EP3233023A1 - Émulsions stabilisées par des particules composites amphiphiles - Google Patents

Émulsions stabilisées par des particules composites amphiphiles

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Publication number
EP3233023A1
EP3233023A1 EP15823354.4A EP15823354A EP3233023A1 EP 3233023 A1 EP3233023 A1 EP 3233023A1 EP 15823354 A EP15823354 A EP 15823354A EP 3233023 A1 EP3233023 A1 EP 3233023A1
Authority
EP
European Patent Office
Prior art keywords
particles
composite particles
emulsion
oil
whose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15823354.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Guillaume Cassin
Bruno Biatry
Romuald SANCHEZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of EP3233023A1 publication Critical patent/EP3233023A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24—Phosphorous; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
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    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
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    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
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    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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    • A61K8/731—Cellulose; Quaternized cellulose derivatives
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
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    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30—Characterized by the absence of a particular group of ingredients
    • A61K2800/33—Free of surfactant
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/612—By organic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/614—By macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/623—Coating mediated by organosilicone compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K2800/624—Coated by macromolecular compounds
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    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
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    • A61K2800/652—The particulate/core comprising organic material
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    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

  • the present invention relates to an emulsion containing no emulsifying surfactant comprising, especially in a physiologically acceptable medium, at least composite particles comprising a core comprising at least organic or inorganic particles A; said core being surface-coated, continuously or discontinuously, with an envelope comprising at least organic or inorganic B particles; said particles A and B having different polarities.
  • the present invention also relates to the use of composite particles as defined above as emulsion stabilizer, in particular an emulsion containing no emulsifying surfactant, and more particularly an oil-in-water emulsion. not containing emulsifying surfactant.
  • the present invention also relates to a process for the cosmetic treatment of a keratin material, comprising applying to the keratin material an emulsion as defined above.
  • emulsions such as oil-in-water (O / W) emulsions.
  • O / W oil-in-water
  • these cosmetic emulsions are, in general, stabilized by surfactants which can be a brake in certain applications.
  • surfactants in particular as emulsifying agents (or emulsifiers) can have an impact on the cosmetics of the products and the powderiness of the deposit, very appreciated by consumers.
  • surfactants are also likely to produce certain adverse effects. , such as a sticky, slippery or soapy effect.
  • the liquid / liquid emulsions in particular the oil-in-water (O / W) emulsions, are inherently unstable and undergo intense stress due to the evaporation of the volatile phase after application.
  • This stress causes coalescence of the droplets of the dispersed phase and the phenomenon is all the more marked that the interface is fluid and non-cohesive, as is the case for conventional surfactants.
  • This instability does not make it possible to control the state of the residual film after application and may lead to degradation of its optical properties (brightness, mattness, absorption) and / or sensory properties.
  • a solution to the problem can be provided by the use of amphiphilic solid particles capable of being adsorbed at the water / oil interface and of stabilizing the emulsion without adding a surfactant. It is particularly interesting to have emulsions without surfactant to limit the problems of safety and awareness, and also reduce the impact on the environment.
  • amphiphilic particles obtained according to the adsorption techniques have the following drawbacks:
  • the adsorbed molecules tend to detach from the surface of the amphiphilic particles according to the environmental conditions around the particles, thus causing the loss of the amphiphilic properties of said particles over time.
  • the processes for preparing the amphiphilic particles are complex to implement. For example, a purification step is necessary to remove unadsorbed molecules.
  • a spraying step and / or a grinding step may be necessary to prepare the amphiphilic particles (for example as indicated in the application JP-A-201 1 -83753). It is difficult to control the amphiphilic properties by adjusting this spraying step and / or this grinding step.
  • the hydrophilic silica particles may be treated with a silane coupling agent to form a hydrophobic film that is covalently bonded to the surface of the silica particles.
  • the treated surface of the silica particles can (Hyomen, Vol 41, No. 6, p.28-34 (2003)).
  • the control of the amphiphilic properties of the particles thus obtained is difficult.
  • Patent EP2643397 describes the use of composite particles, of core / shell structure, obtained by polymerization of an acrylic monomer on the surface of particles with a high refractive index. These particles have Soft Focus optical properties, however their amphiphilic properties at water / oil interfaces and the possibility of stabilizing emulsions have not been described or suggested.
  • composite particles comprising a core comprising at least organic or inorganic particles A; said core being surface-coated, continuously or discontinuously, with an envelope comprising at least organic or inorganic B particles; said particles A and B having different polarities.
  • composite particles having stabilizing properties for preparing surfactant-free emulsions, especially oil-in-water emulsions also called Pickering emulsions.
  • These particles can be easily prepared according to a chemical mechanofusion process which does not require a purification step and which makes it possible to control the amphiphilic properties of these composite particles.
  • the bark particles are firmly attached to the surface of the core particles, making it difficult for the bark particles to become detached from the core particles, which is remarkably , the composite particles retain in time their amphiphilic properties.
  • the present invention also relates to an emulsion containing no emulsifying surfactant, and more particularly to an oil-in-water emulsion containing no emulsifying surfactant and comprising, especially in a physiologically acceptable medium, at least composite particles comprising a core comprising at least organic or inorganic particles A; said core being surface-coated, continuously or discontinuously, with an envelope comprising at least organic or inorganic B particles; said particles A and B having different polarities.
  • the subject of the present invention is the use of said composite particles, as stabilizing agent for an emulsion, in particular an emulsion not containing an emulsifying surfactant, and more particularly an oil-in-water emulsion containing no surfactant.
  • emulsifier for stabilizing an emulsion, in particular an emulsion not containing an emulsifying surfactant, and more particularly an oil-in-water emulsion containing no surfactant.
  • the present invention also relates to a process for the cosmetic treatment of a keratinous material comprising applying to the keratin material an emulsion as defined above.
  • the term "emulsion” is intended to mean any composition comprising at least two phases that are liquid at room temperature (20-25 ° C.) and immiscible with one another; one of the two phases being dispersed in the other phase in the form of droplets so as to observe a mixture which is macroscopically homogeneous with the naked eye.
  • the emulsions according to the invention are oil-in-water (O / W) emulsions also called direct emulsions.
