WO2022129195A1 - Dispersion comprising a polymeric particle, a stabilizer bearing a c3-c12 cycloalkyl group, an oil and water, and process for treating keratin materials using the dispersion - Google Patents

Dispersion comprising a polymeric particle, a stabilizer bearing a c3-c12 cycloalkyl group, an oil and water, and process for treating keratin materials using the dispersion Download PDF

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Publication number
WO2022129195A1
WO2022129195A1 PCT/EP2021/085933 EP2021085933W WO2022129195A1 WO 2022129195 A1 WO2022129195 A1 WO 2022129195A1 EP 2021085933 W EP2021085933 W EP 2021085933W WO 2022129195 A1 WO2022129195 A1 WO 2022129195A1
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Prior art keywords
dispersion
acrylate
weight
chosen
notably
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PCT/EP2021/085933
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French (fr)
Inventor
Philippe Ilekti
Mireille Arnaud-Roux
Simon TAUPIN
Julien PORTAL
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L'oreal
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Publication of WO2022129195A1 publication Critical patent/WO2022129195A1/en

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    • 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
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

  • the present invention relates to a dispersion (A) comprising i) at least one particle consisting of an ethylenic polymer, ii) at least one polymeric stabilizer comprising a (C3- Ci2)cycloalkyl group, iii) at least one hydrocarbon-based fatty substance which is liquid at 20°C and 1 atmosphere, and iv) water.
  • the invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin, the hair, the eyelashes or the eyebrows, involving the application to said materials of at least one dispersion (A); to a process for preparing the dispersion, and to a multi-compartment kit comprising ingredients i) to iv).
  • 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 2010/046229 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 fibres with dye compositions containing direct dyes. These dyes are coloured and colouring molecules that have affinity for keratin fibres. They are applied to the keratin fibres for a time necessary to obtain the desired colouring, 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 colourings that are visible on dark hair.
  • Another dyeing method consists in surface dyeing, notably using pigments.
  • pigments on the surface of keratin fibres generally makes it possible to obtain colourings that are notably visible on dark hair, since the surface pigment masks the natural colour of the fibre.
  • the use of pigment for dyeing keratin fibres is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibres, a composition comprising at least one dispersion of film-forming polymer particles including 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, which is not tacky, which has good persistence with respect to external attacking factors, and over time, does not leach, and is resistant to sweat and sebum and insensitive to oils such as dietary oils.
  • the composition may comprise cosmetic active agents such as those for obtaining a skin-tensioning effect, for caring for the body, the face and the hair, for protecting against ultraviolet (UV), or for making up the face, the lips, the eyelashes, the eyebrows and the hair.
  • Said composition may notably be intended for care and/or makeup, notably for making up the lips.
  • one of the aims of the present invention is to provide a composition with a reduced content of volatile compounds.
  • Another aim is to provide a film-forming composition containing an aqueous phase, affording access to a wider formulation range. For environmental reasons, but also for the purpose of avoiding potential long-term damage to keratin materials, it is sought to use as few surfactants as possible in the cosmetic composition.
  • Another aim of the present invention is to provide a composition for treating keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows, which has good resistance 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 fibres may be subjected, without degrading said fibres, and while keeping the keratin fibre strands perfectly separated.
  • keratin fibres notably human keratin fibres such as the hair, the eyelashes or the eyebrows
  • a dispersion (A) for treating keratin materials in particular a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes and the eyebrows or P) human skin, in particular of the lips
  • the dispersion (A) comprises: i) one or more particles including one or more polymers chosen from a) one or more ethylenic copolymers of: ai) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, and
  • ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a 2 ) is a (Ci-C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) copolymers of:
  • Ci (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate
  • the subject of the invention relates to the use of the 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 fibres and/or for shaping keratin fibres such as the hair, or for making up the skin or for skincare or for providing a non-coloured immediate effect.
  • keratin materials notably human keratin materials such as the hair, the eyelashes, the eyebrows or the skin, preferably for dyeing keratin fibres and/or for shaping keratin fibres such as the hair, or for making up the skin or for skincare or for providing a non-coloured immediate effect.
  • a subject of the invention is also the dispersion (A) as defined previously, and also a process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows, or P) human skin, in particular of the lips, comprising the application to said materials of a dispersion (A), as defined previously.
  • a subject of the invention is also a kit or device comprising several compartments comprising the ingredients i) to iv) as defined previously.
  • a subject of the invention is also a composition, preferably a cosmetic composition, comprising the dispersion (A) as defined previously, and the process for applying said composition to keratin materials.
  • a subject of the invention is also a process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes, the eyebrows or P) human skin, in particular the lips, comprising the application to said materials of at least one dispersion (A), as defined previously; preferentially, after application of the dispersion (A) to the keratin materials, the composition is left to dry on said keratin materials, either naturally, or with the aid of heating devices used in cosmetics, such as a hairdryer.
  • keratin materials preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes, the eyebrows or P) human skin, in particular the lips, comprising the application to said materials of at least one dispersion (A), as defined previously; preferentially, after application of the dispersion (A) to the keratin materials, the composition is left to dry on said keratin materials, either naturally, or
  • the 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 fatty substances such as oils. Furthermore, the dispersion is easy to use in compositions, notably cosmetic compositions, is easy to manufacture and remains stable over time. Specifically, the 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 dispersion (A), notably lip makeup, is particularly resistant to external attacking factors such as liquid fatty substances, in particular with respect to plant oils such as olive oil.
  • the makeup results obtained with the dispersions (A) are very aesthetic and glossy.
  • 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 dispersions (A) of the invention to keratin fibres makes it possible to obtain coatings that are persistent with respect to external attacking factors (sunlight, water, shampoo washing, perspiration, sebum, etc.).
  • the coloured keratin materials have a colouring that is visible on all types of materials, notably on dark keratin materials, which is persistent with respect to soaps, shower gels or shampoos while at the same time preserving the physical qualities of the keratin material.
  • a coating is in particular resistant to the external attacking factors to which the keratin fibres, notably the hair, may be subjected, such as blow-drying and perspiration.
  • dispersion (A) on keratin materials, in particular on keratin fibres makes it possible to obtain a smooth and uniform deposit. Moreover, it has been observed, surprisingly, that the keratin fibre strands remained perfectly separated, and could 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, n-propyl, isopropyl or i-propyl, n-butyl, isobutyl or i-butyl and tert-butyl or t-butyl;
  • 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, and which may be substituted with one or more (Ci-C4)alkyl groups such as methyl, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl; 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 fibres such as head hair, the eyelashes, the eyebrows, and bodily hair, preferentially head hair, the eyebrows and the eyelashes, even more preferentially head hair;
  • keratin fibres with strand separation means keratin fibres, notably the hair, which, after application of the composition and drying, are not stuck together (or of which the strands are all separated from each other) and thus do not form clumps of fibres;
  • the term “insoluble monomer 1 ’ thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e. completely dissolved to 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 fatty substance(s) iii);
  • ethylenic homopolymer means a polymer derived from the polymerization of identical monomers
  • ethylenic 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;
  • 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;
  • fatty substance means an organic compound that is immiscible 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 ethanol, ether, 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;
  • 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, 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 optionally of 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 non-zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour 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);
  • non-volatile oif means an oil with a vapour 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 non-volatile;
  • 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 colour 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 inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.
  • hair dyes refers to the oxidation dyes and direct dyes used for dyeing keratin fibres, notably human keratin fibres 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 coloured 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 coloured 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 and 0.9 pm, and preferably between 0.2 and 0.6 pm;
  • thickening polymer 1 means a polymer which, when introduced at 1 % by weight into an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or into an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s’ 1 . This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like).
  • the thickening polymers may thicken the aqueous phase and/or the fatty phase, preferentially the aqueous phase;
  • organic thickening polymer means a thickening polymer as defined previously, which is formed from carbon and hydrogen, and possibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine or bromine, and also phosphorus, alkali metals such as sodium or potassium, or alkaline-earth metals such as magnesium or calcium.
  • the organic polymers according to the invention do not comprise silicon;
  • non-cellulose-based organic thickening polymer means an organic thickening polymer not including any cellulose units
  • the 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) water.
  • 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 hydrocarbon-based liquid fatty substance(s) iii) optionally containing iv) water.
  • 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 hydrocarbon-based liquid fatty substance(s) iii) optionally containing iv) water.
  • the dispersions according to the invention consist of particles, which are generally spherical, and of at least one surface-stabilized polymer.
  • said particles i) are not or are sparingly crosslinked.
  • the polymer particles i) and the stabilizer(s) ii) are preferably in the hydrocarbonbased liquid fatty substance(s) iii) in an amount of between 2% and 40% by weight, notably between 4% and 35% by weight of soluble monomer (the monomer forming the stabilizer(s) ii)) and between 60% and 98% by weight, notably from 65% to 96% by weight, of insoluble monomer (the monomer forming the particles i)).
  • soluble monomer refers to any monomer of which the polymer, notably the homopolymer, is soluble, to 5% by weight, at 20°C and at atmospheric pressure in the liquid hydrocarbon-based medium consisting of liquid hydrocarbon-based fatty substances iii) of the dispersion.
  • the polymer, notably the homopolymer is completely dissolved in the liquid carbon-based medium, visually at 20°C (no apparent visible deposit, or any insoluble agglomerate or sediment visible to the eye).
  • insoluble monomer refers to any monomer of which the polymer, notably the homopolymer, 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 liquid hydrocarbon-based medium consisting of iii) liquid hydrocarbon-based fatty substances.
  • the monomers i) that are capable of forming the polymeric core of the particle are chosen from monomers that are insoluble in the liquid hydrocarbon-based medium consisting of iii) liquid hydrocarbon-based fatty substances.
  • the insoluble monomers notably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle.
  • the dispersion (A) does not contain a crosslinked and nonelastomeric amphiphilic silicone compound.
  • the dispersion (A) does not contain a silicone resin.
  • the dispersion (A) does not contain a silicone polyamide.
  • the dispersion (A) does not contain polymer containing styrene group.
  • the particle(s) i) of dispersion (A) of the invention consist of one or more ethylenic copolymers derived from the polymerization: a1) of at least one (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer, and a2) of at least one ethylenic monomer comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl; in particular, a2) is a (Ci-C4)(alkyl)acrylic acid.
  • the particle(s) i) consist of an ethylenic polymeric core derived from copolymers a) as defined previously.
  • ethylenic copolymer 1 means a polymer derived from the polymerization of at least two monomers chosen from one or more (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomers a1) and of one or more ethylenic monomers a2) comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as phenyl.
  • the ethylenic compound may also be a cyclic compound, which is preferably 5- or 6-membered, and comprising an ethylenic unsaturation.
  • ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups
  • the monomer is substituted on one of the carbon atoms of the polymeric monomer with one or more groups, preferably only one group, chosen from carboxyl -C(O)-OH, phosphoric acid -O-P(O)(OH)2 or -P(O)(OH)2, and sulfonic acid -O-S(O)2-OH or -S(O)2-OH, maleic anhydride, and aryl such as phenyl.
  • the particle(s) i) include a) ethylenic copolymers of a1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of a2) ethylenic monomers comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as benzyl.
  • 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 , Rb 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 more particularly, a2) is chosen from (1) and (4), in particular (4) and notably (5).
  • a2) 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.
  • a2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid and salts thereof; more preferentially, a2) represents maleic anhydride.
  • the salts may be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminium, manganese or copper; ammonium salts of formula NH4 + ; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, diethylamides, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.
  • alkali metals for example sodium or potassium
  • salts of alkaline-earth metals for example calcium, magnesium or strontium
  • metal salts for example zinc, aluminium, manganese or copper
  • ammonium salts of formula NH4 + quaternary ammonium salts
  • salts of organic amines for instance salt
  • the (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate monomer(s) a1) are chosen from those of formula (I):
  • IW C(R
  • - R represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl
  • - R’ represents a (Ci-C4)alkyl group such as methyl, ethyl, n-propyl, /-propyl, n-butyl, /-butyl or, f-butyl, preferably methyl, ethyl or /-butyl, preferably, (I) represents a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer a) derived from the polymerization:
  • the amount of a2), notably of compound (II) and in particular of acrylic acid is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of monomers of the particle i), even more particularly between 5% and 25% by weight relative to the weight of the polymer of the particles i), better still between 10% and 15% by weight relative to the weight of the polymer of the particles i).
  • the amount of a2), notably of compound (II) and in particular of acrylic acid is greater than 35 % by weight relative to the total weight of the particle i), more particularly between 40 % and 70% by weight relative to the weight of monomers of the particle i), even more particularly between 50% and 60% by weight relative to the weight of the polymer of the particles i), better still 57 % by weight relative to the weight of the polymer of the particles i).
  • a) is a copolymer derived from the copolymerization a2) of acrylic acid with a1) one or more C1-C4 alkyl (meth)acrylate monomers, preferably at least two different C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobutyl (meth)acrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer a) derived from the polymerization:
  • the polymer of the particles i) is a polymer derived from C1-C4 alkyl (meth)acrylate monomers a1).
  • a linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (Ci-Cs)alkyl acrylate, monomer is used.
  • a) is chosen from methyl acrylate and ethyl acrylate.
  • the monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
  • the polymer constituting the particles i) is an acrylate copolymer a) derived from: a1) at least one monomer of formula (I) as defined previously; and a2) at least one ethylenically unsaturated anhydride monomer notably of formula (4) as defined previously.
  • the polymer of the particles a) is a polymer a1) of linear or branched, preferably linear, C1-C4 alkyl (meth)acrylate, in particular (Ci-Cs)alkyl (meth)acrylate monomer, and a2) of ethylenically unsaturated anhydride monomer.
  • the monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate.
  • one or two different linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (Ci-Cs)alkyl acrylate, monomers a1) are used.
  • a1) is chosen from methyl acrylate and ethyl acrylate.
  • one or two different branched (Cs-C4)alkyl (meth)acrylate monomers are used.
  • a1 is chosen from isobutyl acrylate and isobutyl methacrylate.
  • the ethylenically unsaturated anhydride compound(s) a2) of the invention are chosen from the maleic anhydride derivatives (4a) and the itaconic anhydride derivatives (4b) as defined previously.
  • the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and even more preferentially is maleic anhydride.
  • the polymer of the particles may be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers.
  • the copolymer(s) of the particles i) of the dispersion comprise from 80% to 95% by weight of ingredient a1) and from 5% to 20% by weight of ingredient a2), relative to the total weight of the copolymer(s).
  • the copolymer(s) of the particles i) of the dispersion comprise from 80% to 95% by weight of ingredient a1) and from 40% to 70%, particularly from 50 to 60 % by weight of ingredient a2), relative to the total weight of the copolymer(s).
  • the polymer of the particles i) preferably comprises from 80% to 93% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 7% to 20% by weight of ingredient a2) relative to the total weight of the polymer i). More preferentially, the polymer of the particles i) preferably comprises from 85% to 93% by weight, more particularly 87% to 92% by weight and even more preferentially from 85% to 90% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 10% to 20% by weight of ingredient a2) relative to the total weight of the polymer.
  • the polymer of the particles i) is a non-crosslinked polymer.
  • the copolymer(s) i) are chosen from:
  • the polymer of the particles i) of the dispersion preferably has a number-average molecular weight ranging from 2000 to 10 000 000.
  • the polymer of the particles i) may be present in the dispersion (A) in an amount ranging from 20% to 60% by weight relative to the total weight of the dispersion, in particular between 21 % and 58.5% by weight relative to the total weight of the dispersion, preferably ranging from 30% to 50% by weight relative to the total weight of the dispersion, more preferentially ranging from 36% to 42% by weight relative to the total weight of the dispersion (A).
  • the particle(s) i) consist of a copolymer of a1) and a2).
  • the particles i) consist of copolymers derived from the polymerization of monomers a1) and a2) with an a1)/a2) weight ratio inclusively between 4.4 and 20, more particularly between 5.5 and 19, preferably between 6.5 and 16 and even more preferentially between 6.6 and 15.6.
  • the polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 to 600 nm, notably ranging from 10 to 500 nm and better still ranging from 20 to 400 nm.
  • 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) of the invention are constituted of ethylenic polymers chosen from b) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate.
  • the stabilizer(s) of the invention are constituted of ethylenic polymers chosen from c) copolymers of c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate.
  • the stabilizer(s) of the invention consist of ethylenic polymers chosen from b) polymers of (C3-Ci 2 )cycloalkyl(Ci-C6)(alkyl)acrylate monomers particularly of formula (III) as defined previously.
  • the stabilizer(s) of the invention consist of ethylenic polymers chosen from c) copolymers of c1) (C3- Ci 2 )cycloalkyl (Ci-Ce)(alkyl)acrylate particularly of formula (III) as defined previously and of c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate particularly of formula (I) as defined previously.
  • the ingredient c2 is a (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer notably of formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate, more preferentially methyl (meth)acrylate.
  • the ingredient c2 is a mixture of several different (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomers, notably two different (C1- C4)alkyl (Ci-C4)(alkyl)acrylate monomers notably of formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
  • the stabilizer ii) is chosen from b) polymers of (C3-Ci 2 )cycloalkyl (C1- C6)(alkyl)acrylate monomers; and c) statistical copolymers of c1) (C3-Ci 2 )cycloalkyl (C1- C6)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate with a c1/c2 weight ratio of greater than 4.
  • said weight ratio ranges from 4.5 to 19. More advantageously, said weight ratio c1/c2 ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
  • the stabilizer ii) is a polymer chosen from b) isobornyl (meth)acrylate homopolymer and c) statistical copolymers c1) of isobornyl (meth)acrylate and c2) of C1-C4 alkyl (meth)acrylate preferably present in an isobornyl (meth)acrylate/Ci- C4 alkyl (meth)acrylate weight ratio (c1/c2) of greater than 4.
  • said weight ratio c1/c2 ranges from 4.5 to 19.
  • said weight ratio c1/c2 ranges from 5 to 15 and more preferentially said weight ratio c1/c2 ranges from 5.5 to 12.
