weight of the aqueous phase. Advantageously, a composition according to the invention comprises a synthetic polymeric hydrophilic gelling agent chosen from polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid. According to a preferred variant, the synthetic polymeric hydrophilic gelling agent is a crosslinked sodium polyacrylate or, preferably, a copolymer of 2-acrylamido-2-methylpropanesulphonic acid and hydroxyethyl acrylate.
[0090] According to another preferred variant, the synthetic polymeric hydrophilic gelling agent is at least one ammonium 2-acrylamido-2-methylpropane sulfonate acid polymer. III. Other Hydrophilic Gelling Agents These gelling agents are more particularly chosen from mixed silicates and pyrogenic silicas. MY. 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 metals. -terrous (eg Be, Mg, Ca), transition metals and aluminum. According to a particular embodiment, the mixed silicate or silicates are in the form of solid particles containing at least 10% by weight of at least one silicate relative to the total weight of the particles. In the remainder of the present disclosure, these particles are referred to as "silicate particles".
[0091] Preferably, the silicate particles contain less than 1% by weight of aluminum relative to the total weight of the particles. Even more preferably, they contain from 0% to 1% by weight of aluminum relative to the total weight of the particles.
[0092] Preferably, the silicate particles contain at least 50% by weight of silicate, more preferably at least 70% by weight based on 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 ensure good cosmetic properties, these silicates are generally in a finely divided form, and in particular in the form of particles having an average size ranging from 2 nm to 1 μm (from 2 nm to 1000 nm), and preferably from 15 nm to 600 nm, and even more preferably 20 to 250 nm. The silicate particles may have any shape, for example the shape of spheres, flakes, needles, platelets, disks, sheets, or totally random forms. Preferably, the silicate particles are in the form of disks or sheets.
[0093] Also, the term "average size" of the particles means the average size in number of the largest dimension (length) that can be measured between two diametrically opposed points of an individual particle. The size can be determined, for example, by transmission electron microscopy, or from the measurement of the specific surface area by the BET method, or by means of a laser granulometer. When the particles in the form of disks or sheets, they generally have a thickness ranging from about 0.5 nm to 5 nm. The silicate particles may be made 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.
[0094] According to one particular embodiment of the invention, the silicates are phyllosilicates, namely silicates having a structure in which the SiO 4 tetrahedra are organized into sheets between which the metal cations are enclosed.
[0095] The mixed silicates 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.
[0096] A particularly preferred family of silicates in the compositions of the present invention is therefore the laponites. Laponites are silicates of magnesium, sodium and possibly lithium, having a layered structure similar to that of montmorillonites. Lapponite is the synthetic form of the natural mineral called "hectorite". The synthetic origin of this family of silicates presents a considerable advantage over the natural form because it allows a good control of the composition of the product. In addition, laponites have the advantage of having a much smaller particle size than natural hectorite and bentonite. As laponites, mention may be made in particular of the products sold under the following names: Laponite® XLS, Laponite® XLG, Laponite® RD, Laponite® 20 RDS, LAPONITE® XL21 (these products are sodium and magnesium silicates and silicates of sodium, lithium and magnesium) by Rockwood Additives 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 of 0.1% to 5% by weight, and in particular of 0.5% to 3% by weight relative to the total weight of the aqueous phase. MB. Hydrophilic pyrogenic silica The pyrogenic silicas according to the present invention are hydrophilic.
[0097] The pyrogenic hydrophilic silicas are obtained by pyrolysis in continuous flame at 1000 ° C. of silicon tetrachloride (SiC14) in the presence of hydrogen and oxygen. Among the hydrophilic silicas of hydrophilic nature that can be used according to the present invention, mention may be made in particular of those sold by Degussa or Evonik Degussa under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or else by CABOT company under the name Carbosil H5. Such gelling agents may be used in amounts of 0.1% to 10% by weight relative to the total weight of the aqueous phase, in particular from 0.1% to 5% by weight, and in particular from 0.1% to 5% by weight. 0.5% to 3% by weight relative to the total weight of the aqueous phase. LIPOPHILIC GELIFIER For the purpose of the present invention, the term "lipophilic gelling agent" is intended to mean a compound capable of gelling the oily phase of the compositions according to the invention. The gelling agent is therefore lipophilic present in the oily phase of the composition. The gelling agent is liposoluble or lipodispersible.
[0098] As is apparent from the following, the lipophilic gelling agent is advantageously selected from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen-bonded polymers, and mixtures thereof.
[0099] I. Particulate gelling agents The particulate gelling agent used in the composition according to the invention is in the form of particles, preferably spherical. Representative of the lipophilic particulate gelling agents that are suitable for the invention may be especially polar, polar and apolar waxes, modified clays, silicas such as pyrogenic silicas and hydrophobic silica aerogels. Waxes The term "wax" considered 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 a melting greater than or equal to 30 ° C up to 200 ° C and in particular up to 120 ° C.
[0100] 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 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 the 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 as a function of temperature is measured. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of temperature. The waxes that may be used in the compositions according to the invention are chosen from waxes, solid, at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof.
[0101] The waxes, within the meaning of the invention, may be those generally used in the cosmetic or dermatological fields. They may in particular be polar or apolar, silicone hydrocarbonaceous and / or fluorinated, optionally having ester or hydroxyl functions. They can also be of natural or synthetic origin. A) Apolar waxes 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, δa is equal to 0 (J / cm 3). 4. 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 dimensional" sohtbility parameters "J. Paint Technol. 39, 105 (1967). According to this Hansen space: 3025100 56 - SD 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; Δh characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor type, etc.); Δa is determined by the equation: δa = ((Sp2 8h2) 1/4 The parameters δp, δh, 15D and δa are expressed in (J / cm3) 1/4, and apolar waxes are in particular waxes hydrocarbon compounds consisting solely of carbon and hydrogen atoms and free from heteroatoms such as N, O, Si and P. The apolar waxes are chosen from microcrystalline waxes, paraffin waxes, ozokerite, waxes, and the like. polyethylene, and mixtures thereof As ozokerite mention may be made of Ozokerite Wax SP 1020 P.
[0102] Microcrystalline waxes that may be used include Multiwax W 445® sold by Sonneborn, Microwax HW® and Base Wax 30540® sold by Paramelt, and Cerewax® No. 3 sold by Baerlocher. Suitable microwaxes which can be used in the compositions according to the invention as apolar wax include polyethylene microwaxes such as those sold under 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 25 211 sold by the company Honeywell. b) Polar wax For the purposes of the present invention, the term "polar wax" means a wax whose solubility parameter at 25 ° C. δa is other than 0 (J / cm 3) 1/4.
[0103] In particular, "polar wax" is intended to mean a wax whose chemical structure is formed essentially or even consisting of carbon atoms and hydrogen, and comprising at least one highly electronegative heteroatom such as an atom. oxygen, nitrogen, silicon or phosphorus. The polar waxes may especially be hydrocarbon, fluorinated or silicone.
[0104] 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.
[0105] 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 COROR 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- (1,1,1-trimethylolpropane) tetrastearate, sold under the name Hest 2T-4S® by the company Heterene. iii) diester waxes of a dicarboxylic acid of the general formula R3 - (- 000R4-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 C4-C30 aliphatic group (linear or branched alkyl group comprising 4 to 30 carbon atoms) which may or may not contain one or more unsaturated groups, and preferably linear and unsaturated. (iv) Waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched Cg-c32 fatty chains, for example hydrogenated jojoba oil, hydrogenated sunflower oil, etc. , hydrogenated castor oil, hydrogenated coconut oil, and waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol. 30 (v) beeswax, synthetic beeswax, polyglycerolated beeswax, carnauba wax, candelilla wax, oxypropylene lanolin wax, rice bran wax, Ouricury, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax, sumac wax, montan wax, orange wax, Laurier wax 5, hydrogenated Jojoba wax, 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. Examples of alcohol waxes are C30-50 Alcohols Performacol® 550 Alcohol sold by New Phase Technologie, stearyl alcohol and cetyl alcohol. It is also possible to use silicone waxes, which may advantageously be substituted polysiloxanes, preferably at a low melting point. By "silicone wax" is meant an oil comprising at least one silicon atom, and especially including 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.
[0106] In the context of the present invention, mention may be made, as particularly advantageous waxes, of polyethylene waxes, jojoba wax, candelilla wax and silicone waxes, in particular candelilla wax. They may be present in the oily phase in a proportion of 0.5% to 30% by weight relative to the weight of the oily phase, for example between 5% and 20% of the oily phase, and more particularly from 2% to 15% by weight relative to the weight of the oily phase.
[0107] The 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 alkyl ammonium 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.
[0108] Preferably they are selected from hectorites. Preferably, the lipophilic clays used are hectorites modified with a C10 to C22 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.
[0109] 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 surface treated hydrophobic fumed silica. 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: 3025100 - 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, 5 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 sold 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 15% by weight. 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.
[0110] 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 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 specific surface area per unit mass (SM) ranging from 500 to 1500 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 a mean diameter by volume (D [ 0.5]) ranging from 1 to 1500 μm, better still from 1 to 1000 μm, preferably from 1 to 100 μm, in particular from 1 to 30 μm, more preferably from 5 to 25 μm, more preferably from 1 to 100 μm; 5 to 20 lm and even better better from 5 to 15 lm.
[0111] 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 30 μm. 25 iam, better from 5 to 20 iam and even better from 5 to 15 pm
[0112] 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.
[0113] The silica airgel particle sizes can be measured by static light scattering using a MasterSizer 2000 commercial particle size analyzer from Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" diameter of particles. This theory is particularly described in Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957. According to an advantageous embodiment, the airgel particles of hydrophobic silica used in the present invention have a specific surface per unit mass (SM) ranging from 600 to 800 m2 / g.
[0114] 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 2, preferably from 0.03 g / cm 3 to 0.08 g / cm 2, in particular ranging from 0.05 g / cm 3 to 0.08 g / cm 2. 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 cylinder; then the specimen is placed on the STAV 2003 machine from Stampf Volumeter; the test piece is then subjected to a series of 2500 settlements (this operation is repeated until the difference in volume between two consecutive tests is less than 2%); then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio m / Vf, in this case 40 / Vf (Vf being expressed in 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 unit area of SV volume ranging from 5 to 60 m 2 / cm 3, preferably from 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 mass expressed in m2 / g as defined above. Preferably, the hydrophobic silica aerogel particles according to the invention have an oil absorption capacity measured at Wet Point ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and better still from 8 to 18 ml / g. at 12 ml / g. The absorption capacity measured at Wet Point, and denoted 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 measuring the Wet Point, 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 the mixture is triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracks or lumps. The volume Vs (expressed in ml) of oil used is then noted. The oil intake corresponds to the ratio Vs / m.
[0115] 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 alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, in order to functionalize the OH groups by Si-Rn silyl groups, for example trimethylsilyl groups.
[0116] Concerning the preparation of hydrophobic silica airgel particles surface-modified by silylation, reference can be made to US Pat. No. 7,470,725. Hydrophobic silica airgel particles which are surface-modified with trimethylsilyl groups, preferably INCI Silica silylate, will preferably be used. Examples of hydrophobic silica aerogels that can be used in the invention include, for example, the airgel marketed under the name VM-2260 or VM-2270 (INCI name: Silica silylate), by the company Dow Corning, whose The particles have an average size of about 1000 microns and a surface area per unit mass of 600 to 800 m 2 / g. There may also be mentioned the aerogels marketed by Cabot under the references Aerogel TLD 201, Aerogel OGD 201, Aerogel TLD 203, ENOVA Aerogel MT 1100, ENOVA Aerogel MT 1200. The airgel marketed under the name VM- 2270 (INCI name Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5-15 microns and a specific surface area per unit mass ranging from 600 to 800 m2 / g. Such an airgel advantageously makes it possible to promote the resistance of the deposit to sebum and sweat.
[0117] 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. by weight, preferably from 0.2% to 1.5% by weight relative to the total weight of the oily phase.
[0118] 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, especially advantageous for application on the skin. It can also allow an effective filling of the depressions present on the keratin materials. The term "organopolysiloxane elastomer" or "silicone elastomer" means 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 and contraction. This material is able to recover its original shape after stretching.
[0119] 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 a dehydrogenation-dehydrogenation condensation 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. In particular, the organopolysiloxane elastomer can be obtained by reaction of dimethylvinylsiloxy-terminated dimethylpolysiloxane and trimethylsiloxy-terminated methylhydrogenpolysiloxane in the presence of platinum catalyst. The compound (A) is the basic reagent for the formation of organopolysiloxane elastomer and the crosslinking is carried out by addition reaction of the compound (A) with the compound (B) in the presence of the catalyst (C).
[0120] The compound (A) is in particular an organopolysiloxane having at least two hydrogen atoms bonded to separate silicon atoms in each molecule.
[0121] The compound (A) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure. The compound (A) may have a viscosity at 25 ° C ranging from 1 to 50,000 centistokes, in particular to be well miscible with the compound (B).
[0122] The organic groups bonded to the silicon atoms of the compound (A) may be alkyl groups such as methyl, ethyl, propyl, butyl, octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl, 3,3,3-trifluoropropyl; aryl groups such as phenyl, tolyl, xylyl; substituted aryl groups such as phenylethyl; and substituted monovalent hydrocarbon groups such as an epoxy group, a carboxylate ester group, or a mercapto group. The compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogenosiloxane copolymers, and dimethylsiloxane-methylhydrogensiloxane cyclic copolymers.
[0123] The compound (B) is advantageously a diorganopolysiloxane having at least two lower alkenyl groups (for example C 2 -C 4); 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.
[0124] 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. 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-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) -polysiloxane, and terminated dimethylsiloxanemethyl (3,3,3-trifluoropropyl) siloxane copolymers; dimethylvinylsiloxy. In particular, the organopolysiloxane elastomer can 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.
[0125] It is advantageous if the compound (A) is added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in the compound (A) and the total amount of all the groups ethylenically unsaturated in the compound (B) is in the range of 1.5: 1 to 20: 1. Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acidketone complexes, platinum black, and platinum on support. The catalyst (C) is preferably added from 0.1 to 1000 parts by weight, more preferably from 1 to 100 parts by weight, as clean platinum metal per 1000 parts by weight of the total amount of the compounds (A) and (B). The elastomer is advantageously a non-emulsifying elastomer. The term "non-emulsifying" defines organopolysiloxane elastomers that do not contain a hydrophilic chain, and in particular that do not contain polyoxyalkylene (especially polyoxyethylene or polyoxypropylene) units or polyglyceryl units. Thus, according to one particular embodiment of the invention, the composition comprises an organopolysiloxane elastomer devoid of polyoxyalkylene units and a polyglyceryl unit.
[0126] 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 (Name INCI).
[0127] 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 in particular described in patents EP 242 219, EP 285 886, EP 765 656 and in the application 113-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.
[0128] 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 cc at 25 ° C., optionally modified with aliphatic groups, optionally fluorinated, or with functional groups such as hydroxyl, thiol and / or amine groups. Mention may in particular be made of the following INCI name compounds: Dimethicone / Vinyl Dimethicone Crosspolymer, such as USG-105 and USG-107A from Shin Etsu; "DC9506" and "DC9701" from Dow Corning, 3025100 68 - 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 (polydimethylsiloxane mixture cross-linked with hexadiene / polydimethyl siloxane (2 cSt)); - C4-24 Alkyl Dimethicone / DivinylDimethicone Crosspolymer, such as NuLastic Silk MA by the company Alzo.
[0129] 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)).
[0130] 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 polydimethylsiloxane crosslinked with hexadiene / polydimethylsiloxane (5cst) sold under the name DC 9041 by the company Dow Corning or the mixture of 3025100 69 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. As the preferred lipophilic gelling agent of the organopolysiloxane elastomer type, cross-linked organopolysiloxane elastomers can be mentioned in particular chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer. (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), and in particular Dimethicone Crosspolymer (INCI name).
[0131] The organopolysiloxane elastomer may be present in a composition of the present invention at a content of between 0.1% and 35% by weight in 3025100 dry matter especially between 1% and 20% and more particularly between 2% and 20% by weight. % and 10% by weight, relative to the total weight of the composition. 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. For the purposes of the invention, the term "semicrystalline polymer" means polymers having a crystallizable portion and an amorphous portion and having a first-order reversible phase change temperature, in particular melting (solid-liquid transition). ). The crystallizable portion is either a side chain (or pendant chain) or a sequence in the backbone. When the crystallizable portion of the semi-crystalline polymer is a sequence of the polymer backbone, this crystallizable block is of a different chemical nature from that of the amorphous sequences; in this case, the 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 melting temperature of the semi-crystalline 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), the melting point of which is greater than or equal to 30 ° C. The melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the Mettler company, with a temperature rise of 5 or 10 ° C. per minute (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).
[0132] The semi-crystalline polymer (s) according to the invention preferably have a melting point higher than the temperature of the keratinous support intended to receive said composition, in particular the skin, the lips or the eyebrows. According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, 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.
[0133] 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 bearing in the backbone at least one crystallizable block, - polycondensates of polyester type, aliphatic or aromatic or aliphatic / aromatic, - copolymers of ethylene and propylene prepared by metallocene catalysis, and 5 - acrylate / silicone copolymers. 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, and polycondensates, 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 carrying 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 "Intelimere 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 temperature is 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 polydimethylsiloxane grafted stearyl acrylate and acrylic acid copolymers, polydimethylsiloxane grafted stearyl methacrylate copolymers, polydimethylsiloxane grafted stearyl methacrylate 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 (name: CTFA: acrylates / dimethicone and cyclopentasiloxane), 3025100 73 - 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 of the oily phase, for example from 0.5% to 25% by weight, more preferably from 5% to 20%, or from 5% to 12% by weight, relative to the total weight of the oily phase. 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 C 12 to C 24, in particular C 14 to C 18, or mixtures thereof. Preferably, the dextrin ester is a C12-C18, especially C14-C18, fatty acid dextrin ester. Preferably, the dextrin ester is selected from dextrin myristate and / or dextrin palmitate, and mixtures thereof. According to a particular embodiment, the dextrin ester is dextrin myristate, such as that sold especially under the name Rheopearl MKL-2 by Chiba Flour Milling. According to a preferred embodiment, the dextrin ester is dextrin palmitate. This may for example be chosen from those sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling.