  • physiologically acceptable medium means a medium suitable for the administration of a composition topically.
  • a physiologically acceptable medium is a medium that is odorless and / or uncomfortable, and is perfectly compatible with the topical route of administration.
  • keratinous material is meant the skin (body and faces), the lips, and / or the integuments such as the nails.
  • emulsifying surfactant means an amphiphilic molecule, that is to say that it has two parts of different polarity, in general one is lipophilic (soluble dispersible in an oily phase ), the other is hydrophilic (soluble or dispersible in water).
  • the surfactants are characterized by the value of their HLB (hydrophilic lipophilic balance or hydrophilic-lipophilic balance), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule.
  • HLB hydrophilic lipophilic balance or hydrophilic-lipophilic balance
  • the term HLB is well known to those skilled in the art and is described, for example, in "The HLB System, A Time-saving Guide to Emulsifying Selection” (published by ICI Americas Inc., 1984).
  • the HLB generally ranges from 3 to 8 for the preparation of W / O emulsions and from 8 to 18 for the preparation of O / W emulsions.
  • the HLB of the surfactant (s) used according to the invention can be determined by the Griffin method or the Davies method.
  • the term "cosmetic treatment” means any non-therapeutic effect of perfuming, hygiene, skincare, conditioning or make-up which contributes to the improvement of well-being and / or beautification. and / or modifying the appearance or the odor of the keratin material to which said composition is applied.
  • the presence of the composite particles in accordance with the present invention thus proves to be particularly advantageous for improving the stability of emulsions, in particular of oil-in-water emulsions (also called direct emulsions), as well as the stability of compositions comprising said emulsions. .
  • compositions comprising these emulsions have excellent optical properties such as a matifying effect, soft focus. It has also been demonstrated that the composite particles in accordance with the present invention were particularly effective for stabilizing said oil phase / aqueous phase interfaces and forming fine and stable emulsions over time. The use of these composite particles thus makes it possible to reduce the need for surfactants, in particular the surfactants with ionic and / or nonionic characteristics, and therefore to improve the comfort of use of the compositions comprising the emulsion according to the invention. .
  • the composite particles according to the invention comprise a core comprising at least organic or inorganic particles A; said core being surface-coated, continuously or discontinuously, with a shell (or shell) comprising at least organic or inorganic B particles; said particles A and B having different polarities.
  • amphiphilic composite particles means that the composite particles have a hydrophilic part and a hydrophobic part; said hydrophilic and hydrophobic portions having different polarities enabling the composite particles to assemble at the water-oil interface of a composition comprising oil and water.
  • hydrophilic particles is meant that all the particles are individually dispersed in the aqueous phase so as not to form an aggregate.
  • hydrophobic particles is meant that all the particles are individually dispersed in the oily phase so as not to form an aggregate.
  • the polarity of the particles A and B constituting the composite particles of the invention can be determined using the E T scale (30), established by measuring the solvatochromic effect of a dye, such as 4- ( 2,4,6-triphenylpyridinium) -2,6-diphenylphenoxide (Reichardt's dye) in contact with the material.
  • a dye such as 4- ( 2,4,6-triphenylpyridinium) -2,6-diphenylphenoxide (Reichardt's dye) in contact with the material.
  • Dimroth et al. [Justus Liebigs Annalen der Chemie, 661 (1), 1-37, (1963)] for the principle.
  • the E T values (30) have been determined for various materials, in particular by Spange et al., [Langmuir, 15 (6), 2103-21111 (1999)], [J. Phys. Chem. B, 104 (27), 6417-6428, (2000)], ["Natural Fiber Reinforced Polymer Composites from Macro to Nanoscales", Old City Publishing, First Edition 2009, pp. 47-72] and [Macromol. Rapid Common. 21, 643-659 (2000)].
  • the composite particles preferably have an average size ranging from 0.1 to ⁇ ⁇ , more preferably from 0.5 to 15 ⁇ , and more particularly from 1 to 10 ⁇ .
  • average particle size is used to mean the average diameter over 50% by volume of the particles (D [0.5]) obtained using a laser diffraction particle size analyzer (eg Mastersizer 2000 from the Malvern Company).
  • the composite particles according to the invention may be nonspherical or nonspherical.
  • Spherical means that the particle has a sphericity index, that is to say the ratio between its largest diameter and its smallest diameter, less than 1 .2.
  • Non-spherical means particles in three dimensions (length, width, thickness or height) for which the ratio of the largest dimension to the smallest dimension is greater than 1, 2.
  • the dimensions of the particles of the invention are evaluated by scanning electron microscopy and image analysis. They comprise parallelepipedal (rectangular or square surface), discoidal (circular surface) or ellipsoidal (oval surface) particles, characterized by three dimensions: a length, a width and a height.
  • the length and width are identical and correspond to the diameter of a disc, while the height corresponds to the thickness of the disc.
  • the length and the width respectively correspond to the major axis and the minor axis of an ellipse and the height corresponds to the thickness of the elliptical disk formed by the wafer.
  • the length and the width may be of identical or different dimensions: when they are of the same size, the shape of the surface of the parallelepiped is square; otherwise, the shape is rectangular.
  • the height it corresponds to the thickness of the parallelepiped.
  • the composite particles in accordance with the invention comprise an envelope (or bark) which continues to be known, surrounding the entire surface of the heart.
  • the composite particles in accordance with the invention comprise a discontinuous shell (or bark), namely discontinuously surrounding the surface of the core.
  • a discontinuous shell or bark
  • the composite particles in accordance with the invention comprise a discontinuous shell (or bark), namely discontinuously surrounding the surface of the core.
  • from 10 to 90%, more particularly from 10 to 70%, and even more particularly from 30 to 50% of the surface of the core is covered by the envelope.
  • the particles A constituting the core of the composite particles are hydrophilic and the particles B constituting the envelope are hydrophobic.
  • the particles A constituting the core of the composite particles are hydrophobic and the particles B constituting the envelope are hydrophilic.
  • hydrophilic particles is meant that all the particles are individually dispersed in the aqueous phase so as not to form an aggregate.
  • hydrophobic particles is meant that all the particles are individually dispersed in the oily phase so as not to form an aggregate.
