WO2013093869A2 - Gel-type cosmetic composition for making up and/or caring for the skin - Google Patents

Gel-type cosmetic composition for making up and/or caring for the skin Download PDF

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Publication number
WO2013093869A2
WO2013093869A2 PCT/IB2012/057588 IB2012057588W WO2013093869A2 WO 2013093869 A2 WO2013093869 A2 WO 2013093869A2 IB 2012057588 W IB2012057588 W IB 2012057588W WO 2013093869 A2 WO2013093869 A2 WO 2013093869A2
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composition
weight
phase
relative
carboxyalkyl
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PCT/IB2012/057588
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French (fr)
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WO2013093869A3 (en
Inventor
Philippe Gabin
Patrice Styczen
Xavier Ray
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L'oreal
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Publication of WO2013093869A3 publication Critical patent/WO2013093869A3/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/732Starch; Amylose; Amylopectin; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/895Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments

Definitions

  • Gel-type cosmetic composition for making up and/or caring for the skin
  • the present invention is directed toward proposing a novel cream architecture of cosmetic composition, especially of foundation type.
  • Cosmetic compositions are commonly used to give the skin an esthetic color, but also to hide imperfections of the skin relief such as wrinkles and/or fine lines.
  • many solid or fluid, anhydrous or non-anhydrous formulations have been developed to date, namely fluids, creams, compacts, loose powders or sticks.
  • an aqueous architecture which is advantageous with regard to the fresh properties it imparts, does not ensure uniform distribution of the particulate materials within the composition.
  • makeup compositions such as foundations are generally in the form of an emulsion containing an aqueous phase and a fatty phase.
  • Each of these two phases is capable of constituting the continuous phase according to the specific needs, which gives the possibility of formulating direct emulsions (aqueous continuous phase) or inverse emulsions (fatty continuous phase).
  • aqueous continuous phase aqueous continuous phase
  • inverse emulsions fatty continuous phase
  • surfactants the water content of which is conventionally from 20% to 30%, up to 40%, rarely greater than 50% and never greater than 60%.
  • compositions that are simultaneously endowed with the freshness of aqueous formulations and the qualities of oily formulations in terms of comfort and glidance on application, and in which the combination of aqueous phase and oily phase, which is required to gain access to these qualities, also proves to be homogeneous and stabilized over time without, however, requiring the mandatory presence of surfactant.
  • the inventors have found that such an objective may be achieved provided that specific phases are combined within the same composition to form a gel-type composition.
  • the present invention relates to a gel-type cosmetic composition for making up and/or caring for the skin, comprising at least:
  • a gelled aqueous phase containing at least 3% by weight, relative to its total weight, of particles of at least one (d-C 4 ) carboxyalkyl starch and whose particle size ranges from 25 to 300 ⁇ , and
  • the oily phase has a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
  • the dispersed phase and the continuous phase have a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
  • a composition according to the invention is in the form of a creamy gel with a minimum stress below which it does not flow unless it has been subjected to an external mechanical stress.
  • Such a composition also has a certain amount of elasticity.
  • composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa.
  • the (d-C 4 ) carboxyalkyl starch particles are in a swollen and unsplit form.
  • This swelling is the consequence of absorption of the aqueous medium by the (d-C 4 ) carboxyalkyl starch particles.
  • This swelling may be characterized by a swelling power that may be, after 24 hours of contact with the liquid to be absorbed, which is preferably aqueous, between 10 and 30 ml/g and preferably between 15 and 25 ml (volume of liquid absorbed)/g of dry particulate material. It is precisely with regard to this swelling capacity of the (d-C 4 ) carboxyalkyl starch particles that access is gained according to the invention to a gel-type architecture in the aqueous phase partly forming the composition according to the invention.
  • the composition according to the invention has a texture that becomes transformed on application. It enables the makeup result to be rendered more uniform.
  • the composition as defined above when applied to the skin, its structure breaks, leading to a pleasant fresh effect due to the release of the water or the aqueous medium present in the swollen (d-C 4 ) carboxyalkyl starch particles.
  • AMPS 2-Acrylamido-2- methylpropane sulfonic acid
  • This aqueous phase according to the invention lends itself to a homogeneous formulation that is stabilized over time with the combined oily phase to lead to a composition that is endowed with the advantages of an oil-in-water or water-in-oil emulsion and that also advantageously has a gelled, creamy appearance which is, in this respect, appealing to users.
  • the distribution of the associated particulate materials present in said composition proves to be homogeneously and durably stabilized in the gel-type architecture that is accessible according to the invention. No sedimentation or aggregation of these particles is observed.
  • the pigments are present in an individualized particulate form, i.e. not aggregated.
  • compositions according to the invention prove to be particularly advantageous with regard firstly to the sensory feeling that they give the user at the time of application, and secondly to the final makeup result obtained, which proves to be homogeneous and uniform.
  • the composition has a sufficiently thick texture to allow the user to take up the required amount in a single action.
  • the texture of the composition breaks, giving the user a sensation of freshness, due to the shear generated during its spreading on the surface of the skin.
  • the claimed compositions may be easily prepared.
  • the corresponding aqueous and oily gels may be prepared separately and then mixed together in a cold state without further requiring the obligatory presence of surfactant for achieving the expected architecture.
  • a subject of the invention is also a process for making up and/or caring for a keratin material, in particular the skin, comprising at least one step that consists in applying to said keratin material a composition in accordance with the invention.
  • composition according to the invention contains two phases, an aqueous phase and an oily phase, respectively.
  • the claimed composition is different from an emulsion.
  • An emulsion is based generally of an oily liquid phase and a water liquid phase. It is a dispersion of droplets of one of the two liquids in the other.
  • the size of the droplets forming the dispersed phase of an emulsion is typically of the order of a micrometer (0.1 to 100 microns).
  • the stability of an emulsion needs the presence of surfactant or emulsifying silicone.
  • composition according to the invention consists of a homogeneous mixture of two immiscible gels.
  • the aqueous gelified phase and the oily gelified phase interpenetrate and form by this way a stable product due to their consistency almost pasty. This consistency is achieved by a mixture of interpenetrated macro-domains.
  • the claimed composition is related to a gel-type consistency.
  • gels are diluted entangled systems with no flow when they are in the stable state. In mass, gels consist mainly of liquid. However, they behave like solids due to their entangled three-dimensional network within the liquid. These are the tangles that give to gels their structure (hardness) and contribute to their adhesion.
  • homogeneous mixture means a fine or coarse distribution of a gel to another gel uniformly dispersed in the mass.
  • the ratio between the hydrophilic gel and the lipophilic gel is determined according to the expected cosmetic properties.
  • the interpenetrating domains are not measurable objects since their size is inhomogeneous and may vary on a large scale for example from 0.1 to 1.5 mm. Accordingly, it is not possible to characterize the compositions of the invention via a size parameter.
  • the compositions according to the invention are microscopically very different from an emulsion.
  • a composition according to the invention cannot also be characterized as having a "sense", i.e. O/W or W/O sense; both gels are intertwined and are predominant in terms of their ratio in the formulation without any influence on the stability of the finished product.
  • compositions according to the invention is not smooth but only creamy or gelled and the stability of the product is sustainable without emulsifier.
  • a cosmetic composition according to the invention is preferably free of emulsifier.
  • one of its two phases acts as the continuous phase and the other is dispersed therein.
  • a composition according to the invention has an aqueous continuous phase and an oily dispersed phase.
  • a composition according to the invention has an oily continuous phase and an aqueous dispersed phase.
  • the two phases are present in a composition according to the invention in a weight ratio ranging from 95/5 to 5/95.
  • the two phases are present in a composition according to the invention in a weight ratio ranging from 75/25 to 65/35
  • the aqueous phase and the oily phase are present in a 70/30 weight ratio.
  • the aqueous phase and the oily phase are present in a 25/75 weight ratio, a 50/50 weight ratio or in a 60/40 weight ratio.
  • the dispersed phase and the continuous phase have, respectively, a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
  • Characterization of the threshold stresses is performed by oscillating rheology measurements. A method is proposed in the examples section of the present text.
  • RS600 imposed-stress rheometer equipped with a cone-plate measuring body (60 mm diameter) fitted with an anti-evaporation device (bell jar). For each measurement, the sample is placed delicately in position and the measurements start 5 minutes after placing the sample in the jaws (2 mm). The composition is then subjected to a stress ramp from
  • a composition according to the invention also has a certain amount of elasticity.
  • This elasticity may be characterized by a stiffness modulus G* which, under this minimum stress threshold, is at least equal to 400 Pa and preferably greater than 1000 Pa.
  • the value G* of a composition may be obtained by subjecting the composition under consideration to a stress ramp from 10 ⁇ 2 to 10 3 Pa at a set frequency of 1 Hz.
  • the aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.
  • water-soluble solvent denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
  • the water-soluble solvents that may be used in the composition of the invention may also be volatile.
  • the aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 30% to 80% by weight and preferably from 40% to 75% by weight relative to the total weight of said composition.
  • the composition of the invention is water, especially water at room temperature.
  • the aqueous phase contains from 3%) to 10%) by weight, relative to its total weight, of particles of at least one (Ci-C 4 ) carboxyalkyl starch and whose particle size ranges from 25 to 300 ⁇ .
  • the (Ci-C 4 ) carboxyalkyl starches are obtained by grafting carboxyalkyl groups onto one or more alcohol functions of starch, especially by reaction of starch and of sodium monochloroacetate in alkaline medium.
  • the carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1.
  • the degree of substitution with carboxyalkyl units of the (Ci-C 4 ) carboxyalkyl starch preferably ranges from 0.1 to 1 and more particularly from 0.15 to 0.5.
  • the degree of substitution is defined in the present invention as being the mean 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 salts of alkali metals or alkaline-earth metals such as Na, K, Li, NH 4 , or salts of a quaternary ammonium or of an organic amine such as monoethanolamine, diethanolamine or triethanolamine.
  • the (Ci-C 4 ) carboxyalkyl starches are, in the context of the present invention, advantageously carboxymethylstarches.
  • the carboxymethylstarches preferably comprise units having the following formula:
  • X optionally covalently bonded to the carboxyl unit, denotes a hydrogen atom, an alkali metal or alkaline-earth metal such as Na, K, Li, NH 4 , a quaternary ammonium or an organic amine, for instance monoethanolamine, diethanolamine or triethanolamine.
  • X denotes an Na + cation.
  • carboxyalkyl starches that may be used according to the present invention are preferably non-pregelatinized carboxyalkyl starches.