  • 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 stabilizer is chosen from: b) isobornyl acrylate homopolymers, c) statistical copolymers of isobornyl acrylate/methyl acrylate, statistical copolymers of isobornyl acrylate/ethyl acrylate, and statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate in the weight ratio described previously.
  • the stabilizing polymer ii) preferably has a number-average molecular weight ranging from 10 000 to 400 000 and preferably ranging from 20 000 to 200 000.
  • the stabilizer ii) is in contact with the surface of the polymer particles i) and thus makes it possible to stabilize these particles at the surface in order to keep these particles in dispersion in the medium of the dispersion (A).
  • the stabilizer(s) ii) are chosen from c) copolymers of: c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate; and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate; with from 80% to 95% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 5% to 20% by weight of ingredient c2), notably methyl acrylate and ethyl acrylate, relative to the total weight of the stabilizer.
  • the stabilizer(s) ii) comprise from 85% to 94% by weight and more particularly 87% to 93% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 10% to 20% by weight of ingredient of c2), notably methyl acrylate and/or ethyl acrylate, relative to the total weight of the polymer.
  • the sum ii) of stabilizer(s) + i) of polymer particle(s) present in the dispersion (A) comprises from 5% to 60% and in particular comprises from 10% to 40% by weight of polymers b) or c) and from 60% to 90% and in particular from 61% to 89% by weight of polymers a), relative to the total weight of the sum ii) of stabilizer(s) + i) of polymer particle(s).
  • the sum ii) of stabilizer(s) + i) of polymer particle(s) present in the dispersion comprises from 15% to 30% by weight of polymers b) or c) and from 70% to 85% by weight of polymers a), relative to the total weight of the sum ii) of stabilizer(s) + i) of polymer particle(s).
  • the dispersion (A) is such that the sum ii) of stabilizer(s) + i) of polymer particle(s) are present in the dispersion (A) from 2% to 40% by weight, notably from 4% to 35% by weight and preferably from 4.5% to 30% by weight relative to the total weight of the dispersion (A).
  • 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 shiny film-forming deposits which are resistant to fatty substances at room temperature (25°C), and which are notably advantageous for makeup applications.
  • the final size of the particles is 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 analyser (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 analysed 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 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 substance(s) iii) of the invention are chosen from hydrocarbons, in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, esters of fatty acids and/or of fatty alcohols, non-silicone waxes, and silicones; in particular, the liquid hydrocarbon-based fatty substance(s) are hydrocarbon-based oils, which are preferably volatile, or are a mixture of different volatile oils, preferentially chosen from isododecane and octyldodecanol, more particularly isododecane.
  • 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 50 carbon atoms, preferably between Ce and C , and in particular alkanes, oils of animal origin, oils of plant origin, glycerides, fatty alcohols, fatty acid and/or fatty alcohol esters, 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 50 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • Ce-C alkanes they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, undecane, dodecane, tridecane or isoparaffins, such as isohexadecane, isodecane or isododecane, and mixtures thereof such as the combination of undecane and tridecane, for instance Cetiol UT®.
  • the linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, 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 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 non-volatile.
  • the liquid hydrocarbonbased fatty substance(s) are hydrocarbon-based oils which are volatile or are a mixture of different volatile oils.
  • the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and a non-volatile oil such as an isododecane/octyldodecanol mixture.
  • the hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably:
  • Cs-Cu alkanes for instance Cs-Cu isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl,
  • n-undecane (C11), n-dodecane (C12), n-tridecane (C13) 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 2008/155 059 from the company Cognis, and mixtures thereof, also sold under the name Cetiol UT®,
  • oils of plant origin such as triglycerides constituted 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, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower
  • hydrocarbons of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof.
  • the dispersion (A) may comprise a silicone oil. If the 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 more preferentially 2%.
  • the dispersion (A) comprises at least one liquid hydrocarbon-based 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 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 or cereal germ oil;
  • Cs-Ceo isoparaffins which are optionally volatile, such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane or Isopars; or else liquid paraffins, liquid petroleum jelly, or hydrogenated polyisobutylene; notably isododecane;
  • 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; notably octyldodecanol;
  • the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
  • the dispersion (A) comprises at least one apolar liquid hydrocarbonbased fatty substance iii) preferably chosen from:
  • Cs-Cso linear or branched Cs-Cso, in particular C10-C20 and more particularly C10-C16 alkanes, which are volatile or non-volatile, preferably volatile;
  • non-aromatic cyclic C5-C12 alkanes which are volatile or non-volatile, preferably volatile;
  • the liquid hydrocarbon-based fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular containing from 10 to 14 carbon atoms, which are preferably volatile, more particularly the apolar oils, described previously.
  • isoalkanes of petroleum origin also known as isoparaffins
  • isododecane also known as 2,2,4,4,6-pentamethylheptane
  • isodecane and, for example, the oils sold under the Isopar or Permethyl trade names
  • liquid hydrocarbon-based fatty substance(s) iii) of the invention are apolar, more particularly isododecane.
  • the hydrocarbon-based liquid fatty substance(s) are a mixture of non-volatile and volatile oil; preferably, the mixture comprises isododecane as volatile oil or a mixture of oils, notably of undecane and tridecane.
  • the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
  • the liquid hydrocarbon-based fatty substance(s) iii) are in the dispersion of the invention in an amount of between 15% by weight and 80% by weight, more preferentially between 20% and 60% by weight relative to the total weight of said dispersion (A).
  • the weight ratio of the sum of the ingredients [i) + ii)] I iii) is less than or equal to 1 , more particularly, the mass ratio [i) + ii)] / iii) is between 0.5 and 1.
  • a dispersion in iii) notably isododecane, of surface-stabilized polymer particles i) chosen from:
  • dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer + particles) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate;
  • dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer + particles) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate;
  • dispersion in isododecane of methyl acrylate/ethyl acrylate/maleic anhydride 50/37.2/12.8 copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer ii) + particles i)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.
  • a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer ii) + particles i)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
  • the amount of particles i) in the dispersion (A) of the invention preferably ranges from 20% to 50% by weight and more preferentially from 25% to 45% by weight relative to the total weight of the dispersion.
  • the dispersion according to the invention may be prepared in the following manner:
  • the polymerization is performed in “dispersion” 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 b) and c) as defined previously.
  • the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer b) or c) with vi) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
  • the monomers constituting the polymer of the particles i) is added to the stabilizing polymer ii) formed in the preceding step and polymerization of these added monomers is performed in the presence of the radical initiator.
  • water is added and the ingredients i) + ii) are all stirred in the reactor before taking out the dispersion.
  • the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon-based liquid fatty substance (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
  • synthesis solvent apolar organic solvent
  • the synthesis solvent may consist of hydrocarbon-based liquid fatty substance iii) combined with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
  • step 1 when the synthesis solvent is a mixture, the additional solvent including the hydrocarbon-based aliphatic-chain esters as defined previously is removed via a method that is conventional to those skilled in the art, such as distillation.
  • the polymers of the particles i) and the stabilizers ii) are found in the hydrocarbon-based liquid fatty substance iii).
  • the dispersion (A) optionally contains one or more cosmetic active agents v).
  • the cosmetic active agent(s) v) 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. According to another variant, said cosmetic active agent(s) are added during the second step or after the second step.
  • said cosmetic active agent(s) are added during the third step.
  • a synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator vi) are soluble therein, and the polymer particles i) obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.
  • the synthesis solvent chosen is one which is apolar, organic and volatile, preferably chosen from alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.
  • a polar solvent notably chosen from esters such as (Ci-C4)alkyl (Ci-C4)alkylate, for example ethyl acetate.
  • 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 synthesis solvent is a mixture of liquid fatty substance such as iii) and notably isodecane with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate and notably ethyl acetate, said additional solvent being chosen to have a boiling point below that of the liquid fatty substance.
  • an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate and notably ethyl acetate, said additional solvent being chosen to have a boiling point below that of the liquid fatty substance.
  • the additional solvent is removed and a mixture of i) and ii) in the liquid fatty substance is obtained.
  • 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 vi) 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.
  • radical initiators 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.
  • initiators vi) such as:
  • 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) prepared beforehand.
  • 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.
  • 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.
  • the composition according to the invention preferably comprises a content of solids (or active material) of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of the dispersion (A), and preferably ranging from 15% to 60% by weight, notably 20% to 50% by weight relative to the total weight of the dispersion (A).
  • 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 liquid hydrocarbon-based 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 vi) 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.
  • a third step water or an aqueous composition is added, preferably with stirring, at room temperature and at atmospheric pressure.
  • the dispersions are prepared in the presence of one or more liquid hydrocarbonbased fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
  • the process is performed according to the following three steps:
  • Step 1 Synthesis of the polymer particles in the hydrocarbon-based oil iii)
  • the polymer particles are synthesized in the hydrocarbon-based oil iii), which is preferably a volatile apolar oil.
  • An additional solvent may be mixed with the volatile polar hydrocarbon-based oil and will be chosen from esters with a chain containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
  • the dispersion of the polymer particles in the hydrocarbon-based oil iii) or the mixture of hydrocarbon-based oil/short-chain ester may be prepared in the following manner:
  • the polymerization is performed in “dispersion”, i.e. by precipitation of the polymer being formed, with protection of the particles i) formed with one or more stabilizers ii), preferably one stabilizer.
  • Step 1 the stabilizing polymer ii) (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer with a free-radical initiator vi), in a solvent known as the synthesis solvent, and by polymerizing these monomers; [00157] Step 2, the constituent monomer(s) of the polymer of the particles 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 vi).
  • the polymerization is preferentially performed in the presence vi) of one or more free-radical initiators vi) as defined previously.
  • the polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.
  • the polymer particles are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer.
  • step 1 At the end of this step 1 , the short-chain ester is removed by distillation. Thus, the polymer of the particles is found in the volatile polar hydrocarbon-based oil.
  • Step 3 The water is added and stirred with the mixture of polymer of the particles + volatile polar hydrocarbon-based oil before removing the dispersion from the reactor.
  • the polymer according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in making up the eyes (mascara, eyeshadow or eyeliner) and in lipsticks.
  • 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 filmforming deposits that are resistant to fatty substances at the observation temperature (25°C).
  • said dispersion is in oily medium with the presence of water, it becomes easy to formulate it in cosmetic compositions based on oily medium commonly used in cosmetics, in particular in the fatty phases of emulsions, but also in the aqueous phases of emulsions to enable the dissolution of water-soluble or hydrophilic active agents.
  • Step 1 Synthesis of the stabilizing polymer ii)
  • the polymer forming the stabilizer ii) is synthesized in a volatile apolar hydrocarbon-based oil iii), and optionally at least one additional polar solvent such as an ester with a chain containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
  • a volatile apolar hydrocarbon-based oil iii) optionally at least one additional polar solvent such as an ester with a chain containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
  • the polymerization is preferably performed in the presence of at least one radical initiator vi) as defined previously.
  • Step 2 Addition of water [00173] Before the preparation of i), notably of the core of the polymer particles i), water iv) is added to the medium containing the stabilizing polymer(s) ii), the volatile apolar hydrocarbon-based oil iii) and optionally the additional solvent.
  • Step 3 Synthesis of the core of the polymer particles
  • the preparation of i) and notably of the core of the polymer particles i) is preferably performed in the presence of at least one radical initiator vi) as defined previously.
  • the additional solvent(s) are removed by distillation.
  • the polymer particles i) + ii) are found in the volatile apolar hydrocarbon-based oil iii) in the presence of water iv).
  • the dispersion (A) according to the invention finds an application in caring for and/or making up the skin and/or the lips and/or for the care, styling and/or dyeing of keratin fibres, preferably the hair.
  • the dispersion according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in lipsticks and lip glosses, and eyeshadows and mascaras.
  • the dispersion (A) comprises water iv).
  • the amount of water in the dispersion is between 5% and 49% by weight relative to the total weight of the dispersion, particularly between 10% and 47% by weight, more particularly between 15% and 48% by weight, more preferentially between 18% and 45% by weight and even more preferentially between 20% and 44% by weight relative to the total weight of the dispersion.
  • the dispersion (A) comprises one or more copolymers a) derived from a1) and a2), with a2) representing an ethylenic compound comprising one or more anhydride groups such as maleic anhydride, then the dispersion does not contain:
  • any thiol-based compounds chosen from a) an emulsion made with a fluid silicone which comprises thiol groups (supplier ref.: KM-9769) - Shin-Etsu, b)
  • the dispersion (A) does not comprise any polyamine compounds containing several primary amine and/or secondary amine groups, and does not comprise any amino alkoxysilane when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride. Even more particularly, the dispersion (A) does not contain any compound comprising one or more amino groups -NH2 when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride.
  • the dispersion (A) does not comprise any thiol-based polymer when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride. Even more particularly, the dispersion does not contain any compound comprising one or more thiol groups when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride.
  • thiol-based polymer 1 means a star, comb, brush or dendritic homopolymer or copolymer comprising one or more thiol groups which may be present as end groups or side groups.
  • the weight ratio of the hydrocarbon-based liquid fatty substance(s) iii)/the water v) is between 0.2 and 10, more particularly between 0.5 and 8, preferably between 0.6 and 7, more preferentially between 0.7 and 6.
  • the water that is suitable for use in the invention may be tap water, distilled water, spring water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a thermal water.
  • the dispersion may also comprise one or more water-soluble solvents.
  • water-miscible solvent denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
  • water-miscible solvents that may be used in dispersion (A) of the invention may also be volatile.
  • the water may also comprise any water-soluble or water-dispersible compound that is compatible with an aqueous phase, such as associated film-forming polymers, surfactants, and mixtures thereof.
  • surfactant means a “surface agent’, which is a compound that is capable of modifying the surface tension between two surfaces; surfactants are amphiphilic molecules, i.e. they contain two parts of different polarity, one lipophilic and apolar, and the other hydrophilic and polar.
  • the surfactants may be nonionic, anionic, amphoteric or cationic active agents.
  • the dispersion of the invention does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferentially not more than 2% by weight of surfactants relative to the total weight of the dispersion, more particularly not more than 1 % by weight of surfactants relative to the total weight of the dispersion; even more preferentially, the composition does not comprise more than 0.5% by weight of surfactants relative to the total weight of the dispersion, and better still the mixture does not comprise any surfactant.
  • 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 f) 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 iv) one or more cosmetic active agents chosen from pigments.
  • the pigment(s) more particularly represent from 0.5% to 40% by weight and preferably from 1 % to 20% by weight relative to the total weight of the dispersion (A).
  • the pigments are white or coloured 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.
  • 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.
  • mineral pigment refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia 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 coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Colour Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Colour Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Colour Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Colour Index under the references Cl 11725, 45370, 71105, the red pigments codified in the Colour 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,
  • pigment pastes of organic pigments such as the products sold by the company Hoechst under the names:
  • 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 be composed notably 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.
  • the organic pigment may also be a lake.
  • the term “lake” means 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 aluminium borosilicate and aluminium.
  • D&C Red 21 (Cl 45380), 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).
  • 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.
  • pigments with special effects means pigments that generally create a coloured 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 coloured 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 covered with titanium or with bismuth oxychloride, coloured 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 nacres Cellini sold by BASF (mica-TiC>2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2C>3) and Colorona sold by Merck (mica-TiO2-Fe2C>3).
  • particles including 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 aluminium borosilicate and aluminium.
  • 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 colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour 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 do not have a multilayer structure, they 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 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.
  • 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.
  • reflective particles including a mineral substrate coated with a layer of metal
  • 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, aluminium, 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, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
  • a metal substrate such as silver, aluminium, 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, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.
  • Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiC>2 sold under the name Visionaire by the company Eckart.
  • 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 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 their agglomeration or flocculation.
  • 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.
  • 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 aluminium salts of fatty acids, for example aluminium 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.
  • waxes for example carnauba wax and beeswax
  • 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.
  • 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 for instance the AQ surface treatment sold by LCW;
  • methicone treatment for instance the SI surface treatment sold by LCW;
  • dimethicone treatment for instance the Covasil 3.05 surface treatment sold by LCW;
  • dimethicone/trimethyl siloxysilicate treatment for instance the Covasil 4.05 surface treatment sold by LCW;
  • a magnesium myristate treatment for instance the MM surface treatment sold by LCW;
  • an aluminium dimyristate treatment such as the Ml surface treatment sold by Miyoshi
  • a perfluoropolymethyl isopropyl ether treatment for instance the FHC surface treatment sold by LCW;
  • an isostearyl sebacate treatment for instance the HS surface treatment sold by Miyoshi;
  • an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment for instance the FSA surface treatment sold by Daito;
  • a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment for instance the FS01 surface treatment sold by Daito;
  • an acrylate/dimethicone copolymer treatment for instance the ASC surface treatment sold by Daito;
  • an isopropyl titanium tri isostearate treatment for instance the ITT surface treatment sold by Daito;
  • an acrylate copolymer treatment for instance 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 (dispersant: pigment) 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:
  • silicones 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 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 fibre.
  • 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 (V) and (VI) and the azo cationic dyes (VII) and (VIII) 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 represents 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-C4)alkyl group, such as methyl;
  • R 4 represents a hydrogen atom or an electron-donating group such as optionally substituted (Ci-C8)alkyl, optionally substituted (Ci-C8)alkoxy, or (di)(Ci-C8)(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 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 iron oxides, and micas coated with iron oxide, red iron oxides (iron(lll) oxide, also known as ferric 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, the alkali metal salts of lithol red, such as the calcium salt of lithol red B.
  • pigments carbon black, iron oxides, notably black iron oxides, and micas coated with iron oxide, red iron oxides (iron(lll) oxide, also known as ferric 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, the alkali metal salts 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 hair 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;
  • the hair dye(s) 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).
  • 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 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 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.
  • the process of the invention is a process for treating keratin fibres, in particular human keratin fibres, preferably the hair, which involves the application to said fibres of at least one dispersion (A) as defined previously.