  • the weight ratio of the core to the envelope of the composite particles of the invention ranges from 70/30 to 99.9 / 0.1, more preferably from 80/20 to 99/1, and even more particularly from 90/10. at 99/1.
  • the average size of the particles A constituting the core of the composite particles varies, preferably, from 0.001 to 1000 ⁇ , more preferably from 0.05 to 500 ⁇ , more particularly from 0.1 to 200 ⁇ , more particularly from 1 to 10 ⁇ . ,; and still more particularly from 0.1 to 1 ⁇ ..
  • average particle size is used to mean the average particle size of 50% by volume (D [0.5]), measured at 25 ° C. using a laser diffraction particle size analyzer (eg Mastersizer2000). the Malvern Society)
  • the average size of 90% of the particles by volume (D [0.9]), obtained at 25 ° C. using a laser diffraction granulometer can vary from 2 to 7 ⁇ , preferably from 2 to 6 ⁇ , and more preferably from 2 to 5 ⁇ .
  • the core particles A according to the invention may be spherical or nonspherical. According to one particular form of the invention, the ratio of the largest dimension to the smallest dimension may vary from 1 to 2.5, more preferably from 1 to 2, and even more particularly from 1 to 1.5.
  • poly (meth) acrylate and polyalkyl (meth) acrylate polymers cross-linked or otherwise, in particular polymethyl methacrylates, for instance the products sold under the trade names MR-7GC® by the company Soken, the SSX-101® products and SSX-102® sold by Sekisui Plastics Sekisui Plastics;
  • organopolysiloxane elastomer or “silicone elastomer” is meant a flexible, deformable organopolysiloxane having viscoelastic properties and especially the consistency of a sponge or a flexible sphere. Its modulus of elasticity is such that this material resists deformation and has a limited capacity for extension and contraction. This material is able to recover its original shape after stretching.
  • the organopolysiloxane elastomer can be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and diorganopolysiloxane having silicon-bonded ethylenically unsaturated groups, especially in the presence of platinum catalyst; or by condensation-crosslinking dehydrogenation reaction between a hydroxyl-terminated diorganopolysiloxane and a diorganopolysiloxane containing at least one silicon-bonded hydrogen, especially in the presence of an organotin; or by crosslinking condensation reaction of a hydroxyl-terminated diorganopolysiloxane and a hydrolyzable organopolysilane; or by thermal crosslinking of organopolysiloxane, especially in the presence of organoperoxide catalyst; or by crosslinking of organopolysiloxane by high energy radiation such as gamma rays, ultraviolet rays, electron beam.
  • the silicone elastomer used in the present invention is selected from Dimethicone Crosspolymer (INCI name), Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone / Vinyl Dimethicone Crosspolymer (INCI name), Dimethicone Crosspolymer-3 (INCI name) .
  • the organopolysiloxane powder may also be coated with silsesquioxane resin, as described, for example, in US Pat. No. 5,538,793.
  • silsesquioxane resin as described, for example, in US Pat. No. 5,538,793.
  • Such elastomer powders are sold under the names "KSP-100”, “KSP-101", “KSP-102”, “KSP-103", “KSP-104", "KSP-105" by the company Shin Etsu, and have the name INCI: Vinyl Dimethicone / Meth icon Silsesquioxane Crosspolymer.
  • organopolysiloxane powders coated with silsesquioxane resin that can be advantageously used according to the invention include, in particular, organopolysiloxane elastomers of the INCI VINYL DIMETHICONE / METHICONE SILSESQUIOANE CROSSPOLYMER name, such as those sold under the trade reference "KSP-100" of the US Pat. Shin Etsu company.
  • polysaccharides in particular natural polysaccharides or of natural origin.
  • the starches that may be used in the present invention are more particularly macromolecules in the form of polymers consisting of elementary units which are anhydroglucose (dextrose) units, linked by ⁇ (1, 4) bonds, of chemical formula (C 6 H 10 O 5 ) n -
  • the number of these motifs and their assembly make it possible to distinguish amylose, a molecule formed from about 600 to 1000 molecules of linearly chain-linked glucose, and amylopectin, a branched polymer around every 25 glucose residues (a (1, 6) bond).
  • the total chain can make between 10,000 and 100,000 glucose residues.
  • the starch is described in particular in "KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd Edition, Volume 21, pp.
  • amylose and amylopectin as well as their degree of polymerization, vary according to the botanical origin of the starches. . On average, a sample of native starch consists of about 25% amylose and 75% amylopectin. Sometimes, there is presence of phytoglycogen (between 0% and 20% of the starch), an analogue of amylopectin but branched every 10 to 15 glucose residues.
  • the starch can be in the form of semi-crystalline granules: amylopectin is organized in sheets, amylose forms a less well-organized amorphous zone between the different layers. Amyloidosis is organized into a right helix with six glucoses per turn. It dissociates into assimilable glucose under the action of enzymes, amylases, more easily if it is in the form of amylopectin. Indeed, helical formation does not promote the accessibility of starch to enzymes.
  • the starches are generally in the form of a white powder insoluble in cold water, the size of the elementary particles ranges from 3 to 100 microns. By treating it with hot water, we obtain the poisoning. It is used in the industry for its thickener and gelling properties.
  • the starch molecules used in the present invention may have as botanical origin cereals or tubers.
  • the starches are for example chosen from starches of maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, pea.
  • the native starches are represented, for example, by the products sold under the names C * Amilogel TM, Cargill Gel TM, C * Gel TM, Cargill Gum TM, Dry Gel TM, C * Pharm Gel TM by the company Cargill, under the name Amidon de Magnolia by Roquette, and under the name Tapioca Pure by the company National Starch. Modified starches
  • modified starches used in the composition of the invention may be modified by one or more of the following reactions: pre-gelatinization, degradation (acid hydrolysis, oxidation, dextrinization), substitution (esterification, etherification), crosslinking (esterification), bleaching.
  • pre-gelatinization by bursting the starch granules (for example drying and cooking in a drying drum);
  • esterification in an alkaline medium for the grafting of functional groups in particular C1-C6 acyl (acetyl), hydroxyalkyl C1-C6 (hydroxyethyl, hydroxypropyl), carboxymethyl, octenylsuccinic.
