WO2022263603A1 - Composition comprising an oily dispersion of polymer particles, a cationic polymer and an anionic polymer - Google Patents

Composition comprising an oily dispersion of polymer particles, a cationic polymer and an anionic polymer Download PDF

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Publication number
WO2022263603A1
WO2022263603A1 PCT/EP2022/066503 EP2022066503W WO2022263603A1 WO 2022263603 A1 WO2022263603 A1 WO 2022263603A1 EP 2022066503 W EP2022066503 W EP 2022066503W WO 2022263603 A1 WO2022263603 A1 WO 2022263603A1
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Prior art keywords
acrylate
meth
alkyl
composition
acrylates
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PCT/EP2022/066503
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French (fr)
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Guillaume RONCHARD
Virginie SOULIE
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L'oreal
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Publication of WO2022263603A1 publication Critical patent/WO2022263603A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—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
    • A61K8/8188—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bonds, and at least one being terminated by a bond to sulfur or by a hertocyclic ring containing sulfur; Compositions of derivatives of such polymers
    • 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
    • A61K2800/59—Mixtures
    • A61K2800/594—Mixtures of polymers

Definitions

  • composition comprising an oily dispersion of polymer particles, a cationic polymer and an anionic polymer
  • the present invention relates to a composition, preferably an aqueous composition, comprising at least one dispersion of polymer particles stabilized in a non-aqueous medium, at least one cationic polymer and at least one anionic polymer.
  • the present invention also relates to a cosmetic treatment process, notably a process for styling keratin fibers, in particular human keratin fibers such as the hair, using this composition.
  • the present invention relates to the use of this composition for the cosmetic treatment of keratin fibers, in particular of human keratin fibers such as the hair, and in particular for styling the hair, i.e. for shaping and/or fixing the head of hair.
  • Styling products are normally used to construct and structure the hairstyle and to give it hold. They are usually in the form of lotions, gels, foams, creams or sprays.
  • These compositions generally comprise one or more filmforming polymers or “fixing polymers”, enabling the formation of a coating film on the hair strands and thus ensuring hold of the hairstyle and/or the formation of micro-welds between the hair strands, thus ensuring the fixing of the head of hair.
  • compositions are generally applied to wet hair, which is shaped before performing blow-drying or drying.
  • the styling products when they are in the form of mousses, they may have more or less firm textures with limited hold in the hand. Conversely, the textures of gels may be greasy or tacky and may prove difficult to apply to the head of hair. Compositions that do not leave any residues on the hair are also sought.
  • compositions which give good styling properties, notably in terms of flexibility and volume, while at the same time affording a pleasant cosmetic feel, notably a soft, smooth feel, and a clean look, which is neither mattifying nor too shiny. It is also expected that the hair roots should be lifted, so that the head of hair can gain volume.
  • compositions with a non-tacky and non-greasy texture which are easy to apply.
  • the aim of the present invention is also to provide a composition which can afford good hair fixing and hold properties, while at the same time conserving a clean and non-tacky feel of the hair, free of residues, and which may optionally be used directly during showering or shampooing.
  • the Applicant has discovered, surprisingly, that the combination of a particular oily dispersion of polymer particles, of a cationic polymer and of an anionic polymer makes it possible to achieve the objectives outlined above, notably to obtain a styling composition that is easy to apply and that is capable of giving the hairstyle long-lasting fixing while at the same time conserving a natural, non-rigid appearance, and also a soft, smooth feel which is not sticky nor greasy.
  • composition notably a cosmetic composition, comprising:
  • composition of the invention has a pleasant, non-tacky and non- greasy texture, and is easy to apply to the entire head of hair to be styled. It also gives the hair flexibility and volume, while at the same time conserving a natural appearance and a soft, smooth feel.
  • the head of hair thus styled is held without being made rigid, and the styling effects afforded by the composition of the invention are long-lasting throughout the day, or even for several days.
  • a subject of the present invention is also a cosmetic process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising a step of applying a composition as defined previously to said keratin fibers.
  • the present invention also relates to the use of a composition as defined previously for styling, i.e. shaping and/or fixing, keratin fibers, in particular human keratin fibers such as the hair.
  • an “alkyl radical’ is a linear or branched saturated C 1 -Cs, in particular C 1 -C6, preferably C 1 -C 4 hydrocarbon-based group such as methyl, ethyl, isopropyl and tert-butyl;
  • a “(C9-C22)alkyr radical is a saturated, linear or branched C 9 -C22, in particular C 1 0-C20, preferentially C 1 2-C 1 8, more preferentially C 1 2-C 16 hydrocarbon-based group, such as stearyl, behenyl, isodecyl, lauryl, hexadecyl or myristyl;
  • an “alkylene radicar is a linear or branched divalent saturated C-t-Ce, in particular C 1 -C6, preferably C 1 -C 4 hydrocarbon-based group such as methylene, ethylene or propylene;
  • cycloalkyr radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical possibly being substituted with one or more (C 1 -C 4 alkyl groups such as methyl; preferably, the cycloalkyl radical is an isobornyl group;
  • cyclic radical is a cyclic saturated or unsaturated, aromatic or non- aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;
  • an “aryf 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-(C 1 -C 4 )alkyl-0- radical, preferably benzoxy;
  • keratin materials particularly means human skin (keratinized epithelium) and human keratin fibers such as head hair, the eyelashes, the eyebrows, and bodily hair, preferentially head hair, the eyebrows and the eyelashes, even more preferentially head hair;
  • insoluble monomer J 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(s) iii);
  • ethylenic homopolymer J means a polymer derived from the polymerization of identical monomers
  • ethylenic copolymer means a polymer derived from the polymerization of different monomers, in particular at least two different monomers.
  • the ethylenic copolymer of the invention is derived from two or three different monomers, more preferentially derived from two different monomers
  • soluble monomer 1 means any monomer whose homopolymer or copolymer, preferably homopolymer, is soluble to at least 5% by weight, at 20°C, in the hydrocarbon-based 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.
  • the “soluble” monomers may, as monomers, be soluble or insoluble in the carbon-based liquid fatty substance(s) iii), it being understood that they become soluble after polymerization in the hydrocarbon-based liquid(s) iii);
  • fatty substance means an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5% by weight, preferably 1 % and even more preferentially 0.1%). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups.
  • the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated.
  • liquid fatty substance notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C;
  • hydrocarbon-based o ⁇ G means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups;
  • volatile o ⁇ G means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure.
  • the volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a nonzero vapor pressure, at room temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40000 Pa (10 -3 to 300 mmHg), preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg);
  • nonvolatile o ⁇ G means an oil with a vapor pressure of less than 0.13 Pa at room temperature and at atmospheric pressure;
  • silicone oif means an oil comprising at least one silicon atom and notably at least one Si-0 group.
  • the silicone oil may be volatile or nonvolatile;
  • 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;
  • 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;
  • Oily dispersion (A) of polymer particles The oily dispersion (A) of the invention comprises i) one or more particles of at least one polymer that is surface-stabilized with ii) at least one stabilizer in a medium that is preferably anhydrous, also containing iii) at least one hydrocarbon- based liquid fatty substance.
  • a dispersion (A) it is proposed to polymerize particular monomers that are capable of forming the polymeric core i) in the presence of a polymeric statistical stabilizer ii) comprising in major amount a portion ii) that is soluble and in minor amount a portion i) that is insoluble in the dispersion medium, i.e. in the hydrocarbon-based liquid fatty substance(s) iii).
  • the dispersions according to the invention consist of particles, which are generally spherical, of at least one surface-stabilized polymer, in an anhydrous medium.
  • said particles i) are not or are sparingly crosslinked.
  • the particle(s) of the oily dispersion (A) of the invention are preferably constituted of one or more polymers chosen from: a) ethylenic homopolymers of (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)acrylate, preferably ethylenic homopolymers of (C 1 -C 4 )alkyl (meth)acrylate; b) ethylenic copolymers of (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)acrylate, preferably (C 1 -C 4 )alkyl (meth)acrylate, and of (C 1 -C 4 alkylacrylic acid, preferably ethylenic copolymers of (C 1 -C 4 alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)
  • the particle(s) i) are constituted of an ethylenic polymer core obtained from homopolymers a) or from copolymers b) or c), as defined previously, and ii) of one or more polymeric surface stabilizers obtained from homopolymer d) and the copolymers e) defined below.
  • - R represents a hydrogen atom or a (C 1 -C 4 alkyl group such as methyl, and - R’ represents a (C 1 -C 4 alkyl group such as methyl or ethyl, preferably a C 1 -C 4 alkyl acrylate such as methyl acrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
  • - R is as defined previously, in particular acrylic acid.
  • the amount of acrylic acid ranges from 0.1% to 15% by weight relative to the weight of monomers of the particle i) and the polymer of the particles i) is in particular a copolymer derived from the copolymerization of acrylic acid with one or more C 1 -C 4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth)acrylate and ethyl (meth)acrylate.
  • the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
  • the polymer of the particles i) is a polymer derived from C 1 -C 4 alkyl (meth)acrylate monomers.
  • the monomers are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
  • a C 1 -C 4 alkyl acrylate monomer is used.
  • the monomers are chosen from methyl acrylate and ethyl acrylate.
  • a C 1 -C 4 alkyl methacrylate monomer is particularly used.
  • the monomers are chosen from methyl methacrylate and ethyl methacrylate, more particularly methyl methacrylate.
  • the oily dispersion (A) includes from 2% to 40% by weight, in particular from 4% to 25% by weight and notably from 5% to 20% by weight of (C 9 -C 22 )alkyl (C 1 -C 6 )(alkyl)acrylate monomers included in d) or e) in the liquid hydrocarbon-based fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
  • the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96%, of monomers a) to c) relative to the total weight of polymers contained in said dispersion.
  • the monomers that are capable of forming the polymeric core of the particle i) are chosen from monomers that are insoluble in the liquid hydrocarbon- based fatty substance(s) iii) of the dispersion (A).
  • the insoluble monomers preferably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle.
  • the particle(s) i) include b) ethylenic copolymers of b1) (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)acrylate and of b2) ethylenic monomers comprising one or more groups from among carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl such as benzyl.
  • the ethylenic monomer(s) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), (4) and (5):
  • R 1 (R 2 )C C(R 3 )-Acid with R 1 , R 2 and R 3 representing a hydrogen atom or a CO 2 H, H 2 PO 4 or SO 3 H group, and Acid representing a carboxyl group, a phosphoric acid or a sulfonic acid, preferably a carboxyl group, it being understood that R 1 , R 2 and R 3 cannot simultaneously represent a hydrogen atom;
  • H 2 C C(R)-C(0)-N(R’)-Alk-Acid with R and R’, which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 alkyl group;
  • Aik represents a (C 1 -Ce)alkylene group optionally substituted with at least one group chosen from Acid as defined previously and hydroxyl; and Acid is as defined previously, preferably carboxyl or sulfonic acid;
  • R a , R b and R c which may be identical or different, representing a hydrogen atom or a (C 1 i-C 4 alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO 2 H, H 2 PO 4 or SO 3 H, preferably substituted with a CO 2 H or SO 3 H group;
  • R a , R b and R c which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkyl group; preferably, R a , R b , and R c represent a hydrogen atom.
  • b2) is a (C 1 -C 4 )(alkyl)acrylic acid; more particularly, b) is (are) copolymers of a (C 1 -C 4 alkyl (meth)acrylate and of (meth)acrylic acid. More preferentially, b2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and salts thereof, and even more preferentially b2) represents acrylic acid.
  • the polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 to 500 nm, notably ranging from 10 to 400 nm and better still ranging from 20 to 300 nm.
  • the final size of the particles is preferably greater than 100 nm.
  • they have a number-average size ranging from 100 nm to 500 nm, more particularly ranging from 150 nm to 400 nm and even more particularly ranging from 160 nm to 300 nm.
  • the average size of the particles is determined via conventional methods known to those skilled in the art.
  • a Malvern brand NanoZS model laser particle size analyzer (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples.
  • the operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).
  • DLS dynamic light scattering
  • QELS quasi-elastic light scattering
  • PCS photon correlation spectroscopy
  • the sample is pipetted into a disposable plastic cuvette (four transparent faces, side length of 1 cm and volume of 4 ml_) placed in the measuring cell.
  • the data are analyzed on the basis of a cumulant fit method which leads to a monomodal particle size distribution characterized by an intensity-weighted mean diameter d (nm) and a size polydispersity factor Q.
  • the results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode.
  • NTA Nanoparticle Tracking Analysis
  • LS laser scattering
  • AES acoustic extinction spectroscopy
  • the dispersion (A) according to the invention also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention.
  • the stabilizer(s) ii) are chosen from d) ethylenic (C 9 -C 22 )alkyl (C 1 -C 6 )(alkyl)acrylate homopolymers, in particular ethylenic (Cg-C 18 )alkyl (C 1 -C 4 (alkyl)acrylate homopolymers, preferably ethylenic (C 9 -C 22 )alkyl (meth)acrylate homopolymers and more preferentially ethylenic (Cg-C 1 e)alkyl (meth)acrylate homopolymers.
  • R represents isodecyl, lauryl, stearyl, hexadecyl or behenyl.
