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WO2005058274A1 - Composition comportant une dispersion de particules a base d'un polymere ethylenique greffe et d'un agent filmogene - Google Patents

Composition comportant une dispersion de particules a base d'un polymere ethylenique greffe et d'un agent filmogene Download PDF

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Publication number
WO2005058274A1
WO2005058274A1 PCT/IB2004/004127 IB2004004127W WO2005058274A1 WO 2005058274 A1 WO2005058274 A1 WO 2005058274A1 IB 2004004127 W IB2004004127 W IB 2004004127W WO 2005058274 A1 WO2005058274 A1 WO 2005058274A1
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WIPO (PCT)
Prior art keywords
composition according
chosen
polymer
meth
acrylate
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PCT/IB2004/004127
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English (en)
Inventor
Xavier Blin
Nathalie Jager Lezer
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L'oréal
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Publication date
Priority claimed from PCT/FR2003/003713 external-priority patent/WO2004055081A2/fr
Priority claimed from FR0450540A external-priority patent/FR2863493B1/fr
Application filed by L'oréal filed Critical L'oréal
Publication of WO2005058274A1 publication Critical patent/WO2005058274A1/fr

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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
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/044—Suspensions
    • 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
    • A61K8/91—Graft 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

  • Composition comprising a dispersion of particles of a grafted ethylenic polymer and a film-forming agent
  • the present invention relates to a cosmetic makeup or care composition for the skin, including the scalp, of the human face or body, the lips, the nails, and keratin fibres such as the eyelashes, the eyebrows or the hair, comprising a cosmetically acceptable medium containing a film-forming grafted ethylenic polymer combined with another film-forming agent.
  • the composition may be a free or compacted powder, a foundation, a makeup rouge, an eyeshadow, a concealer product, a blusher, a lipstick, a lip balm, a lip gloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a nail varnish, a body makeup product or a skin colouring product.
  • the known compositions have poor staying power and in particular poor resistance of the colour.
  • This poor resistance is characterized by a change in the colour (turning, fading) generally following an interaction with the sebum and/or sweat secreted by the skin in the case of a foundation and a makeup powder, or an interaction with saliva in the case of lipsticks. This obliges the user to freshen the makeup very often, which may constitute a loss of time.
  • "Transfer-resistant" makeup compositions for the lips and the skin are compositions that have the advantage of forming a deposit that does not become deposited, at least partially, onto supports with which they come into contact (glass, clothing, cigarette or fabrics) .
  • An improvement in the staying power and the transfer resistance, in particular of lipsticks may be obtained by combining a volatile oil with a film- forming polymer, for instance silicone resins.
  • a volatile oil with a film- forming polymer, for instance silicone resins.
  • these compositions have the drawback of leaving on the skin and the lips, after evaporation of the volatile silicone oils, a film that becomes uncomfortable over time (sensation of dryness and tautness) , which puts a certain number of women off this type of lipstick.
  • the staying power properties obtained are still below the consumer's expectations.
  • the composition of the invention may in particular constitute a makeup product for the body, the lips, the nails or human keratin fibres, in particular having non-therapeutic care and/or treatment properties. It especially constitutes a lipstick or a lip gloss, a makeup rouge, an eyeshadow, a tattoo product, a makeup or care product for keratin fibres, especially for the eyelashes (mascara) to be applied as a topcoat or as a base coat, an eyeliner, a nail varnish, a product for artificially tanning the skin, a hair-colouring product or a haircare product.
  • One subject of the invention is, more specifically, a cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a grafted ethylenic polymer in a liquid fatty phase and at least one other film-forming agent that is soluble or dispersible in the said liquid fatty phase.
  • a subject of the invention is a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a grafted ethylenic polymer in a liquid fatty phase and at least one other film-forming agent that is soluble or dispersible in the said liquid fatty phase.
  • a subject of the invention is also a cosmetic composition comprising, in a cosmetically acceptable medium, an aqueous phase, a dispersion of particles of a grafted ethylenic polymer in a liquid fatty phase and at least one other film-forming agent that is soluble or dispersible in the said aqueous phase.
  • the invention also relates to a cosmetic process for caring for or making up keratin materials, which consists in applying to the said keratin materials the composition as defined above.
  • the composition according to the invention may be applied to the skin either of the face or of the scalp and body, mucous membranes, for instance the lips, the inside of the lower eyelids, the nails, and keratin fibres, for instance the eyelashes, the hair, the eyebrows, or even other body hairs.
  • the composition according to the invention is preferably a leave-in composition.
  • the invention also relates to the cosmetic use of the composition defined above to improve the staying power and/or the transfer resistance of makeup on keratin materials.
  • an eyelash coating composition or mascara
  • such a composition makes it possible to obtain, after application to the eyelashes, a makeup film that shows good staying power, in particular with respect to water, for example during bathing or showering, to rubbing, especially with the fingers, and/or to tears, sweat or sebum.
  • a subject of the invention is the use of a film-forming agent in a composition containing a grafted ethylenic polymer as described above, to obtain a composition that has a good texture, is easy to apply and gives on the skin, the lips or keratin fibres a deposit that shows good staying power and/or that does not transfer.
  • the composition according to the invention comprises a dispersion of particles of a grafted ethylenic polymer in a liquid fatty phase.
  • ethylenic means a polymer obtained by polymerization of ethylenically unsaturated monomers.
  • the dispersion of grafted ethylenic polymer is especially free of stabilizing polymer different from the said grafted polymer, such as those described in EP 749 747 and described hereinbelow, and the particles of grafted ethylenic polymer are therefore not surface-stabilized with such additional stabilizing polymers.
  • the grafted polymer is therefore dispersed in the liquid fatty phase in the absence of additional surface stabilizer for the particles.
  • grafted polymer means a polymer having a skeleton comprising at least one side chain that is pendent or located at the end of a chain, and preferably pendent.
  • the grafted ethylenic polymer comprises an ethylenic skeleton that is insoluble in the said liquid fatty phase, and side chains covalently bonded to the said skeleton, which are soluble in the liquid fatty phase.
  • the grafted ethylenic polymer is especially a non-crosslinked polymer.
  • the polymer is obtained by polymerization of monomers comprising only one polymerizable group.
  • the grafted ethylenic polymer is preferably a film-forming polymer.
  • film-forming polymer means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, of forming a continuous film that adheres to a support, especially to keratin materials, preferably a cohesive film and better still a film whose cohesion and mechanical properties are such that the said film may be isolated from the said support .
  • the grafted ethylenic polymer is a grafted acrylic polymer.
  • the grafted ethylenic polymer may especially be obtained by free-radical polymerization in an organic polymerization medium:
  • the liquid fatty phase may contain the organic polymerization medium for the grafted ethylenic polymer.
  • the organic liquid dispersion medium corresponding to the medium in which the grafted polymer is supplied, may be identical to the polymerization medium.
  • the polymerization medium may be totally or partially replaced with another organic liquid medium.
  • This other organic liquid medium may be added, after polymerization, to the polymerization medium.
  • the said polymerization medium is then totally or partially evaporated.
  • the liquid fatty phase may contain liquid organic compounds other than those present in the dispersion medium. These other compounds are chosen such that the grafted polymer remains in dispersed form in the liquid fatty phase.
  • the organic liquid dispersion medium is present in the liquid fatty phase of the composition according to the invention due to the introduction into the composition of the dispersion of grafted polymer obtained.
  • the liquid fatty phase comprises, preferably predominantly, one or more liquid organic compounds (or oils) as defined below.
  • the liquid fatty phase is a non-aqueous liquid organic phase that is immiscible with water at room temperature (25°C) .
  • liquid organic compound means a non-aqueous compound that is in liquid form at room temperature (25°C) and therefore flows under its own weight .
  • silicone compound means a compound containing at least one silicon atom.
  • the composition according to the invention advantageously contains a volatile oil as described below.
  • volatile oil means an oil capable of evaporating from the skin, the lips or keratin fibres in less than one hour, especially having a vapour pressure, at room temperature and atmospheric pressure, ranging from IO "3 to 300 mmHg (0.13 Pa to 40 000 Pa) .
  • the volatile oil may be silicone-based or non-silicone-based.
  • the volatile oil is advantageously present in a content ranging from 1% to 70% by weight, preferably ranging from 5% to 50% by weight and preferentially ranging from 10% to 35% by weight, relative to the total weight of the composition.
  • the liquid fatty phase may contain a nonvolatile oil as described below.
  • the non-volatile oil is advantageously present in a content ranging from 1% to 80% by weight, preferably ranging from 5% to 60% by weight and preferentially ranging from 10% to 50% by weight, relative to the total weight of the composition.
  • liquid organic compounds especially silicone-based or non-silicone-based, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 ( Pa) 1 2 and preferably less than or equal to 17 ( Pa) 1/2 , monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1 2 , and
  • liquid organic compounds especially silicone-based or non-silicone-based, having a global solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2
  • oils which may be chosen from natural or synthetic, carbon-based, hydrocarbon-based, fluoro and silicone oils, which are optionally branched, alone or as a mixture.
  • oils formed from fatty acid esters and from polyols, in particular triglycerides, such as sunflower oil, sesame oil or rapeseed oil, or esters derived from acids or alcohols containing a long chain (i.e. a chain containing from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents a higher fatty acid residue containing from 7 to 19 carbon atoms and R' represents a hydrocarbon-based chain containing from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate.
  • polyols in particular triglycerides, such as sunflower oil, sesame oil or rapeseed oil, or esters derived from acids or alcohols containing a long chain (i.e. a chain containing from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents a higher fatty acid residue containing from 7 to 19 carbon
  • Mention may also be made of linear, branched and/or cyclic alkanes which may be volatile, and in particular liquid paraffin, liquid petroleum jelly or hydrogenated polyisobutylene, isododecane or "Isopars", volatile isoparaffins . Mention may also be made of esters, ethers and ketones. Mention may also be made of silicone oils such as polydimethylsiloxanes and polymethylphenyl- siloxanes, optionally substituted with aliphatic and/or aromatic groups, which are optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups, and volatile silicone oils, which are especially cyclic.
  • silicone oils such as polydimethylsiloxanes and polymethylphenyl- siloxanes, optionally substituted with aliphatic and/or aromatic groups, which are optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups, and volatile silicone oils, which
  • volatile and/or non-volatile, optionally branched silicone oils means an oil capable of evaporating from the skin or the lips in less than one hour, and especially having a vapour pressure, at room temperature and atmospheric pressure, ranging from IO "3 to 300 mmHg (0.13 Pa to 40 000 Pa).
  • volatile silicone oils that may be used in the invention, mention may be made of linear or cyclic silicones containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • non-volatile silicone oils that may be mentioned are non-volatile polydialkylsiloxanes, such as non-volatile polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethyl- siloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyltrisiloxanes and polymethyl- phenylsiloxanes; polysiloxanes modified with fatty acids (especially of C 8 -C 2 o) , fatty alcohols (especially of C 8 -C 20 ) or polyoxyalkylenes (especially polyoxyethylene and/or polyoxypropylene) ;
  • liquid monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1 2 means aliphatic fatty liquid monoalcohols containing 6 to 30 carbon atoms, the hydrocarbon-based chain not comprising a substitution group.
  • Monoalcohols according to the invention include oleyl alcohol, decanol, octyldodecanol and linoleyl alcohol.
  • the liquid fatty phase may be a non-silicone liquid fatty phase.
  • non-silicone liquid fatty phase means a fatty phase comprising one or more non-silicone liquid organic compounds or oils, such as those mentioned above, the said non-silicone compounds being predominantly present in the liquid fatty phase, i.e. to at least 50% by weight, especially from 50% to 100% by weight, preferably from 60% to 100% by weight (for example from 60% to 99% by weight) , or alternatively from 65% to 100% by weight (for example from 65% to 95% by weight) , relative to the total weight of the liquid fatty phase.
  • the non-silicone liquid organic compounds may especially be chosen from:
  • the said non-silicone liquid fatty phase may thus optionally comprise silicone liquid organic compounds or oils, such as those mentioned previously, which may be present in an amount of less than 50% by weight, especially ranging from 0.1% to 40% by weight, or even ranging from 1% to 35% by weight, or alternatively ranging from 5% to 30% by weight, relative to the total weight of the liquid fatty phase.
  • the non-silicone liquid fatty phase does not contain any silicone liquid organic compounds or oils.
  • the macromonomers present in the grafted polymer are advantageously carbon-based macro- monomers as described below.
  • the grafted polymer present in the composition is advantageously a non-silicone grafted polymer.
  • non-silicone grafted polymer means a grafted polymer predominantly containing a carbon- based macromonomer and optionally containing not more than 7% by weight and preferably not more than 5% by weight of silicone macromonomer, or even being free of silicone macromonomer.
  • the liquid fatty phase may be a silicone- based liquid fatty phase.
  • silicone-based liquid fatty phase means a fatty phase comprising one or more silicone- based liquid organic compounds or silicone oils such as those described previously, the said silicone compounds being predominantly present in the liquid fatty phase, i.e. to at least 50% by weight, especially from 50% to 100% by weight, preferably from 60% to 100% by weight (for example from 60% to 99% by weight), or even from 65% to 100% by weight (for example from 65% to 95% by weight), relative to the total weight of the liquid fatty phase.
  • the silicone-based liquid organic compounds may especially be chosen from: - liquid organic compounds, which are especially non- silicone-based or silicone-based, with an overall solubility parameter according to the Hansen solubility space of less than or equal to 18 (MPa) 1 2 .
  • the said silicone-based liquid fatty phase may thus optionally comprise non-silicone-based liquid organic compounds or oils, as described previously, which may be present in an amount of less than 50% by weight, especially ranging from 0.1% to 40% by weight, or even ranging from 1% to 35% by weight, or else ranging from 5% to 30% by weight, relative to the total weight of the liquid fatty phase.
  • the silicone-based liquid fatty phase does not contain any non-silicone-based liquid organic compounds.
  • the macromonomers present in the grafted polymer are advantageously silicone-based macromonomers as described below.
  • the grafted polymer present in the composition is advantageously a silicone-based grafted polymer.
  • silicone-based grafted polymer means a grafted polymer predominantly containing a silicone-based macromonomer and optionally containing up to 7% by weight and preferably up to 5% by weight of carbon-based macromonomer, or even being free of carbon-based macromonomer.
  • the grafted ethylenic polymer forming the particles in dispersion thus comprises a skeleton that is insoluble in the said dispersion medium and a portion that is soluble in the said dispersion medium.
  • the grafted ethylenic polymer may be a random polymer.
  • the term "grafted ethylenic polymer” means a polymer that may be obtained by free-radical polymerization:
  • grafted acrylic polymer means a polymer that may be obtained by free-radical polymerization: - of one or more acrylic monomer (s), and optionally of one or more additional non-acrylic vinyl monomer (s) ;
  • the acrylic monomers represent from 50% to 100% by weight, preferably from 55% to 100% by weight (especially from 55% to 95% by weight) and preferentially from 60% to 100% by weight (especially from 60% to 90% by weight) of the mixture of acrylic monomers + optional non-acrylic vinyl monomers.