  • X denotes in particular alkali metals (for example sodium or potassium), alkaline earth metals (for example calcium, magnesium), ammonium salts, amine salts such as those of monoethanolamine, diethanolamine, triethanolamine, amino-3-propanediol-1,2, ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine, citrulline.
  • the phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.
  • the starch molecules can be derived from all plant sources of starch such as, in particular, corn, potato, oats, rice, tapioca, sorghum, barley or wheat. It is also possible to use the hydrolysates of the starches mentioned above.
  • the modified starches are represented for example by the products sold under the names C * Tex-lnstant (pre-gelatinized adipate), C * StabiTex-lnstant (pre-gelatinized phosphate), C * PolarTex-lnstant (pre-gelatinized hydroxypropyl), C * Set (acid hydrolysis, oxidation), C * size (oxidation), C * BatterCrisp (oxidation), C * DrySet (dextrinisation), C * TexTM (acetylated diamidon adipate), C * PolarTexTM (hydroxypropylated diamidon phosphate) , C * StabiTexTM (diamidon phosphate, acetylated diamidon phosphate) by Cargill, diamidon phosphates or compounds rich in diamidon phosphate, such as the product sold under the references PREJEL VA-70-T AGGL (diamidon phosphate) of hydroxypropylated manioc gelatinized) or PREJ
  • the core particles A will be chosen from polysaccharides having: a wet point for oil of at least 25 ml / 100 g, preferably ranging from 35 to 600 ml / 100 g, and more preferably from 40 to 500 ml / g, and
  • a wetted point for water of at least 50 mg / 100 g, preferably 100 to 600 ml / 100 g, and more preferably 40 to 500 ml / 100 g.
  • oil wetting point means the necessary amount of oil to make the particles completely impregnated with the oil, which can be manifested by the formation of a paste with the particles tested. It can be determined according to the following protocol:
  • the weight of the added oil is determined as the oil wetting point
  • Wetting point (ml / 100g) ⁇ (weight of oil added) / 2 g ⁇ x100 / density of the oil.
  • water wetting point means the necessary amount of oil to make the particle completely impregnated with the oil, which can be manifested by the formation of a paste with the tested powder. It can be determined according to the following protocol:
  • the weight of the added water is determined as the wetting point with the water
  • wetting point (ml / 100g) ⁇ (weight of added water) / 2 g ⁇ x100 / density of water. It is preferable that the ratio of the wetting point to the water / oil wetting point of the polysaccharide particles constituting the core of the composite particles is less than or equal to 5, more preferably less than or equal to 4, and even more preferentially less than or equal to 3, and even more particularly less than 2.
  • the celluloses and their derivatives may be used among the polysaccharides and, preferably, said celluloses will be porous.
  • the porosity of the celluloses can be determined by their specific surface area ranging from 0.05 m 2 / g to 1.500 m 2 / g, more preferably from 0.1 m 2 / g to 1000 m 2 / g, and even more preferentially from 0.2 m 2 / g to 500 m 2 / g according to the BET method.
  • the cellulose may be of type I or type II or any equivalent. Type II celluloses will be used on a preferential basis.
  • the particles of celluloses will be spherical.
  • the cellulose particles preferably spherical, can be, for example, prepared according to the following process
  • a calcium carbonate sludge, as an aggregation inhibitor, is added to an alkaline solution of water-soluble anionic polymer and mixed with stirring.
  • the viscose and aqueous solution thus obtained in step (1) are mixed until a dispersion of fine viscose particles is formed.
  • step (3) The dispersion of fine viscose particles obtained in step (2) is heated to aggregate in the dispersion and then neutralized with an acid to form cellulose particles.
  • Viscose is the raw material of cellulose.
  • a viscose having a gamma of 30 to 100% by weight and an alkaline concentration of 4 to 10% by weight are preferably used.
  • the water-soluble anionic polymer it is possible to use a sodium salt of poly (acrylic acid), a sodium salt of polystyrene sulfonic acid. Calcium carbonate is used to prevent the formation of aggregates of viscose particles in the dispersion and to reduce the size of the cellulose particles.
  • the calcium carbonate sludge mention may be made of the Tama Pearl TP-221 GS® product sold by Okutama Kogyo Co., Ltd. in Japan.
  • the cellulose derivatives may be chosen from cellulose esters and cellulose ethers.
  • cellulose ester is meant a polymer consisting of (1-4) partially or completely esterified hydrogenation ring sequences, the esterification being obtained by reaction of one or all of the free hydroxyl functions of said hydroglucose rings with a linear or branched carboxylic acid or a carboxylic acid derivative (acid chloride or acid anhydride) containing from 1 to 4 carbon atoms.
  • the cellulose esters result from the reaction of some free hydroxyl functions of said rings with a carboxylic acid containing from 1 to 4 carbon atoms.
  • the cellulose esters are chosen from cellulose acetates, cellulose propionates, cellulose butyrates, cellulose isobutyrates, cellulose acetobutyrates and cellulose acetopropionates, and mixtures thereof.
  • cellulose esters may have a weight average molecular weight ranging from 3,000 to 1,000,000, preferably from 10,000 to 500,000 and more preferably from 15,000 to 300,000.
  • cellulose ether means a polymer consisting of ) anhydroglucose ring sequences partially or fully etherified, some of the hydroxyl functions of said rings being substituted with a radical -OR, where R is preferably a linear or branched alkyl radical having 1 to 4 carbon atoms.
  • the cellulose ethers are preferably chosen from alkyl ethers of cellulose with a C 1 -C 4 alkyl group such as cellulose methyl ether, cellulose propyl ether, cellulose isopropyl ether, cellulose butyl ether and cellulose isobutyl ether.
  • cellulose ethers may have a weight average molecular weight ranging from 3,000 to 1,000,000, preferably from 10,000 to 500,000 and more preferably from 15,000 to 300,000.
  • core A particles chosen from spherical cellulose particles mention may be made of the following commercial products sold by Daito Kasei in Japan:
  • the Cellulobeads USF® and Cellulobeads D-5® products are preferential and more particularly the Cellulobeads USF® product.