  • carboxyalkyl starches that may be used according to the present invention are preferably partially or totally crosslinked carboxyalkyl starches.
  • a crosslinked carboxyalkyl starch has, as opposed to a non- crosslinked carboxyalkyl starch, an increased, controllable viscosity and greater stability.
  • the crosslinking thus makes it possible to reduce the syneresis and to increase the resistance of the gel to shear effects.
  • the carboxyalkyl starches under consideration according to the invention are more particularly potato carboxyalkyl starches.
  • carboxyalkyl starches that may be used according to the present invention are preferably sodium salts of carboxyalkyl starches, in particular a sodium salt of potato carboxymethyl starch, sold especially under the name Primojel by the company DMV International or Glycolys® and Glycolys LV® by the company Roquette.
  • the potato carboxymethyl starches sold especially under the name Glycolys® by the company Roquette will be used.
  • the (d-C 4 ) carboxyalkyl starch particles are present in the compositions according to the invention in a swollen and unsplit form.
  • This swelling may be characterized by a swelling power Q that may advantageously be between 10 and 30 ml/g and preferably between 15 and 25 ml (volume of liquid absorbed)/g of dry particulate material.
  • the size of the swollen carboxyalkyl starch particles used according to the present invention generally ranges from 25 to 300 ⁇ .
  • the gel Primojel containing 10% by weight of potato carboxyalkyl starch and sodium salt in water contains more than 80% of swollen particles of this starch with a diameter of greater than 50 microns and more particularly greater than 100 microns.
  • these particles are used for the preparation of the compositions according to the invention, in this swollen particulate state.
  • these particles are advantageously used in the form of an aqueous gel that is either prepared beforehand or already commercially available.
  • the gels under consideration according to the invention are advantageously translucent.
  • a carboxymethyl starch gel such as Primojel® which is at a concentration of 10% by weight may be adjusted to the required concentration before being used to prepare the expected cosmetic composition.
  • carboxyalkyl starch particles are advantageously present in a composition according to the invention in an amount adjusted to give this composition the expected properties in terms of architecture and texture.
  • the amount of (d-C 4 ) carboxyalkyl starch is advantageously adjusted to give the gel architecture thus obtained sufficient fluidity to enable easy and pleasant application to the surface of the skin.
  • these properties are present for a use of (d-C 4 ) carboxyalkyl starch particles in a proportion of less than 8% by weight, preferably less than 7% by weight and in particular from 4% to 6.5% of carboxyalkyl starch relative to the total weight of the aqueous phase.
  • the weight of the aqueous phase under consideration previously incorporates the weight of the aqueous phase plus the weight of all of the associated compounds that are soluble in this aqueous phase.
  • the aqueous phase of a composition according to the invention comprises at least one C2-C32 polyol.
  • polyol should be understood as meaning any organic molecule comprising at least two free hydroxyl groups.
  • a polyol in accordance with the present invention is present in liquid form at room temperature.
  • a polyol that is suitable for use in the invention may be a compound of linear, branched or cyclic, saturated or unsaturated alkyl type, bearing on each alkyl chain at least two -OH functions, in particular at least three -OH functions and more particularly at least four -OH functions.
  • the polyols that are advantageously suitable for formulating a composition according to the present invention are those especially containing from 2 to 32 carbon atoms and preferably 3 to 16 carbon atoms.
  • the polyol can be chosen, for example, from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols, such as glycerol oligomers, for example diglycerol, polyethylene glycols, and mixtures thereof.
  • said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof.
  • the composition of the invention comprises at least propylene glycol.
  • composition of the invention comprises at least glycerol.
  • an oily phase comprises at least one oil.
  • oil means any fatty substance that is in liquid form at room temperature and atmospheric pressure.
  • An oily phase that is suitable for preparing the cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluoro oils or non- fluoro oils, or mixtures thereof.
  • the oils may be volatile or non- volatile.
  • oils of plant origin are preferred.
  • non-volatile oil means an oil with a vapor pressure of less than 0.13 Pa.
  • silicon oil is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group.
  • fluoro oil means an oil comprising at least one fluorine atom.
  • hydrocarbon-based oil means an oil mainly containing hydrogen and carbon atoms.
  • the oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
  • volatile oil means any oil that is capable of evaporating on contact with keratin materials in less than one hour, at room temperature and atmospheric pressure.
  • the volatile oil is a volatile cosmetic compound, which is liquid at room temperature, especially having a nonzero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 ⁇ 3 to 300 mniHg), 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 1,300 Pa (0.01 to 10 mrnHg).
  • Volatile oils are volatile cosmetic compound, which is liquid at room temperature, especially having a nonzero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 ⁇ 3 to 300 mniHg), 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 1,300 Pa (0.01
  • the volatile oils may be hydrocarbon-based oils or silicone oils.
  • volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms mention may be made especially of branched Cs-Ci6 alkanes, for instance Cs-Ci6 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permethyl, branched Cs-Ci6 esters, for instance isohexyl neopentanoate, and mixtures thereof.
  • the volatile hydrocarbon-based oil is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isohexadecane.
  • Line volatile 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, with a flash point in the range from 30 to 120°C and more particularly from 40 to 100°C.
  • the flash point is in the range from 70 to 120°C and more particularly from 80 to 100°C, and especially about 89°C.
  • the flash point is in particular measured according to standard ISO 3679.
  • a volatile linear alkane that is suitable for the invention may advantageously be of plant origin.
  • Such an alkane may be obtained, directly or in several steps, from a plant starting material such as an oil, a butter, a wax, etc.
  • a plant starting material such as an oil, a butter, a wax, etc.
  • alkanes that are suitable for use in the invention, mention may be made of the alkanes described in the patent application from the company Cognis WO 2007/068 371 , or WO 2008/155 059 (mixtures of different alkanes differing by at least one carbon).
  • linear alkanes that are suitable for use in the invention, mention may be made of n-nonane (C9), n-decane (C10), n-undecane (Cn), n-dodecane (C12), n- tridecane (C 13 ), n-tetradecane (C 14 ), n-pentadecane (C 15 ), n-hexadecane or n-hexadecane (C 16 ) and n-heptadecane (C 17 ), and mixtures thereof, and in particular mixtures of n- undecane (Cn) and n-tridecane (C 13 ) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, such as the mixture of n-undecane (Cn) and n-tridecane (C 13 ).
  • Volatile silicone oils that may be mentioned include linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane.
  • Volatile cyclic silicone oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethy Icy clo hexasilo xane .
  • Non-volatile oils include linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane.
  • the non- volatile oils may be chosen especially from non- volatile hydrocarbon- based, fluoro and/or silicone oils.
  • Non-volatile hydrocarbon-based oils that may especially be mentioned include: hydrocarbon-based oils of animal origin,
  • esters for instance oils of formula R 1 COOR 2 , in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms, and R 2 represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that Ri + R 2 ⁇ 10.
  • the esters may be chosen especially from alcohol fatty acid esters, for instance cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, alcohol or polyalcohol ricinoleates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, and isononanoic acid esters, for instance isononyl isononanoate and isotridecyl isononanoate,
  • alcohol fatty acid esters for instance cetostearyl oct
  • polyol esters and pentaerythritol esters for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate
  • fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol and oleyl alcohol,
  • C 12 -C 22 higher fatty acids such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof, and
  • phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyl trimethicone with a viscosity of less than or equal to 100 cSt, and mixtures thereof; and also mixtures of these various oils.
  • phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyl trimethicone with a viscosity of less
  • non-volatile oil that is suitable for use in the invention, mention may be made more particularly of pentaerythrityl tetrakis(ethylhexanoate).
  • a composition according to the invention may comprise from 5% to 40% by weight and preferably from 7% to 35% by weight of oil(s) relative to the total weight of said composition.
  • an oily phase that is suitable for use in the invention may be used in the form of a mixture of pentaerythrityl tetrakis(ethylhexanoate) and isohexadecane especially in a 60/40 weight ratio.
  • the oily phase according to the invention has a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
  • This threshold stress value reflects a gel-type texture of this oily phase.
  • This texturing is advantageously obtained via the presence in the oily phase of at least one texturing agent.
  • this texturing agent is an organic or mineral particulate material that is capable of gelling the oil(s) with which it is combined.
  • this material is mineral and may advantageously have a BET specific surface area of greater than or equal to 300 m 2 /g, preferably greater than 500 m 2 /g and preferentially greater than 600 m 2 /g, and especially less than 1500 m 2 /g.
  • the BET specific surface area is determined according to the BET (Brunauer- Emmet-Teller) method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938, which corresponds to International Standard ISO 5794/1.
  • the BET specific surface area corresponds to the total specific surface area (thus including micropores) of the powder.
  • silica silylate powders especially those sold under the name Dow Corning VM-2270 Aerogel Fine Particles by the company Dow Corning and under the name Enova Aerogel MT 1100 by the company Cabot.
  • the oily phase of a composition according to the invention contains at least one silica silylate powder.
  • This particulate material may also be organic.
  • Non-limiting illustrations of such materials that may especially be considered are organopolysiloxane elastomers.
  • organopolysiloxane elastomer means a supple, deformable organopolysiloxane with viscoelastic properties and especially the consistency of a sponge or a supple sphere. Its modulus of elasticity is such that this material withstands deformation and has a limited ability to extend and to contract. This material is capable of regaining its original shape after stretching.
  • the organopolysiloxane elastomer may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups bonded to silicon, especially in the presence of a platinum catalyst; or by dehydrogenation crosslinking condensation reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen bonded to silicon, especially in the presence of an organotin; or by crosslinking condensation reaction of a diorganopolysiloxane containing hydroxyl end groups and of a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or by crosslinking of organopolysiloxane via high- energy radiation such as gamma rays
  • the organopolysiloxane elastomer may be obtained by reaction of dimethylpolysiloxane containing dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane containing trimethylsiloxy end groups, in the presence of a platinum catalyst.
  • the elastomer is a non-emulsifying elastomer.
  • non-emulsifying defines organopolysiloxane elastomers not containing any hydrophilic chains, and in particular not containing any polyoxyalkylene units (especially polyoxy ethylene or polyoxypropylene) or any polyglyceryl units.
  • the organopolysiloxane elastomer particles are conveyed in the form of a gel formed from an elastomeric organopolysiloxane included in at least one hydrocarbon- based oil and/or one silicone oil. In these gels, the organopolysiloxane particles are often non- spherical particles.
  • Non-emulsifying elastomers are especially described in patents EP 242 219, EP 285 886 and EP 765 656 and in patent application JP-A-61-194 009, the content of which is incorporated by way o f reference .
