WO2023057446A1 - Oily dispersion comprising a polymeric particle and a stabilizer bearing a c9-c22 alkyl group and a plasticizer, and process for treating keratin materials using the oily dispersion - Google Patents

Oily dispersion comprising a polymeric particle and a stabilizer bearing a c9-c22 alkyl group and a plasticizer, and process for treating keratin materials using the oily dispersion Download PDF

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Publication number
WO2023057446A1
WO2023057446A1 PCT/EP2022/077577 EP2022077577W WO2023057446A1 WO 2023057446 A1 WO2023057446 A1 WO 2023057446A1 EP 2022077577 W EP2022077577 W EP 2022077577W WO 2023057446 A1 WO2023057446 A1 WO 2023057446A1
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acrylate
alkyl
meth
chosen
notably
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PCT/EP2022/077577
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French (fr)
Inventor
Guillaume Kergosien
Julien PORTAL
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L'oreal
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Publication of WO2023057446A1 publication Critical patent/WO2023057446A1/en

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    • 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
    • A61K8/72—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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/72—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara

Definitions

  • the present invention relates to an oily dispersion (A) comprising: at least one particle consisting of an ethylenic polymer i), at least one polymeric stabilizer comprising a (Cg-C22)alkyl group ii), at least one hydrocarbon-based fatty substance which is liquid at 20°C and 1 atmosphere iii), and at least one plasticizer iv).
  • the invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin, the hair or the eyelashes, involving the application to said materials of at least one oily dispersion (A); to a process for preparing the oily dispersion, and to a multi-compartment kit comprising ingredients i) to iv).
  • keratin materials notably human keratin materials such as the skin, the hair or the eyelashes
  • Cosmetic products often require the use of a film-forming polymer to obtain a deposit of the product on keratin materials that has good cosmetic properties.
  • WO 2010/046 229 describes dispersions in isododecane of acrylic polymers stabilized with stabilizing polymers.
  • FR 1 362 795 describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon-based oils for making up the lips and the eyelashes.
  • Non-permanent dyeing or direct dyeing consists in dyeing keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules that have affinity for keratin fibers. They are applied to the keratin fibers for a time necessary to obtain the desired coloring, and are then rinsed out.
  • the standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural dyes.
  • Some of these dyes may be used under lightening conditions, which enables the production of colorings that are visible on dark hair.
  • pigment for dyeing keratin fibers is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibers, a composition comprising at least one dispersion of film-forming polymer particles comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.
  • FR 3 014 875 describes the use of a dispersion of C1-C4 alkyl (meth)acrylate polymer particles surface-stabilized with an isobornyl (meth)acrylate polymeric stabilizer in a non-aqueous medium containing an oil.
  • the deposits obtained using this technology are not always satisfactory, notably in terms of resistance to sebum.
  • FR 3 029 786 is focused on makeup dispersions of polymer particles stabilized with at least one stabilizer which is a Cs alkyl (meth)acrylate homopolymer or a copolymer of Cs alkyl (2-ethylhexyl) (meth)acrylate and of C1-C4 alkyl (meth)acrylate.
  • stabilizer which is a Cs alkyl (meth)acrylate homopolymer or a copolymer of Cs alkyl (2-ethylhexyl) (meth)acrylate and of C1-C4 alkyl (meth)acrylate.
  • the aim of the present invention is to provide a composition for treating keratin materials, in particular the skin, preferably human skin and more preferentially facial skin, the residual film of which after application to said keratin materials adheres well to the keratin materials, is elastic and shows the least possible fragmentation and the least possible detachment from the substrate, which is not tacky, has good persistence with respect to external attacking factors, and over time, does not leach, is resistant to sweat and to sebum, and is relatively insensitive to oils such as dietary oils, notably to sebum.
  • the keratin material after being treated with the composition of the invention is pleasant to the touch (soft, smooth and touch even), the color when the said composition comprises at least one dye and/or at least one pigment is homogeneous.
  • the appearance keratin material after application on keratin is very aesthetic, from matte, satin to gloss, preferably gloss satin, more preferably gloss.
  • Another aim of the present invention is to provide a composition for treating keratin fibers, notably human keratin fibers such as the hair, the eyelashes or the eyebrows, the residual film of which after application to said fibers adheres well to the fibers, without any fragmentation/detachment from said fibers, which has good persistence with respect to attacking factors such as brushing, does not leach, is resistant to sweat, sebum, light and bad weather, and is persistent with respect to shampoo washing and to the various attacking factors to which said fibers may be subjected, notably to sebum, without degrading said fibers, and while keeping the keratin fibers perfectly individualized.
  • keratin fibers notably human keratin fibers such as the hair, the eyelashes or the eyebrows
  • an oily dispersion (A) for treating keratin materials, notably human keratin materials such as the hair, the eyelashes or the skin
  • the oily dispersion (A) is preferably anhydrous, and comprises: i) one or more particles including one or more polymers chosen from: a) ethylenic homopolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci- C4)alkyl (meth)acrylate; b) ethylenic copolymers of b1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl; in particular, b2) is a (Ci-C4)(alkyl)acrylic acid such
  • the subject of the invention relates to the use of the oily dispersion (A) as defined previously for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, preferably for dyeing keratin fibers and/or for shaping keratin fibers such as the hair, for caring for keratin materials, notably the skin, and/or for making up keratin materials such as the hair or the skin.
  • keratin materials notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin
  • the oily dispersion (A) as defined previously for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, preferably for dyeing keratin fibers and/or for shaping keratin fibers such as the hair, for caring for keratin materials, notably the skin, and/or for making up keratin materials such as the hair or the skin.
  • a subject of the invention is also the oily dispersion (A) as defined previously, and also a process for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, comprising the application to said materials of the oily dispersion (A) as defined previously.
  • keratin materials notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin
  • a subject of the invention is also a multi-compartment kit or device comprising the ingredients i) to iv) and optionally v) as defined previously, in which the ingredients i) to iii) are in the same compartment, iv) is in another compartment, and optionally v) is in another compartment, or in the compartment with i) to iii), or in the compartment with iv).
  • the oily dispersion (A) and the process for treating keratin materials as defined above make it possible to obtain, after application to said materials, a residual film which adheres well to said materials while at the same time remaining elastic, showing little or no fragmentation, and little or no detachment, and which is notably resistant to shampoo washing, sebum, sweat and/or water, but also to fatty substances, notably dietary fats such as oils, notably to sebum. Furthermore, the dispersion is easy to use in compositions, notably cosmetic compositions, is easy to manufacture and remains stable over time.
  • the oily dispersion (A) in accordance with the present invention makes it possible to obtain deposits that are very resistant to external attacking factors, notably to sebum and to the fatty substances found in food, in particular liquid fatty substances such as plant oils and in particular olive oil.
  • the makeup produced with at least one oily dispersion (A), notably lip makeup shows no color fragmentation after application, and is resistant to external attacking factors such as liquid fatty substances, in particular with respect to plant oils such as olive oil.
  • the makeup products obtained with the oily dispersions (A) are very esthetic, comfortable, easy to apply and glossy. Furthermore, these dispersions of polymer particles are found at a high solids content in the hydrocarbon-based liquid fatty substance(s) iii).
  • the oily dispersions (A) of the invention makes it possible to obtain homogeneous coatings that are persistent with respect to external attacking factors (sunlight, water, shampoo washing, perspiration, sebum, etc.).
  • the composition comprises one or more dyes and/or pigments
  • the colored keratin materials according to the invention have a coloring that is visible on all types of materials, notably on dark keratin materials, in a persistent manner with respect to soaps, shower gels or shampoos, while at the same time preserving the physical qualities of the keratin material.
  • Such a coloring is in particular resistant to the external attacking factors to which the keratin fibers, notably the hair, may be subjected, such as daily blow-drying, brushing and styling, and perspiration.
  • the use of the oily dispersion (A) on keratin materials, in particular on keratin fibers, makes it possible to obtain a smooth, homogeneous deposit.
  • the keratin fibers remain perfectly individualized, and can be styled without any problem.
  • an “alkyl radical” is a linear or branched saturated Ci-Cs, in particular Ci-Ce, preferably Ci- 04 hydrocarbon-based group such as methyl, ethyl, isopropyl or /-propyl and f-butyl;
  • (Cg-C22)alkyr radical is a saturated, linear or branched C9-C22, in particular C10-C20, preferentially C12-C18, more preferentially C12-C16 hydrocarbon-based group, such as stearyl, behenyl, isodecyl, lauryl, hexadecyl or myristyl;
  • an “alkylene” radical is a linear or branched divalent saturated Ci-Cs, in particular Ci-Ce, preferably C1-C4 hydrocarbon-based group such as methylene, ethylene or propylene;
  • cycloalkyl radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical possibly being substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is an isobornyl group;
  • cyclic radical is a cyclic saturated or unsaturated, aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;
  • an “aryl” radical is a monocyclic or fused or non-fused bicyclic, unsaturated cyclic aromatic radical comprising from 6 to 12 carbon atoms; preferably, the aryl group comprises 1 ring and contains 6 carbon atoms, such as phenyl;
  • an “aryloxy” radical is an aryl-oxy, i.e. aryl-O-, radical, with aryl as defined previously, preferably phenoxy;
  • an “aryl(Ci-C4)alkoxy’ radical is an aryl-(Ci-C4)alkyl-O- radical, preferably benzoxy;
  • keratin materials particularly means human skin (keratinized epithelium) and human keratin fibers such as head hair, the eyelashes, the eyebrows, and bodily hair, preferentially head hair, the eyebrows and the eyelashes, even more preferentially head hair;
  • individualized keratin fibers means keratin fibers, notably the hair, which, after application of the composition and drying, are not stuck together (or of which all the strands are separated from each other) and thus does not form clumps of fibers;
  • the term “insoluble monomer 1 ’ thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e. not fully dissolved at a concentration of greater than 5% by weight at room temperature (20°C) in said medium.
  • the “insoluble” monomers may, as monomers, be soluble or insoluble in the hydrocarbon-based liquid fatty substance(s) iii), it being understood that they become insoluble after polymerization in the hydrocarbon-based liquid(s) iii);
  • homopolymer 1 means a polymer derived from the polymerization of identical monomers
  • copolymer 1 means a polymer derived from the polymerization of different monomers, in particular at least two different monomers.
  • the ethylenic copolymer of the invention is derived from two or three different monomers, more preferentially derived from two different monomers;
  • soluble monomer 1 means any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble to at least 5% by weight, at 20°C, in the hydrocarbonbased liquid fatty substance(s) iii) of the dispersion.
  • the homopolymer is completely dissolved in the carbon-based liquid(s) iii), visually at 20°C, i.e. there is no visible sign of any deposit, or precipitate, or agglomerate, or insoluble sediment.
  • the soluble monomers may, as monomers, be soluble or insoluble in the carbon-based liquid fatty substance(s) iii), it being understood that they become soluble after polymerization in the hydrocarbon-based liquid(s) iii);
  • fatty substance means an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably 1% and even more preferentially 0.1 %). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups.
  • the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated.
  • liquid fatty substance notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C;
  • hydrocarbon-based fatty substance means a fatty substance which comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or even from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of said fatty substance, of carbon-based compound that is liquid at 25°C, having a global solubility parameter in the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , or a mixture of such compounds;
  • oif means a fatty substance that is liquid at room temperature (25°C) and at atmospheric pressure;
  • hydrocarbon-based oif means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups;
  • volatile oif means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure.
  • the volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a nonzero vapor pressure, at room temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 -3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg);
  • nonvolatile oif means an oil with a vapor pressure of less than 0.13 Pa at room temperature and at atmospheric pressure
  • silicone oif means an oil comprising at least one silicon atom and notably at least one Si-0 group.
  • the silicone oil may be volatile or nonvolatile;
  • the term “dispersant’ refers to a compound which can protect the dispersed particles from agglomerating or flocculating.
  • This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed; in particular, they can attach physically or chemically to the surface of the pigments.
  • These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. Said agent may be charged: it may be anionic, cationic, zwitterionic or neutral;
  • pigment refers to any pigment that gives color and/or a nacreous effect to keratin materials, of synthetic or natural origin, the solubility of the pigments in water at 25°C and at atmospheric pressure (760 mmHg) being less than 0.05% by weight and preferably less than 0.01 %;
  • the term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
  • the mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.
  • organic dyes mention may be made of cochineal carmine;
  • hair dyes refers to the oxidation dyes and direct dyes used for dyeing keratin fibers, notably human keratin fibers such as the hair;
  • anhydrous dispersion or composition means a dispersion or composition containing less than 2% by weight of water, or even less than 0.5% of water, and notably free of water; where appropriate, such small amounts of water may notably be provided by ingredients of the composition which may contain residual amounts thereof;
  • pigments with special effects refers to pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from colored pigments, which afford a standard uniform opaque, semi-transparent or transparent shade; and
  • submicron refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometer (pm), in particular between 0.1 pm and 0.9 pm, and preferably between 0.2 pm and 0.6 pm.
  • pm micrometer
  • the oily dispersion (A) of the invention comprises i) one or more particles of at least one polymer that is surface-stabilized with ii) at least one stabilizer in a medium that is preferably anhydrous, also containing iii) at least one hydrocarbon-based liquid fatty substance and iv) at least one plasticizer.
  • the dispersions according to the invention consist of particles, which are generally spherical, of at least one surface-stabilized polymer, in an anhydrous medium.
  • said particles i) are not or are sparingly crosslinked.
  • the particle(s) of the oily dispersion (A) of the invention are preferably constituted of one or more polymers chosen from: a) ethylenic homopolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably ethylenic homopolymers of (Ci-C4)alkyl (meth)acrylate; b) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci-C4)alkyl (meth)acrylate, and of (Ci-C4)(alkyl)acrylic acid, preferably (meth)acrylic acid ethylenic copolymers; c) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably ethylenic copolymers of (Ci-C4)alkyl (me
  • the particle(s) i) are constituted of an ethylenic polymer core derived from homopolymers a) or from copolymers b) or c) as defined previously.
  • the polymer constituting the particles i) is an ethylenic homopolymer of acrylate a) derived from the polymerization of an identical monomer of formula (I):
  • H2C C(RJ-C(O)-O ⁇ -R’ (I) in which formula (I):
  • - R represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl
  • - R’ represents a (Ci-C4)alkyl group such as methyl or ethyl, preferably a C1-C4 alkyl acrylate such as methyl acrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
  • - R is as defined previously, in particular acrylic acid.
  • the amount of acrylic acid ranges from 0.1 % to 15% by weight relative to the weight of monomers of the particle i) and the polymer of the particles i) is in particular a copolymer derived from the copolymerization of acrylic acid with one or more C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth) acrylate and ethyl (meth)acrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
  • the polymer of the particles i) is a polymer derived from C1-C4 alkyl (meth)acrylate monomers.
  • the monomers are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
  • a C1-C4 alkyl acrylate monomer is advantageously used.
  • the monomers are chosen from methyl acrylate and ethyl acrylate.
  • a C1-C4 alkyl methacrylate monomer is particularly used.
  • the monomers are chosen from methyl methacrylate and ethyl methacrylate, more particularly methyl methacrylate.
  • the oily dispersion (A) includes from 2% to 40% by weight, in particular 4% to 25%, notably from 5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
  • the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96%, of monomers a) to c) relative to the total weight of polymers contained in said dispersion.
  • the monomers that are capable of forming the polymeric core of the particle i) are chosen from monomers that are insoluble in the hydrocarbon-based liquid fatty substance(s) iii) of the dispersion (A).
  • the insoluble monomers preferably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle.
  • the particle(s) i) include b) ethylenic copolymers of b1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as benzyl.
  • the ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), (4) and (5):
  • R 1 (R 2 )C C(R 3 )-Acid with R 1 , R 2 and R 3 representing a hydrogen atom ora CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl, phosphoric acid or sulfonic acid, preferably carboxyl, it being understood that R 1 , R 2 and R 3 cannot simultaneously represent a hydrogen atom;
  • H2C C(R)-C(O)-N(R’)-Alk-Acid with R and R’, which may be identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group;
  • Aik represents a (Ci-Ce)alkylene group optionally substituted with at least one group chosen from Acid as defined previously and hydroxyl; and Acid is as defined previously, preferably carboxyl or sulfonic acid;
  • R a , R b and R c which may be identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO2H, H2PO4 or SO3H, preferably substituted with a CO2H or SO3H group;
  • R a , Rb and R c which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; preferably, R a , Rb, and R c represent a hydrogen atom.
  • the ethylenically unsaturated anhydride monomer of the invention is of formula (4b) and more preferentially is maleic anhydride; and
  • H2C C(R)-C(O)-O-H with R representing a hydrogen atom or a (Ci-C4)alkyl group, such as methyl.
  • b2) is a (Ci-C4)(alkyl)acrylic acid; more particularly, b) is (are) copolymers of a (Ci-C4)alkyl (meth)acrylate and of (meth)acrylic acid.
  • b2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and salts thereof, and even more preferentially b2) represents acrylic acid.
  • the polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 nm to 600 nm, notably ranging from 10 nm to 500 nm and better still ranging from 20 nm to 400 nm.
  • the final size of the particles is preferably greater than 100 nm.
  • they have a number-average size ranging from 100 nm to 600 nm, more particularly ranging from 150 nm to 500 nm and even more particularly ranging from 160 nm to 400 nm.
  • the mean size of the particles is determined via conventional methods known to those skilled in the art.
  • a Malvern brand NanoZS model laser particle size analyzer (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples.
  • the operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).
  • DLS dynamic light scattering
  • QELS quasi-elastic light scattering
  • PCS photon correlation spectroscopy
  • the sample is pipetted into a disposable plastic cuvette (four transparent faces, side length of 1 cm and volume of 4 mL) placed in the measuring cell.
