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
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
  • A61K8/585—Organosilicon compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—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
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone 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
  • A61K8/84—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
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
  • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • 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
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/12—Face or body powders for grooming, adorning or absorbing
• • 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 invention relates to a cosmetic composition intended for horny tissues, especially the skin and lips, hair and nails.
• the invention relates in particular to makeup compositions for the said horny tissues, comprising at least one siloxane resin and at least phenyl silicone oil.
• One of the objectives of the application is to provide makeup compositions intended for horny tissues (skin, mucous membranes, fiber, eyelashes and integument), permitting deposition of a totally non-transfer film, with a good level of gloss and comfort.
• the formulator is therefore on the lookout for raw materials and/or systems that make it possible to obtain compositions whose deposit is characterized by comfort, gloss, a good level of staying power and a non-transfer effect.
• These polymers are of very different chemical natures and are conveyed either in a fatty phase or in an aqueous phase.
• silicone resins especially of the MQ type, the polyacrylates, the latexes, etc.
• the object of the present invention is effectively a composition comprising, in a physiologically acceptable medium:
• compositions according to the invention may also comprise an additional ingredient, preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents, waxes, hydrophilic gelling agents, film-forming polymers, ionic surfactants, fibers and mixtures thereof.
• compositions according to the invention may comprise at least one additional ingredient, preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents with the exception of dimethicone cross-polymers, waxes with the exception of candelilla wax, of ozokerite and of the silicone waxes, hydrophilic gelling agents, fillers, film-forming polymers, ionic surfactants with the exception of lauryl ether sulfate, fibers and mixtures thereof.
• additional ingredient preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents with the exception of dimethicone cross-polymers, waxes with the exception of candelilla wax, of ozokerite and of the silicone waxes, hydrophilic gelling agents, fillers, film-forming polymers, ionic surfactants with the exception of lauryl ether sulfate, fibers and mixtures thereof.
• the waxes are chosen from among beeswax, lanolin wax and Chinese insect wax; rice wax, carnauba wax, ouricurry wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty, linear or branched C8-C32 chains, fluoro waxes, wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, and tacky waxes.
• the ionic surfactants are chosen from among cationic surfactants, amphoteric surfactants, carboxylates, taurates and N-acyl N-methyltaurates, alkylsulfoacetates, polypeptides, anionic derivatives of alkyl polyglycoside, amine-derived salts of C16-C30 fatty acids, salts of polyoxyethylenated fatty acids, phosphoric acids and their salts, sulfosuccinates, alkyl sulfates, isethionates and N-acyl isethionates, acylglutamates, soy derivatives, citrates, proline derivatives, lactylates, sarcosinates, sulfonates and glycinates.
• the fatty-phase thickening or gelling rheological agents are chosen from among crystalline polymers, mineral lipophilic structuring agents, lipophilic polyamides, lipophilic polyureas and polyurethanes, silicone polymers comprising, as the case may be, at least one hydrocarbon moiety composed of two groups capable of establishing hydrogen interactions chosen from among ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof, organo gelling agents, block polymers, cholesteric liquid crystal agents, dimethicone/vinyldimethicone copolymers and vinyldimethicone/alkyl dimethicone copolymers, such as vinyldimethicone/lauryl dimethicone copolymers.
• silicone polymers comprising, as the case may be, at least one hydrocarbon moiety composed of two groups capable of
• Another object of the present invention is a composition comprising, in a physiologically acceptable medium:
• Siloxane resin a referred to as “MQ resin” hereinafter, preferably comprises residual silanol groups (—SiOH).
• the quantity of —OH groups preferably ranges between 2 and 10% by weight of the MQ resin, preferably between 2 and 5% by weight of the MQ resin.
• the R′ groups of the MQ resin are methyl groups.
• Resin b referred to as “propyl T resin” hereinafter, preferably comprises residual silanol groups (—SiOH) and/or alkoxy groups.
• the quantity of —OH groups preferably ranges between 2 and 20% by weight of the propyl T resin, and/or the quantity of alkoxy groups is smaller than or equal to 20% by weight of the propyl T resin.
• the quantity of —OH groups ranges between 6 and 8% by weight of the propyl T resin, and/or the quantity of alkoxy groups is smaller than or equal to 10% by weight of the propyl T resin.
• the propyl T resin according to the invention is such that at least 40 mol % of the R′′ groups are propyl groups; preferably at least 50 mol %, and more preferentially at least 90 mol %.
• covalent bond there is understood a chemical bond between at least 2 atoms (carbon, silicon, oxygen, etc.) in which each of the bonded atoms commonly contributes an electron of one of its outer layers in order to form an electron pair bonding the two atoms.
• the MQ resin according to the invention comprises at least 80 mol % of the units:
• the R′ radical of the MQ resin independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group.
• the alkyl groups may be chosen in particular from among the methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups.
• the alkyl group is a methyl group.
• the aryl groups may be chosen from among the phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups, the aryl group preferentially being a phenyl group.
• carbinol group is understood as any group containing at least one hydroxyl radical bonded to a carbon (COH).
• the carbinol groups may therefore contain more than one COH radical, such as, for example
• carbinol group is free of aryl groups, it contains at least 3 carbon atoms. If the carbinol group comprises at least one aryl group, it contains at least 6 carbon atoms.
• R 1 represents a bivalent hydrocarbon radical containing at least 3 carbon atoms or a bivalent hydrocarbonoxy radical containing at least 3 carbon atoms.
• R 1 group there can be cited alkylene radicals such as —(CH 2 ) x —, the value of x ranging between 3 and 10, —CH 2 CH(CH 3 )—, —CH 2 CH(CH 3 )CH 2 —, —CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 — and —OCH(CH 3 )(CH 2 ) x —, the value of x ranging between 1 and 10.
• alkylene radicals such as —(CH 2 ) x —, the value of x ranging between 3 and 10, —CH 2 CH(CH 3 )—, —CH 2 CH(CH 3 )CH 2 —, —CH 2 CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 — and —OCH(CH 3 )(CH 2 ) x —, the value of x ranging between 1 and 10.
• carbinol groups containing aryl groups having at least 6 carbon atoms there can be cited the groups of formula R 2 OH, in which R 2 represents an arylene radical such as —(CH 2 ) x C 6 H 4 —, x having a value between 0 and 10, —CH 2 CH(CH 3 )—, —CH 2 (CH 2 ) x C 6 H 4 —, x having a value between 0 and 10, —(CH 2 ) x C 6 H 4 (CH 2 ) x —, x having a value between 1 and 10.
• the carbinol groups containing aryl groups generally contain 6 to 14 atoms.
• R 3 represents a bivalent hydrocarbon radical having at least 2 carbon atoms
• R 4 representing a bivalent hydrocarbon radical having at least 2 carbon atoms
• the R 3 group generally represents an alkylene radical having 2 to 20 carbon atoms.
• R 3 groups there can be cited the ethylene, propylene, —CH 2 CHCH 3 —, butylene, —CH 2 CH(CH 3 )CH 2 —, pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene and decamethylene groups.
• the R 4 group generally represents an alkylene radical having 2 to 20 carbon atoms.
• R 4 groups there can be cited the ethylene, propylene, —CH 2 CHCH 3 —, butylene, —CH 2 CH(CH 3 )CH 2 —, pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene and decamethylene groups.
• the amino groups are generally —CH 2 CH 2 CH 2 NH 2 and —CH 2 (CH 3 )CHCH 2 (H)NCH) 3 , —CH 2 CH 2 NHCH 2 CH 2 NH 2 , —CH 2 CH 2 NH 2 , —CH 2 CH 2 NHCH 3 , —CH 2 CH 2 CH 2 CH 2 NH 2 , —(CH 2 CH 2 NH) 3 H and —CH 2 CH 2 NHCH 2 CH 2 NHC 4 H 9 .
• MQ resins suitable for use as component a), as well as their manufacturing methods, are known in the prior art.
• U.S. Pat. No. 2,814,601 of Currie et al., dated 26 Nov. 1957, incorporated into the present document by reference describes a method for manufacturing MQ resins by transformation of a water-soluble silicate into a silicic acid monomer or a silicic acid oligomer by using an acid. Once adequate polymerization has been achieved, trimethylchlorosilane terminal groups are introduced to obtain the MQ resin.
• Another method for preparation of MQ resins is described in U.S. Pat. No. 2,857,356 of Goodwin, dated 21 Oct. 1958, incorporated into the present document by reference. Goodwin describes a method for manufacturing an MQ resin by cohydrolysis of a mixture of an alkyl silicate and of an organopolysiloxane trialkylsilane capable of being hydrolyzed by water.
• Propyl T resin b) according to the invention comprises at least 80 mol % of (R′′SiO 3/2 ) units, in which R′′ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol % of the R′′ groups are propyl groups.
• the propyl T resin according to the invention is such that at least 50 mol % of the R′′ groups are propyl groups, preferably at least 90 mol %.
• propyl T resin b) is film-forming.
• film-forming resin there is understood a resin capable of forming, on its own or in the presence of an auxiliary filmifying agent, a macroscopically continuous film that adheres to horny tissues, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that the said film may be isolated and manipulated in isolation, for example when the said film is formed by casting on a non-sticking surface, such as a Teflon-coated or silicone-coated surface.
• R′′ radical is the same as that of the R′ radical.
• R′ radical is the definition of the R′ radical.
• R′′ radical is the definition of the R′′ radical.
• Propyl T resin b) according to the invention is a silsesquioxane resin.
• Silsesquioxane resins are well known in the prior art and are generally obtained by hydrolysis of an organosilane containing three hydrolyzable groups, such as halogen or alkoxy groups, present in the molecule.
• Propyl T resin b) may therefore be obtained by hydrolysis of propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, or by cohydrolysis of the aforementioned propylalkoxysilanes with diverse alkoxysilanes.
• methyltrimethoxysilane methyltriethoxysilane, methyltriisopropoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane.