  • the stabilizer(s) ii) are chosen from e) ethylenic copolymers of (C 9 -C 22 )alkyl (C 1 -C 6 )(alkyl)acrylate and of (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)acrylate, particularly (Cg-C 1 s)alkyl (C 1 - C 4 alkyl)acrylate and of (C 1 -C 4 alkyl (C 1 -C 4 (alkyl)acrylate, preferably copolymers of (Cg-C 18 )alkyl (meth)acrylate and of (C 1 -C 4 alkyl (meth)acrylate. More preferentially, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) of formulae (III) and (IV):
  • R which may be identical or different, represents a hydrogen atom or a (C 1 - C 4 alkyl group such as methyl,
  • - R’ which may be identical or different, represents a (C 1 -C 4 alkyl group such as methyl or ethyl, and
  • R represents a (C 9 -C 22 )alkyl and preferably (C 10 -C 20 )alkyl group, and in particular a (C2 n )alkyl group with n representing an integer equal to 5, 6, 7, 8, 9 or 10.
  • R represents isodecyl, lauryl, stearyl, hexadecyl or behenyl.
  • the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates, behenyl (meth)acrylates and C 1 -C 4 alkyl (meth)acrylates, preferably methyl (meth)acrylate.
  • the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and C 1 -C 4 alkyl (meth)acrylates, preferably methyl (meth)acrylate or ethyl (meth)acrylate.
  • the stabilizer ii) is chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate homopolymers, and statistical copolymers of isodecyl (meth)acrylate, of lauryl (meth)acrylate, of stearyl (meth)acrylate, of hexadecyl (meth)acrylate, of behenyl (meth)acrylate and of C 1 -C 4 alkyl (meth)acrylate, preferably present in a weight ratio of isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylate/C 1 -C 4 alkyl (meth)acrylate of greater than 4.
  • said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
  • the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization of a monomer of formula (IV) as defined previously and of two different monomers of formula (III) as defined previously.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of one monomer chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of two different C 1 -C 4 alkyl (meth)acrylates, preferably of methyl acrylate and ethyl acrylate.
  • the weight ratio of isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylates/C 1 -C 4 alkyl (meth)acrylate is greater than 4.
  • said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 11.
  • the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization of a monomer of formula (III) as defined previously and of two different monomers of formula (IV) as defined previously.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of one C 1 -C 4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates/C 1 -C 4 alkyl (meth)acrylate is greater than 4.
  • said weight ratio ranges from 4.5 to 10 and more preferentially said weight ratio ranges from 5 to 8.
  • the oily dispersion (A) includes from 2% to 40% by weight, in particular from 4% to 25% by weight and notably from 5.5% to 20% by weight of (C 9 -C 22 )alkyl (C 1 -C 6 )(alkyl)acrylate monomers included in d) or e) in the liquid hydrocarbon-based fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
  • the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of one C 1 -C 4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates/C 1 -C 4 alkyl (meth)acrylate in the dispersion (A) is less than 1. In particular, said weight ratio ranges from 0.05 to 0.5 and more preferentially said weight ratio range
  • the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.
  • the weight ratio of ii) stabilizer(s) and of i) polymer particle(s) present in the dispersion (A) is between 0.5 and 2, preferably from 0.8 to 1.2 and better still equal to 1.
  • the weight ratio of ii) stabilizer(s) and i) polymer particle(s) is less than 1 , relative to the total weight of polymers.
  • the stabilizer(s) ii) are present in a content ranging from 2% to 40% by weight, notably from 3% to 30% by weight, preferably from 4% to 25% by weight, relative to the weight of polymer(s) present in the dispersion (A).
  • the stabilizer(s) ii) and the particle(s) i) have a number-average molecular weight (Mn) of between 1000 and 1 000000 g/mol, notably between 5000 and 500000 g/mol and better still between 10000 and 300000 g/mol.
  • 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 dispersion of polymer particles (A) according to the invention also comprises iii) one or more hydrocarbon-based liquid fatty substances in which said particles are dispersed.
  • the hydrocarbon-based liquid fatty substances iii) are notably chosen from C 6 -C 16 hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms, preferably between C 6 and C 16 , and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, nonsilicone waxes, and silicones.
  • the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 60 carbon atoms, which are optionally substituted, in particular, with one or more (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.
  • the C 6 -C 16 alkanes they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane, isodecane and isododecane.
  • 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 fluorinated and optionally branched, alone or as a mixture.
  • the dispersion (A) according to the invention comprises one or more liquid fatty substances which are one or more hydrocarbon-based oils.
  • the hydrocarbon-based oil(s) may be volatile or non-volatile.
  • the liquid hydrocarbon- based fatty substance(s) are hydrocarbon-based oils which are volatile or are a mixture of different volatile oils more preferentially chosen from isododecane and octyldodecanol.
  • the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and of a nonvolatile oil.
  • Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, notably those with a viscosity ⁇ 8 centistokes (cSt) (8 c 10 -6 m 2 /s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile linear or cyclic silicone oils notably those with a viscosity ⁇ 8 centistokes (cSt) (8 c 10 -6 m 2 /s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • nonvolatile silicone oils mention may be made of linear or cyclic nonvolatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.
  • PDMSs linear or cyclic nonvolatile polydimethylsiloxanes
  • phenyl silicones for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydipheny
  • the hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably: branched C 8 -C 14 alkanes, such as C 8 -C 14 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 (C 1 2) and n-tetradecane (C 1 4) 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 (C 1 1 ) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, 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; linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon atoms; and notably isononyl isononanoate; and more particularly the esters of formula R d -C(0)-0-R e in which R d represents a higher fatty acid residue including from 7 to 19 carbon atoms and R e represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates,
  • 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, - esters of formula R d -C(0)-0-R e in which R d represents a higher fatty acid residue including from 7 to 19 carbon atoms and R e represents a hydrocarbon- based chain including from 3 to 20 carbon atoms, volatile or nonvolatile, linear or branched C 8 -C 60 alkanes, volatile or nonvolatile, nonaromatic cyclic C 5 -C 12 alkanes, - ethers containing 7 to 30 carbon atoms, ketones containing 8 to 30 carbon atoms, aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups, and
  • the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
  • the liquid hydrocarbon-based fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils, described previously.
  • the liquid hydrocarbon-based fatty substance(s) iii) of the invention are isododecane.
  • the liquid hydrocarbon-based fatty substance(s) are a mixture of nonvolatile oil and volatile oil; preferably, the mixture comprises isododecane as volatile oil.
  • the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.
  • the polymerization is performed in “ dispersion ” in nonaqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from d) and e) as defined previously.
  • the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer d) or e) with v) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
  • the constituent monomer(s) of the polymer of the particles i) are added to the stabilizing polymer formed in the preceding step and polymerization of these added monomers is performed in the presence of the free- radical initiator.
  • the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon- based liquid fatty substance (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.
  • synthesis solvent apolar organic solvent
  • the cosmetic active agent(s) 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.
  • a synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator v) are soluble therein, and 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 and organic, preferably chosen from alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.
  • the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent.
  • the monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein.
  • the monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of from 15% to 45% by weight.
  • the total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds.
  • the polymerization is preferentially performed in the presence v) of one or more radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators.
  • 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.
  • - 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.
  • AIBN azobisisobutyronitrile
  • V50 2,2- azobis(2-amidinopropane) dihydrochloride.
  • the polymerization is preferably performed at a temperature ranging from
  • the polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).
  • the stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
  • the stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously. From 4% to 30% by weight and preferably from 4.5% to 20% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)).
  • 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 dispersion (A) 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 composition (A), and preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight relative to the total weight of the dispersion (A).
  • the dispersion (A) according to the invention is an anhydrous composition.
  • the dispersion (A) is in inverse emulsion, i.e. of water-in-oil type (W/O).
  • the composition comprises one or more surfactants, which are preferably nonionic.
  • the inverse emulsions of (A) are preferably chosen when the dispersions (A) are intended for makeup, and notably for making up the eyelashes and/or eyebrows.
  • the statistical stabilizing polymer ii) is prepared in a first step.
  • This stabilizing polymer is soluble in an apolar organic solvent of alkane type, such as isododecane.
  • the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
  • a solution of stabilizing polymer ii) in the 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 v) as defined previously.
  • the monomers which form the core of the particle i) may be polymerized in the presence of said stabilizing polymer ii).
  • This second step may be a conventional radical polymerization.
  • the dispersions are prepared in the presence of one or more liquid hydrocarbon-based fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process.
  • the dispersions according to the invention are thus formed from polymer particles, generally with a diameter preferably greater than 100 nm, and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C). These polymers are notably described in patent application WO 2020/260
  • the total content of particle dispersion(s) (A), present in the composition according to the invention ranges from 0.1% to 20% by weight, more preferentially from 0.5% to 10% by weight and better still from 1% to 8% by weight relative to the total weight of the composition.
  • content of particle dispersion(s) means the sum of the contents of polymer(s) i), of stabilizing polymer(s) ii) and of liquid hydrocarbon-based fatty substances iii).
  • composition according to the present invention also comprises one or more cationic polymers.
  • cationic polymer denotes any non-silicone polymer (not comprising any silicon atoms) containing cationic groups and/or groups that can be ionized into cationic groups.
  • the cationic polymers that may be used preferably have a weight- average molar mass (Mw) of between 500 and 5*10 6 approximately and preferably between 10 3 and 3*10 6 approximately.
  • Mw weight- average molar mass
  • the cationic polymers mention may be made more preferentially of:
  • - R 3 which may be identical or different, denote a hydrogen atom or a CH3 radical
  • - A which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
  • R 4 , R5 and R6, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, and preferably an alkyl group containing from 1 to 6 carbon atoms;
  • R 2 which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
  • - X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • the copolymers of family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C 1 -C 4 ) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • - quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP; - polymers, preferably crosslinked polymers, of methacryloyloxy(C 1 - C 4 alkyltri(C 1 -C 4 alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.
  • Use may be made more particularly of an acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer which is crosslinked or non-crosslinked (for example 20/80 by weight) notably in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil.
  • This dispersion is notably sold under the name Salcare® SC 92 by the company Ciba.
  • Use may also be made of a crosslinked or non- crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer, in particular dispersed at about 50% by weight in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
  • cationic polysaccharides notably cationic celluloses and galactomannan gums.
  • cationic polysaccharides mention may be made more particularly of cellulose ether derivatives including quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
  • the cellulose ether derivatives including quaternary ammonium groups are notably described in FR 1 492597, and mention may be made of the polymers sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.
  • Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described notably in patent US 4 131 576, and mention may be made of hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamido- propyltrimethylammonium or dimethyldiallylammonium salt.
  • the commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
  • the alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably include from 8 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be indicated include the products Quatrisoft LM 200 ® , Quatrisoft LM-X 529-18-A ® , Quatrisoft LM-X 529-18-B ® (C 1 2 alkyl) and Quatrisoft LM-X 529-8 ® (C 1 8 alkyl) sold by the company Amerchol, and the products Crodacel QM ® , Crodacel QL® (C 1 2 alkyl) and Crodacel QS ® (C 1 8 alkyl) sold by the company Croda and the product Softcat SL 100 ® sold by the company Amerchol.
  • guar gums comprising cationic trialkylarnmonium groups.
  • Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, a chloride).
  • a 2,3-epoxypropyltrimethylammonium salt for example, a chloride.
  • Such products are notably sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 by the company Rhodia.
  • water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis- alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polya
  • polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • these derivatives mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.
  • Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxy- propyl/diethylenetriamine copolymer.
  • cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to the following formulae: in which
  • R 12 denotes a hydrogen atom or a methyl radical
  • R 10 and R 11 independently of each other, denote a C 1 -C 6 alkyl group, a C 1 -C 5 hydroxyalkyl group, a C 1 -C 4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R 11 , independently of each other, preferably denote a C 1 -C 4 alkyl group;
  • - Y ' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • R 13 , R 14 , R 15 and R 16 which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C 1 -C 12 hydroxyalkyl aliphatic radicals; or else R 13 , R 14 , R 15 and R 16 , together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non-nitrogen heteroatom; or else R 13 , Ri 4 , R 15 and R 16 represent a linear or branched C 1 -C 6 alkyl radical substituted with a nitrile, ester, acyl, amide or
  • a 1 and B 1 represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted in the main chain, one or more aromatic rings, or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups; and - X ' denotes an anion derived from a mineral or organic acid; it being understood that A 1 , R 13 and R 15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi may also denote a group (CH 2 ) n -CO-D-OC-(CH 2 ) P -, with n and p,
  • X- is an anion, such as chloride or bromide.
  • Mn number-average molar mass
  • Ri, R 2 , R 3 and R 4 which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from a mineral or organic acid.
  • Ri8, Ri9, R20 and R21 which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, b-hydroxyethyl, b-hydroxypropyl or -CH 2 CH 2 COCH 2 CH 2 ) p OH radical, where p is equal to 0 or to an integer of between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent a hydrogen atom,
  • - r and s which may be identical or different, are integers between 1 and 6,
  • - X ' denotes an anion, such as a halide
  • - A denotes a divalent dihalide radical or preferably represents -CH2-CH2-O- CH2-CH2-.
  • Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.
  • polyamines such as Polyquart® FI sold by Cognis, which is referenced under the name Polyethylene Glycol (15) Tallow Polyamine in the CTFA dictionary.
  • these polymers may be notably chosen from homopolymers or copolymers including one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
  • these cationic polymers are chosen from polymers including, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
  • polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
  • the weight-average molecular mass of said polymer, measured by light scattering, may range from 1000 to 3000000 g/mol, preferably from 10000 to 1 000000 and more particularly from 100000 to 500000 g/mol.
  • the polymers including units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
  • vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethac rylamidopropylammonium tosylate terpolymers vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacr ylamidopropylammonium tosylate terpolymers
  • vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacryl amidopropylammonium tosylate or chloride terpolymers are used notably.