[0134] 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 7.5% 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. . The dextrin palmitate 3025100 may especially be that sold under the names Rheopearl TL® or Rheopearl KL® or Rheopearl® KL2 by the company Chiba Flour Milling. V. Hydrogen-Bonded Polymers As a representative of the hydrogen-bonded polymers suitable for the invention, polyamides and in particular hydrocarbon polyamides and silicone polyamides may be particularly mentioned. The polyamides The oily phase of a composition according to the invention may comprise at least one polyamide chosen from hydrocarbon polyamides, silicone polyamides, and mixtures thereof. Preferably, the total content of polyamide (s) is between 0.1% and 30% by weight, expressed as 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 A "hydrocarbon-based polyamide" is understood to mean a polyamide formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and non-carbon atoms. silicon atom or fluorine atom. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.
[0135] For the purposes of the invention, the term "functionalized chain" means an alkyl chain comprising one or more functional groups or reactive groups chosen in particular from hydroxyl, ether, esters, oxyalkylene or polyoxyalkylene groups. Advantageously, this polyamide of the composition according to the invention has a weight average molecular weight of less than 100,000 g / mol, especially ranging from 1,000 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.
[0136] 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): X-HC-R = C-NH-RNHI-CR, = CX Il n (I) 0 0 0 5 in which X represents a group -N (R1) 2 or a group -OR 'in which R1 is a linear or branched Cg to C22 alkyl radical, which may be identical to or different from each other, R2 is a diacid dimer residue at C28-C42, R3 is an ethylene diamine radical, n is 2 to 5; and their mixtures.
[0137] According to a particular embodiment, the polyamide used is an amide-terminated polyamide of formula (Ia): ## STR3 ## in which X represents a group -N (R 1) 2 in which R 1 is a linear or branched alkyl radical. in C 8 to C 22, which may be the same or different from each other, R 2 is a C 28 -C 42 diacid dimer residue, R 3 is an ethylene diamine radical, n is 2 to 5; and their mixtures. The oily phase of a composition according to the invention may furthermore additionally comprise, in this case, at least one additional polyamide of formula (Ib): ## STR2 ## In which X represents a group -OR 'in which R1 is a linear or branched Cg to C22, preferably C16 to C22, alkyl radical which may be identical to or different from each other; R2 is a residue; of C 28 -C 42 diacid dimer, R 3 is an ethylene diamine radical, n is between 2 and 5, such as the commercial products sold by Arizona Chemical under the names Uniclear 80 and Uniclear 100 or Uniclear 3025100 76 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): ## STR1 ## in which: R 4, R 5, R 6 and R7, which may be identical or different, represent a group chosen from: saturated or unsaturated hydrocarbon groups, linear, branched or cyclic, in C 1 to C 40, which may contain in their chain one or more oxygen, sulfur and / or or nitrogen, and may be substituted in part or totally by fluorine atoms, - C6-C10 aryl groups, optionally substituted by one or more C1-C4 alkyl groups, - the polyorganosiloxane chains containing or not a or several oxygen, sulfur and / or nitrogen atoms, the X, identical or different, represent a linear or branched C1 to C30 alkylene di-yl group which may contain in its chain one or more oxygen and / or nitrogen atoms, - Y is u divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, C1 to C50 group, which may comprise one or more oxygen, sulfur and / or nitrogen atoms, and / or carry as substituting one of the following atoms or groups of atoms: fluorine, hydroxy, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C3 alkyl groups, hydroxyalkyl C1 to C3 and amino C1 to C6 alkyl, or Y is a group of the formula: wherein - T represents a linear or branched, saturated or unsaturated, C3 to C24 trivalent or tetravalent hydrocarbon group optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al, and - R8 represents a linear or branched C1-C50 alkyl group, or a polyo chain organosiloxane, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulphonamide groups which may or may not be linked to another polymer chain; 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 a particular embodiment, the silicone polyamide comprises at least one unit of formula (III) where m is from 50 to 200, in particular from 75 to 150, and preferably of the order of 100. More preferably, R4, R5, R6 and R7 independently represent a linear or branched C1 to C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group in the formula (III).
[0138] By way of example of a silicone polymer that may be used, mention may be made of one of the silicone polyamides obtained according to Examples 1 to 3 of US 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 to say Nylon-611 / dimethicone copolymers. The silicone polymers and / or copolymers advantageously have a transition temperature of the solid state in the liquid state ranging from 45 ° C. to 190 ° C. Preferably they have a solid state transition temperature in the liquid state of from 70 to 130 ° C and more preferably from 80 to 105 ° C. Preferably, the total content of polyamide (s) and / or polyamide (s) silicone (s) 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 chosen from the copolymer ethylenediamine / stearyl dimer dilinoleate and copolymers Nylon611 / dimethicone.
[0139] 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.
[0140] GELIFYING (S) HYDROPHILY (S) / GELIFYING (S) LIPOPHILY SYSTEM (S) Preferred synthetic polymeric hydrophilic gelling agents, mention may be made more particularly of 2-acrylamido-2-methylpropane sulfonic acid polymers such as, for example, AMPS. , such as the 2-acrylamido-2-methylpropane-ammonium sulfonate polymer sold under the trade name Hostacerin AMPS® by Clariant, and the 2-acrylamido-2-methylpropane sulfonic acid copolymers and in particular the copolymers of AMPS® and hydroxyethyl acrylate, as for example the copolymer AMPS ') / hydroxyethyl acrylate such as that used in the commercial product sold under the name Simulgel NS® by the company Seppic (CTFA name: Hydoxyethyl Acrylate / Sodium Acryloyl) Dimethyltaurate Copolymer (And) Squalane (And) Polysorbate 60 or as the product sold under the name 5 Copolymer Acrylamido-2-Methyl Propane Sodium Sulfonate / Hydroxyethylacryl Late as the commercial product Sepinov EMT 10 (INCI name: Hydoxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer). As preferred lipophilic gelling agents, mention may be made of organopolysiloxane elastomers, preferably chosen from Dimethicone Crosspolymer (INCI name), Dimethicone (and) Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name), and in particular Dimethicone Crosspolymer (INCI name) and Dimethicone (and) Dimethicone Crosspolymer (INCI name). According to one preferred embodiment, lipophilic gelling agents that may be used more particularly include silicone elastomer gels dispersed in a silicone oil and / or organopolysiloxane elastomer powders coated with silsesquioxane resin. Thus, according to one particular embodiment, a silicone elastomer gel dispersed in a silicone oil chosen from a non-exhaustive list comprising cyclopentadimethylsiloxane, dimethicones, dimethylsiloxanes, methyl trimethicone, phenylmethicone, phenyldimethicone, phenyltrimethicone and the cyclomethicone, preferably a linear silicone oil chosen from polydimethylsiloxanes (PDMS) or dimethicones with a viscosity at 25 ° C. ranging from 1 to 500 cst at 25 ° C., especially the following references: Dimethicone / Vinyl Dimethicone Crosspolymer (and) Dimethicone, such as "KSG-6" and "KSG-16" from Shin Etsu; Dimethicone (and) Dimethicone Crosspolymer, such as "DC9041" from Dow Corning; and Dimethicone (and) Dimethicone Crosspolymer, such as Dow Corning EL-9240 Silicone Elastomer Blend from Dow Corning.
[0141] According to a particularly preferred embodiment, the composition according to the invention comprises, as lipophilic gelling agent, at least one crosslinked silicone elastomer of the INCI name "dimethicone (and) dimethicone crosspolymer", preferably with a viscosity of 1 at 100 ° C., in particular from 1 to 10 ° C. at 25 ° C., such as the mixture of Polydimethylsiloxane with Hexadiene / Polydimethyl Siloxane (5cst) sold under the name DC 9041 Dow Corning and the mixture of Polydimethylsiloxane with hexadiene / Polydimethyl Siloxane (2cst). ) marketed under the name "Dow Corning EL-9240® Silicone Elastomer Blend" by Dow Corning. According to another particularly preferred embodiment, the composition according to the invention comprises at least one organopolysiloxane elastomer powder coated with silsesquioxane resin, INCI name: vinyl dimethicone / methicone silsesquioxane Crosspolymer, such as the reference "KSP-100" sold by the company Shin Etsu.
[0142] By way of nonlimiting illustration, the hydrophilic gelling agent (s) / lipophilic gelling agent (s) that are particularly suitable for the invention may in particular be cited as the polymer (s) or copolymer (s) system. 2-acrylamido-2-methylpropanesulphonic acid / elastomer (s) of organopolysiloxane.
[0143] Thus, a composition according to the invention may advantageously comprise, as hydrophilic gelling / lipophilic gelling systems, a 2-acrylamido-2-methylpropanesulphonic acid / elastomer (s) polymer system. organopolysiloxane or copolymer of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate / elastomer (s) of organopolysiloxane.
[0144] Preferably, a composition according to the invention may comprise, as lipophilic hydrophilic gelling / gelling system (s), a copolymer system of 2-acrylamido-2-methylpropanesulphonic acid and of hydroxyethyl acrylate. elastomer powder of organopolysiloxane.
[0145] HYDROPHOBIC FILMOGENIC POLYMERS As stated above, the claimed compositions comprise at least one hydrophobic film-forming polymer and in particular as detailed below. This type of polymer is particularly advantageous insofar as it makes it possible to increase the resistance to dullness over time significantly. As indicated above, the performance of these polymers is advantageously increased thanks to their use in a composition according to the invention.
[0146] For the purposes of the invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). This or these motifs are repeated at least twice and preferably at least 3 times.
[0147] Within the meaning of the present invention, the term "hydrophobic film-forming polymer" is intended to mean a film-forming polymer devoid of an affinity for water and, as such, does not lend itself to a formulation in the solute state in an aqueous medium. . In particular, hydrophobic polymer means a polymer having a solubility in water at 25 ° C of less than 1% by weight.
[0148] By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on keratin materials, and preferably a cohesive film, and more preferably a film whose cohesion and mechanical properties are such that said film can be isolatable and manipulable in isolation, for example when said film is produced by casting on an antiadherent surface such as a teflon or silicone surface. In particular, the hydrophobic film-forming polymer is a polymer chosen from the group comprising: film-forming polymers that are soluble in an organic solvent medium, in particular liposoluble polymers; this means that the polymer is soluble or miscible in the organic medium and will form a single homogeneous phase when it is incorporated into the medium; the film-forming polymers dispersible in an organic solvent medium, this means that the polymer forms an insoluble phase in the organic medium, the polymer remaining stable and / or compatible once incorporated in this medium. In particular, such polymers may be in the form of nonaqueous dispersions of polymer particles, preferably dispersions in silicone or hydrocarbon oils; in one embodiment, the non-aqueous polymer dispersions comprise polymeric particles stabilized on their surface by at least one stabilizing agent; these nonaqueous dispersions are often referred to as "NAD (non-aqueous dispersions)"; the film-forming polymers in the form of aqueous dispersions of polymer particles, this means that the polymer forms a phase insoluble in water, the polymer remaining stable and / or compatible once incorporated into the water, the polymer particles being which can be stabilized on their surface by at least one stabilizing agent. These polymer particles are often called "latex". Hydrophobic film-forming polymers that may be mentioned include homopolymers and copolymers of ethylene-functional compounds, acrylic polymers and copolymers, polyurethanes, polyesters, polyureas, cellulose polymers such as nitrocellulose and silicone polymers such as resins. silicone polymers, silicone polyamides, non-silicone organic skeleton polymers grafted with polysiloxane-containing monomers, polyamide polymers and copolymers, polyisoprenes. A composition according to the invention may comprise from 0.1% to 30% by weight, preferably from 0.2% to 20% by weight and even more preferably from 0.5% to 15% by weight of polymer (s). hydrophobic film-forming agent (s), relative to the total weight of the composition.
[0149] In particular, the one or more hydrophobic film-forming polymers are present in whole or in part, and preferably only, in the gelled oily phase. As hydrophobic film-forming polymers that are particularly suitable for the invention, mention may be made especially of block ethylenic polymers, vinyl polymers comprising at least one carbosiloxane dendrimer derivative and silicone resins (T resin, MQ resin). I. Silicone Resins According to an alternative embodiment, a composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one silicone resin.
[0150] More generally, the term "resin" means a compound whose structure is three-dimensional. The term "silicone resins" is also referred to as "silicone resins" or "siloxane resins". Thus, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin. The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known under the name "MDTQ", the resin being described according to the different monomeric siloxane units that it comprises, each of the letters "MDTQ" characterizing a type of unit.
[0151] The letter "M" represents the monofunctional unit of formula R1R2R3SiO112, the silicon atom being linked to a single oxygen atom in the polymer comprising this unit. The letter "D" means a Difunctional unit R 1 R 2 SiO 2 12 in which the silicon atom is connected to two oxygen atoms. The letter "T" represents a trifunctional unit of formula R1SiO3 / 2. Such resins are described for example in "Encyclopedia of Polymer Science and Engineering", vol. 15, John and Wiley and Sons, New York, (1989), p. 265270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 10 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484. In the units M, D, T defined above, R, namely R1 and R2, represents a hydrocarbon radical (especially alkyl) having 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group. Finally, the letter "Q" means a tetrafunctional SiO412 unit in which the silicon atom is bonded to four oxygen atoms themselves linked to the rest of the polymer. Various silicone resins of different properties can be obtained from these different units, the properties of these polymers vary depending on the type of monomers (or units), the nature and the number of the radical R, the length of the chain. polymer, the degree of branching and the size of the pendant chains. As silicone resins that can be used in the compositions according to the invention, silicone resins of the MQ, T type or MQT type can be used, for example.
[0152] MQ Resins By way of example of silicone resins of MQ type, mention may be made of alkylsiloxysilicates of formula [(R 1) 3 SiO 1/2] (SiO 4/2) y (MQ units) in which x and y are integers ranging from from 50 to 80, and such that the group R 1 represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group. Examples of solid silicone resins of MQ type trimethylsiloxysilicate type include those sold under the reference SR1000 by the company 3025100 General Electric Co., under the reference TMS 803 by the company Wacker, under the name "KF-7312J" by the company Shin-Etsu, "DC 749", "DC 593" by the company Dow Corning. As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by General Electric). The preparation of such resins is described in particular in US Patent 5,817,302.
[0153] Examples of exemplary silicone resins of type T are polysilsesquioxanes of formula (RSiO 3/2) x (T units) in which x is greater than 100 and such that the group R is an alkyl group having 1 to 10 carbon atoms, said polysilsesquioxanes may further comprise Si-OH end groups. Preferably, it is possible to use the polymethylsilsesquioxane resins in which R represents a methyl group, for instance those marketed: by the company Wacker under the reference Resin MK such as Belsil PMS MK: polymer comprising CH3SiO3 / 2 repeating units (units T), which may also comprise up to 1% by weight of (CH 3) 2 SiO 2/2 units (D units) and having an average molecular weight of about 10,000 g / mol, or - by SHIN-ETSU under references KR-220L which are composed of T units of formula CH3SiO3 / 2 and have Si-OH end groups (silanol), under the reference KR242A which comprise 98% of T units and 2% of dimethyl D units and have terminal Si-OH groups or alternatively under the reference KR-251 comprising 88% of T units and 12% of dimethyl D units and have Si-OH end groups. MQT resins As a resin comprising MQT units, those mentioned in US 5,110,890 are particularly known. A preferred form of MQT resins are MQT-propyl resins (also called MQTPr). Such resins that can be used in the compositions according to the invention are especially those described and prepared in application WO 2005/075542. The MQ-T-propyl resin preferably comprises the units: (i) (R13SiO1 / 2) a; (ii) (R22SiO2 / 2) b; (Iii) (R3 SiO3 / 2) c; and (iv) (SiO4 / 2) d. With: - R1, R2 and R3 independently representing a hydrocarbon radical (especially alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, - a + b + c + d = 1, and a, b, c and d being mole fractions, provided that more than 40 mol% of the R 3 groups of the siloxane resin are propyl groups. Preferably, the siloxane resin comprises the units: (i) (R13SiO1 / 2) a; (iii) (R3 SiO3 / 2) c; and (iv) (SiO4 / 2) d. With: R1 and R3 independently representing an alkyl group having from 1 to 8 carbon atoms, R1 being preferably a methyl group and R3 being preferably a propyl group, - a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0.4, d being between 0.05 and 0.6, preferably between 0.2 and 0. , 6, or between 0.2 and 0.55, - a + b + c + d = 1 and a, b, c and d being molar fractions, provided that more than 40 mol% of the R3 groups 3025100 siloxane resin are propyl groups. The siloxane resins which can be used according to the invention can be obtained by a process comprising the reaction of: A) an MQ resin comprising at least 80 mol% of (R13SiO1 / 2) a and 5 (SiO4 / 2) d units; with - R 1 representing an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, - a and d being greater than zero, the ratio a / d being between 0.5 and 1.5; And B) a propyl resin T comprising at least 80 mol% of units (R3 SiO3 / 2) c; with - R3 representing an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, 15 - c being greater than zero, with the proviso that at least 40 mol% of the R3 groups are propyl groups, where the mass ratio A / B is between 95: 5 and 15:85, preferably the mass ratio AB is 30:70.
[0154] Advantageously, the mass ratio AB is between 95: 5 and 15:85. Preferably, the ratio AB is less than or equal to 70:30. These preferred ratios have been found to provide comfortable deposits due to the absence of percolation of rigid MQ resin particles in the deposit. Thus, preferably, the silicone resin is chosen from the group comprising: a) a resin of MQ type, in particular chosen from (i) alkylsiloxysilicates, which may be trimethylsiloxysilicates, of formula [(R 1) 3 SiO 1/2] (SiO4 / 2) 5, wherein x and y are integers from 50 to 80, and such that the group R1 represents a hydrocarbon radical having 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group. or a hydroxyl group, and preferably is an alkyl group having 1 to 8 carbon atoms, preferably a methyl group, and (ii) phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate, and / or 3025100 87 b) a T-type resin, especially chosen from polysilsesquixanes of formula (RSiO3 / 2) x, in which x is greater than 100 and the group R is an alkyl group having from 1 to 10 carbon atoms, for example a methyl group, said polysilsesquiox which may further comprise Si-OH end groups, and / or c) a MQT type resin, in particular of the MQT-propyl type, which may comprise the units (i) (R13SiO1 / 2) a, (R22SiO2 / 2) b, (iii) (R3SiO3 / 2) c and (iv) (SiO4 / 2) d - with R1, R2 and R3 independently representing a hydrocarbon radical, especially alkyl, having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else a hydroxyl group and preferably an alkyl radical having 1 to 8 carbon atoms or a phenyl group, a being between 0.05 and 0.5, b being between zero and 0; , 3, - c being greater than zero, 15 - d being between 0.05 and 0.6, - a + b + c + d = 1, a, b, c and d being molar fractions, provided that more than 40 mol% of the R 3 groups of the siloxane resin are propyl groups. Advantageously, a composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one trimethylsiloxysilicate resin. II. Lipodispersible film-forming polymers in the form of non-aqueous dispersions of polymer particles, also called "NAD" According to another variant embodiment, a composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one polymer chosen from the lipodispersible film-forming polymers in the form of non-aqueous dispersions of polymer particles, also called "NAD". As the non-aqueous dispersion of hydrophobic film-forming polymer, the dispersions of particles of a grafted, preferably acrylic, ethylenic polymer can be used in a liquid oily phase: - in the form of ethylenic polymer particles dispersed in the absence of additional stabilizer at the surface of the particles as described in particular in WO 04/055081, or in the form of particles, surface-stabilized, dispersed in the liquid fatty phase. The dispersion of surface-stabilized polymer particles can be manufactured as described in EP-A-749747. The polymer particles may be surface stabilized by a stabilizer which may be a block polymer, a graft polymer, and / or a random polymer, alone or in admixture. Dispersions of film-forming polymer in the liquid fatty phase, in the presence of stabilizing agents, are described in particular in documents EP-A-748746, EP-A-923928 and EP-A-930060. Advantageously, dispersions of dispersed ethylenic polymer particles are used in the absence of additional stabilizer at the surface of said particles.
[0155] By way of examples of "NAD" type polymers, mention may be made more particularly of acrylic dispersions in isododecane, such as Mexomere PAP® (acrylic copolymer dispersed in isododecane (25%) with pyrene / isoprene copolymer). marketed by CHIMEX.
[0156] III. Blocked ethylenic copolymer According to a first embodiment of the invention, the hydrophobic film-forming polymer is a block ethylenic copolymer, containing at least a first block having a glass transition temperature (Tg) of greater than or equal to 40.degree. all or part of one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least one second sequence having a transition temperature vitreous less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C , said first sequence and said second sequence being interconnected by an intermediate segment statisti comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2. The block polymer used according to the invention thus comprises at least a first sequence and at least a second sequence.