• Propyltrichlorosilane may also be hydrolyzed alone or in the presence of alcohol. In this case, the cohydrolysis may be achieved by adding methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane or similar chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane or similar methylalkoxysilanes.
• alcohols suitable for this purpose there may be cited methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, methoxyethanol, ethoxyethanol or similar alcohols.
• solvents of hydrocarbon type that may be used simultaneously there may be cited toluene, xylene or similar aromatic hydrocarbons, hexane, heptane, isooctane or similar linear or partly branched saturated hydrocarbons; as well as cyclohexane or similar aliphatic hydrocarbons.
• Propyl T resins b) according to the invention may contain M, D and Q units, with the proviso that at least 80 mol %, even 90 mol % of the total siloxane units are T units.
• the propyl T resins may also contain residual hydroxy and/or alkoxy groups, as mentioned in the foregoing.
• composition according to the invention also comprises a physiologically acceptable medium.
• physiologically acceptable medium there is understood a medium compatible with the skin, the mucous membranes and the integument.
• This medium may comprise at least one volatile silicone or organic solvent, this solvent preferably being compatible with resins a/ and b/ and compatible with a cosmetic use.
• volatile silicone solvent there may be cited the cyclic polysiloxanes, the linear polysiloxanes and mixtures thereof.
• volatile cyclic polysiloxanes there may be cited hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
• the organic solvent may also be an alcohol such as ethanol, isopropanol, butanol, n-propanol; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an aliphatic hydrocarbon such as heptane, hexane, octane or isododecane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether.
• an alcohol such as ethanol, isopropanol, butanol, n-propanol
• a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone
• an aliphatic hydrocarbon such as heptane, hex
• the mixture of resins a/ and b/ may be obtained from each of the resins in solution in a solvent.
• this resin is obtained directly in solution in xylene.
• composition such as described hereinabove comprising, in a physiologically acceptable medium:
• siloxane resin a) and a propyl silsesquioxane resin b) being formulated in the composition via a mixture capable of being obtained according to the following method:
• This method may comprise, after or even during the mixing step, an additional step of partial or complete distillation of the aromatic solvents, while replacing them with a cosmetically acceptable solvent.
• this method may comprise, after or even during the mixing step, an additional step of partial or complete distillation of the aromatic solvents, while discharging the mixture directly in the solid state.
• the final heat-treatment step, or even the heat treatment itself may be achieved in a kneader provided for agitation of very viscous media such as:
• Resin mixtures 1) suitable for use according to the invention are especially those described in Application WO 2005/075567, the contents of which are incorporated here by reference, particularly those described in Tables 1 and 3 of the said Application. It is also possible to use resin mixtures 1) described in Application WO2007/145765, particularly those described in Examples 12 to 14 of that Application, wherein the weight ratios between resins a) and b) are respectively 50/50, 60/40 and 71/29 (70/30).
• resin mixture 1) described in Example 22 of the said Application WO2005/075567, wherein the weight ratio between resin a) and b) is 85/15.
• resin mixture 1) described in Example 13 of the said Application WO2007/145765, wherein the weight ratio between resin a) and b) is 60/40.
• the siloxane resin is present in the composition in a total content of dry resin material ranging from 1% to 80% by weight relative to the total weight of the composition, preferably ranging from 5% to 70% by weight, and better ranging from 6% to 60% by weight.
• compositions according to the invention may assume diverse forms, especially the form of powder, anhydrous dispersion, water-in-oil or water-in wax emulsion, oil-in-water emulsion, multiple emulsions or wax-in-water emulsion, or gel.
• the composition according to the invention comprises less than 3%, or better less than 1% of water by weight relative to the total weight of the composition. Even more preferably, the composition is completely anhydrous.
• anhydrous there is understood in particular that preferably water is not deliberately added to the composition but may be present in the trace state in the different compounds used in the composition.
• composition according to the invention comprises at least one phenyl silicone oil.
• Such an oil is also referred to as phenyl silicone.
• phenyl silicone there is understood an organopolysiloxane substituted by at least one phenyl group.
• oil there is understood a non-aqueous compound, immiscible with water, liquid at room temperature (25° C.) and atmospheric pressure (760 mm Hg).
• sicone oil there is understood an oil comprising at least one silicon atom, and especially comprising Si—O groups.
• the phenyl silicone is preferably non-volatile.
• non-volatile oil there is understood an oil that remains on the horny tissues at room temperature and atmospheric pressure for at least several hours, and having in particular a vapor pressure lower than 10 ⁇ 3 mm Hg (0.13 Pa).
• a non-volatile oil may also be defined as having an evaporation rate such that, under the conditions defined in the foregoing, the quantity evaporated at the end of 30 minutes is smaller than 0.07 mg/cm 2 .
• oils may be of vegetable, mineral or synthetic origin.
• the phenyl silicone oil may be present in a content ranging from 0.1% to 70% by weight relative to the total weight of the non-volatile liquid fatty phase of the composition, preferably ranging from 0.5% to 60% by weight, and preferentially ranging from 1% to 50% by weight.
• the phenyl silicone oil is present in the composition in a total content ranging from 0.5% to 70% by weight relative to the total weight of the composition, preferably ranging from 5% to 50% by weight, and better ranging from 5% to 40% by weight.
• the weight-average molecular weight of the phenyl silicone oil is between 500 and 10,000 g/mol.
• the silicone oil may be chosen from among the phenyl trimethicones, the phenyl dimethicones, the phenyl trimethylsiloxy diphenylsiloxanes, the diphenyl dimethicones, the diphenyl methyldiphenyl trisiloxanes, the 2-phenylethyl trimethylsiloxysilicates.
• the silicone oil may be represented by the formula:
• the silicone oil preferably comprises at least three phenyl groups, for example at least four, at least five or at least six.
• the silicone oil is represented by the formula
• the groups R independently of one another, represent a methyl or a phenyl.
• the said organopolysiloxane preferably comprises at least three phenyl groups, for example at least four or at least five.
• the silicone oil is represented by the formula
• the silicone oil is represented by the formula
• Me represents methyl
• y is between 1 and 1,000
• X represents —CH2-CH(CH3)(Ph).
• the silicone oil is represented by the formula
• the phenyl silicone oil may be chosen from among the phenyl silicones of the following formula (VI):
• the sum of ‘m+n+q’ is between 1 and 100.
• the sum of ‘m+n+p+q’ is between 1 and 900, still better between 1 and 800.
• q is equal to 0.
• the phenyl silicone oil may be chosen from among the phenyl silicones of the following formula (VII):
• R1 to R6 independently of one another, represent a saturated, linear or branched C1-C30 hydrocarbon radical, especially C1-C12, and in particular a methyl, ethyl, propyl or butyl radical.
• R1 to R6 may be identical, and in addition may be a methyl radical.
• a phenyl silicone oil of formula (VI) having a viscosity at 25° C. between 5 and 1,500 mm 2 /s (or 5 to 1500 cSt), preferably having a viscosity between 5 and 1,000 mm 2 /s (or 5 to 1,000 cSt).
• phenyl silicone oil of formula (VII) there may be used in particular the phenyltrimethicones such as DC556 of Dow Corning (22.5 cSt), Silbione oil 70663V30 of Rhone Poulenc (28 cSt), or the diphenyldimethicones such as the Belsil oils, especially Belsil PDM1000 (1,000 cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20 cSt) of Wacker.
• the values in parentheses represent the viscosities at 25° C.
• the non-volatile silicone oil may be chosen from among the silicones of formula:
• R 1 , R 2 , R 5 and R 6 are, together or separately, an alkyl radical having 1 to 6 carbon atoms
• R 3 and R 4 are, together or separately, an alkyl radical having 1 to 6 carbon atoms or an aryl radical
• X is an alkyl radical having 1 to 6 carbon atoms
• n and p are chosen so as to confer on the oil a weight-average molecular weight smaller than 200,000 g/mol, preferably smaller that 150,000 g/mol and more preferably smaller than 100,000 g/mol.
• the phenyl silicone oil may be present in a content ranging from 0.1% to 70% by weight relative to the total weight of the non-volatile liquid fatty phase, preferably ranging from 0.5% to 60% by weight, and preferentially ranging from 1% to 50% by weight.
• compositions according to the invention may comprise at least one paste of non-animal origin.
• compositions according to the invention may therefore comprise at least one paste of non-animal origin and the mixture 1) described hereinabove.
• pasty compound within the meaning of the present invention there is understood a lipophilic fatty compound capable of reversible change of state from solid to liquid and containing, at the temperature of 23° C., a liquid fraction and a solid fraction.
• a pasty compound is in the form of a liquid fraction and a solid fraction.
• the starting melting temperature of the pasty compound is lower than 23° C.
• the liquid fraction of the pasty compound, measured at 23° C. represents 20 to 97% by weight of the pasty compound. More preferentially, at 23° C., this liquid fraction represents 25 to 85% and better 30 to 60% by weight of the pasty compound.
• the liquid fraction by weight of the pasty compound at 23° C. is equal to the ratio of the enthalpy of melting consumed at 23° C. to the enthalpy of melting of the pasty compound.
• the enthalpy of melting consumed at 23° C. is the quantity of energy absorbed by the sample for transition from the solid state to the state in which it exists at 23° C., consisting of a liquid fraction and a solid fraction.
• the enthalpy of melting of the pasty compound is the enthalpy consumed by the compound in changing from the solid state to the liquid state.
• the pasty compound is said to be in the solid state when the entirety of its mass is in solid form.
• the pasty compound is said to be in the liquid state when the entirety of its mass is in liquid form.
• the enthalpy of melting of the pasty compound is equal to the area under the curve of the thermogram obtained by means of a differential scanning calorimeter (D. S. C.), such as the calorimeter sold under the trade name MDSC 2920 by the TA Instrument Company, with a temperature rise of 5 or 10° C. per minute, according to ISO standard 11357-3:1999.
• the enthalpy of melting of the pasty compound is the quantity of energy necessary to make the compound change from the solid state to the liquid state. It is expressed in J/g.