  • cationic polymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolyzates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives such as chitosan.
  • the cationic polymers are chosen from those of families (1), (2), (7), (8) and (12), preferentially families (1), (2) and (7).
  • cationic polysaccharides notably quaternized (poly)hydroxyethylcelluloses modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups including at least 8 carbon atoms, or mixtures thereof.
  • the cationic polymer is chosen from hydroxyethylcelluloses which have reacted with a trimethylammonium epoxide and a lauryldimethylammonium epoxide (INCI name: Polyquaternium- 67).
  • the content of the cationic polymer(s), present in the composition according to the invention preferably ranges from 0.05% to 15% by weight, preferably from 0.5% to 10% by weight, and more preferentially from 1% to 8% by weight relative to the total weight of the composition.
  • the weight ratio between the total content of particle dispersion(s) (A) and the total content of cationic polymer(s), present in the composition according to the invention preferably ranges from 0.1 to 10, preferentially from 0.2 to 5 and better still from 0.25 to 3.
  • composition according to the present invention also comprises one or more anionic polymers other than the anionic polymers 1) i) b).
  • anionic polymer denotes any polymer containing anionic groups and/or groups that can be ionized into anionic groups and not containing any cationic groups and/or groups that can be ionized into cationic groups.
  • Anionic polymers that may be mentioned include polymers including groups derived from carboxylic, sulfonic or phosphoric acids, and having a number- average molecular mass of between 500 and 5000000.
  • the carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers, such as those corresponding to formula (I): in which: n is an integer from 0 to 10,
  • A denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the adjacent methylene group, when n is greater than 1 , via a heteroatom, such as oxygen or sulfur,
  • Ri denotes a hydrogen atom or a phenyl or benzyl group
  • R2 denotes a hydrogen atom, an alkyl group including from 1 to 4 carbon atoms or a carboxyl group
  • R3 denotes a hydrogen atom, an alkyl group including from 1 to 4 carbon atoms, a -CH2-COOH group, a phenyl group or a benzyl group.
  • the alkyl group including from 1 to 4 carbon atoms may in particular denote methyl and ethyl groups.
  • anionic polymers containing carboxylic or sulfonic groups that are preferred are:
  • A) copolymers of acrylic or methacrylic acid or salts thereof including copolymers of acrylic acid and acrylamide, and methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers, in particular Amerhold DR 25 sold by the company Amerchol, and sodium salts of polyhydroxycarboxylic acids. Mention may also be made of methacrylic acid/ethyl acrylate copolymers, notably in aqueous dispersion, such as Luviflex Soft and Luvimer MAE, which are sold by the company BASF.
  • a monoethylenic monomer such as ethylene, styrene, vinyl esters and acrylic or methacrylic acid esters
  • a polyalkylene glycol such as polyethylene glycol and optionally crosslinked.
  • Such polymers are described in particular in French patent 1 222944 and German patent application No. 2330956, the copolymers of this type including an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described notably in Luxembourg patent applications 75370 and 75371. Mention may also be made of copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate.
  • anionic fixing polymer from this class, mention may also be made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name AMP- Acrylates/Allyl Methacrylate Copolymer).
  • crotonic acid-based copolymers such as those including vinyl acetate or propionate units in their chain and optionally other monomers such as allylic esters or methallylic esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon-based chain, such as those including at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or alternatively a vinyl, allylic or methallylic ester of an a- or b-cyclic carboxylic acid.
  • Such polymers are described, inter alia, in French patents 1 222944, 1 580545, 2265782, 2265781, 1 564 110 and 2 439 798. Commercial products that fall within this category are the resins 282930, 261314 and 281310 sold by the company National Starch.
  • Such polymers are described in particular in US patents 2047398, 2723248 and 2 102 113 and GB patent 839 805, and notably those sold under the names Gantrez® AN or ES by the company ISP.
  • Polymers also falling within this category are the copolymers of maleic, citraconic or itaconic anhydrides and of an allylic or methallylic ester optionally including an acrylamide or methacrylamide group, an ct-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions being monoesterified or monoamidated.
  • these polymers are described, for example, in French patents 2 350 384 and 2 357 241 by the Applicant.
  • polymers comprising sulfonic groups.
  • These polymers may be polymers including vinylsulfonic, styrenesulfonic, naphthalenesulfonic, acrylamidoalkylsulfonic or sulfoisophthalate units, and salts thereof.
  • These polymers may notably be chosen from:
  • polyvinylsulfonic acid salts with a molecular mass of between 1000 and 100 000 approximately, and also the copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and esters thereof, and also acrylamide or derivatives thereof, vinyl ethers and vinylpyrrolidone;
  • FI anionic polyurethanes, which may include silicone grafts and silicones bearing hydrocarbon-based grafts.
  • fixing polyurethanes examples include the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols copolymer (also known under the name polyurethane-1 , INCI name) sold under the brand name Luviset® Pur by the company BASF, and the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols/silicone diamine copolymer (also known under the name polyurethane-6, INCI name) sold under the brand name Luviset® Si PUR A by the company BASF.
  • dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols copolymer also known under the name Luviset® Pur by the company BASF
  • Avalure UR 450 Another anionic polyurethane that may also be used is Avalure UR 450.
  • Polymers containing sulfoisophthalate groups such as the polymers AQ55 and AQ48 sold by the company Eastman, may also be used.
  • crosslinked acrylic or methacrylic acid homopolymers that may be mentioned are those crosslinked with an allyl alcohol ether of the sugar series, for instance the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA. These polymers have the INCI name Carbomer.
  • the crosslinked (meth)acrylic acid copolymers may be copolymers of (meth)acrylic acid and of C 1 -C 6 alkyl (meth)acrylate, such as the polymer sold under the name Aqua SF1 by the company Noveon.
  • the crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers are notably sold under the name Hostacerin AMPS ® by the company Clariant.
  • Hostacerin AMPS ® by the company Clariant.
  • the partially or totally neutralized crosslinked copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of acrylamide mention may be made in particular of the product described in Example 1 of EP 503 853, and reference may be made to said document as regards these polymers.
  • composition may similarly comprise ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.
  • ammonium acrylate homopolymers mention may be made of the product sold under the name Microsap PAS 5193 by the company Hoechst.
  • the copolymers of ammonium acrylate and of acrylamide mention may be made of the product sold under the name Bozepol C Wunsch or the product PAS 5193 sold by the company Hoechst.
  • the anionic polymers may also be chosen from anionic polysaccharides notably such as acacia gums and carrageenans, in particular lambda- carrageenans.
  • the anionic polymers are preferably chosen from acrylic acid copolymers, such as the acrylic acid/ethyl acrylate/N-tert- butylacrylamide terpolymer sold under the name Ultrahold Strong® by the company BASF, methacrylic acid/ethyl acrylate copolymers, notably in aqueous dispersion, such as Luviflex Soft and Luvimer MAE sold by the company BASF, crotonic acid-based copolymers, such as the vinyl acetate/vinyl tert- butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and
  • Luviset SI PUR, Mexomere PW, elastomeric or non-elastomeric anionic polyurethanes, polymers bearing sulfoisophthalate groups, and anionic polymers of the B) class and even more particularly, use is preferably made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name: AMP- Acrylates/Allyl Methacrylate Copolymer), crosslinked or non-crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers or copolymers, or salts thereof.
  • Use will preferably be made of crosslinked or non-crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers or copolymers, or salts thereof, more preferentially crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers or salts thereof such as Hostacerin AMPS ® from Clariant (INCI name: Ammonium polyacryloyldimethyl taurate), and anionic polysaccharides, in particular carrageenans.
  • Clariant INCI name: Ammonium polyacryloyldimethyl taurate
  • anionic polysaccharides in particular carrageenans.
  • the content of anionic polymer(s), present in the composition according to the invention preferably ranges from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.2% to 8% by weight, from 0.5% to 5% by weight relative to the total weight of the composition.
  • the weight ratio between the total content of particle dispersion(s) (A) and the total content of anionic polymer(s), present in the composition according to the invention preferably ranges from 0.1 to 15, preferentially from 0.2 to 10 and better still from 0.25 to 5.
  • the cationic polymer(s)/anionic polymer(s) weight ratio preferably ranges from 10/90 to 90/10, better still from 20/80 to 80/20, in particular from 30/70 to 70/30 and more preferentially from 40/60 to 60/40.
  • the composition according to the present invention is aqueous.
  • the water is present in a content generally greater than or equal to 30% by weight relative to the total weight of the composition.
  • the content of water present in the composition of the invention ranges from 30% to 98% by weight, preferably from 50% to 98% by weight and more preferentially from 65% to 95% by weight, relative to the total weight of the composition.
  • composition according to the present invention may optionally comprise one or more organic solvents, or mixtures thereof.
  • organic solvents examples include linear or branched C2 to C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the organic solvent is ethanol or propylene glycol.
  • the content of solvent(s) ranges from 1 % to 30% by weight, preferably from 5% to 20% by weight relative to the total weight of the composition.
  • the pH of the composition according to the invention generally ranges from 1.5 to 12, preferably from 2 to 8 and preferentially from 2.5 to 7.5.
  • the pH of the composition may be adjusted to the desired value by means of the basifying agents or acidifying agents that are customarily used.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkanolamines, and mineral or organic hydroxides.
  • acidifying agents examples which may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
  • composition according to the present invention may also optionally comprise one or more thickeners other than the above cationic and anionic polymers.
  • composition according to the present invention may optionally also comprise one or more silicones other than the non-aqueous medium present in the particle dispersion(s) and the polymers described previously.
  • the silicones that may be used in the present invention may be solid or liquid, and volatile or non-volatile.
  • the silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.
  • the volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
  • cyclic silicones with silicon-derived organic compounds such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of 1,T-oxy(2,2,2’,2’,3,3’- hexatrimethylsilyloxy)bisneopentane;
  • linear polydialkylsiloxanes containing 2 to 9 silicon atoms which generally have a viscosity of less than or equal to 5x1 O '6 m 2 /s at 25°C, such as decamethyltetrasiloxane.
  • non-volatile silicones mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon- based group, and preferably chosen from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.
  • PDMS polydimethylsiloxanes
  • organopolysiloxanes or organomodified polysiloxanes, or alternatively organomodified silicones
  • the organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
  • organopolysiloxanes including: - polyoxyethylene and/or polyoxypropylene groups optionally including C6-C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Corning under the name DC 1248 or the oils Silwet ® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (C 1 2)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2-5200;
  • hydroxylated groups for instance polyorganosiloxanes bearing a hydroxyalkyl function
  • the silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethylsilyl end groups.
  • polydialkylsiloxanes mention may be made of the following commercial products:
  • oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm 2 /s; - the Viscasi! ® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
  • CTFA dimethiconol
  • Products which may be used more particularly in accordance with the invention are mixtures such as:
  • CTFA dimethiconol
  • CTFA cyclic polydimethylsiloxane
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 c 10 -5 to 5 c 10 -2 m 2 /s at 25°C.
  • oils of the SF series from General Electric such as SF 1023, SF 1154, SF 1250 and SF 1265.
  • composition according to the present invention may also optionally comprise one or more additives, other than the compounds of the invention and among which mention may be made of nonionic, cationic, anionic, amphoteric or zwitterionic surfactants, and mixtures thereof, fatty substances other than the non-aqueous medium of the particle dispersion(s) and other than the silicones described previously, nonionic polymers, or mixtures thereof, antidandruff agents, anti-seborrhoea agents, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifying agents, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances, preserving agents, pigments and ceramides.
  • additives other than the compounds of the invention and among which mention may be made of nonionic, cationic, anionic, amphoteric or zwitterionic surfactants, and mixtures thereof, fatty substances other than the non-
  • the composition also comprises one or more additional salts, other than the compounds of the invention.
  • additional salts means alkali metal salts such as sodium chloride; alkaline-earth metal salts such as CaCh; organic acid salts such as sodium citrate, sodium lactate, sodium acetate, and mixtures thereof; more preferentially alkali metal salts and in particular sodium chloride.
  • the above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition.
  • the present invention also relates to a cosmetic treatment process, preferably a process for treating human keratin fibers such as the hair, notably a styling process, i.e. a process for fixing and/or shaping keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a composition as defined previously.
  • a cosmetic treatment process preferably a process for treating human keratin fibers such as the hair, notably a styling process, i.e. a process for fixing and/or shaping keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a composition as defined previously.
  • the shaping process according to the invention may be performed on wet or dry, preferably wet, keratin fibers.
  • the keratin fibers are advantageously rinsed with water before being dried or left to dry.
  • the process comprises:
  • a step of applying to the keratin fibers a composition comprising: a) one or more particle dispersions (A) as described previously, b) one or more cationic polymers, and c) one or more anionic polymers, followed by:
  • the present invention finally relates to the use of a composition as described above for cosmetic treatment, notably for styling keratin fibers, in particular human keratin fibers such as the hair.
  • the present invention relates to the use of a composition as described above for styling the hair, i.e. for shaping and/or fixing (holding) the hairstyle.
  • a composition as described above for styling the hair i.e. for shaping and/or fixing (holding) the hairstyle.
  • the examples that follow serve to illustrate the invention without, however, being limiting in nature.
  • a synthetic example is presented below for the production of an oily dispersion with a C 9 -C22 alkyl (meth)acrylate stabilizer.
  • stearyl methacrylate was used in combination with methyl acrylate for the stabilizing arm and methyl acrylate was adopted for the core of the particle.