[0157] By "at least" a sequence is meant one or more sequences. By "block" polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences. By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
[0158] The sequenced ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers. This means that the sequenced ethylenic polymer used according to the present invention does not contain multifunctional monomers, which make it possible to break the linearity of a polymer in order to obtain a plugged or even cross-linked polymer, as a function of the multifunctional monomer content. The polymer used according to the invention also does not contain macromonomers ("macromonomer" means a monofunctional monomer having a pendant group of a polymeric nature, and preferably having a molecular weight greater than 500 g / mol, or a polymer having at one of its ends a polymerizable terminal group (or ethylenically unsaturated)), which are used in the preparation of a graft polymer. It is specified that in what precedes and what follows the terms "first" and "second" sequences do not condition the order of said sequences (or blocks) in the structure of the polymer. The first and second sequences of the polymer used in the invention may be advantageously incompatible with each other. By "sequences incompatible with each other" is meant that the mixture formed by a polymer corresponding to the first block and by a polymer corresponding to the second block, is not miscible in the polymerization solvent, which is predominantly weight, of the sequenced polymer, at ambient temperature (25 ° C.) and atmospheric pressure (105 Pa), for a content of the mixture of said polymers greater than or equal to 5% by weight, relative to the total weight of the mixture of said polymers and said polymerization solvent, it being understood that: 3025100 i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that ii) each of the polymers corresponding to the first and second sequences has an average molecular weight (by weight or number) equal to that of the +/- 15% sequenced polymer. In the case of a mixture of polymerization solvents, assuming two or more solvents present in identical mass proportions, said polymer mixture is immiscible in at least one of them. Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent. The sequenced polymer according to the invention comprises at least a first sequence and at least a second sequence linked together by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. Intermediate segment 15 (also called intermediate block) has a glass transition temperature Tg between the glass transition temperatures of the first and second blocks. The intermediate segment is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer makes it possible to "compatibilize" these blocks.
[0159] Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer. Preferably, the intermediate sequence is derived essentially from constituent monomers of the first sequence and the second sequence.
[0160] By "essentially" is meant at least 85%, preferably at least 90%, more preferably 95%, and most preferably 100%. The block polymer according to the invention is advantageously a film-forming ethylenic block polymer. By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
[0161] By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, especially on keratin materials. Preferably, the polymer according to the invention does not comprise silicon atoms in its backbone. By "skeleton" is meant the main chain of the polymer, as opposed to the pendant side chains. Preferably, the polymer according to the invention is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without any change in pH, at a solids content of at least 1% by weight, at room temperature (25 ° C). Preferably, the polymer according to the invention is not an elastomer. By "non-elastomeric polymer" is meant a polymer which, when subjected to stress to stretch (e.g. 30% relative to its initial length), does not return to a length substantially identical to its length. initial length when the constraint stops. More specifically, "non-elastomeric polymer" denotes a polymer having an instantaneous recovery R, <50% and a delayed recovery R2h <70% after having undergone an elongation of 30%. Preferably R 1 is <30% and R 2 <50%. More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol: A polymer film is prepared by pouring a solution of the polymer into a Teflon matrix and then drying for 7 days in a controlled atmosphere at 23 ± 25 ° C. and 50 ± 10% relative humidity. A film approximately 100 μm in thickness is then obtained in which are cut rectangular specimens (for example with a punch) of a width of 15 mm and a length of 80 mm. This sample is subjected to tensile stress with the aid of an apparatus marketed under the reference Zwick, under the same conditions of temperature and humidity as for drying.
[0162] The specimens are drawn at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (10) of the specimen. The instantaneous recovery R 1 is determined in the following manner: the specimen is stretched by 30% (smax), that is to say approximately 0.3 times its initial length (10), the stress is released by imposing a return speed equal to the tensile speed of 50 mm / min and the residual elongation of the specimen is measured in percentage, after return to zero load stress (ci). The instantaneous recovery in% (R,) is given by the formula below: R = ((smax-E,) / smax) x 100 To determine the delayed recovery, the elongation rate is measured after 2 hours. residual of the specimen in percentage (s2h), 2 hours after return to the zero load stress. The recovery delayed in% (R2h) is given by the following formula: R2h = (cmax SM) / smax) X 100 For purely indicative purposes, a polymer according to one embodiment of the invention preferably has a recovery. instantaneous R, of 10% and delayed recovery R2h of 30%. The polydispersity index of the polymer of the invention is greater than 2.
[0163] Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8 and more preferably greater than or equal to 2.8 and in particular ranging from 2.8 to 6. The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn. The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The weight average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300,000, for example from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol.
[0164] The number average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 50,000 g / mol. Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better greater than or equal to 2.8 and especially ranging from 2.8 to 6. First sequence having a Tg greater than or equal to 40 ° C. The sequence having a Tg greater than or equal to 40 ° C. has, for example, a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example from 50 ° C to 120 ° C, and more preferably greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C. The indicated glass transition temperatures of the first and second sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as Polymer Handbook, 3rd ed. , 1989, John Wiley, according to the following relationship, called Fox's Law: 1 / Tg = E / Tg i), where mi is the mass fraction of the monomer i in the sequence under consideration and Tg, 20 being the glass transition temperature of the homopolymer of the monomer i. Unless otherwise indicated, the Tg values for the first and second sequences in the present application are theoretical Tg. The difference between the glass transition temperatures of the first and second blocks is generally greater than 10 ° C, preferably greater than 20 ° C, and more preferably greater than 30 ° C. In the present invention, the expression "comprised between ... and ..." is intended to denote an interval of values whose mentioned limits are excluded, and "from ... to" and "ranging from ... to ... ", an interval of values whose terminals are included. The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer. The sequence having a Tg greater than or equal to 40 ° C may be derived in whole or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to at 40 ° C. This sequence can also be called "rigid sequence". In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first block may be a homopolymer consisting of a single type of monomer (the Tg of the corresponding homopolymer is greater than or equal to 40 ° C.). In the case where the first block is a copolymer, it may be derived in whole or in part from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is greater than or equal to 40%. ° C. The copolymer may for example comprise: monomers which are such that the homopolymers prepared from these monomers have Tg greater than or equal to 40 ° C., for example a Tg ranging from 40 ° C. to 150 ° C., preferably greater than or equal to 50 ° C, ranging for example from 50 ° C to 120 ° C, and more preferably greater than or equal to 60 ° C, ranging for example from 60 ° C to 120 ° C, and - monomers which are such that the homopolymers prepared from these monomers have Tg's lower than 40 ° C, chosen from monomers having a Tg of between 20 ° C and 40 ° C and / or monomers having a Tg of less than or equal to at 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably below 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still below 10 ° C, for example ranging from -50 ° C to 0 ° C, as described below. The first monomers whose homopolymers have a glass transition temperature greater than or equal to 40 ° C. are preferably chosen from the following monomers, also called main monomers: methacrylates of formula CH 2 = C (CH 3) -COOR 1; wherein R1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R1 represents a C4 to C12 cycloalkyl group, preferably a C5 cycloalkyl group; C12, such as isobornyl methacrylate; acrylates of formula CH2 = CH-COOR2; in which R2 represents a C4-C12 cycloalkyl group such as an isobornyl group or a tert-butyl group, the (meth) acrylamides of formula: ## STR1 ## where R7 and Rg are identical or different each represents a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or R7 is H and Rg is 1,1-dimethyl-3-oxobutyl, and R 'is H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide, and mixtures thereof.
[0165] The first block is advantageously obtained from at least one acrylate monomer of formula CH2 = CH-COOR2 and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR2 in which R2 represents a C4 cycloalkyl group. C12, preferably a C8 to C12 cycloalkyl, such as isobornyl. The monomers and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C. According to one embodiment, the first block is obtained from: i) at least one acrylate monomer of formula CH2 = CH-COOR2 in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 cycloalkyl group; at C12, such as isobornyl, ii) and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C4-C12 cycloalkyl group, preferably a cycloalkyl group; C 8 to C 12, such as isobornyl. According to one embodiment, the first block is obtained from at least one acrylate monomer of formula CH2 = CH-COOR2 in which R2 represents a C8-C12 cycloalkyl group, such as isobornyl, and from at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C8-C12 cycloalkyl group, such as isobornyl. Preferably, R2 and R'2 represent independently or simultaneously an isobornyl group.
[0166] Preferably, the block copolymer comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid. . The first block can be obtained exclusively from said acrylate monomer and said methacrylate monomer. The acrylate monomer and the methacrylate monomer are preferably in mass proposals of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular of the order of 50:50. The proportion of the first block is preferably 20 to 90% by weight of the polymer, more preferably 30 to 80% and most preferably 60 to 80%. According to one embodiment, the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.
[0167] Second sequence of glass transition temperature below 20 ° C. The second sequence advantageously has a glass transition temperature Tg of less than or equal to 20 ° C., for example a Tg ranging from -100 ° C. to 20 ° C., preferably lower. or at 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still less than or equal to 10 ° C, for example ranging from -100 ° C to 10 ° C, in particular ranging from -30 ° C to 10 ° C. The second sequence is derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C.
[0168] This sequence can also be called a "soft sequence". The monomer having a Tg of less than or equal to 20 ° C (called the second monomer) is preferably chosen from the following monomers: acrylates of formula CH 2 = CHCOOR 3, R 3 representing a linear C 1 to C 12 alkyl group, linear or branched, with the exception of the tert-butyl group, in which is optionally (are) intercalated one or more heteroatoms selected from O, N, S, 3025100 97 - methacrylates of formula CH2 = C (CH3) - COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group in which one or more heteroatoms selected from O, N and S are optionally intercalated; vinyl esters of formula R5-00-0-CH = CH2, where R5 represents a linear or branched C4-C12 alkyl group; vinyl alcohol and C4 to C12 alcohol ethers; C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide; and mixtures thereof. Monomers having a Tg of less than or equal to 20 ° C are preferably isobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in all proportions. Each of the first and second sequences may contain, in a minority proportion, at least one constituent monomer of the other sequence. Thus the first sequence may contain at least one constituent monomer of the second sequence and vice versa. Each of the first and / or second sequences may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above. The nature and amount of this additional monomer (s) are chosen such that the sequence in which they are located has the desired glass transition temperature. This additional monomer is, for example, chosen from: - monomers containing ethylenic unsaturation (s) comprising at least one tertiary amine functional group such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts thereof; methacrylates of formula CH2 = C (CH3) -COOR6, wherein R6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a group methyl, ethyl, propyl or isobutyl, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br , I, F), such as trifluoroethyl methacrylate, methacrylates of formula CH2 = C (CH3) -COOR9, wherein R9 represents a linear or branched C6-C12 alkyl group, wherein is optionally interspersed with one or more heteroatoms selected from O, N and S, said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I , F); the acrylates of formula CH2 = CHCOORio, R10 representing a linear or branched C1-C12 alkyl group substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 is C1-C12-POE (polyoxyethylene) alkyl with 5 to 10-fold oxyethylene repeating, eg methoxy-POE, or R8 represents a polyoxyethylene group comprising from 5 to 10 ethylene oxide units. In particular, the first block may comprise, as additional monomer: (meth) acrylic acid, preferably acrylic acid, tert-butyl acrylate, methacrylates of formula CH 2 = C ( CH 3) -COOR 1, in which R 1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the (meth) acrylamides of the formula Where R7 and R8, which are identical or different, each represents a hydrogen atom or a linear or branched C1-C12 alkyl group, such as a n-butyl, t-butyl, or n-butyl group; isopropyl, isohexyl, isooctyl, or isononyl; or R7 is H and R8 is 1,1-dimethyl-3-oxobutyl, and R 'is H or methyl. Examples of monomers include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide, and mixtures thereof. The additional monomer can represent 0.5 to 30% by weight of the weight of the polymer. According to one embodiment, the polymer of the invention does not contain additional monomer.
[0169] Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block, the first block representing % by weight of the polymer. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the Tg sequence greater than 40 ° C represents 70% by weight of the polymer, and the acrylic acid represents 5% by weight of the polymer. According to one embodiment, the first sequence does not comprise additional monomer. According to a preferred embodiment, the second block comprises acrylic acid as additional monomer. In particular, the second block is advantageously obtained from an acrylic acid monomer and at least one other monomer having a Tg of less than or equal to 20 ° C. The block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and especially from 2 to 15% by weight, for example from 3 to 15% by weight, in particular from 4 to 15% by weight, or even from 4 to 15% by weight. 10% by weight of acrylic acid monomers, based on the total weight of said copolymer.
[0170] The constituent monomers of the second block and their proportions are chosen such that the glass transition temperature of the second block is less than or equal to 20 ° C.
[0171] Intermediate Segment The intermediate segment (also called intermediate sequence) connects the first sequence and the second sequence of the polymer used according to the present invention. The intermediate segment results from the polymerization of: i) the first monomer (s), and optionally additional monomer (s), remaining available after their polymerization at a conversion rate of at most 90% to form the first sequence, ii) and second monomer (s) and optionally additional monomer (s) added to the reaction mixture. The formation of the second sequence is initiated when the first monomers no longer react or become incorporated in the polymer chain either because they are all consumed or because their reactivity no longer allows them to be. Thus, the intermediate segment comprises the first available monomers, resulting from a conversion rate of these first monomers less than or equal to 90%, during the introduction of the second monomer or monomers during the synthesis of the polymer.
[0172] The intermediate segment of the block polymer is a random polymer (can also be called a statistical sequence). That is to say, it comprises a statistical distribution of the first monomer (s) and second monomer (s) and any additional monomer (s) that may be present. Thus, the intermediate segment is a random sequence, as are the first and second sequences if they are not homopolymers (i.e., both are formed from at least two monomers different). Process for preparing the copolymer The block ethylenic copolymer according to the invention is prepared by free radical polymerization, according to the techniques well known in this type of polymerization.
[0173] The free radical polymerization is carried out in the presence of an initiator whose nature is adapted, in known manner, depending on the desired polymerization temperature and the polymerization solvent. In particular, the initiator may be chosen from peroxide-functional initiators, oxidation-reduction pairs, or other radical polymerization initiators known to those skilled in the art. In particular, as a peroxide-functional initiator, there may be mentioned for example a. peroxyesters, such as terbutylperoxyacetate, tertbutylperbenzoate, tertbutylperoxy-2-ethylhexanoate (Akzo Nobel Trigonox 21S), 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane ( Trigonox 141 from Akzo Nobel); b. peroxydicarbonates, such as diisopropylpyroxy di carbonate; c. peroxycetones, such as methyl ethyl ketone peroxide; d. hydroperoxides, such as hydrogen peroxide (H 2 O 2), terbutyl hydroperoxide; e. diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; F. dialkyl peroxides, such as di-tert-butyl peroxide; g. inorganic peroxides, such as potassium peroxodisulfate (K25208). As an initiator in the form of oxidation-reduction pair, mention may be made of the potassium thiosulfate + potassium peroxodisulphate pair, for example. According to a preferred embodiment, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms. Preferably, the initiator used is 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane sold under the reference Trigonox® 141 by Akzo Nobel.
[0174] The block copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the block ethylenic copolymer is carried out in the absence of control agents, and in particular in the absence of a control agent conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines, dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper catalysts, for example.
[0175] As previously indicated, the intermediate segment is a statistical sequence, as are the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers). The block copolymer may be prepared by free radical polymerization, and in particular by a process comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one glass transition monomer greater than or equal to 40 ° C. at least one vitreous transition monomer less than or equal to 20 ° C according to the following sequence: - is poured into the reactor, a part of the polymerization solvent and optionally part of the initiator and monomers of the first casting, mixture which is heated to a reaction temperature of between 60 and 120 ° C, is then poured, in a first casting, said at least a first monomer Tg greater than or equal to 40 ° C and possibly part of the initiator which is allowed to react for a time T corresponding to a conversion rate of said monomers of up to 90%, - then poured into the reactor, in a second neck again, said polymerization initiator, said at least one second glass transition monomer less than or equal to 20 ° C, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought back to room temperature. Preferably, the copolymer may be prepared by free radical polymerization, in particular by a process consisting of mixing, in one and the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one lower glass transition monomer or equal to 20 ° C, at least one acrylate monomer of formula CH2 = CH-COOR2 in which R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula 3025100 103 CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 to C12 cycloalkyl group, according to the following stage sequence: - is poured into the reactor, a portion of the polymerization solvent and optionally a portion of the initiator and the monomers of the first casting , which mixture is heated to a reaction temperature of between 60 and 120 ° C., the at least one acrylate monomer of formula CH 2 = CH-COOR 2 and led is then poured in a first casting. it at least methacrylate monomer of formula CH2 = C (CH3) -COOR'2 as monomers of Tg greater than or equal to 40 ° C, and optionally a part of the initiator which is allowed to react for a period of time T Corresponding to a conversion rate of said monomers of 90% maximum, then pouring into the reactor, in a second casting, again the polymerization initiator, the acrylic acid monomer and said at least one lower glass transition monomer or at 20 ° C, allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought to room temperature. By polymerization solvent is meant a solvent or a mixture of solvents. In particular, as a polymerization solvent that may be used, mention may be made of: ketones that are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; Propylene glycol ethers which are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate Isopentyl - ethers which are liquid at room temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane, isododecane, cyclohexane and isohexadecane; Aromatic cyclic compounds which are liquid at room temperature, such as toluene and xylene; aldehydes which are liquid at room temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.