• the liquid fraction of the pasty compound, measured at 32° C. preferably represents 40 to 100% by weight of the pasty compound, even better 50 to 100% by weight of the pasty compound.
• the temperature of the end of the melting range of the pasty compound is lower than or equal to 32° C.
• the liquid fraction of the pasty compound, measured at 32° C. is equal to the ratio of the enthalpy of melting consumed at 32° C. to the enthalpy of melting of the pasty compound.
• the enthalpy of melting consumed at 32° C. is calculated in the same way as the enthalpy of melting consumed at 23° C.
• non-animal origin there is understood a pasty compound chosen from among the pasty compounds of synthetic and vegetable origin (produced or derived from plants).
• the pasty compound preferably has a hardness at 20° C. ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.
• the hardness is measured according to the method of penetration of an indenter into a sample of the compound, and in particular by means of a texture analyzer (for example the TA-TX2i of Rheo), equipped with a stainless steel cylinder with a diameter of 2 mm.
• the hardness measurement is carried out at 20° C. at the center of 5 specimens.
• the cylinder is introduced into each specimen, the penetration depth being 0.3 mm.
• the value recorded as the hardness is that of the maximum peak.
• the pasty compound of non-animal origin is chosen from among the synthetic compounds and the compounds of vegetable origin.
• a pasty compound of non-animal origin may be obtained by synthesis from starting products of vegetable origin.
• the pasty compound may be a polymer, especially of hydrocarbon type.
• a preferred pasty silicone and fluoro compound is polymethyl-trifluoropropyl-methylalkyl-dimethylsiloxane, manufactured under the trade name X22-1088 by SHIN-ETSU.
• the composition advantageously comprises a compatibilizing agent, such as the short-chain esters, such as isodecyl neopentanoate.
• a compatibilizing agent such as the short-chain esters, such as isodecyl neopentanoate.
• the fat-soluble polyethers there may be cited in particular the copolymers of ethylene oxide and/or propylene oxide with C 6 -C 30 alkylene oxides.
• the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is 5:95 to 70:30.
• block copolymers comprising C 6 -C 30 alkylene oxide blocks having a molecular weight ranging from 1,000 to 10,000, for example, a polyoxyethylene/polydodecylene glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 oxyethylene moieties or OE) sold under the brand ELFACOS ST9 by Akzo Nobel.
• a polyoxyethylene/polydodecylene glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 oxyethylene moieties or OE) sold under the brand ELFACOS ST9 by Akzo Nobel.
• esters there are especially preferred:
• a Guerbet alcohol is the reaction product of the Guerbet reaction, well known to those skilled in the art. It is a reaction in which a primary aliphatic alcohol is transformed into its alkylated dimer alcohol with loss of one equivalent of water.
• the aliphatic carboxylic acids described above generally comprise 4 to 30 and preferably 8 to 30 carbon atoms. They are preferably chosen from among hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid, docosanoic acid and mixtures thereof.
• the aliphatic carboxylic acids are preferably branched.
• esters of hydroxylated aliphatic carboxylic acid are advantageously obtained from a hydroxylated aliphatic carboxylic acid containing 2 to 40 carbon atoms, preferably 10 to 34 carbon atoms and better 12 to 28 carbon atoms, and 1 to 20 hydroxyl groups, preferably 1 to 10 hydroxyl groups and better 1 to 6 hydroxyl groups.
• the esters of hydroxylated aliphatic carboxylic acid are chosen especially from among:
• the pasty compound is chosen from among the compounds of vegetable origin.
• isomerized jojoba oil such as the trans isomerized partly hydrogenated jojoba oil manufactured or sold by the Desert Whale Company under the commercial reference Iso-Jojoba-50®, orange wax such as, for example, that sold under the reference Orange Peel Wax by the Koster Keunen Company, shea butter, partly hydrogenated olive oil such as, for example, the compound sold under the reference Beurrolive by the Soliance Company, cocoa butter, mango oil such as, for example, Lipex 302 of the Aarhuskarlshamm Company.
• isomerized jojoba oil such as the trans isomerized partly hydrogenated jojoba oil manufactured or sold by the Desert Whale Company under the commercial reference Iso-Jojoba-50®, orange wax such as, for example, that sold under the reference Orange Peel Wax by the Koster Keunen Company, shea butter, partly hydrogenated olive oil such as, for example, the compound sold under the reference Beurrolive by the Soliance Company, cocoa butter, mango oil such as, for example,
• the pasty compound or compounds are preferably present in a quantity greater than or equal to 1% by weight relative to the total weight of the composition, for example 1 to 15% by weight, better in a quantity greater than or equal to 2% by weight, ranging for example from 2 to 10% by weight, and even more preferentially from 3 to 8% by weight relative to the total weight of the composition.
• composition according to the invention may comprise a fatty-phase thickening or gelling rheological agent.
• compositions according to the invention may therefore comprise at least one fatty-phase thickening or gelling rheological agent and the mixture of MQ and propyl T resins described hereinabove.
• fatty-phase thickening or gelling rheological agent there is understood a compound capable of increasing the viscosity of the fatty phase of the composition.
• the fatty-phase thickening or gelling rheological agent makes it possible in particular to obtain a composition that may have a texture ranging from fluid to solid textures.
• the fatty-phase thickening or gelling rheological agent may be chosen from among:
• the fatty-phase rheological agent is chosen from among the semi-crystalline polymers, the block polymers, the lipophilic polymers of polyamide type and the silicone polymers comprising at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from among the amide groups, the mineral lipophilic structuring agents, in particular the lipophilic clays and the hydrophobic silicas, and the silicone elastomers.
• oil a fatty substance that is liquid at room temperature.
• volatile compound for example “volatile oil”, there is understood, within the meaning of the invention, any compound (or non-aqueous medium) capable of evaporating on contact with the skin or the horny fiber in less than one hour, at room temperature and atmospheric pressure.
• the volatile compound is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure at room temperature and atmospheric pressure, especially having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ⁇ 3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1,300 Pa (0.01 to 10 mm Hg).
• non-volatile compound for example “non-volatile oil”, there is understood a compound that remains on the skin or horny fiber at room temperature and atmospheric pressure for at least several hours, and having in particular a vapor pressure lower than 10 ⁇ 3 mm Hg (0.13 Pa).
• the oil may be chosen from among the volatile and non-volatile hydrocarbon and/or silicone and/or fluoro oils and their mixtures. These oils may be of animal, vegetable, mineral or synthetic origin.
• hydrocarbon oil there is understood an oil containing mainly carbon and hydrogen atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether, carboxylic functions.
• oil that can be used in the invention, there may be cited:
• the oil has a molecular weight greater than or equal to 250 g/mol, especially between 250 and 10,000 g/mol, preferably greater than or equal to 300 g/mol, especially between 300 and 8,000 g/mol and better, greater than or equal to 400 g/mol, especially between 400 and 5,000 g/mol.
• the ratio of the oil or oils to the particular compound or compounds is from 10/90 to 90/10, preferably from 20/80 to 80/20 and more preferably from 30/70 to 70/30.
• This oil may be chosen from among:
• “semi-crystalline polymer” polymers containing a crystallizable part, crystallizable pendant and/or terminal chain or crystallizable sequence in the skeleton and/or at the ends, and an amorphous part in the skeleton and having a first-order reversible phase-change temperature, particularly of melting (solid-liquid transition).
• the amorphous part of the polymer is in the form of an amorphous sequence; in this case the semi-crystalline polymer is a sequenced copolymer, for example of the diblock, triblock or multiblock type, containing at least one crystalline sequence and at least one amorphous sequence.
• sequence there is generally understood at least 5 identical repeating moieties.
• the crystallizable sequence or sequences are then of chemical nature different from that of the amorphous sequence or sequences.
• the semi-crystalline polymer according to the invention has a melting temperature higher than or equal to 30° C. (especially ranging from 30° C. to 80° C.), preferably ranging from 30° C. to 60° C.
• This melting temperature is a first-order state-change temperature.
• This melting temperature may be measured by any known method and in particular by means of a differential scanning calorimeter (D.S.C.).
• the semi-crystalline polymer or polymers to which the invention applies have a number-average molecular weight greater than or equal to 1,000.
• the semi-crystalline polymer or polymers of the composition of the invention have a number-average molecular weight M n ranging from 2,000 to 800,000, preferably from 3,000 to 500,000, better from 4,000 to 150,000, especially lower than 100,000 and better from 4,000 to 99,000.
• M n number-average molecular weight
• they have a number-average molecular weight greater than 5,600, ranging for example from 5,700 to 99,000.
• crystallizable chain or sequence within the meaning of the invention there is understood a chain or sequence that, if it were alone, would change reversibly from the amorphous state to the crystalline state depending on whether it was above or below the melting temperature.
• a chain within the meaning of the invention is a group of atoms in pendant or side position relative to the polymer skeleton.
• a sequence is a group of atoms belonging to the skeleton, this group constituting one of the repetitive moieties of the polymer.
• the “crystallizable pendant chain” may be a chain containing at least 6 carbon atoms.
• the crystallizable sequence or sequences or chains of semi-crystalline polymers represent at least 30% of the total weight of each polymer and better at least 40%.
• the semi-crystalline polymers of the invention with crystallizable sequences are sequenced or multisequenced polymers. They may be obtained by polymerization of monomers with reactive double (or ethylenic) bonds or by polycondensation.
• the polymers of the invention are polymers with crystallizable side chains, the latter are advantageously in random or statistical form.
• the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not contain any polysaccharide skeleton.
• the crystallizable moieties (chains or sequences) of semi-crystalline polymers according to the invention are derived from monomers with a crystallizable sequence or sequences or chain or chains used for the manufacture of semi-crystalline polymers.
• the semi-crystalline polymer may be chosen from among the sequenced copolymers containing at least one crystallizable sequence and at least one amorphous sequence, the homopolymers and the copolymers carrying at least one crystallizable side chain per repetitive moiety, and mixtures thereof.
• the semi-crystalline polymers that can be used in the invention are in particular:
• the crystallizable side chain or chains or sequence or sequences are hydrophobic.