  • the data are analyzed on the basis of a cumulant fit method which leads to a monomodal particle size distribution characterized by an intensity-weighted mean diameter d (nm) and a size polydispersity factor Q.
  • the results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode.
  • Nanoparticle Tracking Analysis NTA
  • LS laser scattering
  • AES acoustic extinction spectroscopy
  • the dispersion (A) according to the invention also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention.
  • the stabilizer(s) ii) are chosen from d) ethylenic (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate homopolymers, in particular ethylenic (Cg-Cis)alkyl (Ci-C4)(alkyl)acrylate homopolymers, preferably ethylenic (Cg- C22)alkyl (meth)acrylate homopolymers and more preferentially ethylenic (Cg-Cis)alkyl (meth)acrylate homopolymers.
  • R represents isodecyl, lauryl, stearyl, hexadecyl or behenyl.
  • the stabilizer(s) ii) are chosen from e) ethylenic copolymers of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate and of (Ci- C4)alkyl (Ci-C4)(alkyl)acrylate, particularly copolymers of (Cg-Cis)alkyl (Ci- C4)alkyl)acrylate and of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate.
  • the stabilizer(s) ii) are chosen from the ethylenic copolymers e) of formulae (III) and (IV):
  • - R which may be identical or different, represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl,
  • - R’ which may be identical or different, represents a (Ci-C4)alkyl group such as methyl or ethyl, and
  • R represents a (Cg-C22)alkyl, preferably (Cio-C2o)alkyl and in particular (C2n)alkyl group with n being an integer equal to 5, 6, 7, 8, 9 or 10.
  • R represents isodecyl, lauryl, stearyl, hexadecyl or behenyl, more preferentially stearyl.
  • the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, more particularly stearyl (meth)acrylate (even more preferentially stearyl methacrylate), and C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate and/or ethyl (meth)acrylate.
  • the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate or ethyl (meth)acrylate.
  • the stabilizer(s) ii) are chosen from copolymers e) derived from monomers chosen from e1) isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and hexadecyl (meth)acrylate, more particularly stearyl (meth)acrylate (even more preferentially stearyl methacrylate), and e2) C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate, more particularly methyl acrylate.
  • the copolymer e) complies with a weight ratio e1)/e2) of greater than 4.5.
  • said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
  • the stabilizer ii) is chosen from:
  • the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization e1) of a monomer of formula (IV) as defined previously and e2) of two different monomers of formula (III) as defined previously.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of e1) one monomer of formula (IV) as defined previously notably chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate, and e2) of two different monomers of formula (III) as defined previously, notably different C1-C4 alkyl (meth)acrylate, preferably methyl and ethyl acrylate.
  • said weight ratio e1)/e2) ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
  • the stabilizer(s) ii) are chosen from ethylenic copolymers e) derived from the polymerization e2) of a monomer of formula (III) as defined previously and e1) of two different monomers of formula (IV) as defined previously.
  • the stabilizer(s) ii) are chosen from e) ethylenic copolymers of e1) (Cs-C22)alkyl (Ci-Ce)(alkyl)acrylate and of e2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, as defined previously, in a weight ratio of (Cg-C22)alkyl (Ci-C6)(alkyl)acrylate/(Ci-C4)alkyl (Ci- 04) (alky I) aery I ate e1)/e2) of greater than 4.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of e1) two different monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate, and of e2) one C1-C4 alkyl (meth)acrylate monomer, preferably methyl acrylate or ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate e1)/e
  • the oily dispersion (A) includes from 2% to 40% by weight, in particular 4% to 25%, notably from 5.5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, and of one C1-C4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate in the dispersion (A) is less than 1. In particular, said weight ratio ranges from 0.05 to 0.5 and more preferentially said weight
  • the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.
  • the weight ratio of ii) stabilizer(s) and i) polymer particle(s) is less than 1 , relative to the total weight of polymers.
  • the stabilizer(s) ii) are present in a content ranging from 2% to 40% by weight, notably from 3% to 30% by weight, preferably from 4% to 25% by weight, notably from 5.5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
  • the stabilizer(s) ii) as defined previously preferably comprise 80% to 100% by weight of monomer that is soluble in the hydrocarbon-based liquid fatty substances iii), notably from 85% to 95% by weight of soluble monomer, alone or as a mixture.
  • the stabilizing (co)polymer(s) ii) particularly include between 0% and 20% by weight, notably between 5% and 15% by weight, of monomer that is insoluble in the hydrocarbon-based liquid fatty substances iii), alone or as a mixture.
  • the stabilizer(s) ii) and the particle(s) i) have a number-average molecular weight (Mn) of between 1000 and 1 000 000 g/mol, notably between 5000 and 500 000 g/mol and better still between 10 000 and 300 000 g/mol.
  • Mn number-average molecular weight
  • the dispersion (A) according to the invention is finally formed from polymeric particles of relatively large diameter, i.e. preferably greater than 100 nm, and leads to glossy, film-forming deposits which adhere to keratin materials, which are resistant to fatty substances at room temperature (25°C), and which are notably advantageous for makeup applications.
  • the dispersion of polymer particles (A) according to the invention also comprises iii) one or more hydrocarbon-based liquid fatty substances in which said particles are dispersed.
  • the hydrocarbon-based liquid fatty substances iii) are notably chosen from Ce- Cie hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms, preferably between Ce and C , and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, nonsilicone waxes, and silicones.
  • the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 60 carbon atoms, which are optionally substituted, in particular with one or more hydroxyl groups OH (in particular from 1 to 4 hydroxyl groups). If they are unsaturated, these compounds may comprise one to three unsaturations, preferably from one to three conjugated or unconjugated carboncarbon double bonds.
  • Ce-C alkanes these compounds are linear or branched, and optionally cyclic; preferably, the fatty substance(s) iii) of the invention are chosen from linear or branched Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane or isodecane.
  • the linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®.
  • oils which may be chosen from natural or synthetic, hydrocarbon-based oils, which are optionally fluorinated and optionally branched, alone or as a mixture.
  • the dispersion (A) according to the invention comprises one or more liquid fatty substances which are one or more hydrocarbon-based oils.
  • the hydrocarbon-based oil(s) may be volatile or nonvolatile.
  • the hydrocarbon-based liquid fatty substance(s) iii) are linear or branched hydrocarbon-based oils, which are volatile, notably chosen from undecane, dodecane, isododecane, tridecane, and a mixture of various volatile oils thereof preferably comprising isododecane in the mixture, or a mixture of undecane and tridecane.
  • the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and a nonvolatile oil, the mixture of which preferentially comprises dodecane or isododecane as volatile oil.
  • the hydrocarbon-based liquid fatty substance(s) iii) of the invention are a mixture of C9-C12 alkanes, preferably of natural origin, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes.
  • This mixture is notably known under the INCI name C9-12 Alkane E511470, CAS 68608-12-8, Vegelight Silk® sold by BioSynthls.
  • This biodegradable mixture of volatile oils is obtained from coconut oil (the viscosity is 0.9-1 .1 cSt (40°C) and it has a flash point of 65°C).
  • Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, notably those with a viscosity of less than or equal to 8 centistokes (cSt) (8 x 10' 6 m 2 /s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile linear or cyclic silicone oils notably those with a viscosity of less than or equal to 8 centistokes (cSt) (8 x 10' 6 m 2 /s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • nonvolatile silicone oils mention may be made of linear or cyclic nonvolatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.
  • PDMSs linear or cyclic nonvolatile polydimethylsiloxanes
  • phenyl silicones for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydipheny
  • the hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably:
  • Cs-Cu alkanes such as Cs-Cu isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names,
  • esters containing from 3 to 8 carbon atoms in total
  • ethyl acetate methyl acetate
  • propyl acetate n-butyl acetate
  • oils of plant origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil or coconut oil; shea
  • hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof,
  • esters such as the oils of formula R 1 C(O)-O-R 2 in which R 1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R 2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R 1 + R 2 > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, Ci2 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2- octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, de
  • - 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 octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol.
  • the dispersion (A) may comprise a silicone oil. If silicone oil is in the dispersion (A), it is preferably in an amount which does not exceed 10% by weight relative to the weight of the dispersion (A), more particularly in an amount of less than 5% and preferentially 2%.
  • the dispersion (A) comprises at least one hydrocarbon-based liquid fatty substance iii) chosen from:
  • - plant oils formed by fatty acid esters of polyols in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil, coconut oil or cereal germ oil;
  • triglycerides such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil, coconut oil or cereal germ oil;
  • esters of formula R d -C(O)-O-R e in which R d represents a higher fatty acid residue including from 7 to 19 carbon atoms and R e represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; more preferentially esters of formula R d -C(O)-O-R e in which R d represents a higher fatty acid residue including from 8 to 10 carbon atoms and R e represents a hydrocarbon-based chain including from 12 to 18 carbon atoms;
  • volatile or nonvolatile linear, branched and/or cyclic alkanes such as optionally volatile Cs-Ceo isoparaffins, such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or Isopars, and mixtures thereof; or alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane, the mixture of C9-C12 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes, in particular comprising dodecane, or else liquid paraffin, liquid petroleum jelly, or hydrogenated polyisobutylene;
  • Cs-Ceo isoparaffins such as undecane, dodecane, isododecane
  • ketones containing 6 to 30 carbon atoms aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbonbased chain not including any substitution groups, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol;
  • the dispersion (A) comprises at least one hydrocarbon-based liquid fatty substance iii) chosen from: plant oils formed by fatty acid esters of polyols, in particular triglycerides,
  • R d -C(O)-O-R e in which R d represents a higher fatty acid residue including from 7 to 19 carbon atoms and R e represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, more preferentially esters of formula R d -C(O)-O-R e in which R d represents a higher fatty acid residue including from 8 to 10 carbon atoms and R e represents a hydrocarbon-based chain including from 12 to 18 carbon atoms;
  • Cs-Ceo alkanes such as isododecane and alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids obtained from Cocos nucifera (coconut) oil, in particular dodecane;
  • the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
  • the hydrocarbon-based liquid fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils described previously.
  • the liquid fatty substance(s) iii) of the invention are chosen from alkanes such as dodecane, isododecane, fatty alcohols such as octyldodecanol, esters such as isononyl isononanoate, cocoyl caprylate/caprate and mixtures thereof, more preferentially alkanes.
  • alkanes such as dodecane, isododecane, fatty alcohols such as octyldodecanol, esters such as isononyl isononanoate, cocoyl caprylate/caprate and mixtures thereof, more preferentially alkanes.
  • the liquid fatty substance(s) iii) of the invention are chosen from linear or branched Ce-C , preferably Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes, and even more preferentially the alkanes are volatile. More particularly, the liquid fatty substance(s) iii) of the invention are volatile and are chosen from undecane, dodecane, isododecane, tridecane, and a mixture thereof notably comprising dodecane, isododecane or a mixture of undecane and tridecane.
  • liquid fatty substance(s) iii) of the invention are isododecane.
  • the liquid fatty substance(s) iii) are a mixture of nonvolatile oil(s) and volatile oil(s); preferably, the mixture comprises, as volatile oil, undecane, dodecane, isododecane or tridecane, more preferentially isododecane.
  • a mixture of volatile oil and nonvolatile oil that may be mentioned is the mixture of isododecane and of isononyl isononanoate.
  • the amount of volatile oil is greater than the amount of nonvolatile oil.
  • the nonvolatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
  • the dispersion according to the invention may be prepared in the following manner:
  • the polymerization is performed in “dispersion” in nonaqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from d) and e) as defined previously.
  • the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer d) or e) with v) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
  • the constituent monomer(s) of the polymer of the particles i) are added to the stabilizing polymer formed in the preceding step and polymerization of these added monomers is performed in the presence of the free-radical initiator.
  • the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon-based liquid fatty substance (which must be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
  • synthesis solvent apolar organic solvent
  • the plasticizer(s) iv) and optionally one or more cosmetic active agents chosen from f) dyes and/or pigments, g) active agents for caring for keratin materials, notably the skin, and h) UV-screening agents and also j) mixtures thereof, may be added during the first step.
  • the plasticizer(s) iv) are added during the second step.
  • the plasticizer(s) iv) form an integral part of the particles i) and stabilizers ii) in the oil iii).
  • integral part means that the plasticizer(s) have reacted chemically with the particle(s) i) and/or with the stabilizer(s) ii), notably with i) during the polymerization.
  • the plasticizer(s) iv) are added after the second step, in a third step.
  • said cosmetic active agent(s) are added during the second step with said plasticizer(s) iv) or after the second step or even after the third step. It follows that in the second and third variants, the plasticizer(s) iv) do not form an integral part of the particle(s) i) and of the stabilizer(s) ii).
  • the dispersion (A) then comprises: one or more particles i) (preferentially constituting the ethylenic polymeric core derived from homopolymers a) or the copolymers b) or c), as defined previously) associated with ii) one or more stabilizers (preferentially ii) being at the polymeric surface of said cores i), derived from the homopolymer d) and the copolymers e) as defined previously); one or more liquid fatty substances iii); one or more plasticizers iv); and optionally one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and j) UV (A) and/or (B) screening agents, and also m) mixtures thereof; it being understood that the plasticizer(s) iv) do not form an integral part of the particle(s) i) and of the stabilizer(s) i
  • a synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator v) are soluble therein, and such that the polymer particles i) obtained are insoluble therein, so that they precipitate therefrom during their formation, is preferably chosen.
  • the synthesis solvent also dissolves the plasticizer(s) iv) of the invention.
  • the synthesis solvent chosen is one which is an apolar, organic solvent, preferably chosen from liquid fatty substances iii), in particular alkanes such as heptane, cyclohexane, undecane, dodecane, isododecane or tridecane, preferably isododecane.
  • the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent.
  • the monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein.
  • the monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of from 15% to 45% by weight.
  • the total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds.
  • the polymerization is preferentially performed in the presence v) of one or more radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators.
  • tert-butyl peroxy-2-ethylhexanoate Trigonox 21S
  • 2,5- dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane Trigonox 141
  • tert-butyl peroxypivalate Trigonox 25C75 from AkzoNobel; or
  • - azo in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2’-azobis(2- amidinopropane) dihydrochloride.
  • the polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.
  • the polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).
  • the stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
  • the stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously. [00124] From 2% to 40% by weight and notably from 4% to 30% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)), preferably from 5% to 25% by weight and preferably from 4.5% to 20% by weight, relative to the total weight of the dispersion (A).
  • the polymer particle dispersion (A) advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion.
  • composition according to the invention preferably comprises a solids (or active material) content of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of composition (A), preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight, relative to the total weight of composition (A).
  • the dispersion (A) according to the invention is an anhydrous composition.
  • the dispersion (A) is in inverse emulsion, i.e. of water-in-oil (W/O) type.
  • the composition comprises one or more surfactants, which are preferably nonionic.
  • the inverse emulsions of (A) are preferably chosen when the dispersions (A) are intended for makeup, and notably for making up the eyelashes and/or eyebrows.
  • the statistical stabilizing polymer ii) is prepared in a first step. This stabilizing polymer is soluble in an apolar organic solvent of alkane type, such as isododecane.
  • the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
  • a solution of stabilizing polymer ii) in the hydrocarbon-based liquid fatty substance(s) iii) is prepared for the final dispersion, and the polymerization of the monomers which form the core of the particle is performed in the presence of this stabilizer ii).
  • the stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator v) as defined previously.
  • the monomers which form the core of the particle i) may be polymerized in the presence of said stabilizing polymer ii).
  • This second step may be a conventional radical polymerization.
  • the dispersions are prepared in the presence of one or more hydrocarbon-based liquid fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
  • the dispersions according to the invention are thus finally formed from polymer particles, of relatively large diameter (preferably greater than 100 nm), and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C).
  • said dispersion is in oily medium, it becomes easy to formulate it in cosmetic compositions based on oily medium commonly used in cosmetics, in particular anhydrous media or in the fatty phases of emulsions.
  • Emulsions that may be mentioned include “inverse emulsions” of water-in-oil (W/O) type or “direct” emulsions of oil-in-water (O/W) type.
  • the polymer according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in lipsticks, glosses (lip glosses) and eyeshadows and mascaras.
  • plasticizer or “plasticizing agent’ means an organic chemical compound, which is in solid state or in liquid state, at room temperature (20°C) and at atmospheric pressure, and which is generally added to a composition comprising different types of polymerizable ingredients (monomers) to make the polymers more supple, more flexible, and/or to improve their mechanical strength.
  • Plasticizers are known to those skilled in the art; mention may be made, for example, of “Plasticizers”, Encyclopedia of polymer Science and Technology, Helmut Reinecke, Rodrigo Navarro, Monica Perez, https://doi.Org/10.1002/0471440264. pst245.pub215 September 2011.
  • the plasticizers have a molecular weight of between 150 and 1000 g/mol, particularly between 200 and 700 g/mol, preferably between 205 and 500 g/mol and even more preferentially between 210 and 400 g/mol.
  • the plasticizers are also organic compounds consisting of carbon and hydrogen atoms and of one or more heteroatoms chosen from oxygen, sulfur and silicon atoms, in particular chosen from oxygen atoms, preferably at least 2 heteroatoms, even more preferentially between 2 and 10 heteroatoms, and which may contain one or more aryl groups.
  • the plasticizers according to the invention comprise one or more ester functions, notably from 1 to 5 ester functions such as citrates, phthalates, adipates or benzoates, or esters R a -C(O)-O-R b or R a -O-C(O)-R b in which R a denotes a branched (Ci-Ce)alkyl group such as a tert-butyl and R b denotes a branched, preferably saturated, (Cs-C2o)alkyl group such as an isodecyl group or an isostearyl group.