  • the oily dispersions are formed as a whole (polymer particles i) + polymeric stabilizer ii)) containing 94.5% by weight of methyl acrylate and 5.5% of stearyl methacrylate.
  • the synthesis of these oily dispersions was performed in a 1 liter pilot reactor. The synthesis is performed in two steps:
  • stearyl methacrylate is polymerized in isododecane in the presence of a small amount of methyl acrylate and of a radical initiator (T21S).
  • T21S a radical initiator
  • the stearyl methacrylate/methyl acrylate mass ratio is 85/15.
  • the rest of the methyl acrylate is added in the presence of isododecane and of the radical initiator (T21S).
  • Example 1 Composition (A1) was prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of the composition, are mentioned in the table below. [Table 2]
  • the locks treated with composition (A1) have good fixing and good fixing persistence.
  • the locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity. The locks do not have any residue.
  • compositions 2 and 3 have good fixing and good fixing persistence.
  • the locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity.
  • the locks do not have any residue.
  • compositions 4 to 6 were prepared using the ingredients below (as percentage of active material).
  • compositions 4 to 6 have good fixing and good fixing persistence.
  • the locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity.
  • the locks do not have any residue. Examples 7
  • compositions (A1), (A2) (A3), (A4) and (A5) were prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of each composition, are mentioned in the table below.
  • compositions (A1 ) to (A5) thus obtained was applied to 2.7 g locks of natural hair washed beforehand with a DOP shampoo, at a rate of 1 g of composition per lock. The locks of hair were then rinsed with water for 15 seconds. The locks were then towel-dried and then laid flat and left to dry naturally.
  • composition (A1) had good fixing and good fixing persistence which were better than those of compositions comprising only polymers or only dispersion.
  • composition (A1) has a smooth feel that is neither tacky nor greasy.
  • compositions 8 to 11 were prepared using the ingredients below (as percentage of active material).
  • compositions 8 to 11 have good fixing and good fixing persistence.
  • the locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity.
  • the locks do not have any residue.
  • Example 12 Composition 12 was prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of the composition, are mentioned in the table below.
  • the locks had a feel that is neither tacky nor greasy: they had a very satisfactory smooth feel and good homogeneity. The locks did not have any residue.

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Abstract

The present invention relates to a composition comprising at least one dispersion of polymer particles in a liquid hydrocarbon-based fatty substance, at least one cationic polymer and at least one anionic polymer. The present invention also relates to a cosmetic treatment process, notably a process for styling keratin fibers, in particular human keratin fibers such as the hair, using this composition. Finally, the present invention relates to the use of this composition for the cosmetic treatment of keratin fibers, in particular of human keratin fibers such as the hair, and in particular for styling the hair, i.e. for shaping and/or fixing the head of hair.

Description

DESCRIPTION
Title: Composition comprising an oily dispersion of polymer particles, a cationic polymer and an anionic polymer
The present invention relates to a composition, preferably an aqueous composition, comprising at least one dispersion of polymer particles stabilized in a non-aqueous medium, at least one cationic polymer and at least one anionic polymer.
The present invention also relates to a cosmetic treatment process, notably a process for styling keratin fibers, in particular human keratin fibers such as the hair, using this composition.
Finally, the present invention relates to the use of this composition for the cosmetic treatment of keratin fibers, in particular of human keratin fibers such as the hair, and in particular for styling the hair, i.e. for shaping and/or fixing the head of hair. Styling products are normally used to construct and structure the hairstyle and to give it hold. They are usually in the form of lotions, gels, foams, creams or sprays. These compositions generally comprise one or more filmforming polymers or “fixing polymers”, enabling the formation of a coating film on the hair strands and thus ensuring hold of the hairstyle and/or the formation of micro-welds between the hair strands, thus ensuring the fixing of the head of hair.
These compositions are generally applied to wet hair, which is shaped before performing blow-drying or drying.
To obtain satisfactory and long-lasting fixing power, it is known practice to incorporate into styling products polymers with very high fixing power, and/or to increase the concentration of fixing polymer. However, the use of such extremely fixing products causes a certain number of drawbacks.
Although the objective of these products is to ensure the fixing and the hold of the hairstyle over time, they generally have a tendency to make the hairstyle rigid, notably producing a “helmet effect”, which is often poorly perceived by users. The head of hair, thus made rigid, has a dry and rough feel which is not greatly appreciated by consumers.
Moreover, when the styling products are in the form of mousses, they may have more or less firm textures with limited hold in the hand. Conversely, the textures of gels may be greasy or tacky and may prove difficult to apply to the head of hair. Compositions that do not leave any residues on the hair are also sought.
Thus, there is a real need to develop styling compositions which do not have the drawbacks mentioned above, i.e. which afford long-lasting fixing of the hairstyle, with styling effects that persist throughout the day or even for several days, while at the same time maintaining a natural and non-rigid appearance for the hairstyle.
There is in particular a need to develop compositions which give good styling properties, notably in terms of flexibility and volume, while at the same time affording a pleasant cosmetic feel, notably a soft, smooth feel, and a clean look, which is neither mattifying nor too shiny. It is also expected that the hair roots should be lifted, so that the head of hair can gain volume.
There is also a need to develop compositions with a non-tacky and non-greasy texture, which are easy to apply. The aim of the present invention is also to provide a composition which can afford good hair fixing and hold properties, while at the same time conserving a clean and non-tacky feel of the hair, free of residues, and which may optionally be used directly during showering or shampooing.
The Applicant has discovered, surprisingly, that the combination of a particular oily dispersion of polymer particles, of a cationic polymer and of an anionic polymer makes it possible to achieve the objectives outlined above, notably to obtain a styling composition that is easy to apply and that is capable of giving the hairstyle long-lasting fixing while at the same time conserving a natural, non-rigid appearance, and also a soft, smooth feel which is not sticky nor greasy.
One subject of the present invention is notably a composition, notably a cosmetic composition, comprising:
1) one or more oily dispersions (A), which are preferably anhydrous, comprising: 1) one or more particles including one or more polymers chosen from: a) ethylenic homopolymers of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, preferably (C1-C4)alkyl (meth)acrylate; b) ethylenic copolymers of b1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl; in particular, b2) is a (C1- C4)(alkyl)acrylic acid, more particularly copolymers of (C1-C4)alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, preferably (C1- C4)alkyl (meth)acrylate; and of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, ii) one or more polymeric stabilizers chosen from: d) ethylenic homopolymers of (Cg-C22)alkyl (C1-C6)(alkyl)acrylate, preferably ethylenic homopolymers of (C9-C22)alkyl (meth)acrylate; and e) ethylenic copolymers of (Cg-C22)alkyl (C1-C6)(alkyl)acrylate, and of (C1- C4)alkyl (C1-C4)(alkyl)acrylate, preferably copolymers of (C9-C22)alkyl
(meth)acrylate and of (C1-C4)alkyl (meth)acrylate; iii) one or more hydrocarbon-based liquid fatty substances;
2) one or more cationic polymers, and
3) one or more anionic polymers. The composition of the invention has a pleasant, non-tacky and non- greasy texture, and is easy to apply to the entire head of hair to be styled. It also gives the hair flexibility and volume, while at the same time conserving a natural appearance and a soft, smooth feel.
In contrast with the compositions of the prior art, the head of hair thus styled is held without being made rigid, and the styling effects afforded by the composition of the invention are long-lasting throughout the day, or even for several days.
A subject of the present invention is also a cosmetic process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising a step of applying a composition as defined previously to said keratin fibers. The present invention also relates to the use of a composition as defined previously for styling, i.e. shaping and/or fixing, keratin fibers, in particular human keratin fibers such as the hair.
Other subjects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”. Moreover, the expression “at least one” used in the present description is equivalent to the expression “one or more”.
For the purposes of the present invention and unless otherwise indicated: an “alkyl radical’ is a linear or branched saturated C1-Cs, in particular C1-C6, preferably C1-C4 hydrocarbon-based group such as methyl, ethyl, isopropyl and tert-butyl;
- a “(C9-C22)alkyr radical is a saturated, linear or branched C9-C22, in particular C10-C20, preferentially C12-C18, more preferentially C12-C16 hydrocarbon-based group, such as stearyl, behenyl, isodecyl, lauryl, hexadecyl or myristyl; - an “alkylene radicar is a linear or branched divalent saturated C-t-Ce, in particular C1-C6, preferably C1-C4 hydrocarbon-based group such as methylene, ethylene or propylene;
- a “cycloalkyr radical is a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl radical possibly being substituted with one or more (C1-C4 alkyl groups such as methyl; preferably, the cycloalkyl radical is an isobornyl group;
- a “ cyclic ” radical is a cyclic saturated or unsaturated, aromatic or non- aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;
- an “aryf 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-(C1-C4)alkyl-0- radical, preferably benzoxy;
- the term “keratin materials ” particularly means human skin (keratinized epithelium) and human keratin fibers such as head hair, the eyelashes, the eyebrows, and bodily hair, preferentially head hair, the eyebrows and the eyelashes, even more preferentially head hair;
- the term “insoluble monomer J’ 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(s) iii);
- the term “ethylenic homopolymer J’ means a polymer derived from the polymerization of identical monomers; - the term “ethylenic copolymer ” means a polymer derived from the polymerization of different monomers, in particular at least two different monomers. Preferably, the ethylenic copolymer of the invention is derived from two or three different monomers, more preferentially derived from two different monomers; - the term “ethylenic monomer1’ means an organic compound including one or more conjugated or non-corijugated 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 hydrocarbon-based liquid fatty substance(s) iii) of the dispersion. The homopolymer is completely dissolved in the carbon-based liquid(s) iii), visually at 20°C, i.e. there is no visible sign of any deposit, or precipitate, or agglomerate, or insoluble sediment; However, the “soluble” monomers may, as monomers, be soluble or insoluble in the carbon-based liquid fatty substance(s) iii), it being understood that they become soluble after polymerization in the hydrocarbon-based liquid(s) iii);
- the term “fatty substance ” means an organic compound that is insoluble in water at ordinary room temperature (25°C) and at atmospheric pressure (760 mmHg) (solubility of less than 5% by weight, preferably 1 % and even more preferentially 0.1%). They bear in their structure at least one hydrocarbon-based chain including at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane. These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids, since salified fatty acids constitute soaps that are generally soluble in aqueous media; - the term “liquid fatty substance” notably refers to a fatty substance that is liquid at 25°C and 1 atmosphere; preferably, said fatty substance has a viscosity of less than or equal to 7000 centipoises at 20°C;
- the term “hydrocarbon-based fatty substance” means a fatty substance which comprises at least 50% by weight, notably from 50% to 100% by weight, for example from 60% to 99% by weight, or even from 65% to 95% by weight, or even from 70% to 90% by weight, relative to the total weight of said fatty substance, of carbon-based compound that is liquid at 25°C, having a global solubility parameter in the Hansen solubility space of less than or equal to 20 (MPa)1/2, or a mixture of such compounds; - the global solubility parameter d 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 d = (dp2 + dp2 + dH2)1/2 in which: - dp 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 “o/f means a fatty substance that is liquid at room temperature (25°C) and at atmospheric pressure;
The term “hydrocarbon-based oίG means an oil formed essentially from, or even constituted of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups;
- the term “volatile oίG means an oil (or non-aqueous medium) that can evaporate on contact with keratin materials, in particular the skin, in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a nonzero vapor pressure, at room temperature and at atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40000 Pa (10-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg); - the term “nonvolatile oίG means an oil with a vapor pressure of less than 0.13 Pa at room temperature and at atmospheric pressure;
- the term “silicone oif’ means an oil comprising at least one silicon atom and notably at least one Si-0 group. The silicone oil may be volatile or nonvolatile; - the term “dispersant’ refers to a compound which can protect the dispersed particles from agglomerating or flocculating. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed; in particular, they can attach physically or chemically to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. Said agent may be charged: it may be anionic, cationic, zwitterionic or neutral;
- the term “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;
Oily dispersion (A) of polymer particles The oily dispersion (A) of the invention comprises i) one or more particles of at least one polymer that is surface-stabilized with ii) at least one stabilizer in a medium that is preferably anhydrous, also containing iii) at least one hydrocarbon- based liquid fatty substance. In order to obtain such a dispersion (A), it is proposed to polymerize particular monomers that are capable of forming the polymeric core i) in the presence of a polymeric statistical stabilizer ii) comprising in major amount a portion ii) that is soluble and in minor amount a portion i) that is insoluble in the dispersion medium, i.e. in the hydrocarbon-based liquid fatty substance(s) iii). The dispersions according to the invention consist of particles, which are generally spherical, of at least one surface-stabilized polymer, in an anhydrous medium.
Preferably, said particles i) are not or are sparingly crosslinked. Polymer particles i)
The particle(s) of the oily dispersion (A) of the invention are preferably constituted of one or more polymers chosen from: a) ethylenic homopolymers of (C1-C4 alkyl (C1-C4 (alkyl)acrylate, preferably ethylenic homopolymers of (C1-C4)alkyl (meth)acrylate; b) ethylenic copolymers of (C1-C4 alkyl (C1-C4 (alkyl)acrylate, preferably (C1-C4)alkyl (meth)acrylate, and of (C1-C4 alkylacrylic acid, preferably ethylenic copolymers of (C1-C4 alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (C1-C4 alkyl (C1-C4 (alkyl)acrylate, preferably ethylenic copolymers of (C1-C4 alkyl (meth)acrylate. Preferably, the particle(s) i) are constituted of an ethylenic polymer core derived from homopolymers a) or from copolymers b) or c) as defined previously.