• these polymers are chosen in particular from among the homopolymers and copolymers resulting from the polymerization of at least one monomer with crystallizable chain or chains that may be represented by the formula X:
• M representing an atom of the polymer skeleton
• S representing a spacer
• C representing a crystallizable group
• the crystallizable “S—C” chains may be aliphatic or aromatic, possibly fluorinated or perfluorinated.
• “S” represents in particular a linear or branched or cyclic (CH 2 ) n group or (CH 2 CH 2 O) n or (CH 2 O), where n is an integer ranging from 0 to 22.
• n is an integer ranging from 0 to 22.
• “S” is a linear group.
• “S” and “C” are different.
• crystallizable “S—C” chains are aliphatic hydrocarbon chains, they contain alkyl hydrocarbon chains with at least 11 carbon atoms and at most 40 carbon atoms and better at most 24 carbon atoms. In particular, they are aliphatic chains or alkyl chains possessing at least 12 carbon atoms and preferably they are C 14 -C 24 alkyl chains. When they are fluorinated or perfluorinated alkyl chains, they contain at least 6 fluorinated carbon atoms and especially at least 11 carbon atoms, of which at least 6 carbon atoms are fluorinated.
• semi-crystalline polymers or copolymers with a crystallizable chain or chains there may be cited those resulting from the polymerization of one or more of the following monomers: the saturated alkyl(meth)acrylates with the C 14 -C 24 alkyl group, the perfluoroalkyl(meth)acrylates with a C 11 -C 15 perfluoroalkyl group, the N-alkyl(meth)acrylamides with the C 14 to C 24 alkyl group with or without fluorine atoms, the vinyl esters with alkyl or perfluoro (alkyl) chains with the C 14 to C 24 alkyl group (with at least 6 fluorine atoms for a perfluoro alkyl chain), the vinyl ethers with alkyl or perfluoro (alkyl) chains with the C 14 to C 24 alkyl group and at least 6 fluorine atoms for a perfluoroalkyl chain, the C 14 to C 24 alpha-olefins
• the hydrocarbon and/or fluoro crystallizable chains such as defined hereinabove are carried by a monomer, which may be a diacid, a diol, a diamine, a diisocyanate.
• polymers comprising objects of the invention are copolymers, they additionally contain 0 to 50% of groups Y or Z resulting from the copolymerization:
• Y which is a polar or non-polar monomer or a mixture of both:
• Y is a polar monomer, it is either a monomer carrying polyoxyalkylene groups (especially oxyethylene and/or oxypropylene), a hydroxyalkyl(meth)acrylate such as hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl(meth)acrylamide, an N,N-dialkyl (meth)acrylamide such as, for example, N,N-diisopropyl acrylamide or N-vinylpyrrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least one carboxylic acid group such as (meth)acrylic, crotonic, itaconic, maleic, fumaric acids, or carrying a carboxylic acid anhydride group such as maleic anhydride, and mixtures thereof.
• polyoxyalkylene groups especially oxyethylene and/or oxypropylene
• a hydroxyalkyl(meth)acrylate such as hydroxyethyl acrylate,
• Y When Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl(meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted by a C 1 to C 10 alkyl group, such as ⁇ -methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.
• alkyl there is understood within the meaning within the meaning of the invention a saturated group, especially with C 8 to C 24 unless otherwise expressly mentioned, and better with C 14 to C 24 .
• Z which is a polar monomer or a mixture of polar monomers.
• Z has the same definition as “polar Y” defined above.
• the semi-crystalline polymers with crystallizable side chain are homopolymers of alkyl(meth)acrylate or alkyl(meth)acrylamide with an alkyl group such as defined above, and especially with C 14 to C 24 , copolymers of these monomers with a hydrophilic monomer, preferably of different nature from that of (meth)acrylic acid, such as N-vinylpyrrolidone or hydroxyethyl(meth)acrylate and mixtures thereof.
• These polymers are especially sequenced copolymers composed of at least 2 sequences of different chemical nature, one of which is crystallizable.
• the semi-crystalline polymers of the composition of the invention may or may not be partly cross-linked, since the degree of cross-linking does not impair their dissolution or dispersion in the liquid fatty phase by heating above their melting point. They may then be chemically cross-linked, by reaction with a multifunctional monomer during polymerization. They may also be physically cross-linked, which may then be due either to the establishment of bonds of hydrogen or dipole type between groups carried by the polymer, such as, for example, the dipole interactions between carboxylate ionomers, these interactions being of small quantity and carried by the polymer skeleton; or to phase separation between the crystallizable sequences and the amorphous sequences carried by the polymer.
• the semi-crystalline polymers of the composition according to the invention are non-cross-linked.
• the polymer is chosen from among the copolymers resulting from the polymerization of at least one monomer with crystallizable chain chosen from among the saturated C 14 to C 24 alkyl(meth)acrylates, the C 11 to C 15 perfluoroalkyl(meth)acrylates, the N—(C 14 to C 24 )alkyl(meth)acrylamides with or without fluorine atoms, the vinyl esters with C 14 to C 24 alkyl or perfluoroalkyl chains, the vinyl ethers with C 14 to C 24 alkyl or perfluoroalkyl chains, the C 14 to C 24 alpha-olefins, the para-alkylstyrenes with an alkyl group containing 12 to 24 carbon atoms, with at least one ester or amide of C 1 to C 10 monocarboxylic acid, possibly fluorinated, which may be represented by the following formula:
• R 1 is H or CH 3
• R represents a C 1 -C 10 alkyl group, which may be fluorinated
• X represents O, NH or NR 2
• R 2 represents a C 1 -C 10 alkyl group, which may be fluorinated.
• the polymer is obtained from a monomer with crystallizable chain chosen from among the saturated C 14 to C 22 alkyl (meth)acrylates.
• the semi-crystalline polymers may be especially:
• polymer of structure “O” of National Starch such as that described in the document U.S. Pat. No. 5,736,125 of melting point 44° C.
• semi-crystalline polymers with crystallizable pendant chains containing fluoro groups such as described in Examples 1, 4, 6, 7 and 8 of the document of WO A 01/19333.
• the semi-crystalline polymers do not contain any carboxylic group.
• the semi-crystalline polymers according to the invention may also be chosen from among the waxy polymers obtained by metallocene catalysis, such as those described in US Application 2007/0031361.
• These polymers are homopolymers or copolymers of ethylene and/or propylene prepared by metallocene catalysis, or in other words by polymerization at low pressure and in the presence of a metallocene catalyst.
• the weight-average molecular weight (Mw) of the waxes obtained by metallocene catalysis described in that document is smaller than or equal to 25,000 g/mol; for example, it ranges from 2,000 to 22,000 g/mol and better from 4,000 to 20,000 g/mol.
• the number-average molecular weight (Mn) of the waxes obtained by metallocene catalysis described in that document is preferably smaller than or equal to 15,000 g/mol; for example, it ranges from 1,000 to 12,000 g/mol and better from 2,000 to 10,000 g/mol.
• the polydispersity index I of the polymer is equal to the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn.
• the polydispersity index of the waxy polymers is between 1.5 and 10, preferably between 1.5 and 5, preferably between 1.5 and 3 and even better between 2 and 2.5.
• the waxy homopolymers and copolymers may be obtained in known manner from ethylene and/or propylene monomers, for example by metallocene catalysis according to the method described in the document EP 571882.
• the homopolymers and copolymers of ethylene and/or propylene prepared by metallocene catalysis may or may not be modified “polarly” (polar modified waxes, or in other words waxes modified so that they exhibit the properties of a polar wax).
• the polar-modified waxy homopolymers and copolymers may be prepared in known manner from the non-modified waxy homopolymers and copolymers such as those described in the foregoing by oxidation with oxygen-containing gases, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or else with derivatives of these acids.
• the polar modified homopolymers and copolymers of ethylene and/or propylene prepared by metallocene catalysis and particularly preferred are polymers modified so that they exhibit hydrophilic properties.
• polymers modified so that they exhibit hydrophilic properties there may be cited homopolymers or copolymers of ethylene and/or propylene modified by the presence of hydrophilic groups, such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.
• hydrophilic groups such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.
• waxy homopolymers or copolymers of ethylene and/or propylene modified by the presence of hydrophilic groups such as maleic anhydride or acrylate are particularly preferred.
• compositions for the lips there will be preferred a polar-modified waxy polymer having a low degree of crystallinity, preferably of less than 40%.
• esters of dextrin and fatty acids may be chosen especially from among the mono or poly esters of dextrin and at least one fatty acid, and the compounds represented by formula (C):
• R 1 , R 2 and R 3 may represent hydrogen or an acyl group (R—CO—), in which R is a hydrocarbon radical such as defined in the foregoing, with the proviso that at least two of the said radicals R 1 , R 2 or R 3 are different from hydrogen.
• R 1 , R 2 and R 3 may represent an identical or different acyl group (R—CO), and especially identical.
• n advantageously varies from 25 to 50, and especially it is equal to 38 in general formula (C) of the ester according to the invention.
• radicals R 1 , R 2 and/or R 3 may be chosen from among the caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, ethyl-2-butyric, ethylmethylacetic, isoheptanoic, ethyl-2-hexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, lin
• ester of dextrin and fatty acid or acids at least one dextrin palmitate, This may be used alone or in a mixture with other esters.
• the ester of dextrin and fatty acid has a degree of substitution smaller than or equal to 2.5 on the basis of one glucose unit, especially varying from 1.5 to 2.5, preferably from 2 to 2.5.
• the weight-average molecular weight of the dextrin ester may be in particular 10,000 to 150,000, especially 12,000 to 100,000 and even 15,000 to 80,000.
• Dextrin esters in particular dextrin palmitates, are commercially available under the trade name RHEOPEARL TL or RHEOPEARL KL of the Chiba Flour Company.
• the polysaccharide used in the present invention is preferably chosen from among the fructans.
• the fructans or fructosans are oligosaccharides or polysaccharides comprising a chain of anhydrofructose units, possibly associated with one more different saccharidic residues of fructose.