  • the polyamide particles used in the invention may be those sold under the name "Orgasol” by the ATOCHEM Company. The process for obtaining these particles is, for example, that described in document FR 2 619 385 or in document EP 303530. These polyamide particles are moreover known according to their different physicochemical properties under the name "polyamide 12". (INCI name: nylon-12) or "polyamide 6" (INCI name: nylon-6).
  • the particles used in the invention can also be those sold under the name SP500® by the company KOBO.
  • polymethylsilsesquioxanes which are obtained by hydrolysis and condensation of methyltrimethoxysilane such as the products sold under the trade names AEC Silicone Resin Spheres® (A & E Connock (Perfumery & Cosmetics) Ltd.), Belsil PMS MK® (Wacker Chemie AG) , Granpowder BU19® (Grant Industries, Inc.), Gransil PSQ® (Grant Industries, Inc.), Gransil PSQ-W® (Grant Industries, Inc.), KMP-590® (Shin-Etsu Chemical Co.), KMP -599® (Shin-Etsu Chemical Co.), MSP-K050® (Nikko Jamaica Corporation), SilDerm SQ® (Active Concepts LLC), SilForm Flexible Resin® (Momentive Performance Materials), SilPearl 508® (Koda Corporation), Si -Tec PMS® (Ashland Inc.), Tospearl 2000® Tospear
  • metal oxides such as zirconium oxides, cerium oxides, iron oxides and titanium oxides,
  • silicates such as talc, clays, kaolin
  • silica particles Among the silica particles, mention may be made of spherical hollow silica particles such as the products sold under the trade names Silica Beads SB 700® "and” Silica Beads SB 700 from the company Maprecos, "Sunsphere H-33®” and “Sunsphere H” -51® from Asahi Glas.
  • the core particles B will be chosen from hydrophilic organic or inorganic particles.
  • the average particle size constituting the envelope of the composite particles of the invention may be at least 0.01 to 100 ⁇ , more preferably from 0.05 to 50 ⁇ , and more particularly from 0.1 to 1 ⁇ .
  • the term "average particle size” is used to mean the average particle size of 50% by volume (D [0.5]), measured at 25 ° C. using a laser diffraction particle size analyzer (eg Mastersizer2000). the Malvern Society)
  • the particles B according to the invention may be spherical or nonspherical. According to one particular form of the invention, the ratio of the dimension of the largest to the smallest dimension may vary from 1 to 2.5, more preferably from 1 to 2, and even more particularly from 1 to 1.5.
  • the fumed silicas may be hydrophilic or lipophilic.
  • the pyrogenic hydrophilic silicas are obtained by pyrolysis in continuous flame at 1000 ° C of silicon tetrachloride (SiCl4) in the presence of hydrogen and oxygen.
  • SiCl4 silicon tetrachloride
  • hydrophilic silicas of hydrophilic nature that can be used according to the present invention, mention may be made in particular of those sold by Degussa or Evonik Degussa under the trade names AEROSIL® 90, 130, 150, 200, 300 and 380, or by CABOT. under the name Carbosil H5.
  • the fumed lipophilic silicas may be surface treated hydrophobic fumed silicas. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.
  • hydrophobic groups can be:
  • Silicas thus treated are called “Silica silylate” according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by Cabot.
  • silica dimethyl silylate is marketed under the references Aerosil R972®, and Aerosil R974® by Degussa, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by Cabot.
  • hydroxyapatites Calcium Phosphate Hydroxide as the commercial products sold under the names Apatite Powder AD-1® (Advance Company, Ltd.), Hydroxysomes® (Laboratory Skin Care (LSC), Inc.), Pearl Apatite® ( Mikimoto Pharmaceutical Co., Ltd.).
  • titanium oxide particles may be chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium or their mixtures. According to the invention, the titanium oxide particles, coated or uncoated, are particularly preferred.
  • Such metal oxide particles, coated or uncoated are in particular described in the patent application EP-A-0518 773.
  • commercial pigments can be mentioned the products sold by the companies SACHTLEBEN PIGMENTS, TAYCA, MERCK and DEGUSSA .
  • the metal oxide particles may be coated or uncoated. They have an average elementary particle size of less than or equal to 0.5 ⁇ , more preferably between 0.005 and 0.5 ⁇ and even more preferably between 0.01 and 0.2 ⁇ , more preferably between 0.01 and 0. , 1 ⁇ , and more particularly between 0.015 and 0.05 ⁇ .
  • the coated particles are particles which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • a chemical, electronic, mechanochemical and / or mechanical nature such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexa
  • coated particles are more particularly titanium oxides coated with: - silica such as the product "SUNVEIL®” from the company IKEDA,
  • silica and iron oxide such as the product "SUNVEIL F®” from the company IKEDA
  • silica and alumina such as the products “MICROTITANIUM DIOXIDE MT 500 SA®” and “MICROTITANIUM DIOXIDE MT 100 SA” from the company TAYCA, "TIOVEIL” from the company TIOXIDE,
  • alumina such as the products "TIPAQUE TTO-55 (B) ®” and “TIPAQUE TTO-55 (A) ®” from the company ISHIHARA, and "UVT 14/4" from the company SACHTLEBEN
  • alumina and aluminum stearate such as the products "MICROTITANIUM DIOXIDE MT 100 T®, MT 100 TX®, MT 100 Z®, MT-01®” from the company TAYCA, the products “Solaveil CT-10 W ® “and” Solaveil CT 100® “from the company UNIQEMA and the product” Eusolex T-AVO® “from the company MERCK,
  • silica, alumina and alginic acid such as the product "MT-100 AQ®" from the company Tayca,
  • alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE MT 100 S®” from TAYCA,
  • iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F®" from the company Tayca,
  • silica and alumina and treated with a silicone such as the products "MICROTITANIUM DIOXIDE MT 600 SAS®”, “MICROTITANIUM DIOXIDE MT”
  • silica and treated with a silicone such as the product "UV-TITAN X 195®" from SACHTLEBEN PIGMENTS,
  • triethanolamine such as the product "STT-65-S” from the company TITAN KOGYO
  • stearic acid such as the product “TIPAQUE TTO-55 (C) ®” of the company
  • sodium hexametaphosphate such as the product "MICROTITANIUM DIOXIDE MT 150 W®" from the company Tayca,
  • the uncoated titanium oxide particles are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B” or “MICROTITANIUM DIOXIDE MT600 B®", by the company DEGUSSA under the name "P 25”, by the company WACKHER under the name "Transparent titanium oxide PW®”, by the company MIYOSHI KASEI under the name “UFTR®”, by the company TOMEN under the name "ITS®” and by the company TIOXIDE under the name "TIOVEIL AQ®”.