  • the composition is left to dry on said keratin materials, either naturally or using heating devices used in cosmetics, such as a hairdryer.
  • the keratin fibre treatment process is a treatment for shaping said fibres.
  • the keratin fibre treatment process includes at least one shaping step, notably:
  • the keratin fibres are shaped using a conventional shaping means, for example with rollers or a brush of particular shape (cylindrical), and then
  • the dispersion (A) is applied to said fibres, the application method preferably being by means of a spray, and then
  • fibres are dried naturally or dried using conventional devices used in cosmetics, and then
  • the shaping means is removed from said fibres, optionally followed by a rinsing step, a step of shampoo washing and then a step of drying naturally or of drying using conventional devices.
  • the dispersion (A) may be applied to wet or dry keratin fibres, preferably dry keratin fibres.
  • the keratin fibre treatment process of the invention it is also possible via the keratin fibre treatment process of the invention to perform shaping while at the same time providing said fibres with one or more cosmetic active agents, for example dyeing by applying at least one dye and/or pigment, and/or applying at least one IIV(A) and/or IIV(B) screening agent, and/or applying at least one active agent to said fibres. It suffices to apply a dispersion (A) comprising at least one cosmetic agent v) as defined previously. It also appears that the shaping is persistent and, what is more, that the cosmetic active agent(s) iv) applied are also persistent notably with respect to successive shampoo washing and to light rays.
  • one or more cosmetic active agents for example dyeing by applying at least one dye and/or pigment, and/or applying at least one IIV(A) and/or IIV(B) screening agent, and/or applying at least one active agent to said fibres. It suffices to apply a dispersion (A) comprising at least one cosmetic agent v)
  • the fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C and less than 100°C.
  • the fibres are dried, they are dried, in addition to a supply of heat, with a flow of air obtained using a conventional device used in cosmetics, such as a hood, a hairdryer, a straightening iron, a Climazon, etc.
  • a conventional device used in cosmetics such as a hood, a hairdryer, a straightening iron, a Climazon, etc.
  • a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through. This operation may similarly be performed once the fibres have dried, naturally or otherwise.
  • the drying temperature is between 40°C and 110°C and preferably between 50°C and 90°C.
  • the hair undergoes a treatment with a straightening iron. This treatment is then performed once said hair is dry; the temperature of the treatment with the straightening iron is between 110°C and 220°C, preferably between 140°C and 200°C.
  • the dispersion (A) may be used on wet or dry keratin fibres, and also on any type of fair or dark, natural or dyed, permanent-waved, bleached or relaxed fibres.
  • the fibres are washed before applying the dispersion (A).
  • the application to the fibres may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush or with the fingers.
  • the step of applying the dispersion (A) is performed on dry keratin fibres.
  • the step of applying the dispersion (A) is performed on humid or wet keratin fibres.
  • the process for treating keratin fibres is a process for dyeing said fibres, comprising at least one step of applying to said fibres a dispersion (A) as defined previously which comprises h) at least one dye, and/or j) at least one pigment, followed by a drying step.
  • a dispersion (A) as defined previously which comprises h) at least one dye, and/or j) at least one pigment, followed by a drying step.
  • the dispersion (A) may be applied to wet or dry keratin fibres, which are preferably dried naturally or else dried using conventional devices used in cosmetics as defined previously.
  • the process for treating keratin materials is a process for treating the skin and/or the eyelashes or the eyebrows involving the application to the skin and/or the eyelashes or the eyebrows of the dispersion (A) as defined previously, followed by a step of drying naturally or of drying using conventional devices used in cosmetics as defined previously, preferably naturally.
  • 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) according to the invention may also comprise a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, and dyestuffs other than f) dyes and g) pigments.
  • a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, and dyestuffs other than f) dyes and g) pigments.
  • the first step of the process of the invention is the application of the dispersion (A) in one or more apolar solvents, notably isododecane.
  • apolar solvents notably isododecane.
  • the dispersion (A) also comprises vii) one or more thickeners chosen from organic thickening polymers and thickening monoglycerides, diglycerides or triglycerides.
  • thickener 1 means that the agent in question, a polymer or a triglyceride, when introduced at 1 % by weight in an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or in an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s' 1 . This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like).
  • the thickening polymers may be thickeners for the aqueous phase and/or the fatty phase, preferentially the aqueous phase.
  • the thickener(s) are organic polymers.
  • organic thickening polymer means a thickening polymer as defined previously, which is formed from carbon and hydrogen, and possibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine or bromine, and also phosphorus, alkali metals such as sodium or potassium, or alkaline-earth metals such as magnesium or calcium.
  • the organic polymers according to the invention do not comprise silicon.
  • the organic thickening polymers according to the invention may be of natural or synthetic origin.
  • the thickeners may be associative or non-associative anionic, cationic, amphoteric or nonionic polymers, optionally bearing sugar units.
  • the term “sugar unit’ means a unit derived from a carbohydrate of formula C n (H2O) n -i or (CH2O) n , which may be optionally modified by substitution and/or by oxidation and/or by dehydration.
  • sugar units that may be included in the composition of the thickening polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.
  • the thickeners may be thickeners for the aqueous phase, i.e. in water or in the liquid fatty substance(s) iii).
  • the polymers for structuring the oily phase via physical interactions are chosen from polyamides, silicone polyamides, saccharide or polysaccharide mono- or polyalkyl esters, N-acylamino acid amide derivatives, and copolymers comprising an alkylene or styrene block, these copolymers possibly being diblock, triblock, multiblock or radial-block polymers, also known as star copolymers, or alternatively comb polymers.
  • the thickening polymers bear in the backbone at least one crystallizable sequence.
  • polymers that are soluble or dispersible in the oil or fatty phase by heating above their melting point m.p.
  • These polymers are notably block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.
  • polymers bearing in the backbone at least one crystallizable block that are suitable for use in the invention, mention may be made of: i). the polymers defined in US-A-5 156 911 ; ii). block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:
  • block copolymers may be in particular (ethylene/norbornene) block copolymers and (ethylene/propylene/ethylidenenorbornene) block terpolymers.
  • the copolymers contain at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature).
  • These copolymers may also contain two crystallizable blocks of different chemical nature.
  • the preferred copolymers are those that contain, at room temperature, both a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; examples that may be mentioned include semi-crystalline polymers, which may be non-crosslinked or (partly) crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid oily phase by heating above their melting point. It may then be a case of chemical crosslinking, by reaction with a multifunctional monomer during the polymerization.
  • the semi-crystalline polymers that are suitable for use in the invention are non-crosslinked.
  • semicrystalline polymers that can be used in the composition according to the invention, mention may be made of the Intelimer® products from Landec described in the brochure “Intelimer® polymers”. These polymers are in solid form at room temperature (25°C). They bear crystallizable side chains and contain the monomer. Mention may notably be made of Landec IP22®, with a melting point m.p. of 56°C, which is a viscous, impermeable, non-tacky product at room temperature.
  • the thickener(s) are chosen from saccharide or polysaccharide monoalkyl/polyalkyl esters.
  • saccharide or polysaccharide monoalkyl or polyalkyl esters that are suitable for use in the invention, mention may be made of dextrin or inulin alkyl or polyalkyl esters.
  • It may notably be a dextrin monoester or polyester of at least one fatty acid notably corresponding to formula (XI) below:
  • - n is an integer ranging from 3 to 200, notably ranging from 20 to 150 and in particular ranging from 25 to 50,
  • R2 and R3 which may be identical or different, are chosen from hydrogen and an acyl group (R-C(O)-) in which the radical R is a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 7 to 29, in particular from 7 to 21 , notably from 11 to 19, more particularly from 13 to 17, or even 15, carbon atoms, with the proviso that at least one of said radicals R1, R2 or R3 is other than hydrogen.
  • R1, R2 and R3 may represent hydrogen or an acyl group (R-C(O)-) in which R is a hydrocarbon-based radical as defined previously, with the proviso that at least two of said radicals R1, R2 and R3 are identical and other than hydrogen.
  • the radicals R1 , R2 and R3 may all contain an acyl group (R-C(O)), which may be identical or different and notably identical.
  • n mentioned previously advantageously ranges from 25 to 50 and is notably equal to 38 in the general formula of the saccharide ester that may be used in the present invention.
  • these radicals may be chosen from caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethyl methylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorb
  • At least one dextrin palmitate is used as fatty acid ester of dextrin.
  • This ester may be used alone or as a mixture with other esters.
  • the fatty acid ester of dextrin has a degree of substitution of less than or equal to 2.5, notably ranging from 1.5 to 2.5 and preferably from 2 to 2.5 on the basis of one glucose unit.
  • the weight-average molecular weight of the dextrin ester may in particular be from 10 000 to 150 000, notably from 12 000 to 100 000 and even from 15 000 to 80 000.
  • Dextrin esters in particular dextrin palmitates, are commercially available under the name Rheopearl TL or Rheopearl KL from the company Chiba Flour.
  • the thickener(s) contained in the dispersion (A) are chosen from monoglycerides, diglycerides and triglycerides in which at least one hydrogen atom of a hydroxyl group of the glycerol has been substituted with the group -C(O)-R a , with R a representing a linear or branched, cyclic or acyclic, saturated or unsaturated carbonyl-based hydrocarbon-based chain, including from 8 to 40 carbon atoms, said hydrocarbon-based chain possibly being substituted with one or more hydroxyl groups.
  • the thickeners vii) are chosen from triglycerides trisubstituted with -C(O)-R a with R a as defined previously, more particularly chosen from trihydroxystearin.
  • the thickener(s) are chosen from: 1) block polymers of at least two C2-C16 and better still C2-C12 a-olefins, preferably non-crosslinked semi-crystalline polymers, more particularly semi-crystalline polymers, 2) saccharide or polysaccharide monoalkyl/polyalkyl esters, particularly dextrin esters, in particular dextrin palmitates, 3) monoglycerides, diglycerides and triglycerides in which at least one hydrogen atom of a hydroxyl group of the glycerol has been substituted with the group -C(O)-R a , with R a representing a linear or branched, cyclic or acyclic, saturated or unsaturated, carbonyl-
  • the thickener(s) are present in the dispersion according to the invention in a content ranging from 0.01 % to 15% by weight, more preferentially from 0.1% to 7% by weight, even more preferentially from 1% to 6% by weight, relative to the total weight of the dispersion.
  • the kit
  • a subject of the invention is also a kit or device with several separate compartments comprising:
  • a dispersion comprising the ingredients i) to iii) and optionally vii) as defined previously,
  • ingredients v) are distributed among one or more different compartments: f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and/or j) UV(A) and/or UV(B) screening agents, and iv) water, which is in the dispersion, and/or with the ingredients f) to h) and/or in another compartment.
  • composition packaging assembly is, in a known manner, any packaging that is suitable for storing cosmetic compositions (notably a bottle, tube, spray bottle or aerosol can).
  • T able 1 Weight composition of the various illustrated dispersions of the invention
  • a film is prepared on a contrast card with a film spreader (speed: 50 mm/s - Cylinder: 100 pm). The film is left to dry for 24 hours at room temperature. Once dry, the film has a thickness of about 30-50 pm.
  • Example 1 Production of a dispersion with variable amounts of water
  • Step 1 Synthesis of the dispersion of polymer particles in isododecane
  • the polymer particles are synthesized in isododecane.
  • the polymer particles are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
  • the synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
  • a first step isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and of a radical initiator (T21 S).
  • T21 S a radical initiator
  • the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4.
  • the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator (T21S).
  • the polymer After stripping, the polymer is at a solids content of 50% in the isododecane. [00343] The ratios employed to obtain the stabilizer and the core are summarized in
  • Step 1.1
  • Step 1.2
  • Tables 8 Amounts of reagents used for Example 1
  • Isododecane/ethyl acetate (60/40), isobornyl acrylate, methyl acrylate/ethyl 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.
  • isododecane/ethyl acetate 60/40 is introduced into the feedstock.
  • the medium is heated to 90°C.
  • methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
  • Step 2 Addition of water at the end of the synthesis
  • Example 2 Dispersion for polymer particles containing maleic anhydride
  • Step 1 Synthesis of the dispersion of polymer particles in isododecane
  • the polymer particles are synthesized in isododecane.
  • the dispersions are formed as a whole (stabilizer ii + particles i) containing 10% maleic anhydride, 70% ethyl acrylate and 20% isobornyl acrylate.
  • the synthesis of these dispersions was performed in a 1 -litre pilot reactor. The synthesis is performed in two steps:
  • isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of ethyl acrylate and of a radical initiator (T21S).
  • T21S a radical initiator
  • the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.
  • the rest of the ethyl acrylate and the maleic anhydride are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator Trigonox (T21S).
  • the polymer After stripping, the polymer is at a solids content of 50% in the isododecane.
  • Step 1.1
  • isododecane/ethyl acetate 60/40 is introduced into the feedstock.
  • the medium is heated to 90°C.
  • the medium is at 90°C, ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40) and the T21S are introduced over 1 hour by pouring. At the end of the introduction by pouring, the medium is milky.
  • Step 2 Addition of water at the end of the synthesis
  • Example 2 The dispersion of Example 2 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
  • Example 3 Production of a dispersion with variable amounts of water for polymer particles containing more acrylic acid (20%)
  • Step 1 Synthesis of the dispersion of polymer particles in isododecane
  • the polymer particles are synthesized in isododecane.
  • the dispersions are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate.
  • the synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
  • isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and of a radical initiator (T21S).
  • the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4.
  • the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator (T21S).
  • the polymer After stripping, the polymer is at a solids content of 50% in the isododecane.
  • Step 1.1
  • Isododecane/ethyl acetate 60/40
  • isobornyl acrylate methyl acrylate/ethyl acrylate
  • T21S are introduced as feedstock into the reactor.
  • the medium is heated to 90°C (nominal medium temperature) under argon and with stirring.
  • isododecane/ethyl acetate 60/40 is introduced into the feedstock.
  • the medium is heated to 90°C. Once the medium is at 90°C, methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
  • Step 2 Addition of water at the end of the synthesis
  • Example 4 Production of a dispersion with variable amounts of water for polymer particles synthesized in Cetiol UT
  • Step 1 Synthesis of the dispersion of polymer particles in isododecane
  • the polymer particles are synthesized in Cetiol UT/EtOAc.
  • the polymer particles are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
  • the synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
  • isobornyl acrylate is polymerized in Cetiol UT/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and a radical initiator (T21S).
  • T21S a radical initiator
  • the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4.
  • the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of Cetiol UT/ethyl acetate (60/40) and of the radical initiator (T21S).
  • the polymer After stripping, the polymer is at a solids content of 50% in the Cetiol UT.
  • Step 1.1
  • Cetiol UT/ethyl acetate (60/40), isobornyl acrylate, methyl acrylate/ethyl 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.
  • Cetiol UT/ethyl acetate 60/40 is introduced into the feedstock.
  • the medium is heated to 90°C.
  • methyl acrylate/ethyl acrylate/acrylic acid, Cetiol UT/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
  • Step 2 Addition of water at the end of the synthesis
  • Example 4 The dispersion of Example 4 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
  • the stabilizing polymer is synthesized in a first stage.
  • the water is added before the synthesis of the core of the polymer particles.
  • the polymer particles are formed as a whole (stabilizer i + particles ii) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. After stripping off the ethyl acetate, the polymer is at a solids content of 37.5% in the isododecane iii)/water iv).
  • Step 1
  • Step 2 Added isododecane/ethyl acetate and water [Table 30]
  • Isododecane/EtOAc, isobornyl acrylate, ethyl acrylate/methyl acrylate and T21S are introduced as feedstock into the reactor.
  • the medium is sparged with argon for 10 minutes.
  • the medium is heated to 90°C (nominal oil bath temperature) with stirring. After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 99%.
  • methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 1 hour by pouring. At the end of the introduction by pouring, the medium is milky. The solids content is 30%.
  • the final dispersion has the composition shown in Table 32: [Table 32]
  • Example 5 The dispersion of Example 5 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
  • Formulations were prepared by adding a thickener. Three thickeners were added, according to Table 3:
  • Step 1 The first step consists in synthesizing the polymer particles in isododecane. This step is identical to step 1 of Example 1.
  • Step 2 The medium containing the polymer particles in isododecane is cooled to 25°C.
  • the water is added.
  • the medium is stirred at 2500 rpm.
  • Step 3 The thickener is introduced while heating to 80°C and stirring at 1500 rpm. The medium is maintained at 80°C for 20 minutes with stirring and is then cooled under the same stirring conditions.
  • composition of the final formulations is given in Table 34:
  • a deposit is produced on a contrast card (for example the card sold under the reference Byko-Charts by the company Byk-Gardner) and also on the FP40 elastomeric support.
  • FP40 Tellborg, N4I01
  • FP40 is an elastomeric substrate made of butadiene-acrylonitrile copolymer containing a diethylhexyl sebacate oil as plasticizer.
  • a volume V of formulation is applied to obtain a dry deposit of 30 pm.
  • the tack is measured with a Viton rubber ball which comes into contact with the deposit at a speed of 5 mm/s under a force of 1 N and for a time of 5 s. The measurement is repeated five times. The tack was measured mainly on the deposit produced on FP40.
  • Measurement of the tack during drying- A 10 pL drop of formulation is deposited on a contrast card. The tack is measured with a Viton rubber ball which comes into contact with the deposit each minute at a speed of 5 mm/s under the force of 1 N and for a contact time of 5 s.
  • Sensitivity to the water/sebum attacking factors' The sensitivity to water and to sebum is evaluated after depositing a drop of attacking factors (10 pl for sebum and 20 pl for water) onto the surface of the deposit produced on the contrast card. The evaluations are made after 20 minutes of contact between the attacking factor and the deposit.
  • Table 35 Tack measurements on FP40 and water/sebum sensitivity following the addition of thickener in comparison with the same formulation without thickener
  • thickener made it possible to improve the sensitivity to sebum; this effect is more pronounced during the addition of the thickeners trihydroxystearin and Intelimer.