The particle(s) i) are constituted of an ethylenic polymer core obtained from homopolymers a) or from copolymers b) or c), as defined previously, and ii) of one or more polymeric surface stabilizers obtained from homopolymer d) and the copolymers e) defined below.
According to a preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic homopolymer of acrylate a) derived from the polymerization of an identical monomer of formula (I): [Chem 1] H2C=C(R)-C(O)-O-R'( I) in which formula (I):
- R represents a hydrogen atom or a (C1-C4 alkyl group such as methyl, and - R’ represents a (C1-C4 alkyl group such as methyl or ethyl, preferably a C1-C4 alkyl acrylate such as methyl acrylate.
According to another particular embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
- of at least one monomer of formula (I) as defined previously, preferably a C1-C4 alkyl acrylate such as methyl acrylate or ethyl acrylate; and
- of a monomer of formula (II)
[Chem 2] H2C=C(R)-C(O)-O-H (II) in which formula (II)
- R is as defined previously, in particular acrylic acid.
According to this embodiment, the amount of acrylic acid ranges from 0.1% to 15% by weight relative to the weight of monomers of the particle i) and the polymer of the particles i) is in particular a copolymer derived from the copolymerization of acrylic acid with one or more C1-C4 alkyl (meth)acrylate monomers chosen in particular from methyl (meth)acrylate and ethyl (meth)acrylate. According to another preferred embodiment of the invention, the polymer constituting the particles i) is an ethylenic acrylate copolymer b) derived from the polymerization:
- of at least two different monomers of formula (I) as defined previously, preferablyC1-C4 alkyl acrylate such as methyl acrylate and ethyl acrylate; and - optionally of a monomer of formula (II) as defined previously. According to a particular embodiment of the invention, the polymer of the particles i) is a polymer derived from C1-C4 alkyl (meth)acrylate monomers. The monomers are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
Advantageously, a C1-C4 alkyl acrylate monomer is used. Preferentially, the monomers are chosen from methyl acrylate and ethyl acrylate.
Also, a C1-C4 alkyl methacrylate monomer is particularly used. Preferentially, the monomers are chosen from methyl methacrylate and ethyl methacrylate, more particularly methyl methacrylate.
According to a particular embodiment of the invention, the oily dispersion (A) includes from 2% to 40% by weight, in particular from 4% to 25% by weight and notably from 5% to 20% by weight of (C9-C22)alkyl (C1-C6)(alkyl)acrylate monomers included in d) or e) in the liquid hydrocarbon-based fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
According to an advantageous embodiment of the invention, the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96%, of monomers a) to c) relative to the total weight of polymers contained in said dispersion. Preferably, the monomers that are capable of forming the polymeric core of the particle i) are chosen from monomers that are insoluble in the liquid hydrocarbon- based fatty substance(s) iii) of the dispersion (A). The insoluble monomers preferably represent 100% by weight relative to the total weight of the monomers forming the polymeric core of the particle. According to one embodiment of the invention, the particle(s) i) include b) ethylenic copolymers of b1) (C1-C4 alkyl (C1-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.
More particularly, the ethylenic monomer(s) comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups are chosen from (1), (2), (3), (4) and (5):
(1) R1(R2)C=C(R3)-Acid with R1, R2 and R3 representing a hydrogen atom or a CO2H, H2PO4 or SO3H group, and Acid representing a carboxyl group, a phosphoric acid or a sulfonic acid, preferably a carboxyl group, it being understood that R1, R2 and R3 cannot simultaneously represent a hydrogen atom;
(2) H2C=C(R)-C(0)-N(R’)-Alk-Acid with R and R’, which may be identical or different, representing a hydrogen atom or a (C1-C4 alkyl group; Aik represents a (C1-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 (C1i-C4 alkyl group, and Ar representing an aryl group, preferably benzyl, optionally substituted with at least one acid group CO2H, H2PO4 or SO3H, preferably substituted with a CO2H or SO3H group;
(4) maleic anhydride of formulae (4a) and (4b):
[Chem. 3]
Figure imgf000012_0001
in which formulae (4b) and (4b) Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a (C1-C4)alkyl group; preferably, Ra, Rb, and Rc represent a hydrogen atom. Preferentially, the ethylenically unsaturated anhydride monomer of the invention is of formula (4b) and more preferentially is maleic anhydride; and (5) H2C=C(R)-C(0)-0-H with R representing a hydrogen atom or a linear or branched(C1-C4 alkyl group, such as methyl.
Preferably, b2) is a (C1-C4)(alkyl)acrylic acid; more particularly, b) is (are) copolymers of a (C1-C4 alkyl (meth)acrylate and of (meth)acrylic acid. More preferentially, b2) is chosen from crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglycolic acid, acrylic acid and salts thereof, and even more preferentially b2) represents acrylic acid.
The polymer particle(s) i) of the dispersion (A) preferably have a number-mean size ranging from 5 to 500 nm, notably ranging from 10 to 400 nm and better still ranging from 20 to 300 nm.
The final size of the particles is preferably greater than 100 nm. In particular, they have a number-average size ranging from 100 nm to 500 nm, more particularly ranging from 150 nm to 400 nm and even more particularly ranging from 160 nm to 300 nm.
The average size of the particles is determined via conventional methods known to those skilled in the art. A Malvern brand NanoZS model laser particle size analyzer (which is particularly suitable for submicron dispersions) makes it possible to measure the size distribution of these samples. The operating principle of this type of machine is based on dynamic light scattering (DLS), also known as quasi-elastic light scattering (QELS) or photon correlation spectroscopy (PCS).
The sample is pipetted into a disposable plastic cuvette (four transparent faces, side length of 1 cm and volume of 4 ml_) placed in the measuring cell. The data are analyzed on the basis of a cumulant fit method which leads to a monomodal particle size distribution characterized by an intensity-weighted mean diameter d (nm) and a size polydispersity factor Q. The results may also be expressed in the form of statistical data such as D10; D50 (median), D90 and the mode. 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. The stabilizer(s) ii)
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.
According to a particular embodiment of the invention, the stabilizer(s) ii) are chosen from d) ethylenic (C9-C22)alkyl (C1-C6)(alkyl)acrylate homopolymers, in particular ethylenic (Cg-C18)alkyl (C1-C4 (alkyl)acrylate homopolymers, preferably ethylenic (C9-C22)alkyl (meth)acrylate homopolymers and more preferentially ethylenic (Cg-C1e)alkyl (meth)acrylate homopolymers.
More particularly, the stabilizer(s) ii) are constituted of ethylenic polymers chosen from d) ethylenic homopolymers obtained from the polymerization of monomers of formula H2C=C(R)-C(0)-0-R” with R representing a hydrogen atom or a (C1- C4 alkyl group such as methyl, and R” representing a (C9-C22)alkyl and preferably (Cg-C18)alkyl group. Preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl. According to another particular embodiment of the invention, the stabilizer(s) ii) are chosen from e) ethylenic copolymers of (C9-C22)alkyl (C1-C6)(alkyl)acrylate and of (C1-C4 alkyl (C1-C4 (alkyl)acrylate, particularly (Cg-C1s)alkyl (C1- C4 alkyl)acrylate and of (C1-C4 alkyl (C1-C4 (alkyl)acrylate, preferably copolymers of (Cg-C18)alkyl (meth)acrylate and of (C1-C4 alkyl (meth)acrylate. More preferentially, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) of formulae (III) and (IV):
[Chem 4] H2C=C(R)-C(O)--OR’ (Ill)
[Chem 5] H2C=C(R)-C(O)-O-R” (IV) in which formulae (III) and (IV):
- R, which may be identical or different, represents a hydrogen atom or a (C1- C4 alkyl group such as methyl,
- R’, which may be identical or different, represents a (C1-C4 alkyl group such as methyl or ethyl, and
- R” represents a (C9-C22)alkyl and preferably (C10-C20)alkyl group, and in particular a (C2n)alkyl group with n representing an integer equal to 5, 6, 7, 8, 9 or 10. Preferably, R” represents isodecyl, lauryl, stearyl, hexadecyl or behenyl.
Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates, behenyl (meth)acrylates and C1-C4 alkyl (meth)acrylates, preferably methyl (meth)acrylate. More preferentially, the stabilizer(s) ii) are chosen from copolymers derived from monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and C1-C4 alkyl (meth)acrylates, preferably methyl (meth)acrylate or ethyl (meth)acrylate. More particularly, the stabilizer ii) is chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate homopolymers, and statistical copolymers of isodecyl (meth)acrylate, of lauryl (meth)acrylate, of stearyl (meth)acrylate, of hexadecyl (meth)acrylate, of behenyl (meth)acrylate and of C1 -C4 alkyl (meth)acrylate, preferably present in a weight ratio of isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylate/C1 -C4 alkyl (meth)acrylate of greater than 4.
Advantageously, said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 12.
According to another embodiment, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization of a monomer of formula (IV) as defined previously and of two different monomers of formula (III) as defined previously.
Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of one monomer chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of two different C1-C4 alkyl (meth)acrylates, preferably of methyl acrylate and ethyl acrylate.
In particular, the weight ratio of isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylates/C1-C4 alkyl (meth)acrylate is greater than 4. Advantageously, said weight ratio ranges from 5 to 15 and more preferentially said weight ratio ranges from 5.5 to 11.
According to another embodiment, the stabilizer(s) ii) are chosen from the ethylenic copolymers e) derived from the polymerization of a monomer of formula (III) as defined previously and of two different monomers of formula (IV) as defined previously.
Preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of one C1-C4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates/C1-C4 alkyl (meth)acrylate is greater than 4. Advantageously, said weight ratio ranges from 4.5 to 10 and more preferentially said weight ratio ranges from 5 to 8.
According to a particular embodiment of the invention, the oily dispersion (A) includes from 2% to 40% by weight, in particular from 4% to 25% by weight and notably from 5.5% to 20% by weight of (C9-C22)alkyl (C1-C6)(alkyl)acrylate monomers included in d) or e) in the liquid hydrocarbon-based fatty substance(s) iii), relative to the total weight of polymers contained in said dispersion.
According to one embodiment of the invention, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates, and of one C1-C4 alkyl (meth)acrylate monomer, preferably of methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates and behenyl (meth)acrylates/C1-C4 alkyl (meth)acrylate in the dispersion (A) is less than 1. In particular, said weight ratio ranges from 0.05 to 0.5 and more preferentially said weight ratio ranges from 0.08 to 0.2 in the dispersion (A).
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.
Advantageously, the weight ratio of ii) stabilizer(s) and of i) polymer particle(s) present in the dispersion (A) is between 0.5 and 2, preferably from 0.8 to 1.2 and better still equal to 1.
In particular, the weight ratio of ii) stabilizer(s) and i) polymer particle(s) is less than 1 , relative to the total weight of polymers.
According to a particular embodiment of the invention, the stabilizer(s) ii) are present in a content ranging from 2% to 40% by weight, notably from 3% to 30% by weight, preferably from 4% to 25% by weight, relative to the weight of polymer(s) present in the dispersion (A). Preferably, the stabilizer(s) ii) and the particle(s) i) have a number-average molecular weight (Mn) of between 1000 and 1 000000 g/mol, notably between 5000 and 500000 g/mol and better still between 10000 and 300000 g/mol.
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 hydrocarbon-based liquid fatty substance(s) iii)
The dispersion of polymer particles (A) according to the invention also comprises iii) one or more hydrocarbon-based liquid fatty substances in which said particles are dispersed.
The hydrocarbon-based liquid fatty substances iii) are notably chosen from C6-C16 hydrocarbons or hydrocarbons comprising more than 16 carbon atoms and up to 60 carbon atoms, preferably between C6 and C16, and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, nonsilicone waxes, and silicones.
It is recalled that, for the purposes of the invention, the fatty alcohols, fatty esters and fatty acids more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups comprising 6 to 60 carbon atoms, which are optionally substituted, in particular, with one or more (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. As regards the C6-C16 alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane, isodecane and isododecane. 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®.
Among the hydrocarbon-based liquid fatty substances iii) having an overall solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa)1/2, mention may be made of oils, which may be chosen from natural or synthetic, hydrocarbon-based oils, which are optionally fluorinated and optionally branched, alone or as a mixture.
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.
According to a preferred embodiment of the invention, the liquid hydrocarbon- based fatty substance(s) are hydrocarbon-based oils which are volatile or are a mixture of different volatile oils more preferentially chosen from isododecane and octyldodecanol.
According to another particular embodiment, the hydrocarbon-based liquid fatty substance(s) iii) are a mixture of a volatile oil and of a nonvolatile oil.
Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, notably those with a viscosity < 8 centistokes (cSt) (8 c 10-6 m2/s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
As nonvolatile silicone oils, mention may be made of linear or cyclic nonvolatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.
The hydrocarbon-based oil may be chosen from: hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably: branched C8-C14 alkanes, such as C8-C14 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2, 2, 4, 4, 6- pentamethylheptane), isodecane and, for example, the oils sold under the Isopar or Permethyl trade names, linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (C1 1) and of n-tridecane (C13) obtained in examples 1 and 2 of patent application WO 2008/155059 from the company Cognis, and mixtures thereof, short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate; hydrocarbon-based oils of plant origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil 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 by the company Dynamit Nobel, synthetic ethers containing from 10 to 40 carbon atoms, linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof, esters such as the oils of formula R1C(0)-0-R2 in which R1 represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters, fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol and 2-undecylpentadecanol.