  • ⁇ - ⁇ -alanine powders polyethylene powders; tetrafluoroethylene powders (Teflon®), polyurea powders; polyurethane powders such as the copolymer of hexamethylene diisocyanate and trimethylol sold under the name "Plastic Powder D-400®” by Toshiki; hollow expanded particles of vinylidene chloride and acrylonitrile polymer, such as the product sold under the name "Expancel®” by Expancel.
  • the composite particles are chosen from
  • composite particles whose core consists of cross-linked polymethyl methacrylate and whose envelope consists of hydroxyapatite such as those sold under the name PAC-2® by the company Sekisui Plastics;
  • composite particles whose core consists of cross-linked polymethylmethacrylate and whose envelope is made of fumed silica such as the product sold under the trade name Micropearl M330® by the company Matsumoto Yushi;
  • composite particles whose core consists of organopolysiloxane elastomer and whose envelope consists of fumed silica such as particles whose core consists of Dimethicone / Vinyl Dimethicone Crosspolymer and whose envelope is made of fumed silica as the product sold under the name DC 9701 Cosmetic Powder® by Dow Corning (INCI name: Dimethicone / Vinyl Dimethicone Crosspolymer (and) Silica);
  • composite particles whose core consists of a polysaccharide, in particular natural or of natural origin and whose envelope is made of polymethylmethacrylate;
  • the composite particles conform to The invention concerns composite particles whose core consists of a polysaccharide, in particular a natural or naturally occurring polysaccharide, the shell of which consists of polymethylmethacrylate. More preferably, use will be made of a polysaccharide having:
  • a wet point for oil of at least 25 ml / 100 g, preferably ranging from 35 to 600 ml / 100 g, and more preferably from 40 to 500 ml / g, and
  • a wetted point for water of at least 50 mg / 100 g, preferably 100 to 600 ml / 100 g, and more preferably 40 to 500 ml / 100 g. Even more preferentially, use will be made of a polysaccharide whose ratio of wetting point to water / wetting point to oil of the polysaccharide particles constituting the core of the composite particles is less than or equal to 5.0, more preferably less than or equal to 4, still more preferably less than or equal to 3.0, and even more particularly less than or equal to 2.0.
  • porous cellulose and more preferably a type II cellulose, will be used.
  • the composite particles in accordance with the invention may be manufactured according to conventional techniques for manufacturing composite core and shell (core / shell) particles. According to a preferred method of manufacture, the composite particles in accordance with the invention will be synthesized according to a dry coating technique (without a liquid medium), in particular according to the technique of mechanochemical fusion.
  • a method of mechanochemical melting is a method in which mechanical power such as a compressive force, a frictional or shearing force is exerted on a plurality of elements causing said elements to melt.
  • the method of mechanochemical melting can be carried out with an apparatus comprising a rotating chamber and an inner part attached to a scraper such as the apparatus sold under the trade name Hosokawa Micron Corporation in Japan.
  • a mechanochemical fusion hybridization process will be used.
  • the hybridization process was developed in the 1980s. It is a type of mechanochemical melting process in which a high mechanical power is applied to a plurality of particles to cause a mechanochemical reaction to form composite particles.
  • the mechanical power is produced by a high speed rotor having a diameter ranging from 10 cm to 1 m and can rotate at a speed ranging from 1000 to 10000 rev / min.
  • the hybridization process can be carried out in air or in a dry atmosphere. Indeed, the Rotating the rotor at high speed can generate high velocity airflow near the rotor. Liquid materials can be subjected to the hybridization process in the presence of solid materials.
  • the hybridization process can be carried out using a hybridization system sold under the trade name Nara Machinery, in which at least two types of particles, usually core particles and fine particles, are introduced into an equipped hybridizer. a high speed rotor having a plurality of blades in a dry chamber, and the particles are dispersed in the chamber and mechanical and thermal energy is produced on the particles (compression, friction and shear) for a short period such as 1 at 10 minutes and preferably from 1 to 5 minutes. As a result, a type of particles (fine particles) integrated or attached to another type of particles (ie, core particles) to form composite particles.
  • Nara Machinery in which at least two types of particles, usually core particles and fine particles, are introduced into an equipped hybridizer.
  • a high speed rotor having a plurality of blades in a dry chamber, and the particles are dispersed in the chamber and mechanical and thermal energy is produced on the particles (compression, friction and shear) for a short period such as 1 at 10 minutes and preferably from 1 to 5 minutes.
  • the particles be subjected to electrostatic treatment, for example by shaking them to form an "ordered mixture" in which one type of particles is spread to cover the other type of particles.
  • the hybridization process can be carried out using a Theta dialer sold by Tokuju Corporation.
  • the hybridization process can be carried out using a Composi Hybrid or Mechano Hybrid type apparatus sold by Nippon Coke.
  • the present invention relates to an emulsion containing no emulsifying surfactant comprising, in particular in a physiologically acceptable medium at least the particles as defined above.
  • the emulsions according to the invention are of the Pickering type, ie they are stabilized by fillers which are the composite particles as defined above.
  • the emulsions according to the invention are oil-in-water (or direct emulsion) emulsions, namely comprising a continuous aqueous phase and an oily phase dispersed in said aqueous phase in the form of oil droplets forming a macroscopically homogeneous mixture with the naked eye.
  • the average size of the oil droplets, observed at room temperature (25 ° C.) with a binocular magnifier, is preferably from 5 to 600 ⁇ and more preferably from 100 to 500 ⁇ .
  • the composite particles of the invention will be present in the emulsions at concentrations ranging from 0.1 to 10% by weight, and more preferably from 0.5 to 2% by weight relative to the total weight of the composition.