  • the acrylic monomers are chosen from monomers whose homopolymer is insoluble in the dispersion medium under consideration, i.e. the homopolymer is in solid (or non-dissolved) form at a concentration of greater than or equal to 5% by weight at room temperature (20°C) in the said dispersion medium.
  • Macromonomers According to the invention, the expression "macromonomer containing a polymerizable end group” means any polymer comprising on only one of its ends a polymerizable end group capable of reacting during the polymerization reaction with acrylic monomers and optionally the additional non-acrylic vinyl monomers constituting the skeleton.
  • the macromonomer makes it possible to form the side chains of the grafted acrylic polymer.
  • the polymerizable group of the macromonomer may advantageously be an ethylenically unsaturated group capable of free-radical polymerization with the monomers constituting the skeleton.
  • carbon-based macromonomer means a non-silicone-based macromonomer and especially an oligomeric macromonomer obtained by polymerization of ethylenically unsaturated non-silicone-based monomer (s), and mainly by polymerization of acrylic and/or non-acrylic vinyl monomers.
  • sicone-based macromonomer means an organopolysiloxane macromonomer and in particular a polydimethylsiloxane macromonomer .
  • the macromonomer is chosen from macromonomers whose homopolymer is soluble in the dispersion medium under consideration, i.e.
  • the grafted acrylic polymer comprises a skeleton (or main chain) consisting of a sequence of acrylic units resulting from the polymerization especially of one or more acrylic monomers and of side chains (or grafts) derived from the reaction of the macromonomers, the said side chains being covalently bonded to the said main chain.
  • the skeleton (or main chain) is insoluble in the dispersion medium under consideration, whereas the side chains (or grafts) are soluble in the said dispersion medium.
  • acrylic monomers means monomers chosen from (meth) - acrylic acid, (meth) acrylic acid esters (also known as
  • acrylic monomers that may be used to constitute the insoluble skeleton of the polymer, mention may be made, alone or as a mixture, of the following monomers, and also the salts thereof:
  • - Ri denotes a hydrogen atom or a methyl group
  • - R 2 represents a group chosen from: - a linear or branched alkyl group containing from 1 to 6 carbon atoms, the said group possibly comprising in its chain one or more hetero atoms chosen from 0, N and S; and/or possibly comprising one or more substituents chosen from -OH, halogen atoms (F, CI, Br or I) and -NR' R" with R' and R", which may be identical or different, chosen from linear or branched C ⁇ -C alkyls; and/or possibly being substituted with at least one polyoxyalkylene group, in particular with C 2 -C 4 alkylene, especially polyoxyethylene and/or polyoxypropylene, the said polyoxyalkylene group consisting of a repetition of 5 to 30 oxyalkylene units; - a cyclic alkyl group containing from 3 to 6 carbon atoms, the said group possibly comprising in its chain one or more hetero atoms
  • R 2 examples include the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxypolyoxyethylene (350 OE) , trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl or dimethylaminopropyl group;
  • R 3 denotes a hydrogen atom or a methyl group
  • R 4 and R 5 which may be identical or different, represent a hydrogen atom or a linear or branched alkyl group containing from 1 to 6 carbon atoms, which may comprise one or more substituents chosen from -OH, halogen atoms (F, CI, Br or I) and -NR' R" with R' and R", which may be identical or different, chosen from linear or branched C ⁇ -C 4 alkyls; or
  • R 4 represents a hydrogen atom and R 5 represents a 1, l-dimethyl-3-oxobutyl group.
  • alkyl groups that can constitute R 4 and R 5 , mention may be made of n-butyl, t-butyl, n-propyl, dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl; -(iii) (meth) acrylic monomers comprising at least one carboxylic acid, phosphoric acid or sulfonic acid function, such as acrylic acid, methacrylic acid or acrylamidopropanesulfonic acid.
  • acrylic monomers those that may be mentioned most particularly are methyl, ethyl, propyl, butyl and isobutyl (meth) acrylates; methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2- hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide; and the salts thereof; and mixtures thereof.
  • the acrylic monomers are chosen from methyl acrylate, methoxyethyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid and dimethylaminoethyl methacrylate, and mixtures thereof .
  • additional non-acrylic vinyl monomers that may be mentioned are:
  • R 6 -COO-CH CH 2 in which R 6 represents a linear or branched alkyl group containing from 1 to 6 atoms, or a cyclic alkyl group containing from 3 to 6 carbon atoms and/or an aromatic group, for example of benzene, anthracene or naphthalene type;
  • non-acrylic vinyl monomers comprising at least one carboxylic acid, phosphoric acid or sulfonic acid function, such as crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid or vinylphosphoric acid, and the salts thereof;
  • non-acrylic vinyl monomers comprising at least one tertiary amine function, such as 2-vinylpyridine or 4- vinylpyridine;
  • the acrylic monomers present in the grafted polymer comprise at least (meth) acrylic acid and at least one monomer chosen from the (meth) acrylates and (meth) acrylamides described previously in points (i) and (ii) .
  • the acrylic monomers comprise at least (meth) acrylic acid and at least one monomer chosen from C 1 -C 3 alkyl (meth) acrylates.
  • (Meth) acrylic acid may be present in a content of at least 5% by weight, especially ranging from 5% to 80% by weight, preferably of at least 10% by weight, especially ranging from 10% to 70% by weight, and preferentially of at least 15% by weight, especially ranging from 15% to 60% by weight, relative to the total weight of the polymer.
  • the salts that may be mentioned are those obtained by neutralization of acid groups with mineral bases such as sodium hydroxide, potassium hydroxide or ammonium hydroxide, or organic bases such as alkanolamines, for instance monoethanolamine, diethanolamine, triethanolamine or 2-methyl-2-amino-l- propanol .
  • mineral acids that may be mentioned are sulfuric acid, hydrochloric acid, hydrobromic acid, hydriodic acid, phosphoric acid and boric acid.
  • organic acids that may be mentioned are acids comprising one or more carboxylic, sulfonic or phosphonic groups. They may be linear, branched or cyclic aliphatic acids, or alternatively aromatic acids. These acids may also comprise one or more hetero atoms chosen from 0 and N, for example in the form of hydroxyl groups. Acetic acid or propionic acid, terephthalic acid, and citric acid and tartaric acid may especially be mentioned.
  • the grafted ethylenic polymer contains no additional non-acrylic vinyl monomers as described above.
  • the insoluble skeleton of the grafted ethylenic polymer is formed solely from acrylic monomers as described previously. It is understood that these non-polymerized acrylic monomers may be soluble in the dispersion medium under consideration, but the polymer formed with these monomers is insoluble in the dispersion medium.
  • the grafted ethylenic polymer may be obtained by free-radical polymerization in an organic polymerization medium:
  • a main acrylic monomer chosen from C 1 -C3 alkyl (meth) acrylates, alone or as a mixture, and optionally of one or more additional acrylic monomers chosen from (meth) acrylic acid, methacrylic acid and alkyl (meth) - acrylates of formula (I) defined below, and salts thereof, to form the said insoluble skeleton; and
  • Main acrylic monomers that may be used include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate and isopropyl methacrylate, and mixtures thereof. Methyl acrylate, methyl methacrylate and ethyl methacrylate are most particularly preferred.
  • the additional acrylic monomers may be chosen from:
  • R' ⁇ denotes a hydrogen atom or a methyl group
  • R' 2 represents - a linear or branched alkyl group containing from 1 to 6 carbon atoms, the said group comprising in its chain one or more oxygen atoms and/or comprising one or more substituents chosen from
  • halogen atoms F, CI, Br or I
  • -NR'R R' and R" which may be identical or different, being chosen from linear or branched C 1 -C3 alkyls
  • R' and R which may be identical or different, being chosen from linear or branched C 1 -C3 alkyls
  • R' 2 examples include the methoxyethyl, ethoxyethyl, trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl groups.
  • additional acrylic monomers mention may be made most particularly of (meth) acrylic acid, methoxyethyl or ethoxyethyl (meth) acrylates; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
  • the macromonomers comprise at one of the ends of the chain a polymerizable end group capable of reacting during the polymerization with the acrylic monomers and optionally the additional vinyl monomers, to form the side chains of the grafted ethylenic polymer.
  • the said polymerizable end group may in particular be a vinyl or (meth) acrylate (or (meth) - acryloxy) group, and preferably a (meth) acrylate group.
  • the macromonomers are preferably chosen from macromonomers whose homopolymer has a glass transition temperature (Tg) of less than or equal to 25°C, especially ranging from -100°C to 25°C and preferably ranging from -80°C to 0°C.
  • Tg glass transition temperature
  • the macromonomers have a weight-average molecular mass of greater than or equal to 200, preferably greater than or equal to 300, preferentially greater than or equal to 500 and more preferentially greater than 600.
  • the macromonomers have a weight- average molecular mass (Mw) ranging from 200 to 100 000, preferably ranging from 500 to 50 000, preferentially ranging from 800 to 20 000, more preferentially ranging from 800 to 10 000 and even more preferentially ranging from 800 to 6000.
  • Mw weight-average molecular mass
  • Mn number-average molar masses
  • Carbon-based macromonomers that may in particular be mentioned include: -(i) homopolymers and copolymers of linear or branched C 8 -C 22 alkyl acrylate or methacrylate, containing a polymerizable end group chosen from vinyl or (meth) acrylate groups, among which mention may be made in particular of: poly (2-ethylhexyl acrylate) macromonomers with a mono (meth) acrylate end group; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers with a mono (meth) acrylate end group; poly (stearyl acrylate) or poly (stearyl methacrylate) macromonomers with a mono (meth) acrylate end group.
  • macromonomers are described in particular in the patents EP 895 467 and EP 96459, and in the article by Gillman K.F., Polymer Letters, Vol 5, page 477-481 (1967) . Mention may be made in particular of macromonomers based on poly (2-ethylhexyl acrylate) or poly (dodecyl acrylate) with a mono (meth) acrylate end group; -(ii) polyolefins containing an ethylenically unsaturated end group, in particular containing a (meth) acrylate end group.
  • polystyrene foams examples include the following macromonomers, it being understood that they have a (meth) acrylate end group: polyethylene macromonomers, polypropylene macromonomers, macromonomers of polyethylene/polypropylene copolymer, macromonomers of polyethylene/polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; poly (ethylene/butylene) - polyisoprene macromonomers.
  • macromonomers examples include the following macromonomers, it being understood that they have a (meth) acrylate end group: polyethylene macromonomers, polypropylene macromonomers, macromonomers of polyethylene/polypropylene copolymer, macromonomers of polyethylene/polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromono
  • Such macromonomers are described in particular in US 5 625 005, which mentions ethylene/butylene and ethylene/propylene macromonomers containing a (meth) acrylate reactive end group. Mention may be made in particular of the poly (ethylene/butylene) methacrylate such as that sold under the name Kraton Liquid L-1253 by Kraton Polymers. Silicone-based macromonomers that may be mentioned in particular include polydimethylsiloxanes containing mono (meth) acrylate end groups, and especially those of formula (II) below:
  • R 8 denotes a hydrogen atom or a methyl group
  • R 9 denotes a divalent hydrocarbon-based group containing from 1 to 10 carbon atoms and optionally contains one or two ether bonds -0-
  • Rio denotes an alkyl group containing from 1 to 10 carbon atoms and especially from 2 to 8 carbon atoms
  • n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200 and preferentially ranging from 5 to 100.
  • Silicone-based macromonomers that may be used include monomethacryloxypropyl polydimethylsiloxanes such as those sold under the name PS560-K6 by the company United Chemical Technologies Inc. (UCT) or under the name MCR-M17 by the company Gelest Inc.
  • the polymerized macromonomer (constituting the side chains of the grafted polymer) represents from 0.1% to 15% by weight, preferably from 0.2% to 10% by weight and more preferably from 0.3% to 8% by weight, relative to the total weight of the polymer.
  • grafted ethylenic polymer dispersed in a non-silicone liquid fatty phase it is possible to use those obtained by polymerization: - of methyl acrylate and of a polyethylene/polybutylene macromonomer containing a methacrylate end group (especially Kraton L-1253) , in particular in a solvent chosen from isododecane, isononyl isononanoate, octyldodecanol, diisostearyl malate or a C ⁇ 2 -C ⁇ 5 alkyl benzoate (such as Finsolv TN) ;
  • grafted acrylic polymer dispersed in a silicone-based liquid fatty phase it is possible to use those obtained by polymerization:
  • the weight-average molecular mass (Mw) of the grafted polymer is preferably between 10 000 and 300 000, especially between 20 000 and 200 000 and better still between 25 000 and 150 000.
  • the polymers have the capacity of folding over on themselves, thus forming particles of substantially spherical shape, the periphery of these particles having the deployed side chains, which ensure the stability of these particles.
  • Such particles resulting from the characteristics of the grafted polymer have the particular feature of not aggregating in the said medium and thus of being self-stabilized and of forming a particularly stable polymer particle dispersion.
  • the grafted ethylenic polymers of the dispersion are capable of forming nanometre- sized particles, with a mean size ranging from 10 to 400 nm and preferably from 20 to 200 nm.
  • the dispersion of grafted polymer may thus be a dispersion that is stable and does not form sediments when it is placed at room temperature for an extended period (for example 24 hours).
  • the dispersion of grafted polymer particles has a solids content (or dry extract) of polymer of from 40% to 70% by weight of solids and especially from 45% to 65% by weight.
  • the dispersion of grafted polymer particles may be prepared via a process comprising a step free- radical copolymerization, in an organic polymerization medium, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.
  • the liquid organic dispersion medium may be identical to or different from the polymerization medium.
  • the copolymerization may be performed conventionally in the presence of a polymerization initiator.
  • the polymerization initiators may be free- radical initiators.
  • such a polymerization initiator may be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide or tert- butyl peroxy-2-ethylhexanoate; diazo compounds such as azobisisobutyronitrile or azobisdimethylvaleronitrile .
  • the reaction may also be initiated using photoinitiators or with radiation such as UV or neutrons, or with plasma.
  • the organic polymerization medium a portion of the organic polymerization medium, a portion of the additional acrylic and/or vinyl monomers, which will constitute the insoluble skeleton after polymerization, all of the macromonomer (which will constitute the side chains of the polymer) and a portion of the polymerization initiator are introduced into a reactor whose size is suitable for the amount of polymer to be prepared.
  • the reaction medium forms a relatively homogeneous medium.
  • the reaction medium is then stirred and heated up to a temperature to obtain polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion of milky appearance.
  • the grafted polymer may be present in the composition according to the invention in a solids content (or active material content) ranging from 1% to 70% by weight, better still from 5% to 60% by weight, preferably ranging from 6% to 45% by weight and better still ranging from 8% to 40% by weight, relative to the total weight of the composition.
  • composition of the invention also contains at least one film-forming agent, different from the grafted ethylenic polymer described above, which is preferably a film-forming polymer.
  • film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of free- radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.
  • Film-forming polymers that may be mentioned in particular include acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulose-based polymers, for instance nitrocellulose.
  • the film-forming organic polymer is at least one polymer chosen from the group comprising :
  • the non-aqueous dispersions of polymer comprise polymer particles stabilized on their surface, mentioned previously, which are often referred to as "NADs" [non-aqueous dispersions] , - aqueous dispersions of particles of film-forming polymers, which are often known as "latices”; in this case, the composition should comprise an aqueous phase besides the liquid fatty phase, - water-soluble film-forming polymers; in this case, the composition should comprise an aqueous phase besides the liquid fatty phase.