• the fructans may be linear or branched.
• the fructans may be products obtained directly from a vegetable or microbial source or else products whose chain length has been modified (increased or decreased) by fractionation, synthesis or hydrolysis, especially enzymatically.
• the fructans generally have a degree of polymerization of 2 to approximately 1000 and preferably of 2 to approximately 60.
• the first group corresponds to products whose fructose units are for the most part bonded by ⁇ -2-1 bonds. These are substantially linear fructans such as the inulins.
• the second group also corresponds to linear fructoses, but the fructose units are substantially bonded by ⁇ -2-6 bonds. These products are levans.
• the third group corresponds to mixed fructans, or in other words having ⁇ -2-6-1 and ⁇ -2-1 chains. These are substantially branched fructans such as the graminans.
• the fructans used in the compositions according to the invention are inulins.
• Inulin may be obtained, for example, from chicory, dahlia or Jerusalem artichoke.
• the inulin used in the composition according to the invention is obtained, for example, from chicory.
• the polysaccharides, in particular the inulins, used in the composition according to the invention are hydrophobically modified. In particular, they are obtained by grafting hydrophobic chains onto the hydrophilic skeleton of the fructan.
• the hydrophobic chains capable of being grafted onto the main chain of the fructan may be especially saturated or unsaturated, linear or branched hydrocarbon chains having 1 to 50 carbon atoms, such as the alkyl, arylalkyl, alkylaryl, alkoylene groups; divalent cycloaliphatic groups or organopolysiloxane chains.
• These hydrocarbon or organopolysiloxane chains may comprise in particular one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulfonamide functions such as especially methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene.
• the polysaccharide especially inulin, has a degree of polymerization of 2 to approximately 1,000 and preferably of 2 to approximately 60, and a degree of substitution smaller than 2 on the basis of one fructose unit.
• the hydrophobic chains have at least one alkyl carbamate group of formula R—NH—CO—, in which R is an alkyl group having 1 to 22 carbon atoms.
• the hydrophobic chains are lauryl carbamate groups.
• hydrophobically modified inulins that may be used in the compositions according to the invention
• stearoyl inulin such as those sold under the trade names Lifidrem INST by the Engelhard Company and Rheopearl INS by the Chiba Company
• palmitoyl inulin such as those sold under the trade names Lifidrem INUK and Lifidrem INUM by the Engelhard Company
• inulin lauryl carbamate such as that sold under the name INUTEC SP1 by the ORAFTI Company.
• the hydrophobically modified polysaccharide is an inulin grafted with lauryl carbamate, especially resulting from the reaction of lauryl isocyanate with an inulin, in particular resulting from chicory.
• lauryl carbamate especially resulting from the reaction of lauryl isocyanate with an inulin, in particular resulting from chicory.
• the copolymer of crystalline olefins used in the compositions of the present application may be any olefin copolymer, or in other words a copolymer containing only olefinic moieties, having a controlled and moderate crystalline character, or in other words a degree of crystallinity at most equal to 50%, preferably between 5 and 40%, and better between 10 and 35%.
• copolymers are generally elastomers or plastomers and may be synthesized by any known method, in particular by radical reaction, by Ziegler-Natta catalysis or by metallocene catalysis, preferably by metallocene catalysis.
• a first class of crystalline olefin copolymers that can be used in the compositions according to the invention are copolymers of ⁇ -olefin, in particular of C 2 -C 16 and better C 2 -C 12 ⁇ -olefin.
• these copolymers are bipolymers or terpolymers and most particularly bipolymers.
• the bipolymers recommended for the compositions of the invention there may be cited the bipolymers of ethylene and C 4 -C 16 , preferably C 4 -C 12 ⁇ -olefin and the bipolymers of propylene and C 4 -C 16 , preferably C 4 -C 12 ⁇ -olefin.
• the ⁇ -olefin is chosen from among butene-1, pentene-1, hexene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1,3,5,5-trimethylhexene-1,3-methylpentene-1 and 4-methylpentene-1.
• butene-1 and octene-1 are particularly preferred.
• the proportion of ⁇ -olefin in the bipolymer is generally between 2 and 40 mol %, preferably 3 to 30 mol %, and better 4 to 20 mol %.
• the recommended ethylene-octene bipolymers are the plastomers having an octene content between 5.2 and 6.2 mol %, a degree of crystallinity between 28% and 38% and the elastomers having an octene content between 8 and 14 mol % and a degree of crystallinity between 10 and 28%.
• Such bipolymers are sold by the DOW CHEMICAL Company under the trade names AFFINITY (plastomers) and ENGAGE (elastomers).
• Ethylene-butene bipolymers are sold by the EXXON Company under the commercial name EXACT RESINS.
• terpolymers there may be cited the terpolymers of ethylene, propylene and C 4 -C 16 preferably C 4 -C 12 -olefin.
• C 4 -C 16 -olefin contents of C 4 -C 16 -olefin are as indicated in the foregoing, and the preferred ⁇ -olefins are butene, hexene and octene.
• a second class of olefin copolymers suitable for the compositions according to the invention are copolymers of ethylene or propylene and a cycloolefin, in particular the bipolymers.
• the cycloolefin content of the copolymers is smaller than 20 mol %.
• cyclobutene cyclohexene
• cyclooctadiene norbornene
• DMON dimethano-octahydronaphthalene
• ethylidene norbornene vinyl norbornene
• 4-vinylcyclohexene cyclobutene, cyclohexene, cyclooctadiene, norbornene, dimethano-octahydronaphthalene (DMON), ethylidene norbornene, vinyl norbornene and 4-vinylcyclohexene.
• the recommended copolymers of this class are the copolymers of ethylene and norbornene.
• the norbornene content of these copolymers is generally smaller than 18 mol % in order to exhibit the required crystalline character, and these copolymers are synthesized by metallocene catalysis.
• ethylene/norbornene copolymers are sold by the MITSUI PETROCHEMICAL or MITSUI-SEKKA Company under the trade name APEL and by the HOECHST-CELANESE Company under the trade name TOPAS.
• ethylene/cycloolefin copolymers are the ethylene/cyclobutene and ethylene/cyclohexene bipolymers with low cycloolefin content, generally lower than 20 mol %.
• a third class of appropriate olefin copolymers is constituted by the olefin copolymers of controlled tacticity, or in other words copolymers containing moieties of different tacticity.
• copolymers of controlled tacticity there may be cited the isotactic propylene/atactic propylene and syndiotactic propylene/atactic propylene copolymers.
• the isotactic or syndiotactic moieties or sequences confer the crystalline character on the copolymer, while the amorphous atactic moieties or sequences prevent excessive crystallinity of the copolymer and regulate the degree of crystallinity as well as the morphology and size of the crystallites.
• the content of isotactic or syndiotactic moieties, the moieties conferring the crystalline character on the copolymer, is therefore determined so as to obtain the desired percentage crystallinity ( ⁇ 50%) in the copolymer.
• the content of tactic moieties is generally between 10 and 80 mol %. Nevertheless, the content of atactic moieties is preferably smaller than 30 mol %.
• copolymers are synthesized by metallocene catalysis.
• a fourth class of olefin copolymers suitable for the present invention is constituted by the copolymers of monoolefin and diene, for example the ethylene/butadiene, propylene/butadiene, ethylene/isoprene and propylene/isoprene bipolymers and the ethylene/propylene/diene terpolymers, also obtained by metallocene synthesis.
• the proportion of diene moieties in the controlled crystallization copolymer is generally between 3 and 20 mol %.
• additives that impair crystallization and favor formation of small crystals.
• These additives although used in small proportion, constitute numerous and small nucleation “sites” distributed uniformly in the mass.
• These additives are typically crystals of an organic or mineral substance.
• this In the case of an organic additive that must crystallize, this must have a melting point higher than the melting zone of the copolymer and preferably must form small crystals.
• this substance is preferably soluble in the mixture of liquid fatty phase and molten polymer.
• the initially dissolved additive recrystallizes in the form of numerous small crystals, thoroughly distributed in the mixture, then the polymer recrystallizes by forming small crystalline domains due to the presence of the additive crystals. This technique for recrystallization of polymers is traditional.
• the degree of crystallization, the size and the morphology of the olefin copolymers according to the invention may also be adjusted by mixing a first olefin copolymer according to the invention with a second crystalline polymer or copolymer, partly compatible with the first olefin copolymer.
• the second polymer or copolymer may be an olefin copolymer according to the invention, but with a degree of crystallinity different from that of the first copolymer, including a higher degree of crystallinity than the degree of crystallinity of the olefin copolymers according to the invention.
• the second crystallizable polymer may also be a polymer of different nature, for example a copolyethylene/vinyl acetate obtained by radical copolymerization or even a crystallizable polyethylene such as those commonly used in the cosmetic field.
• the usable polycondensate may be capable of being obtained by reaction:
• the polycondensate is capable of being obtained by reaction:
• the polycondensate may also be capable of being obtained by reaction:
• polyol hydroxyl groups
• the said polyol may be in particular a carbon compound, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon compound comprising 3 to 18 carbon atoms, especially 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxy (OH) groups, and being able to comprise additionally one or more oxygen atoms intercalated in the chain (ether function).
• the said polyol is preferably a linear or branched, saturated hydrocarbon compound comprising 3 to 18 carbon atoms, especially 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxy (OH) groups. It may be chosen from among the following compounds, alone or in a mixture:
• the polyol is chosen from among glycerol, pentaerythritol, diglycerol, sorbitol and mixtures thereof; and pentaerythritol is even better.
• the polyol or the polyol mixture preferably represents 10 to 30% by weight, especially 12 to 25% by weight, and better 14 to 22% by weight of the total weight of the final polycondensate.
• Another constituent necessary for the preparation of the polycondensates according to the invention is a linear, branched and/or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms, especially 8 to 28 carbon atoms and still better 10 to 24, even 12 to 20 carbon atoms. Quite obviously a mixture of such non-aromatic monocarboxylic acids may be used.