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%.
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; linear, branched or cyclic esters containing more than 6 carbon atoms, notably 6 to 30 carbon atoms; and notably isononyl isononanoate; and more particularly the esters of formula Rd-C(0)-0-Re in which Rd represents a higher fatty acid residue including from 7 to 19 carbon atoms and Re represents a hydrocarbon-based chain including from 3 to 20 carbon atoms, such as palmitates, adipates, myristates and benzoates, notably diisopropyl adipate and isopropyl myristate; hydrocarbons and notably volatile or nonvolatile, linear, branched and/or cyclic alkanes, such as C5-C60 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; ethers containing 6 to 30 carbon atoms; ketones containing 6 to 30 carbon atoms; aliphatic fatty monoalcohols containing 6 to 30 carbon atoms, the hydrocarbon- based chain not including any substitution groups, such as oleyl alcohol, decanol, dodecanol, octadecanol, octyldodecanol and linoleyl alcohol; polyols containing 6 to 30 carbon atoms, such as hexylene glycol; and mixtures thereof.
Preferably, 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, - esters of formula Rd-C(0)-0-Re in which Rd represents a higher fatty acid residue including from 7 to 19 carbon atoms and Re represents a hydrocarbon- based chain including from 3 to 20 carbon atoms, volatile or nonvolatile, linear or branched C8-C60 alkanes, volatile or nonvolatile, nonaromatic cyclic C5-C12 alkanes, - ethers containing 7 to 30 carbon atoms, ketones containing 8 to 30 carbon atoms, aliphatic fatty monoalcohols containing 12 to 30 carbon atoms, the hydrocarbon-based chain not including any substitution groups, and
- mixtures thereof. Advantageously, the hydrocarbon-based liquid fatty substance(s) of the invention are apolar, i.e. formed solely of carbon and hydrogen atoms.
The liquid hydrocarbon-based fatty substance(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils, described previously. Preferentially, the liquid hydrocarbon-based fatty substance(s) iii) of the invention are isododecane.
According to another advantageous embodiment of the invention, the liquid hydrocarbon-based fatty substance(s) are a mixture of nonvolatile oil and volatile oil; preferably, the mixture comprises isododecane as volatile oil. In particular, in the mixture, the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils. Without this being limiting, in general, the dispersion according to the invention may be prepared in the following manner:
- The polymerization is performed in “ dispersion ” in nonaqueous medium, i.e. by precipitation of the polymer being formed, with protection of the formed particles with one or more stabilizers ii), preferably only one type of stabilizer ii) chosen from d) and e) as defined previously.
- In a first step, the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer d) or e) with v) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers; and then
In a second step, the constituent monomer(s) of the polymer of the particles i) are added to the stabilizing polymer formed in the preceding step and polymerization of these added monomers is performed in the presence of the free- radical initiator.
When the nonaqueous medium is a nonvolatile liquid hydrocarbon-based 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. The cosmetic active agent(s) 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.
A synthesis solvent which is such that the monomers of the polymeric stabilizer(s) ii) and the free-radical initiator v) are soluble therein, and the polymer particles i) obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen. In particular, the synthesis solvent chosen is one which is apolar and organic, preferably chosen from alkanes such as heptane, cyclohexane or isododecane, preferably isododecane.
When the nonaqueous medium is a volatile hydrocarbon-based liquid fatty substance iii), the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent. The monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles i) which is obtained should be insoluble therein.
The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of from 15% to 45% by weight. The total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds.
The polymerization is preferentially performed in the presence v) of one or more radical initiators which may be any initiator known to those skilled in the art for radical polymerization, such as peroxide or azo initiators, redox couples and photochemical initiators.
The following types of initiator may notably be mentioned:
- peroxide, in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; or
- azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2- azobis(2-amidinopropane) dihydrochloride. The polymerization is preferably performed at a temperature ranging from
70°C to 110°C and at atmospheric pressure.
The polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).
The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.
The stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the particles i) are also added continuously. From 4% to 30% by weight and preferably from 4.5% to 20% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)). 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 dispersion (A) 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 composition (A), and preferably ranging from 20% to 60% by weight, notably 30% to 50% by weight relative to the total weight of the dispersion (A). According to a preferred embodiment of the invention, the dispersion (A) according to the invention is an anhydrous composition.
According to another embodiment of the present invention, the dispersion (A) is in inverse emulsion, i.e. of water-in-oil type (W/O). In this case, the composition comprises one or more surfactants, which are preferably nonionic. The inverse emulsions of (A) are preferably chosen when the dispersions (A) are intended for makeup, and notably for making up the eyelashes and/or eyebrows.
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. Next, in a second step, the polymer particles i) are synthesized in the presence of the stabilizing polymer ii).
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).
The stabilizing polymer ii) may be prepared by radical polymerization optionally in the presence of a polymerization initiator v) as defined previously.
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.
The dispersions are prepared in the presence of one or more liquid hydrocarbon-based fatty substances iii), preferably in an apolar organic solvent, in particular of alkane type such as isododecane, according to an industrially feasible process. The dispersions according to the invention are thus formed from polymer particles, generally with a diameter preferably greater than 100 nm, and give glossy film-forming deposits that are resistant to fatty substances at the observation temperature (25°C). These polymers are notably described in patent application WO 2020/260
659.
Preferably, the total content of particle dispersion(s) (A), present in the composition according to the invention, ranges from 0.1% to 20% by weight, more preferentially from 0.5% to 10% by weight and better still from 1% to 8% by weight relative to the total weight of the composition. For the purposes of the present invention, the term “content of particle dispersion(s)” means the sum of the contents of polymer(s) i), of stabilizing polymer(s) ii) and of liquid hydrocarbon-based fatty substances iii). Cationic polymer
The composition according to the present invention also comprises one or more cationic polymers.
For the purposes of the present invention, the term “cationic polymer” denotes any non-silicone polymer (not comprising any silicon atoms) containing cationic groups and/or groups that can be ionized into cationic groups.
The cationic polymers that may be used preferably have a weight- average molar mass (Mw) of between 500 and 5*106 approximately and preferably between 103 and 3*106 approximately. Among the cationic polymers, mention may be made more preferentially of:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and including at least one of the units having the following formulae:
Figure imgf000026_0001
in which:
- R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; - A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
- R4, R5 and R6, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, and preferably an alkyl group containing from 1 to 6 carbon atoms;
- Ri and R2, which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
- X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
The copolymers of family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1-C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules, - copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as the products sold under the name Bina Quat P 100 by the company Ciba Geigy,
- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as the product sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937. These polymers are described in detail in French patents 2077 143 and 2393573;
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP; - vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as the products sold under the name Styleze CC 10 by ISP;
- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP; - polymers, preferably crosslinked polymers, of methacryloyloxy(C1- C4 alkyltri(C1-C4 alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. Use may be made more particularly of an acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer which is crosslinked or non-crosslinked (for example 20/80 by weight) notably in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. This dispersion is notably sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked or non- crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer, in particular dispersed at about 50% by weight in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
(2) cationic polysaccharides, notably cationic celluloses and galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives including quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
The cellulose ether derivatives including quaternary ammonium groups are notably described in FR 1 492597, and mention may be made of the polymers sold under the name Ucare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.
Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described notably in patent US 4 131 576, and mention may be made of hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamido- propyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch. Mention may also be made of quaternized (poly)hydroxyethyl- celluloses modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups including at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably include from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18-B® (C12 alkyl) and Quatrisoft LM-X 529-8® (C18 alkyl) sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18 alkyl) sold by the company Croda and the product Softcat SL 100® sold by the company Amerchol.
The cationic galactomannan gums are described more particularly in patents US 3589578 and US 4031 307, and mention may be made of guar gums comprising cationic trialkylarnmonium groups. Use is made, for example, of guar gums modified with a 2,3-epoxypropyltrimethylammonium salt (for example, a chloride). Such products are notably sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 and Jaguar C162 by the company Rhodia.
(3) polymers formed from piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing linear or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers.
(4) water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis- alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides can be alkylated or, if they include one or more tertiary amine functions, they can be quaternized;
(5) polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz. (6) polymers obtained by reacting a polyalkylene polyamine including two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the resulting polyaminoamide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide preferably of between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxy- propyl/diethylenetriamine copolymer.
(7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to the following formulae:
Figure imgf000030_0001
in which
- k and t are equal to 0 or 1 , the sum k + t being equal to 1 ;
- R12 denotes a hydrogen atom or a methyl radical;
- R10 and R11, independently of each other, denote a C1-C6 alkyl group, a C1-C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R11, independently of each other, preferably denote a C1-C4 alkyl group;
- Y' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) for example sold under the name Merquat 100 by the company Nalco and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, notably sold under the name Merquat 550 or Merquat 7SPR.
(8) quaternary diammonium polymers comprising repeating units of the following formula:
R 13 R 15
N+ _ A1 — N+— B, —
1
R X-
14 R16 X- in which:
- R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals; or else R13, R14, R15and R16, together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non-nitrogen heteroatom; or else R13, Ri4, R15 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or
-CO-O-R17-D or -CO-NH-R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;
- A1 and B1 represent divalent polymethylene groups comprising from 2 to 20 carbon atoms which may be linear or branched, and saturated or unsaturated, and which may contain, linked to or inserted in the main chain, one or more aromatic rings, or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups; and - X' denotes an anion derived from a mineral or organic acid; it being understood that A1, R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi may also denote a group (CH2)n-CO-D-OC-(CH2)P-, with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CH2CH20)x-CH2CH2- and -[CH2CH(CH3)0]y- CH2CH(CH3)-, where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue, such as a piperazine derivative; c) a bis-primary diamine residue of formula -NH-Y-NH-, in which Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -CH2-CH2-S-S-CH2-CH2-; d) a ureylene group of formula -NH-CO-NH-.
Preferably, X- is an anion, such as chloride or bromide. These polymers have a number-average molar mass (Mn) generally of between 1000 and 100000.
Mention may be made more particularly of polymers consisting of repeating units corresponding to the formula:
Figure imgf000032_0001
in which Ri, R2, R3 and R4, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from a mineral or organic acid.
One compound that is particularly preferred is the one consisting of units for which Ri, R2, R3 and R4 represent a methyl radical, n = 3, p = 6 and X = Cl, which is known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.
(9) polyquaternary ammonium polymers comprising units of the following formula:
Figure imgf000033_0001
in which:
- Ri8, Ri9, R20 and R21 , which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, b-hydroxyethyl, b-hydroxypropyl or -CH2CH2COCH2CH2)pOH radical, where p is equal to 0 or to an integer of between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent a hydrogen atom,
- r and s, which may be identical or different, are integers between 1 and 6,
- q is equal to 0 or to an integer between 1 and 34,
- X' denotes an anion, such as a halide,
- A denotes a divalent dihalide radical or preferably represents -CH2-CH2-O- CH2-CH2-.
Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.
(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF.
(11) polyamines such as Polyquart® FI sold by Cognis, which is referenced under the name Polyethylene Glycol (15) Tallow Polyamine in the CTFA dictionary.
(12) polymers including in their structure:
- one or more units corresponding to formula (A) below:
Figure imgf000034_0002
- and optionally one or more units corresponding to formula (B) below:
Figure imgf000034_0001
In other words, these polymers may be notably chosen from homopolymers or copolymers including one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
Preferably, these cationic polymers are chosen from polymers including, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium. The weight-average molecular mass of said polymer, measured by light scattering, may range from 1000 to 3000000 g/mol, preferably from 10000 to 1 000000 and more particularly from 100000 to 500000 g/mol.
The polymers including units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a non-limiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
(13) cationic polyvinyllactam polymers.
Such polymers are described, for example, in patent application WO- 00/68282.
As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethac rylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacr ylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacryl amidopropylammonium tosylate or chloride terpolymers are used notably.
(14) and mixtures of the above polymers. Other cationic polymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolyzates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives such as chitosan.
Preferably, the cationic polymers are chosen from those of families (1), (2), (7), (8) and (12), preferentially families (1), (2) and (7).
Among the cationic polymers mentioned above, use may preferentially be made of cationic polysaccharides, notably quaternized (poly)hydroxyethylcelluloses modified with groups including at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups including at least 8 carbon atoms, or mixtures thereof. More particularly, the cationic polymer is chosen from hydroxyethylcelluloses which have reacted with a trimethylammonium epoxide and a lauryldimethylammonium epoxide (INCI name: Polyquaternium- 67).
The content of the cationic polymer(s), present in the composition according to the invention, preferably ranges from 0.05% to 15% by weight, preferably from 0.5% to 10% by weight, and more preferentially from 1% to 8% by weight relative to the total weight of the composition. The weight ratio between the total content of particle dispersion(s) (A) and the total content of cationic polymer(s), present in the composition according to the invention, preferably ranges from 0.1 to 10, preferentially from 0.2 to 5 and better still from 0.25 to 3.
Anionic polymer The composition according to the present invention also comprises one or more anionic polymers other than the anionic polymers 1) i) b).
For the purposes of the present invention, the term “anionic polymer” denotes any polymer containing anionic groups and/or groups that can be ionized into anionic groups and not containing any cationic groups and/or groups that can be ionized into cationic groups.
Anionic polymers that may be mentioned include polymers including groups derived from carboxylic, sulfonic or phosphoric acids, and having a number- average molecular mass of between 500 and 5000000.
The carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers, such as those corresponding to formula (I):
Figure imgf000036_0001
in which: n is an integer from 0 to 10,
A denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the adjacent methylene group, when n is greater than 1 , via a heteroatom, such as oxygen or sulfur,
Ri denotes a hydrogen atom or a phenyl or benzyl group, R2 denotes a hydrogen atom, an alkyl group including from 1 to 4 carbon atoms or a carboxyl group,
R3 denotes a hydrogen atom, an alkyl group including from 1 to 4 carbon atoms, a -CH2-COOH group, a phenyl group or a benzyl group.
In formula (I) above, the alkyl group including from 1 to 4 carbon atoms may in particular denote methyl and ethyl groups.
The anionic polymers containing carboxylic or sulfonic groups that are preferred are:
A) copolymers of acrylic or methacrylic acid or salts thereof, including copolymers of acrylic acid and acrylamide, and methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers, in particular Amerhold DR 25 sold by the company Amerchol, and sodium salts of polyhydroxycarboxylic acids. Mention may also be made of methacrylic acid/ethyl acrylate copolymers, notably in aqueous dispersion, such as Luviflex Soft and Luvimer MAE, which are sold by the company BASF. B) copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters and acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222944 and German patent application No. 2330956, the copolymers of this type including an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described notably in Luxembourg patent applications 75370 and 75371. Mention may also be made of copolymers of acrylic acid and of C1-C4 alkyl methacrylate. As another anionic fixing polymer from this class, mention may also be made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name AMP- Acrylates/Allyl Methacrylate Copolymer).
C) crotonic acid-based copolymers, such as those including vinyl acetate or propionate units in their chain and optionally other monomers such as allylic esters or methallylic esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon-based chain, such as those including at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or alternatively a vinyl, allylic or methallylic ester of an a- or b-cyclic carboxylic acid. Such polymers are described, inter alia, in French patents 1 222944, 1 580545, 2265782, 2265781, 1 564 110 and 2 439 798. Commercial products that fall within this category are the resins 282930, 261314 and 281310 sold by the company National Starch.
Mention may also be made, as copolymer derived from crotonic acid, of crotonic acid/vinyl acetate/vinyl tert-butylbenzoate terpolymers, and in particular Mexomere PW supplied by the company Chimex.
D) polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters; these polymers may be esterified. Such polymers are described in particular in US patents 2047398, 2723248 and 2 102 113 and GB patent 839 805, and notably those sold under the names Gantrez® AN or ES by the company ISP.
Polymers also falling within this category are the copolymers of maleic, citraconic or itaconic anhydrides and of an allylic or methallylic ester optionally including an acrylamide or methacrylamide group, an ct-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions being monoesterified or monoamidated. These polymers are described, for example, in French patents 2 350 384 and 2 357 241 by the Applicant.
E) polyacrylamides including carboxylate groups.
F) polymers comprising sulfonic groups. These polymers may be polymers including vinylsulfonic, styrenesulfonic, naphthalenesulfonic, acrylamidoalkylsulfonic or sulfoisophthalate units, and salts thereof.
These polymers may notably be chosen from:
- polyvinylsulfonic acid salts with a molecular mass of between 1000 and 100 000 approximately, and also the copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and esters thereof, and also acrylamide or derivatives thereof, vinyl ethers and vinylpyrrolidone;
- polystyrenesulfonic acid salts and sodium salts, with a molecular mass of about 500 000 and of about 100 000. These compounds are described in patent FR 2 198 719;
- polyacrylamidesulfonic acid salts such as those mentioned in patent US 4 128 631 ;
FI) anionic polyurethanes, which may include silicone grafts and silicones bearing hydrocarbon-based grafts.
Examples of fixing polyurethanes that may notably be mentioned include the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols copolymer (also known under the name polyurethane-1 , INCI name) sold under the brand name Luviset® Pur by the company BASF, and the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols/silicone diamine copolymer (also known under the name polyurethane-6, INCI name) sold under the brand name Luviset® Si PUR A by the company BASF.
Another anionic polyurethane that may also be used is Avalure UR 450.
Polymers containing sulfoisophthalate groups, such as the polymers AQ55 and AQ48 sold by the company Eastman, may also be used.
Mention may also be made of crosslinked or non-crosslinked acrylic or methacrylic acid homopolymers or copolymers and salts thereof, crosslinked or non-crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and salts thereof and crosslinked or non-crosslinked copolymers thereof, in particular copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide, copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of vinylpyrrolidone, copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of C1 -C30 and preferably C8-C22 alkyl (meth)acrylate, which are optionally oxyalkylenated, and salts thereof, and ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide, alone or as mixtures.
Among the crosslinked acrylic or methacrylic acid homopolymers that may be mentioned are those crosslinked with an allyl alcohol ether of the sugar series, for instance the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA. These polymers have the INCI name Carbomer.
The crosslinked (meth)acrylic acid copolymers may be copolymers of (meth)acrylic acid and of C1 -C6 alkyl (meth)acrylate, such as the polymer sold under the name Aqua SF1 by the company Noveon.
The crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers are notably sold under the name Hostacerin AMPS® by the company Clariant. Among the partially or totally neutralized crosslinked copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention may be made in particular of the product described in Example 1 of EP 503 853, and reference may be made to said document as regards these polymers.
The composition may similarly comprise ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide.
As examples of ammonium acrylate homopolymers, mention may be made of the product sold under the name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide, mention may be made of the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst. Reference may notably be made to FR 2 416 723, US 2 798 053 and US 2 923 692 as regards the description and preparation of such compounds. The anionic polymers may also be chosen from anionic polysaccharides notably such as acacia gums and carrageenans, in particular lambda- carrageenans.
According to the invention, the anionic polymers are preferably chosen from acrylic acid copolymers, such as the acrylic acid/ethyl acrylate/N-tert- butylacrylamide terpolymer sold under the name Ultrahold Strong® by the company BASF, methacrylic acid/ethyl acrylate copolymers, notably in aqueous dispersion, such as Luviflex Soft and Luvimer MAE sold by the company BASF, crotonic acid-based copolymers, such as the vinyl acetate/vinyl tert- butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, such as the methyl vinyl ether/monoesterified maleic anhydride copolymer sold under the name Gantrez® ES 425 by the company ISP,
Luviset SI PUR, Mexomere PW, elastomeric or non-elastomeric anionic polyurethanes, polymers bearing sulfoisophthalate groups, and anionic polymers of the B) class, and even more particularly, use is preferably made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (INCI name: AMP- Acrylates/Allyl Methacrylate Copolymer), crosslinked or non-crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers or copolymers, or salts thereof.
Use will preferably be made of crosslinked or non-crosslinked 2- acrylamido-2-methylpropanesulfonic acid homopolymers or copolymers, or salts thereof, more preferentially crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers or salts thereof such as Hostacerin AMPS® from Clariant (INCI name: Ammonium polyacryloyldimethyl taurate), and anionic polysaccharides, in particular carrageenans. The content of anionic polymer(s), present in the composition according to the invention, preferably ranges from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight, better still from 0.2% to 8% by weight, from 0.5% to 5% by weight relative to the total weight of the composition.
The weight ratio between the total content of particle dispersion(s) (A) and the total content of anionic polymer(s), present in the composition according to the invention, preferably ranges from 0.1 to 15, preferentially from 0.2 to 10 and better still from 0.25 to 5.
According to the invention, the cationic polymer(s)/anionic polymer(s) weight ratio preferably ranges from 10/90 to 90/10, better still from 20/80 to 80/20, in particular from 30/70 to 70/30 and more preferentially from 40/60 to 60/40.
Preferably, the composition according to the present invention is aqueous. The water is present in a content generally greater than or equal to 30% by weight relative to the total weight of the composition.
Preferably, the content of water present in the composition of the invention ranges from 30% to 98% by weight, preferably from 50% to 98% by weight and more preferentially from 65% to 95% by weight, relative to the total weight of the composition.
Besides water, predominantly contained in the aqueous phase, the composition according to the present invention may optionally comprise one or more organic solvents, or mixtures thereof.
Examples of organic solvents that may be mentioned include linear or branched C2 to C4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof. Preferably, the organic solvent is ethanol or propylene glycol.
Preferably, when present in the composition of the invention, the content of solvent(s) ranges from 1 % to 30% by weight, preferably from 5% to 20% by weight relative to the total weight of the composition.
The pH of the composition according to the invention generally ranges from 1.5 to 12, preferably from 2 to 8 and preferentially from 2.5 to 7.5.
The pH of the composition may be adjusted to the desired value by means of the basifying agents or acidifying agents that are customarily used. Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkanolamines, and mineral or organic hydroxides. Among the acidifying agents, examples which may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
The composition according to the present invention may also optionally comprise one or more thickeners other than the above cationic and anionic polymers.
The composition according to the present invention may optionally also comprise one or more silicones other than the non-aqueous medium present in the particle dispersion(s) and the polymers described previously.
The silicones that may be used in the present invention may be solid or liquid, and volatile or non-volatile.
The silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in the form of oil, wax, resin or gum; silicone oils and gums are preferred.
Silicones are notably described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.
The volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and more particularly from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
- octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;
- cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type having the chemical structure:
Figure imgf000042_0001
Mention may be made of Volatile Silicone FZ 3109 sold by the company Union Carbide.
- mixtures of cyclic silicones with silicon-derived organic compounds, such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of 1,T-oxy(2,2,2’,2’,3,3’- hexatrimethylsilyloxy)bisneopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5x1 O'6 m2/s at 25°C, such as decamethyltetrasiloxane.
Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pages 27-32 - Todd & Byers Volatile silicone fluids for cosmetics; mention may be made of the product sold under the name SH 200 by the company Toray Silicone. Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more organofunctional groups, generally attached via a hydrocarbon- based group, and preferably chosen from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups.
The organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
Among the organomodified silicones, mention may be made of organopolysiloxanes including: - polyoxyethylene and/or polyoxypropylene groups optionally including C6-C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Corning under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (C12)alkylmethicone copolyols, and notably those sold by the company Dow Corning under the name Q2-5200;
- substituted or unsubstituted amine groups, in particular C1-C4 aminoalkyl groups; mention may be made of the products sold under the names GP4 Silicone Fluid and GP7100 by the company Genesee, or under the names Q2- 8220 and DC929 or DC939 by the company Dow Corning;
- thiol groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;
- alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt;
- hydroxylated groups, for instance polyorganosiloxanes bearing a hydroxyalkyl function;
- acyloxyalkyl groups, such as the polyorganosiloxanes described in patent US-A-4 957 732;
- anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic type, such as the product X-22-3701 E from the company Shin-Etsu; or else of the 2-hydroxyalkylsulfonate or 2- hydroxyalkylthiosulfate type, such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255;
- hydroxyacylamino groups, such as the polyorganosiloxanes described in patent application EP 342 834; mention may be made, for example, of the product Q2-8413 from the company Dow Corning.
The silicones may also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes bearing trimethylsilyl end groups. Among these polydialkylsiloxanes, mention may be made of the following commercial products:
- the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
- the oils of the Mirasil® series sold by the company Rhodia;
- the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm2/s; - the Viscasi!® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the oils of the 48 series from Rhodia.
In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are polydi(C1 -C20)alkylsiloxanes.
Products which may be used more particularly in accordance with the invention are mixtures such as:
- mixtures formed from a polydimethylsiloxane with a hydroxy- terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Corning. The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1c10-5 to 5c10-2 m2/s at 25°C.
Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:
- the Silbione® oils of the 70641 series from Rhodia;
- the oils of the Rhodorsil® 70633 and 763 series from Rhodia;
- the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
- the silicones of the PK series from Bayer, such as the product PK20; - the silicones of the PN and PH series from Bayer, such as the products
PN1000 and PH1000;
- certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
The composition according to the present invention may also optionally comprise one or more additives, other than the compounds of the invention and among which mention may be made of nonionic, cationic, anionic, amphoteric or zwitterionic surfactants, and mixtures thereof, fatty substances other than the non-aqueous medium of the particle dispersion(s) and other than the silicones described previously, nonionic polymers, or mixtures thereof, antidandruff agents, anti-seborrhoea agents, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifying agents, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances, preserving agents, pigments and ceramides.
According to the invention, the composition also comprises one or more additional salts, other than the compounds of the invention. For the purposes of the present invention, the term “additional salts” means alkali metal salts such as sodium chloride; alkaline-earth metal salts such as CaCh; organic acid salts such as sodium citrate, sodium lactate, sodium acetate, and mixtures thereof; more preferentially alkali metal salts and in particular sodium chloride. Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition.
The present invention also relates to a cosmetic treatment process, preferably a process for treating human keratin fibers such as the hair, notably a styling process, i.e. a process for fixing and/or shaping keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a composition as defined previously.
The shaping process according to the invention may be performed on wet or dry, preferably wet, keratin fibers.
On conclusion of the process, the keratin fibers are advantageously rinsed with water before being dried or left to dry.
In a preferred embodiment of the invention, the process comprises:
1) a step of applying to the keratin fibers a composition comprising: a) one or more particle dispersions (A) as described previously, b) one or more cationic polymers, and c) one or more anionic polymers, followed by:
2) a step of rinsing the keratin fibers, preferably with water.
The present invention finally relates to the use of a composition as described above for cosmetic treatment, notably for styling keratin fibers, in particular human keratin fibers such as the hair.
More particularly, the present invention relates to the use of a composition as described above for styling the hair, i.e. for shaping and/or fixing (holding) the hairstyle. The examples that follow serve to illustrate the invention without, however, being limiting in nature.