  • the film- forming agent may be a polymer that is soluble in the said oil. In this case, it is referred to as a liposoluble polymer.
  • the liposoluble polymer may be of any chemical type and may especially be chosen from: a) liposoluble, amorphous homopolymers and copolymers of olefins, of cycloolefins, of butadiene, of isoprene, of styrene, of vinyl ethers, esters or amides, or of (meth) acrylic acid esters or amides comprising a linear, branched or cyclic C 4 -C 50 alkyl group and which are preferably amorphous.
  • the preferred liposoluble homopolymers and copolymers are obtained from monomers chosen from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate, or mixtures thereof.
  • Examples that will be mentioned include the alkyl acrylate/cycloalkyl acrylate copolymer sold by Phoenix Chem. under the name Giovarez AC-5099 ML, and vinylpyrrolidone copolymers, such as copolymers of a C 2 -C 30 and in particular C 3 to C 22 alkene, and combinations thereof, may be used.
  • vinylpyrrolidone copolymers such as copolymers of a C 2 -C 30 and in particular C 3 to C 22 alkene, and combinations thereof, may be used.
  • VP copolymers that may be used in the invention, mention may be made of copolymers of VP/vinyl laurate, VP/vinyl stearate, butylated polyvinylpyrrolidone (PVP), VP/hexadecene, VP/triacontene or VP/acrylic acid/lauryl methacrylate.
  • liposoluble copolymers that may be mentioned include: i) acrylic-silicone grafted polymers containing a silicone skeleton and acrylic grafts or containing an acrylic skeleton and silicone grafts, such as the product sold under the name SA 70.5 by 3M and described in patents US 5 725 882, US 5 209 924, US 4 972 037, US 4 981 903, US 4 981 902 and US 5 468 477, and in patents US 5 219 560 and EP 0 388 582; ii) liposoluble polymers belonging to one of the classes described above and bearing fluoro groups, in particular those described in patent US 5 948 393 and the alkyl (meth) acrylate/per- fluoroalkyl (meth) acrylate copolymers described in patents EP 0 815 836 and US 5 849 318; iii) polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic
  • the film-forming agent is a block copolymer comprising at least one block consisting of styrene units or styrene derivatives (for example methylstyrene, chlorostyrene or chloromethyl- styrene) .
  • the copolymer comprising at least one styrene block may be a diblock or triblock copolymer, or even a multiblock copolymer, in starburst or radial form.
  • the copolymer comprising at least one styrene block may also comprise, for example, an alkylstyrene (AS) block, an ethylene/butylene (EB) block, an ethylene/propylene (EP) block, a butadiene (B) block, an isoprene (I) block, an acrylate (A) block, a methacrylate (MA) block or a combination of these blocks.
  • AS alkylstyrene
  • EB ethylene/butylene
  • EP ethylene/propylene
  • B butadiene
  • I isoprene
  • A acrylate
  • MA methacrylate
  • the copolymer comprising at least one block consisting of styrene units or styrene derivatives may be a diblock or triblock copolymer, and in particular of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those sold or manufactured under the name "Luvitol HSB" by BASF, and those of the polystyrene/- copoly (ethylene-propylene) type or alternatively of the polystyrene/copoly (ethylene-butylene) type, such as those sold or manufactured under the brand name "Kraton" by Shell Chemical Co. or Gelled Permethyl 99A by Penreco.
  • Examples that may be mentioned include Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS) , Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton
  • the film-forming agent is chosen from copolymers of a vinyl ester (the vinyl group being directly attached to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer, which may be a vinyl ester (other than the vinyl ester already present), an ⁇ -olefin (containing from 8 to 28 carbon atoms) , an alkyl vinyl ether (the alkyl group of which contains from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to
  • copolymers may be partially crosslinked using crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate .
  • crosslinking agents may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate .
  • copolymers examples include the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/1-octadecene, vinyl acetate/1- dodecene, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2, 2-dimethyloctanoate/vinyl laurate, allyl 2 , 2-dimethylpentanoate/vinyl laurate, vinyl dimethylpropionate/vinyl stearate, allyl dimethyl- propionate/vinyl stearate, vinyl propionat
  • Liposoluble film-forming polymers that may also be mentioned include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 10 to 20 carbon atoms.
  • Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, polyvinyl stearate crosslinked with divinylbenzene, with diallyl ether or with diallyl phthalate, polystearyl (meth) acrylate, polyvinyl laurate and polylauryl (meth) acrylate, these poly (meth) acrylates possibly being crosslinked with ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.
  • the liposoluble copolymers defined above are known and described especially in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.
  • liposoluble polymers that may be used in the invention, mention may be made of poly- alkylenes and C 2 -C 20 alkene copolymers, in particular polybutene.
  • amorphous and liposoluble polycondensates preferably not comprising any groups donating hydrogen interactions, in particular aliphatic polyesters containing C4-50 alkyl side chains or polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone-based segment in the form of a block, graft or end group, as defined in patent application FR 0 113 920.
  • amorphous and liposoluble polysaccharides comprising alkyl (ether or ester) side chains, in particular alkylcelluloses containing a saturated or unsaturated, linear or branched Ci to C 8 alkyl radical, such as ethylcellulose and propylcellulose .
  • the film-forming polymer may be chosen in particular from cellulose-based polymers such as nitro- cellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate or ethylcellulose, or from polyurethanes, acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, such as arylsulfonamide-formaldehyde resins, for instance toluenesulfonamide-formaldehyde resin, and aryl- sulfonamide epoxy resins.
  • cellulose-based polymers such as nitro- cellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate or ethylcellulose
  • polyurethanes acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, such as arylsulf
  • Film-forming polymers that may especially be used include nitrocellulose RS 1/8 sec; RS sec; ⁇ sec; RS 5 sec; RS 15 sec; RS 35 sec; RS 75 sec; RS 150 sec; AS H sec; AS ⁇ sec; SS % sec; SS ⁇ sec; SS 5 sec, sold especially by the company Hercules; the toluenesulfonamide-formaldehyde resins "Ketjentflex MS80" from the company Akzo or "Santolite MHP” and “Santolite MS80” from the company Faconnier or "Resimpol 80" from the company Pan Americana, the alkyd resin "Beckosol Ode 230-70-E” from the company Dainippon, the acrylic resin "Acryloid B66" from the company Rohm & Haas, and the polyurethane resin "Trixene PR 4127" from the company Baxenden.
  • silicone resins which are generally soluble or swellable in silicone oils. These resins are crosslinked polyorganosiloxane polymers.
  • MDTQ The nomenclature of silicone resins is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ” characterizing a type of unit.
  • the letter M represents the monofunctional unit of formula (CH 3 ) 3 SiO ⁇ /2 , the silicon atom being linked to only one oxygen atom in the polymer comprising this unit.
  • the letter D denotes a difunctional unit (CH 3 ) 2 Si0 2/2 in which the silicon atom is linked to two oxygen atoms.
  • the letter T represents a trifunctional unit of formula (CH 3 )Si0 3/2 .
  • the units M, D and T defined above at least one of the methyl groups may be substituted with a group R other than a methyl group, such as a hydrocarbon-based radical (especially alkyl) containing from 2 to 10 carbon atoms or a phenyl group, or alternatively a hydroxyl group.
  • the letter Q means a tetrafunctional unit Si0 4/2 in which the silicon atom is linked to four hydrogen atoms, which are themselves linked to the polymer residue.
  • silicone resins examples include: - siloxysilicates, which may be trimethylsiloxy- silicates of formula [ (CH 3 ) 3 XSiXO] X X (Si0 4/2 ) y (units MQ) in which x and y are integers ranging from 50 to 80, - polysilsesquioxanes of formula (CH 3 Si0 3 / 2 ) x (units T) in which x is greater than 100 and at least one of the methyl radicals of which may be substituted with a group R as defined above, - the polymethylsilsesquioxanes, which are polysilsesquioxanes in which none of the methyl radicals is substituted with another group.
  • Such polymethylsilsesquioxanes are described in document US 5 246 694, the content of which is incorporated by reference.
  • Resin MK such as Belsil PMS MK: polymer comprising CH 3 Si0 3 / 2 repeating units (units T) , which may also comprise up to 1% by weight of (CH 3 ) 2 Si0 2 / 2 units (units D) and having an average molecular weight of about 10 000
  • KR- 220L which are composed of units T of formula CH 3 Si0 3 / 2 and contain Si-OH (silanol) end groups
  • KR-242A which comprise 98% of units T and 2% of dimethyl units D and contain Si- OHOU end groups
  • KR-251 comprising 88% of units T and 12% of
  • Siloxysilicate resins that may be mentioned include trimethylsiloxysilicate resins (TMS) optionally in the form of powders. Such resins are sold under the reference SR1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name "KF-7312J” by the company Shin-Etsu or "DC 749" and "DC 593" by the company Dow Corning.
  • TMS trimethylsiloxysilicate resins
  • solvent such as cyclomethicone
  • Silicone-based polyamides of the polyorganosiloxane type such as 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, these silicone- based polymers may belong to the following two families :
  • polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain;
  • polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches .
  • the polymers comprising two groups capable of establishing hydrogen interactions in the polymer chain may be polymers comprising at least one unit corresponding to the formula:
  • R 4 , R 5 , R 6 and R 7 which may be identical or different, represent a group chosen from: linear, branched or cyclic, saturated or unsaturated, Ci to C 40 hydrocarbon-based groups, possibly containing in their chain one or more oxygen, sulfur and/or nitrogen atoms, and possibly being partially or totally substituted with fluorine atoms, - C 6 to Cio aryl groups, optionally substituted with one or more Ci to C 4 alkyl groups, polyorganosiloxane chains possibly containing one or more oxygen, sulfur and/or nitrogen atoms;
  • the groups X which may be identical or different, represent a linear or branched Ci to C 30 alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms;
  • Y is a saturated or unsaturated, Ci to C 50 linear or branched divalent alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group, possibly comprising one or more oxygen, sulfur and/or nitrogen atoms, and/or bearing as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C 3 to C 8 cycloalkyl, Ci to C 40 alkyl, C to Cio aryl, phenyl optionally substituted with 1 to 3 Ci to C 3 alkyl groups, Ci to C 3 hydroxyalkyl and Ci to e aminoalkyl; or
  • Y represents a group corresponding to the formula:
  • - T represents a linear or branched, saturated or unsaturated, C 3 to C 24 trivalent or tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms chosen from 0, N and S, or T represents a trivalent atom chosen from N, P and Al
  • - R 8 represents a linear or branched Ci to C 5 o alkyl group or a polyorganosiloxane chain, possibly comprising one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, which may possibly be linked to another chain of the polymer;
  • the groups G which may be identical or different, represent divalent groups chosen from:
  • R 9 represents a hydrogen atom or a linear or branched Ci to C 20 alkyl group, on condition that at least 50% of the groups R 9 of the polymer represent a hydrogen atom and that at least two of the groups G of the polymer are a group other than:
  • n is an integer ranging from 2 to 500 and preferably from 2 to 200
  • m is an integer ranging from 1 to 1 000, preferably from 1 to 700 and better still from 6 to 200.
  • 80% of the groups R 4 , R 5 , R 6 and R 7 of the polymer are preferably chosen from methyl, ethyl, phenyl and 3, 3, 3-trifluoropropyl groups .
  • Y can represent various divalent groups, furthermore optionally comprising one or two free valencies to establish bonds with other moieties of the polymer or copolymer.
  • Y represents a group chosen from: a) linear Ci to C 20 and preferably Ci to Cio alkylene groups, b) C 3 o to C 56 branched alkylene groups possibly comprising rings and unconjugated unsaturations, c) C 5 -C 6 cycloalkylene groups, d) phenylene groups optionally substituted with one or more Ci to C 40 alkyl groups, e) Ci to C 20 alkylene groups comprising from 1 to 5 amide groups, f) Ci to C 20 alkylene groups comprising one or more substituents chosen from hydroxyl, C 3 to C 8 cycloalkane, Ci to C 3 hydroxyalkyl and Ci to ⁇ alkylamine groups, g) polyorganosiloxane chains of formula: in which R 4 , R 5 , R 6 , R 7 , T and m are as defined above, and h) polyorganosiloxane chains of formula:
  • the polyorganosiloxanes of the second family may be polymers comprising at least one unit corresponding to formula (III):
  • R 4 and R 6 which may be identical or different, are as defined above for formula (II), - R 10 represents a group as defined above for R 4 and
  • R represents a group of formula -X-G-R 12 in which X and G are as defined above for formula (II) and R 12 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, Ci to C 50 hydrocarbon- based group optionally comprising in its chain one or more atoms chosen from 0, S and N, optionally substituted with one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group optionally substituted with one or more Ci to C 4 alkyl groups, R 11 represents a group of formula -X-G-R 9 in which X, G and R 12 are as defined above, mi is an integer ranging from 1 to 998, and m 2 is an integer ranging from 2 to 500.
  • the polymer used may be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (II) or of formula (III).
  • a polymer consisting of a copolymer comprising several different units of formula (II) that is to say a polymer in which at least one of the groups R 4 , R 5 , R 6 , R 7 , X, G, Y, m and n is different in one of the units.
  • the copolymer may also be formed from several units of formula (III), in which at least one of the groups R 4 , R 6 , R 10 , R 11 , mi and m 2 is different in at least one of the units.
  • copolymer comprising at least one unit of formula (II) and at least one unit of formula (III), the units of formula (II) and the units of formula (III) possibly being identical to or different from each other.
  • a copolymer furthermore comprising at least one hydrocarbon-based unit comprising two groups capable of establishing hydrogen interactions, chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups, and combinations thereof.
  • These copolymers may be block copolymers or grafted copolymers.
  • the polymer of the composition according to the invention is a linear film-forming block ethylenic polymer, referred to hereinbelow as a "block polymer", the particular structure of which being as described below.
  • block polymer means a polymer comprising at least two different blocks and preferably at least three different blocks.
  • the polymer is a polymer of linear structure.
  • a polymer of non-linear structure is, for example, a polymer of branched, starburst or grafted structure, or the like.
  • the block polymer is free of styrene.
  • polymer free of styrene means a polymer containing less than 10% by weight, preferably less than 5% by weight, better still less than 2% by weight and better still less than 1% by weight of styrene monomer, for instance styrene, styrene derivatives such as methylstyrene, chlorostyrene or chloromethylstyrene, or even containing no styrene monomer, relative to the total weight of the polymer.
  • the block polymer comprises at least one first block and at least one second block that have different glass transition temperatures (Tg) , the said first and second blocks being linked together via an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
  • Tg glass transition temperatures
  • the term "at least one block” means one or more blocks.
  • the intermediate block 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 allowing these blocks to be "compatibilized” .
  • the first and second blocks of the block polymer are mutually incompatible.
  • the term "mutually incompatible blocks” means that the mixture formed from the polymer corresponding to the first block and of the polymer corresponding to the second block is not miscible in the organic liquid that is in major amount by weight contained in the liquid fatty phase, at room temperature (25°C) and atmospheric pressure (IO 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 (polymers and solvent), it being understood that: i) the said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and ii) 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 liquid fatty phase comprises a mixture of organic liquids
  • the said polymer mixture is immiscible in at least one of them.
