Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • 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
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • 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
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
  • A61Q1/06—Lipsticks

Definitions

• compositions whose deposit is characterized by gloss (in particular in the case of lip makeup compositions) and preferably a tack-free effect, and which are pleasant to wear (no sensation of tautness) .
• the aim of the present invention is to propose cosmetic compositions for obtaining such a uniform film-forming deposit on keratin materials, the said film combining good gloss properties (in particular in the case of lipsticks) , gloss remanence over time (in particular 1 hour after application) , which are preferably non-tacky, and which are particularly comfortable to wear (no sensation of tautness or dryness) .
• the compositions according to the invention also allow the production of a transfer-free deposit that has a good level of remanence, in particular when it is a makeup composition, and good remanence of the colour of the deposit on keratin materials, and in particular on the skin or the lips.
• One subject of the present invention is thus a cosmetic composition for making up and/or caring for keratin materials (especially the skin or the lips) , comprising, in a cosmetically acceptable medium:
• cosmetic oily or solvent media especially oils, fatty alcohols and/or fatty esters, which facilitates their use in the cosmetic field, especially in lipsticks.
• They show acceptable solubility in varied cosmetic oily media, such as plant oils, alkanes, esters, whether they are short esters such as butyl or ethyl acetate, or fatty esters, and fatty alcohols, and most particularly in media comprising isododecane, sesam, isononyl isononanoate, octyldodecanol and/or a C12-C15 alkyl benzoate .
• the cosmetic compositions according to the invention moreover show good applicability (glidance on application and decaking in the case of solid compositions) and good coverage; good adherence to the support, whether it is to the nails, the eyelashes, the skin or the lips; adequate flexibility and strength of the film, and also an excellent gloss durability.
• the comfort and glidance properties are also very satisfactory .
• the compounds A may be referred to without preference as “supramolecular compounds” for convenience and for greater clarity.
• junction group capable of establishing hydrogen bonds with one or more partner junction groups, each pairing of a junction group involving at least three hydrogen bonds, the said junction group bearing at least one isocyanate or imidazole reactive function capable of reacting with the reactive function borne by the oil, the said junction group also comprising at least one unit of formula (I) or (II) :
• apolar means a compound whose HLB value
• insoluble means that the oil fraction that can dissolve in water, at 25°C and 1 atm., is less than 5% by weight (i.e. 5 g of oil in 100 ml of water); preferably less than 3%.
• the oil that may be used in the context of the present invention bears at least one reactive function capable of reacting with the reactive function borne on the junction group, and is especially capable of reacting chemically with the isocyanate or imidazole groups borne by the junction group; preferably, this function is an OH or N3 ⁇ 4 function.
• the oil comprises only OH functions, in particular 1 to 3 OH functions, preferentially primary or secondary OH functions, and better still only primary functions.
• the carboxylic acid is a monoacid.
• a mixture of carboxylic acids, especially monocarboxylic acids, may also be used.
• trimethylolpropane monoesters and diesters for instance trimethylolpropane monoisostearate, trimethylolpropane diisostearate, trimethylolpropane mono-2-ethylhexanoate and trimethylolpropane bis (2- ethylhexanoate) ;
• lactic acid esters especially C4-40 alkyl lactates, such as 2-ethylhexyl lactate, diisostearyl lactate, isostearyl lactate, isononyl lactate and 2- octyldodecyl lactate;
• an arylalkoxy group in particular an aryl (Ci- C 4 ) alkoxy group
• R' 3 may represent a C1-C4 alkylene, especially 1,2-ethylene.
• junction groups may be chosen from the following groups:
• R3 represents a divalent radical -R' 3-O-C (0) -NH- R'4- in which R' 3 and R'4, which may be identical or different, represent a divalent carbon-based radical chosen from a linear or branched Ci-C 3 o alkyl group, a C 4 -Ci 2 cycloalkyl group and a C 4 -Ci 2 aryl group; or a mixture thereof; and especially R' 3 represents a C1-C4 alkylene, especially 1 , 2-ethylene, and R'4 represents the divalent radical derived from isophorone.
• the junction groups may be attached to the oil by functionalization of the junction group with an isocyanate or imidazole.
• the supramolecular compound according to the invention may be prepared via the processes usually used by those skilled in the art for forming a urethane bond, between the free OH functions of the oil and the isocyanate functions borne by the junction group.
• a general preparation process consists in:
• the use of the compounds according to the invention may lead, after application of the composition to keratin materials, to the formation of a supramolecular polymer in the form of a physically crosslinked network, especially by means of hydrogen bonds, which is generally in the form of a film, and which has very good mechanical strength.
• the number-average molecular mass (Mn) of the supramolecular compound according to the invention is preferably between 180 and 8000, preferably from 200 to 6000, or even from 300 to 4000, better still from 400 to 3000 and preferentially from 500 to 1500.
• the films dewet and do not form a uniform deposit.
• the films obtained with the compounds according to the invention do not dewet and are uniform and cohesive.
• the tribometry results confirm the cohesion properties obtained with the compounds of the invention.
• - film-forming agents chosen from silicone resins and film-forming polymers, preferably chosen from the group comprising:
• the organopolysiloxane elastomer may be obtained via reaction of dimethylpolysiloxane containing dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane containing trimethylsiloxy end groups, in the presence of a platinum catalyst.
• Compound (A) is the base reagent for the formation of elastomeric organopolysiloxane, and the crosslinking takes place via an addition reaction of compound (A) with compound (B) in the presence of the catalyst (C) .
• Compound (A) may have any molecular structure, in particular a linear-chain or branched-chain structure or a cyclic structure.
• Compound (A) may have a viscosity at 25°C ranging from 1 to 50 000 centistokes, in particular in order to show good miscibility with compound (B) .
• the other organic groups linked to the silicon atoms in compound (B) may be alkyl groups such as methyl, ethyl, propyl, butyl or octyl; substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3 , 3 , 3-trifluoro- propyl; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl ; and substituted monovalent hydrocarbon-based groups such as an epoxy group, a carboxylate ester group or a mercapto group .
• alkyl groups such as methyl, ethyl, propyl, butyl or octyl
• substituted alkyl groups such as 2-phenylethyl, 2-phenylpropyl or 3 , 3 , 3-trifluoro- propyl
• aryl groups such as phenyl, tolyl or xylyl
• the organopolysiloxanes (B) may be chosen from methylvinylpolysiloxanes , methylvinylsiloxane-dimethyl- siloxane copolymers, dimethylpolysiloxanes containing dimethylvinylsiloxy end groups, dimethylsiloxane- methylphenylsiloxane copolymers containing dimethylvinylsiloxy end groups, dimethylsiloxane- diphenylsiloxane-methylvinylsiloxane copolymers containing dimethylvinylsiloxy end groups, dimethyl- siloxane-methylvinylsiloxane copolymers containing trimethylsiloxy end groups, dimethylsiloxane-methyl- phenylsiloxane-methylvinylsiloxane copolymers containing trimethylsiloxy end groups, methylsiloxane-methyl- phenylsiloxane-methylvinyl
• the sum of the number of ethylenic groups per molecule of compound (B) and of the number of hydrogen atoms bonded to silicon atoms per molecule of compound (A) is at least 5.
• Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid- diketone complexes, platinum black or platinum on a support .
• emulsifying organopolysiloxane elastomer means an organopolysiloxane elastomer comprising at least one hydrophilic chain, such as polyoxyalkylenated organopolysiloxane elastomers and polyglycerolated silicone elastomers.
• the polyoxyalkylenated crosslinked organopolysiloxane is obtained by a crosslinking addition reaction (Al) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (Bl) of polyoxyalkylene containing at least two ethylenically unsaturated groups, especially in the presence (CI) of a platinum catalyst, as described, for example, in patents US 5 236 986 and US 5 412 004.
• the organic groups bonded to silicon atoms of the compound (Al) may be alkyl groups containing from 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl (or lauryl) , myristyl, cetyl or stearyl; substituted alkyl groups such as 2-phenyl- ethyl, 2-phenylpropyl or 3 , 3 , 3-trifluoropropyl ; aryl groups such as phenyl, tolyl or xylyl; substituted aryl groups such as phenylethyl ; and substituted monovalent hydrocarbon-based groups such as an epoxy group, a carboxylate ester group or a mercapto group.
• alkyl groups containing from 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, octyl, decyl,
• Compound (Al) may thus be chosen from methylhydrogenopolysiloxanes containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogenosiloxane copolymers containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogenosiloxane cyclic copolymers, or dimethylsiloxane-methylhydrogenosiloxane- laurylmethylsiloxane copolymers containing trimethylsiloxy end groups.
• the polyoxyalkylenated silicone elastomers may be formed from divinyl compounds, in particular polyoxyalkylenes containing at least two vinyl groups, reacting with Si-H bonds of a polysiloxane .
• the emulsifying silicone elastomer may also be chosen from polyglycerolated silicone elastomers.
• the crosslinked elastomeric organo ⁇ polysiloxane is obtained by a crosslinking addition reaction (A2) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B2) of glycerolated compounds containing at least two ethylenically unsaturated groups, especially in the presence (C2) of a platinum catalyst.
