Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8194—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
  • A61Q1/06—Lipsticks
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/001—Preparations for care of the lips
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/59—Mixtures
  • A61K2800/594—Mixtures of polymers

Definitions

• the present invention relates to a cosmetic process for making up and/or caring for the skin and/or the lips, comprising at least the application to the said skin and/or the said lips of a cosmetic composition comprising, in a physiologically acceptable medium, at least one supramolecular polymer and at least one hydrophobic film-forming polymer.
• a cosmetic composition comprising, in a physiologically acceptable medium, at least one supramolecular polymer and at least one hydrophobic film-forming polymer.
• the invention also relates to particular compositions that may be used in the process of the invention.
• compositions of this type are commonly introduced into compositions of this type. Illustrations of these polymers that may particularly be mentioned include polyacrylates and latices.
• supramolecular polymers such as those described in patent applications EP 2 189 151 and FR 2 938 758 are known for allowing the production on the skin of a deposit that is both comfortable and endowed with good remanence properties.
• deposits formed from a galenical formulation incorporating such a supramolecular polymer may have insufficient mechanical strength (which may be reflected by staining of clothing).
• their contact with fatty substances for example a food oil in the case of a lipstick applied to the lips, may affect their integrity.
• the aim of the present invention is to overcome these drawbacks and to propose a cosmetic composition that is capable, on the one hand, of affording good cosmetic properties such as good adhesion to the support (skin) and thus good remanence of the composition, where appropriate good sheen, and, on the other hand, of forming a non-tacky or sparingly tacky deposit that is particularly resistant to external attack by fatty substances (oil, meals or sebum) and also to friction, resulting in less wear of the deposit.
• the invention relates to a cosmetic process for making up and/or caring for the skin and/or the lips, comprising at least the application to the said skin and/or the said lips of a composition
• a composition comprising, in a physiologically acceptable medium, at least one supramolecular polymer based on a functionalized polyalkene of formula HO—P—OH in which P represents a homopolymer or a copolymer that may be obtained by polymerization of one or more linear, cyclic and/or branched or polyunsaturated C 2 -C 10 and preferably C 2 -C 4 alkenes, which may be derived from the reaction, especially the condensation, of the said functionalized polyalkene polymer with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group(s) of the functionalized polyalkene polymer, the said junction group being capable of forming at least 3H (hydrogen) bonds, preferably at least 4H bonds, preferentially 4H bonds, and at
• physiologically acceptable medium is intended to denote a medium that is suitable for the application of a composition to the skin or the lips, in particular the skin and especially of the face.
• hydrophobic film-forming polymer is intended to denote a film-forming polymer that has no affinity for water and, in this respect, does not lend itself to formulation in the form of a solute in an aqueous medium.
• the hydrophobic film-forming polymers that are suitable for use in the invention may be chosen advantageously from polyamide silicone block polymers, block ethylenic polymers, vinyl polymers comprising at least one carbosiloxane dendrimer derivative, copolymers comprising carboxylate groups and polydimethylsiloxane groups, silicone resins and lipodispersible polymers in the form of a non-aqueous dispersion of polymer particles, and mixtures thereof.
• compositions under consideration according to the invention are anhydrous or contain less than 3% by weight of water and preferably less than 1% by weight of water relative to the total weight of the composition.
• anhydrous especially means that water is preferably not deliberately added to the composition, but may be present in trace amount in the various compounds used in the composition.
• the combination under consideration according to the invention proves to be most particularly effective for increasing the resistance of the deposit formed on application to the skin or the lips from the corresponding cosmetic composition.
• the deposit thus obtained has improved remanence and significantly reduced affinity for the fatty substances with which it is liable to come into contact. Its transfer-resistance properties are moreover significantly improved.
• such a deposit advantageously proves to be sparingly tacky or even non-tacky.
• compositions especially makeup compositions, whose deposition on keratin materials, and in particular the lips and/or the skin, is uniform and/or sparingly tacky or non-tacky.
• Such a deposit may especially afford a sensation of comfort to the wearer (softness, glidance of the deposit formed).
• such a composition may have improved properties in terms of transfer resistance, remanence of the deposit, especially in terms of colour (no embrittlement or fragmentation of the deposit, which remains uniform and/or resistant to friction), and of resistance to fats.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one hydrophobic film-forming polymer and at least one pigment different from a nacre and from black iron oxide.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, and at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one hydrophobic film-forming polymer and at least 1% by weight relative to the total weight of the said composition of at least one organic or inorganic filler.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one hydrophobic film-forming polymer and at least one oil other than isododecane and cyclopentadimethylsiloxane, in particular a non-volatile oil and preferably at least one silicone oil.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one hydrophobic film-forming polymer and at least 4.5% by weight of ethanol relative to the total weight of the said composition.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above and at least one polyamide silicone block polymer.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above and at least one vinyl polymer comprising at least one carbosiloxane dendrimer derivative.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above and at least one lipodispersible polymer in the form of a non-aqueous dispersion of polymer particles.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above and at least 5% by weight of one or more block ethylenic polymers relative to its total weight.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one block ethylenic polymer and at least one organic or inorganic filler.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one block ethylenic polymer and at least one pigment other than a nacre.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, less than 4.5% by weight of ethanol, in particular less than 2% by weight of ethanol or even less than 1% by weight of ethanol, at least one supramolecular polymer as defined above and at least one block ethylenic polymer.
• the present invention also relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium containing at least one oil other than isododecane or decamethylcyclopentasiloxane, preferably a non-volatile oil and in particular a silicone oil, at least one supramolecular polymer as defined above and at least one block ethylenic polymer.
• a physiologically acceptable medium containing at least one oil other than isododecane or decamethylcyclopentasiloxane, preferably a non-volatile oil and in particular a silicone oil, at least one supramolecular polymer as defined above and at least one block ethylenic polymer.
• a composition intended for caring for and/or making up the lips, especially of lipstick type comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, and at least one block ethylenic polymer, is also considered according to the invention.
• the present also invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above and more than 5% by weight or even at least 6% by weight of silicone resin(s) relative to its total weight.
• the present invention relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one silicone resin and at least 1% by weight of organic or inorganic fillers(s).
• the present invention also relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, at least one silicone resin and at least one pigment other than a nacre.
• the present invention also relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium containing at least one oil other than isododecane or decamethylcyclopentasiloxane, preferably a non-volatile oil and in particular at least one silicone oil, at least one supramolecular polymer as defined above and at least one silicone resin.
• a physiologically acceptable medium containing at least one oil other than isododecane or decamethylcyclopentasiloxane, preferably a non-volatile oil and in particular at least one silicone oil, at least one supramolecular polymer as defined above and at least one silicone resin.
• the present invention also relates to a composition for making up and/or caring for the skin and/or the lips, comprising, in a physiologically acceptable medium containing less than 4.5% by weight of ethanol, in particular less than 2% by weight of ethanol and better still less than 1% by weight of ethanol, at least one supramolecular polymer as defined above and at least one silicone resin.
• a composition intended for caring for and/or making up the lips, especially of lipstick type, comprising, in a physiologically acceptable medium, at least one supramolecular polymer as defined above, and at least one silicone resin, is also considered according to the invention.
• compositions under consideration according to the invention may be in solid or liquid form at 20° C.
• solid characterizes the state of the composition at a temperature of 20° C.
• a solid composition according to the invention has, at a temperature of 20° C. and at atmospheric pressure (760 mmHg), a hardness of greater than 30 Nm ⁇ 1 and preferably greater than 40 Nm ⁇ 1 .
• the hardness of a solid composition especially of lipstick wand type is measured according to the following protocol:
• the lipstick wand is stored at 20° C. for 24 hours before measuring the hardness.
• the hardness may be measured at 20° C. via the “cheese wire” method, which consists in transversely cutting a wand of product, which is preferably a circular cylinder, by means of a rigid tungsten wire 250 ⁇ m in diameter, by moving the wire relative to the stick at a speed of 100 mm/minute.
• the “cheese wire” method which consists in transversely cutting a wand of product, which is preferably a circular cylinder, by means of a rigid tungsten wire 250 ⁇ m in diameter, by moving the wire relative to the stick at a speed of 100 mm/minute.
• the hardness of the samples of compositions of the invention is measured using a DFGS2 tensile testing machine from the company Indelco-Chatillon.
• the measurement is repeated three times and then averaged.
• the average of the three values read using the tensile testing machine mentioned above, noted Y, is given in grams. This average is converted into newtons and then divided by L which represents the longest dimension through which the wire passes. In the case of a cylindrical wand, L is equal to the diameter (in metres).
• the stick is stored for 24 hours at this new temperature before the measurement.
• a solid composition according to the invention has a hardness at 20° C. of greater than or equal to 30 Nm ⁇ 1 , preferably greater than 40 Nm ⁇ 1 and preferably greater than 50 Nm ⁇ 1 .
• the composition according to the invention especially has a hardness at 20° C. of less than 500 Nm ⁇ 1 , especially less than 400 Nm ⁇ 1 and preferably less than 300 Nm ⁇ 1 .
• composition whose hardness is greater than 30 Nm ⁇ 1 is said to be “solid” at 20° C. and at atmospheric pressure (760 mmHg).
• composition intended for caring for and/or making up the skin especially of foundation type, a loose or compact powder or a liquid formulation that may be anhydrous or of the oil-in-water or water-in-oil emulsion type.
• composition according to the invention may also comprise at least one supramolecular polymer as defined above, at least one hydrophobic film-forming polymer, and at least 5% of water or even at least 10% by weight of water relative to its total weight.
• compositions according to the invention are anhydrous.
• a composition according to the invention may be in the form of a skin and/or lip makeup composition, especially for facial or bodily skin; it may be a complexion product such as a foundation, a face powder or an eyeshadow; a lip product such as a lipstick or a lipcare product; a concealer product; a blusher; an eyeliner; a lip pencil or an eye pencil; a body makeup product; a gloss (lip gloss).
• the composition according to the invention is intended for making up the skin and it is then more particularly a foundation, a face powder, an eyeshadow or a body makeup product.
• the composition according to the invention is intended for making up the lips and it is then more particularly a lipstick (lipstick wand) or a gloss (liquid lipstick).
• compositions according to the invention thus comprise a polyalkene-based (i.e. polyolefin) supramolecular polymer.
• polyalkene-based supramolecular polymer means a polymer derived from the reaction, especially the condensation, of at least one polyalkene polymer functionalized with at least one reactive group, with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group(s) of the functionalized polyalkene polymer, the said junction group being capable of forming at least three H (hydrogen) bonds and preferably at least four H bonds, preferentially four H bonds.
• polyalkene or “polyolefin” means a polymer derived from the polymerization of at least one monomer of alkene type, comprising an ethylenic unsaturation, the said monomer possibly being pendent or in the main chain of the said polymer.
• polyalkene or “polyolefin” is thus directed towards polymers that may or may not comprise a double bond.
• the supramolecular polymers used according to the invention are prepared from a polymer derived from the polymerization of an alkene comprising at least two ethylenic unsaturations.
• the supramolecular polymer according to the invention is capable of forming a supramolecular polymer chain or network, by (self)assembly of said polymer according to the invention with at least one other identical or different polymer according to the invention, each assembly involving at least one pair of paired junction groups, which may be identical or different, borne by each of the polymers according to the invention.
• junction group means any group comprising groups that donate or accept H bonds, and capable of forming at least three H bonds and preferably at least four H bonds, preferentially four H bonds, with an identical or different partner junction group. These junction groups may be lateral to the polymer backbone (side branching) and/or borne by the ends of the polymer backbone, and/or in the chain forming the polymer backbone. They may be distributed in a random or controlled manner.
• the polyalkene polymers are functionalized with at least one reactive group and preferably with at least two reactive groups.
• the functionalization preferably occurs at the chain ends. They are then referred to as telechelic polymers.
• the functionalization groups, or reactive groups may be attached to the polyalkene polymer via linkers, preferably linear or branched C 1 -C 4 alkylene groups, or directly via a single bond.
• the functionalized polyalkene polymers have a number-average molecular mass (Mn) of between 1000 and 8000.
• the functionalized polyalkene polymer capable of forming all or part of the polymer backbone of the supramolecular polymer according to the invention (preferably, it forms all of the backbone of the polymer), is of formula HO—P—OH in which:
• P represents a polymer chosen from a polybutylene, a polybutadiene (such as a 1,4-polybutadiene or a 1,2-polybutadiene), a polyisoprene, a poly(1,3-pentadiene) and a polyisobutylene, and copolymers thereof.
• P represents a poly(ethylene/butylene) copolymer.
• the preferred poly(ethylene/butylenes) are copolymers of 1-butene and of ethylene. They may be represented schematically by the following sequence of units:
• P is a polybutadiene homopolymer, preferably chosen from a 1,4-polybutadiene or a 1,2-polybutadiene.
• the polybutadienes may be 1,4-polybutadienes or 1,2-polybutadienes, which may be represented schematically, respectively, by the following sequences of units:
• they are 1,2-polybutadienes.
• P is a 1,2-polybutadiene homopolymer.
• P is a polyisoprene.
• Polyisoprenes may be represented schematically by the following sequences of units:
• a mixture of above units may obviously also be used, so as to form copolymers.
• the functionalized polyalkene polymers may be totally hydrogenated to avoid the risks of crosslinking.
• the functionalized polyalkene polymers used in the compositions according to the invention are hydrogenated.
• the polyalkene polymers are hydrogenated and functionalized with at least two OH reactive groups, preferably at the ends of the polymers.
• hydroxyl end groups of from 1.8 to 3 and preferably in the region of 2.