  • the drop test reveals better resistance to sebum and the tack on FP40 is lower.
  • the effect is less visible on the drop test but is detected via the tack test on FP40, with a reduction of this tack.

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Abstract

The present invention relates to a dispersion (A) comprising i) at least one particle consisting of an ethylenic polymer, ii) at least one polymeric stabilizer comprising a (C3- C12)cycloalkyl group, and iii) at least one hydrocarbon-based fatty substance which is liquid at 20°C and (1) atmosphere. The invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin or the hair, involving the application to said materials of at least one dispersion (A); to a process for preparing the dispersion, and to a multi-compartment kit comprising ingredients i) to iii). The 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 fatty substances such as oils.

Description

Description
Title: DISPERSION COMPRISING A POLYMERIC PARTICLE, A STABILIZER BEARING A C3-C12 CYCLOALKYL GROUP, AN OIL AND WATER, AND PROCESS FOR TREATING KERATIN MATERIALS USING THE DISPERSION
[0001] The present invention relates to a dispersion (A) comprising i) at least one particle consisting of an ethylenic polymer, ii) at least one polymeric stabilizer comprising a (C3- Ci2)cycloalkyl group, iii) at least one hydrocarbon-based fatty substance which is liquid at 20°C and 1 atmosphere, and iv) water. The invention also relates to a process for treating keratin materials, notably human keratin materials such as the skin, the hair, the eyelashes or the eyebrows, involving the application to said materials of at least one dispersion (A); to a process for preparing the dispersion, and to a multi-compartment kit comprising ingredients i) to iv).
[0002] During the ageing process, various signs appear on the skin which are very characteristic of this ageing, reflected notably by a change in the skin structure and functions. The main clinical signs of skin ageing are notably the appearance of fine lines and deep wrinkles, which increase with age.
[0003] It is known practice to treat these signs of ageing by using anti-ageing cosmetic compositions. However, these active agents have the drawback of being effective for the treatment of wrinkles only after repeated application. 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/or 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 eyelashes. WO 2010/046229 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 fibres, it is already known practice to dye keratin fibres 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 fibres with dye compositions containing direct dyes. These dyes are coloured and colouring molecules that have affinity for keratin fibres. They are applied to the keratin fibres for a time necessary to obtain the desired colouring, 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 colourings that are visible on dark hair.
[0010] It is also known practice to dye keratin fibres permanently via oxidation dyeing. This dyeing technique consists in applying to the keratin fibres a composition containing dye precursors such as oxidation bases and couplers. Under the action of an oxidizing agent, these precursors form one or more coloured substances in the hair.
[0011] The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained, and the colourings 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 fibres. This bleaching step, performed with an oxidizing agent such as hydrogen peroxide or persalts, results in appreciable degradation of the keratin fibres, which impairs their cosmetic properties. The hair then has a tendency to become coarse, more difficult to disentangle and more brittle.
[0013] Another dyeing method consists in surface dyeing, notably using pigments. Specifically, the use of pigment on the surface of keratin fibres generally makes it possible to obtain colourings that are notably visible on dark hair, since the surface pigment masks the natural colour of the fibre. The use of pigment for dyeing keratin fibres is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibres, a composition comprising at least one dispersion of film-forming polymer particles including at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.
[0014] The colourings obtained via this dyeing method are generally sparingly persistent and are quite rapidly lost on shampoo washing.
[0015] It is moreover known practice from patent application FR 2 907 678 to perform coloured 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 the fatty substances of 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] 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, which is not tacky, which has good persistence with respect to external attacking factors, and over time, does not leach, and is resistant to sweat and sebum and insensitive to oils such as dietary oils. Furthermore, the composition may comprise cosmetic active agents such as those for obtaining a skin-tensioning effect, for caring for the body, the face and the hair, for protecting against ultraviolet (UV), or for making up the face, the lips, the eyelashes, the eyebrows and the hair. Said composition may notably be intended for care and/or makeup, notably for making up the lips.
[0019] Moreover, consumers are in search of water-based presentation forms, containing as few volatile compounds as possible. For example, in the hair field, it is always desirable, whenever possible, to replace volatile compounds with water in the compositions used, notably in hair salons. Environmental challenges are also tending towards minimizing the use of volatile compounds. Thus, one of the aims of the present invention is to provide a composition with a reduced content of volatile compounds. Another aim is to provide a film-forming composition containing an aqueous phase, affording access to a wider formulation range. For environmental reasons, but also for the purpose of avoiding potential long-term damage to keratin materials, it is sought to use as few surfactants as possible in the cosmetic composition.
[0020] Another aim of the present invention is to provide a composition for treating keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows, which has good resistance 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 fibres may be subjected, without degrading said fibres, and while keeping the keratin fibre strands perfectly separated.
[0021] The technical problem has been solved by the use of a dispersion (A) for treating keratin materials, in particular a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes and the eyebrows or P) human skin, in particular of the lips, in which the dispersion (A) comprises: i) one or more particles including one or more polymers chosen from a) one or more ethylenic copolymers of: ai) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, and
82) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (Ci-C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) copolymers of:
Ci) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate, and
C2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based liquid fatty substances; iv) water; 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; it being understood that the water content is greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the dispersion.
[0022] More particularly, the subject of the invention relates to the use of the 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 fibres and/or for shaping keratin fibres such as the hair, or for making up the skin or for skincare or for providing a non-coloured immediate effect.
[0023] A subject of the invention is also the dispersion (A) as defined previously, and also a process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows, or P) human skin, in particular of the lips, comprising the application to said materials of a dispersion (A), as defined previously. A subject of the invention is also a kit or device comprising several compartments comprising the ingredients i) to iv) as defined previously.
[0024] A subject of the invention is also a composition, preferably a cosmetic composition, comprising the dispersion (A) as defined previously, and the process for applying said composition to keratin materials.
[0025] A subject of the invention is also a process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes, the eyebrows or P) human skin, in particular the lips, comprising the application to said materials of at least one dispersion (A), as defined previously; preferentially, after application of the dispersion (A) to the keratin materials, the composition is left to dry on said keratin materials, either naturally, or with the aid of heating devices used in cosmetics, such as a hairdryer.
[0026] The 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 fatty substances such as oils. Furthermore, the dispersion is easy to use in compositions, notably cosmetic compositions, is easy to manufacture and remains stable over time. Specifically, the 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 dispersion (A), notably lip makeup, is particularly resistant to external attacking factors such as liquid fatty substances, in particular with respect to plant oils such as olive oil. Furthermore, the makeup results obtained with the dispersions (A) are very aesthetic 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 dispersions (A) of the invention to keratin fibres makes it possible to obtain coatings that are persistent with respect to external attacking factors (sunlight, water, shampoo washing, perspiration, sebum, etc.). [0027] In addition, when the composition comprises one or more dyes and/or pigments, the coloured keratin materials have a colouring that is visible on all types of materials, notably on dark keratin materials, which is persistent with respect to soaps, shower gels or shampoos while at the same time preserving the physical qualities of the keratin material. Such a coating is in particular resistant to the external attacking factors to which the keratin fibres, notably the hair, may be subjected, such as blow-drying and perspiration. The use of dispersion (A) on keratin materials, in particular on keratin fibres, makes it possible to obtain a smooth and uniform deposit. Moreover, it has been observed, surprisingly, that the keratin fibre strands remained perfectly separated, and could be styled without any problem.
[0028] 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, n-propyl, isopropyl or i-propyl, n-butyl, isobutyl or i-butyl and tert-butyl or t-butyl;
- 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, and which may be substituted with one or more (Ci-C4)alkyl groups such as methyl, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl; 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 fibres 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 “keratin fibres with strand separation" means keratin fibres, notably the hair, which, after application of the composition and drying, are not stuck together (or of which the strands are all separated from each other) and thus do not form clumps of fibres;
- the term “insoluble monomer1’ thus means any monomer whose homopolymer or copolymer is not in soluble form, i.e. completely dissolved to 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 fatty substance(s) iii);
- the term “ethylenic homopolymer" means a polymer derived from the polymerization of identical monomers;
- the term “ethylenic 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;
- 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;
- the term “fatty substance" means an organic compound that is immiscible 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 ethanol, ether, 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, 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 optionally of 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 non-zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour 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 “non-volatile oif’ means an oil with a vapour 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 non-volatile;
- 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 colour 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 inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. 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 fibres, notably human keratin fibres 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 coloured 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 coloured 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 and 0.9 pm, and preferably between 0.2 and 0.6 pm;
- the term “thickening polymer1’ means a polymer which, when introduced at 1 % by weight into an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or into an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s’1. This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like). The thickening polymers may thicken the aqueous phase and/or the fatty phase, preferentially the aqueous phase;
- the term “organic thickening polymer” means a thickening polymer as defined previously, which is formed from carbon and hydrogen, and possibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine or bromine, and also phosphorus, alkali metals such as sodium or potassium, or alkaline-earth metals such as magnesium or calcium. The organic polymers according to the invention do not comprise silicon;
- according to the invention, the term “non-cellulose-based organic thickening polymer" means an organic thickening polymer not including any cellulose units;
[0029] The dispersion (A)
[0030] The 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) water.
[0031] In order to obtain the 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 hydrocarbon-based liquid fatty substance(s) iii) optionally containing iv) water.
[0032] The dispersions according to the invention consist of particles, which are generally spherical, and of at least one surface-stabilized polymer.
Preferably, said particles i) are not or are sparingly crosslinked.
[0033] The polymer particles i) and the stabilizer(s) ii) are preferably in the hydrocarbonbased liquid fatty substance(s) iii) in an amount of between 2% and 40% by weight, notably between 4% and 35% by weight of soluble monomer (the monomer forming the stabilizer(s) ii)) and between 60% and 98% by weight, notably from 65% to 96% by weight, of insoluble monomer (the monomer forming the particles i)).
[0034] In the present description, the term “soluble monomer” refers to any monomer of which the polymer, notably the homopolymer, is soluble, to 5% by weight, at 20°C and at atmospheric pressure in the liquid hydrocarbon-based medium consisting of liquid hydrocarbon-based fatty substances iii) of the dispersion. The polymer, notably the homopolymer, is completely dissolved in the liquid carbon-based medium, visually at 20°C (no apparent visible deposit, or any insoluble agglomerate or sediment visible to the eye).
[0035] The term “insoluble monomer” refers to any monomer of which the polymer, notably the homopolymer, 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 liquid hydrocarbon-based medium consisting of iii) liquid hydrocarbon-based fatty substances.
[0036] Preferably, the monomers i) that are capable of forming the polymeric core of the particle are chosen from monomers that are insoluble in the liquid hydrocarbon-based medium consisting of iii) liquid hydrocarbon-based fatty substances. The insoluble monomers notably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle.
According to another embodiment of the invention the dispersion (A) does not contain a crosslinked and nonelastomeric amphiphilic silicone compound.
According to another embodiment of the invention the dispersion (A) does not contain a silicone resin.
According to another embodiment of the invention the dispersion (A) does not contain a silicone polyamide.
According to one embodiment of the invention the dispersion (A) does not contain polymer containing styrene group. [0037] Polymer particles i)
[0038] The particle(s) i) of dispersion (A) of the invention consist of one or more ethylenic copolymers derived from the polymerization: a1) of at least one (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer, and a2) of at least one ethylenic monomer comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl; in particular, a2) is a (Ci-C4)(alkyl)acrylic acid.
[0039] Preferably, the particle(s) i), consist of an ethylenic polymeric core derived from copolymers a) as defined previously.
[0040] The term “ethylenic copolymer1’ means a polymer derived from the polymerization of at least two monomers chosen from one or more (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomers a1) and of one or more ethylenic monomers a2) comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as phenyl.
[0041] The term “ethylenic monomer1’ means a compound comprising at least one ethylenic unsaturation -(Ra)C=C(Rb)-, -C(Ra)=C(Rb)-Rc or >C=C(Ra)-Rb, with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom ora (Ci-C4)alkyl group such as methyl, preferably hydrogen.
[0042] The ethylenic compound may also be a cyclic compound, which is preferably 5- or 6-membered, and comprising an ethylenic unsaturation.
[0043] The term “ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups" means that the monomer is substituted on one of the carbon atoms of the polymeric monomer with one or more groups, preferably only one group, chosen from carboxyl -C(O)-OH, phosphoric acid -O-P(O)(OH)2 or -P(O)(OH)2, and sulfonic acid -O-S(O)2-OH or -S(O)2-OH, maleic anhydride, and aryl such as phenyl.
[0044] According to one embodiment of the invention, the particle(s) i) include a) ethylenic copolymers of a1) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of a2) ethylenic monomers comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as benzyl.
[0045] More particularly, the ethylenic monomer(s) a2) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3) and (4): (1) Ri(R2)C=C(R3)-Acid with Ri, 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; preferably, (1) represents (5) H2C=C(R)-C(O)-O-H with R representing a hydrogen atom or a (Ci-C4)alkyl group potentially substituted by one or more hydroxy group, preferably R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl;
(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. 1]
Figure imgf000013_0001
in which formulae (4b) 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 more particularly, a2) is chosen from (1) and (4), in particular (4) and notably (5).
[0046] According to a particular variant of the invention, a2) 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. [0047] According to another variant of the invention, a2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid and salts thereof; more preferentially, a2) represents maleic anhydride.
[0048] The salts may be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminium, manganese or copper; ammonium salts of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, diethylamides, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.
[0049] According to a preferred embodiment of the invention, the (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate monomer(s) a1) are chosen from those of formula (I):
[Chem 2]
IW=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, ethyl, n-propyl, /-propyl, n-butyl, /-butyl or, f-butyl, preferably methyl, ethyl or /-butyl, preferably, (I) represents a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate.
[0050] According to another particular embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer a) derived from the polymerization:
- a1) of at least one monomer of formula (I) as defined previously, preferably a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl acrylate or isobutyl methacrylate; and
- a2) of at least one monomer chosen from (1), (2), (3) and (4) as defined previously and preferentially of formula (II) and also the salts thereof:
[Chem 3]
Figure imgf000014_0001
in which formula (II) R is as defined previously; in particular, (II) represents acrylic acid. [0051] According to a preferred embodiment of the invention, the amount of a2), notably of compound (II) and in particular of acrylic acid, is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of monomers of the particle i), even more particularly between 5% and 25% by weight relative to the weight of the polymer of the particles i), better still between 10% and 15% by weight relative to the weight of the polymer of the particles i).
According to a another preferred embodiment of the invention, the amount of a2), notably of compound (II) and in particular of acrylic acid, is greater than 35 % by weight relative to the total weight of the particle i), more particularly between 40 % and 70% by weight relative to the weight of monomers of the particle i), even more particularly between 50% and 60% by weight relative to the weight of the polymer of the particles i), better still 57 % by weight relative to the weight of the polymer of the particles i).
[0052] In particular, a) is a copolymer derived from the copolymerization a2) of acrylic acid with a1) one or more C1-C4 alkyl (meth)acrylate monomers, preferably at least two different C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobutyl (meth)acrylate.
[0053] According to another preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer a) derived from the polymerization:
- of at least two different monomers: of formula (I) as defined previously, preferably a C1-C4 alkyl acrylate such as methyl acrylate, ethyl acrylate, isobutyl (meth)acrylate; and
- of at least one monomer chosen from (1), (2), (3) and (4) as defined previously, preferably of formula (II) as defined previously.
[0054] 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 a1).
[0055] Advantageously, a linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (Ci-Cs)alkyl acrylate, monomer is used. Preferentially, a) is chosen from methyl acrylate and ethyl acrylate.
[0056] The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
[0057] According to another particular embodiment of the invention, the polymer constituting the particles i) is an acrylate copolymer a) derived from: a1) at least one monomer of formula (I) as defined previously; and a2) at least one ethylenically unsaturated anhydride monomer notably of formula (4) as defined previously.
[0058] Particularly, the polymer of the particles a) is a polymer a1) of linear or branched, preferably linear, C1-C4 alkyl (meth)acrylate, in particular (Ci-Cs)alkyl (meth)acrylate monomer, and a2) of ethylenically unsaturated anhydride monomer.
[0059] The monomers a1) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate.
[0060] Advantageously, one or two different linear or branched, preferably linear, C1-C4 alkyl acrylate, in particular (Ci-Cs)alkyl acrylate, monomers a1) are used. Preferentially, a1) is chosen from methyl acrylate and ethyl acrylate.
[0061] According to a particular embodiment, one or two different branched (Cs-C4)alkyl (meth)acrylate monomers are used. Preferentially, a1) is chosen from isobutyl acrylate and isobutyl methacrylate.
[0062] According to a particular form of the invention, the ethylenically unsaturated anhydride compound(s) a2) of the invention are chosen from the maleic anhydride derivatives (4a) and the itaconic anhydride derivatives (4b) as defined previously.
[0063] More preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4a) and even more preferentially is maleic anhydride.
[0064] The polymer of the particles may be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers.
[0065] According to a preferred embodiment of the invention, the copolymer(s) of the particles i) of the dispersion comprise from 80% to 95% by weight of ingredient a1) and from 5% to 20% by weight of ingredient a2), relative to the total weight of the copolymer(s).
According to another preferred embodiment of the invention, the copolymer(s) of the particles i) of the dispersion comprise from 80% to 95% by weight of ingredient a1) and from 40% to 70%, particularly from 50 to 60 % by weight of ingredient a2), relative to the total weight of the copolymer(s).
[0066] More particularly, the polymer of the particles i) preferably comprises from 80% to 93% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 7% to 20% by weight of ingredient a2) relative to the total weight of the polymer i). More preferentially, the polymer of the particles i) preferably comprises from 85% to 93% by weight, more particularly 87% to 92% by weight and even more preferentially from 85% to 90% by weight of ingredient a1), notably of C1-C4 alkyl (meth)acrylate, and from 10% to 20% by weight of ingredient a2) relative to the total weight of the polymer.
[0067] Advantageously, the polymer of the particles i) is a non-crosslinked polymer.