  • the oily phase of a composition according to the invention contains at least one organopolysiloxane elastomer and more particularly a spherical non-emulsifying organopolysiloxane elastomer.
  • the elastomer may also be an emulsifying elastomer.
  • emulsifying organopolysiloxane elastomer means an organopolysiloxane elastomer comprising at least one hydrophilic chain, such as polyoxyalkylenated organopolysiloxane elastomers and polyglycerolated silicone elastomers.
  • the emulsifying organopolysiloxane elastomer may be chosen from polyoxyalkylenated organopolysiloxane elastomers.
  • the polyoxyalkylenated organopolysiloxane elastomer is a crosslinked organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of a polyoxyalkylene containing at least two ethylenically unsaturated groups.
  • the organopolysiloxane may be obtained by reaction of polyoxyalkylene (especially polyoxyethylene and/or polyoxypropylene) with dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane with trimethylsiloxy end groups, in the presence of a platinum catalyst.
  • the polyoxyalkylenated organopolysiloxane elastomers may be formed from divinyl compounds, in particular polyoxyalkylenes containing at least two vinyl groups, which react with Si-H bonds of a polysiloxane.
  • Polyoxyalkylenated elastomers are especially described in patents US 5 236 986, US 5 412 004, US 5 837 793 and US 5 811 487, the content of which is incorporated by reference.
  • the emulsifying organopolysiloxane elastomer may also be chosen from polyglycerolated organopolysiloxane elastomers.
  • the polyglycerolated organopolysiloxane elastomer according to the invention is an organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of polyglycerolated compounds containing ethylenically unsaturated groups, especially in the presence of a platinum catalyst.
  • the polyglycerolated organopolysiloxane elastomer according to the invention is conveyed in gel form in at least one hydrocarbon-based oil and/or one silicone oil.
  • the polyglycerolated elastomer is often in the form of non-spherical particles.
  • organopolysiloxane elastomers that are suitable for use in the invention are considered provided that they are capable of gelling the oil or the mixture of oils with which they are combined.
  • non-emulsifying elastomers that are suitable for use in the invention, mention may be made especially of those sold under the names KSG-15 and KSG-16 by the company Shin-Etsu.
  • polyoxyalkylenated organopolysiloxane elastomers that are suitable for use in the invention, use may be made of those sold under the names KSG-210 and KSG-310 by the company Shin-Etsu.
  • polyglycerolated organopolysiloxane elastomers that are suitable for use in the invention, use may be made of those sold under the names KSG-710 and KSG-810 by the company Shin-Etsu.
  • the required amount of this material is liable to vary significantly according to the chemical nature and the physicochemical specificities of the material under consideration.
  • the texturing agent is a mineral material, and preferably silica silylate.
  • the silica silylate may be present in a proportion of from 0.5% to 20% by weight, preferably from 1% to 15% and especially from 2% to 10%, and preferably in a proportion of at least 6.5% by weight, relative to the total weight of the oily phase.
  • the texturing agent is an organic material, and preferably an organopolysiloxane elastomer.
  • An organopolysiloxane elastomer gel may be present in a proportion of from 40% to 100% by weight and preferably from 60% to 100% by weight, and preferably in a proportion of at least 80% by weight, relative to the total weight of the oily phase.
  • a composition according to the invention may contain other compounds conventionally considered in a cosmetic composition.
  • These compounds may be dyestuffs, fillers, waxes, pasty compounds, gums, plasticizers, gelling agents, thickeners, antioxidants, preserving agents or fragrances, and mixtures thereof.
  • a composition according to the invention also comprises at least one particulate or non-particulate, water-soluble or water-insoluble dyestuff, preferably in a proportion of at least 3% by weight relative to the total weight of the composition.
  • a composition according to the invention may contain from 3% to 15% by weight or even from 5% to 10%> by weight of dyestuff(s) relative to the total weight of the composition, taking into account, moreover, the parallel limitation imposed in terms of amount of pulverulent phase in the case of using coloring particulate materials such as pigments, which are therefore water-insoluble.
  • water-soluble dyestuf means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of coloring.
  • synthetic or natural water-soluble dyes for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophylline, methylene blue, anthocyanins (enocianin, black carrot, hibiscus and elder), caramel and riboflavin.
  • the water-soluble dyes are, for example, beetroot juice and caramel.
  • the coloring particulate materials may be present in a proportion of from 0.01% to 15% by weight relative to the total weight of the composition containing them.
  • They may especially be pigments, nacres and/or particles with metallic tints.
  • pigments should be understood as meaning white or colored, mineral or organic particles that are insoluble in an aqueous solution, which are intended to color and/or opacify the composition containing them.
  • a composition according to the invention may comprise from 0.01% to 15% by weight, preferably from 0.1% to 15% by weight and better still from 1% to 15% by weight of pigments relative to the total weight of said composition.
  • the pigments may be white or colored, and mineral and/or organic.
  • mineral pigments that may be used in the invention, mention may be made of titanium oxide, titanium dioxide, zirconium oxide, zirconium dioxide, cerium oxide or cerium dioxide and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof.
  • It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type.
  • Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30.
  • pigments having a structure may be, for example, of silica microsphere type containing iron oxide.
  • An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL- 100 P, this pigment consisting of silica microspheres containing yellow iron oxide.
  • the pigments in accordance with the invention are iron oxides and/or titanium dioxides.
  • nacres should be understood as meaning iridescent or non- iridescent colored particles of any shape, especially produced by certain molluscs in their shell or alternatively synthesized, which have a color effect via optical interference.
  • a composition according to the invention may comprise from 0 to 15% by weight of nacres relative to the total weight of said composition.
  • the nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles at the surface of which are superimposed at least two successive layers of metal oxides and/or of organic dyestuffs.
  • nacres examples include natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.
  • pearlescent agents available on the market, mention may be made of the pearlescent agents Timica, Flamenco and Duochrome (based on mica) sold by the company Engelhard, the Timiron pearlescent agents sold by the company Merck, the Prestige mica-based pearlescent agents sold by the company Eckart, and the Sunshine synthetic mica-based pearlescent agents sold by the company Sun Chemical.
  • the nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or glint.
  • the nacres in accordance with the invention are micas coated with titanium dioxide or with iron oxide, and also bismuth oxy chloride.
  • the term "particles with a metallic glint” means any compound whose nature, size, structure and surface finish allow it to reflect the incident light, especially in a non- iridescent manner.
  • the particles with a metallic glint that may be used in the invention are in particular chosen from:
  • - particles of at least one metal and/or of at least one metal derivative - particles comprising a single-material or multi-material organic or mineral substrate, at least partially coated with at least one layer with a metallic glint comprising at least one metal and/or at least one metal derivative;
  • 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 and Se, and mixtures or alloys thereof.
  • Ag, Au, Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof are preferred metals.
  • metal derivatives denotes compounds derived from metals, especially oxides, fluorides, chlorides and sulfides.
  • fillers should be understood as meaning colorless or white solid particles of any form, which are in an insoluble and dispersed form in the medium of the composition.
  • fillers of mineral or organic, natural or synthetic nature, give the composition containing them softness and give the makeup result a matt effect and uniformity.
  • mineral fillers that may be used in the compositions according to the invention, mention may be made most particularly of talc.
  • composition according to the invention may also comprise a dispersant.
  • Such a dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof.
  • a dispersant in accordance with the invention is a surfactant.
  • a composition according to the invention comprises less than 0.1% by weight of surfactant and in particular is surfactant-free.
  • Active agent e.g., sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite
  • composition according to the invention may comprise at least one moisturizer (also known as a humectant).
  • the moisturizer(s) could 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.
  • Humectants or moisturizers that may especially be mentioned include sorbitol, polyhydric alcohols, preferably of C 2 -Cs and more preferably of C3-C6, preferably such as glycerol, propylene glycol, 1 ,3-butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol and diglycerol, and a mixture thereof, glycerol and derivatives thereof, glycol ethers (especially containing from 3 to 16 carbon atoms) such as monopropylene, dipropylene or tripropylene glycol (Ci-C 4 )alkyl ethers, and monoethylene, diethylene or triethylene glycol (Ci-C 4 )alkyl ethers.
  • polyhydric alcohols preferably of C 2 -Cs and more preferably of C3-C6, preferably such as glycerol, propylene glycol, 1 ,3-butylene glycol, penty
  • Use will preferably be made of at least glycerol as moisturizer.
  • active agents examples that may be mentioned include vitamins and sunscreens, and mixtures thereof. It is a matter of routine operations for a person skilled in the art to adjust the nature and amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.
  • composition according to the invention has the advantage of to be prepared without the need for any heating steps by contrast to the preparation of an emulsion.
  • the method considered according to the invention may just have the need steps consisting of preparing, generally at room temperature, each phase, the aqueous gel and the oily gel, under moderate stirring.
  • the mixture of gels may be prepared at room temperature in mixers such as kneader type mixer or ribbon mixer.
  • mixers such as kneader type mixer or ribbon mixer.
  • the preparation of a composition according to the invention requires less shear.
  • a composition of the invention may advantageously be in the form of a cream foundation.
  • compositions are especially prepared according to the general knowledge of a person skilled in the art.
  • the measurements are taken using a Haake RS600 rheometer on a product at rest, at 25°C with a plate-plate rotor 0 60 mm and a 2 mm gap.
  • the measurements in the harmonic regime make it possible to characterize the viscoelastic properties of the products.
  • the technique consists in subjecting a material to a stress that varies sinusoidally over time and in measuring the response of the material to this stress.
  • the stress ( ⁇ ) and the strain ( ⁇ ) are two sinusoidal functions of time that are written in the following manner:
  • 2 ⁇ represents the angular frequency (rad.s -1 ) with N representing the frequency (Hz);
  • represents the phase angle of the stress relative to the strain (rad).
  • the two functions have the same angular frequency, but they are dephased by an angle ⁇ .
  • the behavior of the system may be assessed:
  • a complex stiffness modulus representing the overall resistance of the material to the strain, whether it is of elastic or viscous origin, is then defined by:
  • the parameter retained is the mean stiffness modulus G* recorded at the plateau measured at a frequency of 1 Hz.
  • a foundation formulation in accordance with the invention is prepared from the phases and/or compounds described below.
  • An oily gel, phase Al is prepared in a tank equipped with a "frame" paddle, using the following compounds in the weight proportions specified in the table below.
  • phase "C” is prepared in a suitable container by treatment in a three-roll mill:
  • phase "D” An aqueous solution of preserving agent below, phase "D", is prepared: Weight%
  • phase "E" The powders such as the fillers, nacres or other pulverulent additives to be considered in the foundation formulation compose phase "E".