  • ester functions notably from 1 to 5 ester functions such as citrates, phthalates, adipates or benzoates, or esters R a -C(O)-O-R b or R a -O-C(O)-R b in which R a denotes a branched (Ci-Ce)alkyl group such as
  • the plasticizer(s) of the invention are chosen from those of the families of linear or branched, preferably branched, C8-C20 alkyl phthalates, esters, citrates, benzoates and neopentanoates.
  • the plasticizer(s) are chosen from compounds (V) and (V’) below:
  • Rh-O-CfOJ-L-t-CfOJ-O-RJn Rh-CfOJ-O-L-t-O-CfOJ-RJn
  • R h and R 1 which may be identical or different, represent a group from among: (Ci-C2o)alkyl, aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, preferably (Ci-C4)alkyl such as n-butyl;
  • - n is 0, 1 , 2 or 3, preferably 0, 1 or 2, more preferentially, 1 or 2;
  • - L represents a group from among: a) monovalent, divalent, trivalent or tetravalent C1-C10 alkyl, preferably trivalent (C2-Cs)alkyl, said monovalent, divalent, trivalent or tetravalent alkyl possibly being optionally substituted with one or more hydroxyl groups, optionally interrupted with at least one heteroatom such as O, N or S, preferably O, b) monovalent, divalent or trivalent cycloalkyl, or c) monovalent, divalent, trivalent or tetravalent aryl, preferably divalent or trivalent phenyl; preferably, L represents a group a) or c).
  • the compounds of formula (V) or (V’) are those in which:
  • R h and R 1 which may be identical or different, represent a group from among: (Ci -Ci s)al ky I , aryl(Ci-C4)alkyl such as benzyl, preferably (Ci-C4)alkyl such as n-butyl;
  • - n is 0, 1 or 2, preferably 2; and - L represents a group from among: a) monovalent, divalent or trivalent C2-C8 alkyl, preferably (C2-Ce)alkyl, said alkyl possibly being optionally substituted with one or more hydroxyl groups, preferably substituted with one hydroxyl group.
  • the plasticizer(s) iv) are chosen from those of formula (V).
  • the plasticizer(s) iv) are chosen from those of formula (V’).
  • the plasticizer(s) are chosen from phthalates, preferably chosen from: di-n-hexyl phthalate (DnHP), diisoheptyl phthalate (DIHP), diheptyl phthalate (DnHP), bis(2-ethylhexyl) phthalate (DEHP), diheptylnonyl phthalate (DnHNP) di-n-octyldecyl phthalate (DNODP), diheptylnonylundecyl phthalate (DnHNUP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), di-n-nonyl phthalate (DnNP), diisodecyl phthalate (DIDP), di-n-nonyldecylundecyl phthalate (DnNDUP), dinonylundecyl phthalate (Dn
  • the plasticizer(s) are chosen from adipic acid diesters and notably from: diheptylnonyl adipate (DnHNA), bis(2- ethylhexyl) adipate (DEHA), diisopropyl adipate (DI PA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), benzene 1 ,2,4-tricarboxylic acid triesters such as triheptylnonyl trimellitate (TnHNTM), tris(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), sebacic acid diesters such as bis(2-ethylhexyl) sebacate (DOS), nonanedioic acid diesters such as bis(2-ethylhexyl) azelate (DOZ), esters, adipic acid diesters and notably
  • the plasticizer(s) are chosen from citrates, notably chosen from: tributyl citrate, triethyl citrate, tributyl 2- acetylcitrate.
  • the plasticizer(s) are chosen from benzoates, in particular chosen from: 1 ,2-propylene glycol dibenzoate (PGDB), diethylene glycol dibenzoate (DEGDB), dipropylene glycol dibenzoate (DPGDB), triethylene glycol dibenzoate (TEGDB), isodecyl benzoate, isononyl benzoate and 2- ethylhexyl benzoate.
  • PGDB ,2-propylene glycol dibenzoate
  • DEGDB diethylene glycol dibenzoate
  • DPGDB dipropylene glycol dibenzoate
  • TEGDB triethylene glycol dibenzoate
  • isodecyl benzoate isononyl benzoate
  • 2- ethylhexyl benzoate 2- ethylhexyl benzoate.
  • the plasticizer(s) iv) of the invention are chosen from isodecyl neopentanoate, isostearyl neopentanoate, tributyl citrate, diisopropyl adipate and propylene glycol dibenzoate.
  • the plasticizer(s) are present in an amount of between 0.1% and 50% by weight and preferably from 0.5% to 30% by weight relative to the total weight of the polymer(s) a) to e) of the particles.
  • the dispersion (A) of the invention comprises one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, and j) UV (A) and/or (B) screening agents, and also k) mixtures thereof.
  • the cosmetic active agent(s) of the invention are chosen from g) pigments.
  • the cosmetic active agent(s) of the invention are chosen from h) active agents for caring for keratin materials, preferably skincare active agents.
  • the cosmetic active agent(s) of the invention are chosen from j) IIV(A) and/or IIV(B) screening agents, and a mixture thereof.
  • the dispersion (A) comprises v) one or more cosmetic active agents chosen from g) pigments.
  • the pigment(s) more particularly represent from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the dispersion (A).
  • the pigments are white or colored solid particles which are naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which are rendered insoluble by formulation in the form of a lake, where appropriate. More particularly, the pigments have little or no solubility in aqueous-alcoholic media.
  • the pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry. Pigments that may notably be mentioned include organic and mineral pigments such as those defined and described in Ullmann’s Encyclopedia of Industrial Chemistry “Pigments, organic”, 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, “Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a20_243. pub3
  • These pigments may be in pigment powder or paste form. They may be coated or uncoated.
  • the pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.
  • the pigment may be a mineral pigment.
  • the term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments.
  • the pigment may be an organic pigment.
  • organic pigment refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments.
  • the organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
  • the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the blue pigments codified in
  • the pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including a mineral core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core. [00171]
  • the organic pigment may also be a lake.
  • the term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
  • the inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum.
  • Mention may be made, among the dyes, of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45 380), D&C Orange 5 (Cl 45 370), D&C Red 27 (Cl 45 410), D&C Orange 10 (Cl 45 425), D&C Red 3 (Cl 45 430), D&C Red 4 (Cl 15 510), D&C Red 33 (Cl 17 200), D&C Yellow 5 (Cl 19 140), D&C Yellow 6 (Cl 15 985), D&C Green 5 (Cl 61 570), D&C Yellow 10 (Cl 77 002), D&C Green 3 (Cl 42 053), D&C Blue 1 (Cl 42 090).
  • D&C Red 21 Cl 45 380
  • D&C Orange 5 Cl 45 370
  • D&C Red 27 Cl 45 410
  • D&C Orange 10 Cl 45 425
  • An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (Cl 15 850:1).
  • the pigment may also be a pigment with special effects.
  • the term “pigments with special effects” means pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from colored pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
  • pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
  • pigments with special effects include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride.
  • Nacreous pigments that may be mentioned include the Cellini nacres sold by BASF (mica-TiO2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3), and Colorona sold by Merck (mica-TiO2-Fe2O3).
  • nacres include a borosilicate substrate coated with titanium oxide.
  • Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
  • nacres examples include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver 1 P 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum.
  • the pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light.
  • This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.
  • the reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined, and more particularly so as to optimize this effect in terms of color rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or tint.
  • These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
  • the reflective particles may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material.
  • the reflective particles may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
  • the reflective particles may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material.
  • the substrate may be made of one or more organic and/or mineral materials.
  • glasses may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
  • the reflective material may include a layer of metal or of a metallic material.
  • Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541 , JP-A-07258460 and JP-A-05017710.
  • Particles with a silver-coated glass substrate in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal.
  • Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
  • Use may also be made of particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
  • a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium
  • Pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
  • the variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colors, and also particular optical effects such as metallic effects or interference effects.
  • the size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.
  • the pigments may be dispersed in the composition by means of a dispersant.
  • the dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof.
  • This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments.
  • These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium.
  • esters of 12-hydroxystearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.
  • poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel
  • dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
  • Solsperse 17 000 sold by the company Avecia
  • polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
  • the pigments used in the composition may be surface-treated with an organic agent.
  • the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention.
  • organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
  • the surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have under
  • the surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
  • the surface-treated pigments are coated with an organic layer.
  • the organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.
  • the surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.
  • An organic agent covalently bonded to the pigments will preferably be used.
  • the agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
  • the surface treatments of the pigments are chosen from the following treatments:
  • PEG-silicone treatment such as the AQ surface treatment sold by LCW;
  • methicone treatment such as the SI surface treatment sold by LCW;
  • dimethicone treatment such as the Covasil 3.05 surface treatment sold by LCW;
  • dimethicone/trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment sold by LCW;
  • a magnesium myristate treatment such as the MM surface treatment sold by LCW;
  • an aluminum dimyristate treatment such as the Ml surface treatment sold by Miyoshi;
  • an isostearyl sebacate treatment such as the HS surface treatment sold by Miyoshi;
  • an acrylate/dimethicone copolymer and perfluoalkyl phosphate treatment such as the FSA surface treatment sold by Daito;
  • a polymethylhydrosiloxane/perfluoroalkyl phosphate treatment such as the FS01 surface treatment sold by Daito;
  • an acrylate/dimethicone copolymer treatment such as the ASC surface treatment sold by Daito;
  • an isopropyl titanium triisostearate treatment such as the ITT surface treatment sold by Daito;
  • an acrylate copolymer treatment such as the APD surface treatment sold by Daito;
  • PF + ITT surface treatment sold by Daito.
  • the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition.
  • the dispersant and the pigment(s) are present in an amount (dispersantpigment) of between 1 :4 and 4:1 , particularly between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.
  • the dispersant(s) may thus have a silicone backbone, such as silicone polyether and dispersants of amino silicone type other than the alkoxysilanes described previously.
  • a silicone backbone such as silicone polyether and dispersants of amino silicone type other than the alkoxysilanes described previously.
  • suitable dispersants that may be mentioned are:
  • - aminosilicones i.e. silicones comprising one or more amino groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851 , GP-965, GP-967 and GP-988-1 , sold by Genesee Polymers,
  • Tego® RC 902 Tego® RC 922, Tego® RC 1041 , and Tego® RC 1043, sold by Evonik,
  • PDMS polydimethylsiloxane
  • the dispersant(s) are of amino silicone type other than the alkoxysilanes described previously and are cationic.
  • the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
  • the pigment(s) according to the invention are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds.
  • the pigment(s) according to the invention are mineral pigments.
  • composition may comprise f) one or more direct dyes.
  • direct dye means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fiber.
  • They may be ionic or nonionic, preferably cationic or nonionic.
  • Suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
  • the direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (VI) and (VII) and the azo cationic dyes (VIII) and (IX) below:
  • Het + represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cs)alkyl group such as methyl;
  • Ar + represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C8)alkylammonium, such as trimethylammonium;
  • Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cs)alkyl, ii) optionally substituted (Ci-Cs)alkoxy, iii) (di)(Ci-Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino or alternatively Ar represents a julolidine group;
  • - Ar’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci-Cs)alkyl, hydroxyl, (di)(Ci-Cs)(alkyl)amino, (Ci-Cs)alkoxy or phenyl groups;
  • Ra and Rb which may be identical or different, represent a hydrogen atom or a (Ci- Cs)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or else the substituent Ra with a substituent of Het + and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
  • - Q- represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
  • R 1 representing a (Ci-C4)alkyl group such as methyl
  • R 2 and R 3 which may be identical or different, represent a hydrogen atom or a (Ci-
  • R 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs) alkoxy, or (di)(Ci-Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R 4 is a hydrogen atom,
  • - Z represents a CH group or a nitrogen atom, preferentially CH
  • - Q- is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesyl.
  • the dyes of formulae (IX) and (X) are chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q’ being an anionic counterion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.
  • the dyes are liposoluble. They are chosen, for example, from Sudan Red, D&C Red 17, D&C Green 6, p-carotene, soybean oil, Sudan Brown, D&C Yellow 11 , D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.
  • the water-soluble dyes are, for example, beetroot juice or methylene blue.
  • the cosmetic active agent(s) v) are chosen from the following pigments: carbon black, iron oxides, notably black, and micas coated with iron oxide, red iron oxides (iron(lll) oxide, also known as ferric oxide), triarylmethane pigments, notably blue and violet, such as Blue 1 Lake, azo pigments, notably red, such as D&C Red 7, alkali metal salt of lithol red, such as the calcium salt of lithol red B.
  • the amount of pigments ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the dispersion (A) comprising them.
  • the dispersion (A) comprises iv) one or more cosmetic active agents chosen from oxidation dyes.
  • - oxidation dyes which are generally chosen from one or more oxidation bases, optionally combined with one or more coupling agents.
  • the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts, optionally combined with coupling agents; they may particularly be chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, naphthalene-based coupling agents and heterocyclic coupling agents and also the corresponding addition salts;
  • direct dyes notably azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
  • the direct dyes may be anionic, cationic or neutral;
  • - natural dyes notably chosen from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein, and also extracts or decoctions containing these natural dyes.
  • the pigment(s) of the invention are chosen from carbon black, iron oxides, notably red, brown or black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and purple triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red B; more preferentially, the pigment(s) used are chosen from red iron oxides and azo pigments, notably red azo pigments such as D&C Red 7.
  • the amount of pigments ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the composition and dispersion (A) comprising them.
  • a subject of the invention is also a process for treating keratin materials by applying the dispersion (A) to said materials.
  • the process for treating keratin materials comprises the step of applying the dispersion (A) to said materials.
  • the process of the invention is a process notably for making up keratin materials, preferably facial skin such as the lips.
  • the makeup process of the invention uses the dispersion (A) which comprises at least one cosmetic agent v) chosen from f) dyes and g) pigments; more preferentially, the dispersion comprises g) one or more pigments.
  • the process for treating keratin materials is a process for making up the skin and/or the eyelashes or the eyebrows, involving a step of applying the dispersion (A) comprising at least one dye and/or at least one pigment, preferably at least one pigment.
  • the dispersion (A) used in the process for treating keratin materials comprises one or more cosmetic active agents v).
  • the dispersion (A) according to the invention may also comprise a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, dyestuffs other than f), dyes and g) pigments.
  • a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, dyestuffs other than f), dyes and g) pigments.
  • the dispersions of polymer particles presented in the various examples were prepared in 1 liter pilot reactors.
  • the syntheses are performed in an apolar aprotic organic solvent such as isododecane.
  • the synthetic process is identical for all the dispersions obtained.
  • the statistical stabilizing polymer is synthesized by reaction between the C9-C22 alkyl (meth)acrylate and a small amount of one or two different (Ci-C4)alkyl (C1- C4)(alkyl)acrylates, preferably (Ci-C4)alkyl (meth)acrylate such as methyl acrylate or methyl acrylate + ethyl acrylate.
  • the reaction is performed at 90°C for 2 hours.
  • the particle core is obtained after introducing the (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate ethylenically unsaturated monomers, preferably (Ci-C4)alkyl (meth)acrylate and optionally (C1- C4)(alkyl)acrylic acid, preferably (meth)acrylic acid such as acrylic acid; into the reaction medium containing the stabilizing polymer.
  • This second step is performed at 90°C for 5 hours.
  • the percentage of active material in the hydrocarbon-based liquid fatty substance(s) iii) such as isododecane is finally between 40% and 55%, such as 50%.
  • the polymerization initiator is Trigonox T21S.
  • the CAS and the supplier of this initiator are given in Table 2: Polymerization initiator used in the various examples [00248] [Table 1]:
  • the oily dispersions are formed as a whole (polymer particles i) + polymeric stabilizer ii)) with 94.5% of methyl acrylate and 5.5% of stearyl methacrylate.
  • the synthesis of these oily dispersions was performed in a 1 liter pilot reactor. The synthesis is performed in two steps:
  • stearyl methacrylate is polymerized in isododecane in the presence of a small amount of methyl acrylate and of a radical initiator (T21S).
  • T21S a radical initiator
  • the stearyl methacrylate/methyl acrylate mass ratio is 85/15.
  • the rest of the methyl acrylate is added in the presence of isododecane and of the radical initiator (T21S).
  • Step 1
  • Isododecane, stearyl methacrylate, methyl acrylate and T21S are introduced as feedstock into the reactor.
  • the medium is heated to 90°C (nominal medium temperature) under argon and with stirring.
  • the solids content during this first step is 22%.
  • the plasticizer is added.
  • the amount of plasticizer added is 10% by mass relative to the total weight of the polymer of the particles (stabilizer + core). Thus, for 20% polymer active material of the particles, 2% by mass of plasticizer were added.
  • the plasticizer was added at room temperature (20°C) with stirring. Once the particle dispersion + plasticizer mixture is homogeneous, the cosmetic active agents such as pigments are added, still at room temperature and with stirring.
  • a formulation containing a particle dispersion of the invention was prepared. This formulation was applied to a wet thickness of 50 pm onto two glass supports:
  • FP40 type support FP40 (Trellborg, N4I01)* is an elastomeric substrate made of butadiene-acrylonitrile copolymer containing a diethylhexyl sebacate oil, which approximates to skin sebum, as plasticizer.
  • a polymer conveyed in isododecane is applied to this substrate, extraction of the plasticizer is performed, mimicking the contribution/impact of sebum on the Bioskin type support coating: elastomer support simulating a polyurethane elastomer skin reinforced with elastane (particular polyurethane) - manufactured by Beaulax (Japan).
  • the deposit was left to dry for 24 hours. After 24 hours of drying, the deposits were evaluated. After drying for one day, the BioSkin or FP40 plate is stretched, by hand force, this being done 10 times.
  • the result may then be observed on the formulation film (fragmentation or otherwise).