• A2 crosslinking addition reaction
• B2 of glycerolated compounds containing at least two ethylenically unsaturated groups, especially in the presence (C2) of a platinum catalyst.
• Compound (A2) is the base reagent for the formation of elastomeric organopolysiloxane and the crosslinking is performed by an addition reaction of compound (A2) with compound (B2) in the presence of the catalyst (C2 ) .
• Compound (A2) is in particular an organopolysiloxane containing at least 2 hydrogen atoms bonded to different silicon atoms in each molecule.
• Compound (A2) may have any molecular structure, in particular a linear chain or branched chain structure or a cyclic structure.
• Compound (B2) may be a polyglycerolated compound corresponding to formula ( ⁇ ' ) below:
• compound (A2) it is advantageous for compound (A2) to be added in an amount such that the molar ratio between the total amount of hydrogen atoms bonded to silicon atoms in compound (A2) and the total amount of all the ethylenically unsaturated groups in compound (B2) is within the range from 1/1 to 20/1.
• Compound (C2) is the crosslinking reaction catalyst, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid- diketone complexes, platinum black and platinum on a support .
• weight percentages of a compound are always expressed as weight of active material of the compound under consideration.
• a polyester that is suitable for use in the invention may be preferentially obtained by reacting :
• the contents being expressed as weight percentages relative to the total weight of the polyester.
• a polyester used according to the invention comprises a tetraol.
• tetraol means a polyol comprising 4 hydroxyl groups.
• a tetraol may be pentaerythritol .
• a polyester used according to the invention also comprises a linear or branched, saturated monocarboxylic acid containing from 9 to 23 carbon atoms and especially 12 to 22 carbon atoms.
• lauric acid myristic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid or behenic acid, and mixtures thereof, may be used.
• a cyclic dicarboxylic acid may be chosen from cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, naphthalene-2 , 3-dicarboxylic acid and naphthalene-2 , 6-dicarboxylic acid, or mixtures thereof.
• the cyclic dicarboxylic acid is isophthalic acid.
• the aromatic monocarboxylic acid may be chosen from benzoic acid and 4-tert-butylbenzoic acid.
• the said aromatic monocarboxylic acid, or the mixture of the said acids represents from 0.1% to 10% by weight, especially from 0.5% to 9.95% by weight and better still from 1% to 9.5% by weight, or even from 1.5% to 8% by weight relative to the total weight of the polyester.
• the contents being expressed as weight percentages relative to the total weight of the polyester.
• the said polyester is obtained by reacting:
• the contents being expressed as weight percentages relative to the total weight of the polyester.
• the aromatic monocarboxylic acid is present in a molar amount of less than or equal to that of the linear or branched saturated monocarboxylic acid; in particular, the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of linear or branched saturated monocarboxylic acid ranges from 0.08 to 0.70.
• the said weight ratio preferably ranges between 0.10 and 0.60 and more preferentially from 0.12 to 0.40.
• the polyester has:
• hydroxyl number expressed in mg of potassium hydroxide per g of polyester, of greater than or equal to 40; especially between 40 and 120 and better still between 40 and 80.
• a polyester of the invention has a weight-average molecular mass (Mw) of between 3000 and 1 000 000, or even between 3000 and 300 000.
• the average molecular weight may be determined by gel permeation chromatography or by light scattering, depending on the solubility of the polymer under consideration.
• a polyester of the invention has a viscosity, measured at 110°C, of between 20 and 4000 mPa.s, especially between 30 and 3500 mPa.s or even between 40 and 3000 mPa.s and better still between 50 and 2500 mPa.s. This viscosity is measured in the manner described hereinbelow.
• the polyester may be in liquid form at room temperature.
• a liquid polyester may have a weight-average molecular mass (Mw) ranging from 40 000 to 1 000 000 and preferably ranging from 50 000 to 300 000.
• a liquid polyester may have a viscosity, measured at 110°C, ranging from 1000 to 4000 mPa . s and preferably ranging from 1500 to 3000 mPa.s.
• the film-forming agent combined with the said compound A described previously is a silicone resin.
• the letter Q means a tetrafunctional unit Si0 4 /2 in which the silicon atom is bonded to four hydrogen atoms, which are themselves bonded to the rest of the polymer.
• silicone resins of MQ type mention may be made of the alkyl siloxysilicates of formula [ (Rl) 3S1O 1 /2] x (S1O4/2) y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.
• silicone resins of T type mention may be made of polysilsesquioxanes of formula (RSi03/2) x (T units) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, said polysilsesquioxanes also possibly comprising Si-OH end groups.
• a preferred form of resins of MQT type are MQT- propyl resins (also known as MQTPr) .
• MQT- propyl resins also known as MQTPr
• Such resins that may be used in the compositions according to the invention are especially those described and prepared in patent application WO 2005/075 542, the content of which is incorporated herein by reference.
• the MQ-T-propyl resin preferably comprises the following units:
• d being between 0.05 and 0.6
• the siloxane resin comprises the following units:
• a being between 0.05 and 0.5, preferably between 0.15 and 0.4,
• c being greater than 0, preferably between 0.15 and 0.4
• d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55,
• R3 of the siloxane resin are propyl groups.
• the ratio a/d being between 0.5 and 1.5;
• the silicone resin is chosen from the group comprising:
• a resin of MQ type chosen especially from (i) alkyl siloxysilicates , which may be trimethyl siloxysilicates , of formula [ (Rl) 3S1O1/2] x (S1O4/2) y , in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a hydrocarbon-based radical containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and preferably is an alkyl group containing from 1 to 8 carbon atoms, preferably a methyl group, and (ii) phenylalkyl siloxysilicate resins, such as phenylpropyldimethyl siloxysilicate, and/or
• a resin of T type chosen especially from the polysilsesquioxanes of formula (RSi03/2) x , in which x is greater than 100 and the group R is an alkyl group containing from 1 to 10 carbon atoms, for example a methyl group, the said polysilsesquioxanes also possibly comprising Si-OH end groups, and/or
• Rl, R2 and R3 independently representing a hydrocarbon-based radical, especially alkyl, containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group,
• a being between 0.05 and 0.5
• d being between 0.05 and 0.6
• the silicone resin is present in the composition according to the invention in a total resin solids content ranging from 1% to 40% by weight, preferably ranging from 2% to 30% by weight and better still ranging from 3% to 25% by weight relative to the total weight of the composition.
• film-forming polymer means a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film that adheres to keratin materials, and preferably a cohesive film, and better still a film whose cohesion and mechanical properties are such that the said film can be isolated and manipulated in isolation, for example when the said film is prepared by pouring onto a non-stick surface such as a Teflon-coated or silicone-coated surface.
• the film-forming polymer is a block ethylenic copolymer, containing at least a first block with a glass transition temperature (Tg) of greater than or equal to 40 °C and being derived totally or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40°C, and at least a second block with a glass transition temperature of less than or equal to 20°C and being derived totally or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20°C, the said first block and the said second block being linked together via a random intermediate segment comprising at least one of the said first constituent monomers of the first block and at least one of the said second constituent monomers of the second block, and the said block copolymer having a polydispersity index I of greater than 2.
• Tg glass transition temperature
• the block polymer used according to the invention thus comprises at least a first block and at least a second block.
• At least one block means one or more blocks .
• block polymer means a polymer comprising at least two different blocks and preferably at least three different blocks.
• ethylenic polymer means a polymer obtained by polymerization of ethylenically unsaturated monomers .
• the block ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers .
• first block and second block do not in any way condition the order of the said blocks in the structure of the polymer.
• the first block and the second block of the polymer used in the invention may advantageously be mutually incompatible.
• mutant blocks means that the mixture formed from a polymer corresponding to the first block and from a polymer corresponding to the second block is immiscible in the polymerization solvent present in weight majority for the block polymer, at room temperature (25°C) and atmospheric pressure (10 5 Pa), for a content of the polymer mixture of greater than or equal to 5% by weight, relative to the total weight of the mixture of the said polymers and of the said polymerization solvent, it being understood that:
• each of the polymers corresponding to the first and second blocks has an average (weight-average or number-average) molecular mass equal to that of the block polymer ⁇ 15%.
• the said polymer mixture is immiscible in at least one of them.
• the block polymer according to the invention comprises at least a first block and at least a second block linked together via an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
• the intermediate segment also known as the intermediate block
• the intermediate segment is a block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer, which enables these blocks to be "compatibilized” .
• the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.
• the intermediate block is derived essentially from constituent monomers of the first block and of the second block.
• the block polymer according to the invention is advantageously a film-forming block ethylenic polymer.
• ethylenic polymer means a polymer obtained by polymerization of ethylenically unsaturated monomers .
• film-forming polymer means a polymer that is capable of forming, by itself or in the presence of a film-forming auxiliary agent, a continuous film that adheres to a support, especially to keratin materials.
• the polymer according to the invention comprises no silicon atoms in its backbone.
• backbone means the main chain of the polymer, as opposed to the pendent side chains.
• the polymer according to the invention is not water-soluble, i.e. the polymer is not soluble in water or in a mixture of water and of linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, for instance ethanol, isopropanol or n- propanol, without pH modification, at an active material content of at least 1% by weight, at room temperature (25°C).
• the polymer according to the invention is not an elastomer.