  • This formulation is obtained by mixing together all the constituents of the composition, divided into several phases (Al , B, C, D and E), by considering a combination of phases B, D and of the glycols of phase C, which are intended for forming the aqueous gel in accordance with the invention, in the proportions described below in
  • the phases are introduced into a Clextral BC21 twin-screw extruder continuous mixer by means of volumetric pumps for the liquids and K-Tron dosers for the powders.
  • the mixing is performed at 20°C at a flow rate of 6 kg/hour and at a spin speed of 600 rpm.
  • the foundation composition is described below in Table 2.
  • Figures 1A and B show the rheological profile of the composition thus obtained.
  • composition has advantageous performance in terms of application and of makeup result. It affords an atypical texture that becomes transformed on application.
  • Example 2
  • the oily gel A2 is an organopolysiloxane elastomer sold under the name KSG- 16 by the company Shin-Etsu. It is sold as an oily mixture and is thus used in this form.
  • composition of the foundation formulation thus obtained is as follows.
  • composition has advantageous performance in terms of application and of makeup result. It affords an atypical texture that becomes transformed on application.

Abstract

The present invention relates to a gel-type cosmetic composition for making up and/or caring for the skin, comprising at least one gelled aqueous phase containing at least 3% by weight, relative to its total weight, of particles of at least one (d-C4) carboxyalkyl starch and whose particle size ranges from 25 to 300 μιη, and an oily phase gelled with at least one texturing agent, with one of said phases constituting the continuous phase of said composition in which the other phase is uniformly dispersed.

Description

Gel-type cosmetic composition for making up and/or caring for the skin
The present invention is directed toward proposing a novel cream architecture of cosmetic composition, especially of foundation type.
Cosmetic compositions, especially foundations, are commonly used to give the skin an esthetic color, but also to hide imperfections of the skin relief such as wrinkles and/or fine lines. In this regard, many solid or fluid, anhydrous or non-anhydrous formulations have been developed to date, namely fluids, creams, compacts, loose powders or sticks.
In general, the majority of women, and nowadays even men, particularly appreciate care products of aqueous phase-enriched architecture with regard to the sensory properties experienced on application of this type of architecture. The reason for this is that their texture is very light and they are also capable of affording a fresh effect.
Unfortunately, reproducing this architecture with a makeup formula, which generally conveys a certain amount of particulate material, including pigments intended to give the composition a color effect, is not entirely satisfactory. Specifically, an aqueous architecture, which is advantageous with regard to the fresh properties it imparts, does not ensure uniform distribution of the particulate materials within the composition.
To overcome this defect, these makeup compositions generally also contain a significant amount of fatty substances. Thus, makeup formulations such as foundations are generally in the form of an emulsion containing an aqueous phase and a fatty phase. Each of these two phases is capable of constituting the continuous phase according to the specific needs, which gives the possibility of formulating direct emulsions (aqueous continuous phase) or inverse emulsions (fatty continuous phase). However, the majority of the fluid foundations on the market are inverse emulsions stabilized with surfactants, the water content of which is conventionally from 20% to 30%, up to 40%, rarely greater than 50% and never greater than 60%. These architectures of emulsion type enable the particles they contain to be uniformly stabilized.
However, uses are nowadays more particularly interested in surfactant-free cosmetic compositions. It would therefore be advantageous to offer them compositions that are simultaneously endowed with the freshness of aqueous formulations and the qualities of oily formulations in terms of comfort and glidance on application, and in which the combination of aqueous phase and oily phase, which is required to gain access to these qualities, also proves to be homogeneous and stabilized over time without, however, requiring the mandatory presence of surfactant. Unexpectedly, the inventors have found that such an objective may be achieved provided that specific phases are combined within the same composition to form a gel-type composition.
Thus, according to one of its aspects, the present invention relates to a gel-type cosmetic composition for making up and/or caring for the skin, comprising at least:
- a gelled aqueous phase containing at least 3% by weight, relative to its total weight, of particles of at least one (d-C4) carboxyalkyl starch and whose particle size ranges from 25 to 300 μιη, and
- an oily phase gelled with at least one texturing agent,
with one of said phases constituting the continuous phase of said composition in which the other phase is uniformly dispersed.
According to an advantageous embodiment variant, the oily phase has a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
According to another advantageous embodiment variant, the dispersed phase and the continuous phase have a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
Advantageously, a composition according to the invention is in the form of a creamy gel with a minimum stress below which it does not flow unless it has been subjected to an external mechanical stress.
Such a composition also has a certain amount of elasticity.
As emerges from the text hereinbelow, a composition according to the invention may have a minimum threshold stress of 1.5 Pa and in particular greater than 10 Pa.
It also advantageously has a stiffness modulus G* at least equal to 400 Pa and preferably greater than 1000 Pa.
In the aqueous phase of the composition according to the invention, the (d-C4) carboxyalkyl starch particles are in a swollen and unsplit form. This swelling is the consequence of absorption of the aqueous medium by the (d-C4) carboxyalkyl starch particles. This swelling may be characterized by a swelling power that may be, after 24 hours of contact with the liquid to be absorbed, which is preferably aqueous, between 10 and 30 ml/g and preferably between 15 and 25 ml (volume of liquid absorbed)/g of dry particulate material. It is precisely with regard to this swelling capacity of the (d-C4) carboxyalkyl starch particles that access is gained according to the invention to a gel-type architecture in the aqueous phase partly forming the composition according to the invention.
The presence of the (d-C4) carboxyalkyl starch, in the form of a particle dispersion whose particles are present in a swollen state and in particular with a swelling power of between 10 and 30 ml/g is advantageous in many respects.
Firstly, with regard to the presence of this (d-C4) carboxyalkyl starch, the composition according to the invention has a texture that becomes transformed on application. It enables the makeup result to be rendered more uniform. Thus, when the composition as defined above is applied to the skin, its structure breaks, leading to a pleasant fresh effect due to the release of the water or the aqueous medium present in the swollen (d-C4) carboxyalkyl starch particles.
It has to be noticed that other known polymeric gels do not exhibit this ability to stock water and to liberate it under application. Thus, the 2-Acrylamido-2- methylpropane sulfonic acid (AMPS) is known to provide sweetness but does not have the ability of stocking and releasing water. In other words, it cannot be used as "fresh reservoir".
This aqueous phase according to the invention lends itself to a homogeneous formulation that is stabilized over time with the combined oily phase to lead to a composition that is endowed with the advantages of an oil-in-water or water-in-oil emulsion and that also advantageously has a gelled, creamy appearance which is, in this respect, appealing to users.
What is more, the distribution of the associated particulate materials present in said composition, most particularly including pigments, proves to be homogeneously and durably stabilized in the gel-type architecture that is accessible according to the invention. No sedimentation or aggregation of these particles is observed. Thus, in a composition according to the invention, the pigments are present in an individualized particulate form, i.e. not aggregated.
Moreover, as emerges from the text hereinbelow, and more particularly from the examples, the compositions according to the invention prove to be particularly advantageous with regard firstly to the sensory feeling that they give the user at the time of application, and secondly to the final makeup result obtained, which proves to be homogeneous and uniform.
Further, during its uptake for application to the surface of a keratin material and more particularly the skin, the composition has a sufficiently thick texture to allow the user to take up the required amount in a single action. During application to the surface of the keratin material, the texture of the composition breaks, giving the user a sensation of freshness, due to the shear generated during its spreading on the surface of the skin.
Finally, in addition to the advantages mentioned above (stability, homogeneity), the claimed compositions may be easily prepared. The corresponding aqueous and oily gels may be prepared separately and then mixed together in a cold state without further requiring the obligatory presence of surfactant for achieving the expected architecture.
According to another of its aspects, a subject of the invention is also a process for making up and/or caring for a keratin material, in particular the skin, comprising at least one step that consists in applying to said keratin material a composition in accordance with the invention.
Cosmetic composition
As mentioned previously, a composition according to the invention contains two phases, an aqueous phase and an oily phase, respectively.
However, it is important to note that the claimed composition is different from an emulsion.
An emulsion is based generally of an oily liquid phase and a water liquid phase. It is a dispersion of droplets of one of the two liquids in the other. The size of the droplets forming the dispersed phase of an emulsion is typically of the order of a micrometer (0.1 to 100 microns).
Generally, the stability of an emulsion needs the presence of surfactant or emulsifying silicone.
On the contrary, the composition according to the invention consists of a homogeneous mixture of two immiscible gels.
The aqueous gelified phase and the oily gelified phase interpenetrate and form by this way a stable product due to their consistency almost pasty. This consistency is achieved by a mixture of interpenetrated macro-domains.
Accordingly, the claimed composition is related to a gel-type consistency.
It is reminded that a gel is a solid that can have properties ranging from soft and ductile to hard and brittle. Gels are diluted entangled systems with no flow when they are in the stable state. In mass, gels consist mainly of liquid. However, they behave like solids due to their entangled three-dimensional network within the liquid. These are the tangles that give to gels their structure (hardness) and contribute to their adhesion.
The term "homogeneous mixture" means a fine or coarse distribution of a gel to another gel uniformly dispersed in the mass. The ratio between the hydrophilic gel and the lipophilic gel is determined according to the expected cosmetic properties.
It has to be noticed that the interpenetrating domains are not measurable objects since their size is inhomogeneous and may vary on a large scale for example from 0.1 to 1.5 mm. Accordingly, it is not possible to characterize the compositions of the invention via a size parameter. The compositions according to the invention are microscopically very different from an emulsion.
A composition according to the invention cannot also be characterized as having a "sense", i.e. O/W or W/O sense; both gels are intertwined and are predominant in terms of their ratio in the formulation without any influence on the stability of the finished product.
At last, the texture of compositions according to the invention is not smooth but only creamy or gelled and the stability of the product is sustainable without emulsifier.
Therefore, a cosmetic composition according to the invention is preferably free of emulsifier. In a composition according to the invention, one of its two phases acts as the continuous phase and the other is dispersed therein.
According to one embodiment, a composition according to the invention has an aqueous continuous phase and an oily dispersed phase.
According to another embodiment, a composition according to the invention has an oily continuous phase and an aqueous dispersed phase.
In general, the two phases are present in a composition according to the invention in a weight ratio ranging from 95/5 to 5/95.
Preferably, the two phases are present in a composition according to the invention in a weight ratio ranging from 75/25 to 65/35
More preferentially, the aqueous phase and the oily phase are present in a 70/30 weight ratio.