  • the in vitro substrate before deposition is 10 cm long and 6 cm wide. A coating measuring 6 cm in length and 5 cm in width is applied to this substrate.
  • the substrate + coating assembly is stretched in the same manner with the same force for the various tests to achieve a 40% stretch in the direction of the length of the substrate + coating (14 cm).

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Abstract

The present invention relates to an oily dispersion (A) comprising: at least one particle consisting of an ethylenic polymer i), at least one polymeric stabilizer comprising a (C9- C22)alkyl group ii), at least one hydrocarbon-based fatty substance which is liquid at 20°C and 1 atmosphere iii), and at least one plasticizer iv). The invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin, the hair or the eyelashes, involving the application to said materials of at least one oily dispersion (A); to a process for preparing the oily dispersion, and to a multi-compartment kit comprising ingredients i) to iv). The oily dispersion (A) and the process for treating keratin materials as defined above make it possible to obtain a treatment for said materials which is notably resistant to shampoo washing, to sebum, to sweat and/or to water, but also to fatty substances, notably dietary fats such as oils.

Description

Description
Title: OILY DISPERSION COMPRISING A POLYMERIC PARTICLE AND A STABILIZER BEARING A C9-C22 ALKYL GROUP AND A PLASTICIZER, AND PROCESS FOR TREATING KERATIN MATERIALS USING THE OILY DISPERSION
[0001] The present invention relates to an oily dispersion (A) comprising: at least one particle consisting of an ethylenic polymer i), at least one polymeric stabilizer comprising a (Cg-C22)alkyl group ii), at least one hydrocarbon-based fatty substance which is liquid at 20°C and 1 atmosphere iii), and at least one plasticizer iv). The invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin, the hair or the eyelashes, involving the application to said materials of at least one oily dispersion (A); to a process for preparing the oily dispersion, and to a multi-compartment kit comprising ingredients i) to iv).
[0002] During the aging process, various signs appear on the skin which are very characteristic of this aging, reflected notably by a change in the skin structure and functions. The main clinical signs of skin aging are notably the appearance of fine lines and deep wrinkles, which increase with age.
[0003] It is known practice to treat these signs of aging using cosmetic or dermatological compositions containing active agents that are capable of combating aging, such as a- hydroxy acids, p-hydroxy acids and retinoids. These active agents act on wrinkles by eliminating dead skin cells and by accelerating the cell renewal process. However, these active agents have the drawback of being effective for the treatment of wrinkles only after a certain application time. Now, it is increasingly sought to obtain an immediate effect of the active agents used, rapidly resulting in smoothing-out of wrinkles and fine lines and in the disappearance of fatigue marks.
[0004] Cosmetic products often require the use of a film-forming polymer to obtain a deposit of the product on keratin materials that has good cosmetic properties. In particular, it is necessary for the film-forming deposit to have good persistence, in particular for the deposit not to transfer during contact with the fingers or clothing, and also good resistance on contact with water, notably rain or during showering and for the deposit to be insensitive to perspiration or sebum, and also food fats, notably dietary fats such as oils.
[0005] It is known practice to use dispersions of polymer particles, in organic media such as hydrocarbon-based oils. Polymers are notably used as film-forming agents in makeup products such as mascaras, eyeliners, eyeshadows or lipsticks. EP 0 749 747 describes in the examples dispersions in hydrocarbon-based oils (liquid paraffin, isododecane) of acrylic polymers stabilized with polystyrene/copoly(ethylene-propylene) diblock copolymers. The film obtained after application of the dispersion to the skin is sparingly glossy. FR 1 362 795 also describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon-based oils for making up the lips and the eyelashes. WO 2010/046 229 describes dispersions in isododecane of acrylic polymers stabilized with stabilizing polymers. FR 1 362 795 describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon-based oils for making up the lips and the eyelashes.
[0006] In the field of dyeing keratin fibers, it is already known practice to dye keratin fibers via various techniques using direct dyes for non-permanent dyeing, or dye precursors for permanent dyeing.
[0007] Non-permanent dyeing or direct dyeing consists in dyeing keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules that have affinity for keratin fibers. They are applied to the keratin fibers for a time necessary to obtain the desired coloring, and are then rinsed out.
[0008] The standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural dyes.
[0009] Some of these dyes may be used under lightening conditions, which enables the production of colorings that are visible on dark hair.
[0010] It is also known practice to dye keratin fibers permanently via oxidation dyeing. This dyeing technique consists in applying to the keratin fibers a composition containing dye precursors such as oxidation bases and couplers. Under the action of an oxidizing agent, these precursors form one or more colored substances in the hair.
[0011] The variety of molecules used as oxidation bases and couplers allows a wide range of colors to be obtained, and the colorings resulting therefrom are generally permanent, strong and resistant to external agents, notably to light, bad weather, washing, perspiration and rubbing.
[0012] In order to be visible on dark hair, these two dyeing techniques require prior or simultaneous bleaching of the keratin fibers. This bleaching step, performed with an oxidizing agent such as hydrogen peroxide or persalts, results in appreciable degradation of the keratin fibers, which impairs their cosmetic properties. The hair then has a tendency to become coarse, more difficult to disentangle and more brittle. [0013] Another coloring method consists in using pigments. Specifically, the use of pigment on the surface of keratin fibers generally makes it possible to obtain colorings that are notably visible on dark hair, since the surface pigment masks the natural color of the fiber. The use of pigment for dyeing keratin fibers is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibers, a composition comprising at least one dispersion of film-forming polymer particles comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.
[0014] The colorings obtained via this dyeing method become removed from the very first shampoo wash.
[0015] It is moreover known from patent application FR 2 907 678 to perform colored coating of the hair using a composition comprising a polysiloxane/polyurea block copolymer and a pigment. However, with such a composition, the coating results obtained may occasionally lack homogeneity and the strand separation after combing is not always satisfactory.
[0016] FR 3 014 875 describes the use of a dispersion of C1-C4 alkyl (meth)acrylate polymer particles surface-stabilized with an isobornyl (meth)acrylate polymeric stabilizer in a non-aqueous medium containing an oil. The deposits obtained using this technology are not always satisfactory, notably in terms of resistance to sebum.
[0017] FR 3 029 786 is focused on makeup dispersions of polymer particles stabilized with at least one stabilizer which is a Cs alkyl (meth)acrylate homopolymer or a copolymer of Cs alkyl (2-ethylhexyl) (meth)acrylate and of C1-C4 alkyl (meth)acrylate. These dispersions are not always satisfactory in terms of resistance to fatty substances or sebum, which may be a curb on their use in lip makeup, for example. Furthermore, these dispersions may have a feel that is considered too “tacky” after application to the keratin materials, which may be prohibitive for certain applications such as lip or eyelash makeup, etc.
[0018] It is also known practice to use other polymer particles stabilized with C9-C22 alkyl (alkyl)acrylate polymers, notably for hair treatment (see FR 3 097 756).
[0019] Thus, the aim of the present invention is to provide a composition for treating keratin materials, in particular the skin, preferably human skin and more preferentially facial skin, the residual film of which after application to said keratin materials adheres well to the keratin materials, is elastic and shows the least possible fragmentation and the least possible detachment from the substrate, which is not tacky, has good persistence with respect to external attacking factors, and over time, does not leach, is resistant to sweat and to sebum, and is relatively insensitive to oils such as dietary oils, notably to sebum. Moreover the keratin material after being treated with the composition of the invention is pleasant to the touch (soft, smooth and touch even), the color when the said composition comprises at least one dye and/or at least one pigment is homogeneous. The appearance keratin material after application on keratin is very aesthetic, from matte, satin to gloss, preferably gloss satin, more preferably gloss.
[0020] Another aim of the present invention is to provide a composition for treating keratin fibers, notably human keratin fibers such as the hair, the eyelashes or the eyebrows, the residual film of which after application to said fibers adheres well to the fibers, without any fragmentation/detachment from said fibers, which has good persistence with respect to attacking factors such as brushing, does not leach, is resistant to sweat, sebum, light and bad weather, and is persistent with respect to shampoo washing and to the various attacking factors to which said fibers may be subjected, notably to sebum, without degrading said fibers, and while keeping the keratin fibers perfectly individualized.
[0021] The technical problem has been solved by using an oily dispersion (A) for treating keratin materials, notably human keratin materials such as the hair, the eyelashes or the skin, in which the oily dispersion (A) is preferably anhydrous, and comprises: i) one or more particles including one or more polymers chosen from: a) ethylenic homopolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci- C4)alkyl (meth)acrylate; b) ethylenic copolymers of b1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl; in particular, b2) is a (Ci-C4)(alkyl)acrylic acid such as (meth)acrylic acid, more particularly copolymers of (Ci-C4)alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci-C4)alkyl (meth)acrylate; and ii) one or more polymeric stabilizers chosen from: d) ethylenic homopolymers of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate, preferably ethylenic homopolymers of (Cg-C22)alkyl (meth)acrylate; and e) ethylenic copolymers of e1) (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate, and of e2) (Ci- C4)alkyl (Ci-C4)(alkyl)acrylate; preferably, the copolymers e) are copolymers of (Cg- C22)alkyl (meth) acrylate and of (Ci-C4)alkyl (meth)acrylate; iii) one or more hydrocarbon-based liquid fatty substances; iv) one or more plasticizers; and v) optionally one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and j) UV (A) and/or (B) screening agents, and also m) mixtures thereof.
[0022] More particularly, the subject of the invention relates to the use of the oily dispersion (A) as defined previously for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, preferably for dyeing keratin fibers and/or for shaping keratin fibers such as the hair, for caring for keratin materials, notably the skin, and/or for making up keratin materials such as the hair or the skin.
[0023] A subject of the invention is also the oily dispersion (A) as defined previously, and also a process for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, comprising the application to said materials of the oily dispersion (A) as defined previously.
[0024] A subject of the invention is also a multi-compartment kit or device comprising the ingredients i) to iv) and optionally v) as defined previously, in which the ingredients i) to iii) are in the same compartment, iv) is in another compartment, and optionally v) is in another compartment, or in the compartment with i) to iii), or in the compartment with iv).
[0025] The oily dispersion (A) and the process for treating keratin materials as defined above make it possible to obtain, after application to said materials, a residual film which adheres well to said materials while at the same time remaining elastic, showing little or no fragmentation, and little or no detachment, and which is notably resistant to shampoo washing, sebum, sweat and/or water, but also to fatty substances, notably dietary fats such as oils, notably to sebum. Furthermore, the dispersion is easy to use in compositions, notably cosmetic compositions, is easy to manufacture and remains stable over time. Specifically, the oily dispersion (A) in accordance with the present invention makes it possible to obtain deposits that are very resistant to external attacking factors, notably to sebum and to the fatty substances found in food, in particular liquid fatty substances such as plant oils and in particular olive oil. It appears that the makeup produced with at least one oily dispersion (A), notably lip makeup, shows no color fragmentation after application, and is resistant to external attacking factors such as liquid fatty substances, in particular with respect to plant oils such as olive oil. Furthermore, the makeup products obtained with the oily dispersions (A) are very esthetic, comfortable, easy to apply and glossy. Furthermore, these dispersions of polymer particles are found at a high solids content in the hydrocarbon-based liquid fatty substance(s) iii). It appears that the application of the oily dispersions (A) of the invention to keratin fibers makes it possible to obtain homogeneous coatings that are persistent with respect to external attacking factors (sunlight, water, shampoo washing, perspiration, sebum, etc.). [0026] In addition, when the composition comprises one or more dyes and/or pigments, the colored keratin materials according to the invention have a coloring that is visible on all types of materials, notably on dark keratin materials, in a persistent manner with respect to soaps, shower gels or shampoos, while at the same time preserving the physical qualities of the keratin material. Such a coloring is in particular resistant to the external attacking factors to which the keratin fibers, notably the hair, may be subjected, such as daily blow-drying, brushing and styling, and perspiration. The use of the oily dispersion (A) on keratin materials, in particular on keratin fibers, makes it possible to obtain a smooth, homogeneous deposit. Moreover, it has been observed, surprisingly, that the keratin fibers remain perfectly individualized, and can be styled without any problem.
[0027] For the purposes of the present invention and unless otherwise indicated:
- an “alkyl radical" is a linear or branched saturated Ci-Cs, in particular Ci-Ce, preferably Ci- 04 hydrocarbon-based group such as methyl, ethyl, isopropyl or /-propyl and f-butyl;
- a “(Cg-C22)alkyr radical is a saturated, linear or branched C9-C22, in particular C10-C20, preferentially C12-C18, more preferentially C12-C16 hydrocarbon-based group, such as stearyl, behenyl, isodecyl, lauryl, hexadecyl or myristyl;
- an “alkylene" radical is a linear or branched divalent saturated Ci-Cs, in particular Ci-Ce, preferably C1-C4 hydrocarbon-based group such as methylene, ethylene or propylene;
- a “cycloalkyl" radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical possibly being substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl radical is an isobornyl group;
- a “cyclic” radical is a cyclic saturated or unsaturated, aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;
- an “aryl" radical is a monocyclic or fused or non-fused bicyclic, unsaturated cyclic aromatic radical comprising from 6 to 12 carbon atoms; preferably, the aryl group comprises 1 ring and contains 6 carbon atoms, such as phenyl;
- an “aryloxy” radical is an aryl-oxy, i.e. aryl-O-, radical, with aryl as defined previously, preferably phenoxy;
- an “aryl(Ci-C4)alkoxy’ radical is an aryl-(Ci-C4)alkyl-O- radical, preferably benzoxy;
- the term “keratin materials" particularly means human skin (keratinized epithelium) and human keratin fibers such as head hair, the eyelashes, the eyebrows, and bodily hair, preferentially head hair, the eyebrows and the eyelashes, even more preferentially head hair; - the term “individualized” keratin fibers means keratin fibers, notably the hair, which, after application of the composition and drying, are not stuck together (or of which all the strands are separated from each other) and thus does not form clumps of fibers;
- the term “insoluble monomer1’ thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e. not fully dissolved at a concentration of greater than 5% by weight at room temperature (20°C) in said medium. However, the “insoluble" monomers may, as monomers, be soluble or insoluble in the hydrocarbon-based liquid fatty substance(s) iii), it being understood that they become insoluble after polymerization in the hydrocarbon-based liquid(s) iii);
- the term “homopolymer1’ means a polymer derived from the polymerization of identical monomers;
- the term “copolymer1’ means a polymer derived from the polymerization of different monomers, in particular at least two different monomers. Preferably, the ethylenic copolymer of the invention is derived from two or three different monomers, more preferentially derived from two different monomers;
- the term “ethylenic monomer1’ means an organic compound including one or more conjugated or non-conjugated unsaturations of >C=C< type, which is capable of polymerizing;
- the term “soluble monomer1’ means any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble to at least 5% by weight, at 20°C, in the hydrocarbonbased liquid fatty substance(s) iii) of the dispersion. The homopolymer is completely dissolved in the carbon-based liquid(s) iii), visually at 20°C, i.e. there is no visible sign of any deposit, or precipitate, or agglomerate, or insoluble sediment. However, the soluble monomers may, as monomers, be soluble or insoluble in the carbon-based liquid fatty substance(s) iii), it being understood that they become soluble after polymerization in the hydrocarbon-based liquid(s) iii);
- the term “fatty substance" means an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably 1% and even more preferentially 0.1 %). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids, since salified fatty acids constitute soaps that are generally soluble in aqueous media; - the term “liquid fatty substance” notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C;
- the term “hydrocarbon-based fatty substance” means a fatty substance which comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or even from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of said fatty substance, of carbon-based compound that is liquid at 25°C, having a global solubility parameter in the Hansen solubility space of less than or equal to 20 (MPa)1/2, or a mixture of such compounds;
- the global solubility parameter 6 according to the Hansen solubility space is defined in the article “Solubility parameter values” by Grulke in the book “Polymer Handbook”, 3rd Edition, Chapter VII, pages 519-559, by the relationship 6 = (do2 + dp2 + dn2)1/2 in which: - do characterizes the London dispersion forces arising from the formation of dipoles induced during molecular impacts, - dp characterizes the Debye interaction forces between permanent dipoles, - dn H characterizes the forces of specific interactions (such as hydrogen bonding, acid/base, donor/acceptor, etc.); The definition of solvents in the Hansen three-dimensional solubility space is described in the article by Hansen: The three- dimensional solubility parameters, J. Paint Technol. 39, 105 (1967);
- the term “oif’ means a fatty substance that is liquid at room temperature (25°C) and at atmospheric pressure;
- the term “hydrocarbon-based oif’ means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups;
- the term “volatile oif’ means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a nonzero vapor pressure, at room temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg);
- the term “nonvolatile oif’ means an oil with a vapor pressure of less than 0.13 Pa at room temperature and at atmospheric pressure;
- the term “silicone oif’ means an oil comprising at least one silicon atom and notably at least one Si-0 group. The silicone oil may be volatile or nonvolatile;
- the term “dispersant’ refers to a compound which can protect the dispersed particles from agglomerating or flocculating. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed; in particular, they can attach physically or chemically to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. Said agent may be charged: it may be anionic, cationic, zwitterionic or neutral;
- the term “pigment’ refers to any pigment that gives color and/or a nacreous effect to keratin materials, of synthetic or natural origin, the solubility of the pigments in water at 25°C and at atmospheric pressure (760 mmHg) being less than 0.05% by weight and preferably less than 0.01 %;
- the term “lake" refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The mineral substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum. Among the organic dyes, mention may be made of cochineal carmine;
- the term “hair dyes" refers to the oxidation dyes and direct dyes used for dyeing keratin fibers, notably human keratin fibers such as the hair;
- the term “anhydrous dispersion or composition” means a dispersion or composition containing less than 2% by weight of water, or even less than 0.5% of water, and notably free of water; where appropriate, such small amounts of water may notably be provided by ingredients of the composition which may contain residual amounts thereof;
- the term “pigments with special effects" refers to pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from colored pigments, which afford a standard uniform opaque, semi-transparent or transparent shade; and
- the term “submicron" or “submicronic" refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometer (pm), in particular between 0.1 pm and 0.9 pm, and preferably between 0.2 pm and 0.6 pm.