[0068] According to one embodiment of the invention, the copolymer(s) i) are chosen from:
- copolymers of methyl acrylate/ethyl acrylate/acrylic acid and its salts;
- copolymers of methyl acrylate/ethyl acrylate/maleic anhydride;
- copolymers of methyl acrylate/acrylic acid and its salts;
- copolymers of ethyl acrylate/acrylic acid and its salts;
- copolymers of methyl acrylate/maleic anhydride;
- copolymers of ethyl acrylate/maleic anhydride;
- copolymers of isobutyl acrylate/acrylic acid and its salts; and
- copolymers of isobutyl acrylate/isobutyl methacrylate/acrylic acid and its salts.
[0069] The polymer of the particles i) of the dispersion preferably has a number-average molecular weight ranging from 2000 to 10 000 000.
[0070] The polymer of the particles i) may be present in the dispersion (A) in an amount ranging from 20% to 60% by weight relative to the total weight of the dispersion, in particular between 21 % and 58.5% by weight relative to the total weight of the dispersion, preferably ranging from 30% to 50% by weight relative to the total weight of the dispersion, more preferentially ranging from 36% to 42% by weight relative to the total weight of the dispersion (A).
[0071] Preferably, the particle(s) i) consist of a copolymer of a1) and a2).
[0072] According to a particular embodiment of the invention, the particles i) consist of copolymers derived from the polymerization of monomers a1) and a2) with an a1)/a2) weight ratio inclusively between 4.4 and 20, more particularly between 5.5 and 19, preferably between 6.5 and 16 and even more preferentially between 6.6 and 15.6.
[0073] The polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 to 600 nm, notably ranging from 10 to 500 nm and better still ranging from 20 to 400 nm.
[0074] The stabilizer(s) ii)
[0075] 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. [0076] The stabilizer(s) of the invention are constituted of ethylenic polymers chosen from b) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) copolymers of c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate. Preferably, the stabilizer(s) of the invention are constituted of ethylenic polymers chosen from c) copolymers of c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate.
[0077] According to a preferred embodiment of the invention, the stabilizer(s) ii) are constituted of ethylenic polymers chosen from: b) polymers of monomers of formula H2C=C(R)-C(O)-O-R” (III) with R representing a hydrogen atom or (Ci-C4)alkyl group such as methyl, and R” representing a (Cs- Cio)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and c) copolymers of c1) H2C=C(R)-C(O)-O-R” (III) and of c2) H2C=C(R)-C(O)-O-R’(I) with R, R’ and R” as defined previously.
[0078] According to a particular embodiment, the stabilizer(s) of the invention consist of ethylenic polymers chosen from b) polymers of (C3-Ci2)cycloalkyl(Ci-C6)(alkyl)acrylate monomers particularly of formula (III) as defined previously.
[0079] According to another particular embodiment of the invention, the stabilizer(s) of the invention consist of ethylenic polymers chosen from c) copolymers of c1) (C3- Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate particularly of formula (III) as defined previously and of c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate particularly of formula (I) as defined previously.
[0080] According to a particular form of the invention, the ingredient c2 is a (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer notably of formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate, more preferentially methyl (meth)acrylate.
[0081] According to another particular form of the invention, the ingredient c2 is a mixture of several different (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomers, notably two different (C1- C4)alkyl (Ci-C4)(alkyl)acrylate monomers notably of formula (I) more particularly chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
[0082] Particularly, the stabilizer ii) is chosen from b) polymers of (C3-Ci2)cycloalkyl (C1- C6)(alkyl)acrylate monomers; and c) statistical copolymers of c1) (C3-Ci2)cycloalkyl (C1- C6)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate with a c1/c2 weight ratio of greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19. More advantageously, said weight ratio c1/c2 ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
[0083] More particularly, the stabilizer ii) is a polymer chosen from b) isobornyl (meth)acrylate homopolymer and c) statistical copolymers c1) of isobornyl (meth)acrylate and c2) of C1-C4 alkyl (meth)acrylate preferably present in an isobornyl (meth)acrylate/Ci- C4 alkyl (meth)acrylate weight ratio (c1/c2) of greater than 4. Advantageously, said weight ratio c1/c2 ranges from 4.5 to 19. Advantageously, said weight ratio c1/c2 ranges from 5 to 15 and more preferentially said weight ratio c1/c2 ranges from 5.5 to 12.
[0084] 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.
[0085] Advantageously, the stabilizer is chosen from: b) isobornyl acrylate homopolymers, c) statistical copolymers of isobornyl acrylate/methyl acrylate, statistical copolymers of isobornyl acrylate/ethyl acrylate, and statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate in the weight ratio described previously.
[0086] The stabilizing polymer ii) preferably has a number-average molecular weight ranging from 10 000 to 400 000 and preferably ranging from 20 000 to 200 000.
[0087] The stabilizer ii) is in contact with the surface of the polymer particles i) and thus makes it possible to stabilize these particles at the surface in order to keep these particles in dispersion in the medium of the dispersion (A).
[0088] More particularly, the stabilizer(s) ii) are chosen from c) copolymers of: c1) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate; and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate; with from 80% to 95% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 5% to 20% by weight of ingredient c2), notably methyl acrylate and ethyl acrylate, relative to the total weight of the stabilizer.
More preferentially, the stabilizer(s) ii) comprise from 85% to 94% by weight and more particularly 87% to 93% by weight of ingredient c1), notably of isobornyl (meth)acrylate, and from 10% to 20% by weight of ingredient of c2), notably methyl acrylate and/or ethyl acrylate, relative to the total weight of the polymer.
[0089] Advantageously, the sum ii) of stabilizer(s) + i) of polymer particle(s) present in the dispersion (A) comprises from 5% to 60% and in particular comprises from 10% to 40% by weight of polymers b) or c) and from 60% to 90% and in particular from 61% to 89% by weight of polymers a), relative to the total weight of the sum ii) of stabilizer(s) + i) of polymer particle(s).
[0090] Preferentially, the sum ii) of stabilizer(s) + i) of polymer particle(s) present in the dispersion comprises from 15% to 30% by weight of polymers b) or c) and from 70% to 85% by weight of polymers a), relative to the total weight of the sum ii) of stabilizer(s) + i) of polymer particle(s).
[0091] According to a particular embodiment of the invention, the dispersion (A) is such that the sum ii) of stabilizer(s) + i) of polymer particle(s) are present in the dispersion (A) from 2% to 40% by weight, notably from 4% to 35% by weight and preferably from 4.5% to 30% by weight relative to the total weight of the dispersion (A).
[0092] 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.
[0093] 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 shiny film-forming deposits which are resistant to fatty substances at room temperature (25°C), and which are notably advantageous for makeup applications.
[0094] The final size of the particles is 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.
[0095] 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 analyser (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).
[0096] 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 analysed 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.
[0097] Other particle size 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.
[0098] The hydrocarbon-based liquid fatty substance(s) Hi)
[0099] 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.
[00100] According to a particular embodiment, the hydrocarbon-based liquid fatty substance(s) iii) of the invention are chosen from hydrocarbons, in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluorinated oils of synthetic origin, fatty alcohols, esters of fatty acids and/or of fatty alcohols, non-silicone waxes, and silicones; in particular, the liquid hydrocarbon-based fatty substance(s) are hydrocarbon-based oils, which are preferably volatile, or are a mixture of different volatile oils, preferentially chosen from isododecane and octyldodecanol, more particularly isododecane.
[00101] 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 50 carbon atoms, preferably between Ce and C , and in particular alkanes, oils of animal origin, oils of plant origin, glycerides, fatty alcohols, fatty acid and/or fatty alcohol esters, and silicones.
[00102] 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 50 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
[00103] As regards the Ce-C alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, undecane, dodecane, tridecane or isoparaffins, such as isohexadecane, isodecane or isododecane, and mixtures thereof such as the combination of undecane and tridecane, for instance Cetiol UT®. The linear or branched hydrocarbons containing more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam®.
[00104] 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 branched, alone or as a mixture.
[00105] 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 non-volatile.
[00106] According to a preferred embodiment of the invention, the liquid hydrocarbonbased fatty substance(s) are hydrocarbon-based oils which are volatile or are a mixture of different volatile oils.
[00107] According to another particular embodiment, the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and a non-volatile oil such as an isododecane/octyldodecanol mixture.
[00108] The hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably:
- branched Cs-Cu alkanes, for instance Cs-Cu isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl,
- linear alkanes, for instance n-undecane (C11), n-dodecane (C12), n-tridecane (C13) 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 2008/155 059 from the company Cognis, and mixtures thereof, also sold under the name Cetiol UT®,
- hydrocarbon-based oils of plant origin such as triglycerides constituted 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, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol 810®, 812® and 818®,
- 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.
[00109] In addition to the liquid hydrocarbon-based fatty substance, the dispersion (A) may comprise a silicone oil. If the 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 more preferentially 2%.
[00110] In particular, the dispersion (A) comprises at least one liquid hydrocarbon-based 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 or cereal germ oil;
- hydrocarbons and notably volatile or non-volatile, linear, branched and/or cyclic alkanes, such as Cs-Ceo isoparaffins, which are optionally volatile, such as isododecane, Parleam (hydrogenated polyisobutene), isohexadecane, cyclohexane or Isopars; or else liquid paraffins, liquid petroleum jelly, or hydrogenated polyisobutylene; notably isododecane;
- ethers 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; notably octyldodecanol;
- polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and - mixtures thereof.
[00111] Advantageously, the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
[00112] Preferably, the dispersion (A) comprises at least one apolar liquid hydrocarbonbased fatty substance iii) preferably chosen from:
- linear or branched Cs-Cso, in particular C10-C20 and more particularly C10-C16 alkanes, which are volatile or non-volatile, preferably volatile;
- non-aromatic cyclic C5-C12 alkanes, which are volatile or non-volatile, preferably volatile; and
- mixtures thereof.
[00113] The liquid hydrocarbon-based fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular containing from 10 to 14 carbon atoms, which are preferably volatile, more particularly the apolar oils, described previously.
Among the branched Cs-C and notably C10-C14 alkanes that are suitable for use as liquid hydrocarbon-based fatty substances iii) in the dispersion of the invention, mention may be made of:
- 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 references, respectively, Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and of n-tridecane (C13) from the company Cognis, and mixtures thereof.
[00114] Preferentially, the liquid hydrocarbon-based fatty substance(s) iii) of the invention are apolar, more particularly isododecane.
[00115] According to another advantageous embodiment of the invention, the hydrocarbon-based liquid fatty substance(s) are a mixture of non-volatile and volatile oil; preferably, the mixture comprises isododecane as volatile oil or a mixture of oils, notably of undecane and tridecane.
[00116] In particular, in the mixture, the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
[00117] Preferably, the liquid hydrocarbon-based fatty substance(s) iii) are in the dispersion of the invention in an amount of between 15% by weight and 80% by weight, more preferentially between 20% and 60% by weight relative to the total weight of said dispersion (A). According to a particular embodiment of the invention, the weight ratio of the sum of the ingredients [i) + ii)] I iii) is less than or equal to 1 , more particularly, the mass ratio [i) + ii)] / iii) is between 0.5 and 1. [00118] Preferentially, use will be made of a dispersion in iii), notably isododecane, of surface-stabilized polymer particles i) chosen from:
- a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (24.5/62.8/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer + particles) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate;
- a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer + particles) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate;
- a dispersion in isododecane of methyl acrylate/ethyl acrylate/maleic anhydride (50/37.2/12.8) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer ii) + particles i)) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.
[00119] More preferentially, use will be made of a dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer; the dispersion containing in total (stabilizer ii) + particles i)) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
[00120] The amount of particles i) in the dispersion (A) of the invention preferably ranges from 20% to 50% by weight and more preferentially from 25% to 45% by weight relative to the total weight of the dispersion.
[00121] Method for preparing the dispersion (A)
[00122] 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" 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 b) and c) 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 b) or c) with vi) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
- In a second step, the monomers constituting the polymer of the particles i) is added to the stabilizing polymer ii) formed in the preceding step and polymerization of these added monomers is performed in the presence of the radical initiator. - In a third step, water is added and the ingredients i) + ii) are all stirred in the reactor before taking out the dispersion.
[00123] When the synthesis solvent is a non-volatile 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 should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
[00124] The synthesis solvent may consist of hydrocarbon-based liquid fatty substance iii) combined with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
[00125] At the end of step 1 , when the synthesis solvent is a mixture, the additional solvent including the hydrocarbon-based aliphatic-chain esters as defined previously is removed via a method that is conventional to those skilled in the art, such as distillation. The polymers of the particles i) and the stabilizers ii) are found in the hydrocarbon-based liquid fatty substance iii).
[00126] The dispersion (A) optionally contains one or more cosmetic active agents v).
[00127] The cosmetic active agent(s) v) 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. According to another variant, said cosmetic active agent(s) are added during the second step or after the second step.
[00128] According to another variant, said cosmetic active agent(s) are added during the third step.
[00129] A synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator vi) are soluble therein, and the polymer particles i) obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen. [00130] In particular, the synthesis solvent chosen is one which is apolar, organic and volatile, preferably chosen from alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.
[00131] According to another variant, use is made of a mixture of:
- an apolar solvent as defined previously, notably isododecane,
- a polar solvent notably chosen from esters such as (Ci-C4)alkyl (Ci-C4)alkylate, for example ethyl acetate.
[00132] When the synthesis solvent 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.
[00133] According to a particular form the invention, the synthesis solvent is a mixture of liquid fatty substance such as iii) and notably isodecane with an additional solvent notably chosen from linear or branched hydrocarbon-based aliphatic-chain esters containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate and notably ethyl acetate, said additional solvent being chosen to have a boiling point below that of the liquid fatty substance. When the synthesis of the stabilizers ii) and of the particles i) is complete, the additional solvent is removed and a mixture of i) and ii) in the liquid fatty substance is obtained. 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.
[00134] The polymerization is preferentially performed in the presence vi) 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.
[00135] Mention may notably be made of initiators vi) such as:
- 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.
[00136] The polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.
[00137] The polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii) prepared beforehand.
[00138] The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
[00139] 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.
[00140] From 2% to 40% by weight and particularly from 4% to 35% by weight and preferably from 4.5% to 30% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)).
[00141] 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.
[00142] The composition according to the invention preferably comprises a content of solids (or active material) of polymers of particle i) + dispersing polymers ii) ranging from 10% to 80% by weight, relative to the total weight of the dispersion (A), and preferably ranging from 15% to 60% by weight, notably 20% to 50% by weight relative to the total weight of the dispersion (A).
[00143] 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.
[00144] Next, in a second step, the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
[00145] Preferentially, a solution of stabilizing polymer ii) in the liquid hydrocarbon-based 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).
[00146] The stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator vi) as defined previously.
[00147] 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.
[00148] In a third step, water or an aqueous composition is added, preferably with stirring, at room temperature and at atmospheric pressure.
[00149] The dispersions are prepared in the presence of one or more liquid hydrocarbonbased fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
[00150] According to a preferred embodiment of the invention, the process is performed according to the following three steps:
[00151] For the preparation of these novel dispersions, a process was performed: [00152] Step 1 : Synthesis of the polymer particles in the hydrocarbon-based oil iii) In a first step, the polymer particles are synthesized in the hydrocarbon-based oil iii), which is preferably a volatile apolar oil.
[00153] An additional solvent may be mixed with the volatile polar hydrocarbon-based oil and will be chosen from esters with a chain containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
[00154] The dispersion of the polymer particles in the hydrocarbon-based oil iii) or the mixture of hydrocarbon-based oil/short-chain ester may be prepared in the following manner:
[00155] The polymerization is performed in “dispersion", i.e. by precipitation of the polymer being formed, with protection of the particles i) formed with one or more stabilizers ii), preferably one stabilizer.
[00156] Step 1 , the stabilizing polymer ii) (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer with a free-radical initiator vi), in a solvent known as the synthesis solvent, and by polymerizing these monomers; [00157] Step 2, the constituent monomer(s) of the polymer of the particles 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 vi).
[00158] The polymerization is preferentially performed in the presence vi) of one or more free-radical initiators vi) as defined previously.
[00159] The polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.
[00160] The polymer particles are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer.
[00161] From 2% to 40% by weight and preferably from 3% to 30% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)).
[00162] At the end of this step 1 , the short-chain ester is removed by distillation. Thus, the polymer of the particles is found in the volatile polar hydrocarbon-based oil.
[00163] Step 3: The water is added and stirred with the mixture of polymer of the particles + volatile polar hydrocarbon-based oil before removing the dispersion from the reactor.
[00164] The polymer according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in making up the eyes (mascara, eyeshadow or eyeliner) and in lipsticks.
[00165] 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 filmforming deposits that are resistant to fatty substances at the observation temperature (25°C).
[00166] Furthermore, since said dispersion is in oily medium with the presence of water, it becomes easy to formulate it in cosmetic compositions based on oily medium commonly used in cosmetics, in particular in the fatty phases of emulsions, but also in the aqueous phases of emulsions to enable the dissolution of water-soluble or hydrophilic active agents.
[00167] According to another particular embodiment of the invention, the process is performed according to the following three steps:
[00168] For the preparation of these novel dispersions, a process was performed:
[00169] Step 1: Synthesis of the stabilizing polymer ii)
[00170] The polymer forming the stabilizer ii) is synthesized in a volatile apolar hydrocarbon-based oil iii), and optionally at least one additional polar solvent such as an ester with a chain containing from 3 to 8 carbon atoms in total, such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate.
[00171] The polymerization is preferably performed in the presence of at least one radical initiator vi) as defined previously.
[00172] Step 2: Addition of water [00173] Before the preparation of i), notably of the core of the polymer particles i), water iv) is added to the medium containing the stabilizing polymer(s) ii), the volatile apolar hydrocarbon-based oil iii) and optionally the additional solvent.