According to other embodiments, the aqueous phase and the oily phase are present in a 25/75 weight ratio, a 50/50 weight ratio or in a 60/40 weight ratio.
These two phases both have a gel-type texture. This texture is especially reflected visually by a creamy appearance.
According to an advantageous embodiment variant, the dispersed phase and the continuous phase have, respectively, a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
Characterization of the threshold stresses is performed by oscillating rheology measurements. A method is proposed in the examples section of the present text.
In general, the corresponding measurements are taken at 25 °C using a Haake
RS600 imposed-stress rheometer equipped with a cone-plate measuring body (60 mm diameter) fitted with an anti-evaporation device (bell jar). For each measurement, the sample is placed delicately in position and the measurements start 5 minutes after placing the sample in the jaws (2 mm). The composition is then subjected to a stress ramp from
10~2 to 103 Pa at a set frequency of 1 Hz.
A composition according to the invention also has a certain amount of elasticity. This elasticity may be characterized by a stiffness modulus G* which, under this minimum stress threshold, is at least equal to 400 Pa and preferably greater than 1000 Pa.
The value G* of a composition may be obtained by subjecting the composition under consideration to a stress ramp from 10~2 to 103 Pa at a set frequency of 1 Hz. Aqueous phase
The aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.
In the present invention, the term "water-soluble solvent" denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
The water-soluble solvents that may be used in the composition of the invention may also be volatile.
Among the water-soluble solvents that may be used in the composition in accordance with the invention, mention may be made especially of lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols containing from 2 to 8 carbon atoms, 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 30% to 80% by weight and preferably from 40% to 75% by weight relative to the total weight of said composition.
According to one embodiment variant, the composition of the invention is water, especially water at room temperature.
According to a preferred embodiment variant, the aqueous phase contains from 3%) to 10%) by weight, relative to its total weight, of particles of at least one (Ci-C4) carboxyalkyl starch and whose particle size ranges from 25 to 300 μιη.
(Ci-CV) Carboxyalkyl starch
The (Ci-C4) carboxyalkyl starches, also referred to hereinbelow as "carboxyalkyl starch", are obtained by grafting carboxyalkyl groups onto one or more alcohol functions of starch, especially by reaction of starch and of sodium monochloroacetate in alkaline medium.
The carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1.
The degree of substitution with carboxyalkyl units of the (Ci-C4) carboxyalkyl starch preferably ranges from 0.1 to 1 and more particularly from 0.15 to 0.5. The degree of substitution is defined in the present invention as being the mean 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 salts of alkali metals or alkaline-earth metals such as Na, K, Li, NH4, or salts of a quaternary ammonium or of an organic amine such as monoethanolamine, diethanolamine or triethanolamine.
The (Ci-C4) carboxyalkyl starches are, in the context of the present invention, advantageously carboxymethylstarches.
The carboxymethylstarches preferably comprise units having the following formula:
Figure imgf000009_0001
in which X, optionally covalently bonded to the carboxyl 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, for instance monoethanolamine, diethanolamine or triethanolamine.
Preferably, X denotes an Na+ cation.
The carboxyalkyl starches that may be used according to the present invention are preferably non-pregelatinized carboxyalkyl starches.
The carboxyalkyl starches that may be used according to the present invention are preferably partially or totally crosslinked carboxyalkyl starches.
In general, a crosslinked carboxyalkyl starch has, as opposed to a non- crosslinked carboxyalkyl starch, an increased, controllable viscosity and greater stability. The crosslinking thus makes it possible to reduce the syneresis and to increase the resistance of the gel to shear effects.
The carboxyalkyl starches under consideration according to the invention are more particularly potato carboxyalkyl starches.
Thus, the carboxyalkyl starches that may be used according to the present invention are preferably sodium salts of carboxyalkyl starches, in particular a sodium salt of potato carboxymethyl starch, sold especially under the name Primojel by the company DMV International or Glycolys® and Glycolys LV® by the company Roquette.
According to one particular embodiment, the potato carboxymethyl starches sold especially under the name Glycolys® by the company Roquette will be used.
As stated previously, the (d-C4) carboxyalkyl starch particles are present in the compositions according to the invention in a swollen and unsplit form. This swelling may be characterized by a swelling power Q that may advantageously be between 10 and 30 ml/g and preferably between 15 and 25 ml (volume of liquid absorbed)/g of dry particulate material.
Thus, the size of the swollen carboxyalkyl starch particles used according to the present invention generally ranges from 25 to 300 μιη.
For example, the gel Primojel containing 10% by weight of potato carboxyalkyl starch and sodium salt in water contains more than 80% of swollen particles of this starch with a diameter of greater than 50 microns and more particularly greater than 100 microns.
According to a preferred embodiment variant 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 that is either prepared beforehand or already commercially available. The gels under consideration 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 may be adjusted to the required concentration before being used to prepare the expected cosmetic composition.
As emerges from the foregoing text, the carboxyalkyl starch particles are advantageously present in a composition according to the invention in an amount adjusted to give this composition the expected properties in terms of architecture and texture.
Thus, the amount of (d-C4) carboxyalkyl starch is advantageously adjusted to give the gel architecture thus obtained sufficient fluidity to enable easy and pleasant application to the surface of the skin.
In general, these properties are present for a use of (d-C4) carboxyalkyl starch particles in a proportion of less than 8% by weight, preferably less than 7% by weight and in particular from 4% to 6.5% of carboxyalkyl starch relative to the total weight of the aqueous phase.
The weight of the aqueous phase under consideration previously incorporates the weight of the aqueous phase plus the weight of all of the associated compounds that are soluble in this aqueous phase.
Other compounds of the aqueous phase
According to another embodiment variant, the aqueous phase of a composition according to the invention comprises at least one C2-C32 polyol.
For the purposes of the present invention, the term "polyol" should be understood as meaning any organic molecule comprising at least two free hydroxyl groups.
Preferably, a polyol in accordance with the present invention is present in liquid form at room temperature.
A polyol that is suitable for use in the invention may be a compound of linear, branched or cyclic, saturated or unsaturated alkyl type, bearing on each alkyl chain at least two -OH functions, in particular at least three -OH functions and more particularly at least four -OH functions.
The polyols that are advantageously suitable for formulating a composition according to the present invention are those especially containing from 2 to 32 carbon atoms and preferably 3 to 16 carbon atoms.
Advantageously, the polyol can be chosen, for example, from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols, such as glycerol oligomers, for example diglycerol, polyethylene glycols, and mixtures thereof.
According to a preferred embodiment of the invention, said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof.
According to one particular embodiment, the composition of the invention comprises at least propylene glycol.
According to another particular embodiment, the composition of the invention comprises at least glycerol. Oily phase
For the purposes of the invention, an oily phase comprises at least one oil.
The term "oil" means any fatty substance that is in liquid form at room temperature and atmospheric pressure.
An oily phase that is suitable for preparing the cosmetic compositions according to the invention may comprise hydrocarbon-based oils, silicone oils, fluoro oils or non- fluoro oils, or mixtures thereof.
The oils may be volatile or non- volatile.
They may be of animal, plant, mineral or synthetic origin. According to one embodiment variant, oils of plant origin are preferred.
For the purposes of the present invention, the term "non-volatile oil" means an oil with a vapor pressure of less than 0.13 Pa.
For the purpose of the present invention, the term "silicone oil" is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group.
The term "fluoro oil" means an oil comprising at least one fluorine atom.
The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms.
The oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
For the purposes of the invention, the term "volatile oil" means any oil that is capable of evaporating on contact with keratin materials in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, which is liquid at room temperature, especially having a nonzero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10~3 to 300 mniHg), 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 1,300 Pa (0.01 to 10 mrnHg). Volatile oils
The volatile oils may be hydrocarbon-based oils or silicone oils. Among the volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, mention may be made especially of branched Cs-Ci6 alkanes, for instance Cs-Ci6 isoalkanes (also known as isoparaffins), isododecane, isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permethyl, branched Cs-Ci6 esters, for instance isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon-based oil is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isohexadecane.
Mention may also be made of linear volatile 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, with a flash point in the range from 30 to 120°C and more particularly from 40 to 100°C. In particular, the flash point is in the range from 70 to 120°C and more particularly from 80 to 100°C, and especially about 89°C. The flash point is in particular measured according to standard ISO 3679.
A volatile linear alkane that is suitable for the invention may advantageously be of plant origin.
Such an alkane may be obtained, directly or in several steps, from a plant starting material such as an oil, a butter, a wax, etc. As examples of alkanes that are suitable for use in the invention, mention may be made of the alkanes described in the patent application from the company Cognis WO 2007/068 371 , or WO 2008/155 059 (mixtures of different alkanes differing by at least one carbon).
As examples of linear alkanes that are suitable for use in the invention, mention may be made of n-nonane (C9), n-decane (C10), n-undecane (Cn), n-dodecane (C12), n- tridecane (C13), n-tetradecane (C14), n-pentadecane (C15), n-hexadecane or n-hexadecane (C16) and n-heptadecane (C17), and mixtures thereof, and in particular mixtures of n- undecane (Cn) and n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, such as the mixture of n-undecane (Cn) and n-tridecane (C13).
Volatile silicone oils that may be mentioned include linear volatile silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane. Volatile cyclic silicone oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethy Icy clo hexasilo xane . Non-volatile oils
The non- volatile oils may be chosen especially from non- volatile hydrocarbon- based, fluoro and/or silicone oils.
Non-volatile hydrocarbon-based oils that may especially be mentioned include: hydrocarbon-based oils of animal origin,
- hydrocarbon-based oils of plant origin, synthetic ethers containing from
10 to 40 carbon atoms, such as dicaprylyl ether,
synthetic esters, for instance oils of formula R1COOR2, in which Ri represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms, and R2 represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms provided that Ri + R2≥ 10. The esters may be chosen especially from alcohol fatty acid esters, for instance cetostearyl octanoate, isopropyl alcohol esters, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, alcohol or polyalcohol ricinoleates, hexyl laurate, neopentanoic acid esters, for instance isodecyl neopentanoate, isotridecyl neopentanoate, and isononanoic acid esters, for instance isononyl isononanoate and isotridecyl isononanoate,
polyol esters and pentaerythritol esters, for instance dipentaerythrityl tetrahydroxystearate/tetraisostearate,
fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance 2-octyldodecanol, isostearyl alcohol and oleyl alcohol,
C12-C22 higher fatty acids, such as oleic acid, linoleic acid or linolenic acid, and mixtures thereof, and
- silicone oils, especially phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyl trimethicone with a viscosity of less than or equal to 100 cSt, and mixtures thereof; and also mixtures of these various oils.