  • the oil-in-water emulsions according to the present invention can be prepared at ambient temperature (25 ° C.), according to a preparation process comprising:
  • the invention therefore relates to a method for preparing an oil-in-water emulsion without emulsifying surfactant as defined above, comprising at least the following steps:
  • the aqueous phase of a composition according to the invention comprises water and optionally a water-soluble solvent.
  • the water may be in particular floral water, mineral water and / or spring water such as Vichy Water, Lucas Water or Roche Posay Water.
  • water-soluble solvent in the present invention a liquid compound at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25 ° C and atmospheric pressure).
  • the water-soluble solvents that can be used in the composition of the invention may also be volatile.
  • the aqueous phase water and optionally the water-miscible solvent
  • the aqueous phase of a composition according to the invention may comprise at least one C2-C32 polyol.
  • polyol is meant for the purposes of the present invention, any organic molecule comprising at least two free hydroxyl groups.
  • a polyol according to the present invention is present in liquid form at room temperature.
  • a polyol that is suitable for the invention may be a linear, branched or cyclic alkyl compound, saturated or unsaturated, bearing at least two -OH functions on the alkyl chain, in particular at least three -OH functions, and more particularly at minus four functions -OH.
  • the polyols which are advantageously suitable for formulating a composition according to the present invention are those having in particular 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.
  • the polyol may be, for example, chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol and glycerol.
  • polyglycerols such as oligomers of glycerol such as diglycerol, polyethylene glycols, and mixtures thereof.
  • said polyol is chosen from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, glycerol, polyglycerols, polyethylene glycols, and mixtures thereof.
  • composition of the invention may comprise at least propylene glycol.
  • the fatty phase includes all liquid fatty substances, generally oils (also called liquid or oily fatty phase), or solids like waxes or pasty compounds (also called solid fatty phase).
  • a liquid fatty phase is also called the oily phase and comprises at least one oil.
  • oil means any fatty substance in liquid form at ambient temperature at atmospheric pressure.
  • An oily phase suitable for the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon oils, silicone oils, fluorinated or not, or mixtures thereof.
  • the oils may be volatile or non-volatile. They can be of animal, vegetable, mineral or synthetic origin. According to one variant embodiment, the oils of plant origin are preferred.
  • non-volatile oil means an oil having a vapor pressure of less than 0.13 Pa.
  • silicon oil means an oil comprising at least one silicon atom, and in particular at least one Si-O group.
  • fluorinated oil means an oil comprising at least one atom. of fluorine.
  • hydrocarbon oil means an oil containing mainly hydrogen and carbon atoms.
  • the oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acidic radicals.
  • volatile oil is meant, within the meaning of the invention, any oil capable of evaporating on contact with the skin in less than one hour, at ambient temperature and atmospheric pressure.
  • the volatile oil is a volatile cosmetic compound which is liquid at ambient temperature, in particular having a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 "). 3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); mm Hg).
  • Volatile oils can be hydrocarbon or silicone.
  • volatile hydrocarbon oils having from 8 to 16 carbon atoms mention may be made especially of C 6 -C 16 branched alkanes such as iso-alkanes (also known as isoparaffins) at C 6 -C 16, isododecane, isodecane and isohexadecane. and for example the oils sold under the trade names Isopars or permetyls, branched Cs-C16 esters such as isohexyl neopentanoate, and mixtures thereof.
  • iso-alkanes also known as isoparaffins
  • the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isohexadecane.
  • volatile linear alkanes comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 1 to 13 carbon atoms, for example such as n-dodecane (C12). and n-tetradecane (d 4 ) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the undecane-tridecane mixture, the n-undecane (Cn) and n-undecane mixtures.
  • tridecane (C13) obtained in Examples 1 and 2 of WO 2008/155059 from Cognis, and mixtures thereof.
  • volatile silicone oils mention may be made of linear silicone volatile oils such as hexamethyldisiloxane, octamethylthsiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane.
  • Cyclic silicone volatile oils that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. Cyclohexasiloxane, Cyclopentasiloxane.
  • the non-volatile oils may, in particular, be chosen from hydrocarbon oils, fluorinated oils and / or non-volatile silicone oils.
  • non-volatile hydrocarbon oil mention may notably be made of:
  • linear or branched hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof,
  • hydrocarbon-based oils of plant origin such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; ; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower,nadooulier, passionflower, rose hip, or triglycerides of caprylic / capric acids such as those sold by society Dubo
  • R1COOR2 oils of formula R1COOR2 in which R1 represents a residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon chain, in particular, branched, containing from 1 to 40 carbon atoms, provided that R 1 + R 2 is > 10.
  • the esters may be, in particular, chosen from alcohol and fatty acid esters, for example, cetostearyl octanoate, esters of isopropyl alcohol, such as isopropyl myristate, isopropyl palmitate, ethyl palmitate, 2-ethylhexyl palmitate, isopropyl stearate, octyl stearate, isocetyl stearate, hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, ricinoleates of alcohols or polyalcohols, hexyl laurate, esters of neopentanoic acid, such as isodecyl neopentanoate, isotridecyl neopentanoate, esters of isononanoic acid, such as isononyl isononanoate, isotridecyl isononanoate
  • polyol esters and pentaerythritol esters such as dipentaerythritol tetrahydroxystearate / tetraisostearate
  • non-phenylated silicone oils for example poldimethylsiloxanes
  • phenylated silicone oils for example phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, and 2-phenylethyl trimethylsiloxysilicates, dimethicones or phenyltrimethicone with a viscosity of less than or equal to 100 cSt; trimethylpentaphenyltrisiloxane, and mixtures thereof; as well as the mixtures of these different oils.
  • Another fatty substance that may be present in the oily phase may be, for example:
  • a fatty acid chosen from fatty acids containing from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid;
  • waxes such as lanolin, beeswax, carnauba or candelilla wax, paraffin waxes, lignite waxes or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as waxes polyethylene, Fischer-Tropsch waxes;
  • a gum chosen from silicone gums (dimethiconol),
  • a pasty compound such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, triglycerides of fatty acids and their derivatives,
  • a composition according to the invention comprises oils chosen from fatty alcohols, fatty acid synthesis esters and silicone oils and mixtures thereof, more particularly chosen from isoketyl stearate, isopropyl myristate and alkylbenzoates. C12-C15, octyldodecanol, cyclohexasiloxane, polydimethylsiloxanes, and mixtures thereof.