• non-elastomeric polymer means a polymer which, when it is subjected to a constraint intended to pull it (for example by 30% relative to its initial length) , does not return to a length substantially identical to its initial length when the constraint ceases.
• non-elastomeric polymer denotes a polymer with an instantaneous recovery Ri ⁇ 50% and a delayed recovery R2 h ⁇ 70% after having been subjected to a 30% elongation.
• Ri is ⁇ 30% and R 2h ⁇ 50%.
• non-elastomeric nature of the polymer is determined according to the following protocol :
• a film about 100 ym thick is thus obtained, from which are cut rectangular specimens (for example using a punch) 15 mm wide and 80 mm long.
• the specimens are pulled at a speed of 50 mm/min and the distance between the jaws is 50 mm, which corresponds to the initial length (lo) of the specimen.
• the constraint is released by applying a return speed equal to the tensile speed, i.e. 50 mm/min, and the residual elongation of the specimen is measured as a percentage, after returning to zero load stress ( ⁇ ) .
• the percentage residual elongation of the specimen (S2h) is measured after 2 hours (2 hours after returning to zero load stress) .
• the percentage delayed recovery ( R 2h ) is given by the following formula:
• the polydispersity index of the polymer of the invention is greater than 2.
• the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8 and better still greater than or equal to 2.8, especially ranging from 2.8 to 6.
• the polydispersity index I of the polymer is equal to the ratio of the weight-average mass Mw to the number-average mass Mn .
• the weight-average molar mass (Mw) and number- average molar mass (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector) .
• the weight-average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300 000; it ranges, for example, from 35 000 to 200 000 and better still from 45 000 to 150 000 g/mol.
• the number-average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70 000; it ranges, for example, from 10 000 to 60 000 and better still from 12 000 to 50 000 g/mol.
• the block with a Tg of greater than or equal to 40°C has, for example, a Tg ranging from 40 to 150°C, preferably greater than or equal to 50 °C, for example ranging from 50°C to 120°C, and better still greater than or equal to 60°C, for example ranging from 60°C to 120°C.
• the glass transition temperatures indicated for the first and second blocks may be theoretical Tg values determined from the theoretical Tg values of the constituent monomers of each of the blocks, which may be found in a reference manual such as the Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the following relationship, known as Fox's law:
• G5i being the mass fraction of the monomer i in the block under consideration and Tgi being the glass transition temperature of the homopolymer of the monomer i .
• Tg values indicated for the first and second blocks in the present patent application are theoretical Tg values.
• the expression "between ... and " is intended to denote a range of values for which the limits mentioned are excluded, and "from ... to ! and “ranging from ... to " are intended to denote a range of values for which the limits are included .
• 40 °C may be a homopolymer or a copolymer.
• the block with a Tg of greater than or equal to 40°C may be derived totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40°C.
• This block may also be referred to as a "rigid block”.
• this block is a homopolymer, it is derived from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of greater than or equal to 40°C.
• This first block may be a homopolymer, formed from only one type of monomer (the Tg of the corresponding homopolymer of which is greater than or equal to 40 °C) .
• Tg values of greater than or equal to 40°C, for example a Tg ranging from 40 to 150°C, preferably greater than or equal to 50°C, for example ranging from 50°C to 120°C and better still greater than or equal to 60 °C, for example ranging from 60°C to 120°C, and
• - methacrylates of formula CH 2 C(CH 3 )-COORi in which Ri represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or Ri represents a C 4 to C 1 2 cycloalkyl group, preferably a Cs to C 1 2 cycloalkyl group, such as isobornyl methacrylate,
• R' denotes H or methyl.
• monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide,
• R 2 represents a C 4 to C 12 cycloalkyl group, preferably a Cs to C 12 cycloalkyl, such as isobornyl.
• the monomers and the proportions thereof are preferably chosen such that the glass transition temperature of the first block is greater than or equal to 40°C.
• the first block is obtained from:
• R' 2 represents a C4 to C 12 cycloalkyl group, preferably a Cs to C 12 cycloalkyl, such as isobornyl.
• R 2 and R' 2 simultaneously or independently represent an isobornyl group.
• the block copolymer comprises from 50% to 80% by weight of isobornyl methacrylate/acrylate, from 10% to 30% by weight of isobutyl acrylate and from 2% to 10% by weight of acrylic acid.
• the first block may be obtained exclusively from the said acrylate monomer and from the said methacrylate monomer.
• the acrylate monomer and the methacrylate monomer are preferably in mass proportions of between 30/70 and 70/30, preferably between 40/60 and 60/40 and especially of about 50/50.
• the proportion of the first block advantageously ranges from 20% to 90%, better still from 30% to 80% and even better still from 60% to 80% by weight of the polymer .
• the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.
• the second block advantageously has a glass transition temperature Tg of less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than or equal to 15°C, especially ranging from -80°C to 15°C, and better still less than or equal to 10°C, for example ranging from -100°C to 10°C and especially ranging from -30°C to 10°C.
• Tg glass transition temperature
• the monomer with a Tg of less than or equal to 20°C (known as the second monomer) is preferably chosen from the following monomers:
• R3 representing a linear or branched, unsubstituted Ci- C 1 2 alkyl group, with the exception of a tert-butyl group, in which is (are) optionally intercalated one or more heteroatoms chosen from 0, N and S;
• R 5 represents a linear or branched C4-C 1 2 alkyl group
• the preferred monomers with a Tg of less than or equal to 20°C are isobutyl acrylate and 2-ethylhexyl acrylate, or mixtures thereof in all proportions.
• This additional monomer is chosen, for example, from:
• R6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted with one or more substituents chosen from hydroxyl groups (for instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (CI, Br, I or F) , such as trifluoroethyl methacrylate,
• Rg representing a linear or branched C6 to C 1 2 alkyl group in which one or more heteroatoms chosen from 0, N and S are optionally intercalated, the said alkyl group being substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (CI, Br, I or F) ;
• Rio representing a linear or branched Ci to C 12 alkyl group substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (CI, Br, I or F) , such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or Rio represents a Ci to C 12 alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 10 times, for example methoxy-POE, or Rio represents a polyoxyethylenated group comprising from 5 to 10 ethylene oxide units.
• substituents chosen from hydroxyl groups and halogen atoms (CI, Br, I or F)
• CI, Br, I or F such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate
• Rio represents a Ci to C 12 alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 10 times, for example methoxy-POE, or Rio represents a polyoxyethy
• the first block may comprise as additional monomer:
• R 7 and Rs which may be identical or different, each represent a hydrogen atom or a linear or branched Ci to C 12 alkyl group such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R 7 represents H and Rs represents a 1 , l-dimethyl-3-oxobutyl group,
• R' denotes H or methyl.
• monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, -dimethylacrylamide and N, -dibutylacrylamide, - and mixtures thereof.
• the additional monomer may represent 0.5% to 30% by weight relative to the weight of the polymer. According to one embodiment, the polymer of the invention does not contain any additional monomer.
• the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block.
• the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportion in the first block, and isobutyl acrylate and acrylic acid monomers in the second block, the first block representing 70% of the weight of the polymer.
• the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportion in the first block, and isobutyl acrylate and acrylic acid monomers in the second block.
• the block with a Tg of greater than 40°C represents 70% of the weight of the polymer, and acrylic acid represents 5% of the weight of the polymer.
• the first block does not comprise any additional monomer.
• the second block comprises acrylic acid as additional monomer.
• the second block is advantageously obtained from an acrylic acid monomer and from at least one other monomer with a Tg of less than or equal to 20°C.
• the block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, especially from 2% to 15% by weight, for example from 3% to 15% by weight, in particular from 4% to 15% by weight or even from 4% to 10% by weight of acrylic acid monomers, relative to the total weight of the said copolymer .
• the intermediate segment (also known as the intermediate block) links the first block and the second block of the polymer used according to the present invention.
• the intermediate segment results from the polymerization:
• the formation of the second block is initiated when the first monomers no longer react or are no longer incorporated into the polymer chain, either because they are all consumed or because their reactivity no longer allows them to be.
• the intermediate segment comprises the available first monomers, resulting from a degree of conversion of these first monomers of less than or equal to 90%, during the introduction of the second monomer (s) during the synthesis of the polymer.
• the intermediate segment is a random block, as are the first block and the second block if they are not homopolymers (i.e. if they are both formed from at least two different monomers) .
• the block ethylenic copolymer according to the invention is prepared by free-radical polymerization, according to the well-known techniques for this type of polymerization.
• Free-radical polymerization is performed in the presence of an initiator whose nature is appropriate, in a known manner, as a function of the desired polymerization temperature and of the polymerization solvent.
• the initiator may be chosen from initiators containing a peroxide function, redox couples, or other radical polymerization initiators known to those skilled in the art.
• examples of initiators containing a peroxide function include:
• peroxyesters such as tert-butyl peroxyacetate, tert-butyl perbenzoate, tert-butyl peroxy-2- ethylhexanoate (Trigonox 21S from Akzo Nobel) and 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethyl- hexane (Trigonox 141 from Akzo Nobel) ;
• peroxydicarbonates such as diisopropyl peroxydicarbonate ;
• peroxy ketones such as methyl ethyl ketone peroxide
• hydroperoxides such as hydrogen peroxide (H 2 O 2 ) and tert-butyl hydroperoxide;
• dialkyl peroxides such as di-tert-butyl peroxide
• inorganic peroxides such as potassium peroxodisulfate (K2S2O8) .