• Polydienes containing hydroxyl end groups are especially defined, for example, in FR 2 782 723. They may be chosen from polybutadiene, polyisoprene and poly(1,3-pentadiene) homopolymers and copolymers. Mention will be made in particular of the hydroxylated polybutadienes sold by the company Sartomer, for instance the Krasol Resins and the Poly bd®Resins. Preferably, they are dihydroxylated hydrogenated 1,2-polybutadiene homopolymers, such as the range Nisso-PB 1, GI3000, GI200 and GI1000 sold by the company Nisso, which may be represented schematically by the following formula:
• n is between 14 and 105 and preferably between 20 and 85.
• polystyrene resin with hydroxyl end groups
• the supramolecular polymers according to the invention also have in their structure at least one residue of a junction group capable of forming at least three H bonds and preferably at least four H bonds, the said junction group being initially functionalized with at least one reactive group.
• junction group means in the present description the group without its reactive function.
• the reactive groups are attached to the junction group via linkers L.
• L is a single bond or a saturated or unsaturated C 1-20 divalent carbon-based group chosen in particular from a linear or branched C 1 -C 20 alkylene; a C 5 -C 20 (alkyl)cycloalkylene alkylene (preferably cyclohexylene methylene), a C 11 -C 20 alkylene-biscycloalkylene (preferably alkylene-biscyclohexylene), a C 6 -C 20 (alkyl)arylene, an alkylene-bisarylene (preferably an alkylene-biphenylene), the linker L possibly being substituted with at least one alkyl group and/or possibly comprising 1 to 4 N and/or O heteroatoms, especially in the form of an NO 2 substituent.
• the linker is a group chosen form phenylene; 1,4-nitrophenylene; 1,2-ethylene; 1,6-hexylene; 1,4-butylene; 1,6-(2,4,4-trimethylhexylene); 1,4-(4-methylpentylene); 1,5-(5-methylhexylene); 1,6-(6-methylheptylene); 1,5-(2,2,5-trimethylhexylene); 1,7-(3,7-dimethyloctylene); -isophorone-; 4,4′-methylene bis(cyclohexylene); tolylene; 2-methyl-1,3-phenylene; 4-methyl-1,3-phenylene; 4,4-biphenylenemethylene;
• the linker is chosen from the groups:
• L is chosen from: -isophorone-; —(CH 2 ) 2 —; —(CH 2 ) 6 —; CH 2 CH(CH 3 )—CH 2 —C(CH 3 ) 2 —CH 2 —CH 2 ; 4,4′-methylene biscyclohexylene; 2-methyl-1,3-phenylene.
• the linker is an alkylcycloalkylene alkylene.
• the linker is an isophorone group.
• isophorone means the following group:
• the said reactive groups functionalizing the junction group must be capable of reacting with the —OH reactive group(s) borne by the functionalized polyalkene.
• Reactive groups that may be mentioned include isocyanate (—N ⁇ C ⁇ O) and thioisocyanate (—N ⁇ C ⁇ S) groups.
• —N ⁇ C ⁇ O isocyanate
• —N ⁇ C ⁇ S thioisocyanate
• it is a group —N ⁇ C—O (isocyanate).
• the functionalized junction groups capable of forming at least three H bonds may comprise at least three identical or different functional groups, and preferably at least four functional groups, chosen from:
• junction groups capable of forming at least three H bonds form a basic structural element comprising at least three groups, preferably at least four groups and more preferentially four functional groups capable of establishing H bonds.
• the said basic structural elements capable of establishing H bonds may be represented schematically in the following manner:
• X i is an H-bond accepting functional group (identical or different) and Y i is an HF-bond donating functional group (identical or different).
• each structural element should be capable of establishing H bonds with one or more partner structural elements, which are identical (i.e. self-complementary) or different, such that each pairing of two partner structural elements takes place by formation of at least three H bonds and preferably at least four H bonds, more preferentially four H bonds.
• a proton acceptor X will pair with a proton donor Y.
• Several possibilities are thus offered, for example pairing of:
• the junction groups may establish four H bonds with an identical (or self-complementary) partner group among which are two donor bonds (for example NH) and two acceptor bonds (for example CO and —C ⁇ N—).
• two donor bonds for example NH
• acceptor bonds for example CO and —C ⁇ N—.
• the junction groups capable of forming at least four H bonds are chosen from:
• the radical R2 may be a single bond or a monovalent group chosen from H, CH 2 OH and (CH 2 ) 2 —OH, CH 3 .
• R 2 is H.
• the radical R3 may be a monovalent group chosen from H, CH 2 OH and (CH 2 ) 2 —OH, CH 3 .
• R 3 is a methyl group.
• the junction groups are chosen from 2-ureidopyrimidone and 6-methyl-2-ureidopyrimidone.
• the preferred junction group is 6-methyl-2-ureidopyrimidone.
• junction groups and especially the ureidopyrimidone junction groups, may be added directly or may be formed in situ during the process for preparing the supramolecular polymer.
• the first and second preparation methods described below illustrate these two alternatives, respectively.
• the functionalized junction groups capable of reacting with the functionalized polyalkene polymer to give the supramolecular polymer according to the invention are preferably of formula:
• L is chosen from the groups:
• L is chosen from: -isophorone-; —(CH 2 ) 6 —; 4,4′-methylene biscyclohexylene.
• the junction group is of formula
• the supramolecular polymer of the invention corresponds to the formula:
• L′ and L′′ represent a saturated or unsaturated C 1 -C 20 divalent carbon-based group, chosen in particular from a linear or branched C 1 -C 20 alkylene; a C 5 -C 20 (alkyl)cycloalkylene, an alkylene-biscycloalkylene and a C 6 -C 20 (alkyl)arylene.
• L′ and L′′ represent an -isophorone-; —(CH 2 ) 2 —; —(CH 2 ) 6 —; CH 2 CH(CH 3 )—CH 2 —C(CH 3 ) 2 —CH 2 —CH 2 ; 4,4′-methylene biscyclohexylene; 2-methyl-1,3-phenylene group.
• L′ and L′′ are identical.
• L′ and L′′ are an isophorone group.
• P is hydrogenated and represents a polyethylene, a polybutylene, a polybutadiene, a polyisoprene, a poly(1,3-pentadiene), a polyisobutylene, or a copolymer thereof, especially a poly(ethylene/butylene).
• P is a hydrogenated polybutadiene, preferably a hydrogenated 1,2-polybutadiene.
• the supramolecular polymer of the invention corresponds to the formula:
• the polymer according to the invention may be prepared via the processes usually used by a person skilled in the art, especially for forming a urethane bond between the free OH functions of a polyalkene, and the isocyanate functions borne by the junction group.
• a first general preparation process consists in:
• the reaction may also be monitored by assaying the hydroxyl functions; it is also possible to add ethanol in order to ensure total disappearance of the residual isocyanate functions.
• the reaction may be performed in the presence of a solvent, especially methyltetrahydrofuran, tetrahydrofuran, toluene, propylene carbonate or butyl acetate. It is also possible to add a conventional catalyst for forming a urethane bond. An example that may be mentioned is dibutyltin dilaurate.
• the polymer may finally be washed and dried, or even purified, according to the general knowledge of a person skilled in the art.
• the reaction may comprise the following steps:
• the diisocyanate may optionally be in excess relative to the polymer.
• This first step may be performed in the presence of solvent, at a temperature of between 20° C. and 100° C. This first step may be followed by a period of stirring under a controlled atmosphere for 1 to 24 hours. The mixture may optionally be heated. The degree of progress of this first step may be monitored by assaying the hydroxyl functions;
• this second step may optionally be performed in the presence of a cosolvent such as toluene, butyl acetate or propylene carbonate.
• a cosolvent such as toluene, butyl acetate or propylene carbonate.
• the reaction mixture may be heated to between 80° C. and 140° C. for a time ranging between 1 and 24 hours.
• the presence of a catalyst, especially dibutyltin dilaurate, may promote the production of the desired final product.
• the reaction may be monitored by infrared spectroscopy, by monitoring the disappearance of the characteristic peak of isocyanate between 2200 and 2300 cm ⁇ 1 .
• ethanol may be added to the reaction medium in order to neutralize any residual isocyanate functions.
• the reaction mixture may be optionally filtered.
• the polymer may also be stripped directly in a cosmetic solvent.
• the said supramolecular polymer is dissolved in a hydrocarbon-based oil, which is preferably volatile, in particular isododecane.
• composition of the invention will comprise at least one hydrocarbon-based oil, which is preferably volatile, in particular at least isododecane, especially provided by the supramolecular polymer solution.
• the supramolecular polymer(s) may be present in a composition according to the invention in an amount ranging from 0.1% to 60% by weight of solids, relative to the total weight of the composition.
• the supramolecular polymer(s) may be present in a composition according to the invention in an amount ranging from 0.2% to 50% by weight, relative to the total weight of the composition.
• the supramolecular polymer(s) may be present in a composition according to the invention in an amount ranging from 0.3% to 40% by weight, relative to the total weight of the composition.
• the supramolecular polymer(s) may be present in a composition according to the invention in an amount ranging from 0.5% to 30% by weight, relative to the total weight of the composition.
• these contents are used for a composition in the form of a composition for caring for and/or making up the skin, especially of the face, in particular a foundation.
• a composition is in the form of a composition for caring for and/or making up the skin, especially of the face (e.g.: a foundation) and the supramolecular polymer(s) may be present therein in a content ranging from 2.5% to 60% by weight of solids relative to the total weight of the composition.
• a composition is in the form of a composition for caring for and/or making up the skin, especially of the face (e.g.: a foundation) and the supramolecular polymer(s) may be present therein in a content ranging from 2.5% to 40% by weight of solids relative to the total weight of the composition.
• a composition is in the form of a composition for caring for and/or making up the skin, especially of the face (e.g.: a foundation) and the supramolecular polymer(s) may be present therein in a content ranging from 3% to 30% by weight of solids relative to the total weight of the composition.
• a composition is in the form of a composition for caring for and/or making up the lips (e.g.: a lipstick) and the supramolecular polymer(s) may be present therein in a content ranging from 0.1% to 60% by weight of solids relative to the total weight of the composition.
• a composition for caring for and/or making up the lips e.g.: a lipstick
• the supramolecular polymer(s) may be present therein in a content ranging from 0.1% to 60% by weight of solids relative to the total weight of the composition.
• a composition is in the form of a composition for caring for and/or making up the lips (e.g.: a lipstick) and the supramolecular polymer(s) may be present therein in a content ranging from 0.2% to 40% by weight of solids relative to the total weight of the composition.
• a composition for caring for and/or making up the lips e.g.: a lipstick
• the supramolecular polymer(s) may be present therein in a content ranging from 0.2% to 40% by weight of solids relative to the total weight of the composition.
• a composition is in the form of a composition for caring for and/or making up the lips (e.g.: a lipstick) and the supramolecular polymer(s) may be present therein in a content ranging from 0.5% to 30% by weight of solids relative to the total weight of the composition.
• a composition for caring for and/or making up the lips e.g.: a lipstick
• the supramolecular polymer(s) may be present therein in a content ranging from 0.5% to 30% by weight of solids relative to the total weight of the composition.
• a composition according to the invention in particular in the case of a composition for making up the skin and/or the lips, comprises a content of supramolecular polymer of between 5% and 99% by weight relative to the weight of the composition excluding volatile compound(s) (in particular relative to the weight of the composition excluding volatile oil(s), such as isododecane, for example).
• This content reflects the resulting content of supramolecular polymer(s) in a deposit made with a composition or according to the process of the invention, especially on keratin materials such as the skin and/or lips, for example, after evaporation of the volatile compounds.
• the composition according to the invention in particular in the case of a makeup composition, comprises a content of supramolecular polymer of between 10% and 90% by weight relative to the weight of the composition excluding volatile compound(s), preferably between 15% and 80%.
• polymer means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these units(s) are repeated at least twice and preferably at least three times.
• hydrophobic film-forming polymer is intended to denote a film-forming polymer that has no affinity for water and, in this respect, does not lend itself to formulation in the form of a solute in an aqueous medium.
• hydrophobic polymer means a polymer with a solubility in water at 25° C. of less than 1% by weight.
• film-forming polymer means a polymer that is capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film that adheres to 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 isolable and manipulable in isolation, for example when the said film is prepared by pouring onto a non-stick surface, for instance a Teflon-coated or silicone-coated surface.
• the hydrophobic film-forming polymer is a polymer chosen from the group comprising:
• Hydrophobic film-forming polymers that may especially be mentioned include homopolymers and copolymers of a compound containing an ethylenic unit, acrylic polymers and copolymers, polyurethanes, polyesters, polyureas, cellulose-based polymers, for instance nitrocellulose, silicone polymers such as silicone resins, silicone polyamides, polymers with a non-silicone organic backbone grafted with monomers containing a polysiloxane, polyamide polymers and copolymers, and polyisoprenes.
• a cosmetic makeup composition according to the invention may comprise from 0.1% to 30%, preferably from 0.2% to 20% by weight and even more preferentially from 0.5% to 15% by weight of hydrophobic film-forming polymer(s).
• the polymer according to the invention and the hydrophobic film-forming polymer are used in a polymer(s)/hydrophobic film-forming polymer(s) weight ratio ranging from 1 to 30 and more particularly from 1.5 to 10.
• hydrophobic film-forming polymers that are most particularly suitable for use in the invention, mention may be made especially of:
• composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one silicone resin.
• a polydimethylsiloxane is not a silicone resin.
• silicone resins also known as siloxane resins
• siloxane resins The nomenclature of silicone resins (also known as siloxane resins) is known under the name “.MDTQ”, the resin being described as a function of the various siloxane monomer units that it comprises, each of the letters “MDTQ” characterizing a type of unit.
• the letter “M” represents the Monofunctional unit of formula R1R2R3SiO 1/2 , the silicon atom being connected to only one oxygen atom in the polymer comprising this unit.
• the letter “D” means a Difunctional unit R1R2SiO 2/2 in which the silicon atom is connected to two oxygen atoms.
• T represents a Trifunctional unit of formula R1SiO 3/2 .
• R i.e. R 1 and R 2
• R 1 and R 2 represents a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.