[0028] The oily dispersion (A)
[0029] The oily dispersion (A) of the invention comprises i) one or more particles of at least one polymer that is surface-stabilized with ii) at least one stabilizer in a medium that is preferably anhydrous, also containing iii) at least one hydrocarbon-based liquid fatty substance and iv) at least one plasticizer.
[0030] In order to obtain such a dispersion (A), it is proposed to polymerize particular monomers that are capable of forming the polymeric core i) in the presence of a polymeric statistical stabilizer ii) comprising in major amount a portion ii) that is soluble and in minor amount a portion i) that is insoluble in the dispersion medium, i.e. in the hydrocarbonbased liquid fatty substance(s) iii) and in the absence or presence of plasticizer(s) iv); preferably, the polymerization of i) and ii) is performed in the absence of plasticizer iv).
[0031] The dispersions according to the invention consist of particles, which are generally spherical, of at least one surface-stabilized polymer, in an anhydrous medium.
Preferably, said particles i) are not or are sparingly crosslinked.
[0032] /') Polymer particles
[0033] The particle(s) of the oily dispersion (A) of the invention are preferably constituted of one or more polymers chosen from: a) ethylenic homopolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably ethylenic homopolymers of (Ci-C4)alkyl (meth)acrylate; b) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci-C4)alkyl (meth)acrylate, and of (Ci-C4)(alkyl)acrylic acid, preferably (meth)acrylic acid ethylenic copolymers; c) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably ethylenic copolymers of (Ci-C4)alkyl (meth)acrylate.
[0034] Preferably, the particle(s) i) are constituted of an ethylenic polymer core derived from homopolymers a) or from copolymers b) or c) as defined previously.
[0035] According to a preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic homopolymer of acrylate a) derived from the polymerization of an identical monomer of formula (I):
[Chem 1]
H2C=C(RJ-C(O)-O^-R’ (I) in which formula (I):
- R represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and
- R’ represents a (Ci-C4)alkyl group such as methyl or ethyl, preferably a C1-C4 alkyl acrylate such as methyl acrylate.
[0036] According to another particular embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
- of at least one monomer of formula (I) as defined previously, preferably a C1-C4 alkyl acrylate such as methyl acrylate or ethyl acrylate; and
- of a monomer of formula (II)
[Chem 2]
Figure imgf000012_0001
in which formula (II)
- R is as defined previously, in particular acrylic acid.
[0037] According to this embodiment, the amount of acrylic acid ranges from 0.1 % to 15% by weight relative to the weight of monomers of the particle i) and the polymer of the particles i) is in particular a copolymer derived from the copolymerization of acrylic acid with one or more C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth) acrylate and ethyl (meth)acrylate.
[0038] According to another preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
- of at least two different monomers: of formula (I) as defined previously, preferably a Ci- 04 alkyl acrylate such as methyl acrylate and ethyl acrylate; and
- optionally of a monomer of formula (II) as defined previously, notably acrylic acid.
[0039] According to a particular embodiment of the invention, the polymer of the particles i) is a polymer derived from C1-C4 alkyl (meth)acrylate monomers. The monomers are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
[0040] A C1-C4 alkyl acrylate monomer is advantageously used. Preferentially, the monomers are chosen from methyl acrylate and ethyl acrylate.
[0041] Also, a C1-C4 alkyl methacrylate monomer is particularly used. Preferentially, the monomers are chosen from methyl methacrylate and ethyl methacrylate, more particularly methyl methacrylate.
[0042] According to a particular embodiment of the invention, the oily dispersion (A) includes from 2% to 40% by weight, in particular 4% to 25%, notably from 5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
[0043] According to an advantageous embodiment of the invention, the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96%, of monomers a) to c) relative to the total weight of polymers contained in said dispersion.
[0044] Preferably, the monomers that are capable of forming the polymeric core of the particle i) are chosen from monomers that are insoluble in the hydrocarbon-based liquid fatty substance(s) iii) of the dispersion (A). The insoluble monomers preferably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle. [0045] Ethylenic monomers bearing an acid, anhydride or aryl function:
[0046] According to one embodiment of the invention, the particle(s) i) include b) ethylenic copolymers of b1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as benzyl.
[0047] More particularly, the ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), (4) and (5):
(1) R1(R2)C=C(R3)-Acid with R1, R2 and R3 representing a hydrogen atom ora CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl, phosphoric acid or sulfonic acid, preferably carboxyl, it being understood that R1, R2 and R3 cannot simultaneously represent a hydrogen atom;
(2) H2C=C(R)-C(O)-N(R’)-Alk-Acid with R and R’, which may be identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group; Aik represents a (Ci-Ce)alkylene group optionally substituted with at least one group chosen from Acid as defined previously and hydroxyl; and Acid is as defined previously, preferably carboxyl or sulfonic acid;
(3) Ar-(Ra)C=C(Rb)-Rc with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO2H, H2PO4 or SO3H, preferably substituted with a CO2H or SO3H group;
(4) maleic anhydride of formulae (4a) and (4b):
[Chem. 3]
Figure imgf000013_0001
(4a) (4b) in which formulae (4a) and (4b) Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; preferably, Ra, Rb, and Rc represent a hydrogen atom. Preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4b) and more preferentially is maleic anhydride; and
(5) H2C=C(R)-C(O)-O-H with R representing a hydrogen atom or a (Ci-C4)alkyl group, such as methyl.
[0048] Preferably, b2) is a (Ci-C4)(alkyl)acrylic acid; more particularly, b) is (are) copolymers of a (Ci-C4)alkyl (meth)acrylate and of (meth)acrylic acid. [0049] More preferentially, b2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and salts thereof, and even more preferentially b2) represents acrylic acid.
[0050] Preferably, only one type of polymer particle i) is used in the invention.
[0051] The polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 nm to 600 nm, notably ranging from 10 nm to 500 nm and better still ranging from 20 nm to 400 nm.
[0052] The final size of the particles is preferably greater than 100 nm. In particular, they have a number-average size ranging from 100 nm to 600 nm, more particularly ranging from 150 nm to 500 nm and even more particularly ranging from 160 nm to 400 nm.
[0053] The mean size of the particles is determined via conventional methods known to those skilled in the art. A Malvern brand NanoZS model laser particle size analyzer (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples. The operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).
[0054] The sample is pipetted into a disposable plastic cuvette (four transparent faces, side length of 1 cm and volume of 4 mL) placed in the measuring cell. The data are analyzed on the basis of a cumulant fit method which leads to a monomodal particle size distribution characterized by an intensity-weighted mean diameter d (nm) and a size polydispersity factor Q. The results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode.
[0055] Other particle size analysis techniques make it possible to obtain this type of information, such as analysis of the individual tracking of particles (Nanoparticle Tracking Analysis, NTA), laser scattering (LS), acoustic extinction spectroscopy (AES), spatial-filter Doppler velocimetry or image analysis.
[0056] /'/) The stabilizer(s)
[0057] The dispersion (A) according to the invention also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention.
[0058] According to a particular embodiment of the invention, the stabilizer(s) ii) are chosen from d) ethylenic (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate homopolymers, in particular ethylenic (Cg-Cis)alkyl (Ci-C4)(alkyl)acrylate homopolymers, preferably ethylenic (Cg- C22)alkyl (meth)acrylate homopolymers and more preferentially ethylenic (Cg-Cis)alkyl (meth)acrylate homopolymers. [0059] More particularly, the stabilizer(s) ii) consist of ethylenic polymers chosen from d) ethylenic homopolymers resulting from the polymerization of monomers of formula H2C=C(R)-C(O)-O-R” with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and R” representing a (Cg-C22)alkyl and preferably (Cg-Cis)alkyl group. Preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl.
[0060] According to another particular embodiment of the invention, the stabilizer(s) ii) are chosen from e) ethylenic copolymers of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate and of (Ci- C4)alkyl (Ci-C4)(alkyl)acrylate, particularly copolymers of (Cg-Cis)alkyl (Ci- C4)alkyl)acrylate and of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate. Preferably copolymers of (Cg- Cis)alkyl (meth) acrylate and of (Ci-C4)alkyl (meth)acrylate.
[0061] More preferentially, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) of formulae (III) and (IV):
[Chem 4]
H2C=C(R)-C(O)-O-R’ (III)
[Chem 5]
H2C=C(R)-C(O)-O-R” (IV) in which formulae (III) and (IV):
- R, which may be identical or different, represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl,
- R’, which may be identical or different, represents a (Ci-C4)alkyl group such as methyl or ethyl, and
- R” represents a (Cg-C22)alkyl, preferably (Cio-C2o)alkyl and in particular (C2n)alkyl group with n being an integer equal to 5, 6, 7, 8, 9 or 10. Preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl, more preferentially stearyl.
[0062] Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, more particularly stearyl (meth)acrylate (even more preferentially stearyl methacrylate), and C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate and/or ethyl (meth)acrylate.
[0063] More preferentially, the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate or ethyl (meth)acrylate.
[0064] More preferentially, the stabilizer(s) ii) are chosen from copolymers e) derived from monomers chosen from e1) isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and hexadecyl (meth)acrylate, more particularly stearyl (meth)acrylate (even more preferentially stearyl methacrylate), and e2) C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate, more particularly methyl acrylate. [0065] Preferably, the copolymer e) complies with a weight ratio e1)/e2) of greater than 4.5. Advantageously, said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
[0066] In particular, the stabilizer ii) is chosen from:
- isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate homopolymer d), preferably stearyl (meth)acrylate, and
- statistical copolymers of e1) isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate, preferably stearyl (meth)acrylate and of e2) C1-C4 alkyl (meth)acrylate, preferably present in an e1)/e2) weight ratio of greater than 4.5. Advantageously, said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
[0067] According to one embodiment, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization e1) of a monomer of formula (IV) as defined previously and e2) of two different monomers of formula (III) as defined previously.
[0068] Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of e1) one monomer of formula (IV) as defined previously notably chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate, and e2) of two different monomers of formula (III) as defined previously, notably different C1-C4 alkyl (meth)acrylate, preferably methyl and ethyl acrylate.
[0069] According to a particular embodiment of the invention, the weight ratio of monomer of formula (IV), notably isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate, preferably stearyl (meth)acrylate e1)/monomer of formula (III), notably C1-C4 alkyl (meth)acrylate, preferably methyl (meth)acrylate and/or ethyl (meth)acrylate e2), i.e. e1)/e2), is greater than 4. Advantageously, said weight ratio e1)/e2) ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
[0070] According to another embodiment, the stabilizer(s) ii) are chosen from ethylenic copolymers e) derived from the polymerization e2) of a monomer of formula (III) as defined previously and e1) of two different monomers of formula (IV) as defined previously.
[0071] In particular, the stabilizer(s) ii) are chosen from e) ethylenic copolymers of e1) (Cs-C22)alkyl (Ci-Ce)(alkyl)acrylate and of e2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, as defined previously, in a weight ratio of (Cg-C22)alkyl (Ci-C6)(alkyl)acrylate/(Ci-C4)alkyl (Ci- 04) (alky I) aery I ate e1)/e2) of greater than 4.
[0072] Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of e1) two different monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate, and of e2) one C1-C4 alkyl (meth)acrylate monomer, preferably methyl acrylate or ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, preferably stearyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate e1)/e2) is greater than 4.5, more particularly greater than or equal to 5. Advantageously, said weight ratio e1)/e2) ranges from 4.5 to 10, more preferentially said weight ratio ranges from 5 to 8 and more particularly from 5.5 to 7.
[0073] According to a particular embodiment of the invention, the oily dispersion (A) includes from 2% to 40% by weight, in particular 4% to 25%, notably from 5.5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
[0074] According to one embodiment of the invention, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, and of one C1-C4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate in the dispersion (A) is less than 1. In particular, said weight ratio ranges from 0.05 to 0.5 and more preferentially said weight ratio ranges from 0.08 to 0.2 in the dispersion (A).
[0075] For these statistical copolymers, the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.
[0076] In particular, the weight ratio of ii) stabilizer(s) and i) polymer particle(s) is less than 1 , relative to the total weight of polymers.
[0077] According to a particular embodiment of the invention, the stabilizer(s) ii) are present in a content ranging from 2% to 40% by weight, notably from 3% to 30% by weight, preferably from 4% to 25% by weight, notably from 5.5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) in the hydrocarbon-based liquid fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
[0078] The stabilizer(s) ii) as defined previously preferably comprise 80% to 100% by weight of monomer that is soluble in the hydrocarbon-based liquid fatty substances iii), notably from 85% to 95% by weight of soluble monomer, alone or as a mixture. The stabilizing (co)polymer(s) ii) particularly include between 0% and 20% by weight, notably between 5% and 15% by weight, of monomer that is insoluble in the hydrocarbon-based liquid fatty substances iii), alone or as a mixture. [0079] Preferably, the stabilizer(s) ii) and the particle(s) i) have a number-average molecular weight (Mn) of between 1000 and 1 000 000 g/mol, notably between 5000 and 500 000 g/mol and better still between 10 000 and 300 000 g/mol.
[0080] The dispersion (A) according to the invention is finally formed from polymeric particles of relatively large diameter, i.e. preferably greater than 100 nm, and leads to glossy, film-forming deposits which adhere to keratin materials, which are resistant to fatty substances at room temperature (25°C), and which are notably advantageous for makeup applications.
[0081] Hi) The hydrocarbon-based liquid fatty substance(s)
[0082] The dispersion of polymer particles (A) according to the invention also comprises iii) one or more hydrocarbon-based liquid fatty substances in which said particles are dispersed.
[0083] The hydrocarbon-based liquid fatty substances iii) are notably chosen from Ce- Cie hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms, preferably between Ce and C , and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, nonsilicone waxes, and silicones.
[0084] It is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 60 carbon atoms, which are optionally substituted, in particular with one or more hydroxyl groups OH (in particular from 1 to 4 hydroxyl groups). If they are unsaturated, these compounds may comprise one to three unsaturations, preferably from one to three conjugated or unconjugated carboncarbon double bonds.
[0085] As regards the Ce-C alkanes, these compounds are linear or branched, and optionally cyclic; preferably, the fatty substance(s) iii) of the invention are chosen from linear or branched Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane or isodecane. The linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®.
[0086] Among the hydrocarbon-based liquid fatty substances iii) having an overall solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa)1/2, mention may be made of oils, which may be chosen from natural or synthetic, hydrocarbon-based oils, which are optionally fluorinated and optionally branched, alone or as a mixture.
[0087] According to a very advantageous embodiment, the dispersion (A) according to the invention comprises one or more liquid fatty substances which are one or more hydrocarbon-based oils. The hydrocarbon-based oil(s) may be volatile or nonvolatile.
[0088] According to a preferred embodiment of the invention, the hydrocarbon-based liquid fatty substance(s) iii) are linear or branched hydrocarbon-based oils, which are volatile, notably chosen from undecane, dodecane, isododecane, tridecane, and a mixture of various volatile oils thereof preferably comprising isododecane in the mixture, or a mixture of undecane and tridecane.
[0089] According to another particular embodiment, the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and a nonvolatile oil, the mixture of which preferentially comprises dodecane or isododecane as volatile oil.
[0090] In particular, the hydrocarbon-based liquid fatty substance(s) iii) of the invention are a mixture of C9-C12 alkanes, preferably of natural origin, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes. This mixture is notably known under the INCI name C9-12 Alkane E511470, CAS 68608-12-8, Vegelight Silk® sold by BioSynthls. This biodegradable mixture of volatile oils is obtained from coconut oil (the viscosity is 0.9-1 .1 cSt (40°C) and it has a flash point of 65°C).
[0091] Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, notably those with a viscosity of less than or equal to 8 centistokes (cSt) (8 x 10'6 m2/s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
[0092] As nonvolatile silicone oils, mention may be made of linear or cyclic nonvolatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.
[0093] The hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably:
- branched Cs-Cu alkanes, such as Cs-Cu isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names,
- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and mixtures thereof, and also mixtures of n-undecane (C11) and of n-tridecane (C13) Cetiol Ultimate® from the company BASF,
- short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate,
- hydrocarbon-based oils of plant origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk rose oil or coconut oil; shea butter; or else capryl ic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois orthose sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,
- synthetic ethers containing from 10 to 40 carbon atoms,
- linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof,
- esters such as the oils of formula R1C(O)-O-R2 in which R1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, Ci2 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2- octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters, more preferentially esters of a linear or branched Cs-C fatty acid and of a linear or branched C12-C18 fatty alcohol alone or as a mixture with alkanes derived from the complete hydrogenation/reduction of fatty acids obtained from Cocos nucifera (coconut) oil, particularly dodecane or mixtures of cocoyl caprylate/caprate with dodecane; mention may be made of those having the INCI name Coconut alkanes (and) cococaprylate/caprate sold under the name Vegelight 1212LC® by Grant Industries,
- 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 octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol.
[0094] In addition to the hydrocarbon-based liquid fatty substance, the dispersion (A) may comprise a silicone oil. If silicone oil is in the dispersion (A), it is preferably in an amount which does not exceed 10% by weight relative to the weight of the dispersion (A), more particularly in an amount of less than 5% and preferentially 2%.