• An example of an initiator in the form of a redox couple that may be mentioned is the potassium thiosulfate + potassium peroxodisulfate couple.
• the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms.
• the initiator used is 2 , 5-bis (2-ethylhexanoylperoxy) -2 , 5-dimethyl- hexane sold under the reference Trigonox® 141 by the company Akzo Nobel.
• the block copolymer used according to the invention is prepared by free-radical polymerization rather than by controlled or living polymerization.
• the polymerization of the block ethylenic copolymer is performed in the absence of control agents, and in particular in the absence of control agents conventionally used in living or controlled polymerization processes, for instance nitroxides, alkoxyamines , dithioesters , dithiocarbamates , dithiocarbonates or xanthates, trithiocarbonates and copper-based catalysts.
• the intermediate segment is a random block, as are the first block and the second block if they are not homopolymers (i.e. if they are both formed from at least two different monomers) .
• the block copolymer may be prepared by free- radical polymerization, and in particular via a process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with a glass transition temperature of greater than or equal to 40 °C and at least one monomer with a glass transition temperature of less than or equal to 20°C, according to the following sequence:
• some of the polymerization solvent and optionally some of the initiator and of the monomers of the first addition are placed in the reactor, and the mixture is heated to a reaction temperature of between 60 and 120°C,
• the said at least one first monomer with a Tg of greater than or equal to 40°C and optionally some of the initiator are then introduced, in a first addition, and the mixture is left to react for a time T corresponding to a maximum degree of conversion of the said monomers of 90%,
• reaction mixture is cooled to room temperature .
• the acrylic acid monomer and the said at least one second monomer with a glass transition temperature of less than or equal to 20°C are then placed in the reactor, in a second addition, and the mixture is left to react for a time T" after which the degree of conversion of the said monomers reaches a plateau,
• reaction mixture is cooled to room temperature.
• polymerization solvent means a solvent or a mixture of solvents.
• ketones that are liquid at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone;
• propylene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-n- butyl ether;
• short-chain esters such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate or isopentyl acetate;
• alkanes that are liquid at room temperature such as decane, heptane, dodecane, isododecane, cyclohexane or isohexadecane ;
• the polymerization solvent may be chosen especially from ethyl acetate, butyl acetate, alcohols such as isopropanol or ethanol, and aliphatic alkanes such as isododecane, and mixtures thereof.
• the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.
• the copolymer may be prepared by free-radical polymerization according to the preparation process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with a glass transition temperature of less than or equal to 20°C, and at least one monomer with a Tg of greater than or equal to 40 °C, according to the following sequence of steps:
• the said at least one monomer with a glass transition temperature of less than or equal to 20°C and optionally some of the initiator are then introduced, in a first addition, and the mixture is left to react for a time T corresponding to a maximum degree of conversion of the said monomers of 90%,
• reaction mixture is cooled to room temperature .
• reaction mixture is cooled to room temperature .
• the polymerization temperature is preferably about 90°C.
• the block ethylenic copolymer is present in the composition in an active material content ranging from 0.1% to 60%, better still from 0.5% to 50%, better still from 1% to 30% and even better still from 1% to 40% by weight relative to the total weight of the composition. Distillation of the synthesis solvent
• This step is performed at elevated temperature and optionally under vacuum to distil off a maximum amount of volatile synthesis solvent, and is known to those skilled in the art.
• the film-forming polymer present in the composition according to the invention is a vinyl polymer comprising at least one carbosiloxane dendrimer-based unit.
• the vinyl polymer may especially have a backbone and at least one side chain, which comprises a carbosiloxane dendrimer structure.
• carbosiloxane dendrimer structure in the context of the present invention represents a molecular structure with branched groups of high molecular masses with high regularity in the radial direction starting from the bond to the backbone.
• Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in the laid- open Japanese patent application Kokai 9-171 154.
• the vinyl polymer contains carbosiloxane dendrimer-based units that may be represented by the following general formula: 3
• R 1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms
• R 4 represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the methylene group and the propylene group being preferred
• R represents a hydrogen atom or an alkyl group
• R 7 represents an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, ethyl group, a propyl group or a butyl group, the methyl group being preferred
• R 8 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred
• b is an integer from 0 to 4
• c is 0 or 1 such that if c is 0, -(R 8 ) c - represents a bond
• the vinyl polymer that contains a carbosiloxane dendrimer structure may be the product of polymerization of
• Y represents an organic group that may be polymerized using radicals
• R 1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms
• R represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group containing from 1 to 10 carbon atoms
• R represents a hydrogen atom or an alkyl group
• R represents an alkyl group containing from 1 to 10 carbon atoms
• R 8 represents an alkylene group containing from 1 to 10 carbon atoms
• b is an integer from 0 to 4
• c is 0 or 1.
• the monomer of vinyl type that is component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
• a monomer of vinyl type that contains a radical-polymerizable vinyl group There is no particular limitation as regards the type of such a monomer.
• Multifunctional monomers of vinyl type may also be used.
• the following represent examples of such compounds: trimethylolpropane trimethacrylate, pentaerythrityl trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1 , 4-butanediol dimethacrylate, 1 , 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane- trioxyethyl methacrylate, tris (2-hydroxyethyl) - isocyanurate dimethacrylate, tris (2-hydroxyethyl) - isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.
• the carbosiloxane dendrimer which is component (B) , e following formula:
• radical-polymerizable organic group Y an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4 -vinylphenyl group, a 3-vinylphenyl group, a 4- (2-propenyl) phenyl group, a 3- (2-propenyl) phenyl group, a 2- (4-vinylphenyl) ethyl group, a 2- (3-vinylphenyl) ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
• R 1 represents an alkyl group or an aryl group containing from 1 to 10 carbon atoms, in which the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group; and the aryl group may be a phenyl group or a naphthyl group.
• the methyl and phenyl groups are particularly preferred, the methyl group being preferred among all.
• X 1 represents a silylalkyl group that is represented by the following formula, when
• R represents an alkylene group containing from 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group or a similar linear alkylene group; a methylmethylene group, a methylethylene group, a 1- methylpentylene group, a 1 , 4-dimethylbutylene group or a similar branched alkylene group.
• the ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4- dimethylbutylene groups are preferred among all.
• R 3 represents an alkyl group containing from 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl and isopropyl groups.
• R 1 is the same as defined above.
• a 1 is an integer from 0 to 3
• i is an integer from 1 to 10 that indicates the generation number, which represents the number of repetitions of the silylalkyl group.
• the carbosiloxane dendrimer may be represented by the first general formula shown below, in which Y, R 1 , R 2 and R 3 are the same as defined above, R 12 represents a hydrogen atom or is identical to R 1 ; a 1 is identical to a 1 .
• the mean total number of groups OR 3 in a molecule is within the range from 0 to 7.
• the carbosiloxane dendrimer may be represented by the second general formula shown below, in which Y, R 1 , R 2 , R 3 and R 12 are the same as defined above; a 1 and a 2 represent the a 1 of the indicated generation.
• a carbosiloxane dendrimer that contains a radical- polymerizable organic group may be represented by the following mean structural formulae:
• the carbosiloxane dendrimer may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.
• it may be produced by subjecting an organosilicon compound containing a hydrogen atom linked to a silicon atom, represented by the following general formula:
• the organosilicon compound may be represented by 3-methacryloxypropyltris (dimethyl- siloxy) silane, 3-acryloxypropyltris (dimethylsiloxy) - silane and 4-vinylphenyltris (dimethylsiloxy) silane .
• the organosilicon compound that contains an alkenyl group may be represented by vinyltris (trimethylsiloxy) silane, vinyltris (dimethylphenylsiloxy) silane, and 5-hexenyl- tris (trimethylsiloxy) silane .
• the hydrosilylation reaction is performed in the presence of a chloroplatinic acid, a complex of vinylsiloxane and of platinum, or a similar transition metal catalyst.
• the polymerization ratio between the components (A) and (B) in terms of the weight ratio between (A) and (B) , may be within the range from 0/100 to 99.9/0.1 and preferably within the range from 1/99 to 99/1.
• a ratio between the components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B) .
• the vinyl polymer contains a carbosiloxane dendrimer structure and this polymer may be obtained by copolymerization of the components (A) and (B) , or by polymerization of the component (B) alone.
• the polymerization may be a free-radical polymerization or an ionic polymerization, but free-radical polymerization is preferred.
• the polymerization may be performed by bringing about a reaction between the components (A) and (B) in a solution for a period of from 3 to 20 hours in the presence of a radical initiator at a temperature of from 50°C to 150°C.
• a suitable solvent for this purpose is hexane, octane, decane, cyclohexane or a similar aliphatic hydrocarbon; benzene, toluene, xylene or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate or similar esters; methanol, ethanol, isopropanol, butanol or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane or a similar
• a radical initiator may be any compound known in the art for standard free-radical polymerization reactions.
• the specific examples of such radical initiators are 2, 2' -azobis (isobutyronitrile) , 2,2'- azobis (2-methylbutyronitrile) , 2 , 2 ' -azobis (2 , 4- dimethylvaleronitrile) or similar compounds of azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or a similar organic peroxide.