  • this liquid is the predominant organic liquid.
  • the block polymer comprises no silicon atoms in its skeleton.
  • skeleton means the main chain of a polymer, as opposed to the pendent side chains.
  • the block polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, for instance ethanol, isopropanol or n-propanol, without modifying the pH, at an active material content of at least 1% by weight, at room temperature (25°C) .
  • the block polymer is not an elastomer.
  • non-elastomeric polymer means a polymer which, when it is subjected to a constraint intended to stretch 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 R x ⁇ 50% and a delayed recovery R 2h ⁇ 70% after having been subjected to a 30% elongation.
  • R ⁇ . is ⁇ 30% and R 2h ⁇ 50%.
  • the non-elastomeric nature of the polymer is determined according to the following protocol : a polymer film is prepared by pouring a solution of the polymer in a Teflon-coated mould, followed by drying for 7 days in an environment conditioned at 23 ⁇ 5°C and 50 ⁇ 10% relative humidity.
  • a film about 100 ⁇ m thick is thus obtained, from which are cut rectangular specimens (for example using a punch) 15 mm wide and 80 mm long. This sample is subjected to a tensile stress using a machine sold under the reference Zwick, under the same temperature and humidity conditions as for the drying . 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 (1 0 ) of the specimen.
  • the instantaneous recovery R x is determined in the following manner:
  • a polymer according to one embodiment of the invention has an instantaneous recovery R x of 10% and a delayed recovery R 2h of 30%.
  • the block polymer 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, and especially ranging from 2.8 to 6.
  • the polydispersity index I of the block 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 block polymer 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.
  • the number-average mass (Mn) of the block polymer 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.
  • Each block of the block polymer is derived from one type of monomer or from several different types of monomer.
  • each block may consist of a homopolymer or a copolymer; this copolymer constituting the block may in turn be random or alternating.
  • the intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the block polymer is a random polymer.
  • the intermediate block is derived essentially from constituent monomers of the first block and of the second block.
  • the term "essentially” means at least 85%, preferably at least 90%, better still 95% and even better still 100%.
  • the intermediate block has a glass transition temperature Tg that is between the glass transition temperatures of the first and second blocks.
  • 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
  • Tg ⁇ 1 (ro ⁇ Tg )
  • Tg x 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 difference between the glass transition temperatures of the first and second blocks is generally greater than 10°C, preferably greater than 20°C and better still greater than 30°C.
  • the first block of the block polymer may be chosen from: a) a block with a Tg of greater than or equal to 40°C, b) a block with a Tg of less than or equal to 20°C, c) a block with a Tg of between 20 and 40°C, and the second block can be chosen from a category a) , b) or c) different from the first block.
  • 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.
  • Block with a Tg of greater than or equal to 40°C 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 block with a Tg of greater than or equal to 40 °C may be a homopolymer or a copolymer. In the case where 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 consisting of only one type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40°C) .
  • the first block may be totally or partially derived from one or more monomers, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is greater than or equal to 40°C.
  • the copolymer may comprise, for example: - monomers which are such that the homopolymers prepared from these monomers have 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
  • Tg values of less than 40°C chosen from monomers with a Tg of between 20 and 40 °C and/or monomers with a Tg of less than or equal to 20 °C, for example a Tg ranging from -100 to 20°C, preferably less than 15°C, especially ranging from -80°C to 15°C and better still less than 10°C, for example ranging from -50°C to 0°C, as described later.
  • R 7 and R 8 which may be identical or different, each represent a hydrogen atom or a linear or branched Ci to C i2 alkyl group such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R 7 represents H and R 8 represents a 1, l-dimethyl-3-oxobutyl group, and R' denotes H or methyl.
  • monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N,N-dibutylacrylamide, - and mixtures thereof.
  • Main monomers that are particularly preferred are methyl methacrylate, isobutyl (meth) acrylate and isobornyl (meth) acrylate, and mixtures thereof.
  • Block with a Tg of less than or equal to 20°C The block with a Tg of less than or equal to 20°C has, for example, a Tg ranging from -100 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 C, for example ranging from -50°C to 0°C.
  • 20 °C may be a homopolymer or a copolymer.
  • this block is derived from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20°C.
  • This second block may be a homopolymer consisting of only one type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20 ° C ) .
  • the block with a Tg of less than or equal to 20°C is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is less than or equal to 20°C.
  • It may comprise, for example - one or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20°C, for example a Tg ranging from -100°C to 20°C, preferably less than 15°C, especially ranging from -80°C to 15°C and better still less than 10°C, for example ranging from -50°C to 0°C, and - one or more monomers whose corresponding homopolymer has a Tg of greater than 20°C, such as monomers with a Tg 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/or monomers with a Tg of between 20 and 40°C, as described above.
  • the block with a Tg of less than or equal to 20 °C is a homopolymer.
  • the main monomers that are particularly preferred for the block with a Tg of less than or equal to 20°C are alkyl acrylates whose alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
  • Block with a Tg of between 20 and 40°C The block with a Tg of between 20 and 40°C may be a homopolymer or a copolymer.
  • this block is a homopolymer, it is derived from monomers (or main monomer) which are such that the homopolymers prepared from these monomers have glass transition temperatures of between 20 and 40°C.
  • This first block may be a homopolymer, consisting of only one type of monomer (for which the Tg of the corresponding homopolymer ranges from 20°C to 40°C) .
  • the monomers whose homopolymer has a glass transition temperature of between 20 and 40°C are preferably chosen from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide, and mixtures thereof.
  • the block with a Tg of between 20 and 40°C is a copolymer, it is totally or partially derived from one or more monomers (or main monomer) whose nature and concentration are chosen such that the Tg of the resulting copolymer is between 20 and 40°C.
  • the block with a Tg of between 20 and 40°C is a copolymer totally or partially derived from:
  • - main monomers whose corresponding homopolymer has a Tg of greater than or equal to 40°C for example a Tg ranging from 40°C to 150°C, preferably greater than or equal to 50°C, for example ranging from 50 to 120°C and better still greater than or equal to 60°C, for example ranging from 60°C to 120°C, as described above
  • - main monomers whose corresponding homopolymer has a Tg of less than or equal to 20°C for example a Tg ranging from -100 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 -50°C to 0°C, as described above, the said monomers being chosen such that the Tg of the copolymer forming the first block is between 20 and 40°C.
  • Such main monomers are chosen, for example, from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
  • the proportion of the second block with a Tg of less than or equal to 20°C ranges from 10% to 85% by weight, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer .
  • each of the blocks may contain in small proportion at least one constituent monomer of the other block.
  • the first block may contain at least one constituent monomer of the second block, and vice versa .
  • Each of the first and/or second blocks of the block polymer may comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, which are different from the main monomers mentioned above.
  • additional monomers known as additional monomers, which are different from the main monomers mentioned above.
  • the nature and amount of this or these additional monomer (s) are chosen such that the block in which they are present has the desired glass transition temperature.
  • This additional monomer is chosen, for example, from: hydrophilic monomers such as:
  • the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.
  • This or these additional monomer (s) generally represent (s) an amount of less than or equal to 30% by weight, for example from 1% to 30% by weight, preferably from 5% to 20% by weight and more preferably from 7% to 15% by weight, relative to the total weight of the first and/or second blocks.
  • each of the first and second blocks comprises at least one monomer chosen from (meth) acrylic acid esters, and optionally at least one monomer chosen from (meth) acrylic acid, and mixtures thereof .
  • each of the first and second blocks of the block polymer is totally derived from at least one monomer chosen from acrylic acid and
  • the block polymer may be obtained by free- radical solution polymerization according to the following preparation process: a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization is reached (typically between 60 and 120°C), once this temperature is reached, the constituent monomers of the first block are introduced in the presence of some of the polymerization initiator, after a time T corresponding to a maximum degree of conversion of 90%, the constituent monomers of the second block and the rest of the initiator are introduced, - the mixture is left to react for a time T'
  • polymerization solvent means a solvent or a mixture of solvents.
  • 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 block polymer comprises a first block with a Tg of greater than or equal to 40°C, as described above in a) and a second block with a Tg of less than or equal to 20°C, as described above in b) .
  • the first block with a Tg of greater than or equal to 40°C is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40°C, such as the monomers described above.
  • the second block with a Tg of less than or equal to 20°C is a homopolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20°C, such as the monomers described above.
  • the proportion of the block with a Tg of greater than or equal to 40°C ranges from 20% to 90%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
  • the proportion of the block with a Tg of less than or equal to 20°C ranges from 5% to 75%, preferably from 15% to 50% and better still from 25% to 45% by weight of the polymer.
  • the polymer block may comprise :
  • the block polymer comprises a first block having a glass transition temperature (Tg) of between 20 and 40°C, in accordance with the blocks described in c) and a second block having a glass transition temperature of less than or equal to 20°C, as described above in b) or a glass transition temperature of greater than or equal to 40°C, as described in a) above.
  • Tg glass transition temperature
  • the proportion of the first block with a Tg of between 20 and 40°C ranges from 10% to 85%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
  • the second block is a block with a Tg of greater than or equal to 40°C, it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 30% to 70% by weight of the polymer.
  • the second block is a block with a Tg of less than or equal to 20°C, it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
  • the first block with a Tg of between 20 and 40 °C is a copolymer derived from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40°C, and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20°C.
  • the second block with a Tg of less than or equal to 20°C or with a Tg of greater than or equal to 40°C is advantageously a homopolymer.
  • the block polymer comprises:
  • the block polymer may comprise:
  • the block polymer may comprise:
  • first block with a Tg of greater than or equal to 40°C, for example ranging from 60 to 90°C, which is an isobornyl acrylate/isobutyl methacrylate copolymer
  • second block with a Tg of less than or equal to
  • an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
  • the composition according to the invention may contain a film-forming agent chosen from non- aqueous dispersions of polymer particles, different from the dispersion of grafted ethylenic polymer in liquid fatty phase.
  • the particles are generally spherical.
  • the particles are generally dispersed in a physiologically acceptable liquid fatty medium, such as hydrocarbon-based oils or silicone oils, which may be the same as the liquid fatty phase of the composition according to the invention.
  • these dispersions are generally known as NADs (non-aqueous dispersions) of polymer, as opposed to latices, which are aqueous dispersions of polymer.
  • These dispersions may especially be in the form of nanoparticles of polymers in stable dispersion in the said fatty phase.
  • the nanoparticles are between 5 nm and 600 nm in size.
  • One advantage of such a polymer dispersion is the possibility of varying the glass transition temperature (Tg) of the polymer or the polymer system (polymer plus additive of the plasticizer type) , and of thus going from a hard polymer to a more or less soft polymer, making it possible to adjust the mechanical properties of the composition depending on the intended application and in particular on the film deposited.
  • Tg glass transition temperature
  • the polymers in dispersion which may be used in the composition of the invention preferably have a molecular weight of about from 2000 to 10 000 000 and a Tg of from -100°C to 300°C and better still from -50°C to 50°C and preferably from -10°C to 100°C. It is possible to use film-forming polymers, that preferably have a low Tg, of less than or equal to the temperature of the skin and especially less than or equal to 40°C. A dispersion is thus obtained which can form a film when it is applied to a support.
  • free-radical acrylic or vinyl homo- polymers or copolymers, preferably having 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.
  • free-radical polymer means a polymer obtained by polymerization of monomers containing unsaturation, especially ethylenic unsaturation, each monomer being capable of homo- polymerizing (unlike polycondensates) .
  • the free-radical polymers may especially be vinyl polymers or copolymers, especially acrylic polymers.
  • the vinyl polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acidic monomers and/or amides of these acids.
  • monomers bearing an acidic group it is possible to use ⁇ , ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid.
  • (Meth) acrylic acid and crotonic acid are preferably used, and more preferentially (meth) acrylic acid.
  • esters of acidic monomers are advantageously chosen from the esters of (meth) acrylic acid (also known as (meth) acrylates) , for instance alkyl (meth) acrylates, in particular of a C ⁇ -C 20 and preferably a Ci-Ce alkyl, aryl (meth) acrylates, in particular of a C 6 -C ⁇ 0 aryl, and hydroxyalkyl (meth)- acrylates, in particular of a C 2 -C ⁇ hydroxyalkyl.
  • Alkyl (meth) acrylates which may be mentioned include methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth) - acrylate.
  • Hydroxyalkyl (meth) acrylates which may be mentioned include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate .
  • Aryl (meth) acrylates which may be mentioned include benzyl or phenyl acrylate.
  • the (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .
  • Free-radical polymers that are preferably used are copolymers of (meth) acrylic acid and of an alkyl (meth) acrylate, especially of a C ⁇ -C 4 alkyl. More preferentially, methyl acrylates may be used, optionally copolymerized with acrylic acid.
  • Amides of the acidic monomers which may be mentioned include (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular of a C 2 -C ⁇ 2 alkyl, such as N-ethylacrylamide, N-t-butylacrylamide and N-octylacrylamide; N-di (C ⁇ -C 4 ) alkyl (meth) acryl- amides.
  • the vinyl film-forming polymers can result from the polymerization of monomers containing ethylenic unsaturation and containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers.
  • Monomers bearing an acidic group which may be used are ⁇ , ⁇ -ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid.
  • (Meth) acrylic acid and crotonic acid are preferably used, and more preferably (meth) acrylic acid.
  • esters of acidic monomers are advantageously chosen from (meth) acrylic acid esters (also known as (meth) acrylates) , especially (meth) acrylates of an alkyl, in particular of a C ⁇ -C 30 and preferably C1-C20 alkyl, (meth) acrylates of an aryl, in particular of a C ⁇ -Cio aryl, and (meth) acrylates of a hydroxyalkyl, in particular of a C 2 -C 6 hydroxyalkyl.
  • acrylic acid esters also known as (meth) acrylates
  • alkyl in particular of a C ⁇ -C 30 and preferably C1-C20 alkyl
  • aryl in particular of a C ⁇ -Cio aryl
  • hydroxyalkyl in particular of a C 2 -C 6 hydroxyalkyl.
  • alkyl (meth) acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate.
  • hydroxyalkyl (meth) acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
  • aryl (meth) acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
  • the (meth) acrylic acid esters that are particularly preferred are the alkyl (meth) acrylates .
  • the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • amides of the acidic monomers that may be mentioned are (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular of a C 2 -C 12 alkyl.
  • N-alkyl (meth) acrylamides that may be mentioned are N-ethylacrylamide, N-t- butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide .
  • the vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acidic monomers and/or esters thereof and/or amides thereof, such as those mentioned above.
  • vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
  • the polymers in dispersion of the invention may be chosen from the following polymers or copolymers: polyurethanes, polyurethane-acrylics, polyureas, polyurea- polyurethanes, polyester-polyurethanes, polyether- polyurethanes, polyesters, polyesteramides, fatty-chain polyesters, alkyds; acrylic and/or vinyl polymers or copolymers; acrylic-silicone copolymers; polyacryl- amides; silicone polymers, for example silicone polyurethanes or silicone acrylics, and fluoro polymers, and mixtures thereof.