[0176] Typically, the polymerization solvent is a volatile oil having a flash point below 80 ° C. The flash point is measured in particular according to ISO Standard 3679. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol, ethanol, alkanes and the like. aliphatics such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane. According to another embodiment, the copolymer may be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one lower glass transition monomer. or equal to 20 ° C, and at least one monomer of Tg greater than or equal to 40 ° C, according to the following step sequence: - is poured into the reactor, a part of the polymerization solvent and possibly part of the initiator and monomers of the first casting, which mixture is heated to a reaction temperature of between 60 and 120 ° C., said at least one glass transition monomer which is less than or equal to at 20 ° C. and optionally a part of the initiator which is allowed to react for a duration T corresponding to a conversion rate of said monomers of 90% maximum, is then poured into the reactor, in a second casting, again the polymerization initiator, said at least one monomer of Tg greater than or equal to 40 ° C, which is allowed to react for a period T 'after which the conversion rate said monomers reaches a plateau, the reaction mixture is brought back to ambient temperature. According to a preferred embodiment, the copolymer may be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one vitreous transition monomer less than or equal to 20 ° C, at least one monomer of Tg greater than or equal to 40 ° C, and in particular as monomers of Tg greater than or equal to 40 ° C, at least one acrylate monomer of formula Wherein R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2, represents a C4 to C12 cycloalkyl group, according to the following step sequence: 3025100 - is poured into the reactor, a portion of the polymerization solvent and optionally a portion of the initiator and monomers of the first casting mixture that is heated to a temperature reaction temperature of between 60 ° and 120 ° C., the acrylic acid monomer and at least one glass transition monomer of less than or equal to 20 ° C. and optionally a portion of the initiator, are then poured in a first casting. it is allowed to react for a duration T corresponding to a conversion rate of said monomers of 90% maximum, - then poured into the reactor, in a second casting, again the polymerization initiator, said at least one monomer acrylate of formula CH2 = CH-COOR2 and said at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2, as a monomer of Tg greater than or equal to 40 ° C, which is allowed to react during a the time T 'after which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature.
[0177] The polymerization temperature is preferably of the order of 90 ° C. The reaction time after the second casting is preferably between 3 and 6 hours. Preferably, the block ethylenic copolymer is present in the composition in a solids content ranging from 0.1 to 60%, more preferably 0.5 to 50%, more preferably 1 to 30% and more preferably 1 to 40% by weight. weight relative to the total weight of the composition. Distillation of the Synthetic Solvent It is possible to proceed to a step of total or partial elimination of said solvent or volatile oil (typically isododecane). It is then carried out in particular by distillation, optionally under vacuum, and optional addition of nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, such as octyledodecyl neopentanoate (especially 2-octyledodecyl neopentanoate). This step is carried out hot and optionally under vacuum to distill a maximum volatile synthesis solvent and is known to those skilled in the art.
[0178] Polyamide silicone block polymer According to another embodiment variant, a composition according to the invention comprises, as hydrophobic film-forming polymer, at least one polyamide silicone block polymer, also called silicone polyamide. The silicone polyamides are preferably solid at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). For the purposes of the invention, the term "polymer" means a compound having at least 2 repeating units, preferably at least 3 repeating units and more preferably 10 repeating units. The silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type, for instance those described in documents US Pat. No. 5,874,069, US Pat. No. 5,919,441, US Pat. No. 6,051,216 and US Pat. No. 5,981,680. . According to the invention, the silicone polymers may belong to the following two families: (1) polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and / or (2) polyorganosiloxanes comprising at least two two amide groups, these two groups being located on grafts or branches. According to a first variant, the silicone polymers are polyorganosiloxanes as defined above and whose units capable of establishing hydrogen interactions are arranged in the polymer chain. The silicone polymers may more particularly be polymers comprising at least one unit corresponding to the general formula I: ## STR3 ## in which - R 4, R 5, R 6 and R 7, identical or different, represent a group chosen from: 3025100 107 - saturated or unsaturated, linear, branched or cyclic, C1-C40 hydrocarbon-based groups which may contain in their chain one or more oxygen, sulfur and / or nitrogen atoms, and which may be substituted in part or totally by fluorine atoms, C 6 -C 10 aryl groups, optionally substituted with one or more C 1 -C 4 alkyl groups, polyorganosiloxane chains containing or not containing one or more oxygen atoms, Sulfur and / or nitrogen, the X, which may be identical or different, represent a linear or branched C1 to C30 alkylene di-yl group which may contain in its chain one or more oxygen atoms and / or nitrogen, - Y is a gro divalent alkylene linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, C 1 -C 50, which may comprise one or more oxygen atoms, sulfur and / or nitrogen, and / or carry as substitute l one of the following atoms or groups of atoms: fluorine, hydroxy, C 3 -C 8 cycloalkyl, C 1 -C 4 alkyl, C 5 -C 10 aryl, phenyl optionally substituted with 1 to 3 C 1 -C 3 alkyl groups, hydroxyalkyl C1 to C3 and C1 to C6 alkyl, or - Y is a group of the formula: wherein - T is a linear or branched, saturated or unsaturated, C3 to C24 saturated or unsaturated, trivalent or tetravalent hydrocarbon group optionally substituted with a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and R8 represents a linear or branched C1-C50 alkyl group, or a polyorg chain anosiloxane, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and / or sulphonamide groups which may or may not be linked to another chain of the polymer, the G, which may be identical or different, represent the divalent groups chosen from: 3025100 108 - C 0 N (R 9) -C 0 - CN (R 9) N (R 9) SO, s N (R 9) O - N (R 9) C 0 o CN (R 9) N (R 9) C - OC - N (R 9) N (R 9) CN (R 9) O N (R 9) CN (R 9) s N (R 9) CCO NH NH NH NH C NH and C NH NH N (R 9) O NI I 5 where R9 represents a hydrogen atom or a linear or branched C1-c20 alkyl group, provided that at least 50% of the R9 of the polymer represents a hydrogen atom and at least two of the G groups of the polymer a group other than: and n is an integer from 2 to 500, preferably from 2 to 200, and m is an integer from 1 to 1000, preferably from 1 to 700 and more preferably from 6 to 200. According to the invention, 80% of the R4, R5, R6 and R7, of the polymer are chosen from reference among methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.
[0179] According to the invention, Y may represent various divalent groups, optionally additionally having one or two free valences to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from: linear C 1 to C 20, preferably C 1 to C 10, alkylene groups, the branched alkylene groups possibly comprising rings and C 3 to C 56 non-conjugated unsaturations; C 5 -C 6 cycloalkylene groups; phenylene groups optionally substituted with one or more C 1 -C 4 alkyl groups; C 1 -C 20 alkylene groups having 1 to 5 amide groups; C 1 -C 20 alkylene groups; , comprising one or more substituents, selected from hydroxyl, C3-C8 cycloalkane, C1-C3 hydroxyalkyl and C1-C6 alkylamines, polyorganosiloxane chains of formula: R5-R4 R4 SiO Si O R7 R6 Si R7 in which R4, R5, R6, R7, T and m are as defined above, and - the polyorganosiloxane chains of formula: R5-R4 Si Si O R7 R-, Si T / R7 According to the second alternatively, the polyorganosiloxanes may be co polymers. comprising at least one unit corresponding to formula (II): wherein R4 and R6, which may be identical or different, are as defined above for formula (I); R10 represents a group as defined above for R4 and R6, or represents the group of formula -XG-R12 in which X and G are as defined above for formula (I) and R12 represents an atom of hydrogen or a linear, branched or cyclic, saturated or unsaturated C 1 -C 50 hydrocarbon-based group optionally comprising in its chain one or more atoms chosen from O, S and N, optionally substituted with one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted with one or more C1-C4 alkyl groups; -R11 represents the group of formula -XG-R12 in which X, G and R12 are as defined above, - ml is an integer from 1 to 998, and - m2 is a number from 1 to 500. According to the invention, the silicone polymer used as a structuring agent can be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (I) or of formula (II).
[0180] According to the invention, it is also possible to use a silicone polymer constituted by a copolymer comprising several different units of formula (I), that is to say a polymer in which at least one of R4, R5, R6, R7, X, G, Y, m and n is different in one of the patterns. The copolymer may also be formed of several units of formula (II), wherein at least one of R4, R6, R10, R11, ml and m2 is different in at least one of the units.
[0181] It is also possible to use a polymer comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical or different from those of formula (II). each other. According to a variant of the invention, it is also possible to use a polymer comprising in addition at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea and urethane groups. , thiourea, oxamido, guanidino, biguanidino and their combinations. These copolymers can be block polymers, block polymers or graft polymers. According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula -C (O) NH- and -HN-C (O) -. In this case, the structuring agent can be a polymer comprising at least one unit of formula (III) or (IV): R 4 X SiO Si XC NH YO R 6 O NT.F 1 X SiO R 6 n 15 OR (IV) in which R4, R5, R6, R7, X, Y, m and n are as defined above. Such a unit can be obtained: either by a condensation reaction between a silicone having α, co-carboxylic acid and one or more diamines, according to the following reaction scheme: ## STR1 ## 1 + H -R4 -R5 If XCO NH Y NH, m R is by reaction of two molecules of α-unsaturated carboxylic acid with a diamine according to the following reaction scheme: CH = CH-X1-COOH-FH2N-Y -NH 2 CH 2 = CH-X 1 -CO-NH-Y-NH-CO-X 1 -CH = CH 2 followed by the addition of a siloxane to the ethylenic unsaturations, according to the following scheme: CH 2 = CH-X 1- In which X1- (CH2) 2- corresponds to the X defined above and Y, R4, R5, R6, R7 and R4 are as follows: ## STR2 ## m are as defined above, either by reaction of a silicone with a, to-NH 2 ends and a diacid of the formula HOOC-Y-COOH according to the following reaction scheme: + 11 SiO R 6 m R 7 CO 10 If ## STR2 ## olyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500 and in particular from 50 to 200, and is especially from 1 to 500, preferably from 1 to 100 and better still from 4 to at 25.
[0182] X is preferably a linear or branched alkylene chain having 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially 5 to 15 carbon atoms and more particularly 10 carbon atoms, and Y is preferably a linear or branched alkylene chain or which may comprise rings and / or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and more preferably from 2 to 6 carbon atoms, in particular of 6 carbon atoms. In the formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements: 1 to 5 amide groups, urea, urethane or carbamate, a C 5 or C 6 cycloalkyl group; and a phenylene group optionally substituted with 1 to 3 identical or different C 1 to C 3 alkyl groups. In the formulas (III) and (IV), the alkylene groups may also be substituted by at least one member selected from the group consisting of: - a hydroxy group, - a C3-C8 cycloalkyl group, - one to three groups C1 to C40 alkyl, - phenyl optionally substituted with one to three C1 to C3 alkyl groups, H2N-R4 SiO R6 HN SiO R6 n 3025100 114 - C1 to C3 hydroxyalkyl, and - C1 to aminoalkyl at C6. In these formulas (III) and (IV), Y may also represent: R8 where R8 represents a polyorganosiloxane chain, and T represents a group of formula: R "CRI (CH2) to N (C12-12) b (CH2) C (CH2) b (CH1), (CHA) wherein a, b and c are independently integers from 1 to 10, and R13 is a hydrogen atom or a group such as those defined for R4, R5, R6 and R7 In formulas (III) and (IV), R4, R5, R6 and R7 are preferably independently C1-C40 alkyl, linear or branched, preferably CH3, C2H5 , n-C3H7 or isopropyl, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.
[0183] As has been seen previously, the polymer may comprise identical or different units of formula (III) or (IV). Thus, the polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, that is to say a polyamide corresponding to formula (V): ## STR1 ## where XC (O) NH Y NH C (E-NH) -Y-NH (O) -X SiO R 3025100 wherein X, Y, n, R4 to R7 have the meanings given above, ml and m2 which are different, are selected from the range of 1 to 1000, and p is an integer of from 2 to 300. In this formula, the units may be structured to form either a block copolymer, a random copolymer, or an alternating copolymer In this copolymer, the units may be not only different lengths, but also of different chemical structures, for example having different Y's, in which case the polymer may have formula VI: R 'SiO Si XC (O) -Y 1 NH n, I R6 -H 4 (0 ) X [SiO [co () Si XC (O) Y NH n, n (VI) wherein R4 to R7, X, Y, ml, m2, n and p have the meanings given above and Y 1 is different from Y but chosen from the groups defined for Y. As previously, the different units may be structured to form either a block copolymer, a random copolymer or an alternating copolymer. In this first embodiment of the invention, the structuring agent may also consist of a graft copolymer. Thus, the polyamide with silicone units can be grafted and optionally crosslinked with silicone chains containing amide groups. Such polymers can be synthesized with trifunctional amines. In this case, the polymer may comprise at least one unit of formula (VII): ## STR1 ## in which X 1 and X 2 which are identical or different, have the meaning given. for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), R14 to R21 are groups selected from the same group as R4 at R7, ml and m2 are numbers in the range of 1 to 1000, and p is an integer from 2 to 500. In formula (VII), it is preferred that: p is from 1 to 25, more preferably 1 to 7, - R 14 to R 21 are methyl groups, 10 - T corresponds to one of the following formulas: ## STR2 ## wherein R 22 is a hydrogen atom or a group selected from the groups defined for R4 to R7, and R23, R24 and R25 are independently linear or branched alkylene groups, more preferably, the formula: R23 NR R 25, especially with R 23, R 24 and R 25 representing -CH 2 -CH 2 -, ml and m 2 range from 15 to 500, and more preferably from 15 to 45, X 1 and X 2 represent - (CH 2) 10 -, and Y represents - CH2. These silicone-grafted polyamides of formula (VII) may be copolymerized with silicone polyamides of formula (II) to form block copolymers, alternating copolymers or random copolymers. The weight percentage of grafted silicone units (VII) in the copolymer can range from 0.5 to 30% by weight. According to the invention, as seen above, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described above. In the pendant or grafted chains, the siloxane units may appear individually or in segments. According to an alternative embodiment of the invention, it is possible to use a copolymer 20 of silicone polyamide and of hydrocarbon polyamide, ie a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units. In this case, the polyamide-silicone units may be disposed at the ends of the hydrocarbon polyamide. According to a preferred embodiment, the silicone polyamide comprises units of formula III, preferably in which the groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents an alkylene group of 6 carbon atoms. and the other an alkylene group of 11 carbon atoms, where n is the degree of polymerization DP of the polymer. By way of example of such silicone polyamides, mention may be made of the compounds marketed by Dow Corning under the name DC 2-8179 3025100 118 (DP 100) and DC 2-8178 (DP 15) whose INCI name is "Nylon -611 / dimethicone copolymers ". Advantageously, the composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) having an index m of about 15 values. More preferably, the composition according to the invention comprises at least one polymer comprising at least one a unit of formula (III) in which m is from 5 to 100, in particular from 10 to 75 and more particularly is of the order of 15; more preferably, 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 formula (III). According to a preferred embodiment, the polyamide silicone polymer marketed by Dow Corning under the name DC 2-8179 (DP 100) is used. 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. IV. Vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer According to a particular embodiment, a composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one vinyl polymer comprising at least one unit derived from a carbosiloxane dendrimer. . The vinyl polymer used according to the invention has in particular a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer derived unit having a carbosiloxane dendrimer structure.
[0184] In particular, it is possible to use the vinyl polymers comprising at least one carbosiloxane dendrimer unit as described in applications WO 03/045337 and EP 963 751 from Dow Corning. The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular weights, said structure having a high regularity in the radial direction from the backbone bond. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer 3025100 119 in Japanese Patent Application Laid-open Kokai 9-171,154. A vinyl polymer according to the invention may contain units derived from carbosiloxane dendrimers which may be represented by the following general formula: wherein R 'represents an aryl group or an alkyl group having from 1 to 10 carbon atoms, and X' represents a silylalkyl group which, when i = 1 is represented by the formula: wherein R 'is as defined above, R2 is an alkylene group having 2 to 10 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms, X1 + 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a 'is an integer of 0 to 3; Y represents a radical-polymerizable organic group chosen from: organic groups containing a methacrylic group or an acrylic group and which are represented by the formulas: and R40 1 C NIT 20 4 0 -C -C Y Si 3025100 in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group having from 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group, the methylene group and propylene being preferred, and styryl-containing organic groups represented by the formula: wherein R 6 is hydrogen or alkyl, R 7 is alkyl of 1 to 10 atoms carbon, such as a methyl group, an ethyl group, a propyl group, or a butyl group, the methyl group being preferred, R8 represents an alkylene group having from 1 to 10 at carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred, b is an integer of 0 to 4, and c is 0 or 1 so that if c is 0, - (R8), - represents a bond.
[0185] In one embodiment, R 'may be an aryl group or an alkyl group having 1 to 10 carbon atoms. The alkyl group may preferably be methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl, cyclohexyl. The aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred. A vinyl polymer having at least one carbosiloxane dendrimer derived unit has a side molecular chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization: (A) from 0 to 99.9 parts by weight of a vinyl monomer ; and (B) from 100 to 0.1 parts by weight of a radical-polymerizable organic group-containing carbosiloxane dendrimer, represented by the general formula: wherein Y represents an organic group polymerizable with R 1 is an aryl group or an alkyl group having 1 to 10 carbon atoms, and X 'is a silylalkyl group which, when i = 1, is represented by the formula: wherein R 1 is as defined above, R2 represents an alkylene group having 2 to 10 carbon atoms, R3 represents an alkyl group having 1 to 10 carbon atoms, X '+' represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a 'is an integer of 0 to 3; wherein said radical-polymerizable organic group contained in component (B) is selected from: - organic groups containing a methacrylic group or an acrylic group and which are represented by the formulas: o and H2 in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group having 1 to 10 carbon atoms; and styryl-containing organic groups represented by the formula: wherein R 6 is hydrogen or alkyl, R 7 is alkyl of 1 to 10 carbon atoms, R 8 is an alkylene group having 1 to 10 carbon atoms, b is an integer from 0 to 4, and c is 0 or 1, so that if c is 0, - (R8), - represents a bond. The vinyl monomer component (A) in the vinyl polymer is a vinyl type monomer which contains a radical-polymerizable vinyl group. There is no particular limitation with respect to such a monomer. The following are examples of this vinyl type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower alkyl analogue methacrylate; glycidyl methacrylate 15; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, or a higher analogous methacrylate; Vinyl acetate, vinyl propionate, or a lower analogous fatty acid vinyl ester; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher analogous fatty acid ester; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxymethacrylamide, N, N-dimethylmethacrylamide, or analogous vinyl monomers which contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or vinyl-like monomers which contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or analogous vinyl monomers which contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl ether and vinyl, or a vinyl-like monomer with ether linkages; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a silicone-like compound having unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutylfumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl ether and glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid ; an unsaturated monomer polymerizable with radicals having a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and an ester of methacrylic acid of an alcohol having a tertiary amine group such as an ester of methacrylic acid and diethylamine.
[0186] The multifunctional vinyl type monomers can also be used. The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, dimethacrylate of 1,6 hexanediol, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethylmethacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate, tris- (2-hydroxyethyl) isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on both ends or analogous silicone compounds having unsaturated groups.
[0187] A carbosiloxane dendrimer, which is the component (B), may be represented by the following formula: R 1 in which Y represents an organic group polymerizable with 5 radicals as defined above. The following is a preferred example of a radical-polymerizable organic group Y: acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-methacryloxymethyl group vinyl (2- (2-propenyl) phenyl, 3- (2-propenyl) phenyl, 2- (4-vinylphenyl) ethyl, 2- (3-vinylphenyl) ethyl, a vinyl, an allyl group, a methallyl group, and a 5-hexenyl group. R 'is as defined previously. X 'represents a silylalkyl group which is represented by the following formula, when i is equal to one: wherein R 1 is as defined above. R2 represents an alkylene group having 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group, or a similar linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group, or a similar branched alkylene group. Ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene are most preferred.