Step 3: Synthesis of the core of the polymer particles
[00174] The preparation of i) and notably of the core of the polymer particles i) is preferably performed in the presence of at least one radical initiator vi) as defined previously.
[00175] At the end of this step 3, the additional solvent(s) are removed by distillation. Thus, the polymer particles i) + ii) are found in the volatile apolar hydrocarbon-based oil iii) in the presence of water iv).
[00176] The dispersion (A) according to the invention finds an application in caring for and/or making up the skin and/or the lips and/or for the care, styling and/or dyeing of keratin fibres, preferably the hair.
[00177] The dispersion according to the invention finds a quite particular application in the cosmetic field, notably in the makeup field and notably in lipsticks and lip glosses, and eyeshadows and mascaras.
[00178] Water iv)
[00179] The dispersion (A) comprises water iv). Preferably, the amount of water in the dispersion is between 5% and 49% by weight relative to the total weight of the dispersion, particularly between 10% and 47% by weight, more particularly between 15% and 48% by weight, more preferentially between 18% and 45% by weight and even more preferentially between 20% and 44% by weight relative to the total weight of the dispersion.
[00180] According to a particular embodiment of the invention, when the dispersion (A) comprises one or more copolymers a) derived from a1) and a2), with a2) representing an ethylenic compound comprising one or more anhydride groups such as maleic anhydride, then the dispersion does not contain:
- any thiol-based compounds chosen from a) an emulsion made with a fluid silicone which comprises thiol groups (supplier ref.: KM-9769) - Shin-Etsu, b)
Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers (CAS Number: [102783-03- 9]); supplier ref.: SMS-042, Gelest, and c) Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers (CAS Number: [102783-03-9]) supplier ref.: SMS-992: Gelest, or- any amine compounds chosen from poly(dimethylsiloxane), bis(3-aminopropyl)- terminated (PDMS-diNH2) (CAS Number: 106214-84-0) and Bis-Cetearyl Amodimethicone, 2-[(2-aminoethyl)amino]propyl Me, di-Me, [(Ci4-2o-alkyldimethylsilyl)oxy]-terminated (CAS Number: 1126942-72-0) (Mn = 50 000 g/mol) polyamine compounds bearing several primary amine and/or secondary amine groups. [00181] More particularly, the dispersion (A) does not comprise any polyamine compounds containing several primary amine and/or secondary amine groups, and does not comprise any amino alkoxysilane when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride. Even more particularly, the dispersion (A) does not contain any compound comprising one or more amino groups -NH2 when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride.
[00182] More particularly, the dispersion (A) does not comprise any thiol-based polymer when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride. Even more particularly, the dispersion does not contain any compound comprising one or more thiol groups when a2) is an ethylenic compound comprising one or more anhydride groups such as maleic anhydride.
[00183] The term “thiol-based polymer1’ means a star, comb, brush or dendritic homopolymer or copolymer comprising one or more thiol groups which may be present as end groups or side groups.
[00184] According to a particular embodiment of the invention, the weight ratio of the hydrocarbon-based liquid fatty substance(s) iii)/the water v) is between 0.2 and 10, more particularly between 0.5 and 8, preferably between 0.6 and 7, more preferentially between 0.7 and 6.
[00185] The water that is suitable for use in the invention may be tap water, distilled water, spring water, a floral water such as cornflower water and/or a mineral water such as Vittel water, Lucas water or La Roche Posay water and/or a thermal water.
[00186] The dispersion may also comprise one or more water-soluble solvents.
[00187] According to the present invention, the term “water-miscible solvent’ denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at 25°C and atmospheric pressure).
[00188] The water-miscible solvents that may be used in dispersion (A) of the invention may also be volatile.
[00189] Among the water-miscible solvents that may be used in the composition according to the invention, mention may notably be made of lower monoalcohols containing from 2 to 5 carbon atoms such as ethanol and isopropanol, and glycols containing from 3 to 8 carbon atoms such as hexylene glycol, propylene glycol, 1 ,3-butylene glycol and dipropylene glycol. [00190] The water may also comprise any water-soluble or water-dispersible compound that is compatible with an aqueous phase, such as associated film-forming polymers, surfactants, and mixtures thereof.
[00191] The term “surfactant’ means a “surface agent’, which is a compound that is capable of modifying the surface tension between two surfaces; surfactants are amphiphilic molecules, i.e. they contain two parts of different polarity, one lipophilic and apolar, and the other hydrophilic and polar. The surfactants may be nonionic, anionic, amphoteric or cationic active agents.
[00192] According to a preferred embodiment of the invention, the dispersion of the invention does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferentially not more than 2% by weight of surfactants relative to the total weight of the dispersion, more particularly not more than 1 % by weight of surfactants relative to the total weight of the dispersion; even more preferentially, the composition does not comprise more than 0.5% by weight of surfactants relative to the total weight of the dispersion, and better still the mixture does not comprise any surfactant.
[00193] The cosmetic active agent(s) v)
[00194] 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.
[00195] According to a preferred embodiment of the present invention, the cosmetic active agent(s) of the invention are chosen from f) pigments.
[00196] 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.
[00197] 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.
[00198] According to a particular embodiment of the invention, the dispersion (A) comprises iv) one or more cosmetic active agents chosen from pigments.
[00199] The pigment(s) more particularly represent from 0.5% to 40% by weight and preferably from 1 % to 20% by weight relative to the total weight of the dispersion (A).
[00200] The pigments are white or coloured 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. [00201] 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.
[00202] These pigments may be in pigment powder or paste form. They may be coated or uncoated.
[00203] 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.
[00204] The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia 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.
[00205] The pigment may be an organic pigment.
[00206] The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments.
[00207] 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.
[00208] In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Colour Index under the references Cl 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Colour Index under the references Cl 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Colour Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Colour Index under the references Cl 11725, 45370, 71105, the red pigments codified in the Colour 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.
[00209] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names:
- Cosmenyl Yellow IOG: Yellow 3 pigment (Cl 11710); - Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);
- Cosmenyl Orange GR: Orange 43 pigment (Cl 71105);
- Cosmenyl Red R: Red 4 pigment (Cl 12085);
- Cosmenyl Carmine FB: Red 5 pigment (Cl 12490);
- Cosmenyl Violet RL: Violet 23 pigment (Cl 51319);
- Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74160);
- Cosmenyl Green GG: Green 7 pigment (Cl 74260);
- Cosmenyl Black R: Black 7 pigment (Cl 77266).
[00210] 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 be composed notably 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.
[00211] The organic pigment may also be a lake. The term “lake” means dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
[00212] The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.
[00213] Among the dyes, mention may be made of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45380), 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).
[00214] 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).
[00215] The pigment may also be a pigment with special effects. The term “pigments with special effects” means pigments that generally create a coloured 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 coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.
[00216] 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.
[00217] Examples of pigments with special effects that may be mentioned include nacreous pigments such as mica covered with titanium or with bismuth oxychloride, coloured 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 nacres Cellini sold by BASF (mica-TiC>2-lake), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2C>3) and Colorona sold by Merck (mica-TiO2-Fe2C>3).
[00218] Mention may also be made of the gold-coloured 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.
[00219] Still as examples of nacres, mention may also be made of particles including a borosilicate substrate coated with titanium oxide.
[00220] Particles comprising a glass substrate coated with titanium oxide are notably sold under the name Metashine MC1080RY by the company Toyal.
[00221] 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 aluminium borosilicate and aluminium.
[00222] 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.
[00223] The reflective particles may be selected so as not to significantly alter the colouring effect generated by the colouring agents with which they are combined, and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
[00224] These particles may have varied forms and may notably be in platelet or globular form, in particular in spherical form.
[00225] 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.
[00226] 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.
[00227] 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.
[00228] 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.
[00229] The reflective material may include a layer of metal or of a metallic material.
[00230] Reflective particles are notably described in JP-A-09188830, JP-A-10158450, JP-A-10158541 , JP-A-07258460 and JP-A-05017710.
[00231] 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.
[00232] 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.
[00233] Use may also be made of particles comprising a metal substrate, such as silver, aluminium, 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, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof. [00234] Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiC>2 sold under the name Visionaire by the company Eckart.
[00235] 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.
[00236] The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.
[00237] 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.
[00238] The pigments may be dispersed in the composition by means of a dispersant.
[00239] The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. 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.
[00240] 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.
[00241] The pigments used in the composition may be surface-treated with an organic agent.
[00242] 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 aluminium salts of fatty acids, for example aluminium 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.
[00243] 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.
[00244] 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.
[00245] Preferably, the surface-treated pigments are coated with an organic layer.
[00246] 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.
[00247] 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.
[00248] An organic agent covalently bonded to the pigments will preferably be used.
[00249] 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.
[00250] Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;
- a methicone treatment, for instance the SI surface treatment sold by LCW;
- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;
- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;
- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;
- an aluminium dimyristate treatment, such as the Ml surface treatment sold by Miyoshi; - a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;
- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;
- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;
- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;
- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;
- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;
- an isopropyl titanium tri isostearate treatment, for instance the ITT surface treatment sold by Daito;
- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;
- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.
[00251] 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. [00252] According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersant: pigment) 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.
[00253] 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:
- amino silicones, 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.
[00254] According to a particular embodiment, the dispersant(s) are of amino silicone type other than the alkoxysilanes described previously and are cationic.
[00255] Preferably, the pigment(s) are chosen from mineral, mixed mineral-organic or organic pigments.
[00256] 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.
[00257] The composition may comprise one or more direct dyes.
[00258] The term “direct dye" means natural and/or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fibre.
[00259] They may be ionic or nonionic, preferably cationic or nonionic.
[00260] 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.
[00261] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (V) and (VI) and the azo cationic dyes (VII) and (VIII) below:
[Chem. 6] Het+-C(Ra)=N-N(Rb)-Ar, Q’ (V)
[Chem. 7] Het+-N(Ra)-N=C(Rb)-Ar, Q- (VI)
[Chem. 8] Het+-N=N-Ar, Q- (VII)
[Chem. 9] Ar+-N=N-Ar”, Q- (VIII) in which formula (V) to (VIII):
- 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.
[00262] In particular, mention may be made of the azo and hydrazono direct dyes bearing an endocyclic cationic charge of formulae (V) to (VIII) 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 imgf000040_0001
[Chem. 11]
Figure imgf000040_0002
in which (IX) and (X) formulae:
- R1 represents 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-C8)alkyl, optionally substituted (Ci-C8)alkoxy, or (di)(Ci-C8)(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.
[00263] 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 halide such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.
[00264] 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.
[00265] 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.
[00266] Preferably, the cosmetic active agent(s) v) are chosen from the following pigments: carbon black, iron oxides, notably black iron oxides, and micas coated with iron oxide, red iron oxides (iron(lll) oxide, also known as ferric 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, the alkali metal salts of lithol red, such as the calcium salt of lithol red B.
[00267] 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.
[00268] According to a particular embodiment of the invention, the dispersion (A) comprises iv) one or more cosmetic active agents chosen from hair dyes.
[00269] Among the hair 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. [00270] The hair dye(s) 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).
[00271] 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 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 pigments such as D&C Red 7.
[00272] 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.
[00273 ] Process for treating keratin materials using the dispersion (A):
[00274] According to an advantageous variant of the invention, the process of the invention is a process for treating keratin fibres, in particular human keratin fibres, preferably the hair, which involves the application to said fibres of at least one dispersion (A) as defined previously.
[00275] According to a particular embodiment of the invention, after applying the dispersion (A) to the keratin materials, the composition is left to dry on said keratin materials, either naturally or using heating devices used in cosmetics, such as a hairdryer.
[00276] According to a particular embodiment of the invention, the keratin fibre treatment process is a treatment for shaping said fibres.
[00277] More particularly, the keratin fibre treatment process includes at least one shaping step, notably:
- in a first step of the process, the keratin fibres are shaped using a conventional shaping means, for example with rollers or a brush of particular shape (cylindrical), and then
- in a second step, the dispersion (A) is applied to said fibres, the application method preferably being by means of a spray, and then
- in a third step, said fibres are dried naturally or dried using conventional devices used in cosmetics, and then
- the shaping means is removed from said fibres, optionally followed by a rinsing step, a step of shampoo washing and then a step of drying naturally or of drying using conventional devices.
[00278] Once the dispersion (A) has been applied, before the third step, rinsing or shampoo washing may optionally be performed. [00279] The dispersion (A) may be applied to wet or dry keratin fibres, preferably dry keratin fibres.
[00280] It is also possible via the keratin fibre treatment process of the invention to perform shaping while at the same time providing said fibres with one or more cosmetic active agents, for example dyeing by applying at least one dye and/or pigment, and/or applying at least one IIV(A) and/or IIV(B) screening agent, and/or applying at least one active agent to said fibres. It suffices to apply a dispersion (A) comprising at least one cosmetic agent v) as defined previously. It also appears that the shaping is persistent and, what is more, that the cosmetic active agent(s) iv) applied are also persistent notably with respect to successive shampoo washing and to light rays.
[00281] After the application of the dispersion (A), the fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C and less than 100°C.
[00282] Preferably, if the fibres are dried, they are dried, in addition to a supply of heat, with a flow of air obtained using a conventional device used in cosmetics, such as a hood, a hairdryer, a straightening iron, a Climazon, etc.
[00283] During drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through. This operation may similarly be performed once the fibres have dried, naturally or otherwise.
[00284] When the drying step is performed with a hood or a hairdryer, the drying temperature is between 40°C and 110°C and preferably between 50°C and 90°C.
[00285] According to one embodiment of the keratin fibre treatment process of the invention, the hair undergoes a treatment with a straightening iron. This treatment is then performed once said hair is dry; the temperature of the treatment with the straightening iron is between 110°C and 220°C, preferably between 140°C and 200°C.
[00286] The dispersion (A) may be used on wet or dry keratin fibres, and also on any type of fair or dark, natural or dyed, permanent-waved, bleached or relaxed fibres.
[00287] According to a particular embodiment of the process of the invention, the fibres are washed before applying the dispersion (A).
[00288] The application to the fibres may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush or with the fingers.
[00289] According to one preferred embodiment of the invention, the step of applying the dispersion (A) is performed on dry keratin fibres.
[00290] According to another particular embodiment of the process of the invention, the step of applying the dispersion (A) is performed on humid or wet keratin fibres.
[00291] Preferably, after applying the dispersion (A), there is a waiting time of between 1 minute and 2 hours, in particular between 5 minutes and 1 hour, more particularly between 10 minutes and 30 minutes, preferably in the open air and at room temperature. [00292] According to another particular embodiment of the invention, the process for treating keratin fibres, notably human keratin fibres such as the hair, is a process for dyeing said fibres, comprising at least one step of applying to said fibres a dispersion (A) as defined previously which comprises h) at least one dye, and/or j) at least one pigment, followed by a drying step. Once the application of the dispersion (A) of the invention to the keratin fibres has been performed, rinsing and/or shampoo washing may optionally be performed.
[00293] The dispersion (A) may be applied to wet or dry keratin fibres, which are preferably dried naturally or else dried using conventional devices used in cosmetics as defined previously.
[00294] According to a particular embodiment of the invention, the process for treating keratin materials is a process for treating the skin and/or the eyelashes or the eyebrows involving the application to the skin and/or the eyelashes or the eyebrows of the dispersion (A) as defined previously, followed by a step of drying naturally or of drying using conventional devices used in cosmetics as defined previously, preferably naturally.
[00295] 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.
[00296] The dispersion (A) according to the invention may also comprise a cosmetic additive chosen from fragrances, preserving agents, fillers, waxes, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers, polymers other than a), b), c), d) and e), thickeners, and dyestuffs other than f) dyes and g) pigments.
[00297] Preferentially, the first step of the process of the invention is the application of the dispersion (A) in one or more apolar solvents, notably isododecane.
[00298] vii) the thickener(s)
[00299] According to an advantageous variant of the invention, the dispersion (A) also comprises vii) one or more thickeners chosen from organic thickening polymers and thickening monoglycerides, diglycerides or triglycerides.
[00300] The term “thickener1’ means that the agent in question, a polymer or a triglyceride, when introduced at 1 % by weight in an aqueous solution or an aqueous-alcoholic solution containing 30% ethanol, and at pH 7, or in an oil chosen from liquid petroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a shear rate of 1 s'1. This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like). The thickening polymers may be thickeners for the aqueous phase and/or the fatty phase, preferentially the aqueous phase. [00301] According to a particular embodiment of the invention, the thickener(s) are organic polymers.
[00302] The term “organic thickening polymer” means a thickening polymer as defined previously, which is formed from carbon and hydrogen, and possibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine or bromine, and also phosphorus, alkali metals such as sodium or potassium, or alkaline-earth metals such as magnesium or calcium. The organic polymers according to the invention do not comprise silicon.
[00303] The organic thickening polymers according to the invention may be of natural or synthetic origin.
[00304] The thickeners may be associative or non-associative anionic, cationic, amphoteric or nonionic polymers, optionally bearing sugar units.
[00305] For the purposes of the present invention, the term “sugar unit’ means a unit derived from a carbohydrate of formula Cn(H2O)n-i or (CH2O)n, which may be optionally modified by substitution and/or by oxidation and/or by dehydration. The sugar units that may be included in the composition of the thickening polymers of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturonic acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrogalactose sulfate and fructose.
[00306] The thickeners may be thickeners for the aqueous phase, i.e. in water or in the liquid fatty substance(s) iii).
[00307] Preferably, the polymers for structuring the oily phase via physical interactions are chosen from polyamides, silicone polyamides, saccharide or polysaccharide mono- or polyalkyl esters, N-acylamino acid amide derivatives, and copolymers comprising an alkylene or styrene block, these copolymers possibly being diblock, triblock, multiblock or radial-block polymers, also known as star copolymers, or alternatively comb polymers.
[00308] According to one embodiment, the thickening polymers bear in the backbone at least one crystallizable sequence.
[00309] They are also polymers that are soluble or dispersible in the oil or fatty phase by heating above their melting point m.p. These polymers are notably block copolymers consisting of at least two blocks of different chemical nature, one of which is crystallizable.