  • a composition according to the invention may comprise from 5% to 95% by weight, better still from 5% to 40% by weight, preferably from 7% to 35% by weight of oil (s) relative to the total weight of said composition.
  • compositions according to the invention may also comprise, in addition, additional cosmetic and dermatological active ingredients.
  • the cosmetic compositions according to the invention may comprise cosmetic adjuvants chosen from among softeners, antioxidants, opacifiers, stabilizers, moisturizing agents, vitamins, bactericides, preservatives, sunscreens, polymers, perfumes , organic or inorganic fillers; thickening agents, gelling or suspending agents, or any other ingredient usually used in cosmetics for this type of application.
  • Thickeners that may be mentioned include carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-C14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic ; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as Poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by the company Clariant under the trademark "Hostacerin AMPS" (name CTFA: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold
  • the cosmetic compositions according to the invention may for example be used as a makeup product for the skin of the face and / or the body and / or the lips and / or the nails.
  • the cosmetic compositions according to the invention can, for example, be used as a care product, a hygiene product, and / or a sun protection product for the skin of the face and / or of the body, and / or of the lips, and / or for the nails , of liquid to semi-liquid consistency, such as milks, creams more or less creamy, gel-creams, pasta.
  • They may optionally be packaged in aerosol and be in the form of foam or spray.
  • compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied to keratin materials in the form of fine particles by means of pressurizing devices.
  • Devices suitable for the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517.
  • the aerosol-conditioned compositions in accordance with the invention generally contain conventional propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane. They are present preferably in amounts ranging from 15 to 50% by weight relative to the total weight of the composition. Expressions “between ... and Obviously and "from ... to " must be understood as inclusive terms unless otherwise specified.
  • propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane.
  • Example. 1 O / W emulsion
  • phase A demineralised water
  • phase B maintaining the agitation at 300 rpm for 1 h.
  • Phase C was then added with gentle stirring.
  • a stable oil-in-water emulsion was obtained after 24 hours at room temperature (25 ° C.) with drops of oil with a mean diameter of 300 ⁇ m measured using a binocular loupe.
  • Example. 2 O / W emulsion
  • Ethanol 2 g According to the same protocol as the example. 1, a stable oil-in-water emulsion was obtained after 24 hours at room temperature (25 ° C.) with drops of oil with a mean diameter of 350 m.
  • the components indicated in the above table were mixed in the weight ratio shown in the same table in a plastic bag which was shaken for a few minutes. The mixture was then placed in a hybridization device sold under the trade name Nara Machinery® with a rotor rotating at 8000 rpm (linear speed 100 m / s) for 3 minutes to obtain the composite pigments.
  • Example 7 O / W Emulsion Phase A
  • Example 8 O / W Emulsion
  • Example 10 to 12 O / W emulsions
  • MFP-6 Silica particles Particles of pyrogenic heart Polymethylsilsesquioxane
  • Demineralized water 39.5 g
  • phase A demineralized water
  • phase B demineralized water
  • Demineralized water 39.5 g
  • phase A At room temperature (25 ° C), 1 g of MFP-2 particles were dispersed in phase A with a paddle (Heidolph RZR2041) for 5 min. at 300 rpm, then phase B was slowly introduced maintaining stirring at 300 rpm for 1 h. Phase C was then added with gentle stirring, then successively phase D and E.
  • a stable O / W emulsion was obtained after 24 hours at room temperature (25 ° C.) with drops of oil having a mean diameter of 150 ⁇ m.
  • EXAMPLE 14 O / W Emulsion with Emulsifying Surfactant (Excluding the Invention)
  • the brightness of a deposit resulting from the application of a composition may be commonly measured according to various methods, such as that using a Byk Micro Gloss 60 ° gloss meter.
  • the apparatus illuminates the sample to be analyzed according to a certain incidence and measures the intensity of the specular reflection.
  • the intensity of the reflected light depends on the material and the angle of illumination. For non-ferrous materials (paint, plastic), the reflected light intensity increases with the illumination angle. The remainder of the incident light penetrates into the material and according to the hue of the color, it is either partially absorbed or diffused.
  • the measurement results of the reflectometer are not based on the amount of incident light but on a black and polished glass standard of defined refractive index.
  • the measurement is normalized to an internal standard and reduced to 100:
  • the measured value is set to 100 units of gloss (calibration). The closer the measured value is to 100, the more brilliant the sample.
  • the unit of measurement is the Gloss Unit (UB).
  • the angle of illumination used greatly influences the value of the reflectometer.
  • standardization has defined 3 geometries, or 3 measurement domains.
  • the layer covers the white background and the black background of the map,
  • Composite particles have been found to have matting properties which are maximized when used to stabilize the oil / water interface.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Colloid Chemistry (AREA)
EP15823354.4A 2014-12-17 2015-12-17 Émulsions stabilisées par des particules composites amphiphiles Withdrawn EP3233023A1 (fr)

Applications Claiming Priority (2)

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FR1462576A FR3030227B1 (fr) 2014-12-17 2014-12-17 Emulsion stabilisees par des particules composites amphiphiles
PCT/FR2015/053608 WO2016097641A1 (fr) 2014-12-17 2015-12-17 Émulsions stabilisées par des particules composites amphiphiles

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US20170360661A1 (en) 2017-12-21
BR112017012932B1 (pt) 2021-04-27
JP2018501242A (ja) 2018-01-18
BR112017012932A2 (pt) 2018-03-13
FR3030227A1 (fr) 2016-06-24
FR3030227B1 (fr) 2018-01-26
CN107205893B (zh) 2022-02-18
KR20170097709A (ko) 2017-08-28
CN107205893A (zh) 2017-09-26
US11622923B2 (en) 2023-04-11
WO2016097641A1 (fr) 2016-06-23
JP6847836B2 (ja) 2021-03-24

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