• the letter “Q” means a tetrafunctional unit SiO 4/2 in which the silicon atom is linked to four oxygen atoms, which are themselves linked to the rest of the polymer.
• silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type, of T type or of MQT type.
• silicone resins of MQ type mention may be made of the alkyl siloxysilicates of formula [(R1) 3 SiO 1/2 ] x (SiO 4/2 ) y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms, preferably a methyl group.
• silicone resins of type T examples include the polysilsesquioxanes of formula (RSiO 3/2 ) x (units T) in which x is greater than 100 and such that the group R is an alkyl group containing from 1 to 10 carbon atoms, the said polysilsesquioxanes also possibly comprising Si—OH end groups.
• Polymethylsilsesquioxane resins that may preferably be used are those in which R represents a methyl group, for instance those sold:
• Resins comprising MQT units that are especially known are those mentioned in document U.S. Pat. No. 5,110,890.
• a preferred form of resins of MQT type are MQT-propyl (also known as MQTPr) resins.
• MQT-propyl resins Such resins that may be used in the compositions according to the invention are especially the resins described and prepared in patent application WO 2005/075 542, the content of which is incorporated herein by reference.
• the MQ-T-propyl resin preferably comprises the following units:
• R1, R2 and R3 independently representing a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group,
• d being between 0.05 and 0.6
• the siloxane resin comprises the following units:
• R1 and R3 independently representing an alkyl group containing from 1 to 8 carbon atoms, R1 preferably being a methyl group and R3 preferably being a propyl group,
• a being between 0.05 and 0.5 and preferably between 0.15 and 0.4
• c being greater than 0 and preferably between 0.15 and 0.4
• d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or alternatively between 0.2 and 0.55,
• siloxane resins that may be used according to the invention may be obtained via a process comprising the reaction of:
• an MQ resin comprising at least 80 mol % of units (R1 3 SiO 1/2 ) a and (SiO 4/2 ) d
• R1 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group
• the ratio a/d being between 0.5 and 1.5;
• T-propyl resin comprising at least 80 mol % of units (R3SiO 3/2 ) c ,
• R3 representing an alkyl group containing from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group
• the mass ratio A/B is between 95/5 and 15/85 and the mass ratio A/B is preferably 30/70.
• the mass ratio A/B is between 95/5 and 15/85.
• the ratio A/B is less than or equal to 70/30.
• the silicone resin is chosen from the group comprising:
• a resin of MQ type chosen especially from (i) alkyl siloxysilicates, which may be trimethyl siloxysilicates, of formula [(R1) 3 SiO 1/2 ] x (SiO 4/2 ) y , in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a hydrocarbon-based radical containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and preferably is an alkyl group containing from 1 to 8 carbon atoms, preferably a methyl group, and (ii) phenylalkyl siloxysilicate resins, such as phenylpropyldimethyl siloxysilicate, and/or
• a resin of T type chosen especially from the polysilsesquioxanes of formula (RSiO 3/2 ) x , in which x is greater than 100 and the group R is an alkyl group containing from 1 to 10 carbon atoms, for example a methyl group, the said polysilsesquioxanes also possibly comprising Si—OH end groups, and/or
• a resin of MQT type especially of MQT-propyl type, which may comprise units (i) (R1 3 SiO 1/2 ) a , (ii) (R2 2 SiO 2/2 ) b , (iii) (R3SiO 3/2 ) and (iv) (SiO 4/2 ) d ,
• R1, R2 and R3 independently representing a hydrocarbon-based radical, especially alkyl, containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group and preferably an alkyl radical containing from 1 to 8 carbon atoms or a phenyl group,
• a being between 0.05 and 0.5
• d being between 0.05 and 0.6
• composition according to the invention may comprise, as hydrophobic film-forming polymer, at least one polymer chosen from lipodispersibie film-forming polymers in the form of non-aqueous dispersions of polymer particles, also known as NADs.
• Non-aqueous dispersions of hydrophobic film-forming polymer that may be used include dispersions of particles of a grafted ethylenic polymer, preferably an acrylic polymer, in a liquid oily phase:
• dispersions of ethylenic polymer particles dispersed in the absence of additional stabilizer at the surface of the said particles are used.
• polymers of NAD type that may be mentioned more particularly include acrylic dispersions in isododecane, for instance Mexomer PAP® (acrylic copolymer as a dispersion in isododecane (25%) with pyrene/isoprene copolymer) sold by the company Chimex.
• Mexomer PAP® acrylic copolymer as a dispersion in isododecane (25%) with pyrene/isoprene copolymer
• the hydrophobic film-forming polymer is a block ethylenic copolymer, containing at least a first block with a glass transition temperature (Tg) of greater than or equal to 40° C. and being totally or partly derived from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C., and at least a second block with a glass transition temperature of less than or equal to 20° C.
• Tg glass transition temperature
• the said first block and the said second block being connected together via a statistical intermediate segment comprising at least one of the said first constituent monomers of the first block and at least one of the said second constituent monomers of the second block, and the said block copolymer having a polydispersity index I of greater than 2.
• the block polymer used according to the invention thus comprises at least one first block and at least one second block.
• At least one block means one or more blocks.
• block polymer means a polymer comprising at least two different blocks and preferably at least three different blocks.
• ethylenic polymer means a polymer obtained by polymerization of ethylenically unsaturated monomers.
• the block ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers.
• the block ethylenic polymer used according to the present invention does not contain any multifunctional monomers, which make it possible to break the linearity of a polymer so as to obtain a branched or even crosslinked polymer, as a function of the content of multifunctional monomer.
• the polymer used according to the invention does not, either, contain any macromonomers (the term “macromonomer” means a monofunctional monomer containing pendent groups of polymeric nature, and preferably having a molecular mass of greater than 500 g/mol, or alternatively a polymer comprising on only one of its ends a polymerizable (or ethylenically unsaturated) end group), which are used in the preparation of a grafted polymer.
• the first block and the second block of the polymer used in the invention may be advantageously mutually incompatible.
• mutant blocks means that the mixture formed from the polymer corresponding to the first block and form the polymer corresponding to the second block is not miscible in the polymerization solvent that is in major amount by weight for the block polymer, at room temperature (25° C.) and atmospheric pressure (10′ Pa), for a content of the mixture of the said polymers of greater than or equal to 5% by weight, relative to the total weight of the mixture of the said polymers and of the said polymerization solvent, it being understood that:
• the said polymer mixture is immiscible in at least one of them.
• this solvent is the solvent that is in major amount.
• the block polymer according to the invention comprises at least a first block and at least a second block that are connected together via an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
• the intermediate segment also known as the intermediate block
• the intermediate segment has a glass transition temperature Tg that is between the glass transition temperatures of the first and second blocks.
• the intermediate segment is a block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer allowing these blocks to be “compatibilized”.
• the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the block polymer is a statistical 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 block polymer according to the invention is advantageously a film-forming block ethylenic polymer.
• ethylenic polymer means a polymer obtained by polymerization of ethylenically unsaturated monomers.
• the polymer according to the invention does not comprise any silicon atoms in its backbone.
• backbone means the main chain of the polymer, as opposed to the pendent side chains.
• the polymer according to the invention is not water-soluble, i.e. the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, for instance ethanol, isopropanol or n-propanol, without modifying the pH, at the solids content of at least 1% by weight, at room temperature (25° C.).
• the polymer according to the invention is not an elastomer.
• non-elastomeric polymer means a polymer which, when it is subjected to a constraint intended to stretch it (for example by 30% relative to its initial length), it 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 i ⁇ 50% and a delayed recovery R 2h ⁇ 70% after having been subjected to a 30% elongation.
• R i is ⁇ 30% and R 2h ⁇ 50%.
• 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 (I 0 ) of the specimen.
• the instantaneous recovery Ri is determined in the following manner:
• the percentage residual elongation of the specimen ( ⁇ 2h ) is measured 2 hours after returning to zero constraint.
• a polymer according to one embodiment of the invention preferably has an instantaneous recovery R i of 10% and a delayed recovery R 2h of 30%.
• the polydispersity index of the polymer of the invention is greater than 2.
• the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8 and better still greater than or equal to 2.8, and especially ranging from 2.8 to 6.
• the polydispersity index I of the polymer is equal to the ratio of the weight-average molecular mass Mw to the number-average molecular mass Mn.
• the weight-average molar mass (Mw) and number-average molar mass (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
• the weight-average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300 000; it ranges, for example, from 35 000 to 200 000 and better still from 45 000 to 150 000 g/mol.
• the number-average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70 00; it ranges, for example, from 10 000 to 60 000 and better still from 12 000 to 50 000 g/mol.
• the polydispersity index of the polymer according to the invention is 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 block with a Tg of greater than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., for example ranging from 50° C. to 120° C. and better still greater than or equal to 60° C., for example ranging from 60° C. to 120° C.
• the glass transition temperatures indicated for the first and second blocks may be theoretical Tg values determined from the theoretical Tg values of the constituent monomers of each of the blocks, which may be found in a reference manual such as the Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the following relationship, known as Fox's law:
• ⁇ i being the mass fraction of the monomer i in the block under consideration and Tg i being the glass transition temperature of the homopolymer of the monomer i.
• Tg values indicated for the first and second blocks in the present patent application are theoretical Tg values.
• the 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 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.
• the block with a Tg of greater than or equal to 40° C. may be a homopolymer or a copolymer.
• the block with a Tg of greater than or equal to 40° C. may be derived totally or partially from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.
• This block may also be referred to as a “rigid block”.
• this block is a homopolymer, it is derived from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of greater than or equal to 40° C.
• This first block may be a homopolymer 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 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 greater than or equal to 40° C.
• the copolymer may comprise, for example:
• the first monomers whose homopolymers have a glass transition temperature of greater than or equal to 40° C. are chosen, preferably, from the following monomers, also known as the main monomers:
• R 1 represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R 1 represents a C 4 to C 12 cycloalkyl group, preferably a C 8 to C 12 cycloalkyl, such as isobornyl methacrylate,
• R 2 represents a C 4 to C 12 cycloalkyl group such as an isobornyl group or a tert-butyl group
• R 7 and R 8 which may be identical or different, each represent a hydrogen atom or a linear or branched C 1 to C 12 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 1,1-dimethyl-3-oxobutyl group, and
• the first block is advantageously obtained from at least one acrylate monomer of formula CH 2 ⁇ CH—COOR 2 and from at least one methacrylate monomer of formula CH 2 ⁇ C(CH 3 )—COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, preferably a C 8 to C 12 cycloalkyl, such as isobornyl.
• R 2 represents a C 4 to C 12 cycloalkyl group, preferably a C 8 to C 12 cycloalkyl, such as isobornyl.
• the monomers and the proportions thereof are preferably chosen such that the glass transition temperature of the first block is greater than or equal to 40° C.
• the first block is obtained from:
• R 2 represents a C 4 to C 12 cycloalkyl group, preferably a C 8 to C 12 cycloalkyl, such as isobornyl,
• R′ 2 represents a C 4 to C 12 cycloalkyl group, preferably a C 8 to C 12 cycloalkyl, such as isobornyl.
• the first block is obtained from at least one acrylate monomer of formula CH 2 ⁇ CH—COOR 2 in which R 2 represents a C 8 to C 12 cycloalkyl group, such as isobornyl, and from at least one methacrylate monomer of formula CH 2 ⁇ C(CH 3 )—COOR′ 2 in which R′ 2 represents a C 8 to C 12 cycloalkyl group, such as isobornyl.
• R 2 and R′ 2 represents, independently or simultaneously, an isobornyl group.
• the block copolymer comprises from 50% to 80% by weight of isobornyl methacrylate/acrylate, from 10% to 30% by weight of isobutyl acrylate and from 2% to 10% by weight of acrylic acid.
• the first block may be obtained exclusively from the said acrylate monomer and from the said methacrylate monomer.
• the acrylate monomer and the methacrylate monomer are preferably in mass proportions of between 30/70 and 70/30, preferably between 40/60 and 60/40, especially about 50/50.
• the proportion of the first block advantageously ranges from 20% to 90%, better still from 30% to 80% and even better still from 60% to 80% by weight of the polymer.
• the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.
• the second block advantageously has a glass transition temperature Tg of less than or equal to 20° C., for example, a Tg ranging from ⁇ 100° C. to 20° C., preferably less than or equal to 15° C., especially ranging from ⁇ 80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from ⁇ 100° C. to 10° C., especially ranging from ⁇ 30° C. to 10° C.
• the second block is totally or partially derived from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.
• This block may also be referred to as a “flexible block”.
• the monomer with a Tg of less than or equal to 20° C. (known as the second monomer) is preferably chosen from the following monomers:
• the preferred monomers with a Tg of less than or equal to 20° C. are isobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in all proportions.
• Each of the first and second 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 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.
• This additional monomer is chosen, for example, from:
• the first block may comprise as additional monomer:
• R 7 and R 8 which may be identical or different, each represent a hydrogen atom or a linear or branched C 1 to C 12 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 1,1-dimethyl-3-oxobutyl group, and
• the additional monomer may represent 0.5% to 30% by weight relative to the weight of the polymer. According to one embodiment, the polymer of the invention does not contain any additional monomer.
• the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block.
• the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportion in the first block and isobutyl acrylate and acrylic acid monomers in the second block.
• the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportion in the first block and isobutyl acrylate and acrylic acid monomers in the second block, the first block representing 70% by weight of the polymer.
• the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent weight proportion in the first block and isobutyl acrylate and acrylic acid monomers in the second block.
• the block with a Tg of greater than 40° C. represents 70% by weight of the polymer, and acrylic acid represents 5% by weight of the polymer.
• the first block does not comprise any additional monomer.
• the second block comprises acrylic acid as additional monomer.
• the second block is advantageously obtained from an acrylic acid monomer and from at least one other monomer with a Tg of less than or equal to 20° C.