[00310] As polymers bearing in the backbone at least one crystallizable block that are suitable for use in the invention, mention may be made of: i). the polymers defined in US-A-5 156 911 ; ii). block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:
- cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo(2,2,1)-2-heptene),
5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene,
5,5,6-trimethylnorbornene, 5-ethylidenenorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1 ,4,5,8-dimethano-1 , 2, 3, 4, 4a, 5,8a- octahydronaphthalene, dicyclopentadiene, or mixtures thereof,
- with ethylene, propylene, 1 -butene, 3-methyl-1 -butene, 1 -hexene, 4-methyl-1 -pentene, 1 -octene, 1 -decene or 1-eicosene, or mixtures thereof. These block copolymers may be in particular (ethylene/norbornene) block copolymers and (ethylene/propylene/ethylidenenorbornene) block terpolymers.
[00311] Those resulting from the block copolymerization of at least two C2-C16, and better still C2-C12, a-olefins such as those mentioned previously and in particular block bipolymers of ethylene and of 1 -octene may also be used.
[00312] In particular, the copolymers contain at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers may also contain two crystallizable blocks of different chemical nature. The preferred copolymers are those that contain, at room temperature, both a crystallizable block and an amorphous block that are both hydrophobic and lipophilic, sequentially distributed; examples that may be mentioned include semi-crystalline polymers, which may be non-crosslinked or (partly) crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid oily phase by heating above their melting point. It may then be a case of chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a case of physical crosslinking, which may then be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, for instance dipolar interactions between carboxylate ionomers, these interactions being in small amount and borne by the polymer backbone; or due to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer.
[00313] Preferably, the semi-crystalline polymers that are suitable for use in the invention are non-crosslinked. As particular examples of semicrystalline polymers that can be used in the composition according to the invention, mention may be made of the Intelimer® products from Landec described in the brochure “Intelimer® polymers”. These polymers are in solid form at room temperature (25°C). They bear crystallizable side chains and contain the monomer. Mention may notably be made of Landec IP22®, with a melting point m.p. of 56°C, which is a viscous, impermeable, non-tacky product at room temperature. [00314] According to one embodiment, the thickener(s) are chosen from saccharide or polysaccharide monoalkyl/polyalkyl esters.
[00315] Among the saccharide or polysaccharide monoalkyl or polyalkyl esters that are suitable for use in the invention, mention may be made of dextrin or inulin alkyl or polyalkyl esters.
[00316] It may notably be a dextrin monoester or polyester of at least one fatty acid notably corresponding to formula (XI) below:
[Chem. 12]
Figure imgf000047_0001
in which formula (XI):
- n is an integer ranging from 3 to 200, notably ranging from 20 to 150 and in particular ranging from 25 to 50,
- Ri, R2 and R3, which may be identical or different, are chosen from hydrogen and an acyl group (R-C(O)-) in which the radical R is a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 7 to 29, in particular from 7 to 21 , notably from 11 to 19, more particularly from 13 to 17, or even 15, carbon atoms, with the proviso that at least one of said radicals R1, R2 or R3 is other than hydrogen.
[00317] In particular, R1, R2 and R3 may represent hydrogen or an acyl group (R-C(O)-) in which R is a hydrocarbon-based radical as defined previously, with the proviso that at least two of said radicals R1, R2 and R3 are identical and other than hydrogen. The radicals R1 , R2 and R3 may all contain an acyl group (R-C(O)), which may be identical or different and notably identical. In particular, n mentioned previously advantageously ranges from 25 to 50 and is notably equal to 38 in the general formula of the saccharide ester that may be used in the present invention.
[00318] Notably, when the radicals R1, R2 and/or R3, which may be identical or different, contain an acyl group (R-C(O)), these radicals may be chosen from caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethyl methylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic and stearolic radicals, and mixtures thereof.
[00319] Preferably, at least one dextrin palmitate is used as fatty acid ester of dextrin. This ester may be used alone or as a mixture with other esters.
[00320] Advantageously, the fatty acid ester of dextrin has a degree of substitution of less than or equal to 2.5, notably ranging from 1.5 to 2.5 and preferably from 2 to 2.5 on the basis of one glucose unit. The weight-average molecular weight of the dextrin ester may in particular be from 10 000 to 150 000, notably from 12 000 to 100 000 and even from 15 000 to 80 000.
[00321] Dextrin esters, in particular dextrin palmitates, are commercially available under the name Rheopearl TL or Rheopearl KL from the company Chiba Flour.
[00322] According to another particular embodiment of the invention, the thickener(s) contained in the dispersion (A) are chosen from monoglycerides, diglycerides and triglycerides in which at least one hydrogen atom of a hydroxyl group of the glycerol has been substituted with the group -C(O)-Ra, with Ra representing a linear or branched, cyclic or acyclic, saturated or unsaturated carbonyl-based hydrocarbon-based chain, including from 8 to 40 carbon atoms, said hydrocarbon-based chain possibly being substituted with one or more hydroxyl groups.
[00323] Preferably, the thickeners vii) are chosen from triglycerides trisubstituted with -C(O)-Rawith Ra as defined previously, more particularly chosen from trihydroxystearin. Notably, the thickener(s) are chosen from: 1) block polymers of at least two C2-C16 and better still C2-C12 a-olefins, preferably non-crosslinked semi-crystalline polymers, more particularly semi-crystalline polymers, 2) saccharide or polysaccharide monoalkyl/polyalkyl esters, particularly dextrin esters, in particular dextrin palmitates, 3) monoglycerides, diglycerides and triglycerides in which at least one hydrogen atom of a hydroxyl group of the glycerol has been substituted with the group -C(O)-Ra, with Ra representing a linear or branched, cyclic or acyclic, saturated or unsaturated, carbonyl-based, hydrocarbon-based chain, including from 8 to 40 carbon atoms, said hydrocarbon-based chain possibly being substituted with one or more hydroxyl groups, preferably chosen from triglycerides trisubstituted with -C(O)-Ra with Ra as defined previously, more particularly chosen from trihydroxystearin.
[00324] Preferably, the thickener(s) are present in the dispersion according to the invention in a content ranging from 0.01 % to 15% by weight, more preferentially from 0.1% to 7% by weight, even more preferentially from 1% to 6% by weight, relative to the total weight of the dispersion. [00325] The kit
[00326] A subject of the invention is also a kit or device with several separate compartments comprising:
- in one compartment: a dispersion comprising the ingredients i) to iii) and optionally vii) as defined previously,
- the following ingredients v) are distributed among one or more different compartments: f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and/or j) UV(A) and/or UV(B) screening agents, and iv) water, which is in the dispersion, and/or with the ingredients f) to h) and/or in another compartment.
[00327] The composition packaging assembly is, in a known manner, any packaging that is suitable for storing cosmetic compositions (notably a bottle, tube, spray bottle or aerosol can).
[00328] The invention is illustrated in greater detail in the examples that follow.
[00329] EXAMPLES
The following dispersions (A) were prepared:
[Table 1]:
Figure imgf000049_0001
Figure imgf000050_0001
[00330] T able 1 : Weight composition of the various illustrated dispersions of the invention
[00331] The monomers used for the various examples for i), ii) and the polymerization initiator vi) are all collated in Tables 2 and 3 below: [Table 2]:
Figure imgf000050_0002
Table 2: Monomers used in the various examples
[Table 3]:
Figure imgf000050_0003
Table 3: Thickeners
[Table 4]:
Figure imgf000051_0001
Table 4: Polymerization initiator used in the various examp es
[00332] For all the dispersions, an evaluation of the cosmetic properties on a dry film was performed.
[00333] A film is prepared on a contrast card with a film spreader (speed: 50 mm/s - Cylinder: 100 pm). The film is left to dry for 24 hours at room temperature. Once dry, the film has a thickness of about 30-50 pm.
[00334] An evaluation of the resistance to the attacking factors water/olive oil/sebum is performed on the dry film:
[00335] Measurement of the resistance to water and to fats
[00336] Three drops of olive oil or of sebum were placed on the dry film present on the black part of the contrast card (one for each time of observation of the resistance to the attacking factor), each drop corresponds to about 30 pL of attacking factor (use of a micropipette).
[00337] The drop is left in contact with the dry film for 20 minutes. Once the time has elapsed, the drop of olive oil, sebum or water is wiped off and observation of the deterioration of the polymer film is performed. If the film was attacked by the drop of attacking factor, the polymer film is regarded as being non-resistant to this attacking factor.
[00338] Example 1: Production of a dispersion with variable amounts of water
[00339] Step 1 : Synthesis of the dispersion of polymer particles in isododecane [00340] In a first stage, the polymer particles are synthesized in isododecane.
[00341] The polymer particles are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. The synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and of a radical initiator (T21 S). In the first step, the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4. In the second step, the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator (T21S).
[00342] After stripping, the polymer is at a solids content of 50% in the isododecane. [00343] The ratios employed to obtain the stabilizer and the core are summarized in
[Table 5]:
Figure imgf000052_0001
Table 5: Specific ratios in the stabilizer and core for the polymer particles of Example 1 [00344] Amount of reagents:
Step 1.1 :
[Table 6]:
Figure imgf000052_0002
[00345] Isododecane/ethyl acetate added between the two steps: [Table 7]:
Figure imgf000052_0003
[00346] Step 1.2:
[Table 8]:
Figure imgf000052_0004
Figure imgf000053_0001
Tables 8: Amounts of reagents used for Example 1
[00347] Experimental protocol:
Isododecane/ethyl acetate (60/40), isobornyl acrylate, methyl acrylate/ethyl 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.
After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 97% (methyl acrylate consumption: 96% and ethyl acrylate: 96%).
After 2 hours of reaction, isododecane/ethyl acetate (60/40) is introduced into the feedstock. The medium is heated to 90°C.
Once the medium is at 90°C, methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
After 7 hours of synthesis, a 99% consumption of the methyl acrylate/ethyl acrylate/acrylic acid is obtained (isobornyl acrylate consumption: 100%).
3 L of isododecane and of ethyl acetate are then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is 50%.
Step 2: Addition of water at the end of the synthesis
In a second stage, water is added while keeping the polymer in the reactor.
[Table 9]:
Figure imgf000053_0002
Figure imgf000054_0001
Table 9: Influence of the amount of water on the stability of the final dispersion
Evaluation of the cosmetic properties of the various stable dispersions was subsequently performed. The measurements of the sensitivity to fatty substances (olive oil and sebum) and to water are collated in Table 10:
[Table 10]:
Figure imgf000054_0002
Table 10: Cosmetic properties of Example 1
(-): no resistance, (+) resistance, (++), very high resistance after wiping with the same cotton fabric soaked with the same amount of sebum, olive oil or water.
[00348] The dispersions containing less volatile hydrocarbon-based oil iii) of Examples 1-1 and 1-2 lead to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
Example 2: Dispersion for polymer particles containing maleic anhydride
Step 1: Synthesis of the dispersion of polymer particles in isododecane In a first stage, the polymer particles are synthesized in isododecane.
The dispersions are formed as a whole (stabilizer ii + particles i) containing 10% maleic anhydride, 70% ethyl acrylate and 20% isobornyl acrylate. The synthesis of these dispersions was performed in a 1 -litre pilot reactor. The synthesis is performed in two steps:
In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of ethyl acrylate and of a radical initiator (T21S). In the first step, the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.
In the second step, the rest of the ethyl acrylate and the maleic anhydride are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator Trigonox (T21S).
After stripping, the polymer is at a solids content of 50% in the isododecane.
The ratios employed to obtain the stabilizer and the core are summarized in Table 11 : [Table 11]:
Figure imgf000055_0001
Amount of reagents:
Step 1.1 :
[Table 12]:
Figure imgf000055_0002
Isododecane/ethyl acetate added between the two steps:
[Table 13]:
Figure imgf000055_0003
Step 1.2: [Table 14]:
Figure imgf000055_0004
Tables 14: Amounts of reagents used for Example 2
Experimental protocol: Isododecane/ethyl acetate (60/40), isobornyl acrylate, ethyl 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.
After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 97% (ethyl acrylate consumption: 97%).
After 2 hours of reaction, isododecane/ethyl acetate (60/40) is introduced into the feedstock. The medium is heated to 90°C.
Once the medium is at 90°C, ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40) and the T21S are introduced over 1 hour by pouring. At the end of the introduction by pouring, the medium is milky.
After 7 hours of synthesis, traces of the starting monomers remain.
1 L of isododecane and of ethyl acetate is then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is 50%.
Step 2: Addition of water at the end of the synthesis
In a second stage, water is added at the end of the operation while keeping the polymer in the reactor. A test was performed with introduction of 40% of water. It is summarized in Table 15:
[Table 15]:
Figure imgf000056_0001
Table 15: New dispersion containing maleic anhydride - Example 2
A stable dispersion containing up to 40% of water was obtained.
Evaluation of the cosmetic properties of the new dispersion was subsequently performed. The measurements of the sensitivity to fatty substances (olive oil and sebum) and to water are collated in Table 16:
[Table 16]
Figure imgf000056_0002
Figure imgf000057_0001
Table 16: Cosmetic properties of Example 2
(-): no resistance, (+) resistance, (++), very high resistance after wiping with the same cotton fabric soaked with the same amount of sebum, olive oil or water.
[00349] The dispersion of Example 2 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
Example 3: Production of a dispersion with variable amounts of water for polymer particles containing more acrylic acid (20%)
Step 1: Synthesis of the dispersion of polymer particles in isododecane In a first stage, the polymer particles are synthesized in isododecane.
The dispersions are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate. The synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and of a radical initiator (T21S). In the first step, the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4.
In the second step, the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator (T21S).
After stripping, the polymer is at a solids content of 50% in the isododecane.
The ratios employed to obtain the stabilizer and the core are summarized in Table 17:
[Table 17]
Figure imgf000057_0002
Table 17 Specific ratios in the stabilizer and core for the dispersion of Example 3 Amount of reagents:
Step 1.1 :
[Table 18]
Figure imgf000058_0001
Isododecane/ethyl acetate added between the two steps:
[Table 19]
Figure imgf000058_0002
Step 1.2: [Table 20]
Figure imgf000058_0003
Tables 20: Amounts of reagents used for Example 3
Experimental protocol:
Isododecane/ethyl acetate (60/40), isobornyl acrylate, methyl acrylate/ethyl 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.
After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 98% (methyl acrylate consumption: 96% and ethyl acrylate: 98%).
After 2 hours of reaction, isododecane/ethyl acetate (60/40) is introduced into the feedstock.
The medium is heated to 90°C. Once the medium is at 90°C, methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
After 7 hours of synthesis, a 99% consumption of the methyl acrylate/ethyl acrylate/acrylic acid is obtained (isobornyl acrylate consumption: 100%).
3 L of isododecane and of ethyl acetate are then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is 50%.
Step 2: Addition of water at the end of the synthesis
In a second stage, water is added at the end of the operation while keeping the polymer in the reactor. Two tests were performed. They are summarized in Table 21 :
[Table 21]
Figure imgf000059_0001
Table 21: Influence of the amount of water - Example 3
Evaluation of the cosmetic properties of the various stable dispersions was performed. The measurements of the sensitivity to fatty substances (olive oil and sebum) and to water are collated in Table 22:
[Table 22]
Figure imgf000059_0002
Table 22: Cosmetic properties of Example 3
(-): no resistance, (+) resistance, (++), very high resistance after wiping with the same cotton fabric soaked with the same amount of sebum, olive oil or water. [00350] The dispersions containing less volatile hydrocarbon-based oil iii) of Examples 3- 1 and 3-2 lead to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
Example 4: Production of a dispersion with variable amounts of water for polymer particles synthesized in Cetiol UT
Step 1: Synthesis of the dispersion of polymer particles in isododecane In a first stage, the polymer particles are synthesized in Cetiol UT/EtOAc.
The polymer particles are formed as a whole (stabilizer ii + particles i) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. The synthesis of these dispersions was performed in a 6-litre pilot reactor. The synthesis is performed in two steps:
In a first step, isobornyl acrylate is polymerized in Cetiol UT/ethyl acetate (60/40) in the presence of a small amount of methyl acrylate/ethyl acrylate and a radical initiator (T21S). In the first step, the isobornyl acrylate/methyl acrylate/ethyl acrylate mass ratio is 92/4/4.
In the second step, the rest of the methyl acrylate/ethyl acrylate and the acrylic acid are added in the presence of Cetiol UT/ethyl acetate (60/40) and of the radical initiator (T21S).
After stripping, the polymer is at a solids content of 50% in the Cetiol UT.
The ratios employed to obtain the stabilizer and the core are summarized in Table 23:
[Table 23]
Figure imgf000060_0001
Table 23: Specific ratios in the stabilizer and core for the polymer particles of Example 4
Amount of reagents:
Step 1.1 :
[Table 24]
Figure imgf000060_0002
Figure imgf000061_0001
Cetiol UT/ethyl acetate added between the two steps:
[Table 25]
Figure imgf000061_0002
Step 1.2: [Table 26]
Figure imgf000061_0003
Tables 26: Amounts of reagents used for Example 4 Experimental protocol:
Cetiol UT/ethyl acetate (60/40), isobornyl acrylate, methyl acrylate/ethyl 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.
After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 97% (methyl acrylate consumption: 96% and ethyl acrylate: 96%).
After 2 hours of reaction, Cetiol UT/ethyl acetate (60/40) is introduced into the feedstock. The medium is heated to 90°C.
Once the medium is at 90°C, methyl acrylate/ethyl acrylate/acrylic acid, Cetiol UT/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky.
After 7 hours of synthesis, a 99% consumption of the methyl acrylate/ethyl acrylate/acrylic acid is obtained (isobornyl acrylate consumption: 100%). 3 L of Cetiol UT and of ethyl acetate are then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is 50%.