• non-aromatic monocarboxylic acid there is understood a compound of formula RCOOH, in which R is a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon radical comprising 5 to 31 carbon atoms, especially 7 to 27 carbon atoms, and still better 9 to 23 carbon atoms, even 11 to 19 carbon atoms.
• R is saturated.
• the said R radical is linear or branched, and preferentially with C5-C31, even C11-C21.
• the non-aromatic monocarboxylic acid has a melting point higher than or equal to 25° C., especially higher than or equal to 28° C., even to 30° C.; in fact it has been observed that, when such an acid is employed, in particular in large quantity, it is possible on the one hand to obtain good gloss and staying power of the said gloss and, on the other hand, to reduce the quantity of waxes usually present in the envisioned composition.
• non-aromatic monocarboxylic acids capable of being employed there may be cited, alone or in mixtures:
• non-aromatic monocarboxylic acids having a melting temperature higher than or equal to 25° C. there may be cited, alone or in mixtures:
• 2-ethylhexanoic acid isooctanoic acid, lauric acid, myristic acid, isoheptanoic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone.
• the said non-aromatic monocarboxylic acid or the mixture of the said acids preferably represents 30 to 80% by weight, especially 40 to 75% by weight, even 45 to 70% by weight, and better 50 to 65% by weight of the total weight of the final polycondensate.
• aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, possibly substituted in addition by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms, especially 2 to 12, even 3 to 8 carbon atoms. Quite obviously a mixture of such aromatic monocarboxylic acids may be used.
• aromatic monocarboxylic acid there is understood a compound of formula R′COOH, in which R′ is an aromatic hydrocarbon radical comprising 6 to 10 carbon atoms, and in particular the benzoic and naphthoic radicals.
• the said R′ radical may be substituted additionally by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms, especially 2 to 12, even 3 to 8 carbon atoms; and especially chosen from among methyl, ethyl, propyl, isopropyl, butyl, isobutyl, terbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl.
• aromatic monocarboxylic acids capable of being employed there may be cited, alone or in mixtures, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-napthoic acid.
• the said aromatic monocarboxylic acid or the mixture of the said acids preferably represents 0.1 to 10% by weight, especially 0.5 to 9.95% by weight, still better 1 to 9.5% by weight, even 1.5 to 8% by weight of the total weight of the final polycondensate.
• Another constituent necessary for the preparation of the polycondensates according to the invention is a linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acid comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid. Quite obviously a mixture of such polycarboxylic acids and/or anhydrides may be used.
• the said polycarboxylic acid may be especially chosen from among the linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acids comprising 2 to 50, especially 2 to 40 carbon atoms, in particular 3 to 36, even 3 to 18, and still better 4 to 12 carbon atoms, even 4 to 10 carbon atoms; the said acid comprises at least two carboxylic groups COOH, preferably 2 to 4 COON groups.
• the said polycarboxylic acid is linear, saturated, aliphatic and comprises 2 to 36 carbon atoms, especially 3 to 18 carbon atoms, even 4 to 12 carbon atoms; or else it is aromatic and comprises 8 to 12 carbon atoms. Preferably it comprises 2 to 4 COOH groups.
• the said cyclic anhydride of such a polycarboxylic acid may be represented in particular by one of the following formulas:
• polycarboxylic acids or their anhydrides capable of being employed there may be cited, alone or in mixtures.
• adipic acid Preferably there may be used adipic acid, phthalic anhydride and/or isophthalic acid, and even better isophthalic acid alone.
• the said polycarboxylic acid and/or its cyclic anhydride preferably represents 5 to 40% by weight, especially 10 to 30% by weight, and better 14 to 25% by weight of the total weight of the final polycondensate.
• the polycondensate according to the invention may additionally comprise a silicone with hydroxyl (OH) and/or carboxylic (COOH) function.
• It may comprise 1 to 3 hydroxyl and/or carboxylic functions and it preferably comprises two hydroxyl functions or else two carboxylic functions.
• silicones having a weight-average molecular weight (Mw) between 300 and 20,000, especially 400 and 10,000, even 800 and 4,000.
• This silicone may have the formula:
• the ⁇ , ⁇ -diol or ⁇ , ⁇ -dicarboxylic polyalkylsiloxanes and especially the ⁇ , ⁇ -diol polydimethylsiloxanes and the ⁇ , ⁇ -dicarboxylic polydimethylsiloxanes; the ⁇ , ⁇ -diol or ⁇ , ⁇ -dicarboxylic polyarylsiloxanes, and especially the ⁇ , ⁇ -diol or ⁇ , ⁇ -dicarboxylic polyphenylsiloxanes; the polyarylsiloxanes with silanol functions, such as polyphenylsiloxane; the polyalkylsiloxanes with silanol functions such as polydimethylsiloxane; the polyaryl/alkylsiloxanes with silanol functions such as polyphenyl/methylsiloxane or else polyphenyl/propylsiloxane.
• ⁇ , ⁇ -diol polydimethylsiloxanes of weight-average molecular weight (Mw) between 400 and 10,000, even between 500 and 5,000, and especially between 800 and 4,000.
• the said silicone may preferably represent 0.1 to 15% by weight, especially 1 to 10% by weight, even 2 to 8% by weight of the weight of the polycondensate.
• the aromatic monocarboxylic acid is present in molar quantity smaller than or equal to that of the non-aromatic monocarboxylic acid; in particular the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acid is preferably between 0.08 and 0.70, especially between 0.10 and 0.60, in particular between 0.12 and 0.40.
• the polycondensate according to the invention is capable of being obtained by reaction:
• the polycondensate according to the invention is capable of being obtained by reaction:
• the polycondensate according to the invention may be prepared by esterification/polycondensation methods usually employed by those skilled in the art.
• a general preparation method consists in:
• esterification catalysts for example of sulfonic acid type (especially in a concentration between 1 and 10% by weight) or of titanate type (especially in a concentration between 5 and 100 ppm by weight).
• the said preparation method may also comprise a step of addition of at least one antioxidant agent into the reaction mixture, especially in a concentration between 0.01 and 1% by weight relative to the total weight of monomers, so as to limit possible degradation associated with prolonged heating.
• the antioxidant agent may be of primary type or of secondary type, and may be chosen from among the hindered phenols, the secondary aromatic amines, the organophosphorus compounds, the sulfur compounds, the lactones, the acryl bisphenols; and mixtures thereof.
• the fatty-phase thickening or gelling rheological agent may be a mineral structuring lipophilic agent.
• the lipophilic clays such as the clays that have been modified if necessary, such as the hectorites modified by a C 10 to C 22 fatty acid ammonium chloride, such as hectorite modified by distearyldimethylammonium chloride.
• hydrophobic silicas such as pyrogenic silica, which has been hydrophobically surface-treated if necessary, whose particle size is smaller than 1 ⁇ m. It is in fact possible to modify the surface of the silica chemically, by chemical reaction causing a decrease in the number of silanol groups present at the surface of the silica.
• silanol groups may be substituted by hydrophobic groups: a hydrophobic silica is then obtained.
• the hydrophobic groups may be:
• the hydrophobic pyrogenic silica preferably has a particle size that may be nanometric to micrometric, for example ranging approximately from 5 to 200 nm.
• polymer within the meaning of the invention there is understood a compound having at least 2 repeating moieties, preferably at least 3 repeating moieties and still better 10 repeating moieties.
• polyamides As preferred lipophilic structuring polyamides that can be used in the invention, there may be cited the polyamides branched by pendant fatty chains and/or terminal fatty chains having 12 to 120 carbon atoms and especially 12 to 68 carbon atoms, the terminal fatty chains being bonded to the polyamide skeleton by ester groups.
• These polymers are more specially those described in the document U.S. Pat. No. 5,783,657 of the Union Camp Company. Each of these polymers satisfies especially the following formula (I):
• n denotes an integral number of amide moieties such that the number of ester groups represents 10% to 50% of the total number of ester and amide groups
• R 1 independently in each occurrence, is an alkyl or alkenyl group having at least 4 carbon atoms
• R 2 independently in each occurrence, represents a C 4 to C 42 group, with the proviso that 50% of the R 2 groups represent a C 30 to C 42 hydrocarbon group
• R 3 independently in each occurrence, represents an organic group provided with at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms
• R 4 independently in each occurrence, represents a hydrogen atom, a C 1 to C 10 alkyl group or a direct bond to R 3 or to another R 4 , so that the nitrogen atom to which both R 3 and R 4 are bonded is part of a heterocyclic structure defined by R 4 —N—R 3 , with at least 50% of the R 4 groups representing a hydrogen atom.
• ester groups of formula (I), which make up part of the terminal and/or pendant fatty chains within the meaning of the invention, represent 15 to 40% of the total number of ester and amide groups and better 20 to 35%.
• n advantageously represents an integral number ranging from 1 to 5.
• R 1 is a C 12 to C 22 alkyl group, and preferably C 16 to C 22 .
• R 2 may be a C 10 to C 42 hydrocarbon group (especially alkyl or alkenyl) having a polymerized fatty acid structure or a dimer structure whose carboxylic acid groups have been removed (these groups being used to form the amide).
• at least 50% and better 75% of the R groups are groups having 30 to 42 carbon atoms.
• R 2 groups are C 4 to C 19 and even C 4 to C 12 hydrogenated groups.
• R 3 represents a C 2 to C 36 hydrocarbon group or a polyoxyalkylene group and R 4 represents a hydrogen atom.
• R 3 represents a C 2 to C 12 hydrocarbon group.
• the hydrocarbon groups may be saturated or unsaturated, linear, cyclic or branched groups.
• the alkyl and alkenyl groups may be linear or branched groups.
• the polymer of the composition of the invention comprises a weight-average molecular weight ranging from 2,000 to 20,000 and better from 2,000 to 10,000.
• structuring of the oil is achieved by means of one or more polymers of formula (I).
• the polymers of formula (I) have the form of mixtures of polymers, these mixtures additionally being able to contain a synthetic product such that n is equal to 0, or in other words a diester.
• polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds having more than 2 carbonyl groups and more than 2 amine groups), the carbonyl and amine groups of adjacent unitary moieties being condensed via an amide bond.
• These polyamide resins are especially those sold under the brand Versamid® by General Mills, Inc. and the Henkel Corp. (Versamid 930, 744 or 1655) or by Olin Mathieson Chemical Corp. under the brand Onamid®, especially Onamid S or C. These resins have a weight-average molecular weight ranging from 6,000 to 9,000.
• Versamid® 930 or 744 is used.
• the structuring polymers in the composition of the invention advantageously have a softening temperature higher than 70° C. and possibly ranging up to 190° C. Preferably, it has a softening temperature ranging from 80 to 130°.
• These polymers are in particular non-waxy polymers.
• fatty-phase rheological agent there may also be cited the polyurethanes and the polyureas soluble or dispersible in the hydrocarbon oil or oils, and containing:
• long hydrocarbon chain there is understood a linear or branched hydrocarbon chain containing at least 8 carbon atoms and preferably 10 to 500 carbon atoms.
• polymers preferred according to the invention are defined by one of the following three formulas:
• n denotes an integral number from 1 to 10,000, and preferably from 1 to 1,000
• x represents, separately or together, —O— or —NH—
• R is a divalent radical chosen from among the alkylene, cycloalkylene, aromatic radicals and mixtures thereof, if necessary functionalized
• a 1 and A 2 be identical or different, denote monovalent linear, branched or cyclic hydrocarbon radicals, which may be saturated or contain unsaturations, containing 1 to 80 carbon atoms
• D is 1) a divalent saturated or unsaturated aliphatic and/or cycloaliphatic hydrocarbon sequence, and/or aliphatic polyester with long hydrocarbon chain, or 2) a graft
• Z is a trivalent hydrocarbon radical that may contain one or more hetero atoms
• ⁇ is a linear, branched or cyclic aliphatic chain
• Monovalent hydrocarbon radicals A 1 and A 2 are preferably chosen from among the saturated or unsaturated aliphatic, cycloaliphatic and aromatic radicals. Radicals A 1 and A 2 are derivèd from monoalcohols and/or monoamines, used if necessary to consume the residual isocyanate groups at the end of polymerization.
• D is a saturated or unsaturated aliphatic and/or cycloaliphatic hydrocarbon sequence, it is derived:
• D is an aliphatic polyester sequence with a long hydrocarbon chain
• it is preferably derived from branched polyesters with long hydrocarbon chains, such as, for example, poly(12-hydroxystearate).
• ⁇ is a saturated or unsaturated, linear, branched or cyclic aliphatic chain containing 8 to 40 carbon atoms.
• the possible hetero atoms of trivalent radical Z are preferably —O—, —N—, and —S—.
• the structuring polyurethanes and/or polyureas according to the invention result from the polymerization reaction between:
• the isocyanates used in the polymerization reaction may be aliphatic, cycloaliphatic or aromatic.
• hexamethylene diisocyanate isophorone diisocyanate, toluene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate.
• the difunctional derivatives H—X-D-X—H may be chosen from among the dimer diols and their derivatives, the alkane diols, the polydienes with hydroxyl ends, preferably hydrogenated, the polyolefins with hydroxyl ends, the branched polyesters with long alkyl chain carrying at least two reactive groups, the natural or synthetic oils carrying two to three hydroxyl groups, and finally the dimer diamines and the diamines with long aliphatic chain.
• the dimer diols are C 36 branched aliphatic and/or alicyclic diols and/or a mixture of the said dimers. These diols are prepared from “corresponding dimeric fatty acids”.
• corresponding dimeric fatty acids there is understood the dimeric fatty acids that have the same structure as these diols but which possess two carboxylic acid ends instead of the diol ends.
• the transformation of dimeric fatty acids into dimer diols may be achieved either by hydrogenation of methyl esters of the dimeric fatty acids or by direct dimerization of oleic alcohol.
• the dimer diols sold by the COGNIS Company under the commercial names of SOVERMOL 908 (97% purity) and SOVERMOL 650 NS (68% purity).
• polyether-diol and the polycarbonate-diol oligomers prepared by subsequent etherification or esterification of these same C 36 branched dimer diols.
• These oligomers generally have a number-average molecular weight on the order of 500 to 2,000 and possess two hydroxyl functions.
• the polydienes with hydroxyl ends are, for example, those defined in French Patent FR 2782723. They are chosen in the group comprising the homopolymers and copolymers of polybutadiene, polyisoprene and poly(1,3-pentadiene). These oligomers have a number-average molecular weight smaller than 7,000, and preferably 1,000 to 5,000. They have a functionality of 1.8 to 3 and preferably close to 2 at the end of the chain.
• polydienes with hydroxyl ends are, for example, the hydroxylated polybutadienes sold by the ELF ATOCHEM Company under the brands POLY BD-45H® and POLY BD R-20 LM®. These products are preferably used in hydrogenated form.
• H—X-D-X—H it is possible to use a branched polyester having a long alkyl chain and containing at least two reactive groups, such as, for example, poly(12-hydroxystearate) with hydroxyl ends.
• This polyester is obtained by auto-condensation of 1,2-hydroxystearic acid on itself, then reaction with a polyol to consume the residual acid groups.
• This oligomer has the structure
• m+n is such that the oligomer has a number-average molecular weight on the order of 2,000 and a hydroxyl functionality on the order of 1.8.
• oils carrying two hydroxyl groups per chain and preferably the monoglycerides of the structure:
• R 1 being a C 8 to C 30 linear or branched alkyl chain, such as, for example, glycerol monostearate.
• Such glycerol monoesters correspond, for example, to the difunctional derivatives H—X-D-X—H, where:
• R 1 is defined as in the foregoing.
• H—X-D-X—H chosen from among the oils carrying three hydroxyl groups per chain, such as, for example, hydrogenated or non-hydrogenated castor oil.
• the polymerization reaction is carried out with a deficit of diisocyanate compared with the stoichiometry of the reaction, to avoid cross-linking of the polymer and to preserve good solubility thereof.
• diols with long aliphatic chains.
• diols of structure HO-D-OH, where D is a linear or branched alkyl chain containing 8 to 40 carbon atoms.
• VIKINOL® a linear or branched alkyl chain containing 8 to 40 carbon atoms.
• 1,12-dodecanediol and 1,10-decanediol are sold by the COGNIS Company under the commercial name of SOVERMOL 110®.
• R 2 is an alkyl chain containing 8 to 40 carbon atoms.
• diols with long aliphatic chains are preferably used with one or the other of the H—X-D-X—H derivatives cited in the foregoing, to be used as chain couplers during synthesis of polyurethanes and/or polyureas.
• H—X-D-X—H derivative the dimer diamines or the diamines with long aliphatic chain.
• dimer diamines having the same structure as the dimer diols described in the foregoing, or in other words dimer diamines containing two primary amine functions instead of hydroxyl groups.
• dimer diamines may be obtained from the transformation of dimeric fatty acids, such as the dimer diols.
• diamines of structure H 2 N-D-NH 2 where D is a linear or branched alkyl chain containing 8 to 40 carbon atoms.
• diamines are preferably used in mixtures with a difunctional derivative H—X-D-X—H chosen from among the dimer diols and their derivatives, the polydienes and polyolefins with hydroxyl ends, the branched polyesters with long alkyl chains, and the oils carrying 2 to 3 hydroxyl groups, cited in the foregoing.
• the monofunctional derivatives A 1 -XH and A 2 -XH are advantageously chosen from among the monoalcohols or monoamines having linear or branched alkyl chains containing 1 to 80 carbon atoms, the natural or synthetic oils carrying a single hydroxyl group per chain, such as, for example, the diesters of glycerols or the triesters of citric acid and fatty alcohol.
• the envisioned polycondensation reactions are traditionally carried out in an organic solvent capable of dissolving the reagents and the formed polymer.
• This solvent is preferably easy to eliminate at the end of the reaction, especially by distillation, and it does not react with the isocyanate groups.
• each of the reagents is dissolved in a portion of the organic solvent prior to the polymerization reaction.
• a catalyst to activate the polymerization. This will generally be chosen from among the catalysts commonly used in the chemistry of polyurethanes and polyureas, such as, for example, tin 2-ethyl hexanoate.
• the molar proportion between the main reagents of the polymerization reaction depends on the chemical structure and molecular weight of the polymers (polyurethanes and/or polyureas) that are desired to be obtained, as is traditionally the case in the chemistry of polyurethanes and polyureas. Similarly, the order of introduction of the reagents will be adapted to this chemistry.
• this reaction will then be carried out by simultaneous addition, into a reactor, of an organic solution of one mole of H—X-D-X—H, such as, for example, a POLYTAIL® described in the foregoing, and an organic solution of one mole of diisocyanate, such as, for example, 4,4′-dicyclohexylmethane diisocyanate.
• an organic solution of one mole of H—X-D-X—H such as, for example, a POLYTAIL® described in the foregoing
• diisocyanate such as, for example, 4,4′-dicyclohexylmethane diisocyanate.
• double decantation At the end of double decantation, the reaction mixture is heated to 60° C. for 5 hours. Then a sample of the reaction medium is withdrawn to determine the residual isocyanates by using a method known to those skilled in the art.
• ⁇ is a linear, branched or cyclic aliphatic chain containing 8 to 20 carbon atoms
• Such a polymer is obtained in the following manner:
• any residual isocyanates will be able to be consumed by addition of an appropriate quantity of monofunctional reagent A 1 -XH.
• the lipophilic silicone polymer structuring agents are, for example, polymers of the polyorganosiloxane type, such as those described in the documents U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680.
• the polymers used as structuring agent may belong to the following two families:
• the groups capable of establishing hydrogen interactions may be chosen from among the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof.
• the silicone polymers are polyorganosiloxanes such as defined above and whose moieties capable of hydrogen interactions are disposed in the polymer chain.