• the block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and especially from 2% to 15% by weight, for example from 3% to 15% by weight, in particular from 4% to 15% by weight or even from 4% to 10% by weight of acrylic acid monomers, relative to the total weight of the said copolymer.
• the constituent monomers of the second block and the proportions thereof are preferably chosen such that the glass transition temperature of the second block is less than or equal to 20° C.
• the intermediate segment (also known as the intermediate block) connects the first block and the second block of the polymer used according to the present invention.
• the intermediate segment results from the polymerization:
• the formation of the second block is initiated when the first monomers no longer react or are no longer incorporated into the polymer chain either because they are all consumed or because their reactivity no longer allows them to be.
• the intermediate segment comprises the first available monomers, resulting from a degree of conversion of these first monomers of less than or equal to 90%, during the introduction of the second monomer(s) during the synthesis of the polymer.
• the intermediate segment of the block polymer is a statistical polymer (which may also be referred to as a statistical block). This means that it comprises a statistical distribution of the first monomer(s) and of the second monomer(s) and also of the additional monomer(s) that may be present.
• the intermediate segment is a statistical block, as are the first block and the second block if they are not homopolymers (i.e. if they are both formed from at least two different monomers).
• the block ethylenic copolymer according to the invention is prepared by free radical polymerization, according to the techniques that are well known for this type of polymerization.
• the free radical polymerization is performed in the presence of an initiator, whose nature is adapted, in a known manner, as a function of the desired polymerization temperature and of the polymerization solvent.
• the initiator may be chosen from initiators containing a peroxide function, redox couples, or other radical polymerization initiators known to those skilled in the art.
• examples of initiators containing a peroxide function include:
• An example of an initiator in the form of a redox couple that may be mentioned is the potassium thiosulfate+potassium peroxodisulfate couple.
• the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms.
• the initiator used is 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane sold under the reference Trigonox® 141 by the company Akzo Nobel.
• the block copolymer used according to the invention is prepared by free-radical polymerization rather than by controlled or living polymerization.
• the polymerization of the block ethylenic copolymer is performed in the absence of control agents, and in particular in the absence of control agents conventionally used in living or controlled polymerization processes, for instance nitroxides, alkoxyamines, dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates and copper-based catalysts.
• the intermediate segment is a statistical block, as are the first block and the second block if they are not homopolymers (i.e. if they are both formed from at least two different monomers).
• the block copolymer may be prepared by free-radical polymerization, and in particular via a process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with a glass transition temperature of greater than or equal to 40° C. and at least one monomer with a glass transition temperature of less than or equal to 20° C., according to the following sequence:
• the copolymer may be prepared by free-radical polymerization, in particular via a process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer with a glass transition temperature of less than or equal to 20° C., at least one acrylate monomer of formula CH 2 ⁇ CH—COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer of formula CH 2 ⁇ C(CH 3 )—COOR 12 in which R′ 2 represents a C 4 to C 12 cycloalkyl group, according to the following sequence of steps:
• some of the polymerization solvent and optionally some of the initiator and of the monomers of the first addition are placed in the reactor, and the mixture is heated to a reaction temperature of between 60 and 120° C.
• the said at least one acrylate monomer of formula CH 2 ⁇ CH—COOR 2 and the said at least one methacrylate monomer of formula CH 2 ⁇ C(CH 3 )—COOR 12 as monomers with a Tg of greater than or equal to 40° C., and optionally some of the initiator, are then introduced, in a first addition, and the mixture is left to react for a time T corresponding to a maximum degree of conversion of the said monomers of 90%,
• the acrylic acid monomer and the said at least one second monomer with a glass transition temperature of less than or equal to 20° C. are then placed in the reactor, in a second addition, and the mixture is left to react for a time T′ after which the degree of conversion of the said monomers reaches a plateau,
• reaction mixture is cooled to room temperature.
• polymerization solvent means a solvent or a mixture of solvents.
• the polymerization solvent is a volatile oil with a flash point of less than 80° C.
• the flash point is measured in particular according to standard ISO 3679.
• the polymerization solvent may be chosen especially from ethyl acetate, butyl acetate, alcohols such as isopropanol or ethanol, and aliphatic alkanes such as isododecane, and mixtures thereof.
• the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.
• the copolymer may be prepared by free-radical polymerization according to a preparation process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with a glass transition temperature of less than or equal to 20° C., and at least one monomer with a Tg of greater than or equal to 40° C., according to the following sequence of steps:
• the copolymer may be prepared by free-radical polymerization according to a preparation process that consists in mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer with a glass transition temperature of less than or equal to 20° C., at least one monomer with a Tg of greater than or equal to 40° C., and, in particular as monomers with a Tg of greater than or equal to 40° C., at least one acrylate monomer of formula CH 2 ⁇ CH—COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer of formula CH 2 ⁇ C(CH 3 )—COOR 12 in which R′ 2 represents a C 4 to C 12 cycloalkyl group, according to the following sequence of steps:
• the polymerization temperature is preferably about 90° C.
• the reaction time after the second addition is preferably between 3 and 6 hours.
• the block ethylenic copolymer is present in the composition in an active material content ranging from 0.1% to 60%, better still from 0.5% to 50%, better still from 1% to 30% and even better still from 1% to 40% by weight relative to the total weight of the composition.
• This step is performed at elevated temperature and optionally under vacuum to distil off a maximum amount of volatile synthesis solvent, and is known to those skilled in the art.
• a composition according to the invention comprises, as hydrophobic film-forming polymer, at least one polyamide silicone block polymer, also known as a silicone polyamide.
• the silicone polyamides are preferably solid at room temperature (25° C.) and atmospheric pressure (760 mmHg).
• polymer means a compound containing at least two repeating units, preferably at least three repeating units and better still ten repeating units.
• the silicone polyamides of the composition of the invention may be polymers of the polyorganosiloxane type, for instance those described in documents U.S. Pat. No. 874 , 069 , U.S. Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680.
• the silicone polymers may belong to the following two families:
• polyorganosiloxanes comprising at least two amide groups, these two groups being located in the polymer chain, and/or
• the silicone polymers are polyorganosiloxanes as defined above in which the units capable of establishing hydrogen interactions are located in the polymer chain.
• the silicone polymers may more particularly be polymers comprising at least one unit corresponding to the general formula I:
• R4, R5, R6 and R7 which may be identical or different, represent a group chosen from:
• 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 C1 to C30 alkylenediyl group, possibly containing in its chain one or more oxygen and/or nitrogen atoms;
• Y is a saturated or unsaturated C1 to C50 linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene divalent group, which may comprise one or more oxygen, sulfur and/or nitrogen atoms and/or which may bear as substituent one of the following atoms or groups of atoms: fluorine, hydroxyl, C3 to C8 cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl optionally substituted with 1 to 3 C1 to C3 alkyl, C1 to C0 hydroxyalkyl and C1 to C6 aminoalkyl groups, or
• Y represents a group corresponding to the formula:
• T represents a linear or branched, saturated or unsaturated, C3 to C24 trivalent or tetravalent hydrocarbon-based group optionally substituted with a polyorganosiloxane chain, and possibly containing one or more atoms chosen from O, N and S, or T represents a trivalent atom chosen from N, P and Al, and
• R8 represents a linear or branched C1 to C50 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:
• R9 represents a hydrogen atom or a linear or branched C1 to C20 alkyl group, on condition that at least 50% of the groups R9 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 1000, preferably from 1 to 700 and better still from 6 to 200.
• 80% of the groups R4, R5, R6 and R7 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 units of the polymer or copolymer.
• Y represents a group chosen from:
• phenylene groups optionally substituted with one or more C1 to C40 alkyl groups
• C1 to C20 alkylene groups comprising one or more substituents chosen from hydroxyl, C3 to C8 cycloalkane, C1 to C3 hydroxyalkyl and C1 to C6 alkylamine groups,
• the polyorganosiloxanes may be polymers comprising at least one unit corresponding to formula (II):
• R4 and R6, which, may be identical or different, are as defined above for formula (I),
• R10 represents a group as defined above for R4 and R6, or represents a group of formula —X-G-R12 in which X and G are as defined above for formula (I) and R12 represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated, C1 to C50 hydrocarbon-based group optionally comprising in its chain one or more atoms chosen from O, 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 C1 to C4 alkyl groups,
• R11 represents the group of formula —X-G-R12 in which X, G and R12 are as defined above,
• n1 is an integer ranging from 1 to 998
• m2 is an integer ranging from 2 to 500.
• the silicone polymer used as structuring agent may be a homopolymer, i.e. a polymer comprising several identical units, in particular units of formula (I) or of formula (II).
• a silicone polymer formed from a copolymer comprising several different units of formula (I), i.e. a polymer in which at least one of the groups R4, R5, R6, R7, X, G, Y, in and n is different in one of the units.
• the copolymer may also be formed from several units of formula (II), in which at least one of the groups R4, R6, R10, R11, m1 and m2 is different in at least one of the units.
• a polymer 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.
• copolymers may be block polymers or grafted polymers.
• the groups capable of establishing hydrogen interactions are amide groups of formulae —C(O)NH— and —HN—C(O)—.
• the structuring agent may be a polymer comprising at least one unit of formula (III) or (IV):
• R4, R5, R6, R7, X, Y, m and n are as defined above.
• X1-(CH 2 ) 2 — corresponds to X defined above and Y, R4, R5, R6, R7 and m are as defined above,
• m ranges from to 700, in particular from 15 to 500 and especially from 50 to 200, and n ranges in particular from 1 to 500, preferably from 1 to 100 and better still from 4 to 25,
• X is preferably a linear or branched alkylene chain containing from 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially from 5 to 15 carbon atoms and more particularly 10 carbon atoms, and
• Y is preferably an alkylene chain that is linear or branched, or which may comprise rings and/or unsaturations, containing from 1 to 40 carbon atoms, in particular 1 to 20 carbon atoms and better still from 2 to 6 carbon atoms, in particular 6 carbon atoms.
• the alkylene group representing X or Y can optionally contain in its alkylene part at least one of the following components:
• a phenylene group optionally substituted with 1 to 3 identical or different C1 to C3 alkyl groups.
• alkylene groups may also be substituted with at least one component chosen from the group consisting of:
• a phenyl group optionally substituted with one to three C1 to C3 alkyl groups
• Y may also represent:
• R8 represents a polyorganosiloxane chain and T represents a group of formula:
• a, b and c are, independently, integers ranging from 1 to 10, and R13 is a hydrogen atom or a group such as those defined for R4, R5, R6 and R7.
• R4, R5, R6 and R7 preferably represent, independently, a linear or branched C 1 to C 40 alkyl group, preferably a CH 3 , C 2 H 5 , n-C 3 H 7 or isopropyl group, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups.
• the polymer may comprise identical or different units of formula (III) or (IV).
• the polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, i.e. a polyamide corresponding to formula (V):
• X, Y, n and R4 to R7 have the meanings given above, m1 and m2, which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 to 300.
• the units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.
• the units may be not only of different lengths, but also of different chemical structures, for example containing different groups Y.
• the polymer may correspond to formula VI:
• R4 to R7, X, Y, m1, m2, n and p have the meanings given above and Y1 is different from Y but chosen from the groups defined for Y.
• the various units may be structured to form either a block copolymer, or a random copolymer or an alternating copolymer.
• the structuring agent may also be formed from a grafted copolymer.
• the polyamide containing silicone units may be grafted and optionally crosslinked with silicone chains containing amide groups.
• Such polymers may be synthesized with trifunctional amines.
• the polymer may comprise at least one unit of formula (VII):
• X1 and X2 which are identical or different, have the meaning given for X in formula (I)
• n is as defined in formula (I)
• Y and T are as defined in formula (I)
• R14 to R21 are groups chosen from the same group as R4 to R7
• m1 and m2 are numbers located in the range from 1 to 1000
• p is an integer ranging from 2 to 500.
• p ranges from 1 to 25 and better still from 1 to 7,
• R14 to R21 are methyl groups
• T corresponds to one of the following formulae:
• R22 is a hydrogen atom or a group chosen from the groups defined for R4 to R7, and R23, R24 and R25 are, independently, linear or branched alkylene groups, more preferably corresponding to the formula:
• R23, R24 and R25 representing —CH2-CH2-
• n1 and m2 range from 15 to 500 and better still from 15 to 45
• X1 and X2 represent —(CH 2 )10-
• Y represents —CH2—.
• polyamides containing a grafted silicone unit of formula (VII) may be copolymerized with polyamide silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers.
• the weight percentage of grafted silicone units (VII) in the copolymer may range from 0.5% to 30% by weight.
• the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendent chains.
• the siloxane units may be in the form of segments as described above.
• the siloxane units may appear individually or in segments.
• a copolymer of silicone polyamide and of hydrocarbon-based polyamide or a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units, may be used.
• the silicone polyamide units may be located at the ends of the hydrocarbon-based polyamide.
• the silicone polyamide comprises units of formula III, preferably in which the groups R4, R5, R6 and R7 represent methyl groups, one from among X and Y represents an alkylene group of 6 carbon atoms and the other represents an alkylene group of 11 carbon atoms, a representing the degree of polymerization, DP, of the polymer.
• the groups R4, R5, R6 and R7 represent methyl groups, one from among X and Y represents an alkylene group of 6 carbon atoms and the other represents an alkylene group of 11 carbon atoms, a representing the degree of polymerization, DP, of the polymer.
• silicone polyamides mention may be made of the compounds sold by the company Dow Corning under the names DC2-8179 (DP 100) and DC2-8178 (DP 15), the INCI name of which is Nylon-611/dimethicone copolymer.
• composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) with an index m of about 15.
• the composition according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m ranges from 5 to 100, in particular from 10 to 75 and even more particularly is about 15; even more preferably, R4, R5, R6 and R7 independently represent a linear or branched C1 to C40 alkyl group, preferably a group CH 3 , C 2 H 5 , n-C 3 H, or isopropyl in formula (III).