• These radical initiators may be used alone or in a combination of two or more.
• the radical initiators may be used in an amount of from 0.1 to 5 parts by weight per 100 parts by weight of the components (A) and (B) .
• a chain-transfer agent may be added.
• the chain-transfer agent may be 2- mercaptoethanol , butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethyl- siloxane containing a mercaptopropyl group or a similar compound of mercapto type; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3- chloropropyltrimethoxysilane or a similar halogenated compound.
• the residual unreacted vinyl monomer may be removed under conditions of heating under vacuum.
• the number- average molecular mass of the vinyl polymer containing a carbosiloxane dendrimer may be chosen within the range between 3000 and 2 000 000 and preferably between 5000 and 800 000. It may be a liquid, a gum, a paste, a solid, a powder or any other form.
• the preferred forms are solutions consisting of the dilution of a dispersion or of a powder in solvents.
• the vinyl polymer may be a dispersion of a polymer of vinyl type having a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
• the vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain is the same as that described above.
• the liquid may be a silicone oil, an organic oil, an alcohol or water.
• the silicone oil may be a dimethylpolysiloxane with the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3 , 3 , 3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethyl- cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclo- hexas
• the organic oils may be liquid paraffin, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef tallow, lard, polypropylene glycol monooleate, neopentyl glycol 2-ethyl
• the alcohol may be any type that is suitable for use in combination with a cosmetic product starting material.
• it may be methanol, ethanol, butanol, isopropanol or similar lower alcohols.
• a solution or a dispersion of the alcohol should have a viscosity within the range from 10 to 10 9 mPa at 25°C. To improve the sensory use properties in a cosmetic product, the viscosity should be within the range from 100 to 5 x 10 8 mPa.s.
• the solutions and dispersions may be readily prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure with a silicone oil, an organic oil, an alcohol or water.
• the liquids may be present in the step of polymerization of the polymer of vinyl type having a carbosiloxane dendrimer structure.
• the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure.
• the dispersity of the polymer of vinyl type may be improved by adding a surfactant.
• Such an agent may be hexyl- benzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethyl- ammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow- trimethylammonium hydroxide, coconut oil- trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether
• the solvents and dispersions may be combined with iron oxide suitable for use with cosmetic products, or a similar pigment, and also zinc oxide, titanium oxide, silicon oxide, mica, talc or similar mineral oxides in powder form.
• a mean particle diameter of the polymer of vinyl type may be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns. The reason for this is that, outside the recommended range, a cosmetic product mixed with the emulsion will not have a nice enough feel on the skin or to the touch, or sufficient spreading properties or a pleasant feel .
• the vinyl polymer contained in the dispersion or the solution may have a concentration in the range between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
• the vinyl polymer may be one of the polymers described in the examples of patent application EP 0 963 751 or, for example, the product TIB-4-200 sold by Dow Corning.
• the vinyl polymer also comprises at least one organofluorine group.
• polymerized vinyl units constitute the backbone and carbosiloxane dendritic structures and also organofluorine groups are attached to side chains are particularly preferred.
• the groups represented by -CH 2 CH 2 - (CF 2 ) m -CFR 14 - [OCF 2 CF (CF 3 ) ] n -OC 3 F 7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups.
• the index "m” is 0 or 1
• "n” is 0, 1, 2, 3, 4 or 5
• R 14 is a fluorine atom CF 3 .
• fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxy- fluoroalkylene groups represented by the formulae presented below:
• the number-average molecular weight of the vinyl polymer used in the present invention may be between 3000 and 2 000 000 and more preferably between 5000 and 800 000.
• R 15 is a hydrogen atom or a methyl group
• R f is an organofluorine group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above.
• the compounds represented by the formulae presented below are suggested as specific examples of the component (A) . In the formulae presented below "z" is an integer from 1 to 4.
• CH 2 CCH 3 COO-nC 6 F 13
• CH 2 CCH 3 COO-nC 8 F 17
• CH 2 CCH 3 COO-CH 2 CF 3
• CH 2 CCH 3 COO-CH 2 CH 2 CH 2 (CF 2 ) 2 F
• CH 2 CCH 3 COO-CH 2 CH 2 CH 2 (CF 2 ) 2 H
• CH 2 CCH 3 COO-CH 2 (CF 2 ) 4 H
• CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 3 H
• CH 2 CCH 3 COO-CH 2 CH 2 CF (CF 3 ) - [OCF 2 CF (CF 3 ) ] z -OC 3 F 7 ,
• CH 2 CHCOO-CH 2 CF 3
• CH 2 CHCOO-CH (CF 3 ) 2
• CH 2 CHCOO- CH 2 CH(CF 3 ) 2
• CH 2 CHCOO-CH 2 (CF 2 ) 2 F
• CH 2 CHCOO-CH 2 (CF 2 ) 3 F
• CH 2 CHCOO-CH 2 (CF 2 ) 4 F
• CH 2 CHCOO-CH 2 (CF 2 ) 6 F
• CH 2 CHCOO- CH 2 (CF 2 ) 8 F
• CH 2 CHCOO-CH 2 CH 2 CF 3
• CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 2 F
• CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 3 F
• CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 4 F
• CH 2 CHCOO-CH 2 CH 2 CH 2 (CF 2 ) 2 H
• CH 2 CHCOO-CH 2 (CF 2 ) 4 H
• vinyl polymers represented by the formulae presented below are preferable:
• CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 6 F
• CH 2 CHCOO-CH 2 CH 2 (CF 2 ) 8 F
• CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 6 F
• CH 2 CCH 3 COO-CH 2 CH 2 (CF 2 ) 8 F
• CH 2 CHCOO-CH 2 CF 3
• CH 2 CCH 3 COO-CH 2 CF 3
• the vinyl polymers represented by the formulae presented below are particularly preferable.
• CH 2 CHCOO-CH 2 CF 3
• CH 2 CCH 3 COO-CH 2 CF 3 .
• the vinyl monomers (B) not containing any organofluorine groups in the molecule may be any monomer containing radical-polymerizable vinyl groups illustrated, for example, by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate , n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates ; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl acrylate, n-hexyl acrylate, n-hex
• vinyl monomers (B) the polyfunctional vinyl monomers illustrated, for example, by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrityl triacrylate, pentaerythrityl trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1 , 4-butanediol diacrylate, 1 , 4-butanediol dimethacrylate, 1 , 6-hexanediol diacrylate, 1,6-hexane- diol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane- trioxyethyl acrylate, trimethylolpropane- trioxyethyl
• the weight ratio of compound (A) to compound (B) should be within the range from 0.1:99.9 to 100:0 and preferably within the range 1:99 to 100:0.
• R 4 and R 6 are hydrogen atoms or methyl groups
• R 5 and R 8 are alkylene groups of 1 to 10 carbon atoms
• R 7 is an alkyl group of 1 to 10 carbon atoms.
• the index "b” is an integer from 0 to 4 and "c” is 0 or 1.
• the index "i" in formula (II), which is an integer from 1 to 10, is the number of generations of the said silylalkyl group, in other words the number of times that the silylalkyl group is repeated.
• the carbosiloxane dendrimer of this component with a generation number of 1 is represented by the general formula:
• the carbosiloxane dendrimers of this component with a generation number of 2 are represented by the general formula:
• the carbosiloxane dendrimers of this component with a generation number of 3 are represented by the ge
• CH a CH- Si tOSi-C 3 ⁇ 4 H - Si-(OSi-H) 3 ⁇ 3
• the carbosiloxane dendrimers of the component (C) may be prepared using the process for preparing siloxane/silylalkylene branched copolymers described in document EP 1 055 674.
• they may be prepared by subjecting organic alkenyl silicones and silicone compounds comprising hydrogen atoms linked to silicon, represented by the general formula:
• the copolymerization ratio of the component (C) in terms of its weight ratio relative to the total weight of compound (A) and (B) should be within the range from 0.1:99.9 to 99.9:0.1, preferably within the range from 1:99 to 99:1 and even more preferably within the range from 5:95 to 95:5.
• Amino groups may be introduced into the side chains of the vinyl polymer using, included in the component (B) , vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethyl- aminoethyl methacrylate, followed by performing a modification with potassium acetate monochloride , ammonium acetate monochloride, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids; otherwise, carboxylic acid groups may be introduced into the side chains of the vinyl polymer using, included in the component (B) , vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid, and the like,
• the vinyl polymer may be present in a content ranging from 0.1% to 70% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 50% by weight, preferentially ranging from 1% to 40% by weight and more preferably ranging from 5% to 15% by weight.
• the vinyl polymer may be present in the composition in a proportion of at least 3% by weight in the composition, preferably between 5% and 25% by weight, more preferably between 5% and 15% by weight and especially about 10% by weight.
• the film-forming polymer present in the composition according to the invention is a dispersion of acrylic or vinyl radical homopolymer or copolymer particles dispersed in the liquid fatty phase of the composition.
• composition according to the invention advantageously comprises at least one stable dispersion of generally spherical polymer particles of one or more polymers, in a volatile liquid fatty phase.