  • the polymer (s) in oily dispersion may represent (as solids or active material) from 0.1% to 60% by weight, preferably from 2% to 40% and better still from 4% to 25% of the weight of the composition.
  • the amount of solids in the dispersion represents the total amount of polymer and of stabilizer.
  • the liposoluble or dispersible polymers in the composition of the invention may also be used in an amount ranging from 0.01% to 20% (as active material), for instance from 1% to 10%, where appropriate, relative to the total weight of the composition.
  • the film- forming polymer may be chosen from aqueous dispersions of polymer particles, in the case where the composition according to the invention comprises an aqueous phase.
  • the aqueous dispersion comprising one or more film-forming polymers may be prepared by a person skilled in the art on the basis of his general knowledge, especially by emulsion polymerization or by dispersion of the preformed polymer.
  • the film-forming polymers which may be used in the composition according to the present invention, mention may be made of synthetic polymers, of polycondensate type or of free-radical type, polymers of natural origin and mixtures thereof.
  • polyurethanes examples include anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane- polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea- polyurethanes, and mixtures thereof.
  • the polyurethanes may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane, polyurea/polyurethane or polyurea copolymer, containing, alone or as a mixture,
  • - at least one substituted or unsubstituted, branched or unbranched silicone block for example polydimethylsiloxane or polymethylphenylsiloxane, and/or - at least one block comprising fluoro groups.
  • the polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds containing mobile hydrogens, which are modified by means of a polyaddition with a diisocyanate and a difunctional organic co-reactive compound (for example dihydro, diamino or hydroxyamino) , also containing either a carboxylic acid or carboxylate group, or a sulfonic acid or sulfonate group, or alternatively a neutralizable tertiary amine group or a quaternary ammonium group. Mention may also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxyester resins.
  • the polyesters may be obtained, in a known manner, by polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or polyols.
  • Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid may be used as aliphatic diacids.
  • Terephthalic acid or isophthalic acid, or alternatively a derivative such as phthalic anhydride may be used as aromatic diacids.
  • Ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and 4, 4-N- (1-methyl- propylidene) bisphenol may be used as aliphatic diols.
  • Glycerol, pentaerythritol, sorbitol and trimethylolpropane may be used as polyols.
  • the polyesteramides may be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or amino alcohols.
  • Ethylenediamine, hexamethylenediamine or meta- or para- phenylenediamine may be used as diamine.
  • Monoethanolamine may be used as amino alcohol.
  • monomer bearing an anionic group which may be used during the polycondensation
  • the fatty-chain polyesters may be obtained using fatty-chain diols during the polycondensation.
  • the epoxy ester resins may be obtained by polycondensation of fatty acids with a condensate having ⁇ , ⁇ -diepoxy ends.
  • the free-radical polymers may especially be acrylic and/or vinyl polymers or copolymers.
  • Anionic radical polymers are preferred.
  • monomer bearing an anionic group which may be used during the radical polymerization mention may be made of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride or 2- acrylamido-2-methylpropane-sulfonic acid.
  • the acrylic polymers may result from the copolymerization of monomers chosen from the esters and/or amides of acrylic acid or of methacrylic acid.
  • monomers of ester type mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate.
  • monomers of amide type mention may be made of N-t- butylacrylamide and N-t-octylacrylamide.
  • the vinyl polymers may result from the homopolymerization or copolymerization of monomers chosen from vinyl esters, styrene or butadiene.
  • vinyl esters mention may be made of vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate .
  • Acrylic/silicone copolymers or nitrocellulose/acrylic copolymers may also be used.
  • the solids content of the said aqueous dispersion may be from about 3% to 60% and preferably from 10% to 50% by weight.
  • the size of the polymer particles in aqueous dispersion may be between 10 and 500 nm and is preferably between 20 and 150 nm, allowing the production of a film of noteworthy gloss. However, particle sizes ranging up to 1 micron may be used.
  • Aqueous dispersions of film-forming polymers that may be used include the acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, Dow Latex 432® by the company Dow Chemical, Daitosol 5000 AD® or Daitosol 5000 SJ by the company Daito Kasey Kogyo; Syntran 5760 by the company Interpolymer or the aqueous dispersions of polyurethane sold under the names Neorez R-981® and Neorez R-974® by the company Avecia-Neoresins, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure 2060® by the company Goodrich,
  • the film-forming polymer may be a water-soluble polymer.
  • the water-soluble polymer is thus dissolved in the aqueous phase of the composition.
  • the water-soluble film-forming polymers that may be mentioned are the following cationic polymers : (1) acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; the copolymers of the family (1) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone- acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, or vinyl esters .
  • these copolymers of the' family (1) mention may be made of:
  • Such products are sold in particular under the trade names Jaguar C13S, Jaguar C15 and Jaguar C17 by the company Meyhall.
  • the products sold corresponding to this definition are, more particularly, the products sold under the name "Celquat L 200" and "Celquat H 100" by the company National Starch.
  • film-forming water-soluble polymers that may be mentioned are the following amphoteric polymers : (1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, ⁇ -chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and -acrylamide.
  • polymers comprising zwitterionic units.
  • chitosan-based polymers polymers derived from the N-carboxy- alkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name "Evalsan” by the company Jan Dekker.
  • These copolymers may also comprise other vinyl comonomers, such as vinylcaprolactam.
  • the water-soluble film-forming polymers are preferably chosen from the group consisting of:
  • proteins of plant origin such as wheat proteins and soybean proteins
  • proteins of animal origin such as keratin, for example keratin hydrolysates and sulfonic keratins
  • - anionic, cationic, amphoteric or nonionic chitin or chitosan polymers - polymers of cellulose such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, and quaternized cellulose derivatives;
  • vinyl polymers for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of maleic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate;
  • - polymers of natural origin which are optionally modified, such as: . gum arabic, guar gum, xanthan derivatives, karaya gum;
  • glycosaminoglycans hyaluronic acid and derivatives thereof
  • shellac resin san.darac gum
  • dammar resins elemi gums and copal resins
  • the film-forming polymer may be chosen from polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane .
  • polymers may be liposoluble, lipodispersible, water-soluble or dispersible in aqueous medium, where appropriate.
  • the polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane consist of an organic main chain formed from organic monomers not comprising silicone, onto which is grafted, within the said chain and also optionally on at least one of its ends, at least one polysiloxane macromer.
  • polysiloxane macromer is understood to refer to any monomer containing a polysiloxane-type polymer chain in its structure.
  • the non-silicone organic monomers constituting the main chain of the grafted silicone polymer can be chosen from free-radical-polymerizable monomers containing ethylenic unsaturation, polycondensation-polymerizable monomers, such as those forming polyamides, polyesters or polyurethanes, and ring-opening monomers, such as those of the oxazoline or caprolactone type.
  • the polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane can be obtained according to any means known to those skilled in the art, in particular by reaction between (i) a starting polysiloxane macromer which is correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, themselves correctly functionalized with a function which is capable of reacting with the functional group (s) borne by the said silicone, forming a covalent bond; a classic example of such a reaction is the free-radical reaction between a vinyl group borne on one of the ends of the silicone with a double bond of a monomer containing ethylenic unsaturation in the main chain.
  • polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane are more preferably chosen from those described in patents US 4 693 935, US 4 728 571 and US 4 972 037 and patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578.
  • copolymers obtained by free-radical polymerization starting with monomers containing ethylenic unsaturation and monomers having a terminal vinyl group or alternatively copolymers obtained by reaction of a polyolefin comprising functionalized groups and a polysiloxane macromer having a terminal function which is reactive with the said functionalized groups.
  • One particular family of grafted silicone polymers which is suitable for carrying out the present invention consists of grafted silicone polymers comprising: a) from 0% to 98% by weight of at least one free- radical-polymerizable lipophilic monomer (A) of low polarity containing ethylenic unsaturation; b) from 0% to 98% by weight of at least one polar hydrophilic monomer (B) containing ethylenic unsaturation, which is copolymerizable with the monomer (s) of the type (A); c) from 0.01% to 50% by weight of at least one polysiloxane macromer (C) of general formula: X(Y) n Si(R) 3 .
  • X denotes a vinyl group which is copolymerizable with the monomers (A) and (B) ;
  • Y denotes a divalent bonding group;
  • R denotes hydrogen, Ci-C ⁇ alkyl or alkoxy, or C 6 ⁇ C ⁇ 2 aryl ;
  • Z denotes a monovalent polysiloxane unit with a number- average molecular weight of at least 500; n is 0 or 1 and m is an integer ranging from 1 to 3; the percentages being calculated relative to the total weight of the monomers (A) , (B) and (C) .
  • These polymers have a number-average molecular weight ranging from 10 000 to 2 000 000 and preferably a glass transition temperature Tg or a crystal melting temperature Tm of at least -20°C.
  • lipophilic monomers (A) mention may be made of acrylic or methacrylic acid esters of Ci-Ci ⁇ alcohols; methacrylic acid esters of C ⁇ 2 -C 30 alcohols, styrene; polystyrene macromers; vinyl acetate; vinyl propionate; -methylstyrene; tert- butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; acrylic or methacrylic acid esters of a 1, 1-dihydroperfluoroalkanol or of homologues thereof; acrylic or methacrylic acid esters of an ⁇ -hydrofluoroalkanol; acrylic or methacrylic acid esters of a fluoroalkylsulfonamido alcohol; acrylic or methacrylic acid esters of fluoroalkyl alcohols; acrylic or methacrylic acid esters of fluoroether alcohols; or mixtures thereof.
  • the preferred monomers (A) are chosen from the group consisting of n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2- (N-methylperfluorooctanesulfonamido) ethyl acrylate and 2- (N-butylperfluorooctanesulfonamido) ethyl acrylate, and mixtures thereof.
  • polar monomers (B) mention may be made of acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth) acrylamide, N-t-butylacrylamide, maleic acid, maleic anhydride and hemiesters thereof, hydroxyalkyl (meth) acrylates, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinyl- pyridine, vinylimidazole, heterocydic vinyl polar compounds, styrene sulfonate, allyl alcohol, vinyl alcohol and vinylcaprolactam, or mixtures thereof.
  • the preferred monomers (B) are chosen from the group consisting of acrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate and vinylpyrrolidone, and mixtures thereof. Mention is made especially of the product KP
  • R 1 is hydrogen or -COOH (preferably hydrogen) ;
  • R 2 is hydrogen, methyl or -CH 2 COOH (preferably methyl);
  • R 3 is C ⁇ -C 6 alkyl, alkoxy, or alkylamino, C 6 -C ⁇ 2 aryl or hydroxyl (preferably methyl) ;
  • R 4 is C ⁇ -C 6 alkyl, alkoxy or alkylamino, C 6 ⁇ C ⁇ 2 aryl or hydroxyl (preferably methyl) ; q is an integer from 2 to 6 (preferably 3); p is 0 or 1; r is an integer from 5 to 700; m is an integer from 1 to 3 (preferably 1) .
  • One embodiment of the invention consists in using a copolymer which may be obtained by free-radical polymerization starting with the monomer mixture consisting of: a) 60% by weight of tert-butyl acrylate; b) 20% by weight of acrylic acid; c) 20% by weight of silicone macromer of formula:
  • n a number ranging from 5 to 700 and 1 being an integer between 0 and 3; the weight percentages being calculated relative to the total weight of the monomers .
  • Another particular embodiment of the invention consists in using a copolymer which may be obtained by free-radical polymerization starting with the monomer mixture consisting of: a) 80% by weight of tert-butyl acrylate; b) 20% by weight of silicone macromer of formula:
  • the reactive polyolefins are preferably chosen from polyethylenes and polymers of ethylene- derived monomers such as propylene, styrene, alkylstyrene, butylene, butadiene, (meth) acrylates, vinyl esters or equivalents, comprising reactive functions capable of reacting with the terminal function of the polysiloxane macromer.
  • the silicone macromers are preferably chosen from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or close to the end of the said chain, chosen from the group consisting of alcohols, thiols, epoxy groups and primary and secondary amines, and more particularly from those corresponding to the general formula: T- (CH 2 ) 6 -Si- [- (OSiR 5 R 6 ) t -R 7 ] y (HI) in which T is chosen from the group consisting of NH 2 , NHRN and an epoxy, OH, or SH function; R 5 , R 6 , R 7 and RN independently denote a C ⁇ -C 6 alkyl, phenyl, benzyl, or C 6 -Ci 2 alkylphenyl or hydrogen; s is a number from 2 to 100; t is a number from 0 to 1000 and y is a number from 1 to 3.
  • the film-forming polymer may be purchased from the Minnesota Mining and Manufacturing Company under the trade name "Silicone Plus" polymers.
  • poly (isobutyl methacrylate-co-methyl FOSEA) -g- poly (dimethylsiloxane) is sold under the trade name SA 70-5 IBMMF.
  • the film-forming polymer is chosen from silicone polymers grafted with non-silicone organic monomers. These polymers may be liposoluble, lipodispersible, water-soluble or dispersible in aqueous medium, where appropriate.
  • the said grafted silicone polymer (s) containing a polysiloxane skeleton grafted with non- silicone organic monomers comprise a silicone (or polysiloxane (/Si-0-) n ) main chain onto which is grafted, within the said chain and also optionally on at least one of its ends, at least one organic group not comprising silicone.
  • the silicone polymer containing a polysiloxane skeleton grafted with non-silicone organic monomers which is used comprises the result of the free-radical copolymerization between, on the one hand, at least one non-silicone anionic organic monomer containing ethylenic unsaturation and/or a non-silicone hydrophobic organic monomer containing ethylenic unsaturation, and, on the other hand, a silicone containing in its chain at least one, and preferably several, functional group (s) capable of reacting with the said ethylenic unsaturations of the said non-silicone monomers, forming a covalent bond, in particular thio functional groups .
  • the said anionic monomers containing ethylenic unsaturation are preferably chosen, alone or as mixtures, from linear or branched, unsaturated carboxylic acids, optionally partially or totally neutralized in the form of a salt, it being possible for this or these unsaturated carboxylic acid(s) to be, more particularly, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and crotonic acid.
  • the suitable salts are, in particular, alkali metal salts, alkaline-earth metal salts and ammonium salts.
  • the organic group of anionic nature which comprises the result of the free-radical (homo) polymerization of at least one anionic monomer of unsaturated carboxylic acid type can, after reaction, be post-neutralized with a base (sodium hydroxide, aqueous ammonia, etc) in order to place it in the form of a salt.
  • a base sodium hydroxide, aqueous ammonia, etc
  • the hydrophobic monomers containing ethylenic unsaturation are preferably chosen, alone or as mixtures, from acrylic acid esters of alkanols and/or methacrylic acid esters of alkanols.
  • the alkanols are preferably C ⁇ -C 3 o and more particularly C ⁇ -C 22 .
  • the preferred monomers are chosen from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate, or mixtures thereof.