EXAMPLES
Example 1 of preparing the dispersion (A)
A synthetic example is presented below for the production of an oily dispersion with a C9-C22 alkyl (meth)acrylate stabilizer. For this example, stearyl methacrylate was used in combination with methyl acrylate for the stabilizing arm and methyl acrylate was adopted for the core of the particle.
The oily dispersions are formed as a whole (polymer particles i) + polymeric stabilizer ii)) containing 94.5% by weight of methyl acrylate and 5.5% of stearyl methacrylate. The synthesis of these oily dispersions was performed in a 1 liter pilot reactor. The synthesis is performed in two steps:
- In a first step, stearyl methacrylate is polymerized in isododecane in the presence of a small amount of methyl acrylate and of a radical initiator (T21S). In the first step, the stearyl methacrylate/methyl acrylate mass ratio is 85/15. In the second step, the rest of the methyl acrylate is added in the presence of isododecane and of the radical initiator (T21S).
The ratios employed to obtain the stabilizer and the core are summarized in Table 3: Specific ratios in the stabilizer and core for the dispersion
[Table 3]
Figure imgf000047_0001
Figure imgf000048_0001
* R.T. = room temperature
Composition examples
Example 1 Composition (A1) was prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of the composition, are mentioned in the table below. [Table 2]
Figure imgf000048_0002
The locks treated with composition (A1) have good fixing and good fixing persistence.
Furthermore, the locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity. The locks do not have any residue.
Examples 2 and 3 Compositions 2 and 3 were prepared using the ingredients below (as percentage of active material). [Table 4]
Figure imgf000049_0001
The locks treated with compositions 2 and 3 have good fixing and good fixing persistence. The locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity. The locks do not have any residue.
Examples 4 to 6
Compositions 4 to 6 were prepared using the ingredients below (as percentage of active material).
[Table 5]
Figure imgf000049_0002
Figure imgf000050_0001
The locks treated with compositions 4 to 6 have good fixing and good fixing persistence. The locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity. The locks do not have any residue. Examples 7
Compositions (A1), (A2) (A3), (A4) and (A5) were prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of each composition, are mentioned in the table below.
[Table 6]
Figure imgf000050_0002
Figure imgf000051_0001
Each of the compositions (A1 ) to (A5) thus obtained was applied to 2.7 g locks of natural hair washed beforehand with a DOP shampoo, at a rate of 1 g of composition per lock. The locks of hair were then rinsed with water for 15 seconds. The locks were then towel-dried and then laid flat and left to dry naturally.
After this treatment, the fixing and the shape hold were evaluated on the dry hair, by six trained experts:
- The fixing was evaluated by applying pressure to the lock between two fingers of the hand: the more difficult the lock of hair is to crack, the stronger the fixing
- The hold was evaluated by passing the fingers through the lock three times from the root to the end: the more the lock conserves its initial structure after passing the fingers through, the greater the hold. These two parameters are graded from 0 to 5. The minimum limit of these two parameters is acquired after wetting an untreated lock with water: the fixing and hold are thus zero. The maximum limit is obtained after applying to the lock Vivelle Dop brand “beton” (ultra-strong hold) fixing styling gel: its fixing and hold parameters are each 5 out of 5. the greasy aspect, the sticky feel and the homogeneity were evaluated on the dry hair, by four trained experts:
- sticky touch and homogeneity were evaluated by passing the fingers through the lock three times from the root to the end: These parameters were graded from 0 to 5.
The more greasy was graded 5 (oil), the lesser greasy was graded 0 The more sticky was graded 5, the lesser sticky was graded 0 The more homogeneous was graded 5, the lesser homogeneous was graded 0
Results
[Table 7]
Figure imgf000052_0001
The locks treated with composition (A1) had good fixing and good fixing persistence which were better than those of compositions comprising only polymers or only dispersion.
Furthermore, the locks treated with composition (A1) have a smooth feel that is neither tacky nor greasy.
Examples 8 to 11
Compositions 8 to 11 were prepared using the ingredients below (as percentage of active material).
[Table 8]
Figure imgf000052_0002
Figure imgf000053_0001
The locks treated with compositions 8 to 11 have good fixing and good fixing persistence. The locks have a feel that is neither tacky nor greasy: they have a very satisfactory smooth feel and good homogeneity. The locks do not have any residue.
Example 12 Composition 12 was prepared using the ingredients of which the contents, expressed as mass percentages of active material, relative to the total weight of the composition, are mentioned in the table below.
[Table 9]
Figure imgf000054_0001
The locks treated with composition 12 had good fixing and good fixing persistence.
Furthermore, the locks had a feel that is neither tacky nor greasy: they had a very satisfactory smooth feel and good homogeneity. The locks did not have any residue.

Claims

1 . A composition comprising:
1 ) one or more oily dispersions (A), which are preferably anhydrous, comprising:
1) one or more particles including one or more polymers chosen from: a) ethylenic homopolymers of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, preferably (C1-C4)alkyl (meth)acrylate; b) ethylenic copolymers of b1) (C1-C4)alkyl (C1-C4)(alkyl)acrylate and of b2) ethylenic monomers comprising one or more carboxyl, anhydride, phosphoric acid, sulfonic acid and/or aryl groups such as benzyl; in particular, b2) is a (C-i- C4)(alkyl)acrylic acid, more particularly copolymers of (C1-C4)alkyl (meth)acrylate and of (meth)acrylic acid; c) ethylenic copolymers of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, preferably (C-i- C4)alkyl (meth)acrylate; and of (C1-C4)alkyl (C1-C4)(alkyl)acrylate, ii) one or more polymeric stabilizers chosen from: d) ethylenic homopolymers of (C9-C22)alkyl (C1-C6)(alkyl)acrylate, preferably ethylenic homopolymers of (C9-C22)alkyl (meth)acrylate; and e) ethylenic copolymers of (C9-C22)alkyl (C1-C6)(alkyl)acrylate, and of (C-i- C4)alkyl (C1-C4)(alkyl)acrylate, preferably copolymers of (C9-C22)alkyl (meth)acrylate and of (C1-C4)alkyl (meth)acrylate; iii) one or more hydrocarbon-based liquid fatty substances;
2) one or more cationic polymers, and
3) one or more anionic polymers.
2. The composition as claimed in claim 1 , characterized in that the particle(s) i) are constituted of an ethylenic polymer core obtained from homopolymers a) or from copolymers b) or c), as defined in the preceding claim, and ii) of one or more polymeric surface stabilizers obtained from homopolymer d) and from the copolymers e) as defined in the preceding claim.
3. The composition as claimed in either of the preceding claims, characterized in that the polymer(s) constituting the particles i) are chosen from acrylate ethylenic copolymers b) resulting from the polymerization:
- of at least two different (C1-C4 alkyl (C1-C4 (alkyl)acrylate and preferably C1-C4 alkyl acrylate monomers such as methyl acrylate and ethyl acrylate; and
- optionally of a (C1-C4 (alkyl)acrylic acid monomer, in particular acrylic acid;
- of at least two different (C1-C4 alkyl (C1-C4 (alkyl)acrylate and preferably
C1-C4 alkyl acrylate monomers such as methyl acrylate and ethyl acrylate; and
- optionally of a (C1-C4 (alkyl)acrylic acid monomer, in particular acrylic acid.
4. The composition as claimed in any one of the preceding claims, in which the monomers are chosen from C1 -C4 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate or tert-butyl (meth)acrylate, more preferentially chosen from methyl (meth)acrylate and ethyl (meth)acrylate.
5. The composition as claimed in any one of the preceding claims, in which the oily dispersion (A) includes from 60% to 98% by weight, notably from 75% to 96% of monomers a) to c) relative to the total weight of polymers contained in said dispersion.
6. The composition as claimed in any one of the preceding claims, in which the stabilizing polymer(s) ii) are chosen from d) (C9-C22)alkyl (C1 - C6)(alkyl)acrylate ethylenic homopolymers; in particular (C9-C18)alkyl (C1 - C4 )(alkyl)acrylate ethylenic homopolymers.
7. The composition as claimed in any one of the preceding claims, in which the stabilizing polymer(s) ii) are chosen from isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hexadecyl (meth)acrylate or behenyl (meth)acrylate homopolymers, and statistical copolymers of isodecyl (meth)acrylate, of lauryl (meth)acrylate, of stearyl (meth)acrylate, of hexadecyl (meth)acrylate, of behenyl (meth)acrylate and of C1 -C4 alkyl (meth)acrylate, preferably present in a weight ratio of 2-ethylhexyl, isooctyl, isodecyl, lauryl, stearyl, hexadecyl, behenyl (meth)acrylate/C1 -C4 alkyl (meth)acrylate of greater than 4; advantageously, said weight ratio ranges from 5 to 15; more preferentially, said weight ratio ranges from 5.5 to 12.
8. The composition as claimed in any one of the preceding claims, in which the stabilizing polymer(s) ii) are chosen from e) ethylenic copolymers of (C9-C22)alkyl (C1 -C6)(alkyl)acrylate and of (C1 -C4 )alkyl (C1 - C4 )(alkyl)acrylate, and more particularly copolymers of (C9-C18)alkyl (meth)acrylate and of (C1 -C4 )alkyl (meth)acrylate.
9. The composition as claimed in any one of claims 1 to 6, in which the stabilizing polymer(s) ii) are chosen from ethylenic copolymers e) derived from the polymerization of a (C9-C22)alkyl (C1 -C4 )(alkyl)acrylate monomer and of two different (C1 -C4 )alkyl (C1 -C4 )(alkyl)acrylate monomers; preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of a monomer chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates or behenyl (meth)acrylates and of two different C1 -C4 alkyl (meth)acrylate monomers, preferably methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates, behenyl (meth)acrylates/C1 -C4 alkyl (meth)acrylate is greater than 4; advantageously, said weight ratio ranges from 5 to 15; more preferentially, said weight ratio ranges from 5.5 to 11 .
10. The composition as claimed in any one of claims 1 to 6, in which the stabilizing polymer(s) ii) are chosen from ethylenic copolymers e) derived from the polymerization of two different (C9-C22)alkyl (C1 -C4 )(alkyl)acrylate monomers and of a (C1 -C4 )alkyl (C1 -C4 )(alkyl)acrylate monomer; preferentially, the stabilizer(s) ii) are chosen from copolymers derived from the polymerization of two different monomers chosen from isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates or behenyl (meth)acrylates and of a C1 -C4 alkyl (meth)acrylate monomer, preferably methyl acrylate and ethyl acrylate; in particular, the weight ratio of isodecyl (meth)acrylates, lauryl (meth)acrylates, stearyl (meth)acrylates, hexadecyl (meth)acrylates, behenyl (meth)acrylates/C1 -C4 alkyl (meth)acrylate is greater than 4; advantageously, said weight ratio ranges from 4.5 to 10; more preferentially, said weight ratio ranges from 5 to 8.
11 . The composition as claimed in any one of the preceding claims, in which the weight ratio of ii) the stabilizing polymer(s) and of i) the polymer particle(s) present in the dispersion (A) is between 0.5 and 2, preferably from 0.8 to 1 .2 and better still equal to 1 .
12. The composition as claimed in 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 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.
13. The composition as claimed in any one of the preceding claims, characterized in that the total content of particle dispersion(s) (A) ranges from 0.1 % to 20% by weight, more preferentially from 0.5% to 10% by weight and better still from 1 % to 8% by weight relative to the weight of the composition.
14. The composition as claimed in any one of the preceding claims, characterized in that the cationic polymers are chosen from homopolymers or copolymers including one or more units derived from vinylamine and optionally one or more units derived from vinylformamide, quaternized or non- quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, cationic polysaccharides, alkyldiallylamine or dialkyldiallylammonium cyclopolymers, and preferably cationic polysaccharides and mixtures thereof.
15. The composition as claimed in any one of the preceding claims, characterized in that the content of the cationic polymer(s) ranges from 0.05% to 15% by weight, preferably from 0.5% to 10% by weight and more preferentially from 1 % to 8% by weight, relative to the total weight of the composition.
16. The composition as claimed in any one of the preceding claims, characterized in that the anionic polymers are chosen from crosslinked or non- crosslinked acrylic or methacrylic acid homopolymers or copolymers and salts thereof, crosslinked or non-crossl inked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers and salts thereof, the branched block butyl acrylate/acrylic acid/methacrylic acid anionic polymer (INCI name: AMP- acrylates/allyl methacrylate copolymer), anionic polysaccharides, alone or as mixtures.
17. The composition as claimed in any one of the preceding claims, characterized in that the content of the anionic polymer(s) ranges from 0.05% to 15% by weight, more preferentially from 0.1% to 10% by weight and better still from 0.5% to 8% by weight, relative to the total weight of the composition.
18. The composition as claimed in any one of the preceding claims, characterized in that it comprises water.
19. The composition as claimed in any one of the preceding claims, characterized in that the composition comprises water in a content ranging from 30% to 98% by weight, preferably from 50% to 98% by weight and more preferentially from 65% to 95% by weight, relative to the total weight of the composition.
20. A cosmetic process for treating keratin fibers, in particular human keratin fibers such as the hair, comprising the application to said keratin fibers of a composition as defined in any one of the preceding claims.
21. The use of a composition as defined in any one of claims 1 to 20, for styling keratin fibers, in particular human keratin fibers such as the hair.
PCT/EP2022/066503 2021-06-16 2022-06-16 Composition comprising an oily dispersion of polymer particles, a cationic polymer and an anionic polymer WO2022263603A1 (en)

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