• the silicone polyamide sold by the company Dow Corning under the name DC2-8179 (DP 100) is used.
• a composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one vinyl polymer comprising at least one carbosiloxane dendrimer-based unit.
• the vinyl polymer used according to the invention especially has a backbone and at least one side chain, which comprises a carbosiloxane dendrimer-based unit having a carbosiloxane dendrimer structure.
• Vinyl polymers comprising at least one carbosiloxane dendrimer unit as described in patent applications WO 03/045 337 and EP 963 751 by the company Dow Corning may be used in particular.
• carbosiloxane dendrimer structure in the context of the present invention represents a structure with branched groups of high molecular masses, the said structure having high regularity in the radial direction starting from the bond to the backbone.
• Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in the laid-open Japanese patent application Kokai 9-171 154.
• a vinyl polymer according to the invention may contain carbosiloxane dendrimer-based units that may be represented by the following general formula:
• R 1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms
• R 1 is the same as defined above
• R 2 represents an alkylene group containing from 2 to 10 carbon atoms
• R 3 represents an alkyl group containing from 1 to 10 carbon atoms
• i is an integer from 1 to 10 which represents the generation of the said silylalkyl group
• a i is an integer from 0 to 3
• Y represents a radical-polymerizable organic group chosen from:
• R 4 represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the methylene group and the propylene group being preferred
• R 6 represents a hydrogen atom or an alkyl group
• R 7 represents an alkyl group containing from 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, the methyl group being preferred
• R 8 represents an alkylene group containing from 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the ethylene group being preferred
• b is an integer from 0 to 4
• c is 0 or 1 such that if c is 0, —(R 8 ) c — represents a bond.
• R 1 may represent an aryl group or an alkyl group containing from 1 to 10 carbon atoms.
• the alkyl group may preferably be represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group.
• the aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is preferred among all.
• a vinyl polymer containing at least one carbosiloxane dendrimer-based unit has a molecular side chain containing a carbosiloxane dendrimer structure, and may be the product of polymerization of:
• Y represents a radical-polymerizable organic group
• R 1 represents an aryl group or an alkyl group containing from 1 to 10 carbon atoms
• R 4 represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group containing from 1 to 10 carbon atoms
• R 6 represents a hydrogen atom or an alkyl group
• R 7 represents an alkyl group containing from 1 to 10 carbon atoms
• R S represents an alkylene group containing from 1 to 10 carbon atoms
• b is an integer from 0 to 4
• c is 0 or 1, such that if c is 0, —(R 8 ) c — represents a bond.
• the monomer of vinyl type that is the component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
• this monomer of vinyl type methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate or a methacrylate of a lower alkyl analogue; glycidyl methacrylate; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate or a higher-analogue methacrylate; or a higher-analogue methacrylate; vinyl acetate, vinyl
• Multifunctional monomers of vinyl type may also be used.
• trimethylolpropane trimethacrylate pentaerythrityl trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris(2-hydroxyethyl) isocyanurate dimeth acrylate, tris(2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups containing divinylbenzene groups on both ends, or similar silicone compounds containing unsaturated groups.
• a carbosiloxane dendrimer which is the component (B), may be represented by the following formula:
• Y represents a radical-polymerizable organic group as defined previously.
• radical-polymerizable organic groups Y an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
• R′ is as defined previously.
• X i represents a silylalkyl group that is represented by the following formula, when i is equal to 1:
• R 1 is as defined above.
• R 2 represents an alkylene group containing from 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group or a similar linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group or a similar branched alkylene group.
• ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are preferred above all.
• R 3 represents an alkyl group containing from 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl and isopropyl groups.
• a i is an integer from 0 to 3
• i is an integer from 1 to 10 that indicates the generation number, which represents the number of repetitions of the silylalkyl group.
• the carbosiloxane dendrimer may be represented by the first general formula shown below, in which Y, R 1 , R 2 and R 3 are the same as defined above, R 12 represents a hydrogen atom or is identical to R 1 ; a 1 is identical to a i .
• the mean total number of groups OR 3 in a molecule is within the range from 0 to 7.
• the carbosiloxane dendrimer may be represented by the second general formula shown below, in which Y, R 1 , R 2 , R 3 and R 12 are the same as defined above; a 1 and a 2 represent the a i of the indicated generation.
• the mean total number of groups OR 3 in a molecule is within the range from 0 to 25.
• the carbosiloxane dendrimer is represented by the third general formula shown below, in which Y, R 1 , R 2 , R 3 and R 12 are the same as defined above; a 1 , a 2 and a 3 represent the a i of the indicated generation.
• the mean total number of groups OR 3 in a molecule is within the range from 0 to 79.
• a carbosiloxane dendrimer that contains a radical-polymerizable organic group may be represented by the following mean structural formulae:
• the carbosiloxane dendrimer may be manufactured according to the process for manufacturing a branched silalkylene siloxane described in Japanese patent application Hei 9-171 154.
• organosilicon compound containing a hydrogen atom linked to a silicon atom represented by the following general formula:
• the organosilicon compound may be represented by 3-methacryloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane and 4-vinylphenyltris(dimethylsiloxy)silane.
• the organosilicon compound that contains an alkenyl group may be represented by vinyltris(trimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane, and 5-hexenyltris(trimethylsiloxy)silane.
• the hydrosilylation reaction is performed in the presence of a chloroplatinic acid, a complex of vinylsiloxane and of platinum, or a similar transition metal catalyst.
• a vinyl polymer containing at least one carbosiloxane dendrimer-based unit may be chosen from polymers such that the carbosiloxane dendrimer-based unit is a carbosiloxane dendritic structure represented by formula (I):
• Z represents a divalent organic group
• p is 0 or 1
• R 1 is an aryl or alkyl group containing from 1 to 10 carbon atoms
• X is a silylalkyl group represented by formula (II):
• R 1 is as defined above
• R 2 is an alkylene group containing from 1 to 10 carbon atoms
• R 3 is an alkyl group containing from 1 to 10 carbon atoms
• X i+1 is a group chosen from the group comprising hydrogen atoms, aryl groups and alkyl groups containing up to 10 carbon atoms
• the polymerization ratio between the components (A) and (B), in terms of the weight ratio between (A) and (B), may be within a range from 0/100 to 99.9/0.1, or even from 0.1/99.9 to 99.9/0.1 and preferably within a range from 1/99 to 99/1.
• a ratio between the components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B).
• a vinyl polymer containing at least one carbosiloxane dendrimer-based unit may be obtained by copolymerization of the components (A) and (B), or by polymerization of component (B) alone.
• the polymerization may be a free-radical polymerization or an ionic polymerization, but free-radical polymerization is preferred.
• the polymerization may be performed by bringing about a reaction between the components (A) and (B) in a solution for a period of from 3 to 20 hours in the presence of a radical initiator at a temperature of from 50° C. to 150° C.
• a suitable solvent for this purpose is hexane, octane, decane, cyclohexane or a similar aliphatic hydrocarbon; benzene, toluene, xylene or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate or similar esters; methanol, ethanol, isopropanol, butanol or similar alcohols; octamethylcyclotetraslotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane
• a radical initiator may be any compound known in the art for standard free-radical polymerization reactions.
• Specific examples of such radical initiators are 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile) or similar compounds of azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or a similar organic peroxide.
• These radical initiators may be used alone or in a combination of two or more.
• the radical initiators may be used in an amount of from 0.1 to 5 parts by weight per 100 parts by weight of the components (A) and (B).
• a chain-transfer agent may be added.
• the chain-transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane containing a mercaptopropyl group or a similar compound of mercapto type; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane or a similar halogenated compound.
• the residual unreacted vinyl monomer may be removed under conditions of heating under vacuum.
• the number-average molecular mass of the vinyl polymer containing a carbosiloxane dendrimer may be chosen within the range between 3000 and 2 000 000 and preferably between 5000 and 800 000. It may be a liquid, a gum, a paste, a solid, a powder or any other form.
• the preferred forms are solutions formed from the dilution of a dispersion or of a powder in solvents.
• the vinyl polymer may be a dispersion of a polymer of vinyl type having a carbosiloxane dendrimer structure in its molecular side chain, in a liquid such as a silicone oil, an organic oil, an alcohol or water.
• the silicone oil may be a dimethylpolysiloxane with the two molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having the two molecular ends capped with trimethylsiloxy groups, or similar unreactive linear silicone oils, and also hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethyleyclohexasiloxane or a similar cyclic compound.
• modified polysiloxanes containing functional groups such as such as silanol groups, amino groups and polyether groups on the ends or within the molecular side chains may
• the organic oils may be isododecane, liquid paraffin, isoparaffin, hexyl laurate, isopropyl my state, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil, camellia oil, squalane, castor oil, cottonseed oil, coconut oil, egg yolk oil, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or
• the alcohol may be any type that is suitable for use in combination with a cosmetic product starting material.
• it may be methanol, ethanol, butanol, isopropanol or similar lower alcohols.
• a solution or a dispersion of the alcohol should have a viscosity within the range from 10 to 10 9 mPa at 25° C. To improve the sensory use properties in a cosmetic product, the viscosity should be within the range from 100 to 5 ⁇ 10 8 mPa ⁇ s.
• the solutions and dispersions may be readily prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure with a silicone oil, an organic oil, an alcohol or water.
• the liquids may be present in the step of polymerization of a vinyl polymer containing at least one carbosiloxane dendrimer-based unit. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric pressure or reduced pressure.
• the dispersity of the polymer of vinyl type may be improved by adding a surfactant.
• Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylamnonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammoniurn hydroxide, beef tallow-trimethylammonium hydroxide, coconut oil-trimethylammonium hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether,
• the solvents and dispersions may be combined with iron oxide suitable for use with cosmetic products, or a similar pigment, and also zinc oxide, titanium oxide, silicon oxide, mica, talc or similar mineral oxides in powder form.
• a mean particle diameter of the polymer of vinyl type may be within a range of between 0.001 and 100 microns and preferably between 0.01 and 50 microns. The reason for this is that, outside the recommended range, a cosmetic product mixed with the emulsion will not have a nice enough feel on the skin or to the touch, or sufficient spreading properties or a pleasant feel.
• a vinyl polymer contained in the dispersion or the solution may have a concentration in the range between 0.1% and 95% by weight and preferably between 5% and 85% by weight. However, to facilitate the handling and the preparation of the mixture, the range should preferably be between 10% and 75% by weight.
• a vinyl polymer that is suitable for use in the invention may be one of the polymers described in the examples of patent application EP 0 963 751.
• a vinyl polymer grafted with a carbosiloxane dendrimer may be the product of polymerization of:
• (B) from 100 to 0.1 part by weight of an acrylate or methacrylate monomer of a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]silylpropyl carbosiloxane dendrimer.
• a vinyl polymer containing at least one carbosiloxane dendrimer-based unit may comprise a tris[tri(trimethylsiloxy)silylethyldimethylsiloxy]sil-ylpropyl carbosiloxane dendrimer-based unit corresponding to one of the formulae:
• a vinyl polymer containing at least one carbosiloxane dendrimer-based unit used in the invention comprises at least one butyl acrylate monomer.
• a vinyl polymer may also comprise at least one fluoro organic group.
• a fluoro vinyl polymer may be one of the polymers described in the examples of patent application WO 03/045 337.
• a vinyl polymer grafted in the sense of the present invention may be conveyed in an oil or a mixture of oils, which are preferably volatile, chosen in particular from silicone oils and hydrocarbon-based oils, and mixtures thereof.
• a silicone oil that is suitable for use in the invention may be cyclopentasiloxane.
• a hydrocarbon-based oil that is suitable for use in the invention may be isododecane.
• Vinyl polymers grafted with at least one carbosiloxane dendrimer-based unit that may be particularly suitable for use in the present invention are the polymers sold under the names TIB 4-100, TIB 4-101, TIB 4-120, TIB 4-130, TIB 4-200, FA 4002 ID (TIB 4-202), TIB 4-220 and FA 4001 CM (TIB 4-230) by the company Dow Corning.
• the polymers sold under the names FA 4002 ID (TIB 4-202) and FA 4001 CM (TIB 4-230) by the company Dow Corning will preferably be used.
• the vinyl polymer grafted with at least one carbosiloxane dendrimer-based unit that may be used in a composition of the invention is an acrylate/polytrimethyl siloxymethacrylate copolymer, especially the product sold in isododecane under the name Dow Corning FA 4002 ID Silicone Acrylate by the company Dow Corning.
• composition used according to the invention may comprise, as hydrophobic film-forming polymer, at least one copolymer comprising carboxylate groups and polydimethylsiloxane groups.
• copolymer comprising carboxylate groups and polydimethylsiloxane groups means a copolymer obtained from (a) one or more carboxylic (acid or ester) monomers, and (b) one or more polydimethylsiloxane (PDMS) chains.
• carboxylic monomer means both carboxylic acid monomers and carboxylic acid ester monomers.
• the monomer (a) may be chosen, for example, from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, esters thereof and mixtures of these monomers.
• Esters that may be mentioned include the following monomers: acrylate, methacrylate, maleate, fumarate, itaconate and/or crotonate.
• the monomers in ester form are more particularly chosen from linear or branched, preferably C 1 -C 24 and better still C 1 -C 22 alkyl acrylates and methacrylates, the alkyl radical preferably being chosen from methyl, ethyl, stearyl, butyl and 2-ethylhexyl radicals, and mixtures thereof.
• the copolymer comprises as carboxylate groups at least one group chosen from acrylic acid and methacrylic acid, and methyl, ethyl, stearyl, butyl or 2-ethylhexyl acrylate or methacrylate, and mixtures thereof.