[0095] In particular, the dispersion (A) comprises at least one hydrocarbon-based liquid fatty substance iii) chosen from:
- plant oils formed by fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil, coconut oil or cereal germ oil;
- linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon atoms; and notably isononyl isononanoate; and more particularly esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 7 to 19 carbon atoms and Re represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; more preferentially esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 8 to 10 carbon atoms and Re represents a hydrocarbon-based chain including from 12 to 18 carbon atoms;
- hydrocarbons and notably volatile or nonvolatile linear, branched and/or cyclic alkanes, such as optionally volatile Cs-Ceo isoparaffins, such as undecane, dodecane, isododecane, tridecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or Isopars, and mixtures thereof; or alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane, the mixture of C9-C12 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes, in particular comprising dodecane, or else liquid paraffin, liquid petroleum jelly, or hydrogenated polyisobutylene;
- ethers containing 6 to 30 carbon atoms;
- ketones containing 6 to 30 carbon atoms; aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbonbased chain not including any substitution groups, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol;
- polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and - mixtures thereof, such as mixtures of esters of linear or branched Cs-C fatty acid and C12-C18 fatty alcohol and alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids from Cocos nucifera (coconut) oil, in particular dodecane, such as mixtures of cococaprylate/caprate and dodecane; mention may be made of those having the INCI name Coconut alkanes (and) coco-caprylate/caprate sold under the name Vegelight 1212LC® by Grant Industries; or mixtures of C9-C12 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes, in particular comprising dodecane; mention may be made of the oil mixture having the INCI name C9-12 Alkane, Vegelight Silk® sold by BioSynthls.
[0096] Preferably, the dispersion (A) comprises at least one hydrocarbon-based liquid fatty substance iii) chosen from: plant oils formed by fatty acid esters of polyols, in particular triglycerides,
- esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 7 to 19 carbon atoms and Re represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, more preferentially esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 8 to 10 carbon atoms and Re represents a hydrocarbon-based chain including from 12 to 18 carbon atoms;
- volatile or nonvolatile, linear or branched Cs-Ceo alkanes, such as isododecane and alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids obtained from Cocos nucifera (coconut) oil, in particular dodecane;
- volatile or nonvolatile, nonaromatic cyclic C5-C12 alkanes;
- ethers containing 7 to 30 carbon atoms;
- ketones containing 8 to 30 carbon atoms;
- aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups; and
- mixtures thereof.
[0097] Advantageously, the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
[0098] The hydrocarbon-based liquid fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils described previously.
[0099] Preferentially, the liquid fatty substance(s) iii) of the invention are chosen from alkanes such as dodecane, isododecane, fatty alcohols such as octyldodecanol, esters such as isononyl isononanoate, cocoyl caprylate/caprate and mixtures thereof, more preferentially alkanes.
[00100] More particularly, the liquid fatty substance(s) iii) of the invention are chosen from linear or branched Ce-C , preferably Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes, and even more preferentially the alkanes are volatile. More particularly, the liquid fatty substance(s) iii) of the invention are volatile and are chosen from undecane, dodecane, isododecane, tridecane, and a mixture thereof notably comprising dodecane, isododecane or a mixture of undecane and tridecane.
[00101] Preferentially, the liquid fatty substance(s) iii) of the invention are isododecane.
[00102] According to another advantageous embodiment of the invention, the liquid fatty substance(s) iii) are a mixture of nonvolatile oil(s) and volatile oil(s); preferably, the mixture comprises, as volatile oil, undecane, dodecane, isododecane or tridecane, more preferentially isododecane. A mixture of volatile oil and nonvolatile oil that may be mentioned is the mixture of isododecane and of isononyl isononanoate.
[00103] More preferentially, when the fatty substance(s) are a mixture of volatile oil and of nonvolatile oil, the amount of volatile oil is greater than the amount of nonvolatile oil.
[00104] In particular, in the mixture, the nonvolatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
[00105] Method for preparing the dispersion (A)
[00106] Without this being limiting, in general, the dispersion according to the invention may be prepared in the following manner:
- The polymerization is performed in “dispersion" in nonaqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from d) and e) as defined previously.
- In a first step, the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer d) or e) with v) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
- In a second step, the constituent monomer(s) of the polymer of the particles i) are added to the stabilizing polymer formed in the preceding step and polymerization of these added monomers is performed in the presence of the free-radical initiator.
[00107] When the nonaqueous medium is a nonvolatile hydrocarbon-based liquid fatty substance iii), the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon-based liquid fatty substance (which must be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
[00108] The plasticizer(s) iv) and optionally one or more cosmetic active agents chosen from f) dyes and/or pigments, g) active agents for caring for keratin materials, notably the skin, and h) UV-screening agents and also j) mixtures thereof, may be added during the first step.
[00109] According to a first variant, the plasticizer(s) iv) are added during the second step. In this case, the plasticizer(s) iv) form an integral part of the particles i) and stabilizers ii) in the oil iii). [00110] The term “integral part” means that the plasticizer(s) have reacted chemically with the particle(s) i) and/or with the stabilizer(s) ii), notably with i) during the polymerization.
[00111] According to a second preferred variant, the plasticizer(s) iv) are added after the second step, in a third step.
[00112] According to a third preferred variant, said cosmetic active agent(s) are added during the second step with said plasticizer(s) iv) or after the second step or even after the third step. It follows that in the second and third variants, the plasticizer(s) iv) do not form an integral part of the particle(s) i) and of the stabilizer(s) ii).
[00113] More particularly, the dispersion (A) then comprises: one or more particles i) (preferentially constituting the ethylenic polymeric core derived from homopolymers a) or the copolymers b) or c), as defined previously) associated with ii) one or more stabilizers (preferentially ii) being at the polymeric surface of said cores i), derived from the homopolymer d) and the copolymers e) as defined previously); one or more liquid fatty substances iii); one or more plasticizers iv); and optionally one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and j) UV (A) and/or (B) screening agents, and also m) mixtures thereof; it being understood that the plasticizer(s) iv) do not form an integral part of the particle(s) i) and of the stabilizer(s) ii).
[00114] A synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator v) are soluble therein, and such that the polymer particles i) obtained are insoluble therein, so that they precipitate therefrom during their formation, is preferably chosen. Preferably, the synthesis solvent also dissolves the plasticizer(s) iv) of the invention.
[00115] In particular, the synthesis solvent chosen is one which is an apolar, organic solvent, preferably chosen from liquid fatty substances iii), in particular alkanes such as heptane, cyclohexane, undecane, dodecane, isododecane or tridecane, preferably isododecane.
[00116] When the nonaqueous medium is a volatile hydrocarbon-based liquid fatty substance iii), the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent. The monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein.
[00117] The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of from 15% to 45% by weight. The total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds. [00118] The polymerization is preferentially performed in the presence v) of one or more radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators.
[00119] The following types of initiator may notably be mentioned:
- peroxide, in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5- dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141 ; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; or
- azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2’-azobis(2- amidinopropane) dihydrochloride.
[00120] The polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.
[00121] The polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).
[00122] The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
[00123] The stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously. [00124] From 2% to 40% by weight and notably from 4% to 30% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)), preferably from 5% to 25% by weight and preferably from 4.5% to 20% by weight, relative to the total weight of the dispersion (A).
[00125] The polymer particle dispersion (A) advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion.
[00126] The composition according to the invention preferably comprises a solids (or active material) content of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of composition (A), preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight, relative to the total weight of composition (A).
[00127] According to a preferred embodiment of the invention, the dispersion (A) according to the invention is an anhydrous composition.
[00128] According to another embodiment of the present invention, the dispersion (A) is in inverse emulsion, i.e. of water-in-oil (W/O) type. In this case, the composition comprises one or more surfactants, which are preferably nonionic. The inverse emulsions of (A) are preferably chosen when the dispersions (A) are intended for makeup, and notably for making up the eyelashes and/or eyebrows. [00129] In a particular preparation method, the statistical stabilizing polymer ii) is prepared in a first step. This stabilizing polymer is soluble in an apolar organic solvent of alkane type, such as isododecane.
[00130] Next, in a second step, the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
[00131] Preferentially, a solution of stabilizing polymer ii) in the hydrocarbon-based liquid fatty substance(s) iii) is prepared for the final dispersion, and the polymerization of the monomers which form the core of the particle is performed in the presence of this stabilizer ii).
[00132] The stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator v) as defined previously.
[00133] In a second step, the monomers which form the core of the particle i) may be polymerized in the presence of said stabilizing polymer ii). This second step may be a conventional radical polymerization.
[00134] The dispersions are prepared in the presence of one or more hydrocarbon-based liquid fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
[00135] The dispersions according to the invention are thus finally formed from polymer particles, of relatively large diameter (preferably greater than 100 nm), and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C).
[00136] Furthermore, since said dispersion is in oily medium, it becomes easy to formulate it in cosmetic compositions based on oily medium commonly used in cosmetics, in particular anhydrous media or in the fatty phases of emulsions. Emulsions that may be mentioned include “inverse emulsions” of water-in-oil (W/O) type or “direct” emulsions of oil-in-water (O/W) type.
[00137] The polymer according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in lipsticks, glosses (lip glosses) and eyeshadows and mascaras.
[00138] iv) The plasticizer(s)
[00139] The term “plasticizer” or “plasticizing agent’ means an organic chemical compound, which is in solid state or in liquid state, at room temperature (20°C) and at atmospheric pressure, and which is generally added to a composition comprising different types of polymerizable ingredients (monomers) to make the polymers more supple, more flexible, and/or to improve their mechanical strength. Plasticizers are known to those skilled in the art; mention may be made, for example, of “Plasticizers”, Encyclopedia of polymer Science and Technology, Helmut Reinecke, Rodrigo Navarro, Monica Perez, https://doi.Org/10.1002/0471440264. pst245.pub215 September 2011.
[00140] For the purposes of the invention, the plasticizers have a molecular weight of between 150 and 1000 g/mol, particularly between 200 and 700 g/mol, preferably between 205 and 500 g/mol and even more preferentially between 210 and 400 g/mol. The plasticizers are also organic compounds consisting of carbon and hydrogen atoms and of one or more heteroatoms chosen from oxygen, sulfur and silicon atoms, in particular chosen from oxygen atoms, preferably at least 2 heteroatoms, even more preferentially between 2 and 10 heteroatoms, and which may contain one or more aryl groups. In particular, the plasticizers according to the invention comprise one or more ester functions, notably from 1 to 5 ester functions such as citrates, phthalates, adipates or benzoates, or esters Ra-C(O)-O-Rb or Ra-O-C(O)-Rb in which Ra denotes a branched (Ci-Ce)alkyl group such as a tert-butyl and Rb denotes a branched, preferably saturated, (Cs-C2o)alkyl group such as an isodecyl group or an isostearyl group.
[00141] Preferably, the plasticizer(s) of the invention are chosen from those of the families of linear or branched, preferably branched, C8-C20 alkyl phthalates, esters, citrates, benzoates and neopentanoates.
[00142] According to a particular embodiment of the invention, the plasticizer(s) are chosen from compounds (V) and (V’) below:
[00143] [Chem. 6]
Rh-O-CfOJ-L-t-CfOJ-O-RJn Rh-CfOJ-O-L-t-O-CfOJ-RJn
(V) (V’) in which formulae (V) and (V’):
- Rh and R1, which may be identical or different, represent a group from among: (Ci-C2o)alkyl, aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, preferably (Ci-C4)alkyl such as n-butyl;
- n is 0, 1 , 2 or 3, preferably 0, 1 or 2, more preferentially, 1 or 2; and
- L represents a group from among: a) monovalent, divalent, trivalent or tetravalent C1-C10 alkyl, preferably trivalent (C2-Cs)alkyl, said monovalent, divalent, trivalent or tetravalent alkyl possibly being optionally substituted with one or more hydroxyl groups, optionally interrupted with at least one heteroatom such as O, N or S, preferably O, b) monovalent, divalent or trivalent cycloalkyl, or c) monovalent, divalent, trivalent or tetravalent aryl, preferably divalent or trivalent phenyl; preferably, L represents a group a) or c).
[00144] According to a particular embodiment of the invention, the compounds of formula (V) or (V’) are those in which:
- Rh and R1, which may be identical or different, represent a group from among: (Ci -Ci s)al ky I , aryl(Ci-C4)alkyl such as benzyl, preferably (Ci-C4)alkyl such as n-butyl;
- n is 0, 1 or 2, preferably 2; and - L represents a group from among: a) monovalent, divalent or trivalent C2-C8 alkyl, preferably (C2-Ce)alkyl, said alkyl possibly being optionally substituted with one or more hydroxyl groups, preferably substituted with one hydroxyl group.
[00145] According to one particular embodiment of the invention, the plasticizer(s) iv) are chosen from those of formula (V).
[00146] According to another particular embodiment of the invention, the plasticizer(s) iv) are chosen from those of formula (V’).
[00147] According to a particular embodiment of the invention, the plasticizer(s) are chosen from phthalates, preferably chosen from: di-n-hexyl phthalate (DnHP), diisoheptyl phthalate (DIHP), diheptyl phthalate (DnHP), bis(2-ethylhexyl) phthalate (DEHP), diheptylnonyl phthalate (DnHNP) di-n-octyldecyl phthalate (DNODP), diheptylnonylundecyl phthalate (DnHNUP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), di-n-nonyl phthalate (DnNP), diisodecyl phthalate (DIDP), di-n-nonyldecylundecyl phthalate (DnNDUP), dinonylundecyl phthalate (DnNUP), diundecyl phthalate (DUP), diisoundecyldodecyl phthalate (UDP), ditridecyl phthalate (DTDP), bis(2-ethylhexyl) terephthalate (DOTP), and butyl benzyl phthalate (BBP).
[00148] According to a particular embodiment of the invention, the plasticizer(s) are chosen from adipic acid diesters and notably from: diheptylnonyl adipate (DnHNA), bis(2- ethylhexyl) adipate (DEHA), diisopropyl adipate (DI PA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), benzene 1 ,2,4-tricarboxylic acid triesters such as triheptylnonyl trimellitate (TnHNTM), tris(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), sebacic acid diesters such as bis(2-ethylhexyl) sebacate (DOS), nonanedioic acid diesters such as bis(2-ethylhexyl) azelate (DOZ), esters such as isodecyl neopentanoate, and isostearyl neopentanoate.
[00149] According to a particular embodiment of the invention, the plasticizer(s) are chosen from citrates, notably chosen from: tributyl citrate, triethyl citrate, tributyl 2- acetylcitrate.
[00150] According to a particular embodiment of the invention, the plasticizer(s) are chosen from benzoates, in particular chosen from: 1 ,2-propylene glycol dibenzoate (PGDB), diethylene glycol dibenzoate (DEGDB), dipropylene glycol dibenzoate (DPGDB), triethylene glycol dibenzoate (TEGDB), isodecyl benzoate, isononyl benzoate and 2- ethylhexyl benzoate.
[00151] Even more preferentially, the plasticizer(s) iv) of the invention are chosen from isodecyl neopentanoate, isostearyl neopentanoate, tributyl citrate, diisopropyl adipate and propylene glycol dibenzoate. [00152] According to a particular embodiment of the invention, the plasticizer(s) are present in an amount of between 0.1% and 50% by weight and preferably from 0.5% to 30% by weight relative to the total weight of the polymer(s) a) to e) of the particles.
[00153] v) The cosmetic active a ent(s)
[00154] According to a particular embodiment of the invention, the dispersion (A) of the invention comprises one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, and j) UV (A) and/or (B) screening agents, and also k) mixtures thereof.
[00155] According to a preferred embodiment of the present invention, the cosmetic active agent(s) of the invention are chosen from g) pigments.
[00156] According to a particular embodiment of the present invention, the cosmetic active agent(s) of the invention are chosen from h) active agents for caring for keratin materials, preferably skincare active agents.
[00157] According to yet another particular embodiment of the present patent application, the cosmetic active agent(s) of the invention are chosen from j) IIV(A) and/or IIV(B) screening agents, and a mixture thereof.
[00158] According to a particular embodiment of the invention, the dispersion (A) comprises v) one or more cosmetic active agents chosen from g) pigments.
[00159] The pigment(s) more particularly represent from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of the dispersion (A).
[00160] The pigments are white or colored solid particles which are naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which are rendered insoluble by formulation in the form of a lake, where appropriate. More particularly, the pigments have little or no solubility in aqueous-alcoholic media.
[00161] The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry. Pigments that may notably be mentioned include organic and mineral pigments such as those defined and described in Ullmann’s Encyclopedia of Industrial Chemistry “Pigments, organic”, 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, “Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007. a20_243. pub3
[00162] These pigments may be in pigment powder or paste form. They may be coated or uncoated.
[00163] The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof. [00164] The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.
[00165] The pigment may be an organic pigment.
[00166] The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments.
[00167] The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.
[00168] In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.
[00169] Mention may also be made, by way of example, of pigment pastes of organic pigments, such as the products sold by Hoechst under the names:
- Cosmenyl Yellow 10G: Pigment Yellow 3 (Cl 11710);
- Cosmenyl Yellow G: Pigment Yellow 1 (Cl 11680);
- Cosmenyl Orange GR: Pigment Orange 43 (Cl 71105);
- Cosmenyl Red R: Pigment Red 4 (Cl 12085);
- Cosmenyl Carmine FB: Pigment Red 5 (Cl 12490);
- Cosmenyl Violet RL: Pigment Violet 23 (Cl 51319);
- Cosmenyl Blue A2R: Pigment Blue 15.1 (Cl 74160);
- Cosmenyl Green GG: Pigment Green 7 (Cl 74260);
- Cosmenyl Black R: Black 7 pigment (Cl 77266).
[00170] The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may notably be composed of particles including a mineral core, at least one binder for attaching the organic pigments to the core, and at least one organic pigment which at least partially covers the core. [00171] The organic pigment may also be a lake. The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
[00172] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate, and aluminum.