Step 2: Addition of water at the end of the synthesis
In a second stage, water is added at the end of the operation while keeping the polymer in the reactor. A test was performed. It is summarized in Table 27:
[Table 27]
Figure imgf000062_0001
Table 27 New dispersion containing Cetiol UT - Example 4
Evaluation of the cosmetic properties of the new dispersion was subsequently performed. The measurements of the sensitivity to fatty substances (olive oil and sebum) and to water are collated in Table 28:
[Table 28]
Figure imgf000062_0002
Table 28: Cosmetic properties of Example 4
(-): no resistance, (+) resistance, (++), very high resistance after wiping with the same cotton fabric soaked with the same amount of sebum, olive oil or water.
The dispersion of Example 4 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
Example 5: Modification of the order of introduction of the water:
For this example, in a first stage, the stabilizing polymer is synthesized. Next, the water is added before the synthesis of the core of the polymer particles.
The polymer particles are formed as a whole (stabilizer i + particles ii) containing 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate. After stripping off the ethyl acetate, the polymer is at a solids content of 37.5% in the isododecane iii)/water iv).
The ratios employed to obtain the stabilizer and the core are summarized in Table 28: [Table 28]
Figure imgf000063_0001
Table 28: Specific ratios in the stabilizer and core for the polymer particles of Example 5
Amount of reagents:
Step 1 :
[Table 29]
Figure imgf000063_0002
Step 2: Added isododecane/ethyl acetate and water [Table 30]
Figure imgf000063_0003
Step 3:
[Table 31]
Figure imgf000063_0004
Figure imgf000064_0001
Tables 31: Amounts of reagents used for Example 5
Experimental protocol:
Isododecane/EtOAc, isobornyl acrylate, ethyl acrylate/methyl acrylate and T21S are introduced as feedstock into the reactor. The medium is sparged with argon for 10 minutes. The medium is heated to 90°C (nominal oil bath temperature) with stirring. After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 99%.
After 2 hours of reaction, isododecane/ethyl acetate (60/40) and water are introduced into the feedstock. The medium is heated to 90°C.
Once the medium is at 90°C, methyl acrylate/ethyl acrylate/acrylic acid, isododecane/ethyl acetate (60/40) and T21S are introduced over 1 hour by pouring. At the end of the introduction by pouring, the medium is milky. The solids content is 30%.
After 7 hours of synthesis, a 99% consumption of the methyl acrylate/ethyl acrylate/acrylic acid is obtained (isobornyl acrylate consumption: 100%).
The ethyl acetate is stripped off.
The final dispersion has the composition shown in Table 32: [Table 32]
Figure imgf000064_0002
Table 32: Composition of the final dispersion - Example 5
Evaluation of the cosmetic properties of the dispersion obtained according to another process was subsequently performed. The measurements of the sensitivity to fatty substances (olive oil and sebum) and to water are collated in Table 33:
[Table 33]
Figure imgf000064_0003
Table 33: Cosmetic properties of Example 5
The dispersion of Example 5 leads to a deposit which is resistant to sebum and very highly resistant to water and to olive oil.
Addition of thickener
Formulations were prepared by adding a thickener. Three thickeners were added, according to Table 3:
Preparation process:
Step 1: The first step consists in synthesizing the polymer particles in isododecane. This step is identical to step 1 of Example 1.
Step 2: The medium containing the polymer particles in isododecane is cooled to 25°C.
The water is added. The medium is stirred at 2500 rpm.
Step 3: The thickener is introduced while heating to 80°C and stirring at 1500 rpm. The medium is maintained at 80°C for 20 minutes with stirring and is then cooled under the same stirring conditions.
The composition of the final formulations is given in Table 34:
[Table 34]:
Figure imgf000065_0001
Table 32: Composition of the formulations with thickener
Evaluations
Preparation of the deposits
In a first stage, a deposit is produced on a contrast card (for example the card sold under the reference Byko-Charts by the company Byk-Gardner) and also on the FP40 elastomeric support. FP40 (Trellborg, N4I01) is an elastomeric substrate made of butadiene-acrylonitrile copolymer containing a diethylhexyl sebacate oil as plasticizer. When a polymer conveyed in isododecane is applied to this substrate, extraction of the plasticizer is performed, minimizing the supply/impact of sebum on the coating. A volume V of formulation is applied to obtain a dry deposit of 30 pm. The formulation is dried for 7 days at a temperature of 25°C and a relative humidity RH = 45%.
Evaluation protocols:
Tack measurement, the tack is measured with a Viton rubber ball which comes into contact with the deposit at a speed of 5 mm/s under a force of 1 N and for a time of 5 s. The measurement is repeated five times. The tack was measured mainly on the deposit produced on FP40.
Measurement of the tack during drying-. A 10 pL drop of formulation is deposited on a contrast card. The tack is measured with a Viton rubber ball which comes into contact with the deposit each minute at a speed of 5 mm/s under the force of 1 N and for a contact time of 5 s.
Sensitivity to the water/sebum attacking factors'. The sensitivity to water and to sebum is evaluated after depositing a drop of attacking factors (10 pl for sebum and 20 pl for water) onto the surface of the deposit produced on the contrast card. The evaluations are made after 20 minutes of contact between the attacking factor and the deposit.
Results:
Tack measurement on FP40 and sebum/water sensitivity
[Table 35]:
Figure imgf000066_0001
Table 35: Tack measurements on FP40 and water/sebum sensitivity following the addition of thickener in comparison with the same formulation without thickener
(-): no resistance, (+) resistance, (++), very high resistance after wiping with the same cotton fabric soaked with the same amount of sebum, olive oil or water.
It is seen that the addition of thickener made it possible to improve the sensitivity to sebum; this effect is more pronounced during the addition of the thickeners trihydroxystearin and Intelimer. For these two thickeners, the drop test reveals better resistance to sebum and the tack on FP40 is lower. For dextrin palmitate, the effect is less visible on the drop test but is detected via the tack test on FP40, with a reduction of this tack.
Measurement of the tack during drying It was observed and measured that the addition of thickener makes it possible to modify the tack profiles during drying. In the case of the dispersion without thickener, the tack profile tends towards the maximum and remains at this maximum for a long stage. During the addition of the thickeners, the tack peak reaches a maximum at a significantly lower value before returning to 0.

Claims

67
1. Dispersion (A), which comprises: i) one or more particles including one or more polymers chosen from: a) one or more ethylenic copolymers of: ai) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, and
82) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups; in particular, a2) is a (Ci-C4)(alkyl)acrylic acid; and ii) one or more polymeric stabilizers chosen from: b) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) copolymers of:
Ci) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate, and
C2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based liquid fatty substances; iv) water; 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; it being understood that the water content is greater than or equal to 2% by weight and less than 50% by weight relative to the total weight of the dispersion.
2. Dispersion (A) according to the preceding claim, in which the particle(s) i) consist of an ethylenic polymeric core obtained from copolymers a) as defined in the preceding claim, and ii) of one or more polymeric surface stabilizers obtained from polymer b) or from copolymers c) as defined in the preceding claim.
3. Dispersion (A) according to Claim 1 or 2, in which the polymer(s) constituting the particles i) are chosen from acrylate ethylenic copolymers a1) resulting from the polymerization of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer(s) of formula (I): )-C(O)-O-R’ (I)
Figure imgf000068_0001
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, ethyl, n-propyl, /-propyl, n-butyl, /-butyl or f-butyl, preferably methyl, ethyl or /-butyl; particularly methyl, ethyl or isobutyl; preferably, (I) is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and tert-butyl (meth)acrylate; and more preferentially chosen from 68 methyl (meth)acrylates, ethyl (meth)acrylate and isobutyl (meth)acrylate; more preferentially, (I) preferentially represents methyl acrylate, ethyl acrylate, isobutyl acrylate and isobutyl methacrylate.
4. Dispersion (A) according to any one of the preceding claims, in which the polymer(s) constituting the particles i) are chosen from 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, particularly chosen from (1), (2), (3) and (4):
(1) R1(R2)C=C(R3)-Acid with R1, R2 and R3 representing a hydrogen atom or a CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl, phosphoric acid or sulfonic acid, preferably carboxyl; preferably, (1) represents (5) H2C=C(R)-C(O)-O- H with R representing a hydrogen atom or a (Ci-C4)alkyl group potentially substituted by one or more hydroxy group, preferably R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl;
(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
Figure imgf000069_0002
(4a)
Figure imgf000069_0001
in which formulae (4b) 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; more particularly, a2) is chosen from (1) and (4), preferably (4) and notably (5). 69
5. Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the ethylenic monomer(s) a2) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are 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; even more preferentially, a2) represents acrylic acid and salts thereof or maleic anhydride, more preferentially acrylic acid.
6. Dispersion (A) according to any one of the preceding claims, in which the amount of a2) is greater than 2.5% by weight relative to the total weight of the particle i), more particularly between 3% and 35% by weight relative to the weight of monomers of the particle i), even more particularly between 5% and 25% by weight relative to the weight of the polymer of the particles i), better still between 10% and 15% by weight relative to the weight of the polymer of the particles i); in particular, a) is a copolymer derived from the copolymerization of acrylic acid with one or more C1-C4 alkyl (meth)acrylate monomers, preferably two different C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth)acrylate and ethyl (meth)acrylate.
7. Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizer(s) ii) consist of ethylenic polymers chosen from: b) polymers of monomers of formula H2C=C(R)-C(O)-O-R” (III) with R representing a hydrogen atom or (Ci-C4)alkyl group such as methyl, and R” representing a (C5- Cio)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and c) copolymers of c1) H2C=C(R)-C(O)-O-R” (III) and of c2) H2C=C(R)-C(O)-O-R’ (I) with R, R’ and R” as defined previously in Claim 3; particularly, the stabilizer ii) is chosen from: isobornyl acrylate homopolymers, statistical copolymers of isobornyl acrylate/methyl acrylate, statistical copolymers of isobornyl acrylate/ethyl acrylate, and statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate according to the weight ratio described previously.
8. Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizer(s) ii) are chosen from polymers of
(C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and c) statistical copolymers of Ci) (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and c2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate with a ci/c2 weight ratio greater than 4; advantageously, said weight ratio ranges from 4.5 to 19, preferentially said ci/c2 weight ratio ranges from 5 to 15, more preferentially said weight ratio ranges from 5.5 to 12. 70 Dispersion according to any one of the preceding claims, in which the dispersion is such that the polymer of the particles i) comprises from 80% to 93% by weight of the ingredient ai), notably of C1-C4 alkyl (meth)acrylate and from 7% to 20% by weight of the ingredient a2) relative to the total weight of the polymer i); more preferentially, the polymer of the particles i) preferably comprises from 85% to 93% by weight, more particularly 87% to 92% by weight, even more preferentially from 85% to 90% by weight of the ingredient ai), notably of C1-C4 alkyl (meth)acrylate, and from 10% to 20% by weight of the ingredient a2) relative to the total weight of the polymer i). Dispersion (A) according to any one of the preceding claims, in which the dispersion is such that the stabilizer(s) ii) are chosen from c) copolymers of Ci) (C3- Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and C2) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate with from 85% to 94% by weight of the ingredient Ci), notably of isobornyl (meth)acrylate and from 5% to 20% by weight of the ingredient C2) relative to the total weight of the stabilizer; more preferentially, the stabilizer(s) ii) comprise from 85% to 98% by weight and more particularly 87% to 94% by weight of the ingredient Ci), notably of isobornyl (meth)acrylate, and from 10% to 20% by weight of the ingredient C2) relative to the total weight of the stabilizer. Dispersion (A) according to any one of the preceding claims, in which the polymer of the particles i) is present in a content ranging from 21% to 58.5% by weight relative to the total weight of the dispersion, preferably ranging from 30% to 50% by weight relative to the total weight of the dispersion, more preferentially ranging from 36% to 42% by weight relative to the total weight of the dispersion (A). Dispersion (A) according to any one of the preceding claims, in which the sum ii) of stabilizer(s) + i) of polymer particle(s) is present in the dispersion (A) from 2% to 40% by weight, notably from 4% to 35% by weight and preferably from 4.5% to 30% by weight relative to the total weight of the dispersion (A). Dispersion (A) according to any one of the preceding claims, in which the liquid hydrocarbon-based fatty substance(s) iii) are chosen from: hydrocarbons, in particular alkanes, oils of animal origin, oils of plant origin, glycerides, fatty alcohols, esters of fatty acids and/or of fatty alcohols, non-silicone waxes, and silicones; in particular, the liquid hydrocarbon-based fatty substance(s) are hydrocarbon-based oils, which are preferably volatile, or are a mixture of 71 different volatile oils, preferentially chosen from isododecane and octyldodecanol, more particularly isododecane.
14. Dispersion (A) according to any one of the preceding claims, in which the liquid hydrocarbon-based fatty substance(s) iii) are chosen from: apolar oils, i.e. oils formed solely from carbon and hydrogen atoms; preferably, the dispersion (A) comprises at least one apolar hydrocarbon-based liquid fatty substance iii), preferably chosen from:
- linear or branched Cs-Cso, in particular C10-C20 and more particularly C10-C16 alkanes, which are volatile or non-volatile, preferably volatile;
- non-aromatic cyclic C5-C12 alkanes, which are volatile or non-volatile, preferably volatile; and
- mixtures thereof; preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, in particular containing from 10 to 14 carbon atoms, notably chosen from:
- isoalkanes of petroleum origin such as isododecane;
- linear alkanes, such as undecane (C11), n-dodecane (C12), n-tridecane (C13) and n-tetradecane (C14), and also mixtures thereof, the undecane-tridecane mixture, mixtures of n-undecane (C11) and n-tridecane (C13); preferentially, the liquid hydrocarbon-based fatty substance(s) iii) are apolar, more particularly isododecane.
15. Dispersion (A) according to any one of the preceding claims, in which the liquid hydrocarbon-based fatty substance(s) iii) are present n the dispersion a content of between 15% by weight and 80% by weight, more preferentially between 20% and 60% by weight relative to the total weight of said dispersion (A); in particular, the weight ratio of the sum of the ingredients [i) + ii)] I iii) is less than or equal to 1 , more particularly, the mass ratio [i) + ii)] I iii) is between 0.5 and 1.
16. Dispersion (A) according to any one of the preceding claims, in which the amount of water iv) in the dispersion is between 5% and 49% by weight relative to the total weight of the dispersion, more particularly between 10% and 47% by weight, between 15% and 48% by weight, preferentially between 18% and 45%, even more preferentially between 20% and 40% by weight relative to the total weight of the dispersion (A).
17. Dispersion (A) according to any one of the preceding claims, which also comprises vii) one or more thickeners chosen from organic thickening polymers and thickening monoglycerides, diglycerides or triglycerides; notably, the thickener(s) are chosen 72 from: 1) block polymers of at least two C2-C16 and better still C2-C12 a-olefins, preferably non-crosslinked semi-crystalline polymers, more particularly semicrystalline polymers, 2) saccharide or polysaccharide monoalkyl/polyalkyl esters, particularly dextrin esters, in particular dextrin palmitates, 3) monoglycerides, diglycerides and triglycerides in which at least one hydrogen atom of a hydroxyl group of the glycerol has been substituted with the group -C(O)-Ra, with Ra representing a linear or branched, cyclic or acyclic, saturated or unsaturated, carbonyl-based, hydrocarbon-based chain, including from 8 to 40 carbon atoms, said hydrocarbon-based chain possibly being substituted with one or more hydroxyl groups, preferably chosen from triglycerides trisubstituted with -C(O)-Ra with Ra as defined previously, more particularly chosen from trihydroxystearin. Dispersion (A) according to any one of the preceding claims, in which said dispersion does not comprise more than 3% by weight of surfactants relative to the total weight of the dispersion, preferentially not more than 2% by weight of surfactants relative to the total weight of the dispersion, more particularly not more than 1% by weight of surfactants relative to the total weight of the dispersion; even more preferentially, the composition does not comprise more than 0.5% by weight of surfactants relative to the total weight of the dispersion, and better still the mixture does not comprise any surfactant. Dispersion (A) according to any one of the preceding claims, in which the cosmetic active agent(s) iv) are chosen from:
- organic pigments and mineral or inorganic pigments,
- pigments with special effects such as fluorescent, thermochromic or photochromic pigments, nacres, which may be coated or uncoated, in pigment powder or paste form, lakes, 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) iv) 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 coloured 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) iv) 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.
20. Process for treating keratin materials, preferably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows or [3) human skin, in particular of the lips, comprising the application to said materials of at least one dispersion (A), as defined in any one of the preceding claims; preferentially, after application of the dispersion (A) to the keratin materials, the composition is left to dry on said keratin materials, either naturally, or with the aid of heating devices used in cosmetics, such as a hairdryer.
21. Kit or device with several separate compartments, comprising:
- in one compartment: the dispersion (A) comprising the ingredients i) to iii) as defined in any one of Claims 1 to 16 and optionally vii) as defined in Claim 17, and
- the following ingredients are distributed among one or more different compartments: f) dyes, g) pigments; h) active agents for caring for keratin materials, notably the skin, and/or j) IIV(A) and/or IIV(B) screening agents as defined in either of Claims 1 and 19.
22. Use of a dispersion (A) as defined in any one of Claims 1 to 19 for treating keratin materials, notably a) keratin fibres, notably human keratin fibres such as the hair, the eyelashes or the eyebrows or ) human skin, in particular of the lips, comprising the application to said materials of at least one dispersion (A) for dyeing the keratin fibres and/or shaping the keratin fibres such as the hair, or for making up the skin.
PCT/EP2021/085933 2020-12-18 2021-12-15 Dispersion comprising a polymeric particle, a stabilizer bearing a c3-c12 cycloalkyl group, an oil and water, and process for treating keratin materials using the dispersion WO2022129195A1 (en)

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FR2013737A FR3117786B1 (en) 2020-12-18 2020-12-18 DISPERSION COMPRISING A POLYMERIC PARTICLE, A STABILIZING AGENT WITH A C3-C12 CYCLOALKYL GROUP, AN OIL AND WATER, METHOD FOR TREATMENT OF KERATIN MATERIALS USING THE DISPERSION

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