• polydimethylsiloxanes also known as organopolysiloxanes and abbreviated as PDMS
• PDMS polydimethylsiloxanes
• the PDMS chains that may be used to obtain the copolymer used according to the invention comprise at least one polymerizable radical group, preferably located on at least one of the ends of the chain, i.e. the PDMS may contain, for example, a polymerizable radical group on the two ends of the chain or one polymerizable radical group on one end of the chain and one trimethylsilyl end group on the other end of the chain.
• copolymers used in the composition of the invention are generally obtained according to the usual methods of polymerization and grafting, for example by free-radical polymerization (A) of a PDMS comprising at least one polymerizable radical group (for example on one of the ends of the chain or on both ends) and (B) of at least one carboxylic monomer, as described, for example, in documents U.S. Pat. No. 5,061,481 and U.S. Pat. No. 5,219,560.
• the copolymers obtained generally have a molecular weight ranging from about 3000 to 200 000 and preferably from about 5000 to 100 000.
• the copolymer used in the composition of the invention may be in its native form or in dispersed form in a solvent such as lower alcohols containing from 2 to 8 carbon atoms, for instance isopropyl alcohol, or oils, for instance volatile silicone oils (for example cyclopentasiloxane).
• a solvent such as lower alcohols containing from 2 to 8 carbon atoms, for instance isopropyl alcohol, or oils, for instance volatile silicone oils (for example cyclopentasiloxane).
• KP561 is preferably used; this copolymer is not dispersed in a solvent, but is in waxy form, its melting point being about 30° C.
• a cosmetic makeup and/or care composition according to the invention also comprises a cosmetically acceptable medium that may comprise the usual ingredients, as a function of the intended use of the composition.
• composition according to the invention may also comprise at least one organic or inorganic filler.
• a composition may comprise from 0.01% to 35% by weight and preferably from 0.1% to 20% by weight of filler(s) relative to its total weight.
• fillers examples include talc, mica, silica, kaolin, calcium carbonate, barium sulfate, Nylon (especially Orgasol) powder and polyethylene powder, Teflon, starch, boron nitride, copolymer microspheres such as Expancel (Nobel Industrie) and silicone resin microbeads (for example Tospearls from Toshiba); and also mixtures thereof.
• a composition according to the invention contains at least one filler that is capable of absorbing an oil.
• a composition according to the invention comprises at least one filler with capacity for absorbing and/or adsorbing an oil or a liquid fatty substance, for instance sebum (from the skin).
• This oil-absorbing filler may also advantageously have a BET specific surface area of greater than or equal to 300 m 2 /g, preferably greater than 500 m 2 /g and preferentially greater than 600 m 2 /g, and especially less than 1500 m 2 /g.
• the BET specific surface area is determined according to the BET (Brunauer-Emmet-Teller) method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D).
• the BET specific surface area corresponds to the total specific surface area (thus including micropores) of the powder.
• the filler under consideration according to the invention is thus characterized in that it has an oil uptake of greater than or equal to 1 ml/g, especially ranging from 1 ml/g to 20 ml/g, or even ranging from 1.5 ml/g to 15 ml/g. It preferably has an oil uptake of greater than or equal to 2 ml/g, especially ranging from 2 ml/g to 20 ml/g, or even ranging from 2 ml/g to 15 ml/g.
• This oil uptake which corresponds to the amount of oil absorbed and/or adsorbed by the filler, may be characterized by measuring the wet point according to the method described below.
• the oil uptake of a powder is measured according to the method for determining the oil uptake of a powder are described in standard NF T 30-022. It corresponds to the amount of oil adsorbed onto the available surface of the pulverulent material, by measuring the wet point.
• isononyl isononanoate After addition of 4 to 5 drops of isononyl isononanoate, the isononyl isononanoate is incorporated into the filler using a spatula, and addition of the isononyl isononanoate is continued until a conglomerate of isononyl isononanoate and powder has formed. At this point, the isononyl isononanoate is added one drop at a time and the mixture is then triturated with the spatula. The addition of isononyl isononanoate is stopped when a firm, smooth paste is obtained. This paste must be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of isononyl isononanoate used is then noted.
• the oil uptake corresponds to the ratio Vs/m.
• This oil-absorbing filler may be a mineral powder or an organic powder; it may be chosen from silica, polyamide (Nylon®) powders, acrylic polymer powders, especially polymethyl methacrylate powder, polymethyl methacrylate/ethylene glycol dimethacrylate powder polyallayl methacrylate/ethylene glycol dimethacrylate powder or ethylene glycol dimethacrylate/lauryl methacrylate copolymer powder; powders of silicone elastomers obtained especially by polymerization of organopolysiloxane containing at least two hydrogen atoms each bonded to a silicon atom and of an organopolysiloxane comprising at least two ethylenically unsaturated groups (especially two vinyl groups) in the presence of a platinum catalyst.
• silica polyamide (Nylon®) powders
• acrylic polymer powders especially polymethyl methacrylate powder, polymethyl methacrylate/ethylene glycol dimethacrylate powder polyallayl methacrylate/ethylene glycol dim
• the oil-absorbing filler may be a powder coated with a hydrophobic treatment agent.
• fillers with an oil uptake of greater than or equal to 1.5 ml/g are described below, with their oil uptake value measured according to the protocol defined previously.
• Silica powders that may be mentioned include:
• Acrylic polymer powders that may be mentioned include:
• Polyamide powders that may be mentioned include:
• a perlite powder that may especially be mentioned is the product sold under the name Optimat 1430 OR by the company World Minerals (oil uptake equal to 2.4 ml/g).
• a magnesium carbonate powder that may especially be mentioned is the product sold under the name Tipo Carbomagel by the company Buschle & Lepper (oil uptake equal to 2.14 ml/g).
• the oil-absorbing filler that is particularly preferred is a silica powder and more particularly a silica powder with an oil uptake at least equal to 3.70 ml/g, and especially the products sold under the name Sunsphere® H33 by the company Asahi Glass and under the name Dow Corning VM-2270 Aerogel Fine Particles by the company Dow Corning.
• the filler(s) that are especially capable of absorbing an oil may be present in a composition according to the invention in a content ranging from 0.5% to 40% by weight, preferably ranging from 1% to 20% by weight and preferentially ranging from 1% to 15% by weight relative to the total weight of the composition.
• a composition according to the invention may use at least one filler and at least one supramolecular polymer in a polymer(s)/oil-absorbing filler(s) weight ratio of greater than 1, preferably greater than 1.5 and better still greater than 2.
• a composition according to the invention contains at least one filler with an oil uptake of greater than or equal to 1.5 ml/g.
• composition according to the invention also contains at least one silicone filler.
• the silicone filler may be chosen from:
• the organopolysiloxane powder may especially be coated with silsesquioxane resin, as described, for example, in U.S. Pat. No. 5,538,793.
• silsesquioxane resin as described, for example, in U.S. Pat. No. 5,538,793.
• Such elastomeric powders are sold under the names KSP-100, KSP-101, KSP-102, KSP-103, KSP-104 and KSP-105 by the company Shin-Etsu, and have the INCI name: vinyl dimethicone/methicone silsesquioxane crosspolymer.
• Polymethylsilsesquioxane powders that may especially be mentioned include silicone resin microbeads, such as those sold under the name Tospearl by the company Momentive Performance Materials, and especially under the reference Tospearl 145 A; and mixtures thereof.
• a composition for making up and/or caring for the skin and/or the lips according to the invention comprises at least one dyestuff, in particular at least one pulverulent dyestuff,
• the dyestuff is especially chosen from organic or mineral dyestuff, especially such as the pigments or nacres conventionally used in cosmetic compositions, liposoluble or water-soluble dyes, materials with a specific optical effect, and mixtures thereof.
• pigments should be understood as meaning white or coloured, mineral or organic particles, which are insoluble in an aqueous solution and which are intended to colour and/or opacify the resulting film.
• These pigments may be in the form of powder or of pigmentary paste. They may be coated or uncoated.
• mineral pigments that may be used in the invention, mention may be made of titanium oxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide or chromium oxide, ferric blue, manganese violet, ultramarine blue and chromium hydrate.
• the mineral pigments are chosen from iron oxides and titanium oxides, and mixtures thereof.
• DPP diketopyrrolopyrroles
• lake means dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.
• the pigments may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be especially composed of particles comprising a mineral core, at least one binder for binding the organic pigments to the core, and at least one organic pigment at least partially covering the core.
• nacres should be understood as meaning iridescent or non-iridescent coloured particles of any form, especially produced by certain molluscs in their shell, or else synthesized, and which have a colour effect by optical interference.
• the nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride. They may also be mica particles at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.
• nacres examples include natural mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride.
• nacres available on the market, mention may be made of the nacres Timica, Flamenco and Duochrome (based on mica) sold by the company Engelhard, the Timiron nacres sold by the company Merck, the Prestige mica-based nacres, sold by the company Eckart, and the Sunshine synthetic mica-based nacres, sold by the company Sun Chemical.
• the nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.
• nacres that may be used in the context of the present invention, mention may be made especially of the gold-coloured nacres sold especially by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233 ⁇ (Cloisonne); the bronze nacres sold especially by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown nacres sold especially by the company Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the n
• the cosmetic composition according to the invention may also comprise water-soluble or liposoluble dyes.
• dyes should be understood as meaning compounds that are generally organic, which are soluble in fatty substances such as oils or in an aqueous-alcoholic phase.
• the liposoluble dyes are, for example, Sudan red, DC Red 17, DC Green 6, ⁇ -carotene, Sudan brown, DC Yellow 11, DC Violet 2, DC Orange 5 and quinoline yellow.
• the water-soluble dyes are, for example, beetroot juice and caramel.
• the cosmetic composition according to the invention may also contain at least one material with a specific optical effect.
• the term “stabilized” means lacking an effect of variability of the colour as a function of the angle of observation or alternatively in response to a temperature change.
• this material may be chosen from particles with a metallic tint, goniochromatic colouring agents, diffracting pigments, thermochromic agents, optical brighteners, and also fibres, especially interference fibres. Needless to say, these various materials may be combined so as to afford the simultaneous manifestation of two effects, or even of a novel effect in accordance with the invention.
• the particles with a metallic tint that may be used in the invention are chosen in particular from:
• metals that may be present in the said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof.
• Ag, Au, Cu, Al, Zn, Ni, Mo and Cr and mixtures or alloys thereof are preferred metals.
• copper metal powders or alloy mixtures such as the reference 2844 sold by the company Radium Bronze
• metallic pigments such as aluminium or bronze
• metal alloy particles such as those sold under the name Rotosafe 700 from the company Eckart
• silica-coated aluminium particles sold under the name Visionaire Bright Silver from the company Eckart and metal alloy particles for instance the silica-coated-bronze (alloy of copper and zinc) powders sold under the name Visionaire Bright Natural Gold from the company Eckart.
• They may also be particles comprising a glass substrate, such as those sold by the company Nippon Sheet Glass under the name Microglass Metashine.
• the goniochromatic colouring agent may be chosen, for example, from interference multilayer structures and liquid-crystal colouring agents.
• Examples of symmetrical interference multilayer structures that may be used in compositions produced in accordance with the invention are, for example, the following structures: Al/SiO 2 /Al/SiO 2 /Al, pigments having this structure being sold by the company Dupont de Nemours; Cr/MgF 2 /Al/MgF 2 /Cr, pigments having this structure being sold under the name Chromaflair by the company Flex; MoS 2 /SiO 2 /Al/SiO 2 /MoS 2 ; Fe 2 O 3 /SiO 2 /Al/SiO 2 /Fe 2 O 3 , and Fe 2 O 3 /SiO 2 /Fe 2 O 3 /SiO 2 /Fe 2 O 3 , pigments having these structures being sold under the name Sicopearl by the company BASF; MoS 2 /SiO 2 /mica-oxide/SiO 2 /MoS 2 ; Fe 2 O 3 /
• these pigments may be the pigments of silica/titanium oxide/tin oxide structure sold under the name Xirona Magic by the company Merck, the pigments of silica/brown iron oxide structure sold under the name Xirona Indian Summer by the company Merck and the pigments of silica/titanium oxide/mica/tin oxide structure sold under the name Xirona Caribbean Blue by the company Merck. Mention may also be made of the infinite Colors pigments from the company Shiseido. Depending on the thickness and the nature of the various coats, different effects are obtained.
• the colour changes from green-golden to red-grey for SiO 2 layers of 320 to 350 nm; from red to golden for SiO 2 layers of 380 to 400 nm; from violet to green for SiO 2 layers of 410 to 420 nm; from copper to red for SiO 2 layers of 430 to 440 nm.
• pigments with a polymeric multilayer structure examples include those sold by the company 3M under the name Color Glitter.
• liquid-crystal goniochromatic particles examples include those sold by the company Chenix and also the product sold under the name Helicone HC by the company Wacker.
• the amount of dyestuffs in a composition according to the invention is between 0.01% and 40% by weight and especially between 0.1% and 30% by weight, or even between 1% and 20% by weight relative to the total weight of the composition.
• a composition according to the invention may comprise a fatty phase, which may represent from 1% to 98% by weight, especially 5% to 95% by weight or even 10% to 90% by weight relative to the total weight of the composition.
• This fatty phase may comprise oils, waxes and/or pasty compounds and/or silicone compounds as defined below.
• oils preferably silicone oils, and/or silicone compounds may be present in a proportion ranging from 0.1% to 60% by weight and preferably from 0.5% to 40% by weight relative to the total weight of the composition.
• composition according to the invention may advantageously comprise one or more oils, which may be chosen especially from hydrocarbon-based oils and fluoro oils, and mixtures thereof.
• oils may be of animal, plant, mineral or synthetic origin.
• oil means a water-immiscible non-aqueous compound that is liquid at room temperature (25° C.) and at atmospheric pressure (760 mmHg).
• the oils may be volatile or non-volatile.
• volatile oil means any oil that is capable of evaporating on contact with keratin materials in less than one hour, at room temperature and atmospheric pressure. Volatile oils preferably have a non-zero vapour pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa to 40 000 Pa, in particular from 1.3 Pa to 13 000 Pa and more particularly from 1.3 Pa to 1300 Pa.