[00173] Mention may be made, among the dyes, of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45 380), D&C Orange 5 (Cl 45 370), D&C Red 27 (Cl 45 410), D&C Orange 10 (Cl 45 425), D&C Red 3 (Cl 45 430), D&C Red 4 (Cl 15 510), D&C Red 33 (Cl 17 200), D&C Yellow 5 (Cl 19 140), D&C Yellow 6 (Cl 15 985), D&C Green 5 (Cl 61 570), D&C Yellow 10 (Cl 77 002), D&C Green 3 (Cl 42 053), D&C Blue 1 (Cl 42 090).
[00174] An example of a lake that may be mentioned is the product known under the following name: D&C Red 7 (Cl 15 850:1).
[00175] The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a colored appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from colored pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
[00176] Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.
[00177] Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and notably with ferric blue or with chromium oxide, mica covered with titanium and with an organic pigment as defined previously, and also nacreous pigments based on bismuth oxychloride. Nacreous pigments that may be mentioned include the Cellini nacres sold by BASF (mica-TiO2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3), and Colorona sold by Merck (mica-TiO2-Fe2O3).
[00178] Mention may also be made of the gold-colored nacres sold notably by the company BASF under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold notably by the company BASF under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold notably by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company BASF under the name Copper 340A (Timica); the nacres with a red tint sold notably by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company BASF under the name Yellow (4502) (Chromalite); the red nacres with a gold tint sold notably by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres sold notably by the company BASF under the name Tan opale G005 (Gemtone); the black nacres with a gold tint sold notably by the company BASF under the name Nu antique bronze 240 AB (Timica), the blue nacres sold notably by the company Merck under the name Matte blue (17433) (Microna), the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver, and the golden-green pink-orange nacres sold notably by the company Merck under the name Indian summer (Xirona), and mixtures thereof.
[00179] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.
[00180] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
[00181] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate glitter flakes, notably those sold by the company Meadowbrook Inventions under the name Silver 1 P 0.004X0.004 (silver glitter flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum.
[00182] The pigments with special effects may also be chosen from reflective particles, i.e. notably from particles whose size, structure, notably the thickness of the layer(s) of which they are made and their physical and chemical nature, and surface state, allow them to reflect incident light. This reflection may, where appropriate, have an intensity sufficient to create at the surface of the composition or of the mixture, when it is applied to the support to be made up, highlight points that are visible to the naked eye, i.e. more luminous points that contrast with their environment making them appear to sparkle.
[00183] The reflective particles may be selected so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined, and more particularly so as to optimize this effect in terms of color rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or tint.
[00184] These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
[00185] The reflective particles, whatever their form, may or may not have a multilayer structure and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, notably of a reflective material. [00186] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, notably titanium or iron oxides obtained synthetically.
[00187] When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, notably a synthetic substrate at least partially coated with at least one layer of a reflective material, notably of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials.
[00188] More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, notably aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.
[00189] The reflective material may include a layer of metal or of a metallic material.
[00190] Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541 , JP-A-07258460 and JP-A-05017710.
[00191] Again as an example of reflective particles including a mineral substrate coated with a layer of metal, mention may also be made of particles including a silver-coated borosilicate substrate.
[00192] Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by this same company.
[00193] Use may also be made of particles comprising a metal substrate, such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
[00194] Examples that may be mentioned include aluminum powder, bronze powder or copper powder coated with SiO2, sold under the name Visionaire by the company Eckart. [00195] Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.
[00196] The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colors, and also particular optical effects such as metallic effects or interference effects. [00197] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferentially between 30 nm and 50 pm.
[00198] The pigments may be dispersed in the composition by means of a dispersant.
[00199] The dispersant serves to protect the dispersed particles against agglomeration or flocculation thereof. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.
[00200] As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C.
[00201] The pigments used in the composition may be surface-treated with an organic agent.
[00202] Thus, the pigments surface-treated beforehand that are useful in the context of the invention are pigments which have been completely or partially subjected to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described notably in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, notably polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds. [00203] The surface-treated pigments that are useful in the composition may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.
[00204] The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.
[00205] Preferably, the surface-treated pigments are coated with an organic layer.
[00206] The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments. [00207] The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.
[00208] An organic agent covalently bonded to the pigments will preferably be used.
[00209] The agent for the surface treatment may represent from 0.1% to 50% by weight relative to the total weight of the surface-treated pigment, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 20% by weight relative to the total weight of the surface-treated pigment.
[00210] Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-silicone treatment, such as the AQ surface treatment sold by LCW;
- a methicone treatment, such as the SI surface treatment sold by LCW;
- a dimethicone treatment, such as the Covasil 3.05 surface treatment sold by LCW;
- a dimethicone/trimethylsiloxysilicate treatment, such as the Covasil 4.05 surface treatment sold by LCW;
- a magnesium myristate treatment, such as the MM surface treatment sold by LCW;
- an aluminum dimyristate treatment, such as the Ml surface treatment sold by Miyoshi;
- a perfluoropolymethylisopropyl ether treatment, such as the FHC surface treatment sold by LCW;
- an isostearyl sebacate treatment, such as the HS surface treatment sold by Miyoshi;
- a perfluoroalkyl phosphate treatment, such as the PF surface treatment sold by Daito;
- an acrylate/dimethicone copolymer and perfluoalkyl phosphate treatment, such as the FSA surface treatment sold by Daito;
- a polymethylhydrosiloxane/perfluoroalkyl phosphate treatment, such as the FS01 surface treatment sold by Daito;
- an acrylate/dimethicone copolymer treatment, such as the ASC surface treatment sold by Daito;
- an isopropyl titanium triisostearate treatment, such as the ITT surface treatment sold by Daito;
- an acrylate copolymer treatment, such as the APD surface treatment sold by Daito;
- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, such as the PF + ITT surface treatment sold by Daito.
[00211] According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the dye composition.
[00212] According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersantpigment) of between 1 :4 and 4:1 , particularly between 1.5:3.5 and 3.5:1 or better still between 1.75:3 and 3:1.
[00213] The dispersant(s) may thus have a silicone backbone, such as silicone polyether and dispersants of amino silicone type other than the alkoxysilanes described previously. Among the suitable dispersants that may be mentioned are:
- aminosilicones, i.e. silicones comprising one or more amino groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851 , GP-965, GP-967 and GP-988-1 , sold by Genesee Polymers,
- silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 , and Tego® RC 1043, sold by Evonik,
- polydimethylsiloxane (PDMS) silicones bearing carboxyl groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP- 514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401 , Tego® RC 1403, Tego® RC 1412 by Evonik.
[00214] According to a particular embodiment, the dispersant(s) are of amino silicone type other than the alkoxysilanes described previously and are cationic.
[00215] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
[00216] In one variant of the invention, the pigment(s) according to the invention are organic pigments, preferentially organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) according to the invention are mineral pigments.
[00217] The composition may comprise f) one or more direct dyes.
[00218] The term “direct dye” means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fiber.
[00219] They may be ionic or nonionic, preferably cationic or nonionic.
[00220] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. [00221] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (VI) and (VII) and the azo cationic dyes (VIII) and (IX) below:
[Chem. 6]
Figure imgf000037_0001
[Chem. 7]
Het+-N(Ra)-N=C(Rb)-Ar5 Q- (V||)
[Chem. 8]
Figure imgf000037_0002
[Chem. 9]
Figure imgf000037_0003
in which formulae (VI) to (IX):
- Het+ represents a cationic heteroaryl radical, preferentially bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially with at least one (Ci-Cs)alkyl group such as methyl;
- Ar+ represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci-C8)alkylammonium, such as trimethylammonium;
- Ar represents an aryl group, notably phenyl, which is optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (Ci-Cs)alkyl, ii) optionally substituted (Ci-Cs)alkoxy, iii) (di)(Ci-Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(Ci-C8)alkyl-N-aryl(Ci-C8)alkylamino or alternatively Ar represents a julolidine group;
- Ar’ represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more (Ci-Cs)alkyl, hydroxyl, (di)(Ci-Cs)(alkyl)amino, (Ci-Cs)alkoxy or phenyl groups;
- Ra and Rb, which may be identical or different, represent a hydrogen atom or a (Ci- Cs)alkyl group, which is optionally substituted, preferentially with a hydroxyl group; or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; in particular, Ra and Rb represent a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl group;
- Q- represents an organic or mineral anionic counterion, such as a halide or an alkyl sulfate.
[00222] In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (VI) to (IX) as defined previously, more particularly the cationic direct dyes bearing an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP 714 954, preferentially the following direct dyes:
[Chem. 10]
Figure imgf000038_0001
[Chem. 11]
Figure imgf000038_0002
in which formulae (X) and (XI):
- R1 representing a (Ci-C4)alkyl group such as methyl;
- R2 and R3, which may be identical or different, represent a hydrogen atom or a (Ci-
C4)alkyl group, such as methyl; and
- R4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-Cs)alkyl, optionally substituted (Ci-Cs) alkoxy, or (di)(Ci-Cs)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a hydrogen atom,
- Z represents a CH group or a nitrogen atom, preferentially CH,
- Q- is an anionic counterion as defined previously, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesyl.
[00223] In particular, the dyes of formulae (IX) and (X) are chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or derivatives thereof with Q’ being an anionic counterion as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.
[00224] Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions containing these natural dyes and notably henna-based poultices or extracts.
[00225] According to one embodiment of the invention, the dyes are liposoluble. They are chosen, for example, from Sudan Red, D&C Red 17, D&C Green 6, p-carotene, soybean oil, Sudan Brown, D&C Yellow 11 , D&C Violet 2, D&C Orange 5, quinoline yellow and annatto. The water-soluble dyes are, for example, beetroot juice or methylene blue. [00226] Preferably, the cosmetic active agent(s) v) are chosen from the following pigments: carbon black, iron oxides, notably black, and micas coated with iron oxide, red iron oxides (iron(lll) oxide, also known as ferric oxide), triarylmethane pigments, notably blue and violet, such as Blue 1 Lake, azo pigments, notably red, such as D&C Red 7, alkali metal salt of lithol red, such as the calcium salt of lithol red B.
[00227] According to a particular embodiment of the invention, the amount of pigments ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the dispersion (A) comprising them.
[00228] According to a particular embodiment of the invention, the dispersion (A) comprises iv) one or more cosmetic active agents chosen from oxidation dyes.
[00229] Among the oxidation dyes that may be mentioned are:
- oxidation dyes, which are generally chosen from one or more oxidation bases, optionally combined with one or more coupling agents.
By way of example, the oxidation bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts, optionally combined with coupling agents; they may particularly be chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, naphthalene-based coupling agents and heterocyclic coupling agents and also the corresponding addition salts;
- direct dyes, notably azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. The direct dyes may be anionic, cationic or neutral;
- natural dyes, notably chosen from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein, and also extracts or decoctions containing these natural dyes.
[00230] The hair dye(s), whether they are direct dyes or oxidation dyes, more particularly represent from 0.001 % to 10% by weight relative to the total weight of the composition of the dispersion (A), and preferably from 0.005% to 5% by weight relative to the total weight of the dispersion (A).
[00231] Preferably, the pigment(s) of the invention are chosen from carbon black, iron oxides, notably red, brown or black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and purple triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red B; more preferentially, the pigment(s) used are chosen from red iron oxides and azo pigments, notably red azo pigments such as D&C Red 7. [00232] According to a particular embodiment of the invention, the amount of pigments ranges from 0.5% to 40% and preferably from 1% to 20% relative to the weight of the composition and dispersion (A) comprising them.
[00233] Process for treating keratin materials using the dispersion (A):
[00234] A subject of the invention is also a process for treating keratin materials by applying the dispersion (A) to said materials.
[00235] According to a particular embodiment of the invention, the process for treating keratin materials, notably human keratin materials such as the skin, notably of the face, such as the lips, comprises the step of applying the dispersion (A) to said materials.
[00236] More preferentially, the process of the invention is a process notably for making up keratin materials, preferably facial skin such as the lips. The makeup process of the invention uses the dispersion (A) which comprises at least one cosmetic agent v) chosen from f) dyes and g) pigments; more preferentially, the dispersion comprises g) one or more pigments.
[00237] According to a particular embodiment of the invention, the process for treating keratin materials is a process for making up the skin and/or the eyelashes or the eyebrows, involving a step of applying the dispersion (A) comprising at least one dye and/or at least one pigment, preferably at least one pigment.
[00238] According to a particular embodiment, the dispersion (A) used in the process for treating keratin materials comprises one or more cosmetic active agents v).
[00239] The dispersion (A) according to the invention may also comprise a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, dyestuffs other than f), dyes and g) pigments.
[00240] The invention is illustrated in greater detail in the examples that follow.
[00241] EXAMPLES
[00242] The dispersions of polymer particles presented in the various examples were prepared in 1 liter pilot reactors. The syntheses are performed in an apolar aprotic organic solvent such as isododecane.
[00243] The synthetic process is identical for all the dispersions obtained. In a first step, the statistical stabilizing polymer is synthesized by reaction between the C9-C22 alkyl (meth)acrylate and a small amount of one or two different (Ci-C4)alkyl (C1- C4)(alkyl)acrylates, preferably (Ci-C4)alkyl (meth)acrylate such as methyl acrylate or methyl acrylate + ethyl acrylate.
[00244] The reaction is performed at 90°C for 2 hours. In the second step, the particle core is obtained after introducing the (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate ethylenically unsaturated monomers, preferably (Ci-C4)alkyl (meth)acrylate and optionally (C1- C4)(alkyl)acrylic acid, preferably (meth)acrylic acid such as acrylic acid; into the reaction medium containing the stabilizing polymer. This second step is performed at 90°C for 5 hours.
[00245] Several purification steps by distillation of the solvent (isododecane), also known as “strippings”, may be performed at the end of the synthesis to remove the residual unreacted monomers.
[00246] The percentage of active material in the hydrocarbon-based liquid fatty substance(s) iii) such as isododecane is finally between 40% and 55%, such as 50%.
[00247] The polymerization initiator is Trigonox T21S. The CAS and the supplier of this initiator are given in Table 2: Polymerization initiator used in the various examples [00248] [Table 1]:
Figure imgf000041_0001
[00249] Examples of implementation of the invention
[00250] Synthesis of the oily dispersions with a stabilizer bearing a C9-C22 alkyl group [00251] A synthetic example is presented below for the production of an oily dispersion with a C9-C22 alkyl (meth)acrylate stabilizer. For this example, stearyl methacrylate was used in combination with methyl acrylate for the stabilizing arm and methyl acrylate was adopted for the core of the particle.
[00252] Example of synthesis of a stearyl methacrylate/methyl acrylate oily dispersion Example 10 of FR 3 097 756
[00253] The oily dispersions are formed as a whole (polymer particles i) + polymeric stabilizer ii)) with 94.5% of methyl acrylate and 5.5% of stearyl methacrylate. The synthesis of these oily dispersions was performed in a 1 liter pilot reactor. The synthesis is performed in two steps:
- In a first step, stearyl methacrylate is polymerized in isododecane in the presence of a small amount of methyl acrylate and of a radical initiator (T21S). In the first step, the stearyl methacrylate/methyl acrylate mass ratio is 85/15.
In the second step, the rest of the methyl acrylate is added in the presence of isododecane and of the radical initiator (T21S).
[00254] After stripping, the polymer is at a solids content of 50% in the isododecane. [00255] The ratios employed to obtain the stabilizer and the core are summarized in [00256] Table 2: Specific ratios in the stabilizer ii) and the core i) for the dispersion [00257] [Table 2]
Step 1 :
Figure imgf000042_0004
Isododecane added between the two steps
Figure imgf000042_0002
Figure imgf000042_0001
Figure imgf000042_0003
[00258] [Table 3]: Amounts of reagents used for the Dispersion with Example 10 of FR 3 097 756
Figure imgf000043_0002
Figure imgf000043_0001
[00259] Experimental protocol:
Isododecane, stearyl methacrylate, methyl acrylate and T21S are introduced as feedstock into the reactor. The medium is heated to 90°C (nominal medium temperature) under argon and with stirring. The solids content during this first step is 22%.
[0001] After heating for 2 hours, NMR indicates a stearyl methacrylate consumption of 99% (methyl acrylate consumption: 98%).
[0002] After 2 hours of reaction, isododecane is introduced. The medium is heated to 90°C.
[0003] Once the medium is at 90°C, methyl acrylate, isododecane and T21S are introduced over 1 hour by pouring. At the end of the introduction, the medium is milky.
[0004] After 7 hours of synthesis, virtually total consumption of the methyl acrylate and quantitative consumption of the stearyl methacrylate are obtained.
[0005] 400 mL of isododecane are then stripped out (the reaction progress is monitored by NMR).
[0006] Plasticizers iv)
[0007] Once the particles are dispersed in isododecane, the plasticizer is added. The amount of plasticizer added is 10% by mass relative to the total weight of the polymer of the particles (stabilizer + core). Thus, for 20% polymer active material of the particles, 2% by mass of plasticizer were added. The plasticizer was added at room temperature (20°C) with stirring. Once the particle dispersion + plasticizer mixture is homogeneous, the cosmetic active agents such as pigments are added, still at room temperature and with stirring.
[0008]
[0009] [Table 4]:
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000044_0003
[0010] Evaluation on keratin material:
[0011] The various combinations were evaluated in terms of making up the skin.
[0012] A formulation containing a particle dispersion of the invention was prepared. This formulation was applied to a wet thickness of 50 pm onto two glass supports:
FP40 type support: FP40 (Trellborg, N4I01)* is an elastomeric substrate made of butadiene-acrylonitrile copolymer containing a diethylhexyl sebacate oil, which approximates to skin sebum, as plasticizer. When a polymer conveyed in isododecane is applied to this substrate, extraction of the plasticizer is performed, mimicking the contribution/impact of sebum on the Bioskin type support coating: elastomer support simulating a polyurethane elastomer skin reinforced with elastane (particular polyurethane) - manufactured by Beaulax (Japan).