• These dispersions may especially be in the form of polymer nanoparticles in stable dispersion in the said liquid organic phase.
• the nanoparticles preferably have a mean size of between 5 and 800 nm and better still between 50 and 500 nm. However, it is possible to obtain polymer particles ranging up to 1 ym in size.
• the polymer particles in dispersion are insoluble in water-soluble alcohols, for instance ethanol.
• the polymers in dispersion that may be used in the composition of the invention preferably have a molecular weight of about from 2000 to 10 000 000 g/mol and a Tg of from -100°C to 300°C, better still from -50°C to 100°C and preferably from -10°C to 50°C.
• film-forming polymers preferably having a low Tg, of less than or equal to skin temperature and especially less than or equal to 40°C.
• the polymer used is film-forming, i.e. it is capable of forming an isolable film, by itself or in combination with a plasticizer. It is, however, possible to use a non-film-forming polymer.
• non-film-forming polymer means a polymer that is incapable of forming an isolable film by itself. This polymer can, in combination with a nonvolatile compound of the oil type, form a continuous, uniform deposit on the skin and/or the lips.
• film-forming polymers that may be mentioned are acrylic or vinyl radical homopolymers or copolymers, preferably with a Tg of less than or equal to 40°C and especially ranging from -10°C to 30°C, used alone or as a mixture.
• non-film-forming polymers that may be mentioned are optionally crosslinked vinyl or acrylic radical homopolymers or copolymers preferably with a Tg of greater than 40°C and especially ranging from 45°C to 150°C, used alone or as a mixture.
• radical polymer means a polymer obtained by polymerization of unsaturated and especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates ) .
• the radical polymers may especially be vinyl polymers or copolymers, especially acrylic polymers.
• the acrylic polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acid monomers and/or amides of these acids.
• the acid monomer esters are advantageously chosen from (meth) acrylic acid esters (also known as (meth) acrylates ) , for instance alkyl (meth) acrylates , in particular of a C1 - C20 and preferably Ci - Cs alkyl, aryl (meth) acrylates , in particular of a C6- C10 aryl, and hydroxyalkyl (meth) acrylates , in particular of a C2-C6 hydroxyalkyl.
• Alkyl (meth) acrylates that may be mentioned include methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth) acrylate .
• Hydroxyalkyl (meth) acrylates that may be mentioned include hydroxy- ethyl (meth) acrylate and 2-hydroxypropyl (meth) - acrylate.
• Aryl (meth) acrylates that may be mentioned include benzyl or phenyl acrylate.
• the (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .
• Radical polymers that are preferably used include copolymers of (meth) acrylic acid and of alkyl (meth) acrylate, especially of a C1-C4 alkyl. Methyl acrylates optionally copolymerized with acrylic acid may more preferentially be used.
• Amides of the acid monomers that may be mentioned include (meth) acrylamides , especially N-alkyl (meth) - acrylamides, in particular of a C2 - C12 alkyl, such as N-ethylacrylamide, N-t-butylacrylamide and N-octylacrylamide ; N-di (C 1 -C4) alkyl (meth) acrylamides .
• the vinyl polymers may also result from the homopolymerization or copolymerization of at least one monomer chosen from vinyl esters and styrene monomers.
• these monomers may be polymerized with acid monomers and/or esters thereof and/or amides thereof, such as those mentioned previously.
• vinyl esters that may be mentioned include vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate .
• Styrene monomers that may be mentioned include styrene and -methylstyrene .
• N-vinylpyrrolidone N-vinylcaprolactam
• vinyl-N- (C1-C6) alkylpyrroles vinyloxazoles
• vinylthiazoles vinylpyrimidines and vinylimidazoles
• the vinyl polymer may be crosslinked with one or more difunctional monomers especially comprising at least two ethylenic unsaturations , such as ethylene glycol di (meth) acrylate or diallyl phthalate.
• grafted polymers that may be mentioned are silicone polymers grafted with a hydrocarbon-based chain; hydrocarbon-based polymers grafted with a silicone chain.
• grafted-block or block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a polyether.
• the polyorganosiloxane block may especially be a polydimethylsiloxane or a poly (C 2 -C18) alkylmethyl- siloxane;
• the polyether block may be a poly (C 2 -C18) - alkylene, in particular polyoxyethylene and/or polyoxy- propylene.
• dimethicone copolyols or (C 2 - C18) alkyldimethicone copolyols such as those sold under the name Dow Corning 3225C by the company Dow Corning, and lauryl methicones such as those sold under the name Dow Corning Q2-5200 by the company Dow Corning, may be used .
• Grafted-block or block copolymers that may also be mentioned include those comprising at least one block resulting from the polymerization of at least one ethylenic monomer containing one or more optionally conjugated ethylenic bonds, for instance ethylene or dienes such as butadiene and isoprene, and of at least one block of a vinyl polymer and better still a styrene polymer.
• the ethylenic monomer comprises several optionally conjugated ethylenic bonds
• the residual ethylenic unsaturations after the polymerization are generally hydrogenated .
• polystyrene/polyisoprene SI
• polystyrene/polybutadiene SB
• Luvitol HSB Luvitol HSB
• SEP polystyrene/copoly (ethylene-propylene)
• polystyrene/copoly (ethylene- butylene) SEB
• Kraton G1650 SEBS
• Kraton G1651 SEBS
• Kraton G1652 SEBS
• Kraton G1657X SEBS
• Kraton G1701X SEP
• Kraton G1702X SEP
• Kraton G1726X SEB
• Kraton D-1101 SBS
• SBS Kraton D-1102
• SIS Kraton D-1107
• the polymers are generally known as hydrogenated or non- hydrogenated diene copolymers.
• polystyrene/methacrylate copolymer may also be used.
• grafted-block or block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer containing one or more ethylenic bonds and of at least one block of an acrylic polymer, mention may be made of poly (methyl methacrylate) /polyisobutylene diblock or triblock copolymers or grafted copolymers containing a poly (methyl methacrylate) skeleton and polyisobutylene grafts .
• Copolymers based on alkyl acrylates or (meth) acrylates derived from C 1 -C4 alcohols and on alkyl acrylates or (meth) acrylates derived from C8-C30 alcohols may thus be used. Mention may be made in particular of stearyl (meth) acrylate/methyl methacrylate copolymer.
• the stabilizer is preferably chosen from the group consisting of grafted-block or block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a free-radical polymer or of a polyether or of a polyester, for instance polyoxypropylene and/or polyoxyethylene blocks.
• the stabilizer is preferably chosen from the group formed by:
• grafted-block or block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or of a polyether or a polyester, (b) copolymers of alkyl acrylates or methacrylates derived from C1-C4 alcohols and of alkyl acrylates or methacrylates derived from C8-C30 alcohols, - (c) grafted-block or block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer containing conjugated ethylenic bonds,
• Diblock polymers are preferably used as stabilizer.
• a plasticizer may be combined therewith.
• the plasticizer may be chosen from the plasticizers usually used in the field of application and especially from compounds liable to be solvents for the polymer. Coalescers may also be used in order to aid the polymer to form a continuous and homogeneous deposit.
• coalescers or plasticizers that may be used in the invention are especially those mentioned in document FR-A-2 782 917.
• the composition may contain a polymer plasticizer, so as to lower the Tg of the polymer film and to improve the adhesion of the polymer film to its support, in particular to keratin materials.
• the plasticizer especially lowers the glass transition temperature of the polymer by at least 2, 3 or 4°C and preferably from 5°C to 20°C. In one preferred embodiment, the plasticizer especially lowers the glass transition temperature of the polymer by at least 2, 3 or 4°C and preferably from 5°C to 20°C, when the plasticizer represents not more than 10% by weight of the polymer.
• the polyol according to the invention is preferably a disaccharide .
• disaccharides that may be mentioned are sucrose ( -D-glucopyranosyl- ( 1-2 ) - ⁇ -D-fructofuranose) , lactose ( ⁇ -D-galactopyranosyl- ( 1- 4 ) - ⁇ -D-glucopyranose) and maltose ( -D-glucopyranosyl- ( 1-4 ) - ⁇ -D-glucopyranose) .
• the plasticizer may be formed from a polyol substituted with at least two different monocarboxylic acids, or with at least three different monocarboxylic acids.
• the acid is preferably a monocarboxylic acid chosen in particular from acids comprising 1 to 7 carbon atoms and preferably 1 to 5 carbon atoms, for example acetic acid, n-propanoic acid, isopropanoic acid, n-butanoic acid, isobutanoic acid, tert-butanoic acid, n-pentanoic acid and benzoic acid.
• the ester is sucrose diacetate hexakis (2-methylpropanoate) .
• the polymer dispersion may be manufactured as described in document EP-A-749 747.
• a mixture comprising the initial monomers and also a radical initiator is prepared. This mixture is dissolved in a solvent referred to hereinbelow in the present description as the "synthesis solvent".
• the fatty phase is a non-volatile oil
• the polymerization may be performed in an apolar organic solvent (synthesis solvent) , followed by adding the non-volatile oil (which should be miscible with the said synthesis solvent) and selectively distilling off the synthesis solvent.
• a synthesis solvent which is such that the initial monomers and the radical initiator are soluble therein, and the polymer particles obtained are insoluble therein, so that they precipitate during their formation, is chosen.