• fluoro oil means an oil comprising at least one fluorine atom.
• hydrocarbon-based oil means an oil mainly containing hydrogen and carbon atoms.
• the oils may optionally comprise oxygen, nitrogen, sulfuer and/or phosphorus atoms, for example in the form of hydroxyl or acid radicals.
• the volatile oils may be chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially C 8 -C 16 branched alkanes (also known as isoparaffins), for instance isododecane, isodecane and isohexadecane.
• hydrocarbon-based oils containing from 8 to 16 carbon atoms, and especially C 8 -C 16 branched alkanes (also known as isoparaffins), for instance isododecane, isodecane and isohexadecane.
• the volatile hydrocarbon-based oil may also be a linear volatile alkane containing 7 to 17 carbon atoms, in particular 9 to 15 carbon atoms and more particularly 11 to 13 carbon atoms. Mention may be made especially of n-nonadecane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-hexadecane, and mixtures thereof.
• Non-volatile oils that may especially be mentioned include:
• one or more oils according to the invention may be present in a composition according to the invention in a content ranging from 1% to 90% by weight, preferably ranging from 2% to 75% by weight or even from 3% to 60% by weight relative to the total weight of the composition.
• this weight percentage of oil takes into account the weight of oil used for the formulation of the associated supramolecular polymer, if present.
• a composition according to the invention may also comprise at least one silicone compound with a viscosity of less than 10 000 000 cSt at 25° C.
• a silicone compound with a viscosity of less than 10 000 000 cSt at 25° C.
• Such a compound is advantageously chosen from silicone gums, volatile silicone oils and non-volatile silicone oils.
• the silicone compound under consideration according to the invention may be a silicone oil with a viscosity of between 3 centistokes (cSt) (3 ⁇ 10 ⁇ 6 m 2 /s) and 800 000 centistokes (cSt) (80000 000 ⁇ 10 ⁇ 6 m 2 /s).
• the silicone compound under consideration according to the invention may be a non-volatile silicone oil with a viscosity of between 9 centistokes (cSt) (9 ⁇ 10 ⁇ 6 m 2 is) and 600 000 centistokes (cSt) (600 000 ⁇ 10 16 m2/s).
• cSt centistokes
• cSt centistokes
• oil means a water-immiscible non-aqueous compound that is liquid at room temperature (25° C.) and at atmospheric pressure (760 mmHg).
• silicon oil means an oil comprising at least one silicon atom, and especially at least one Si—O group.
• the volatile or non-volatile silicone oils that may be used in the invention preferably have a viscosity at 25° C. of less than 800 000 cSt, preferably less than or equal to 600 000 cSt and preferably less than or equal to 500 000 cSt.
• the viscosity of these silicone oils may be measured according to standard ASTM D-445.
• composition according to the invention and/or under consideration according to a process of the invention contains at least one silicone oil other than cyclopentasiloxane.
• an oil also known as decamethylcyclopentasiloxane, is especially sold under the name DC-245 by the company Dow Corning or Mirasil CM 5.
• composition according to the invention or under consideration according to a process of the invention may contain a mixture of silicone oils formed only partly from such an oil.
• the silicone oils that may be used according to the invention may be volatile and/or non-volatile.
• composition according to the invention or under consideration according to a process of the invention may contain a mixture of volatile and non-volatile silicone oil.
• volatile oil means an oil that can evaporate on contact with the skin in less than one hour, at room temperature (25° C.) and atmospheric pressure.
• the volatile oil is a volatile cosmetic oil, which is liquid at room temperature, especially having a non-zero vapour pressure, at room temperature and atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10 ⁇ 3 to 300 mmHg), preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.1 to 10 mmHg).
• non-volatile oil means an oil whose vapour pressure at room temperature and atmospheric pressure is non-zero and less than 0.02 mmHg (2.66 Pa) and better still less than 10 ⁇ 3 nm mHg (0.13 Pa).
• compositions according to the invention comprise at least one volatile silicone oil.
• the volatile silicone oils that may be used in the invention may be chosen from silicone oils especially having a viscosity of 8 centistokes (cSt) (8 ⁇ 10 ⁇ 6 m 2 /s).
• Volatile silicone oils that may be mentioned include:
• volatile silicone oils are non-cyclic and are chosen in particular from:
• R which may be identical or different, denotes:
• R which may be identical or different, denotes:
• the ratio between the number of carbon atoms and the number of silicon atoms is between 2.25 and 4.33.
• the silicones of formulae (I) to (III) may be prepared according to the known processes for synthesizing silicone compounds.
• silicones of formula (I) that may be mentioned are:
• DC 200 Fluid 1 cSt by the company Dow Corning
• 3-pentyl-1,1,1,3,5,5,5-heptamethyltrisiloxane 1-hexyl-1,1,3,3,5,5,5-heptamethyltrisiloxane; 1,1,1,3,3,5,5-heptanethyl5-octyltrisiloxane; 1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane, sold especially under the name Silsoft 034 by the company OSI
• DC2-1731 by the company Dow Corning
• Volatile silicone oils that may more particularly be mentioned include decamethylcyclopentasiloxane sold especially under the name DC-245 by the company Dow Corning, dodecamethylcyclohexasiloxane sold especially under the name DC-246 by the company Dow Corning, octamethyltrisiloxane sold especially under the name DC-200 Fluid 1 cSt by the company Dow Corning, decamethyltetrasiloxane sold especially under the name DC-200 Fluid 1.5 cSt by the company Dow Corning and DC-200 Fluid 5 cSt sold by the company Dow Corning, octamethylcyclotetrasiloxane, heptamethylhexyltrisiloxane, heptamethylethyltrisiloxane, heptamethyloctyltrisiloxane and dodeca nethylpentasiloxane, and mixtures thereof.
• the linear oils prove to be particularly advantageous.
• compositions according to the invention comprise at least one non-volatile silicone oil.
• the non-volatile silicone oils that may be used in the invention may be chosen from silicone oils with a viscosity at 25° C. of greater than or equal to 9 centistokes (cSt) (9 ⁇ 10 ⁇ 6 m 2 /s) and less than 800 000 cSt, preferably between 50 and 600 000 cSt and preferably between 100 and 500 000 cSt.
• the viscosity of this silicone oil may be measured according to standard ASTM D-445.
• silicone oils two types of oil may be distinguished, according to whether or not they contain phenyl.
• non-volatile linear silicone oils include polydimethylsilxanes; alkyl dimethicones; vinyl methyl methicones; and also silicones modified with optionally fluorinated aliphatic groups, or with functional groups such as hydroxyl, thiol and/or amine groups.
• non-phenyl non-volatile silicone oils that may be mentioned include:
• a composition according to the invention contains at least one non-phenyl linear silicone oil.
• the non-phenyl linear silicone oil may be chosen especially from the silicones of formula:
• R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,
• X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical,
• n and p are integers chosen so as to have a fluid compound.
• non-volatile silicone oils that may be used according to the invention, mention may be made of those for which:
• a composition according to the invention contains at least one phenyl silicone oil.
• non-volatile phenyl silicone oils that may be mentioned include:
• the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
• the phenyl silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.
• the groups R represent, independently of each other, a methyl or a phenyl, with the proviso that at least one group R represents a phenyl.
• the said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five. Mixtures of the phenyl organopolysiloxanes described previously may be used. Examples that may be mentioned include mixtures of triphenyl, tetraphenyl or pentaphenyl organo-polysiloxanes.
• Me represents methyl and Ph represents phenyl.
• a phenyl silicone is especially manufactured by Dow Corning under the reference PH-1555 HRI or Dow Corning 555 Cosmetic Fluid (chemical name: 1,3,5-trimethyl-,1,3,5,5-pentaphenyltrisiloxane; INCI name: trimethyl pentaphenyl trisiloxane).
• the reference Dow Corning 554 Cosmetic Fluid may also be used.
• y ranges between 1 and 1000.
• Use may be made, for example, of trimethyl siloxyphenyl dimethicone, sold especially under the reference Belsil PDM 1000 sold by the company Wacker.
• y is equal to 0.
• Use may be made, for example, of phenyl trimethylsiloxy trisiloxane, sold especially under the reference Dow Corning 556 Cosmetic Grade Fluid.
• the sum m+n+q is between 1 and 100.
• the sum m+n+p+q is between 1 and 900 and better still between 1 and 800.
• q is equal to 0.
• R 1 to R 6 independently of each other, represent a saturated, linear or branched C 1 -C 30 and especially C 1 -C 12 hydrocarbon-based radical and in particular a methyl, ethyl, propyl or butyl radical.
• R 1 to R 6 may especially be identical, and in addition may be a methyl radical.
• radicals R of formula (VIII) and R 1 to R 10 defined previously may each represent a linear or branched, saturated or unsaturated alkyl radical, especially of C 2 -C 20 , in particular C 3 -C 16 and more particularly C 4 -C 10 , or a monocyclic or polycyclic C 6 -C 14 and especially C 10 -C 13 aryl radical, or an aralkyl radical whose aryl and alkyl residues are as defined previously.
• R of formula (VIII) and R 1 to R 10 may each represent a methyl, ethyl, propyl, isopropyl, decyl, dodecyl or octadecyl radical, or alternatively a phenyl, tolyl, benzyl or phenethyl radical.
• a phenyl silicone oil of formula (VIII) with a viscosity at 25° C. of between 5 and 1500 mm 2 /s (i.e. 5 to 1500 cSt), and preferably with a viscosity of between 5 and 1000 mm 2 /s (i.e. 5 to 1000 cSt) may be used.
• phenyl silicone oils of formula (VIII) it is especially possible to use phenyl trimethicones such as DC556 from Dow Corning (22.5 cSt), the oil Silbione 70663V30 from Rhône-Poulenc (28 cSt) or diphenyl dimethicones such as Belsil oils, especially Belsil PDM1000 (1000 cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20 cSt) from Wacker.
• the values in parentheses represent the viscosities at 25° C.
• R 1 , R 2 , R 5 and R 6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms,
• R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical,
• X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,
• n and p being chosen so as to give the oil a weight-average molecular mass of less than 200 000 g/mol, preferably less than 150 000 g/mol and more preferably less than 100 000 g/mol.
• phenyl silicones that are most particularly suitable for use in the invention are those corresponding to formulae II, especially to formula (III), and V hereinabove.
• the phenyl silicones are chosen from phenyl trimethicones, phenyl dimethicones, phenyl-trimethlylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl, trimethylsiloxysilicates, and mixtures thereof.
• the weight-average molecular weight of the non-volatile phenyl silicone oil according to the invention ranges from 500 to 10 000 g/mol.
• a composition according to the invention contains, as silicone compound, at least one silicone gum.
• the silicone gum that may be used in the invention may be chosen from silicone gums with a viscosity at 25° C. of greater than or equal to 800 000 centistokes (cSt) (8 ⁇ 10 ⁇ 6 m 2 /s), especially between 800 000 000 and 10 000 000 cSt, preferably between 100 000 and 5 000 000 cSt and preferably between 1 000 000 and 2 500 000 cSt.
• the viscosity of this silicone gum may be measured according to standard ASTM D-445.
• the molecular mass of the silicone gums is generally greater than 350 000 g/mol, between 350 000 and 800 000 g/mol and preferably from 450 000 to 700 000 g/mol.
• the silicone gum may be chosen especially from the silicones of formula:
• R 1 , R 2 , R 5 and R 6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms,
• R 3 and R 4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,
• X is an alkyl radical containing from to 6 carbon atoms, a hydroxyl radical or an amine radical,
• n and p being integers chosen such that the viscosity of the compound is greater than 800 000 cSt.
• silicone gums that may be used according to the invention, mention may be made of those for which:
• a cosmetic makeup and/or care composition according to the invention also comprises the usual ingredients, as a function of the intended use of the composition.
• a composition according to the invention may also comprise at least one solid fatty substance especially chosen from waxes and/or pasty fatty substances.
• the amount of pasty substance in the makeup and/or care composition according to the invention is between 0.5% and 50% by weight, especially from 1% to 40% by weight or even 2% to 30% by weight, relative to the total weight of the composition.
• the composition is free of wax.
• the composition comprises at least one wax.
• wax means a lipophilic compound that is solid at room temperature (25° C.), with a reversible solid/liquid change of state, having a melting point of greater than or equal to 30° C., which may be up to 200° C.
• the waxes may be chosen from waxes of animal, plant, mineral or synthetic origin, and mixtures thereof.
• hydrogenated sunflower oil hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil and bis(1,1,1-trimethylolpropane)tetrastearate.
• Mention may also be made of silicone waxes and fluoro waxes.
• the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol may also be used.
• the composition is free of pasty fatty substances.
• the composition comprises at least one pasty fatty substance.
• pasty fatty substance refers to a lipophilic fatty compound with a reversible solid/liquid change of state and comprising, at a temperature of 23° C., a liquid fraction and a solid fraction.
• the 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 pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound may be obtained by synthesis from starting materials of plant origin. Mention may be made especially, alone or as a mixture, of:
• the pasty compound may also be of plant origin. Mention may be made especially of isomerized jojoba oil, such as trans-isomerized partially hydrogenated jojoba oil; orange wax, shea butter, partially hydrogenated olive oil, cocoa butter and mango oil.
• a composition according to the invention may also comprise an aqueous phase, which may represent 0 to 80% by weight, especially 1% to 70% by weight or even 3% to 60% by weight relative to the total weight of the composition.
• This aqueous phase may be formed essentially from water, or may comprise a mixture of water and of water-miscible solvent (miscibility in water of greater than 50% by weight at 25° C.) chosen especially from monoalcohols containing 1 to 5 carbon atoms such as ethanol, isopropanol, glycols containing 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C3-C4 ketones and C2-C4 aldehydes, and mixtures thereof.