As another non-volatile oil that is suitable for use in the invention, mention may be made more particularly of pentaerythrityl tetrakis(ethylhexanoate).
A composition according to the invention may comprise from 5% to 40% by weight and preferably from 7% to 35% by weight of oil(s) relative to the total weight of said composition.
More particularly, an oily phase that is suitable for use in the invention may be used in the form of a mixture of pentaerythrityl tetrakis(ethylhexanoate) and isohexadecane especially in a 60/40 weight ratio.
As mentioned above, the oily phase according to the invention has a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa. This threshold stress value reflects a gel-type texture of this oily phase.
This texturing is advantageously obtained via the presence in the oily phase of at least one texturing agent.
According to one embodiment variant, this texturing agent is an organic or mineral particulate material that is capable of gelling the oil(s) with which it is combined.
The choice of such a material clearly falls within the competence of a person skilled in the art.
According to an advantageous embodiment of this variant, this material is mineral and may advantageously have a BET specific surface area of greater than or equal to 300 m2/g, preferably greater than 500 m2/g and preferentially greater than 600 m2/g, and especially less than 1500 m2/g.
The BET specific surface area is determined according to the BET (Brunauer- Emmet-Teller) method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938, which corresponds to International Standard ISO 5794/1. The BET specific surface area corresponds to the total specific surface area (thus including micropores) of the powder.
As mineral particulate materials that are capable of gelling the oils with which they are combined, mention may be made more particularly of silica silylate powders, especially those sold under the name Dow Corning VM-2270 Aerogel Fine Particles by the company Dow Corning and under the name Enova Aerogel MT 1100 by the company Cabot.
According to one preferred embodiment variant, the oily phase of a composition according to the invention contains at least one silica silylate powder.
This particulate material may also be organic. Non-limiting illustrations of such materials that may especially be considered are organopolysiloxane elastomers.
The term "organopolysiloxane elastomer" means a supple, deformable organopolysiloxane with viscoelastic properties and especially the consistency of a sponge or a supple sphere. Its modulus of elasticity is such that this material withstands deformation and has a limited ability to extend and to contract. This material is capable of regaining its original shape after stretching.
It is more particularly a crosslinked organopolysiloxane elastomer.
Thus, the organopolysiloxane elastomer may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of diorganopolysiloxane containing ethylenically unsaturated groups bonded to silicon, especially in the presence of a platinum catalyst; or by dehydrogenation crosslinking condensation reaction between a diorganopolysiloxane containing hydroxyl end groups and a diorganopolysiloxane containing at least one hydrogen bonded to silicon, especially in the presence of an organotin; or by crosslinking condensation reaction of a diorganopolysiloxane containing hydroxyl end groups and of a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of an organoperoxide catalyst; or by crosslinking of organopolysiloxane via high- energy radiation such as gamma rays, ultraviolet rays or an electron beam.
In particular, the organopolysiloxane elastomer may be obtained by reaction of dimethylpolysiloxane containing dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane containing trimethylsiloxy end groups, in the presence of a platinum catalyst. According to one embodiment variant, the elastomer is a non-emulsifying elastomer. The term "non-emulsifying" defines organopolysiloxane elastomers not containing any hydrophilic chains, and in particular not containing any polyoxyalkylene units (especially polyoxy ethylene or polyoxypropylene) or any polyglyceryl units.
The organopolysiloxane elastomer particles are conveyed in the form of a gel formed from an elastomeric organopolysiloxane included in at least one hydrocarbon- based oil and/or one silicone oil. In these gels, the organopolysiloxane particles are often non- spherical particles.
Non-emulsifying elastomers are especially described in patents EP 242 219, EP 285 886 and EP 765 656 and in patent application JP-A-61-194 009, the content of which is incorporated by way o f reference .
According to a preferred embodiment variant, the oily phase of a composition according to the invention contains at least one organopolysiloxane elastomer and more particularly a spherical non-emulsifying organopolysiloxane elastomer. According to another embodiment variant, the elastomer may also be an emulsifying elastomer.
The term "emulsifying organopolysiloxane elastomer" means an organopolysiloxane elastomer comprising at least one hydrophilic chain, such as polyoxyalkylenated organopolysiloxane elastomers and polyglycerolated silicone elastomers.
The emulsifying organopolysiloxane elastomer may be chosen from polyoxyalkylenated organopolysiloxane elastomers.
The polyoxyalkylenated organopolysiloxane elastomer is a crosslinked organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of a polyoxyalkylene containing at least two ethylenically unsaturated groups.
In particular, the organopolysiloxane may be obtained by reaction of polyoxyalkylene (especially polyoxyethylene and/or polyoxypropylene) with dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane with trimethylsiloxy end groups, in the presence of a platinum catalyst. Advantageously, the polyoxyalkylenated organopolysiloxane elastomers may be formed from divinyl compounds, in particular polyoxyalkylenes containing at least two vinyl groups, which react with Si-H bonds of a polysiloxane.
Polyoxyalkylenated elastomers are especially described in patents US 5 236 986, US 5 412 004, US 5 837 793 and US 5 811 487, the content of which is incorporated by reference.
The emulsifying organopolysiloxane elastomer may also be chosen from polyglycerolated organopolysiloxane elastomers.
The polyglycerolated organopolysiloxane elastomer according to the invention is an organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of polyglycerolated compounds containing ethylenically unsaturated groups, especially in the presence of a platinum catalyst.
The polyglycerolated organopolysiloxane elastomer according to the invention is conveyed in gel form in at least one hydrocarbon-based oil and/or one silicone oil. In these gels, the polyglycerolated elastomer is often in the form of non-spherical particles.
As emerges from the foregoing text, the organopolysiloxane elastomers that are suitable for use in the invention are considered provided that they are capable of gelling the oil or the mixture of oils with which they are combined.
As non-emulsifying elastomers that are suitable for use in the invention, mention may be made especially of those sold under the names KSG-15 and KSG-16 by the company Shin-Etsu.
As polyoxyalkylenated organopolysiloxane elastomers that are suitable for use in the invention, use may be made of those sold under the names KSG-210 and KSG-310 by the company Shin-Etsu.
As polyglycerolated organopolysiloxane elastomers that are suitable for use in the invention, use may be made of those sold under the names KSG-710 and KSG-810 by the company Shin-Etsu.
For obvious reasons, the required amount of this material is liable to vary significantly according to the chemical nature and the physicochemical specificities of the material under consideration. By virtue of his competence, a person skilled in the art is capable of adjusting this amount in order to reach the stress threshold required according to the invention. According to a preferred embodiment variant, the texturing agent is a mineral material, and preferably silica silylate.
The silica silylate may be present in a proportion of from 0.5% to 20% by weight, preferably from 1% to 15% and especially from 2% to 10%, and preferably in a proportion of at least 6.5% by weight, relative to the total weight of the oily phase.
According to another preferred embodiment variant, the texturing agent is an organic material, and preferably an organopolysiloxane elastomer.
An organopolysiloxane elastomer gel may be present in a proportion of from 40% to 100% by weight and preferably from 60% to 100% by weight, and preferably in a proportion of at least 80% by weight, relative to the total weight of the oily phase.
A person skilled in the art will know how to adjust the contents of organopolysiloxane elastomer gel and/or of organopolysiloxane elastomer active material combined with the oils of the oily phase, such that the oily phase advantageously has the desired rheological properties. Besides the abovementioned compounds, a composition according to the invention may contain other compounds conventionally considered in a cosmetic composition.
These compounds may be dyestuffs, fillers, waxes, pasty compounds, gums, plasticizers, gelling agents, thickeners, antioxidants, preserving agents or fragrances, and mixtures thereof.
Dyestuffs
A composition according to the invention also comprises at least one particulate or non-particulate, water-soluble or water-insoluble dyestuff, preferably in a proportion of at least 3% by weight relative to the total weight of the composition.
For obvious reasons, this amount is liable to vary significantly with regard to the intensity of the desired color effect and of the color intensity afforded by the dyestuffs under consideration, and its adjustment clearly falls within the competence of a person skilled in the art.
However, a composition according to the invention may contain from 3% to 15% by weight or even from 5% to 10%> by weight of dyestuff(s) relative to the total weight of the composition, taking into account, moreover, the parallel limitation imposed in terms of amount of pulverulent phase in the case of using coloring particulate materials such as pigments, which are therefore water-insoluble.
For the purposes of the invention, the term "water-soluble dyestuf ' means any natural or synthetic, generally organic compound, which is soluble in an aqueous phase or water-miscible solvents and which is capable of coloring.
As water-soluble dyes that are suitable for use in the invention, mention may be made especially of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophylline, methylene blue, anthocyanins (enocianin, black carrot, hibiscus and elder), caramel and riboflavin.
The water-soluble dyes are, for example, beetroot juice and caramel. The coloring particulate materials may be present in a proportion of from 0.01% to 15% by weight relative to the total weight of the composition containing them.
They may especially be pigments, nacres and/or particles with metallic tints.
The term "pigments" should be understood as meaning white or colored, mineral or organic particles that are insoluble in an aqueous solution, which are intended to color and/or opacify the composition containing them.
A composition according to the invention may comprise from 0.01% to 15% by weight, preferably from 0.1% to 15% by weight and better still from 1% to 15% by weight of pigments relative to the total weight of said composition.
The pigments may be white or colored, and mineral and/or organic. As mineral pigments that may be used in the invention, mention may be made of titanium oxide, titanium dioxide, zirconium oxide, zirconium dioxide, cerium oxide or cerium dioxide and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate, and mixtures thereof. It may also be a pigment having a structure that may be, for example, of sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold, for example, under the reference Coverleaf NS or JS by the company Chemicals and Catalysts, and has a contrast ratio in the region of 30.
They may also be pigments having a structure that may be, for example, of silica microsphere type containing iron oxide. An example of a pigment having this structure is the product sold by the company Miyoshi under the reference PC Ball PC-LL- 100 P, this pigment consisting of silica microspheres containing yellow iron oxide.
Advantageously, the pigments in accordance with the invention are iron oxides and/or titanium dioxides.
The term "nacres" should be understood as meaning iridescent or non- iridescent colored particles of any shape, especially produced by certain molluscs in their shell or alternatively synthesized, which have a color effect via optical interference.
A composition according to the invention may comprise from 0 to 15% by weight of nacres relative to the total weight of said composition.
The nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles at the surface of which are superimposed at least two successive layers of metal oxides and/or of organic dyestuffs.