[0188] R3 represents an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and isopropyl. X '+' represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group with i = i + 1. a 'is an integer of 0 to 3, and i is an integer of 1 to 10 which indicates the generation number which represents the number of repeats of the silylalkyl group. For example, when the generation number is one, the carbosiloxane dendrimer may be represented by the first general formula shown below, wherein Y, R 1, R 2 and R 3 are as defined above, R '2 represents a hydrogen atom or is identical to R1; a 'is identical to a'. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 7. When the generation number is 2, the carbosiloxane dendrimer may be represented by the second general formula shown below, wherein Y, R 1, R 2, R 3 and R '2 are the same as defined above; a 'and a2 are the a' of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 25. In the case where the generation number is 3, the carbosiloxane dendrimer is represented by the third general formula shown below, in which Y, R 1, R 2, R 3 and R '2 are the same as defined above; al, a2 and a3 represent the a 'of the indicated generation. Preferably, the total average number of OR3 groups in a molecule is in the range of 0 to 79. ## STR2 ## A carbosiloxane dendrimer which contains a radical-polymerizable organic group may be represented by the following average structural formulas: ## STR1 ## ## STR1 ## The carbosiloxane dendrimer may be made by the process for making a branched silalkane siloxane described in Japanese Patent Application Hei 9-171,154.
[0189] For example, it can be produced by subjecting a hydrosilylation reaction to an organosilicon compound which contains a hydrogen atom attached to a silicon atom, represented by the following general formula: ## STR2 ## And the organosilicon compound which contains an alkenyl group In the above formula, the organosilicon compound may be represented by 3-methacryloxypropyltris- (dimethylsiloxy) silane, the 3-acryloxypropyltris- may be selected from the group consisting of polymers such as the unit derived from a carbosiloxane dendrimer is 5 (dimethylsiloxy) silane, and 4-vinylphenyltris- (dimethylsiloxy) silane The organosilicon compound which contains an alkenyl group may be represented by vinyltris- (trimethylsiloxy) silane, vinyltris- (dimethylphenylsiloxy) silane, and 5-hexenyltri s- (trimethyl siloxy) silane The hydrosilylation reaction is carried out in the presence of a chloroplatinic acid, a vinylsiloxane and platinum complex, or a transition metal analogue catalyst. A vinyl polymer having at least one unit derived from a carbosiloxane dendrimer may be selected from polymers such that the unit of a carbosiloxane dendrimer derivative is a carbosiloxane dendritic structure represented by the formula (I): wherein Z is a divalent organic group, "p" is 0 or 1, R 1 is an aryl or alkyl group of 1 to 10 carbon atoms, and X 'is a silylalkyl group represented by the formula (II): wherein R 1 is as defined above, R2 is an alkylene group of 1 to 10 carbon atoms, R3 is an alkyl group of 1 to 10 carbon atoms, and X '+ 1 is a group selected from the group consisting of hydrogen atoms, aryl groups and alkyl groups having up to 10 carbon atoms, and silylalkyl groups X 'where the exponent "i" is an integer of 1 to 10 indicating the 3025100 generation of the silylalkyl group beginning in each structure carbosiloxane dendritic with a value of 1 for the group X 'in the formula (I) and the index "" is an integer of 0 to 3. In a vinyl polymer having at least one unit derived from a carbosiloxane dendrimer, the ratio of polymerization between the components (A) and (B), in terms of weight ratio between (A) and (B), can be in a range of 0/100 to 99.9 / 0.1, or even 0.1 / 99.9 to 99.9 / 0.1, and preferably in a range of 1/99 to 99/1. A ratio between components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B).
[0190] A vinyl polymer having at least one unit derived from carbosiloxane dendrimer can be obtained by the copolymerization of the components (A) and (B), or by the polymerization of the single component (B). The polymerization may be free-radical polymerization or ionic polymerization, however radical polymerization is preferred.
[0191] The polymerization can be carried out by causing a reaction between components (A) and (B) in a solution for a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50 ° C to 150 ° C . A suitable solvent for this purpose is hexane, octane, decane, cyclohexane, or a similar aliphatic hydrocarbon; benzene, toluene, xylene, or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, or similar ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-isobutyl ketone, or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, or analogous esters; methanol, ethanol, isopropanol, butanol, or similar alcohols; Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, or a similar organosiloxane oligomer. A radical initiator may be any compound known in the art for conventional radical polymerization reactions. Specific examples of such radical initiators are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), or analogous compounds of azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, or a similar organic peroxide. These radical initiators can be used alone or in a combination of two or more. The radical initiators may be used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent can be added. The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane having a mercaptopropyl group or a mercapto-like compound; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, or a similar halogenated compound.
[0192] In the manufacture of the vinyl polymer, after the polymerization, the unreacted residual vinyl monomer can be removed under vacuum heating conditions. In order to facilitate the mixing of the cosmetics raw material, the number average molecular weight of the vinyl polymer which contains a carbosiloxane dendrimer may be selected in the range of from 3,000 to 2,000,000, preferably from 5,000 to 800 000. It can be a liquid, an eraser, a paste, a solid, a powder, or any other form. Preferred forms are solutions consisting of dilution in solvents, a dispersion, or a powder. The vinyl polymer may be a dispersion of a vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol, or water. The silicone oil may be dimethylpolysiloxane having both trimethylsiloxy-capped molecular ends, a copolymer of methylphenylsiloxane and dimethylsiloxane having both trimethylsiloxy-terminated molecular ends, a methyl-3,3,3-trifluoropropylsiloxane copolymer, and of dimethylsiloxane having both trimethylsiloxy-capped molecular ends, or analogous non-reactive linear silicone oils, as well as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, or a similar cyclic compound. In addition to the non-reactive silicone oils, modified polysiloxanes having functional groups such as silanol groups, amino groups, and polyether groups on the ends or within the side molecular chains may be used. The organic oils may be isododecane, paraffin oil, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol, cetostearyl alcohol, oleic alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum, sunflower oil, soybean oil, camellia oil, squalane, castor oil, cottonseed oil, coconut oil, egg yolk, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate, or a similar glycol ester oil; triglyceryl isostearate, triglyceride of a coconut oil fatty acid, or a similar polyhydric alcohol ester oil; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether, or a similar polyoxyalkylene ether. The alcohol may be of any type suitable for use in conjunction with a raw material of cosmetics. For example, it may be methanol, ethanol, butanol, isopropanol or lower alcohols. A solution or dispersion of the alcohol should have a viscosity in the range of 10 to 109 mPa at 25 ° C. To improve the feel properties of use in a cosmetic product, the viscosity should be in the range of 100 to 5 x 108 mPa.s. The solutions and dispersions can easily be prepared by mixing a vinyl polymer having at least one carbosiloxane dendrimer derived unit, a silicone oil, an organic oil, an alcohol, or water. The liquids may be present in the polymerization step a vinyl polymer having at least one unit derived from carbosiloxane dendrimer. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric or reduced pressure. In the case of a dispersion, the dispersity of the vinyl-type polymer can be improved by adding a surfactant. Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, or anionic surfactants of the sodium salts thereof. acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyl dimethylammonium hydroxide, oxytrimethylammonium tallow hydroxide, coconut trimethylammonium oil hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenol, a polyoxyalkylene alkyl ester, the polyoxyalkylene sorbitol ester, polyethylene glycol, polypropylene glycol, a diethylene glycol trimethylnonanol ethylene oxide additive, and polyoxyalkylene alkyl esters; nonionic surfactants of polyester type, as well as mixtures. In addition, the solvents and dispersions can be combined with iron oxide suitable for use with cosmetics, or an analogous pigment, as well as zinc oxide, titanium oxide, silicon oxide, mica, talc or similar inorganic oxides in powder form. In the dispersion, a mean diameter of the vinyl polymer particles may be in the range of 0.001 to 100 microns, preferably 0.01 to 50 microns. Indeed, beyond the recommended range, a cosmetic product mixed with the emulsion will not have a sufficiently good feel on the skin or touch, nor sufficient spreading properties nor a pleasant sensation. A vinyl polymer contained in the dispersion or solution may have a concentration in a range of from 0.1 to 95% by weight, preferably from 5 to 85% by weight. However, for ease of handling and mixing, the range should preferably be from 10 to 75% by weight. According to one preferred embodiment, a vinyl polymer that is suitable for the invention may be one of the polymers described in the examples of application EP 0 963 751. According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer may be derived from the polymerization: (A) from 0.1 to 99 parts by weight of one or more acrylate or methacrylate monomer (s); and 3025100 134 (B) from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer. According to one embodiment, a vinyl polymer having at least one carbosiloxane dendrimer derived unit may comprise a unit derived from tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer having one of the formulas: ## STR2 ## According to a preferred embodiment, a vinyl polymer having at least one carbosiloxane dendrimer derived unit used in the invention comprises at least one butyl acrylate monomer. According to one embodiment, a vinyl polymer may further comprise at least one fluorinated organic group. A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03/045337. According to a preferred embodiment, a grafted vinyl polymer in the sense of the present invention may be carried in an oil or a mixture of oil (s), preferably volatile (s) in particular, chosen (s) from the oils of silicones and hydrocarbon oils and mixtures thereof. According to a particular embodiment, a silicone oil that is suitable for the invention may be cyclopentasiloxane. According to another particular embodiment, a hydrocarbon oil suitable for the invention may be isododecane.
[0193] The vinyl polymers grafted with at least one carbosiloxane dendrimer-derived unit which may be particularly suitable for the present invention are the polymers 3025100 sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB. 4-200, FA 4002 ID (TIB 4-202), TIB 4-220, FA 4001 CM (TIB 4-230) by Dow Corning. Preferably, the polymers sold under the names FA 4002 ID (TIB 4-202) and FA 4001 CM (TIB 4-230) by the company Dow Corning will preferably be used. Preferably, the vinyl polymer grafted with at least one derived unit The carbosiloxane dendrimer used in a composition of the invention is an acrylate / polytrimethylsiloxymethacrylate copolymer, especially that marketed in the isododecane under the name Dow Corning FA 4002 ID silicone acrylate by Dow Corning.
[0194] V. Silicone Acrylate Copolymers According to a particular embodiment, a composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups. By "copolymer having carboxylate groups and polydimethylsiloxane groups" is meant in the present application, a copolymer obtained from (a) one or more carboxylic monomers (acid or ester), and (b) one or more polydimethylsiloxane chains ( PDMS).
[0195] As used herein, the term "carboxylic monomer" is understood to mean both the carboxylic acid monomers and the carboxylic acid ester monomers. Thus, the monomer (a) may be chosen for example from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, their esters and mixtures thereof. monomers. As esters, there may be mentioned the following monomers: acrylate, methacrylate, maleate, fumarate, itaconoate and / or crotonoate. According to a preferred embodiment of the invention, the monomers in the form of esters are more particularly chosen from linear or branched, preferably C 1 -C 24 and better still C 1 -C 22 alkyl acrylates and methacrylates, the alkyl radical being preferably selected from methyl, ethyl, stearyl, butyl, 2-ethylhexyl, and mixtures thereof.
[0196] Thus, according to one particular embodiment of the invention, the copolymer comprises, as carboxylate groups, at least one group chosen from acrylic acid, methacrylic acid, methyl acrylates, methyl methacrylates and the like. stearyl, butyl, 2-ethylhexyl, and mixtures thereof. In the present application, the term "polydimethylsiloxanes" (also called organopolysiloxanes or, in abbreviation, PDMS) is understood to mean, in accordance with the general acceptance, any organosilicon polymer or oligomer with linear structure, of variable molecular weight, obtained by polymerization. and / or polycondensation of suitably functionalized silanes, essentially constituted by a repetition of main units in which the silicon atoms are connected to one another by oxygen atoms (siloxane bond comprising trimethyl radicals directly bound by the intermediate of a carbon atom on said silicon atoms The PDMS chains that can be used to obtain the copolymer used according to the invention comprise at least one radical polymerizable group, preferably located on at least one end of the chain. that is, the PDMS may have, for example, a radical group polymerized ble on both ends of the chain or have a polymerizable radical group on one end of the chain and a trimethylsilyl end group on the other end of the chain. The polymerizable radical group may in particular be an acrylic or methacrylic group, in particular a CH2 = CRi-CO-O-R2 group, where R1 represents a hydrogen or a methyl group, and R2 represents -CH2-, - (CH2) .- with n = 3, 5, 8 or 10, -CH 2 -CH (CH 3) -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -CH (CH 3) -CH 2 -, -CH 2 -CH 2 -O-CH 2 CH 2 -O-CH 2 -CH 2 -CH 2 -. The copolymers used in the composition of the invention are generally obtained according to the usual methods of polymerization and grafting, for example by radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of ends of the chain or both) and (B) of at least one carboxylic monomer, as described for example in US-A-5,061,481 and US-A-5,219,560. The copolymers obtained generally have a molecular weight ranging from about 3000 to 200,000 and preferably from about 5,000 to 100,000.
[0197] The copolymer used in the composition of the invention may be present as such or in dispersed form in a solvent such as lower alcohols having 2 to 30 carbon atoms, such as isopropyl alcohol, or oils such as volatile silicone oils (eg cyclopentasiloxane). Copolymers which can be used in the composition of the invention include, for example, copolymers of acrylic acid and of stearyl acrylate with polydimethylsiloxane grafts, copolymers of polydimethylsiloxane grafted stearyl methacrylate, copolymers of acrylic acid and of polydimethylsiloxane grafted stearyl methacrylate, copolymers of methyl methacrylate, butyl methacrylate, ethyl-2-hexyl acrylate and stearyl methacrylate with polydimethylsiloxane grafts. In particular, the copolymers sold by the company SHIN-ETSU under the names KP-561 (CTFA name: acrylates / dimethicone), KP-541, in which the copolymer is dispersed at room temperature, can be mentioned in particular as copolymers which can be used in the composition of the invention. 60% by weight in isopropyl alcohol (CTFA name: acrylates / dimethicone and isopropyl alcohol), KP-545 where the copolymer is 30% dispersed in cyclopentasiloxane (CTFA name: acrylates / dimethicone and Cyclopentasiloxane). According to a preferred embodiment of the invention, KP561 is preferably used; this copolymer is not dispersed in a solvent, but is in a waxy form, its melting point being about 30 ° C. It is also possible to mention the graft copolymer of polyacrylic and dimethylpolysiloxane dissolved in isododecane marketed by Shin Etsu under the name KP-550. AQUEOUS PHASE The aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.
[0198] By "water-soluble solvent" is meant in the present invention a liquid compound at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25 ° C and atmospheric pressure). The water-soluble solvents that can be used in the composition of the invention may also be volatile.
[0199] Among the water-soluble solvents which can be used in the composition in accordance with the invention, there may be mentioned lower monoalcohols having from 1 to 5 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. The aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 5% to 95%, more preferably from 30% to 80% by weight, preferably from 40% to 75% by weight. % by weight, relative to the total weight of said composition. According to another variant embodiment, the aqueous phase of a composition according to the invention may comprise at least one C2-C32 polyol. For the purposes of the present invention, the term "polyol" means any organic molecule comprising at least two free hydroxyl groups. Preferably, a polyol according to the present invention is present in liquid form at room temperature. A polyol suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing on the alkyl chain at least two -OH functions, in particular at least three -OH functions, and more particularly at least four functions -OH. The polyols which are advantageously suitable for formulating a composition according to the present invention are those having in particular 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.
[0200] Advantageously, the polyol may be, for example, chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol glycerol, polyglycerols, such as oligomers of glycerol such as diglycerol, polyethylene glycols, and mixtures thereof.
[0201] 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.
[0202] According to another particular embodiment, the composition of the invention may comprise at least glycerol.
[0203] 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.
[0204] An oily phase suitable for the preparation of the compositions, especially cosmetic compositions, according to the invention may comprise hydrocarbon, silicone, fluorinated or non-fluorinated oils, or mixtures thereof. The oils may be volatile or non-volatile. They can be of animal, vegetable, mineral or synthetic origin. According to an alternative embodiment, the oils of silicone origin are preferred. For the purposes of the present invention, the term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa. For the purposes of the present invention, the term "silicone oil" means an oil comprising at least a silicon atom, and in particular at least one Si-O group.
[0205] The term "fluorinated oil" means an oil comprising at least one fluorine atom. The term "hydrocarbon oil" means an oil containing mainly hydrogen and carbon atoms. The oils may optionally include oxygen, nitrogen, sulfur and / or phosphorus atoms, for example as hydroxyl or acid radicals. By "volatile oil" is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa. at 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 10 mm). of Hg).
[0206] Volatile oils Volatile oils may be hydrocarbon or silicone.
[0207] Examples of volatile hydrocarbon oils having from 8 to 16 carbon atoms include branched C8-C16 alkanes, for example iso-alkanes (also known as isoparaffins) with C8-C16, isododecane, isodecane, and the like. isohexadecane and for example the oils sold under the trade names 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 1497, 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 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.
[0208] Cyclic silicone volatile oils that may be mentioned are hexamethylcyclotriosiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. Nonvolatile oils The nonvolatile oils may in particular be chosen from hydrocarbon oils, fluorinated oils and / or nonvolatile silicone oils. As non-volatile hydrocarbon oil, mention may be made in particular of: 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 R 1 COROR 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, branched, containing from 1 to 40 carbon atoms provided that R1 + R2 is 10. The esters may be, in particular, chosen from alcohol and fatty acid esters, such as, for example, cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethyl hexyl palmitate, isopropyl stearate, octyl stearate, hydroxyl esters, such as lactate, isostearyl, hydroxyl octyl stearate, ricinoleates of alcohols or polyalcohols, hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, such as 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 from 12 to 26 carbon atoms, such as 2-octyldodecanol, isostearyl alcohol, oleic alcohol, - higher C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid, and mixtures thereof, non-phenylated silicone oils, for example caprylyl methycone, and phenylated silicone oils, for example phenyl trimethicones, phenyl dimethicones, phenyl ters. trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone with viscosities less than or equal to 100 cSt, trimethylpentaphenyltrisiloxane, and mixtures thereof; as well as the blends of these different oils. Preferably, a composition according to the invention comprises volatile and / or nonvolatile silicone oils. Such silicone oils are particularly preferred when the lipophilic gelling agent is an organopolysiloxane elastomer. 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.
[0209] As stated 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.
[0210] COLORING MATERIALS A composition according to the invention may further comprise at least one particulate or non-particulate matter, water-soluble or not, and preferably at least 0.01% by weight relative to the total weight of the composition. For obvious reasons, this amount is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the dyestuffs considered and its adjustment is clearly within the competence of the man of the art. 'art. A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 15% by weight. % by weight of dyestuffs, relative to the total weight of said composition. As specified above, the dyestuffs that are suitable for the invention can be water-soluble but also fat-soluble. For the purposes of the invention, the term "water-soluble dyestuff" means any generally organic compound, natural or synthetic, soluble in an aqueous phase, or water-miscible and colorable solvents. As water-soluble dyes that are suitable for the invention, water-soluble synthetic or natural dyes, such as, for example, FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC 25 Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanin (beet), carmine, copper chlorophylline, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry), caramel, riboflavin. Water-soluble dyes are, for example, beet juice and caramel.