• compositions under consideration according to the invention are advantageously anhydrous or contain less than 3% by weight of water and preferably less than 1% by weight of water relative to the total weight of the composition.
• anhydrous especially means that water is preferably not deliberately added to the composition, but may be present in trace amount in the various compounds used in the composition.
• a composition according to the invention may also comprise at least one surfactant, which may be present in a proportion of from 0.1% to 10% by weight, especially 0.5% to 8% by weight, or even 1% to 6% by weight relative to the total weight of the composition.
• the surfactant may be chosen from amphoteric, anionic, cationic and nonionic, preferably nonionic, surfactants. Mention may especially be made, alone or as a mixture, of:
• nonionic surfactants with an HLB of less than 8 at 25° C., optionally combined with one or more nonionic surfactants with an HLB of greater than 8 at 25° C., as mentioned below, for instance:
• nonionic surfactants with an HLB of greater than or equal to 8 at 25° C., for instance:
• anionic surfactants such as:
• cationic surfactants such as:
• amphoteric surfactants for instance N-acylamino acids, such as N-alkylaminoacetates and disodium cocoamphodiacetate, and anmine oxides such as stearanmine oxide.
• a makeup and/or care composition according to the invention may also comprise at least one agent usually used in cosmetics, chosen, for example, from reducing agents, thickeners, silicone elastomers, softeners, antifoams, moisturizers, UV-screening agents, ceramides; cosmetic active agents; peptizers, fragrances, proteins, vitamins, propellants, hydrophilic or lipophilic, film-forming or non-film-forming polymers; lipophilic or hydrophilic gelling agents.
• the above additives are generally present in an amount for each of them of between 0.01% and 10% by weight relative to the total weight of the composition. Needless to say, a person skilled in the art will take care to select the constituents of the composition such that the advantageous properties associated with the invention are not, or are not substantially, adversely affected.
• composition according to the invention may also comprise a thickener.
• the thickener may be chosen from:
• the thickener may be present in a content ranging from 0.1% to 5% by weight and better still from 0.4% to 3% by weight relative to the total weight of the composition.
• a composition according to the invention may also comprise at least one silicone elastomer, in other words an organopolysiloxane elastomer.
• organopolysiloxane elastomer means a deformable, flexible organopolysiloxane with viscoelastic properties and especially the consistency of a sponge or of a supple sphere. Its modulus of elasticity is such that this material withstands deformation and has limited stretchability and contractability. This material is capable of regaining its original shape after stretching.
• the organopolysiloxane elastomer is obtained by crosslinking addition reaction (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) of diorganopolysiloxane containing at least two ethylenically unsaturated groups bonded to silicon, especially in the presence (C) of a platinum catalyst, as described, for instance, in patent application EP-A-295 886.
• the organopolysiloxane elastomer may be obtained by reaction of a dimethylpolysiloxane with dimethylvinylsiloxy end groups and of methylhydrogenopolysiloxane with trimethylsiloxy end groups, in the presence of a platinum catalyst.
• Compound (A) may especially be chosen from methylhydrogenopolysiloxanes containing trimethylsiloxy end groups, dimethylsiloxane-methylhydrogenosiloxane copolymers containing trirethylsiloxy end groups, dimethylsiloxane-methylhydrogenosiloxane cyclic copolymers.
• the organopolysiloxanes (B) may be chosen in particular from methylvinylpolysiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes containing dimethylvinylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane copolymers containing dimethylvinylsiloxy end groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers containing dimethylvinylsiloxy end groups, dimethylsiloxane-methylvinylsiloxane copolymers containing trimethylsiloxy end groups, dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers containing trimethylsiloxy end groups, methyl(3,3,3-trifluoropropyl)polysiloxanes containing dimethyl
• compound (A) it is advantageous for compound (A) to be added in an amount such that the molecular ratio between the total amount of hydrogen atoms bonded to silicon atoms in compound (A) and the total amount of all the ethylenically unsaturated groups in compound (B) is within the range from 1.5/1 to 20/1.
• Compound (C) is the catalyst for the crosslinking reaction, and is especially chloroplatinic acid, chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black and platinum on a support.
• the catalyst (C) is preferably added in an amount of from 0.1 to 1000 parts by weight and better still from 1 to 100 parts by weight, as clean platinum metal, per 1000 parts by weight of the total amount of compounds (A) and (B).
• the elastomer is advantageously a non-emulsifying elastomer.
• non-emulsifying defines organopolysiloxane elastomers not containing a hydrophilic chain, and in particular not containing any polyoxyalkylene units (especially polyoxyethylene or polyoxypropylene) or on any polyglyceryl units.
• the organopolysiloxane elastomer particles are conveyed in the form of a gel formed from an elastomeric organopolysiloxane included in at least one hydrocarbon-based oil and/or one silicone oil. In these gels, the organopolysiloxane particles are often non-spherical particles.
• Non-emulsifying elastomers are especially described in patents EP 242 219, EP 285 886 and EP 765 656 and in patent application JP-A-61-194 009, the content of which is incorporated by way of reference.
• Spherical non-emulsifying elastomers that may be used include those sold under the names DC 9040, DC 9041, DC 9509, DC 9505 and DC 9506 by the company Dow Corning.
• Organopolysiloxane elastomers with groups MQ such as those sold by the company Wacker under the names Belsil RG100, Belsil RPG33 and, preferentially, RG80 may also be used in the compositions according to the invention.
• the elastomer may also be an emulsifying elastomer.
• emulsifying organopolysiloxane elastomer means an organopolysiloxane elastomer comprising at least one hydrophilic chain, such as polyoxyalkylenated organopolysiloxane elastomers and polyglycerolated silicone elastomers.
• the emulsifying organopolysiloxane elastomer may be chosen from polyoxyalkylenated organopolysiloxane elastomers.
• the polyoxyalkylenated organopolysiloxane elastomer is a crosslinked organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of a polyoxyalkylene containing at least two ethylenically unsaturated groups.
• the polyoxyalkylenated organopolysiloxane elastomers may be formed from divinyl compounds, in particular polyoxyalkylenes containing at least two vinyl groups, which react with Si—H bonds of a polysiloxane.
• Polyoxyalkylenated elastomers are especially described in U.S. Pat. No. 236,986, U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No. 5,811,487, the content of which is incorporated by reference.
• Polyoxyalkylenated organopolysiloxane elastomers that may be used include those sold under the names KSG-21, KSG-20, KSG-30, KSG-31, KSG-32, KSG-33, KSG-210, KSG-310, KSG-320, KSG-330 and KSG-340 by the company Shin-Etsu, and DC9010 and DC9011 by the company Dow Corning.
• the emulsifying organopolysiloxane elastomer may also be chosen from polyglycerolated organopolysiloxane elastomers.
• the polyglycerolated organopolysiloxane elastomer according to the invention is an organopolysiloxane elastomer that may be obtained by crosslinking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and of polyglycerolated compounds containing ethylenically unsaturated groups, especially in the presence of a platinum catalyst.
• the polyglycerolated organopolysiloxane elastomer according to the invention is conveyed in gel form in at least one hydrocarbon-based oil and/or one silicone oil.
• the polyglycerolated elastomer is often in the form of non-spherical particles.
• Polyglycerolated organopolysiloxane elastomers that may be used include those sold under the names KSG-710, KSG-810, KSG-820, KSG-830 and KSG-840 by the company Shin-Etsu.
• Non-emulsifying elastomers that may be used more particularly include those sold under the names KSG-6, KSG-15, KSG-16, KSG-18, KSG-41, KSG-42, KSG-43 and KSG-44 by the company Shin-Etsu, DC9040 and DC9041 by the company Dow Corning, and SFE 839 by the company General Electric.
• Emulsifying elastomers that may be used more particularly include those sold under the names KSG-31, KSG-32, KSG-33, KSG-210 and KSG-710 by the company Shin-Etsu.
• the organopolysiloxane elastomer under consideration according to the invention is chosen from spherical non-emulsifying organopolysiloxane elastomers, polyglycerolated organopolysiloxane elastomers and polyoxyalkylenated organopolysiloxane elastomers.
• a makeup and/or care 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 emulsion (O/W), water-in-oil emulsion (W/O) or multiple emulsion (W/O/W or polyol/O/W or O/W/O), or in the form of a cream, a mousse, a stick, a dispersion of vesicles, especially of ionic or nonionic lipids, a two-phase or multi-phase lotion, a spray, a powder or a paste.
• compositions according to the invention are anhydrous.
• 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 application of the composition.
• dihydroxylated hydrogenated 1,2-polybutadiene polymer 99 g are heated in the presence of 22 mg of catalyst (dibutyltin dilaurate) at 80° C., under reduced pressure, for two hours.
• catalyst dibutyltin dilaurate
• the temperature of the mixture is reduced to 20° C., under argon, followed by addition of 30 ml of isododecane and 11 g of isophorone diisocyanate (IPDI).
• IPDI isophorone diisocyanate
• the temperature of the mixture is reduced to 20° C., under argon, followed by addition of 60 ml of isododecane and 11.6 g of 4,4′-dicyclohexylmethane diisocyanate.
• the mixture is stirred for 16 hours at 20° C. under a controlled atmosphere, and is then heated to 120° C., followed by addition of 40 ml of propylene carbonate.
• 300 g of isododecane are placed in a 1 litre reactor, and the temperature is then increased so as to go from room temperature (25° C.) to 90° C. in 1 hour.
• the mixture is maintained at 90° C. for 1 hour 30 minutes.
• the mixture is maintained at 90° C. for 3 hours and is then cooled.
• a copolymer comprising a first poly(isobornyl acrylate/isobornyl methacrylate) block with a Tg of 128° C., a second poly(isobutyl acrylate/acrylate/acrylic acid) block with a Tg of ⁇ 9° C. and an intermediate block, which is an isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate/acrylic acid copolymer.
• the Tg of the copolymer is 74° C.
• copolymer (DC 2-8179 Gellant, Dow corning) prediluted to 20% in isododecane Acrylates/Dimethicone copolymer diluted to 60% in isododecane (KP 550, Shin-Etsu) Butyl acrylate copolymer containing dendritic silicone side chains diluted to 40% in isododecane (FA 4002 ID Silicone acrylate, Dow Corning) Acrylic acid/isobutyl acrylate/isobornyl acrylate copolymer diluted to 50% in isododecane (Mexomer PAS, Chimex) Acrylic copolymer as a 63 (i.e.
• phase A3 The constituents of phase A3 are weighed out. The mixture is ground in a three-roll mill.
• phase A1 the constituents of phase A1 are weighed out in the main beaker and placed in a Rayneri blender. Phase A2 is then added, after which phase A3 is added. After stirring for a few minutes, phase B is incorporated.
• the nine formulae are applied individually to the forearm according to the following protocol.
• the forearm is freed of makeup with a non-greasy makeup remover (such as Effacil from Lanc agencies) and then with cotton wool and water. After 5 minutes, each foundation formula (formulae 1 to 9) is applied by finger to the forearm. The amount applied is 0.05 g onto an area 5 cm by 5 cm in size.
• a paper tissue (handkerchief) is wiped five times over the forearm in the following manner: the tissue is folded into four, it is applied to the skin, with a suitable pressure, at one of the edges of the foundation and is then moved slowly towards the other edge. The amount of foundation deposit that has transferred onto the tissue is then evaluated.
• the handkerchief is very slightly coloured (i.e.: the composition. shows good transfer-resistance properties for the deposit)
• the number of “+”s reflects the decreasing transfer-resistance properties (i.e. the more “+”s there are, the greater the makeup, deposit has a tendency to transfer).
• Table 3 below gives the formulation of four compositions according to the invention.
• a ground pigmentary material was prepared in some of the isododecane by grinding the mixture three times in a three-roll mill.
• the ground material required for the composition was weighed out in a beaker.
• the supramolecular polymer according to the invention was mixed with the rest of the isododecane and the ground pigmentary material in a beaker or heating pan. Next, the mixture was stirred in a Rayneri blender until homogeneous.
• 80-micron deposits were applied to an FP40 plate (butadiene nitrite elastomer support). The plates were then maintained at 37° C. for 24 hours. After 24 hours, the deposits were wiped with makeup-removing wipes (L'Oréal Demaq'expert).
• 80-micron deposits were applied to beige bioskin. The deposits were then maintained at 37° C. for 24 hours.
• a lip makeup formula according to the invention having the following composition was prepared (the percentages indicated are weight percentages).
• a ground pigmentary material was prepared in some of the isododecane by grinding the mixture three times in a three-roll mill.
• the ground material required for the composition was weighed out in a beaker.
• the supramolecular polymer according to the invention was mixed with the rest of the isododecane and the ground pigmentary material in a beaker or heating pan. Next, the mixture was stirred in a Rayneri blender until homogeneous.
• 80-micron deposits were applied to an FP4O plate (butadiene nitrile elastomer support). The plates were then maintained at 37° C. for 24 hours. After 24 hours, the deposits were wiped with makeup-removing wipes (L'Oréal Demaq'expert).
• Example 6 (Mexomer PAS from Chimex) solids) Acrylic copolymer as a dispersion in 30% isododecane with styrene/isoprene (i.e. 7.35% copolymer (Kraton G1701) solids) (Mexomer PAP from Chimex) (24.5% copolymer solids in isododecane)
• a ground pigmentary material was prepared in some of the silicone oil by grinding the mixture three times in a three-roll mill.
• the ground material required for the composition was weighed out in a beaker.
• the supramolecular polymer according to the invention was mixed with the rest of the silicone oil, the film-forming compound and the ground pigmentary material in a beaker or heating pan. Next, the mixture was stirred in a Rayneri blender until homogeneous.
• 80-micron deposits were applied to an FP40 plate (butadiene nitrile elastomer support). The plates were then maintained at 37° C. for 24 hours. After 24 hours, the deposits were wiped with makeup-removing wipes (L'Oréal Demaq'expert).

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• 2010
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