• the synthesis solvent may be chosen from alkanes such as heptane, isododecane and cyclohexane.
• the polymerization may be performed directly in the said oil, which thus also acts as synthesis solvent.
• the monomers should also be soluble therein, as should the radical initiator, and the polymer obtained should be insoluble therein.
• the monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5-20% by weight of the reaction mixture.
• the total amount of monomers may be present in the solvent before the start of the reaction, or part of the monomers may be added gradually as the polymerization reaction proceeds.
• the radical initiator may especially be azobisisobutyronitrile or tert-butylperoxy-2-ethyl hexanoate .
• the volatile phase of the composition may be formed from or comprise the synthesis solvent for the dispersed polymer particles.
• composition according to the invention may comprise as additional ingredient, combined with the said compound A described previously, at least one structuring agent chosen from semicrystalline polymers and thickeners comprising at least one group and preferably at least two groups capable of establishing hydrogen interactions, chosen from polymeric thickeners and organogelling agents.
• structuring agent chosen from semicrystalline polymers and thickeners comprising at least one group and preferably at least two groups capable of establishing hydrogen interactions, chosen from polymeric thickeners and organogelling agents.
• the presence of such a structuring agent may especially make it possible to improve the application qualities of the composition and the comfort of the deposit when it is applied to keratin materials.
• the structuring agent is a semicrystalline polymer.
• a supramolecular compound as described previously with a semicrystalline polymer especially makes it possible, in particular in compositions for making up or caring for keratin materials, and particularly the skin or the lips, to obtain uniform mixing and a glossy, non-tacky deposit on the keratin materials.
• the total amount of semicrystalline polymer (s) represents from 0.1% to 50%, better still from 0.5% to 40% and even better still from 1% to 20% of the total weight of the composition.
• polymers means compounds containing at least two repeating units, preferably at least three repeating units and more especially at least ten repeating units.
• the term "semicrystalline polymers” means polymers comprising a crystallizable portion and an amorphous portion in the backbone and having a first-order reversible change of phase temperature, in particular of melting (solid- liquid transition) .
• the crystallizable portion is either a side chain (or pendent chain) or a block in the backbone.
• the crystallizable portion of the semicrystalline polymer is a block of the polymer backbone
• this crystallizable block has a different chemical nature from that of the amorphous blocks; in this case, the semicrystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type.
• the semicrystalline polymer may be a homopolymer or a copolymer .
• organic compound and “having an organic structure” mean compounds containing carbon atoms and hydrogen atoms and optionally heteroatoms such as S, 0, N or P, alone or in combination.
• the melting point of the semicrystalline polymer is preferably less than 150°C.
• the semicrystalline polymer (s) according to the invention are solid at room temperature (25°C) and atmospheric pressure (760 mmHg) , with a melting point of greater than or equal to 30°C.
• the melting point values correspond to the melting point measured using a differential scanning calorimeter (DSC) , such as the calorimeter sold under the name DSC 30 by the company Mettler, with a temperature rise of 5 or 10°C per minute. (The melting point under consideration is the point corresponding to the temperature of the most endothermic peak of the thermogram) .
• the semicrystalline polymer (s) according to the invention preferably have a melting point that is higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the lips.
• the semicrystalline polymer (s) according to the invention may be capable, alone or as a mixture, of structuring the composition without addition of a particular surfactant, or filler or wax.
• the semicrystalline polymers are advantageously soluble in the fatty phase, especially to at least 1% by weight, at a temperature that is higher than their melting point.
• the blocks of the polymers are amorphous.
• the expression “crystallizable chain or block” means a chain or block which, if it were obtained alone, would change from the amorphous state to the crystalline state reversibly, depending on whether one is above or below the melting point.
• a “chain” is a group of atoms, which are pendent or lateral relative to the polymer backbone.
• a “block” is a group of atoms belonging to the backbone, this group constituting one of the repeating units of the polymer.
• the polymer backbone of the semicrystalline polymers is soluble in the fatty phase.
• the crystallizable blocks or chains of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%.
• the semicrystalline polymers containing crystallizable side chains are homopolymers or copolymers.
• the semicrystalline polymers of the invention containing crystallizable blocks are block or multiblock copolymers. They may be obtained by polymerizing a monomer containing reactive (or ethylenic) double bonds or by polycondensation .
• the polymers of the invention are polymers containing crystallizable side chains, these side chains are advantageously in random or statistical form.
• the semicrystalline polymers of the invention are of synthetic origin. According to one preferred embodiment of the invention, the semicrystalline polymers of the invention do not comprise a polysaccharide backbone.
• the semicrystalline polymer is chosen from:
• homopolymers and copolymers comprising units resulting from the polymerization of one or more monomers bearing crystallizable hydrophobic side chains ,
• the semicrystalline polymers that may be used in the invention may be chosen in particular from:
• polycondensates especially of aliphatic or aromatic polyester type or of aliphatic/aromatic polyester type,
• homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing at least one crystallizable block in the backbone for instance those described in document US-A-5 156 911,
• They are homopolymers or copolymers comprising from 50% to 100% by weight of units resulting from the polymerization of one or more monomers bearing a crystallizable hydrophobic side chain.
• the polymerization especially the free- radical polymerization, of one or more monomers containing reactive or ethylenic double bond(s) with respect to a polymerization, namely a vinyl, (meth) acrylic or allylic group,
• polyesters from the polycondensation of one or more monomers bearing co-reactive groups (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate) , for instance polyesters, polyurethanes , polyethers, polyureas or polyamides.
• monomers bearing co-reactive groups for instance polyesters, polyurethanes , polyethers, polyureas or polyamides.
• the crystallizable units (chains or blocks) of the semicrystalline polymers according to the invention are derived from monomer (s) containing crystallizable block (s) or chain (s), used for manufacturing semicrystalline polymers. These polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain (s) that may be represented by formula X:
• the crystallizable chains "-S-C” may be aliphatic or aromatic, and optionally fluorinated or perfluorinated .
• “S” especially represents a group (CH 2 ) n , (CH 2 CH 2 0) n or (CH 2 0) , which may be linear or branched or cyclic, with n being an integer ranging from 0 to 22.
• “S” is a linear group.
• "S" and “C” are different.
• the crystallizable chains are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least 11 carbon atoms and not more than 40 carbon atoms and better still not more than 24 carbon atoms. They are especially aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably C14-C24 , preferably C16-C22 alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least 11 carbon atoms, at least 6 of which carbon atoms are fluorinated .
• semicrystalline homopolymers or copolymers containing crystallizable chain mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth) acrylates of saturated alkyls with the alkyl group being C14- C24 , perfluoroalkyl (meth) acrylates with a C11-C15 perfluoroalkyl group, N-alkyl (meth) acrylamides with the alkyl group being C14 to C24 with or without a fluorine atom, vinyl esters containing alkyl or perfluoroalkyl chains with the alkyl group being C14 to C24 (with at least 6 fluorine atoms per perfluoroalkyl chain) , vinyl ethers containing alkyl or perfluoroalkyl chains with the alkyl group being C14 to C24 and at least 6 fluorine atoms per perfluoroalkyl chain, C14 to C24 oc-olefin
• the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate .
• polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization :
• Y which is a polar or non-polar monomer or a mixture of the two;
• Y is a polar monomer, it is either a monomer bearing polyoxyalkylenated groups (especially oxyethylenated and/or oxypropylenated groups), a hydroxyalkyl (meth) acrylate, for instance hydroxyethyl acrylate, (meth) acrylamide, an N-alkyl (meth) acrylamide, an N, -dialkyl (meth) acrylamide such as, for example, N, -diisopropylacrylamide or N-vinylpyrrolidone (NVP) , N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride, and mixtures thereof.
• a monomer bearing polyoxyalkylenated groups especially oxyethylenated and/
• Y When Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth) acrylate type, a vinyl ester, an alkyl vinyl ether, an OC-olefin, styrene or styrene substituted with a Ci to Cio alkyl group, for instance -methylstyrene, or a macromonomer of the polyorganosiloxane type containing vinyl unsaturation .
• alkyl means a saturated group especially of Cs to C24, except where otherwise mentioned.
• Z which is a polar monomer or a mixture of polar monomers.
• Z has the same definition as the "polar Y" defined above.
• the semicrystalline polymers containing a crystallizable side chain are alkyl (meth) acrylate or alkyl (meth) acrylamide homopolymers with an alkyl group as defined above, and especially of C14-C24, copolymers of these monomers with a hydrophilic monomer preferably of different nature from (meth) acrylic acid, for instance N-vinylpyrrolidone or hydroxyethyl (meth) acrylate, and mixtures thereof.
• the semicrystalline polymer (s) containing a crystallizable side chain has (have) a weight-average molecular mass Mp ranging from 5000 to 1 000 000, preferably from 10 000 to 800 000, preferentially from 15 000 to 500 000 and more preferably from 100 000 to 200 000.
• the product Intelimer® IPA 13-1 from the company Landec is chosen, which is a polystearyl acrylate with a molecular weight of about 145 000 and a melting point of 49°C.
• the semicrystalline polymers may in particular be semicrystalline polymers with crystallizable pendent chains comprising fluoro groups, as described in Examples 1, 4, 6, 7 and 8 of document WO-A-01/19333.