[0211] For the purposes of the invention, the term "liposoluble coloring matter" means any generally organic compound, natural or synthetic, soluble in an oily phase, or solvents which are miscible with a fatty substance and capable of coloring. As liposoluble dyes that are suitable for the invention, liposoluble, synthetic or natural dyes, such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow may be mentioned. 11, DC Violet 2, DC Orange 5, Sudan red, carotenes ((3-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, yellow quinoline, annatto, curcumin.
[0212] The particulate coloring materials may be present in a proportion of from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 15% by weight, relative to the total weight of said composition containing them.
[0213] It may especially be pigments, pearlescent agents and / or particles with metallic reflections. The term "pigments" should be understood to mean white or colored, mineral or organic particles, insoluble in an aqueous solution, intended to color and / or opacify the composition containing them.
[0214] A composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 25% by weight and preferably from 5% to 15% by weight. % by weight of pigments, relative to the total weight of said composition. Preferably, when the composition according to the invention is a makeup composition, it may comprise at least 5%, and preferably at least 10% by weight of pigments, relative to the total weight of said composition. The pigments can be white or colored, mineral and / or organic. As inorganic pigments that can be used in the invention, mention may be made of oxides or dioxides of titanium, zirconium or cerium, as well as oxides of zinc, iron or chromium, ferric blue, manganese violet, blue ultramarine and chromium hydrate, and mixtures thereof.
[0215] It may also be a pigment having a structure which may for example be of sericite / brown iron oxide / titanium dioxide / silica type. Such a pigment is marketed for example under the reference Coverleaf NS or JS by the company Chemicals And Catalysts and has a contrast ratio of about 30.
[0216] It may also be pigments having a structure which may be, for example, silica microsphere type containing iron oxide. An example of a pigment having this structure is that marketed by Miyoshi under the reference PC Ball PC-LL-100 P, this pigment consisting of silica microspheres containing yellow iron oxide.
[0217] Advantageously, the pigments according to the invention are iron oxides and / or titanium dioxides. The term "nacres" must be understood to mean colored particles of any shape, iridescent or otherwise, in particular produced by certain shellfish in their shell or else synthesized, and which exhibit a color effect by optical interference. A composition according to the invention may comprise from 0% to 15%, in particular from 1% to 8% by weight of nacres, relative to the total weight of said composition. The nacres may be chosen from pearlescent pigments, such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica. covered with an organic dye, as well as pearlescent pigments based on bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs. Mention may also be made, by way of example of nacres, of natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride. Among the nacres available on the market, mention may be made of the nacres Timica, Flamenco and Duochrome (based on mica) marketed by ENGELHARD, 30 the nacres Timiron marketed by Merck, nacres based on mica Prestige marketed by the Eckart company and the nacres based on Sunshine synthetic mica sold by the company Sun Chemical.
[0218] 3025100 Nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or reflection. Advantageously, the nacres according to the invention are micas coated with titanium dioxide or iron oxide and bismuth oxychloride.
[0219] For the purposes of the present invention, the term "metal-reflecting particles" means any compound whose nature, size, structure and surface state enables it to reflect incident light, in particular in a non-iridescent manner. The particles with a metallic sheen that can be used in the invention are chosen in particular from: the particles of at least one metal and / or at least one metal derivative; particles comprising a substrate, organic or inorganic, monomaterial or multimaterial, at least partially covered by at least one metal-reflecting layer comprising at least one metal and / or at least one metal derivative; and mixtures of said particles. Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te. Se and their mixtures or alloys. Ag, Au, Cu, Al, Zn, Ni, Mo, Cr, and mixtures or alloys thereof (eg, bronzes and brasses) are preferred metals.
[0220] By "metal derivatives" are meant compounds derived from metals including oxides, fluorides, chlorides and sulfides. As an illustration of these particles, mention may be made of aluminum particles, such as those sold under the names Starbrite 1200 EAC® by the company Siberline and Metalure® by the company Eckart, and glass particles coated with a metal layer. especially those described in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710. Hydrophobic treatment of dyestuffs The pulverulent dyestuffs as described above may be surface-treated, totally or partially, with a hydrophobic agent, to make them more compatible with the oily phase of the composition of the invention, especially for they have good wettability with oils. Thus, these treated pigments are well dispersed in the oily phase. Hydrophobic-treated pigments are described in particular in document EP-A-1086683.
[0221] The hydrophobic treating agent may be selected from silicones such as meticones, dimethicones, perfluoroalkylsilanes; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates; hexafluoropropylene polyoxides; perfluoropolyethers; amino acids; N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof. The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.
[0222] POLAR (S) ADDITIVE (S) Advantageously, a composition according to the invention may further comprise one or more polar additive (s), in particular when it contains pigments. According to the present invention, the use of such a polar additive facilitates the homogenization of the dispersion in the presence of pigments. The polar additive may be chosen from compounds considered to be good donors or acceptors of hydrogen bonds, for example fatty alcohols, fatty acids, diols, esters and mixtures thereof. According to one embodiment, the polar additives of the invention may be polar oils such as for example: high-triglyceride hydrocarbon vegetable oils consisting of fatty acid esters (C 8 to C 24) and glycerol whose fatty acids may have various chain lengths, the latter may be linear or branched, saturated or unsaturated; these oils include wheat germ, corn, sunflower, shea, castor oil, sweet almond, macadamia, apricot, soya, rapeseed, cotton, alfalfa, poppy , pumpkin, sesame, squash, avocado, hazelnut, grape seed or black currant, evening primrose, millet, barley, quinoa, olive, rye, safflower, 3025100 147 of bancoulier, passionflower, muscat rose; or alternatively caprylic / capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; synthetic oils of formula R 5 COOR 6 in which R 5 represents the residue of a linear or branched higher fatty acid containing from 7 to 40 carbon atoms and R 6 represents a branched hydrocarbon-based chain containing from 3 to 40 carbon atoms, for example Purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alcohol benzoate; esters and synthetic ethers such as isopropyl myristate, ethyl 2-hexyl palmitate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, hydroxyl esters such as isostearyl lactate, malate diisostearyl; and pentaerythritol esters; fatty acids having from 12 to 22 carbon atoms, such as oleic, linoleic or linolenic acid; and their mixtures. According to another embodiment, the polar additives of the invention may be amphiphilic compounds. The amphiphilic compound or compounds that can be used in the composition of the invention comprise a lipophilic part bonded to a polar part, the lipophilic part possibly comprising a carbon chain having at least 8 carbon atoms in particular, from 18 to 32 carbon atoms and better from 18 to 28 carbon atoms. Preferably, the polar part of this or these amphiphilic compounds is the residue of a compound chosen from alcohols and polyols having from 1 to 12 hydroxyl groups, the polyoxyalkylenes comprising at least 2 oxyalkylenated units and having from 0 to 20 oxypropylene units. and / or from 0 to 20 oxyethylenated units. In particular, the amphiphilic compound is an ester chosen from hydroxystearates, oleates, iso-stearates of glycerol, sorbitan or methylglucose or branched C 6 to C 26 fatty alcohols such as octyldodecanol and mixtures thereof. Of these esters, monoesters and mixtures of mono- and di-esters are particularly preferred. The amphiphilic compounds can also be silicones. These amphiphilic silicones comprise a silicone part which is compatible with the highly silicone medium of the compositions of the invention, and a hydrophilic part which may be, for example, the remainder of a compound chosen from alcohols and polyols, having from 1 to 12 hydroxyl groups, the polyoxyalkylenes comprising at least two oxyalkylenated units and having from 0 to 20 oxypropylene units and / or from 0 to 20 oxyethylenated units. This hydrophilic part therefore has an affinity for the hydrophilic particles and promotes their dispersion in the silicone medium. The polar additives of the invention may be filtering agents UV-B and / or UV-A rays, the total amount of filters may be between 0.01% and 10% by weight relative to the total weight of the composition .
[0223] A composition according to the invention may comprise from 0.01% to 10% by weight, in particular from 0.05% to 5% by weight, in particular from 0.05% to 1% by weight of additive (s). Advantageously, a composition according to the invention may further comprise one or more filler (s) conventionally used in skincare and / or makeup compositions. These fillers are colorless or solid white particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition.
[0224] Of mineral or organic nature, natural or synthetic, they make it possible to confer on the composition containing them softness, dullness and uniformity in makeup. In addition, these fillers advantageously make it possible to fight against various aggressions such as sebum or sweat. As an illustration of these fillers, mention may be made of talc, mica, silica, kaolin, poly-13-alanine and polyethylene powders, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine , starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), acrylic acid copolymers, silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, barium sulfate, aluminum oxides, polyurethane powders, composite fillers, hollow silica microspheres, and glass or ceramic microcapsules. It is also possible to use particles, which are in the form of portions of hollow spheres, as described in patent applications JP-2003 128 788 and JP-2000 191 789. In particular, such fillers may be present in a composition according to the invention in a content of between 0.01% and 25% by weight, in particular between 0.1% and 20% by weight, in particular between 1% and 10% by weight, relative to 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 fillers. Advantageously, a composition according to the invention may comprise from 0.01% to 25% by weight, in particular from 0.1% to 25% by weight, in particular from 1% to 20% by weight and preferably from 5% to 15% by weight of solid particles, relative to the total weight of the composition.
[0225] DISPERSANT AGENT Advantageously, a composition according to the invention may further comprise a dispersing agent. Such a dispersing agent may 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. ACTIVE A composition according to the invention may comprise at least one moisturizing agent (also called humectant), in particular for a care application. Preferably, the moisturizing agent is glycerin. The moisturizing agent (s) may be present in the composition in a content ranging from 0.1% to 15% by weight, especially from 0.5% to 10% by weight, or even from 1% to 6% by weight, relative to the total weight of said composition. Other active agents which may be used in the composition of the invention include, for example, vitamins, sunscreens and mixtures thereof.
[0226] Preferably, a composition according to the invention comprises at least one active ingredient. It is a matter of routine practice for those skilled in the art to adjust the nature and amount of the additives present in the compositions according to the invention, so that the desired cosmetic properties thereof do not are not affected. According to one embodiment, a composition of the invention may advantageously be in the form of a care composition of the skin and / or keratin fibers, the body or the face, in particular the face.
[0227] According to another embodiment, a composition of the invention may advantageously be in the form of a makeup composition for the skin and / or keratinous fibers, the body or the face, in particular the face. Thus, according to a sub-mode of this embodiment, a composition of the invention may advantageously be in the form of a make-up makeup base composition. A composition of the invention may advantageously be in the form of a foundation. According to another sub-mode of this embodiment, a composition of the invention may advantageously be in the form of a make-up composition for the skin and in particular the face. It can be an eyeshadow or a blush. According to yet another sub mode of this embodiment, a composition of the invention may advantageously be in the form of a lip product, especially a lipstick.
[0228] According to yet another sub-mode of this embodiment, a composition of the invention may be in the form of a product for the eyelashes, in particular a mascara. According to yet another sub-mode of this embodiment, a composition of the invention may advantageously be in the form of a product for the eyebrows, in particular an eyebrow pencil. Such compositions are especially prepared according to the general knowledge of those skilled in the art.
[0229] In the entire description, including the claims, the phrase "having one" is to be understood as being synonymous with "having at least one" unless the contrary is specified. The terms "between ... and ..." and "from ... to ..." are to be understood inclusive unless otherwise stated. The invention is illustrated in greater detail by the examples and figures presented hereinafter. Unless otherwise indicated, the quantities indicated are expressed as a percentage by mass.
[0230] 10 METHODOLOGY FOR DYNAMIC OSCILLATION RHEOLOGY MEASUREMENTS These are harmonic rheological measurements that measure the elastic modulus.
[0231] The measurements are carried out using a Haake RS600 rheometer on a product at rest, at 25 ° C. with a plane plane 60 mm and a 2 mm gap. The measurements in harmonic regime make it possible to characterize the viscoelastic properties of the products. The technique involves subjecting a material to a sinusoidally varying stress over time and measuring the response of the material to that stress. In a domain where the behavior is linear viscoelastic (zone where the deformation is proportional to the stress), the stress (T) and the deformation (y) are two sinusoidal functions of the time which are written in the following way: T (t ) = To sin (wt) 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 S represents the phase shift of the stress with respect to the deformation (rad).
[0232] Thus, the two functions have the same angular frequency but they are out of phase by an angle δ. According to the phase shift S between T (t) and y (t), the behavior of the system can be apprehended: - If S = 0, the material is purely elastic; 5 - If S = II / 2, the material is purely viscous (Newtonian fluid); and - If 0 <S <II / 2, the material is viscoelastic. In general, the stress and the deformation are written in complex form: T * (t) = To etwt y * (t) = yo e (iwt + δ) 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 15 stored and totally restored during a cycle, G '= (To / yo) cos S, and G "is the loss module or viscous modulus which characterizes the energy dissipated by internal friction during a cycle, G "= (To / yo) sin Ô The parameter used is the modulus of average stiffness G * measured at the plateau measured at a frequency of 1 Hz.
[0233] EXAMPLES Example 1: Care Compositions Care formulations according to the invention are prepared as described below. The components of phase A are weighed in a beaker and stirred with rayneri at room temperature. The components of phase B are weighed and added to phase A with vigorous stirring at room temperature.
[0234] The walls and bottom of the beaker are scraped with a sponge and the mixture is allowed to homogenize with vigorous stirring at room temperature until the mixture becomes completely homogeneous.
[0235] A white bi-gel composition is formed. The formula is prepared from the weight proportions described below. The percentages are by weight relative to the total weight of the composition. Phase Compounds Formula 1 Formula 2 Formula 3 Formula 4 Out According According According to According to the invention the invention the invention the invention Phase A Deionized water microbiologically Qsp 100 Qsp 100 Qsp 100 Qsp 100 clean Glycerin (Concerine CD 99.5 Nat) 6.6 % 6.1% 6.1% 6.1% Phenoxyethanol (NEOLONE PH 100 1.0% 0.9% 0.9% 0.9% Preservative marketed by DOW CHEMICAL) Copolymer Acrylamido-2-Methyl 3, 0% 2.8% 2.8% 2.8% Sodium Propane Sulfonate / Hydroxyethylacrylate in powder form (SEPINOV® EMT 10 sold by the company SEPPIC) Phase B Polydimethylsiloxane mixture 17.5% 16.3% 16, 3% 16.3% crosslinked with hexadiene and polydimethylsiloxane CST (Dow Corning EL-9240® silicone elastomer blend marketed by Dow Corning) Cross-linked polydimethylsiloxane CST 10.0% 9.3% 9.3% 9.3% (Xiameter PMX-200 silicone fluid 5CS marketed by the company Dow Corning) Trimethyl siloxysilicate resin / 6.9% / / Copolym butyl acrylate / 17.2% / containing dendritic silicone side chains diluted to 40% in isododecane (Dow Corning® FA 4002 ID Silicone Acrylate marketed by Dow Corning) Copolymer Acrylic Acid / Acrylate isobutyl / isobornyl acrylate diluted to 50% in isododecane (Mexomere / / / 13.7% PAS marketed by Chimex) Protocol for evaluating the technical effect of the compositions In order to evaluate the behavior of the dullness compositions, an in vitro gloss test was performed. For this purpose, a 25 μm deposit of each formula is made on a contrast card.
[0236] 3025100 154 Using a BYK glossmeter (angle 60 °), several brightness measurements are performed at T = 0 and then at T = 24 hours. The results clearly demonstrate that the compositions 2, 3 and 4 exhibit a much greater resistance to mattness than the control composition 1. Thus, the presence of hydrophobic film-forming polymer in a gel-gel composition makes it possible to guarantee a lasting behavior. much more important dullness. In other words, the compositions according to the invention significantly improve the behavior of the dullness after 24 hours.
[0237] Example 2: Foundation composition according to the invention A foundation formulation according to the invention is prepared as described below. The components of phase A are weighed and stirred with rayneri at room temperature.
[0238] The components of phase B are weighed and stirred with rayneri at room temperature. The components of phase B are added to phase A with vigorous stirring at room temperature. The walls and the bottom of the beaker are scraped using a sponge and the mixture is allowed to homogenize with vigorous stirring at room temperature until complete homogenization. A gel-gel composition is formed. The formula is prepared from the weight proportions described below. The percentages are by weight relative to the total weight of the composition.
[0239] 3025100 Phase Compounds Formula 5 Formula 6 According to the Invention According to the Invention Phase A Microbiologically Clean Deionized Water Qsp 100 Qsp 100 Glycerin (Concerine CD 99.5 Nat) 3.0 0.3 1,3-Butylene Glycol 3.0 / Polydimethylsiloxane connected with 0.6 0.6 triglycerol groups and PDMS (KF-6100 marketed by SHIN-ETSU) Hydroxyethyl Acrylate / Sodium Acryloydimethyl 1.8 1.8 Taurate Copolymer (SEPINOV® EMT 10 marketed by the company SEPPIC) Phase B Polydimethylsiloxane blend crosslinked with 2.5 hexadiene and polydimethylsiloxane CST (Dow Corning EL-9240® silicone elastomer blend sold by Dow Corning) Trimethyl Siloxysilicate resin 5.9 5.9 Cyclohexadimethylsiloxane 8 CST (Xiameter PMX-5 13 0246 cyclohexasiloxane marketed by the company Dow Corning) Isohexadecane 8 / silica gel treated with hexamethyldisiloxane 0.4 0.4 (VM-2270 airgel fine particles marketed by the company DOW CORNING) Hemispheres of crosslinked methyl polymethacrylate (PMMA) (Sepimat H 10 sold by the company 2.1 2.1 SEPPIC) Titanium oxide (NAI-TAO-77891 sold by MIYOSHI KASEI) 9.4 9, 4 Iron oxides (NAI-C33-9001-10, NAI-C33-7001-10 2,4 2,4 and NAI-C33-8001-10 marketed by MIYOSHI KASEI) Protocol for evaluating the technical effect Compositions The compositions were tested in vivo in conventional intrumental evaluation for 3 hours at room temperature to test their sebum resistance and under extreme conditions (30 minutes at 37 ° C., 60% RH) to test their resistance to sweat. Compared to a multiphase composition containing no hydrophobic film-forming polymers, the compositions according to the invention have a better resistance to sebum and sweat.
[0240] Example 3: Eyebrow makeup composition An eyebrow makeup formulation according to the invention is prepared as described hereinafter.
[0241] The components of phase A are weighed and stirred with rayneri at room temperature. The components of phase B are weighed and stirred with rayneri at room temperature.
[0242] The components of phase B are added to phase A with vigorous stirring at room temperature. The walls and bottom of the beaker are scraped using a sponge and the mixture is allowed to homogenize with vigorous stirring at room temperature until complete homogenization.
[0243] A gel-gel composition is formed. The formula is prepared from the weight proportions described below. The percentages are by weight relative to the total weight of the composition.
[0244] 3025100 157 Phase Compounds Formula 7 According to the invention Phase A Deionized water microbiologically clean Qsp 100 Glycerin (Concerine CD 99.5 Nat) 4.5 Copolymer Acrylamido-2-methylpropane Sulfonate 1.6 Sodium / Hydroxyethylacrylate in powder form ( SEPINOV® EMT 10 sold by the company SEPPIC) Polydimethylsiloxane branched with 0.6 triglycerol and PDMS groups (KF-6100 sold by the company Shin-Etsu) Preservative 0.9 Phase B Trimethyl siloxysilicate resin 5.3 Cyclohexadimethylsiloxane 8 CST ( Xiameter PMX-10.7 0246 cyclohexasiloxane sold by the company Dow Corning) Mixture of polydimethylsiloxane crosslinked with 2.5 hexadiene and polydimethylsiloxane CST (Dow Corning EL-9240® silicone elastomer blend sold by the company Dow Corning Dodecamethylpentasiloxane, PDMS 2 CST (DM-7.2 FLUID-2cs marketed by SHIN-ETSU) Silica gel treated with hexamethyldisiloxane 0.3 (its ns loose powder) (VM-2270 aerogel fine particles marketed by the company Dow Corning) Copolymer di-ethylene methacrylate 2,3 glycol / Lauryl methacrylate (POLYTRAP® 6603 Adsorber) Hemispheres of crosslinked methyl polymethacrylate (PM MA) ( Septimat H 10 sold by the company 4,5 SEPPIC) Titanium oxide (NAI-TAO-77891 sold by MIYOSHI KASEI) 26 Iron oxides (NAI-C33-9001-10, NAI-C33-7001-10 74 and NAI-C33-8001-10 marketed by MIYOSHI KASEI The composition allows to bring freshness and lightness on the eyebrows. It brings a good pay-off, that is to say a good deposit on the eyebrows and allows to redraw them naturally.
[0245] The holding in time of the makeup result is very good as well as its comfort during the day.