Examples of nacres that may also be mentioned include natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.
Among the pearlescent agents available on the market, mention may be made of the pearlescent agents Timica, Flamenco and Duochrome (based on mica) sold by the company Engelhard, the Timiron pearlescent agents sold by the company Merck, the Prestige mica-based pearlescent agents sold by the company Eckart, and the Sunshine synthetic mica-based pearlescent agents sold by the company Sun Chemical.
The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or glint. Advantageously, the nacres in accordance with the invention are micas coated with titanium dioxide or with iron oxide, and also bismuth oxy chloride.
For the purposes of the present invention, the term "particles with a metallic glint" means any compound whose nature, size, structure and surface finish allow it to reflect the incident light, especially in a non- iridescent manner.
The particles with a metallic glint that may be used in the invention are in particular chosen from:
- particles of at least one metal and/or of at least one metal derivative; - particles comprising a single-material or multi-material organic or mineral substrate, at least partially coated with at least one layer with a metallic glint 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 and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof (for example bronzes and brasses) are preferred metals.
The term "metal derivatives" denotes compounds derived from metals, especially oxides, fluorides, chlorides and sulfides.
Illustrations of these particles that may be mentioned include 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 metallic layer, especially those described in documents JP-A-09188830, JP-A-10158450, JP-A- 10158541, JP-A-07258460 and JP-A-05017710.
Fillers
For the purposes of the present invention, the term "fillers" should be understood as meaning colorless or white solid particles of any form, which are in an insoluble and dispersed form in the medium of the composition.
These fillers, of mineral or organic, natural or synthetic nature, give the composition containing them softness and give the makeup result a matt effect and uniformity. Among the mineral fillers that may be used in the compositions according to the invention, mention may be made most particularly of talc.
Dispersant
Advantageously, a composition according to the invention may also comprise a dispersant.
Such a dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof.
According to one particular embodiment, a dispersant in accordance with the invention is a surfactant.
However, according to a preferred embodiment variant, a composition according to the invention comprises less than 0.1% by weight of surfactant and in particular is surfactant-free. Active agent
For a particular care application, a composition according to the invention may comprise at least one moisturizer (also known as a humectant).
The moisturizer(s) could 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.
Humectants or moisturizers that may especially be mentioned include sorbitol, polyhydric alcohols, preferably of C2-Cs and more preferably of C3-C6, preferably such as glycerol, propylene glycol, 1 ,3-butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol and diglycerol, and a mixture thereof, glycerol and derivatives thereof, glycol ethers (especially containing from 3 to 16 carbon atoms) such as monopropylene, dipropylene or tripropylene glycol (Ci-C4)alkyl ethers, and monoethylene, diethylene or triethylene glycol (Ci-C4)alkyl ethers.
Use will preferably be made of at least glycerol as moisturizer.
As other active agents that may be used in the composition of the invention, examples that may be mentioned include vitamins and sunscreens, and mixtures thereof. It is a matter of routine operations for a person skilled in the art to adjust the nature and amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.
Cold state method
As mentioned above, the composition according to the invention has the advantage of to be prepared without the need for any heating steps by contrast to the preparation of an emulsion.
The method considered according to the invention may just have the need steps consisting of preparing, generally at room temperature, each phase, the aqueous gel and the oily gel, under moderate stirring.
Both gels are then mixed in selected proportions depending on the desired cosmetic properties. The choice of such proportions clearly falls within the competence of a person skilled in the art.
For example, the mixture of gels may be prepared at room temperature in mixers such as kneader type mixer or ribbon mixer. Indeed, unlike the emulsions preparation, the preparation of a composition according to the invention requires less shear.
According to one embodiment, a composition of the invention may advantageously be in the form of a cream foundation.
Such compositions are especially prepared according to the general knowledge of a person skilled in the art.
Throughout the description, including the claims, the expression "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified.
The terms "between... and..." and "ranging from... to..." should be understood as being inclusive of the limits, unless otherwise specified.
The invention is illustrated in greater detail by the examples and figures presented below. Unless otherwise mentioned, the amounts indicated are expressed as mass percentages. Methodology for the oscillating dynamic rheology measurements
These are rheological measurements in the harmonic regime, which measure the elastic modulus.
The measurements are taken using a Haake RS600 rheometer on a product at rest, at 25°C with a plate-plate rotor 0 60 mm and a 2 mm gap.
The measurements in the harmonic regime make it possible to characterize the viscoelastic properties of the products. The technique consists in subjecting a material to a stress that varies sinusoidally over time and in measuring the response of the material to this stress. In a region in which the behavior is linearly viscoelastic (zone in which the strain is proportional to the stress), the stress (τ) and the strain (γ) are two sinusoidal functions of time that are written in the following manner:
τ(ί) = το sin (rot)
y(t) = γο sin (ωί + δ)
in which:
To represents the maximum amplitude of the stress (Pa);
Yo represents the maximum amplitude of the strain (-);
ω = 2ΠΝ represents the angular frequency (rad.s-1) with N representing the frequency (Hz); and
δ represents the phase angle of the stress relative to the strain (rad). Thus, the two functions have the same angular frequency, but they are dephased by an angle δ. According to the phase angle δ between τ(ί) and γ(ί), the behavior of the system may be assessed:
- if δ = 0, the material is purely elastic;
- if δ = Π/2, the material is purely viscous (Newtonian fluid); and - if 0 < δ < Π/2, the material is viscoelastic.
In general, the stress and the strain are written in complex form:
T*(t) = το e1C0t
Y*(t) = Yo e(lcot + S)
A complex stiffness modulus, representing the overall resistance of the material to the strain, whether it is of elastic or viscous origin, is then defined by:
G* = τ*/ γ* = G' + iG"
in which: G' is the storage modulus or elastic modulus, which characterizes the energy stored and totally restituted in the course of a cycle, G' = (τ0/ γ0) cos δ; and
G" is the loss modulus or viscous modulus, which characterizes the energy dissipated by internal friction in the course of a cycle, G" = (τ0/ γ0) sin δ.
The parameter retained is the mean stiffness modulus G* recorded at the plateau measured at a frequency of 1 Hz.
Example 1
A foundation formulation in accordance with the invention is prepared from the phases and/or compounds described below.
1) Preparation of phases Al. B. C. D and E
An oily gel, phase Al, is prepared in a tank equipped with a "frame" paddle, using the following compounds in the weight proportions specified in the table below.
Weight%
Phase "ΑΓ
Aerogel® VM-2270 sold
Trimethyl silica by the company Dow 8
Corning
Nikkol pentarate 408
Pentaerythrityl
sold by the company
tetrakis(ethylhexanoate) 56
Nikko
Isohexadecane sold by
Isohexadecane
the company Ineos 36
Rheological characteristics
Threshold stress 288 Pa
G* 13 000 Pa
Sparingly crosslinked potato carboxymethylstarch sold in powder form by the company DMV Fonterra Excipients under the reference Primojel composes phase "B".
A "dye composition" below, phase "C", is prepared in a suitable container by treatment in a three-roll mill:
Figure imgf000027_0001
An aqueous solution of preserving agent below, phase "D", is prepared: Weight%
Phase "D"
Demineralized water 99.5
Preserving agents 0.5
The powders such as the fillers, nacres or other pulverulent additives to be considered in the foundation formulation compose phase "E".
2) Preparation of the foundation formulation
This formulation is obtained by mixing together all the constituents of the composition, divided into several phases (Al , B, C, D and E), by considering a combination of phases B, D and of the glycols of phase C, which are intended for forming the aqueous gel in accordance with the invention, in the proportions described below in
Table 1.
Table 1
Phase B + Phase D Proportions (in Weight% + Glycols of Phase C
grams)
. Carboxymethyl potato
Phase B starch, sodium salt, 4.675 8.06 sparingly crosslinked
. Deionized water
Phase D 42.075 72.54
. Preserving agents
. Glycerol
Glycols of Phase C 11.25 19.40
. Propylene glycol
Total 58 100
Rheological characteristics of such a set
Threshold stress 114 Pa
G* 4970 Pa To prepare the foundation formulation, the phases are introduced into a Clextral BC21 twin-screw extruder continuous mixer by means of volumetric pumps for the liquids and K-Tron dosers for the powders.
The mixing is performed at 20°C at a flow rate of 6 kg/hour and at a spin speed of 600 rpm.
The foundation composition is described below in Table 2.
Table 2
Figure imgf000029_0001
Figures 1A and B show the rheological profile of the composition thus obtained.
The composition has advantageous performance in terms of application and of makeup result. It affords an atypical texture that becomes transformed on application. Example 2
Another foundation formulation is obtained from the phases used in Example 1, keeping the same proportions with the exception of the oily phase Al, which is replaced with the oily phase A2, the composition of which is specified below.
The oily gel A2 is an organopolysiloxane elastomer sold under the name KSG- 16 by the company Shin-Etsu. It is sold as an oily mixture and is thus used in this form.
Figure imgf000030_0001
The composition of the foundation formulation thus obtained is as follows.
Table 3
% Phase Example 2
Phase A2 30 . KSG-16 30
. Carboxymethyl potato starch,
4.675
Phase B 4.675 sodium salt, sparingly crosslinked
. Glycerol 5.625
. Propylene glycol 5.625
Phase C 21.25
. Metal oxides 10
. Deionized water 41.865
Phase D 42.075
. Preserving agents 0.21
Phase E 2 . Talc 2
Rheolosical characteristics
Threshold stress 262 Pa
G* 5080 Pa Figures 2A and B show the rheological profile of the composition thus obtained.
The composition has advantageous performance in terms of application and of makeup result. It affords an atypical texture that becomes transformed on application.

Claims

1. A gel-type cosmetic composition for making up and/or caring for the skin, comprising at least:
a gelled aqueous phase containing at least 3% by weight, relative to its total weight, of particles of at least one (d-C4) carboxyalkyl starch and whose particle size ranges from 25 to 300 μιη, and
an oily phase gelled with at least one texturing agent,
with one of said phases constituting the continuous phase of said composition in which the other phase is uniformly dispersed.
2. The composition as claimed in the preceding claim, in which the oily phase has a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
3. The composition as claimed in either of the preceding claims, in which the dispersed phase and the continuous phase have a threshold stress of greater than 1.5 Pa and preferably greater than 10 Pa.
4. The composition as claimed in any one of the preceding claims, in which said phases are present in the weight ratio ranging from 95/5 to 5/95, and preferably ranging from 75/25 to 65/35.
5. The composition as claimed in any one of the preceding claims, in which said aqueous phase and said oily phase are present in a 70/30 weight ratio.