  • silicone polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers that is particularly suitable for carrying out the present invention consists of silicone polymers comprising in their structure the unit of formula IV below: 9. ? • (-Si-O-)- ⁇ (—Si-0-) 6 (— ?Si ⁇ -o—) c (G 2 ) n -S-G 2 G, (G 2 )-S-G 4 (IV) in which the radicals Gi, which may be identical or different, represent hydrogen, a Ci-Cio alkyl radical or a phenyl radical; the radicals G 2 , which may be identical or different, represent a Ci-Cio alkylene group; G 3 represents a polymer residue resulting from the (homo) polymerization of at least one anionic monomer containing ethylenic unsaturation; G 4 represents a polymer residue resulting from the (homo) polymerization of at least one hydrophobic mono
  • radicals Gi denote an alkyl radical, preferably a methyl radical
  • radicals G 2 represent a divalent C 1 -C 3 radical, preferably a propylene radical
  • - G 3 represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the carboxylic acid type containing ethylenic unsaturation, preferably acrylic acid and/or methacrylic acid;
  • - G 4 represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the (Ci-Cio) alkyl (meth) acrylate type, preferably isobutyl or methyl (meth) acrylate .
  • silicone polymers corresponding to formula (IV) are, in particular, polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, mixed polymer units of the poly (meth) acrylic acid type and of the polyalkyl (meth) acrylate type.
  • Other examples of silicone polymers corresponding to formula (IV) are, in particular, polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, polymer units of the polyisobutyl (meth) acrylate type.
  • Such polymers comprise polymers comprising at least one group of formula:
  • a, b and c which may be identical or different, are each a number ranging from 1 to 100 000; and the end groups, which may be identical or different, are each chosen from linear C ⁇ -C 2 o alkyl groups, C 3 -C 2 o branched- chain alkyl groups, C 3 -C 2 o aryl groups, linear C ⁇ -C 20 alkoxy groups and branched C 3 -C 20 alkoxy groups.
  • Such polymers are disclosed in patents US 4 972 037, 5 061 481, 5 209 924, 5 849 275, 6 033 650 and WO 93/23446 and WO 95/06078.
  • Another family of silicone polymers having a polysiloxane skeleton grafted with non-silicone organic monomers which is particularly suitable for performing the present invention, consists of silicone polymers comprising in their structure the unit of formula (V) below:
  • G 5 represents a polymer residue resulting from the (homo) polymerization of at least one ethylenically unsaturated hydrophobic monomer or from the copolymerization of at least one ethylenically unsaturated anionic monomer and of at least one ethylenically unsaturated hydrophobic monomer; n is equal to 0 or 1; a is an integer ranging from 0 to 50; b is an integer that may be between 10 and 350; on condition that a is other than 0.
  • the unit of formula (V) in the above text preferably has at least one, and even more preferably all, of the following characteristics:
  • radicals Gi denote an alkyl radical, preferably a methyl radical
  • the radicals G represent a C 1 -C 3 divalent radical, preferably a propylene radical.
  • the number-average molecular mass of the silicone polymers with a polysiloxane skeleton grafted with non-silicone organic monomers of the invention preferably ranges from about 10 000 to 1 000 000 and even more preferably from about 10 000 to 100 000.
  • the composition may contain from 0.5% to 60% by weight, better still from 1% to 40% and preferably from 2% to 30% by weight of solids of film-forming agent relative to the total weight of the composition.
  • the total amount of polymer should be an amount sufficient to form on the skin and/or the lips a cohesive film capable of following the movements of the skin and/or the lips without becoming detached or cracking.
  • a plasticizer may be combined therewith so as to lower this temperature of the mixture used.
  • the plasticizer may be chosen from the plasticizers usually used in the field of application, and especially from compounds that may be solvents for the polymer.
  • the composition according to the invention may comprise an aqueous medium, constituting an aqueous phase, which may form the continuous phase of the composition.
  • the aqueous phase may consist essentially of water; it may also comprise a mixture of water and of water-miscible solvent (water miscibility of greater than 50% by weight at 25°C) , for instance lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol or isopropanol, glycols containing from 2 to 8 carbon atoms, such as propylene glycol, ethylene glycol, 1,3-butylene glycol or dipropylene glycol, C 3 -C 4 ketones and C 2 -C 4 aldehydes, and mixtures thereof.
  • water-miscible solvent water miscibility of greater than 50% by weight at 25°C
  • lower monoalcohols containing from 1 to 5 carbon atoms, such as ethanol or isopropanol
  • glycols containing from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol or dipropylene glycol, C 3 -C 4 ketones
  • the aqueous phase (water and optionally the water-miscible solvent) may be present in a content ranging from 0.1% to 95% by weight and preferably ranging from 1% to 80% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises a cosmetically acceptable medium (acceptable tolerance, toxicology and feel).
  • the composition according to the invention may also comprise at least one fatty substance that is solid at room temperature, especially chosen from waxes, pasty fatty substances and gums, and mixtures thereof. These fatty substances may be of animal, plant, mineral or synthetic origin.
  • the composition according to the invention may comprise a wax or a mixture of waxes.
  • the wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25°C) , with a solid/liquid reversible change of state, having a melting point of greater than or equal to 30°C, which may be up to 120°C.
  • the waxes that are suitable for the invention may have a melting point of greater than about 45°C and in particular greater than 55°C.
  • the melting point of the wax may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler.
  • DSC differential scanning calorimeter
  • the measuring protocol is as follows: A sample of 15 mg of product placed in a crucible is subjected to a first temperature rise ranging from 0°C to 120°C, at a heating rate of 10°C/minute, it is then cooled from 120°C to 0°C at a cooling rate of 10°C/minute and is finally subjected to a second temperature increase ranging from 0°C to 120°C at a heating rate of 5°C/minute.
  • the variation of the difference in power absorbed by the empty crucible and by the crucible containing the sample of product is measured as a function of the temperature.
  • the melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in absorbed power as a function of the temperature.
  • the waxes that may be used in the compositions according to the invention are chosen from waxes that are solid and rigid at room temperature of animal, plant, mineral or synthetic origin, and mixtures thereof.
  • the wax may also have a hardness ranging from 0.05 MPa to 30 MPa, preferably ranging from 6 MPa to 15 MPa.
  • the hardness is determined by measuring the compression force, measured at 20°C using a texturometer sold under the name TA-XT2i by the company Rheo, equipped with a stainless-steel cylindrical spindle 2 mm in diameter, travelling at a measuring speed of 0.1 mm/s, and penetrating into the wax to a penetration depth of 0.3 mm.
  • the measuring protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 20°C. The molten wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25°C) for 24 hours and is then stored for at least 1 hour at 20°C, before performing the hardness measurement.
  • the hardness value is the maximum compression force measured, divided by the area of the texturometer spindle in contact with the wax.
  • Hydrocarbon-based waxes for instance beeswax, lanolin wax, Chinese insect waxes, rice wax, carnauba wax, candelilla wax, ouricurry wax, esparto grass wax, cork fibre wax, sugar cane wax, Japan wax and sumach wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy copolymers, and also esters thereof, may especially be used.
  • waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C 8 -C 32 fatty chains may also be made especially.
  • isomerized jojoba oil such as the partially hydrogenated isomerized jojoba oil manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50 ® , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, bis (1, 1, 1-trimethylolpropane) tetrastearate sold under the name "Hest 2T-4S" by the company Heterene and bis (1, 1, 1-trimethylolpropane) tetrabehenate sold under the name Hest 2T-4B by the company Heterene.
  • compositions according to the invention may comprise at least one "tacky" wax, i.e.
  • a wax with a tack of greater than or equal to 0.7 N.s and a hardness of less than or equal to 3.5 MPa may especially make it possible to obtain a cosmetic composition that is easy to apply to keratin fibres, shows good attachment to the keratin fibres and leads to the formation of a smooth, uniform and thickening makeup result.
  • the tacky wax used may especially have a tack ranging from 0.7 N.s to 30 N.s, in particular greater than or equal to 1 N.s, especially ranging from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, especially ranging from 2 N.s to 10 N.s and in particular ranging from 2 N.s to 5 N.s.
  • the tack of the wax is determined by measuring the change in force (compression force or stretching force) as a function of time, at 20°C, using the texturometer sold under the name "TA-XTTX2i ® " by the company Rheo, equipped with a conical acrylic polymer spindle forming an angle of 45°.
  • the measuring protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 10°C. The molten wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25°C) for 24 hours such that the surface of the wax is flat and smooth, and the wax is then stored for at least 1 hour at 20°C before measuring the tack.
  • the texturometer spindle is displaced at a speed of 0.5 mm/s then penetrates the wax to a penetration depth of 2 mm.
  • the spindle is held still for 1 second (corresponding to the relaxation time) and is then withdrawn at a speed of 0.5 mm/s .
  • the force compression force
  • the force decreases greatly until it becomes zero, and then, during the withdrawal of the spindle, the force (stretching force) becomes negative and then rises again to the value 0.
  • the tack corresponds to the integral of the curve of the force as a function of time for the part of the curve corresponding to negative values of the force (stretching force) .
  • the tack value is expressed in N.s.
  • the tacky wax that may be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa or even ranging from 0.1 MPa to 2.5 MPa. The hardness is measured according to the protocol described previously.
  • Tacky waxes that may be used include a C 20 -C 40 alkyl (hydroxystearyloxy) stearate (the alkyl group containing from 20 to 40 carbon atoms), alone or as a mixture, in particular a C 20 -C 4 o alkyl 12- (12'- hydroxystearyloxy) stearate, of formula (II):
  • the waxes mentioned above generally have a starting melting point of less than 45°C.
  • the wax(es) may be in the form of an aqueous microdispersion of wax.
  • aqueous microdispersion of wax means an aqueous dispersion of wax particles in which the size of the said wax particles is less than or equal to about 1 ⁇ m.
  • Wax microdispersions are stable dispersions of colloidal wax particles, and are described especially in "Microemulsions Theory and Practice", L.M. Prince Ed., Academic Press (1977) pages 21-32.
  • these wax microdispersions may be obtained by melting the wax in the presence of a surfactant, and optionally of a portion of water, followed by gradual addition of hot water with stirring. The intermediate formation of an emulsion of the water-in-oil type is observed, followed by a phase inversion, with final production of a microemulsion of the oil-in-water type. On cooling, a stable microdispersion of solid wax colloidal particles is obtained.
  • the wax microdispersions may also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high-pressure homogenizers or turbomixers.
  • the particles of the wax microdispersion preferably have mean sizes of less than 1 ⁇ m
  • These particles consist essentially of a wax or a mixture of waxes. However, they may comprise a small proportion of oily and/or pasty fatty additives, a surfactant and/or a common liposoluble additive/active agent.
  • pasty fatty substance means a lipophilic fatty compound comprising at a temperature of 23°C a liquid fraction and a solid fraction. The said pasty compound preferably has a hardness at 20°C ranging from 0.001 to 0.5 MPa and preferably from 0.002 to 0.4 MPa.
  • the hardness is measured according to a method of penetration of a probe in a sample of compound and in particular using a texture analyzer (for example the TA-XT2i machine from Rheo) equipped with a stainless-steel spindle 2 mm in diameter.
  • the hardness measurement is performed at 20°C at the centre of five samples.
  • the spindle is introduced into each sample at a pre-speed of 1 mm/s and then at a measuring speed of 0.1 mm/s, the penetration depth being 0.3 mm.
  • the hardness value revealed is that of the maximum peak.
  • the liquid fraction of the pasty compound measured at 23°C preferably represents 9% to 97% by weight of the compound.
  • This liquid fraction at 23°C preferably represents between 15% and 85% and more preferably between 40% and 85% by weight.
  • the liquid fraction by weight of the pasty compound at 23°C is equal to the ratio of the heat of fusion consumed at 23°C to the heat of fusion of the pasty compound.
  • the heat of fusion of the pasty compound is the heat consumed by the compound to change from the solid state to the liquid state.
  • the pasty compound is said to be in the solid state when all of its mass is in solid crystalline form.
  • the pasty compound is said to be in the liquid state when all of its mass is in liquid form.
  • the heat of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name MDSC 2920 by the company TA Instrument, with a temperature rise of 5 or 10°C per minute, according to standard ISO 11357-3:1999.
  • the heat of fusion of the pasty compound is the amount of energy required to make the compound change from the solid state to the liquid state. It is expressed in J/g.
  • the heat of fusion consumed at 23°C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23°C, consisting of a liquid fraction and a solid fraction.
  • the liquid fraction of the pasty compound, measured at 32°C preferably represents from 30% to
  • the liquid fraction of the pasty compound measured at 32 °C is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 °C.
  • the liquid fraction of the pasty compound measured at 32°C is equal to the ratio of the heat of fusion consumed at 32°C to the heat of fusion of the pasty compound.
  • the heat of fusion consumed at 32°C is calculated in the same manner as the heat of fusion consumed at 23°C.
  • the pasty substances are generally hydrocarbon-based compounds, for instance lanolins and derivatives thereof, or PDMSs. The nature and amount of the solid substances depend on the desired mechanical properties and textures.
  • the composition may contain from 0.1% to 50% by weight, better still from 1% to 40% and even better still from 5% to 30% by weight of waxes, relative to the total weight of the composition.
  • the composition according to the invention may also comprise one or more dyestuffs chosen from water-soluble dyes, and pulverulent dyestuffs, for instance pigments, nacres and flakes that are well known to those skilled in the art.
  • the dyestuffs may be present in the composition in a content ranging from 0.01% to 50% by weight and preferably from 0.01% to 30% by weight relative to the weight of the composition.
  • pigments should be understood as meaning white or coloured, mineral or organic particles of any form, which are insoluble in physiological medium, and which are intended to colour the composition.
  • nacres should be understood as meaning iridescent particles of any form, especially produced by certain molluscs in their shell, or alternatively synthesized.
  • the pigments may be white or coloured, and mineral and/or organic.
  • mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders, for instance aluminium powder or copper powder.
  • organic pigments that may be mentioned are carbon black, pigments of D & C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium. Mention may also be made of pigments with an effect, such as particles comprising a natural or synthetic, organic or mineral substrate, for instance glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate possibly being coated with metallic substances, for instance aluminium, gold, silver, platinum, copper, bronze or metal oxides, for instance titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
  • metallic substances for instance aluminium, gold, silver, platinum, copper, bronze or metal oxides, for instance titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
  • the nacreous pigments may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica coated with iron oxides, titanium mica coated especially with ferric blue or with chromium oxide, titanium mica coated with an organic pigment of the abovementioned type and also nacreous pigments based on bismuth oxychloride. It is also possible to use interference pigments, especially containing liquid crystals or multilayers.
  • one subject of the present invention is a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, a dispersion of particles of a non-silicone grafted ethylenic polymer in a liquid fatty phase, at least one other film- forming agent and a pulverulent dyestuff, especially in the form of pigments.
  • the liposoluble dyes are, for example, Sudan Red, D & C Red 17, D & C Green 6, ⁇ -carotene, soybean oil, Sudan Brown, D & C Yellow 11, D & C Violet 2, D & C Orange 5, quinoline yellow or annatto.
  • the water- soluble dyes are, for example, beetroot juice, methylene blue, the disodium salt of ponceau, the disodium salt of alizarin green, quinoline yellow, the trisodium salt of amaranth, the disodium salt of tartrazine, the monosodium salt of rhodamine, the disodium salt of fuchsin, or xanthophyll.
  • the composition according to the invention may comprise at least one filler, especially in a content ranging from 0.01% to 50% by weight and preferably ranging from 0.01% to 30% by weight relative to the total weight of the composition.