[0013] The deposit was left to dry for 24 hours. After 24 hours of drying, the deposits were evaluated. After drying for one day, the BioSkin or FP40 plate is stretched, by hand force, this being done 10 times.
[0014] The result may then be observed on the formulation film (fragmentation or otherwise).
[0015] The following dispersions were prepared: [0016] [Table 5]:
Figure imgf000045_0001
AM: Active Material
[0017] The in vitro substrate before deposition is 10 cm long and 6 cm wide. A coating measuring 6 cm in length and 5 cm in width is applied to this substrate. The substrate + coating assembly is stretched in the same manner with the same force for the various tests to achieve a 40% stretch in the direction of the length of the substrate + coating (14 cm).
[0018] The evaluation is then made visually as follows: +++ No visible striae
++ Between 1 and 5 visible striae
+ Between 5 and 10 visible striae
More than 10 visible striae. [0019] Results:
[0020] [Table 6]
Figure imgf000046_0001
It is seen that the addition of plasticizer to the dispersion makes it possible, after application to the keratin materials and evaporation of the solvents, to obtain a film which adheres significantly more to the substrate than the comparative. In addition, the appearance of the film remains unchanged after stretching, i.e. esthetic satiny glossy red for dispersions 2 to 6.

Claims

1. An oily dispersion (A), which is preferably anhydrous, comprising: i) one or more particles including one or more polymers chosen from: a) ethylenic homopolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci- C4)alkyl (meth)acrylate; b) ethylenic copolymers of b1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl; in particular, b2) is a (Ci- C4)(alkyl)acrylic acid such as (meth)acrylic acid, more particularly copolymers of (Ci- C4)alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, preferably (Ci-C4)alkyl (meth)acrylate; and ii) one or more polymeric stabilizers chosen from: d) ethylenic homopolymers of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate, preferably ethylenic homopolymers of (Cg-C22)alkyl (meth)acrylate; and e) ethylenic copolymers of e1) (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate, and of e2) (Ci- C4)alkyl (Ci-C4)(alkyl)acrylate; preferably, the copolymers e) are copolymers of (Cg- C22)alkyl (meth) acrylate and of (Ci-C4)alkyl (meth)acrylate; iii) one or more hydrocarbon-based liquid fatty substances; iv) one or more plasticizers; and v) optionally one or more cosmetic active agents chosen from f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and j) UV (A) and/or (B) screening agents, and also m) mixtures thereof.
2. The oily dispersion (A) as claimed in the preceding claim, in which the particle(s) i) consist of an ethylenic polymeric core obtained from homopolymers a) or from copolymers b) or c), as defined in the preceding claim, and ii) of one or more polymeric surface stabilizers obtained from the homopolymer d) and the copolymers e) as defined in the preceding claim.
3. The oily dispersion (A) as claimed in claim 1 or 2, in which the polymer(s) constituting the particles i) are chosen from acrylate ethylenic homopolymers c) resulting from the polymerization of an identical monomer of formula (I):
H2C=C(R)-C(O)-O-R’ (I) in which formula (I):
- R represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and
- R’ represents a (Ci-C4)alkyl group such as methyl or ethyl, preferably a C1-C4 alkyl acrylate such as methyl acrylate.
4. The oily dispersion (A) as claimed in claim 1 or 2, in which the polymer(s) constituting the particles i) are chosen from acrylate ethylenic copolymers b) resulting from the polymerization:
- of at least two different monomers of formula (I) as defined in the preceding claim, preferably a C1-C4 alkyl acrylate such as methyl acrylate and ethyl acrylate; and
- optionally of a monomer of formula (II) H2C=C(R)-C(O)-O-H with R as defined in the preceding claim, in particular acrylic acid.
5. The oily dispersion (A) as claimed in any one of the preceding claims, in which the monomers are chosen from C1-C4 alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate or tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
6. The oily dispersion (A) as claimed in any one of the preceding claims, in which the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96% of monomers a) to c) relative to the total weight of polymers contained in said dispersion.
1. The oily dispersion (A) as claimed in any one of the preceding claims, in which the stabilizer(s) ii) are chosen from: d) ethylenic homopolymers resulting from the polymerization of monomers of formula H2C=C(R)-C(O)-O-R” with R representing a hydrogen atom or a (C1- C4)alkyl group such as methyl, and R” representing a (Cg-C22)alkyl and preferably (Cg-Ci8)alkyl group; preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl; and e) ethylenic copolymers of monomers of formulae (III) and (IV):
H2C=C(R)-C(O)-O-R’ (III) and H2C=C(R)-C(O)-O-R” (IV) in which formulae (III) and (IV):
- R, which may be identical or different, represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl;
- R’, which may be identical or different, represents a (Ci-C4)alkyl group such as methyl or ethyl; and
- R” represents a (Cg-C22)alkyl, preferably (Cio-C2o)alkyl and in particular (C2n)alkyl group with n being an integer equal to 5, 6, 7, 8, 9 or 10; preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl, more preferentially stearyl.
8. The oily dispersion (A) as claimed in the preceding claim, in which the stabilizer(s) ii) are chosen from ethylenic copolymers of monomers of formulae (III) and (IV); in particular, the weight ratio of the monomer of formula (IV), in particular isodecyl, lauryl, stearyl, hexadecyl or behenyl (meth)acrylate, preferably stearyl (meth)acrylate e1) / monomer of formula (III), in particular C1-C4 alkyl (meth)acrylate, preferably methyl and/or ethyl (meth)acrylate e2), i.e. e1)/e2), is greater than 4; advantageously, said weight ratio e1)/e2) ranges from 5 to 15; more preferentially, said weight ratio ranges from 5.5 to 12.
9. The oily dispersion (A) as claimed in any one of the preceding claims, in which the stabilizers(s) ii) are chosen from ethylenic copolymers e) resulting from the polymerization of a monomer of formula (IV) as defined in claim 7 or 8 and of two different monomers of formula (III) as defined in claim 7 or 8; preferentially, the stabilizer(s) ii) are chosen from copolymers resulting from the polymerization of one monomer chosen from isodecyl, lauryl, stearyl, hexadecyl or behenyl (meth)acrylate and of two different C1-C4 alkyl (meth)acrylate monomers, preferably methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl, lauryl, stearyl, hexadecyl or behenyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate is greater than 4; advantageously, said weight ratio ranges from 5 to 15; more preferentially said weight ratio ranges from 5.5 to 12.
10. The oily dispersion (A) as claimed in any one of the preceding claims, in which the oily dispersion (A) includes from 2% to 40% by weight, in particular 4% to 25%, notably from 5.5% to 20% by weight of (Cg-C22)alkyl (Ci-Ce)(alkyl)acrylate monomers included in d) or e) with the hydrocarbon-based liquid(s) iii), relative to the total weight of polymers contained in said dispersion.
11. The oily dispersion (A) as claimed in any one of the preceding claims, in which the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate and behenyl (meth)acrylate, and of one C1-C4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl, lauryl, stearyl, hexadecyl or behenyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate in the dispersion (A) is less than 1 ; in particular, said weight ratio ranges from 0.05 to 0.5; more preferentially, said weight ratio ranges from 0.08 to 0.2 in the dispersion (A).
12. The oily dispersion (A) as claimed in any one of the preceding claims, in which the ii) stabilizer(s) + i) polymer particle(s) assembly present in the dispersion (A) comprises from 2% to 40% by weight, notably from 4% to 30% by weight, preferably from 5% to 25% by weight relative to the total weight of the dispersion (A) and preferably from 4.5% to 20% by weight.
13. The oily dispersion (A) as claimed in any one of the preceding claims, in which the hydrocarbon-based liquid fatty substance(s) iii) are chosen from hydrocarbons, in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, nonsilicone waxes and silicones; in particular the hydrocarbon-based liquid fatty substance(s) are preferably volatile hydrocarbon-based oils or are a mixture of different volatile oils, preferably chosen from linear or branched Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes, more particularly chosen from undecane, dodecane, tridecane and isododecane; or a mixture of different oils, which are preferably volatile, comprising isododecane in the mixture, or a mixture of undecane and tridecane.
14. The oily dispersion (A) as claimed in any one of the preceding claims, in which the hydrocarbon-based liquid fatty substance(s) iii) are chosen from:
- plant oils formed by fatty acid esters of polyols, in particular triglycerides, such as sunflower oil, sesame oil, rapeseed oil, macadamia oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, corn oil, arara oil, cottonseed oil, apricot oil, avocado oil, jojoba oil, olive oil or cereal germ oil;
- linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon atoms; and notably isononyl isononanoate; and more particularly esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 7 to 19 carbon atoms and Re represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; more particularly esters of formula Rd-C(O)-O-Re in which Rd represents a higher fatty acid residue including from 8 to 10 carbon atoms and Re represents a hydrocarbon-based chain including from 12 to 18 carbon atoms;
- hydrocarbons and notably volatile or nonvolatile linear, branched and/or cyclic alkanes, such as optionally volatile Cs-Ceo isoparaffins, such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane, or Isopars, and mixtures thereof; or alkanes resulting from the complete hydrogenation/reduction of mixtures of fatty acids derived from Cocos nucifera (coconut) oil, such as dodecane; or the mixture of C9-C12 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes, in particular comprising dodecane, or else liquid paraffin, liquid petroleum jelly, or hydrogenated polyisobutylene;
- ethers containing 6 to 30 carbon atoms;
- ketones containing 6 to 30 carbon atoms; aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol;
- polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and
- mixtures thereof such as mixtures of esters of linear or branched Cs-C fatty acid and C12-C18 fatty alcohol and alkanes resulting from the complete hydrogenation/reduction of fatty acid mixtures obtained from Cocos nucifera (coconut) oil, in particular dodecane, such as mixtures of cocoyl caprylate/caprate and dodecane; or mixtures of C9-C12 alkanes, the chains of which comprise from 9 to 12 carbon atoms, preferably linear or branched C9-C12 alkanes, in particular comprising dodecane; preferably the hydrocarbon-based liquid fatty substance(s) iii) are chosen from linear or branched Ce-C , preferably Cs-Cu, more preferentially C9-C13 and even more preferentially C9-C12 alkanes, and even more preferentially the alkanes are volatile and are chosen from undecane, dodecane, isododecane, tridecane, and a mixture thereof notably comprising dodecane, isododecane or a mixture of undecane and tridecane; or else the liquid fatty substance(s) iii) are a mixture of nonvolatile oil(s) and volatile oil(s), notably comprising, as volatile oil, isododecane, undecane, dodecane, isododecane and/or tridecane, more preferentially isododecane; as a mixture of volatile and nonvolatile oil, mention may be made of the mixture of isododecane and isononyl isononanoate; and more preferentially, when the fatty substance(s) are a mixture of volatile and nonvolatile oil, the amount of volatile oil is greater than the amount of nonvolatile oil.
15. The oily dispersion (A) as claimed in any one of the preceding claims, which comprises a silicone oil which is preferably in an amount which does not exceed 10% by weight relative to the weight of the dispersion (A), more particularly in an amount of less than 5% and more preferentially 2%.
16. The oily dispersion (A) as claimed in any one of the preceding claims, in which the plasticizer(s) are chosen from those of the families of linear or branched, preferably branched, C8-C20 alkyl phthalates, esters, citrates, benzoates or neopentanoates, in particular chosen from compounds (V) and (V’) below:
Figure imgf000051_0001
in which formulae (V) and (V’):
- Rh and R1, which may be identical or different, represent a group from among: (C1- C2o)alkyl, aryl such as phenyl, aryl(Ci-C4)alkyl such as benzyl, preferably (C1- C4)alkyl such as n-butyl;
- n is 0, 1 , 2 or 3, preferably 0, 1 or 2, more preferentially, 1 or 2; and
- L represents a group from among: a) monovalent, divalent, trivalent or tetravalent C1-C10 alkyl, preferably trivalent (C2-Cs)alkyl, said monovalent, divalent, trivalent or tetravalent alkyl possibly being optionally substituted with one or more hydroxyl groups, optionally interrupted with at least one heteroatom such as O, N or S, preferably O, b) monovalent, divalent or trivalent cycloalkyl, or c) monovalent, divalent, trivalent or tetravalent aryl, preferably divalent or trivalent phenyl; preferably, L represents a group a) or c), in particular, the plasticizer(s) are chosen from:
* phthalates, preferably chosen from: di-n-hexyl phthalate (DnHP), diisoheptyl phthalate (DIHP), diheptyl phthalate (DnHP), bis(2-ethylhexyl) phthalate (DEHP), diheptylnonyl phthalate (DnHNP), di-n-octyldecyl phthalate (DNODP), diheptylnonylundecyl phthalate (DnHNUP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), di-n-nonyl phthalate (DnNP), diisodecyl phthalate (DIDP), di-n- nonyldecylundecyl phthalate (DnNDUP), dinonylundecyl phthalate (DnNUP), diundecyl phthalate (DUP), diisoundecyldodecyl phthalate (UDP), ditridecyl phthalate (DTDP), bis(2-ethylhexyl) terephthalate (DOTP), and butyl benzyl phthalate (BBP);
* adipic acid diesters and notably chosen from: diheptylnonyl adipate (DnHNA), bis(2-ethylhexyl) adipate (DEHA), diisopropyl adipate (DI PA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), benzene 1 ,2,4-tricarboxylic acid triesters such as triheptylnonyl trimellitate (TnHNTM), tris(2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), sebacic acid diesters such as bis(2-ethylhexyl) sebacate (DOS), nonanedioic acid diesters such as bis(2-ethylhexyl) azelate (DOZ), esters such as isodecyl neopentanoate, and isostearyl neopentanoate;
* citrates, notably chosen from: tributyl citrate, triethyl citrate, tributyl 2-acetylcitrate;
* benzoates, in particular chosen from: 1 ,2-propylene glycol dibenzoate (PGDB), diethylene glycol dibenzoate (DEGDB), dipropylene glycol dibenzoate (DPGDB), triethylene glycol dibenzoate (TEGDB), isodecyl benzoate, isononyl benzoate and 2-ethylhexyl benzoate; even more preferentially, the plasticizer(s) iv) of the invention are chosen from isodecyl neopentanoate, isostearyl neopentanoate, tributyl citrate, diisopropyl adipate and propylene glycol dibenzoate. The oily dispersion (A) as claimed in any one of the preceding claims, which comprises one or more cosmetic active agents v) particularly chosen from:
- organic pigments and mineral or inorganic pigments,
- pigments with special effects such as fluorescent pigments, thermochromic pigments, photochromic pigments, coated or uncoated nacres, in the form of pigment powder or paste, lakes, and glitter flakes, or mixtures thereof;
- said pigments may be dispersed in the product by means of a dispersant and the pigments may be surface-treated with an organic agent; in particular, the cosmetic active agent(s) v) are chosen from:
- nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone organic pigments;
- white or colored organic pigments which are chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references Blue 1 Lake Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenolic derivatives;
- mineral pigments or inorganic pigments chosen from iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide; preferably, the cosmetic active agent(s) v) are chosen from carbon black, iron oxides, notably red, brown or black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, an alkali metal salt of lithol red, such as the calcium salt of lithol red B; more preferentially, the pigment(s) used are chosen from red iron oxides and azo pigments, notably red azo pigments such as D&C Red 7.
18. A process for treating keratin materials, notably human keratin materials such as the hair or the skin, comprising the application to said materials of the oily dispersion (A) as defined in any one of the preceding claims.
19. A process for preparing the dispersion (A) as defined in any one of claims 1 to 17, comprising the following steps:
- in a first step, the stabilizer ii) is prepared by mixing the constituent monomer(s) of the stabilizing polymer d) or e) with v) a free-radical initiator, in a solvent, and polymerizing these monomers;
- in a second step, the constituent monomers of the polymer of the particles i) are added to the stabilizer formed in the preceding step and polymerization of these monomers is performed in the presence of the free-radical initiator v);
- the plasticizer(s) iv) and optionally one or more cosmetic active agents chosen from f) dyes and/or pigments, g) active agents for caring for keratin materials, notably the skin, and h) UV-screening agents and also j) mixtures thereof, may be added during the first step; or - the plasticizer(s) iv) are added during the second step; or
- the plasticizer(s) iv) are added after the second step, in a third step, or
- said cosmetic active agent(s) are added during the second step with said plasticizer(s) iv) or after the second step or even after the third step; it being understood that:
• when the nonaqueous medium is a nonvolatile hydrocarbon-based liquid fatty substance iii), the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the nonvolatile hydrocarbon-based liquid fatty substance (which must be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent; and
• the polymeric stabilizer monomer(s) ii), and the radical initiator v), are soluble in the synthesis solvent, which synthesis solvent is preferably an apolar organic solvent more preferentially chosen from liquid fatty substances iii), in particular alkanes such as heptane, cyclohexane, undecane, dodecane, isododecane or tridecane, preferably isododecane.
20. The use of an oily dispersion (A) as defined in any one of claims 1 to 17, for treating keratin materials, notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, preferably for dyeing keratin fibers and/or for shaping keratin fibers such as the hair, or for making up the skin.
21. A multi-compartment device comprising ingredients i) to iv) and optionally v), in which ingredients i) to iii) as defined in any one of claims 1 to 15 are in the same compartment, iv) as defined in claim 16 is in another compartment, and optionally v) is in another compartment, or in the compartment with i) to iii), or in the compartment with iv).
PCT/EP2022/077577 2021-10-05 2022-10-04 Oily dispersion comprising a polymeric particle and a stabilizer bearing a c9-c22 alkyl group and a plasticizer, and process for treating keratin materials using the oily dispersion WO2023057446A1 (en)

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