权利要求:
Claims (24)
[0001]
REVENDICATIONS1. Composition in particular cosmetic makeup and / or care of keratin materials, in particular of the skin and / or lips, and keratinous fibers, in particular the eyebrows, comprising: at least one aqueous phase gelled with at least one hydrophilic gelling agent ; and at least one oily phase gelled with at least one lipophilic gelling agent; Said phases forming a macroscopically homogeneous mixture therein; said composition further comprising at least one hydrophobic film-forming polymer.
[0002]
2. Composition according to the preceding claim, comprising from 0.1% to 30% by weight, preferably from 0.2% to 20% by weight and even more preferably from 0.5% to 15% by weight of polymer ( s) hydrophobic film-forming (s), relative to the total weight of the composition.
[0003]
3. Composition according to claim 1 or 2, wherein the hydrophobic film-forming polymer or polymers are present in whole or in part, and preferably only, in the gelled oily phase. 20
[0004]
4. Composition according to any one of the preceding claims, in which the hydrophobic film-forming polymer or polymers are chosen from block ethylenic polymers, the vinyl polymers comprising at least one carbosiloxane dendrimer derivative and the silicone resins (T resin, MQ resin). .
[0005]
5. A composition according to any one of the preceding claims, wherein the hydrophobic film-forming polymer is a trimethylsiloxysilicate resin.
[0006]
6. Composition according to any one of the preceding claims, comprising, as hydrophilic gelling agent, at least one synthetic polymeric gelling agent.
[0007]
7. The composition according to claim 6, wherein the synthetic polymeric hydrophilic gelling agent is selected from 2-acrylamido-2-methylpropane sulfonic acid polymers and copolymers. 3025100 159
[0008]
8. Composition according to any one of claims 6 or 7, wherein the synthetic polymeric hydrophilic gelling agent is at least one ammonium 2-acrylamido-2-methylpropane sulfonate acid polymer.
[0009]
9. A composition according to any one of claims 6 or 7, wherein the synthetic polymeric hydrophilic gelling agent is at least one 2-acrylamido-2-methylpropanesulphonic acid and hydroxyethyl acrylate copolymer.
[0010]
A composition according to any one of the preceding claims, wherein said lipophilic gelling agent is selected from particulate gelling agents, organopolysiloxane elastomers, semi-crystalline polymers, dextrin esters, hydrogen bonded polymers, and the like. mixtures.
[0011]
11. Composition according to any one of the preceding claims, comprising, as lipophilic gelling agent, at least one organopolysiloxane elastomer, preferably chosen from Dimethicone Crosspolymer, Dimethicone (and) Dimethicone Crosspolymer, Vinyl Dimethicone Crosspolymer, Dimethicone / Vinyl Dimethicone. Crosspolymer, Dimethicone Crosspolymer-3, and especially Dimethicone Crosspolymer and Dimethicone (and) Dimethicone Crosspolymer.
[0012]
12. Composition according to any one of the preceding claims, comprising, as lipophilic gelling agent, 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. in particular 1 to 10 is at 25 ° C.
[0013]
13. A composition according to any one of the preceding claims, containing as a hydrophilic gelling system (s) / gelling (s) lipophilic (s), a system (s) or copolymer (s) acid 2 2-methyl-propane sulfonic acrylamido / organopolysiloxane elastomer (s). 25
[0014]
14. Composition according to any one of the preceding claims, containing the aqueous and oily phases in an aqueous phase / oily phase weight ratio ranging from 95/5 to 5/95, preferably from 30/70 to 80/20.
[0015]
15. A composition according to any one of the preceding claims, further comprising at least solid particles such as pigments and / or fillers.
[0016]
16. Composition according to any one of the preceding claims, comprising pigments in combination with a polar additive. 3025100 160
[0017]
17. Composition according to any one of the preceding claims, further comprising volatile and / or nonvolatile silicone oils.
[0018]
18. Composition according to any one of the preceding claims, further comprising at least one moisturizing agent, preferably glycerine.
[0019]
19. Composition according to any one of the preceding claims, in the form of a make-up composition for the skin and / or keratinous fibers, the body or the face, in particular the face.
[0020]
20. A process for preparing a composition, especially a cosmetic makeup and / or skincare composition for keratinous substances, in particular skin and / or lips, and keratinous fibers, in particular the eyebrows, comprising at least one mixing step: an aqueous phase gelled with at least one hydrophilic gelling agent; and at least one oily phase gelled with at least one lipophilic gelling agent; under conditions conducive to obtaining a macroscopically homogeneous mixture, said composition further comprising at least one hydrophobic film-forming polymer.
[0021]
21. The process according to claim 20, comprising a step of mixing at least three gelled phases.
[0022]
22. A process according to any one of claims 20 or 21 wherein the mixing is carried out at ambient temperature.
[0023]
23. A cosmetic process for making up and / or caring for a keratinous material, in particular the skin and / or the lips, and for keratinous fibers, in particular the eyebrows, comprising at least one step consisting in applying to said keratin material a composition as defined in any one of claims 1 to 19.
[0024]
24. A cosmetic process for makeup and / or care of a keratinous material, in particular the skin and / or the lips, and keratinous fibers, in particular the eyebrows, comprising at least the application on said material of a composition macroscopically homogeneous obtained by extemporaneous mixing, before application or at the time of application on said keratinous material, of at least one aqueous phase gelled by at least one hydrophilic gelling agent, and at least one gelled oily phase 3025100 161 by at least one lipophilic gelling agent; and said composition further comprising at least one hydrophobic film-forming polymer.