  • fillers should be understood as meaning colourless or white, mineral or synthetic particles of any form, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or texture of the composition.
  • the fillers may be mineral or organic and of any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc) .
  • composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, fibres, agents for preventing hair loss, eyelash care agents, antidandruff agents and propellants, or mixtures thereof.
  • cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, fibres, agents for preventing hair loss, eyelash care agents, antidandruff agents and propellants, or mixtures thereof.
  • the term "fibre” should be understood as meaning an object of length L and diameter D such that L is very much greater than D, D being the diameter of the circle within which the cross section of the fibre is inscribed.
  • the ratio L/D is chosen within the range from 3.5 to 2500, preferably from 5 to
  • the fibres have a length ranging from 1 ⁇ m to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm.
  • the fibres that may be used in the composition of the invention may be chosen from rigid and non-rigid fibres, and they may be of synthetic or natural, mineral or organic origin.
  • non- rigid fibres such as polyamide (Nylon ® ) fibres, or rigid fibres, such as polyimide-amide fibres, for instance those sold under the name “Kermel” or “Kermel Tech” by the company Rhodia, or poly (p-phenyleneterephthalamide) (or aramid) fibres, sold especially under the name Kevlar ® by the company DuPont de Nemours.
  • the fibres may be present in the composition according to the invention in a content ranging from 0.1% to 10% by weight and better still from 0.5% to 5% by weight relative to the total weight of the composition.
  • the gelling agents that may be used in the compositions according to the invention may be organic or mineral, and polymeric or molecular, hydrophilic or lipophilic gelling agents.
  • Mineral lipophilic gelling agents that may be mentioned include optionally modified clays, for instance hectorites modified with a C ⁇ 0 to C 22 fatty acid ammonium chloride, for instance hectorite modified with distearyldimethylammonium chloride, for instance the product sold under the name "Bentone 38V ® " by the company Elementis. Mention may also be made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size of which is less than 1 ⁇ m.
  • silica it is possible to chemically modify the surface of the silica, by chemical reaction generating a reduced number of silanol groups present at the surface of the silica. It is especially possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.
  • the hydrophobic groups may be: - trimethylsiloxyl groups, which are obtained especially by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "silica silylate" according to the CTFA (6th edition, 1995) .
  • the hydrophobic fumed silica particularly has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.
  • the polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes of three- dimensional structure, for instance those sold under the names "KSG6 ® “, “KSG16 ® “ and “KSG18 ® “ from Shin-Etsu, “Trefil E-505C ® “ and “Trefil E-506C ® “ from Dow Corning, "Gransil SR-CYC ® “, “SR DMF 10 ® “, “SR-DC556 ® “, “SR 5CYC gel ® “, “SR DMF 10 gel ® “ and “SR DC 556 gel ® “ from Grant Industries and "SF 1204 ® “ and “JK 113 ® “ from General Electric; polycondensates of polyamide type resulting from the condensation between ( ⁇ ) at least one acid chosen from dicarboxylic acids comprising at least 32 carbon atoms, such as fatty acid dimers, and ( ⁇ ) an alkylene diamine and in particular
  • lipophilic gelling agents that may be used in the compositions according to the invention, mention may also be made of fatty acid esters of dextrin, such as dextrin palmitates, especially the products sold under the name “Rheopearl TL “ or “Rheopearl KL ® " by the company Chiba Flour.
  • the lipophilic gelling agents may be present in the composition according to the invention in a content ranging from 0.05% to 40% by weight, preferably from 0.5% to 20% and better still from 1% to 15% by weight relative to the total weight of the composition.
  • Hydrophilic or water-soluble gelling agents that may be mentioned include: - homopolymers or copolymers of acrylic or methacrylic acid or the salts and esters thereof, and in particular the products sold under the names
  • - nonionic associative polymers which are preferably chosen from:
  • celluloses modified with groups comprising at least one fatty chain mention may be made, for example, of: - hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C 8 -C 22 , such as the product Natrosol Plus Grade 330 CS (C ⁇ 6 alkyls) sold by the company Aqualon, or the product Bermocoll EHM 100 sold by the company Berol Nobel, - those modified with polyalkylene glycol alkylphenol ether groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol.
  • - hydroxyethylcelluloses modified with groups comprising at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof
  • the alkyl groups are preferably C 8
  • hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product Esaflor HM 22 (C 22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C ⁇ 4 alkyl chain) and RE205-1 (C 20 alkyl chain) sold by the company Rh ⁇ ne-Poulenc .
  • polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences.
  • Ser Ad FX1100 which is a molecule containing urethane functions and having a weight- average molecular weight of 1300
  • OE being an oxyethylene unit
  • Rheolate 205 containing urea functions sold by the company Rheox
  • Rheolate 208 or 204 (these polymers being sold
  • a unit of formula (I) that is more particularly preferred according to the present invention is a unit in which R' denotes H, n is equal to 10 and R denotes a stearyl (Cis) radical.
  • Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.
  • the hydrophilic gelling agents may be present in the composition according to the invention in a content ranging from 0.05% to 20% by weight, preferably from 0.5% to 10% and better still from 0.8% to 5% by weight relative to the total weight of the composition.
  • composition according to the invention may contain emulsifying surfactants, which are especially present in a proportion ranging from 0.5% to 30% by weight, better still from 1% to 15% and even better still from 3% to 10% relative to the total weight of the composition.
  • surfactants may be chosen from anionic, cationic and nonionic surfactants.
  • the surfactants preferably used in the composition according to the invention are chosen from: a) nonionic surfactants with an HLB of greater than or equal to 8 at 25°C, used alone or as a mixture; mention may be made especially of: - oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol; - oxyethylenated and/or oxypropylenated ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C 8 -C 24 and preferably C ⁇ 2 -C 18 alcohol), such as oxyethylenated cetearyl alcohol ether containing 30 oxyethylene groups (CTFA name "Ceteareth-30”) and the oxyethylenated ether of the mixture of C ⁇ 2 -C ⁇ 5 fatty alcohols comprising 7 oxyethylene groups (CTFA
  • Varionic LI 13 sold by the company Sherex, glyceryl isostearate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat L sold by the company Goldschmidt, and glyceryl laurate polyethoxylated with 30 ethylene oxide groups, for instance the product Tagat I from the company Goldschmidt; - fatty acid esters (especially of a C 8 -C 24 and preferably C ⁇ 6 -C 22 acid) of oxyethylenated and/or oxypropylenated sorbitol ethers (which may comprise from 1 to 150 oxyethylene and/or oxypropylene groups), for instance polysorbate 60 sold under the name "Tween 60" by the company Uniqema; - dimethicone copolyol, such as the product sold under the name "Q2-5220" by the company Dow Corning, - dimethicone copolyol benzoate (Finsolv SLB 101 and 201 by the company Finetex
  • nonionic surfactants with an HLB of less than or equal to 8 at 25°C optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25°C, as mentioned above, such as: - saccharide esters and ethers, such as sucrose stearate, sucrose cocoate and sorbitan stearate, and mixtures thereof, for instance Arlatone 2121 sold by the company ICl; - fatty acid esters (especially of a C 8 -C 24 and preferably Ci6-C 22 acid) of polyols, especially of glycerol or of sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name Tegin M by the company Goldschmidt, glyceryl laurate such as
  • anionic surfactants such as: - Ci 6 -C 30 fatty acid salts, especially those derived from amines, for instance triethanolamine stearate; - polyoxyethylenated fatty acid salts, especially those derived from amines or alkali metal salts, and mixtures thereof; - phosphoric esters and salts thereof, such as "DEA oleth-10 phosphate” (Crodafos N ION from the company Croda) ; - sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate” and “Disodium ricinoleamido MEA sulfosuccinate”; - alkyl ether sulfates, such as sodium lauryl ether sulfate; - isethionates; - acylglutamates such as "Disodium hydrogenated tallow glutamate" (Amisoft HS-21 R sold
  • Triethanolamine stearate is most particularly suitable for the invention.
  • This surfactant is generally obtained by simple mixing of stearic acid and triethanolamine .
  • Surfactants that allow an oil-in-water or wax-in-water emulsion to be obtained are preferably used.
  • the composition according to the invention advantageously has a solids content of greater than or equal to 40%, better still greater than
  • the composition according to the invention may especially be in the form of a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W, polyol/O/W or 0/W/O) , in the form of a cream, a paste, a mousse, a vesicular dispersion, especially of ionic or nonionic lipids, a two-phase or multi-phase lotion, a spray, a powder or a paste, especially a soft paste.
  • the composition may be anhydrous; for example, it may be an anhydrous paste or stick.
  • the composition may be a leave-in composition.
  • a person skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended use of the composition .
  • composition according to the invention may especially be in the form of a stick, a suspension, a dispersion, a solution, a gel, an emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W, polyol/O/W or O/W/0) , in the form of a cream, a paste, a mousse, a vesicular dispersion, especially of ionic or nonionic lipids, a two-phase or multi-phase lotion, a spray, a powder, a paste, especially a soft paste (especially a paste with a dynamic viscosity at 25°C of about from 0.1 to 40 Pa.s under a shear rate of 200 s "1 , after 10 minutes of measurement in cone/plate geometry) .
  • a soft paste especially a paste with a dynamic viscosity at 25°C of about from 0.1 to 40 Pa.s
  • the composition may be anhydrous; for example, it may be an anhydrous paste.
  • a person skilled in the art may select the appropriate galenical form, and also the method for preparing it, on the basis of his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and secondly the intended use of the composition.
  • the composition according to the invention may be a makeup composition, for instance products for the complexion (foundations), makeup rouges, eyeshadows, lipsticks, concealer products, blushers, mascaras, eyeliners, eyebrow makeup products, lip pencils, eye pencils, nail products, such as nail varnishes, body makeup products or hair makeup products (hair mascara or hair lacquer) .
  • the composition according to the invention may also be a skincare product for body and facial skin, especially an antisun product or a skin colouring product (such as a self-tanning product) .
  • the composition according to the invention may also be a hair product, especially for holding the hairstyle or for shaping the hair.
  • the hair compositions are preferably shampoos, gels, hairsetting lotions, blow-drying lotions, or fixing and styling compositions such as lacquers or sprays.
  • a subject of the invention is a composition for coating keratin fibres (such as the eyelashes, the eyebrows or the hair) .
  • Such a composition may be in various forms: for example in the form of a wax-in-water or water-in- wax two-phase emulsions, or aqueous or anhydrous dispersions .
  • the composition is an eyelash coating composition, or mascara.
  • a subject of the present invention is also a cosmetic assembly comprising: a container delimiting at least one compartment, the said container being closed by a closing member; and a composition as described above, placed inside the said compartment.
  • the container may be in any adequate form. It may especially be in the form of a bottle, a tube, a jar, a case, a box, a sachet or a carton.
  • the closing member may be in the form of a removable stopper, a lid, a cap, a tear-off strip or a capsule, especially of the type comprising a body attached to the container and a cover cap articulated on the body. It may also be in the form of a member for selectively closing the container, especially a pump, a valve or a flap valve.
  • the container may be combined with an applicator, especially in the form of a brush comprising an arrangement of bristles maintained by a twisted wire.- Such a twisted brush is described especially in patent US 4 887 622. It may also be in the form of a comb comprising a plurality of application members, obtained especially by moulding. Such combs are described, for example, in patent FR 2 796 529.
  • the applicator may be in the form of a fine brush, as described, for example, in patent
  • the applicator may be in the form of a block of foam or of elastomer, a felt or a spatula.
  • the applicator may be free (tuft or sponge) or securely fastened to a rod borne by the closing member, as described, for example, in patent US 5 492 426.
  • the applicator may be securely fastened to the container, as described, for example, in patent FR 2 761 959.
  • the product may be contained directly in the container, or indirectly.
  • the product may be arranged on an impregnated support, especially in the form of a wipe or a pad, and arranged (individually or in plurality) in a box or in a sachet.
  • the closing member may be coupled to the container by screwing.
  • the coupling between the closing member and the container is done other than by screwing, especially via a bayonet mechanism, by click-fastening, gripping, welding, bonding or by magnetic attraction.
  • click- fastening in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, especially of the closing member, followed by return to the elastically unconstrained position of the said portion after the crossing of the bead or cord.
  • the container may be at least partially made of thermoplastic material. Examples of thermoplastic materials that may be mentioned include polypropylene or polyethylene.
  • the container is made of non- thermoplastic material, especially glass or metal (or alloy) .
  • the container may have rigid walls or deformable walls, especially in the form of a tube or a tubular bottle.
  • the container may comprise means for distributing or facilitating the distribution of the composition.
  • the container may have deformable walls so as to allow the composition to exit in response to a positive pressure inside the container, this positive pressure being caused by elastic (or non-elastic) squeezing of the walls of the container.
  • the product may be driven out by a piston mechanism.
  • the container may comprise a mechanism, especially a rack mechanism, a threaded-rod mechanism or a helical groove mechanism, and may be capable of moving a stick in the direction of the said aperture.
  • a mechanism is described, for example, in patent FR 2 806 273 or in patent FR 2 775 566.
  • Such a mechanism for a liquid product is described in patent FR 2 727 609.
  • the container may consist of a carton with a base delimiting at least one housing containing the composition, and a lid, especially articulated on the base, and capable of at least partially covering the said base.
  • Such a carton is described, for example, in patent application WO 03/018423 or in patent FR 2 791 042.
  • the container may be equipped w;Lth a drainer arranged in the region of the aperture of the container.
  • a drainer makes it possible to wipe the applicator and possibly the rod to which it may be securely fastened.
  • Such a drainer is described, for example, in patent FR 2 792 618.
  • the composition may be at atmospheric pressure inside the container (at room temperature) or pressurized, especially by means of a propellent gas (aerosol) . In the latter case, the container is equipped with a valve (of the type used for aerosols) .
  • Examples 1 and 2 illustrate the preparation of a dispersion of grafted ethylenic polymer according to the invention.
  • the weight-average (Mw) and number- average (Mn) molar masses of the polymer, the glass transition temperature (Tg) of the polymer, the solids content (or dry extract) of the dispersion and the size of the polymer particles are determined.
  • the weight-average (Mw) and number-average (Mn) molar masses are determined by gel-permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector) .
  • the measurement of the glass transition temperature (Tg) is performed according to standard ASTM D3418-97, by differential thermal analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range of between -100°C and +150°C, at a heating rate of 10°C/minute in 150 ⁇ l aluminium crucibles .
  • the crucibles are prepared in the following manner: 100 ⁇ l of the dispersion obtained are introduced into a 150 ⁇ l aluminium crucible and the solvent is allowed to evaporate over 24 hours at room temperature and at 50% RH. The operation is repeated and the crucible is then introduced into a Mettler DSC30 calorimeter.
  • the amount of non-volatile matter may be measured in various ways: mention may be made, for example, of the methods by oven-drying or the methods by drying by exposure to infrared radiation.
  • the solids content of the polymer dispersion obtained is preferably measured by heating the sample with infrared rays with a wavelength of from 2 ⁇ m to 3.5 ⁇ m.
  • the substances contained in the composition that have a high vapour pressure evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition.
  • These measurements are performed using an LP16 commercial infrared desiccator from Mettler. This technique is fully described in the documentation for the machine supplied by Mettler.