6. The composition as claimed in the preceding claim, in which said (d-C4) carboxyalkyl starch has a degree of substitution with carboxyalkyl units ranging from 0.1 to 1 and more particularly from 0.15 to 0.5.
7. The composition as claimed in any one of the preceding claims, in which said (C1-C4) carboxyalkyl starch is crosslinked.
8. The composition as claimed in any one of the preceding claims, in which said (C1-C4) carboxyalkyl starch is a carboxymethylstarch.
9. The composition as claimed in the preceding claim, in which said carboxymethylstarch is formed from units of formula:
Figure imgf000033_0001
in which X, optionally covalently bonded to the carboxyl 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.
10. The composition as claimed in any one of the preceding claims, in which the (Ci-C4) carboxyalkyl starch particles have a swelling power Q of between 10 and 30 ml/g and preferably between 15 and 25 ml (volume of absorbed liquid)/g of dry particulate material.
11. The composition as claimed in any one of the preceding claims, comprising from 30% to 80% by weight and in particular from 40% to 75% by weight of aqueous phase relative to its total weight.
12. The composition as claimed in any one of the preceding claims, comprising less than 8%> by weight, or even less than 7%> and preferably from 4%> to 6.5%> by weight of (Ci-C4) carboxyalkyl starch relative to the total weight of the aqueous phase.
13. The composition as claimed in any one of the preceding claims, comprising from 5%> to 40%> by weight and preferably from 7%> to 35%> by weight of oil(s) relative to the total weight of said composition.
14. The composition as claimed in any one of the preceding claims, in which said oily phase comprises at least pentaerythrityl tetrakis(ethylhexanoate) and isohexadecane especially in a 60/40 weight ratio.
15. The composition as claimed in any one of the preceding claims, in which the texturing agent is an organic or mineral particulate material that is capable of gelling the oil(s) with which it is combined.
16. The composition as claimed in any one of the preceding claims, in which the texturing agent is a mineral material, and preferably silica silylate.
17. The composition as claimed in the preceding claim, comprising from 0.5% to 20%) by weight, preferably from 1%> to 15%> and especially from 2%> to 10%>, and preferably a proportion of at least 6.5% by weight, of silica silylate relative to the total weight of the oily phase.
18. The composition as claimed in any one of claims 1 to 15, in which the texturing agent is an organic material and preferably an organopolysiloxane elastomer.
19. The composition as claimed in the preceding claim, comprising from 40% to 100% by weight and preferably from 60% to 100% by weight, and preferably a proportion of at least 80% by weight, of organopolysiloxane elastomer relative to the total weight of the oily phase.
20. The composition as claimed in any one of the preceding claims, comprising less than 0.1% by weight of surfactant, and in particular being surfactant- free.
21. The composition as claimed in any one of the preceding claims, being free of emulsifier.
22. A process for making up and/or caring for a composition of keratin materials, in particular the skin, comprising at least one step of applying to said keratin material a composition as defined according to any one of claims 1 to 21.
PCT/IB2012/057588 2011-12-21 2012-12-21 Gel-type cosmetic composition for making up and/or caring for the skin WO2013093869A2 (en)

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FR1162158 2011-12-21
FR1162158A FR2984736B1 (en) 2011-12-21 2011-12-21 COSMETIC COMPOSITION FOR MAKE-UP AND / OR CARE OF SKIN TYPE GEL.
US201261586237P 2012-01-13 2012-01-13
US61/586,237 2012-01-13

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* Cited by examiner, † Cited by third party
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WO2014167543A1 (en) * 2013-04-12 2014-10-16 L'oreal Gel-type cosmetic composition
WO2015181733A1 (en) * 2014-05-28 2015-12-03 L Oreal Cosmetic composition for make up and for taking care of keratin materials
WO2016030842A1 (en) * 2014-08-28 2016-03-03 L'oreal Gel-type cosmetic composition with improved staying power
WO2016030839A1 (en) 2014-08-28 2016-03-03 L'oreal Gel composition and gel comprising a uv filter
FR3025075A1 (en) * 2014-08-28 2016-03-04 Oreal NEW CARE AND / OR MAKE-UP DEVICE COMPRISING A GEL / GEL ARCHITECTURE COMPOSITION
WO2018067984A1 (en) * 2016-10-06 2018-04-12 Ken Nguyen Cosmetic composition
US10238584B2 (en) 2013-02-25 2019-03-26 L'oreal Gel-type cosmetic composition
US10398631B2 (en) 2013-02-25 2019-09-03 L'oreal Gel-type cosmetic composition
WO2020064245A1 (en) * 2018-09-29 2020-04-02 Beiersdorf Ag A cosmetic preparation with unique sensory properties and an appealing appearance
US20210246285A1 (en) * 2018-06-05 2021-08-12 Bio-Gate Ag Thixotropic Composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3025099B1 (en) * 2014-08-28 2016-12-16 Oreal GEL-TYPE COSMETIC COMPOSITION IMPROVED AND NOT COLLAPSIBLE
FR3026639B1 (en) * 2014-10-03 2018-04-13 Marlix Developpement COSMETIC COMPOSITION
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61194009A (en) 1985-02-21 1986-08-28 Toray Silicone Co Ltd Makeup cosmetic
EP0242219A2 (en) 1986-04-17 1987-10-21 Toray Silicone Company, Ltd. Method for producing silicone rubber powder
EP0285886A1 (en) 1987-04-10 1988-10-12 Ramisch Kleinewefers GmbH Method and apparatus for gas heating of calender rolls
JPH0517710A (en) 1991-07-08 1993-01-26 Kansai Paint Co Ltd Metallic paint and method for coating therewith
US5236986A (en) 1991-02-27 1993-08-17 Shin-Etsu Chemical Co., Ltd. Silicone polymers and water-dispersable, pasty silicone oil compositions comprising the same
US5412004A (en) 1991-11-21 1995-05-02 Kose Corporation Silicone polymer, paste-like silicone composition, and w/o-type cosmetic composition comprising the same
JPH07258460A (en) 1994-03-22 1995-10-09 Teijin Chem Ltd Resin composition
EP0765656A1 (en) 1995-09-29 1997-04-02 Shiseido Company Limited Water-in-oil type emulsion cosmetic composition
JPH09188830A (en) 1996-01-05 1997-07-22 Nisshin Steel Co Ltd Highly bright metallic pigment
JPH10158541A (en) 1996-11-27 1998-06-16 Nisshin Steel Co Ltd Dark silver color metallic pigment excellent in weather resistance and brilliance
JPH10158450A (en) 1996-11-28 1998-06-16 Shin Etsu Polymer Co Ltd Polyvinyl chloride resin composition for food packaging
US5811487A (en) 1996-12-16 1998-09-22 Dow Corning Corporation Thickening silicones with elastomeric silicone polyethers
US5837793A (en) 1996-03-22 1998-11-17 Dow Corning Toray Silicone Co., Ltd. Silicone rubber powder and method for the preparation thereof
WO2007068371A1 (en) 2005-12-14 2007-06-21 Cognis Ip Management Gmbh Method for producing hydrocarbons
WO2008155059A2 (en) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Hydrocarbon mixtures and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2806733B1 (en) * 2000-03-21 2002-05-10 Oreal COMPOSITION IN THE FORM OF A WATER-IN-OIL EMULSION AND ITS COSMETIC USES
FR2838335A1 (en) * 2002-04-10 2003-10-17 Oreal Mascara composition comprises an aqueous dispersion of a film-forming polymer and a superabsorbent polymer
FR2844448B1 (en) * 2002-09-17 2006-06-23 Lcw Les Colorants Wackherr METHOD FOR THE EXTEMPORANEOUS PREPARATION OF COSMETIC COMPOSITIONS HAVING THE TEXTURE OF A CREAM, AND COMPOSITIONS FOR CARRYING OUT SAID METHOD
DE10343413A1 (en) * 2003-09-19 2005-04-14 Universität Hamburg Crosslinked, long-term stable carboxymethyl starch as absorbent for water, their use and process for their preparation
EP1694287A1 (en) * 2003-12-01 2006-08-30 Degussa AG Spreadable cosmetic preparation with high water content
FR2874174B1 (en) * 2004-08-11 2006-11-24 Bourjois Soc Par Actions Simpl COSMETIC COMPOSITION COMPRISING A SUPERABSORBENT POLYMER
KR101432354B1 (en) * 2009-02-06 2014-08-20 더 프록터 앤드 갬블 캄파니 Collapsible water-containing capsules

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61194009A (en) 1985-02-21 1986-08-28 Toray Silicone Co Ltd Makeup cosmetic
EP0242219A2 (en) 1986-04-17 1987-10-21 Toray Silicone Company, Ltd. Method for producing silicone rubber powder
EP0285886A1 (en) 1987-04-10 1988-10-12 Ramisch Kleinewefers GmbH Method and apparatus for gas heating of calender rolls
US5236986A (en) 1991-02-27 1993-08-17 Shin-Etsu Chemical Co., Ltd. Silicone polymers and water-dispersable, pasty silicone oil compositions comprising the same
JPH0517710A (en) 1991-07-08 1993-01-26 Kansai Paint Co Ltd Metallic paint and method for coating therewith
US5412004A (en) 1991-11-21 1995-05-02 Kose Corporation Silicone polymer, paste-like silicone composition, and w/o-type cosmetic composition comprising the same
JPH07258460A (en) 1994-03-22 1995-10-09 Teijin Chem Ltd Resin composition
EP0765656A1 (en) 1995-09-29 1997-04-02 Shiseido Company Limited Water-in-oil type emulsion cosmetic composition
JPH09188830A (en) 1996-01-05 1997-07-22 Nisshin Steel Co Ltd Highly bright metallic pigment
US5837793A (en) 1996-03-22 1998-11-17 Dow Corning Toray Silicone Co., Ltd. Silicone rubber powder and method for the preparation thereof
JPH10158541A (en) 1996-11-27 1998-06-16 Nisshin Steel Co Ltd Dark silver color metallic pigment excellent in weather resistance and brilliance
JPH10158450A (en) 1996-11-28 1998-06-16 Shin Etsu Polymer Co Ltd Polyvinyl chloride resin composition for food packaging
US5811487A (en) 1996-12-16 1998-09-22 Dow Corning Corporation Thickening silicones with elastomeric silicone polyethers
WO2007068371A1 (en) 2005-12-14 2007-06-21 Cognis Ip Management Gmbh Method for producing hydrocarbons
WO2008155059A2 (en) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Hydrocarbon mixtures and use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, February 1938 (1938-02-01), pages 309

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