• the polymer bearing at least one crystallizable block in the backbone may be chosen from block copolymers of olefin or of cycloolefin containing a crystallizable chain, for instance those derived from the block polymerization of:
• cyclobutene cyclohexene, cyclooctene, norbornene (i.e. bicyclo (2.2.1 ) -2-heptene)
• norbornene i.e. bicyclo (2.2.1 ) -2-heptene
• 5- methylnorbornene 5-ethylnorbornene, 5, 6- dimethylnorbornene, 5, 5, 6-trimethylnorbornene, 5- ethylidenenorbornene, 5-phenylnorbornene, 5- benzylnorbornene, 5-vinylnorbornene, 1, 4, 5, 8-dimethano- 1,2,3,4, 4a, 5, 8a-octahydronaphthalene,
• copoly (ethylene/norbornene) blocks and (ethylene/propylene/ethylidene-norbornene) block terpolymers Those resulting from the block copolymerization of at least two C2-C16, better still C2-C 1 2 -olefins such as those mentioned above and in particular block bipolymers of ethylene and of 1-octene may also be used.
• the polymer bearing at least one crystallizable block in the backbone may be chosen from copolymers containing at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature) . These copolymers may also contain two crystallizable blocks of different chemical nature.
• Amorphous and lipophilic block for instance: amorphous polyolefins or copoly (olefin) s such as poly (isobutylene) , hydrogenated polybutadiene or hydrogenated poly (isoprene) .
• amorphous polyolefins or copoly (olefin) s such as poly (isobutylene) , hydrogenated polybutadiene or hydrogenated poly (isoprene) .
• poly ( ⁇ -caprolactone) -b-poly (butadiene) block copolymers preferably used hydrogenated, such as those described in the article D6 "Melting behavior of poly (-caprolactone) -block-polybutadiene copolymers" from S. Nojima, Macromolecules , 32, 3727-3734 (1999), ⁇ ) the hydrogenated block or multiblock poly (butylene terephthalate) -b-poly (isoprene) block copolymers cited in the article D7 "Study of morphological and mechanical properties of PP/PBT" by B. Boutevin et al . , Polymer Bulletin, 34, 117-123 (1995) ,
• the polyester polycondensates may be chosen from aliphatic polyesters. Their molar mass is preferably greater than or equal to 200 and less than or equal to 10 000, and more preferably greater than or equal to 300 and less than or equal to 5000, preferably greater than or equal to 500 and greater than or equal to 2000 g/mol.
• the polyester polycondensates are in particular chosen from polycaprolactones .
• the polycaprolactones may be chosen from ⁇ -caprolactone homopolymers .
• the homopolymeri zation may be initiated with a diol, especially a diol containing from 2 to 10 atoms, such as diethylene glycol, 1 , 4-butanediol or neopentyl glycol.
• Polycaprolactones may be used for example, especially those sold under the name CAPA® 240 (melting point of 68°C and molecular weight of 4000), 223 (melting point of 48°C and molecular weight of 2000), 222 (melting point of 48°C and molecular weight of 2000), 217 (melting point of 44°C and molecular weight of 1250), 2125 (melting point of 45°C and molecular weight of 1250), 212 (melting point of 45°C and molecular weight of 1000), 210 (melting point of 38°C and molecular weight of 1000), 205 (melting point of 39°C and molecular weight of 830) by the company Solvay, or PCL-300 and PCL-700 by the company Union Carbide .
• CAPA® 240 melting point of 68°C and molecular weight of 4000
• 223 melting point of 48°C and molecular weight of 2000
• 222 melting point of 48°C and molecular weight of 2000
• the semicrystalline polymers in the composition of the invention may or may not be partially crosslinked, provided that the degree of crosslinking does not interfere with their dissolution or dispersion in the fatty phase by heating above their melting point. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It may also be a physical crosslinking which may, in this case, be due either to the establishment of bonds of hydrogen or dipolar type between groups borne by the polymer, such as, for example, the dipolar interactions between carboxylate ionomers, these interactions being of small amount and borne by the polymer backbone; or to a phase separation between the crystallizable blocks and the amorphous blocks borne by the polymer.
• the semicrystalline polymers in the composition according to the invention are non- crosslinked.
• the semicrystalline polymer of the composition of the invention may also be a waxy polymer obtained via metallocene catalysis, such as those described in patent US 2007/0 031 361, the content of which is incorporated herein by reference.
• the weight-average molecular mass (Mw) of the waxes obtained via metallocene catalysis described in this document is less than or equal to 25 000 g/mol and ranges, for example, from 2000 to 22 000 g/mol and better still from 4000 to 20 000 g/mol.
• the number-average molecular mass (Mn) of the waxes obtained via metallocene catalysis described in this document is preferably less than or equal to 15 000 g/mol and ranges, for example, from 1000 to 12 000 g/mol and better still from 2000 to 10 000 g/mol.
• the polydispersity index I of the polymer is equal to the ratio of the weight-average molecular mass Mw to the number-average molecular mass Mn .
• the polydispersity index of the waxy polymers is between 1.5 and 10, preferably between 1.5 and 5, preferably between 1.5 and 3 and better still between 2 and 2.5.
• the waxy homopolymers and copolymers may be obtained in a known manner from ethylene and/or propylene monomers, for example via metallocene catalysis according to the process described in document EP 571 882, the content of which is incorporated herein by reference.
• the ethylene and/or propylene homopolymers and copolymers prepared via metallocene catalysis may be unmodified or "polar"-modified (i.e. modified such that they contain polar groups) .
• the polar-modified waxy homopolymers and copolymers may be prepared in a known manner from unmodified waxy homopolymers and copolymers such as those described previously by oxidation with gases containing oxygen, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or alternatively derivatives of these acids.
• the polar- modified ethylene and/or propylene homopolymers and copolymers prepared via metallocene catalysis that are particularly preferred are polymers modified such that they have hydrophilic properties.
• examples that may be mentioned include ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP) , etc.
• Waxy ethylene and/or propylene homopolymers or copolymers modified by the presence of hydrophilic groups such as maleic anhydride or acrylate are particularly preferred.
• polypropylene waxes modified with maleic anhydride (PPMA) sold by the company Clariant or polypropylene-ethylene-maleic anhydride copolymers, such as those sold by the company Clariant under the name LicoCare, for instance LicoCare PP207 LP3349, LicoCare CM401 LP3345, LicoCare CA301 LP3346 and LicoCare CA302 LP3347, or
• a polar-modified waxy polymer with a low degree of crystallinity preferably of less than 40%, will be preferred .
• the total amount of modified or unmodified waxy polymers represents from 0.1% to 30%, better still from 0.5% to 20% and even better still from 1% to 15% of the total weight of the composition.
• the composition according to the invention comprises at least one thickener comprising at least one group and preferably at least two groups capable of establishing hydrogen interactions, chosen from polymeric thickeners and organogelling agents.
• a supramolecular compound as described previously with a thickener capable of establishing hydrogen interactions especially makes it possible, in particular in compositions for making up or caring for keratin materials, and particularly the skin or the lips, to obtain uniform mixing and a glossy and preferably non-tacky deposit on the keratin materials .
• the polymeric thickeners used comprising at least one unit comprising at least one group and preferably at least two groups capable of establishing hydrogen interactions may belong to the following two families:
• polymers comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.
• polymer means a compound containing at least two repeating units and preferably at least three repeating units .
• hydrocarbon-based repeating unit means a unit comprising from 2 to 80 carbon atoms and preferably from 2 to 60 carbon atoms, bearing hydrogen atoms and optionally oxygen atoms, which may be linear, branched or cyclic, and saturated or unsaturated. These units each also comprise one or more nonpendent heteroatoms that are in the polymer backbone. These heteroatoms are chosen from nitrogen, sulfur, phosphorus and silicon atoms and combinations thereof, optionally combined with one or more oxygen atoms.
• these groups are chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.
• polymeric thickeners comprising at least one unit comprising at least one group and preferably at least two groups capable of establishing hydrogen interactions
• examples that may be mentioned include:
• polymers with a weight-average molecular mass of less than 100 000 comprising a) a polymer backbone with hydrocarbon-based repeating units containing at least one heteroatom, and optionally b) at least one pendent fatty chain and/or at least one terminal fatty chain, optionally functionalized, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon- based units, as described in patent applications WO-A- 02/056 847 and WO-A-02/47619, the content of which is incorporated herein by reference; in particular polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in US-A-5 783 657, the content of which is incorporated herein by reference,
• organopolysiloxanes comprising at least one carboxyl group, and preferably organopolysiloxanes comprising at least two carboxyl groups, per unit.
• the polymeric structuring agent comprising groups capable of establishing hydrogen bonds is a silicone polyamide .
• the silicone polyamides are preferably solid at room temperature (25°C) and atmospheric pressure (760 mmHg) .
• polymer means a compound containing at least two repeating units, preferably at least three repeating units and better still 10 repeating units.
• the silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type, for instance those described in documents US-A- 5 874 069, US-A-5 919 441, US-A-6 051 216 and US-A- 5 981 680. According to the invention, the silicone polymers may belong to the following two families:
• polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and/or

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