  • the particle sizes may be measured by various techniques; mention may be made in particular of light- scattering techniques (dynamic and static) , Coulter counter methods, sedimentation rate measurements (related to the size via Stokes' law) and microscopy.
  • the sizes and size distributions of the particles in the compositions according to the invention are preferably measured by static light scattering using a commercial granulometer such as the MasterSizer 2000 from Malvern.
  • the data are processed on the basis of the Mie scattering theory.
  • This theory which is exact for isotropic particles, makes it possible to determine an "effective" particle diameter in the case of non-spherical particles. This theory is described especially in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.
  • the composition is characterized by its mean "effective" diameter by volume D[4.3], defined in the following manner:
  • V x represents the volume of the particles with an effective diameter d x .
  • This parameter is described especially in the technical documentation of the granulometer .
  • the measurements are performed at 25 °C on a dilute particle dispersion, obtained from the composition in the following manner: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) standing of the solution for 18 hours, 4) recovery of the whitish uniform supernatant.
  • the "effective" diameter is obtained by taking a refractive index of 1.33 for water and a mean refractive index of 1.42 for the particles.
  • Example 1 This example illustrates the preparation of a dispersion of particles of a polymer in isododecane, the said polymer being obtained by polymerization of methyl acrylate and the corresponding macromonomer with a polyethylene/polybutylene copolymer containing methacrylate end groups (Kraton L-1253) .
  • 2 kg of heptane, 2 kg of isododecane, 2.8 kg of methyl acrylate and 1.2 kg of macromonomer of the polyethylene/polybutylene type containing methacrylate end groups (Kraton L-1253) and 320 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S) are loaded into a reactor.
  • the reaction mixture is stirred and heated from room temperature to 90 °C over 1 hour. After 15 minutes at 90°C, a change is observed in the appearance of the reaction medium, which passes from a transparent appearance to a milky appearance. Heating with stirring is continued for a further 15 minutes, and a mixture consisting of 16 kg of methyl acrylate and 200 g of Trigonox 21S is then added dropwise over 1 hour. Next, the mixture is heated for 4 hours at 90°C and the heptane is then distilled from the reaction medium. After this distillation operation, a stable dispersion of particles of polymer thus prepared in isododecane is obtained.
  • the grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer. The characteristics of the polymer and of the particles formed by the said polymer are as follows:
  • - particle size 46 nm with polydispersity of 0.05, performed on a Malvern Autosizer Lo-C at 25°C.
  • the stability of the dispersion obtained is demonstrated by performing the following stability protocol: 8 ml of the dispersion prepared are placed in a haemolysis tube and centrifuged at 4000 rpm for 15 minutes using a Jouan C100-S5 centrifuge. After 15 minutes, it is found that there is no phase separation, which demonstrates that the dispersion is stable.
  • Example 2 This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon- based solvent, the said polymer being obtained by polymerization of methyl acrylate, acrylic acid and the corresponding macromonomer with a polyethylene/polybutylene copolymer containing methacrylate end groups (Kraton L-1253) .
  • the grafted polymer comprises 6% by weight of macromonomer relative to the weight of the polymer.
  • Example 3 Mascara The following mascara according to the invention was prepared:
  • the dry extract of the composition is measured according to the protocol described previously.
  • the staying power of the film formed by the composition according to the invention is evaluated by measuring the water resistance, as a function of time, of a film of polymer spread onto a glass plate and subjected to stirring in aqueous medium.
  • the protocol is as follows: A layer of composition 300 ⁇ m thick (before drying) with a surface area of 9 cm x 9 cm is spread onto a glass plate with a surface area of 10 cm x 10 cm, and is then left to dry for 24 hours at 30°C and 50% relative humidity.
  • This mascara after application to the eyelashes, was judged as having good staying power and also a satisfactory volumizing (charging) effect.
  • This composition may be prepared in a standard manner by hot formation of a wax-in-water emulsion.
  • the fatty phase (phase A) containing the wax and the stearic acid is heated until the mixture of constituents has completely melted.
  • the dispersion of polymer of Example 2 and the pigments are incorporated with stirring into the oily phase.
  • the aqueous phase (phase B) containing the neutralizer (triethanolamine) and the gelling polymers are brought to a temperature at least equal to the temperature of the fatty phase.
  • the aqueous phase is then added to the oily phase, with vigorous stirring (3000 rpm) to form the hot emulsion. Stirring and the temperature are maintained for about 30 minutes. Moderate paddle stirring is then applied until the mixture has cooled to room temperature.
  • Example 5 Lipstick a) A liposoluble film-forming agent, which is a poly- (isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate) copolymer, is prepared according to the following procedure: 100 g of isododecane are introduced into a 1 litre reactor, and the temperature is then raised so as to pass from room temperature (25°C) to 90°C over 1 hour. 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane
  • a polymer comprising a first block of poly- (isobornyl acrylate/isobornyl methacrylate) with a Tg of 110°C, a second block of poly (2-ethylhexyl acrylate) with a Tg of -70°C and an intermediate block, which is an isobornyl acrylate/isobornyl methacrylate/2-ethyl- hexyl acrylate random polymer, is obtained.
  • This polymer has a weight-average mass of 103 900 and a number-average mass of 21 300, i.e. a polydispersity index I of 4.89.
  • the following lipstick composition is prepared:
  • Transfer measurement The transfer of the deposit obtained with the composition according to the invention is determined according to the protocol described below.
  • a support (rectangle of 40 mm x 70 mm and 3 mm thick) of polyethylene foam that is adhesive on one of the faces, having a density of 33 kg/m 3 (sold under the name RE40X70EP3 from the company Joint Technique Lyonnais Ind) is preheated on a hotplate maintained at a temperature of 40°C in order for the surface of the support to be maintained at a temperature of 33°C ⁇ 1°C.
  • the composition is applied over the entire non-adhesive surface of the support, by spreading it using a fine brush to obtain a deposit of about 15 ⁇ m of the composition, while leaving the support on the hotplate, and the support is then left to dry for 30 minutes .
  • the support is bonded via its adhesive face onto an anvil of diameter 20 mm and equipped with a screw pitch.
  • the support/deposit assembly is then cut up using a punch 18 mm in diameter.
  • the anvil is then screwed onto a press (Statif Manuel Imada SV-2 from the company Someco) equipped with a tensile testing machine (Imada DPS-20 from the company Someco) .
  • a total transfer reference is prepared by applying the composition directly onto a paper identical to the one used previously, at room temperature (25°C), by spreading the composition using a fine brush and so as to obtain a deposit of about 15 ⁇ m of the composition, and the deposit is then left to dry for 30 minutes at room temperature (25°C) .
  • the colorimetric parameters L*', a*' and b*' of the colour of the deposit placed on the paper, corresponding to the reference colour of total transfer is measured directly.
  • the colorimetric parameters L*'o, a*'o and b*'o of the colour of the plain paper used are determined.
  • the difference in colour ⁇ E2 between the reference colour of total transfer relative to the colour of the plain paper are then determined by means of the following relationship.
  • ⁇ E2 (L* '-L 0 * ') 2 +(a* '-a 0 * ' ) 2 +(b* '-b 0 * ') 2
  • the mascara according to the invention has good staying power and also a satisfactory volumizing effect.

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Abstract

La présente invention se rapporte à une composition cosmétique comportant une dispersion de particules d'un polymère éthylénique greffé en phase grasse liquide et d'un agent filmogène. L'agent filmogène peut être soluble ou dispersible dans ladite phase grasse liquide. Ladite composition peut renfermer une phase aqueuse, auquel cas l'agent filmogène peut être soluble ou dispersible dans la phase aqueuse. L'invention se rapporte également à l'application d'une combinaison d'un tel polymère éthylénique greffé et d'un agent filmogène dans le but d'améliorer l'endurance et/ou la résistance au transfert de ladite composition sur les matières kératiniques.
PCT/IB2004/004127 2003-12-12 2004-12-10 Composition comportant une dispersion de particules a base d'un polymere ethylenique greffe et d'un agent filmogene WO2005058274A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
PCT/FR2003/003713 WO2004055081A2 (fr) 2002-12-12 2003-12-12 Composition de revetement des fibres keratiniques comprenant une dispersion de particules de polymere
PCT/FR2003/003712 WO2004055080A2 (fr) 2002-12-12 2003-12-12 Composition comprenant une dispersion de particules d’un polymere ethylenique greffe et un agent gelifiant
FRPCT/FR03/003712 2003-12-12
PCT/FR2003/003714 WO2004055082A2 (fr) 2002-12-12 2003-12-12 Composition cosmetique comprenant une dispersion de particules d'un polymere ethylenique greffe non silicone dans une phase grasse liquide
FRPCT/FR03/003713 2003-12-12
FRPCT/FR03/003714 2003-12-12
FR0450540 2004-03-18
FR0450540A FR2863493B1 (fr) 2003-12-12 2004-03-18 Composition comprenant une dispersion de particules d'un polymere ethylenique greffe et un agent filmogene
US55606304P 2004-03-25 2004-03-25
US60/556,063 2004-03-25

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1604648A1 (fr) * 2004-06-11 2005-12-14 L'oreal Composition cosmétique comprenant un polymère éthylénique greffé
FR2887770A1 (fr) * 2005-07-04 2007-01-05 Oreal Produit de maquillage et/ou de soin "double-geste"
WO2013119561A1 (fr) * 2012-02-08 2013-08-15 Dow Corning Corporation Émulsions de résine de silicone
EP1743627B1 (fr) * 2005-07-13 2014-12-17 L'Oréal Composition de maquillage des lèvres de bonne tenue comprenant une résine de faible poids moléculaire
EP2185127A4 (fr) * 2007-07-30 2015-03-25 Elc Man Llc Compositions cosmétiques contenant un mélange de polymères
EP1944015A3 (fr) * 2007-01-12 2015-05-06 L'Oréal Composition cosmétique comprenant une copolymère bloque, un agent collant et une cire ou une résine de silsesquisiloxane
EP1946745A3 (fr) * 2007-01-12 2015-05-06 L'Oréal Composition cosmétique contenant un copolymère bloc, un agent collant et un ester de viscosité élevé
WO2017176826A1 (fr) * 2016-04-06 2017-10-12 Sun Chemical Corporation Encre d'impression polyvalente pour manchon rétractable
EP3225640A4 (fr) * 2014-12-15 2018-05-09 LG Chem, Ltd. Polymère
US10316125B2 (en) 2014-12-15 2019-06-11 Lg Chem, Ltd. Polymer
CN110903531A (zh) * 2019-12-12 2020-03-24 山东东宏管业股份有限公司 一种碳纳米管改性的聚烯烃双抗材料及其制备方法和应用
US10808060B2 (en) 2014-12-15 2020-10-20 Lg Chem, Ltd. Polymer
CN112424287A (zh) * 2018-08-14 2021-02-26 帝斯曼知识产权资产管理有限公司 用于具有硬度和光泽度的出色平衡的涂料的氧化型、离子型和短油型醇酸树脂
CN116917399A (zh) * 2021-03-03 2023-10-20 日产化学株式会社 用于形成剥离层的组合物和剥离层

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388582A2 (fr) * 1989-03-20 1990-09-26 Kosé Corporation Composition cosmétique
US5219560A (en) * 1989-03-20 1993-06-15 Kobayashi Kose Co., Ltd. Cosmetic composition
US5804173A (en) * 1996-09-04 1998-09-08 The Procter & Gamble Company Personal care compositions
US5916548A (en) * 1996-09-04 1999-06-29 The Procter & Gamble Company Personal care compositions
FR2785529A1 (fr) * 1998-11-09 2000-05-12 Oreal Composition cosmetique sans transfert comprenant une dispersion de particules de polymere dans une phase grasse liquide
US6342239B1 (en) * 1998-01-13 2002-01-29 KOSéCORPORATION Powder composition, a powder dispersion in oil and a cosmetic composition containing said powder composition and a powder dispersion in oil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388582A2 (fr) * 1989-03-20 1990-09-26 Kosé Corporation Composition cosmétique
US5219560A (en) * 1989-03-20 1993-06-15 Kobayashi Kose Co., Ltd. Cosmetic composition
US5804173A (en) * 1996-09-04 1998-09-08 The Procter & Gamble Company Personal care compositions
US5916548A (en) * 1996-09-04 1999-06-29 The Procter & Gamble Company Personal care compositions
US6342239B1 (en) * 1998-01-13 2002-01-29 KOSéCORPORATION Powder composition, a powder dispersion in oil and a cosmetic composition containing said powder composition and a powder dispersion in oil
FR2785529A1 (fr) * 1998-11-09 2000-05-12 Oreal Composition cosmetique sans transfert comprenant une dispersion de particules de polymere dans une phase grasse liquide

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EP1604648A1 (fr) * 2004-06-11 2005-12-14 L'oreal Composition cosmétique comprenant un polymère éthylénique greffé
FR2887770A1 (fr) * 2005-07-04 2007-01-05 Oreal Produit de maquillage et/ou de soin "double-geste"
EP1743627B1 (fr) * 2005-07-13 2014-12-17 L'Oréal Composition de maquillage des lèvres de bonne tenue comprenant une résine de faible poids moléculaire
EP1944015A3 (fr) * 2007-01-12 2015-05-06 L'Oréal Composition cosmétique comprenant une copolymère bloque, un agent collant et une cire ou une résine de silsesquisiloxane
EP1946745A3 (fr) * 2007-01-12 2015-05-06 L'Oréal Composition cosmétique contenant un copolymère bloc, un agent collant et un ester de viscosité élevé
EP2185127A4 (fr) * 2007-07-30 2015-03-25 Elc Man Llc Compositions cosmétiques contenant un mélange de polymères
WO2013119561A1 (fr) * 2012-02-08 2013-08-15 Dow Corning Corporation Émulsions de résine de silicone
EP3225640A4 (fr) * 2014-12-15 2018-05-09 LG Chem, Ltd. Polymère
US10316125B2 (en) 2014-12-15 2019-06-11 Lg Chem, Ltd. Polymer
US10550213B2 (en) 2014-12-15 2020-02-04 Lg Chem, Ltd. Polymer
US10808060B2 (en) 2014-12-15 2020-10-20 Lg Chem, Ltd. Polymer
WO2017176826A1 (fr) * 2016-04-06 2017-10-12 Sun Chemical Corporation Encre d'impression polyvalente pour manchon rétractable
US11034850B2 (en) 2016-04-06 2021-06-15 Sun Chemical Corporation Multipurpose shrink sleeve printing ink
CN112424287A (zh) * 2018-08-14 2021-02-26 帝斯曼知识产权资产管理有限公司 用于具有硬度和光泽度的出色平衡的涂料的氧化型、离子型和短油型醇酸树脂
CN112424287B (zh) * 2018-08-14 2023-03-28 科思创(荷兰)有限公司 用于具有硬度和光泽度的出色平衡的涂料的氧化型、离子型和短油型醇酸树脂
CN110903531A (zh) * 2019-12-12 2020-03-24 山东东宏管业股份有限公司 一种碳纳米管改性的聚烯烃双抗材料及其制备方法和应用
CN116917399A (zh) * 2021-03-03 2023-10-20 日产化学株式会社 用于形成剥离层的组合物和剥离层

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