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同族专利:

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公开号 | 公开日

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US20170290747A1|2017-10-12|

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WO2016030842A1|2016-03-03|

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JP6446539B2|2018-12-26|

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CN106794135A|2017-05-31|

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FR3025100B1|2016-12-09|

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EP3185958A1|2017-07-05|

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ES2773636T3|2020-07-13|

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CN106794135B|2020-12-22|

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EP3185958B1|2019-12-04|

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JP2017531617A|2017-10-26|

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法律状态:
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2016-03-04| PLSC| Search report ready|Effective date: 20160304 |

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优先权:

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申请号 | 申请日 | 专利标题

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FR1458064A|FR3025100B1|2014-08-28|2014-08-28|GEL-TYPE COSMETIC COMPOSITION IMPROVED|FR1458064A| FR3025100B1|2014-08-28|2014-08-28|GEL-TYPE COSMETIC COMPOSITION IMPROVED|

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JP2017511309A| JP6446539B2|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved durability|

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PCT/IB2015/056474| WO2016030842A1|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved staying power|

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US15/507,440| US20170290747A1|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved staying power|

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EP15774974.8A| EP3185958B1|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved staying power|

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CN201580046714.9A| CN106794135B|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved retention|

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ES15774974T| ES2773636T3|2014-08-28|2015-08-26|Gel-type cosmetic composition with improved staying power|