• the silicone polymers may be more particularly polymers comprising at least one moiety according to the general formula I:
• R 4 , R 5 , R 6 and R 7 identical or different, represent a group chosen from among:
• the groups X identical or different, represent a linear or branched C 1 to C 30 di-yl alkylene group, which may contain one or more oxygen and/or nitrogen atoms in its chain,
• Y is a saturated or unsaturated, linear or branched divalent C 1 to C 50 alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group which may contain one or more oxygen, sulfur and/or nitrogen atoms and/or carry as substituent one of the following atoms or groups of atoms: fluorine, hydroxy, C 3 to C 8 cycloalkyl, C 1 to C 40 alkyl, C 5 to C 10 aryl, phenyl, possibly substituted by 1 to 3 C 1 to C 3 alkyl groups, C 1 to C 3 hydroxyalkyl and C 1 to C 6 aminoalkyl, or
• Y represents a group according to the formula:
• the groups G identical or different, represent the divalent groups chosen from among:
• R 9 represents a hydrogen atom or a linear or branched C 1 to C 20 alkyl group, with the proviso that at least 50% of the R 9 groups of the polymer represent a hydrogen atom and that at least two of the groups G of the polymer are another group such as:
• n is an integral number ranging from 2 to 500, preferably 2 to 200
• m is an integral number ranging from 1 to 1,000, preferably 1 to 700 and still better from 6 to 200.
• 80% of the R 4 , R 5 , R 6 and R 7 of the polymer are preferably chosen from among the methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.
• Y may represent diverse divalent groups, possibly containing one or two free valences to establish bonds with other moieties of the polymer or copolymer.
• Y represents a group chosen from among:
• R 4 , R 5 , R 6 , R 7 , T and m are such as defined hereinabove, and
• the polyorganosiloxanes may be polymers comprising at least one moiety according to formula (II):
• the silicone polymer used as structuring agent may be a homopolymer, or in other words a copolymer containing several identical moieties, in particular moieties of formula (I) or formula (II).
• a silicone polymer constituted by a copolymer containing several different moieties of formula (I), or in other words a polymer in which at least one of R 4 , R 5 , R 6 , R 7 , X, G, Y, m and n is different in one of the moieties.
• the copolymer may also be formed from several moieties of formula (II), in which at least one of R 4 , R 6 , R 10 , R 11 , m1 and m2 is different in at least one of the moieties.
• a polymer comprising at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions, chosen from among the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof.
• These copolymers may be block polymers, sequenced polymers or graft polymers.
• the groups capable of establishing hydrogen interactions are amide groups of formula —C(O)NH— and —HN—C(O)—.
• the structuring agent may be a polymer comprising at least one moiety of formula (III) or (IV):
• R 4 , R 5 , R 6 , R 7 , X, Y, m and n are such as defined hereinabove.
• X 1 —(CH 2 ) 2 — corresponds to X defined hereinabove and Y, R 4 , R 5 , R 6 , R 7 and m are such as defined hereinabove,
• m ranges from 1 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 still better from 4 to 25,
• the alkylene group representing X or Y may possibly contain, in its alkylene part, at least one of the following elements:
• alkylene groups may also be substituted by at least one element chosen in the group constituted by:
• Y may also represent:
• R 8 represents a polyorganosiloxane chain and T represents a group of the following formula:
• R 13 is a hydrogen atom or a group such as those defined for R 4 , R 5 , R 6 and R 7 .
• R 4 , R 5 , R 6 and R 7 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, possibly substituted by one to three methyl or ethyl groups.
• the polymer may comprise identical or different moieties of formula (III) or (IV).
• polymer may be a polyamide containing several moieties of formula (III) or (IV) of different lengths, or in other words a polyamide according to formula (V):
• X, Y, n, R 4 to R 7 have the meanings given hereinabove, m 1 , and m 2 , which are different, are chosen in the interval ranging from 1 to 1,000, and p is an integral number ranging from 2 to 300.
• the moieties may be structured so as to form either a block copolymer or a random copolymer or an alternating copolymer.
• the moieties may be not only of different lengths but also of different chemical structures, for example having different Y groups.
• the polymer may be represented by formula VI:
• R 4 to R 7 , X, Y, m 1 , m 2 , n and p have the meanings given hereinabove and Y 1 is different from Y but is chosen from among the groups defined for Y.
• the different moieties may be structured so as to form either a block copolymer or a random copolymer or an alternating copolymer.
• the structuring agent may also be constituted by a graft copolymer.
• the polyamide containing silicone units may be grafted and possibly cross-linked by silicone chains containing amide groups.
• Such polymers may be synthesized with trifunctional amines.
• the polymer may comprise at least one moiety of formula (VII):
• X 1 and X 2 which are identical or different, have the meaning given for X in formula (I)
• n is such as defined in formula (I)
• Y and T are such as defined in formula (I)
• R 14 to R 21 are groups chosen in the same group as R 4 to R 7
• m 1 , and m 2 are numbers in the interval ranging from 1 to 1,000
• p is an integral number ranging from 2 to 500.
• R 22 is a hydrogen atom or a group chosen from among the groups defined for R 4 to R 7 , and R 23 , R 24 and R 25 are, independently, linear or branched alkylene groups, more preferably, with the formula:
• R 23 , R 24 and R 25 representing —CH 2 —CH 2 —
• polyamides with grafted silicone moiety of formula (VII) may be copolymerized with silicone polyamides of formula (II) to form block copolymers, alternating copolymers or random copolymers.
• the percentage by weight of grafted silicone moieties (VII) in the copolymer may range from 0.5 to 30% by weight.
• the siloxane units may be in the main chain or skeleton of the polymer, but they may also be present in grafted or pendant chains.
• the siloxane units may be in the form of segments as described hereinabove.
• the siloxane units may be present individually or in segments.
• a copolymer of silicone polyamide and hydrocarbon polyamide or a copolymer containing moieties of formula (III) or (IV) and hydrocarbon polyamide moieties.
• the silicone polyamide moieties may be disposed at the ends of the hydrocarbon polyamide.
• the preferred compounds are those of formula III, whose INCI name is Nylon 611/dimethicone copolymers.
• the groups R4, R5, R6 and R7 represent methyl groups
• one of X and Y represents an alkylene group with 6 carbon atoms and the other an alkylene group groups of 11 carbon atoms.
• composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) possessing an index m whose value is approximately 15.
• the composition according to the invention comprises at least one polymer comprising at least one moiety of formula (III), where m ranges from 5 to 100, in particular from 10 to 75 and more particularly is on the order of 15; more preferably, R 4 , R 5 , R 6 and R 7 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 in formula (III).
• the polymer is constituted by a homopolymer or copolymer containing urethane or urea groups.
• These polymers are described in detail in Application WO 2003/106614, published 24 Dec. 2003, the content of which is incorporated into this application by reference.
• such a polymer may contain polyorganosiloxane moieties containing two or more urethane and/or urea groups, either in the polymer skeleton or on side chains or as pendant groups.
• the polymers containing at least two urethane and/or urea groups in the skeleton may be polymers comprising at least one moiety according to the following formula (VIII):
• R 4 , R 5 , R 6 , R 7 , X, Y, m and n have the meanings given hereinabove for formula (I), and U represents —O— or —NH—, in order that:
• Y may be a linear or branched C 1 to C 40 alkylene group, possibly substituted by a C 1 to C 15 alkyl group or a C 5 to C 10 aryl group. Preferably there will be used a —(CH 2 ) 6 — group.
• Y may also represent a C 5 to C 12 cycloaliphatic or aromatic group, which may be substituted by a C 1 to C 15 alkyl group or a C 5 to C 10 aryl group, for example a radical chosen from among the methylene-4-4-biscyclohexyl radical, the radical derived from isophorone diisocyanate, 2,4 and 2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4′-biphenylene methane.
• Y preferably represents a linear or branched C 1 to C 40 alkylene radical, or a C 4 to C 12 cycloalkylene radical.
• Y may also represent a polyurethane or polyurea sequence corresponding to the condensation of several diisocyanate molecules with one or more coupler molecules or the diol or diamine type.
• Y comprises several urethane or urea groups in the alkylene chain.
• B 1 is a group chosen from among the groups given hereinabove for Y, U is —O— or —NH—, and B 2 is chosen from among:
• T is a trivalent hydrocarbon radical, which may contain one or more hetero atoms such as oxygen, sulfur and nitrogen
• R 8 is a polyorganosiloxane chain or a linear or branched C 1 to C 50 alkyl chain.
• T may represent:
• w is an integral number ranging from 1 to 10 and R 8 is a polyorganosiloxane chain.
• Y is a linear or branched C 1 to C 40 alkylene group
• the —(CH 2 ) 2 — and —(CH 2 ) 6 — groups are preferred.
• d may be an integer ranging from 0 to 5, preferably from 0 to 3, more preferably equal to 1 or 2.
• B 2 is a linear or branched C 1 to C 40 alkylene, in particular —(CH 2 ) 2 — or —(CH 2 ) 6 —, or the group:
• R 8 is a polyorganosiloxane chain.
• the polymer constituting the texturizing copolymer may be formed from urethane silicone and/or urea silicone moieties of different length and/or constitution, and may have the form of block, sequenced or statistical (random) copolymers.
• the polymers of formula (VIII) containing urea or urethane groups in the silicone polymer chain may be obtained by reaction between a silicone with ⁇ , ⁇ -NH 2 or OH terminal groups, of formula:
• m, R 4 , R 5 , R 6 , R 7 and X are such as defined for formula (I), and a diisocyanate OCN—Y—NCO, where Y has the meaning given in formula (I); and possibly a diol or diamine coupler of formula H 2 N—B 2 —NH 2 or HO—B 2 —OH, where B 2 is such as defined in formula (IX).
• Y will be able to have formula (IX) with d equal to 0 or d equal to 1 to 5.
• silicone polyamides of formula (IV), (II) or (III) there may be used in the invention silicone polyurethanes or polyureas having moieties of different length and structure, in particular moieties of different lengths due to the number of silicone units.
• the copolymer may be represented, for example, by the formula:
• R 4 , R 5 , R 6 , R 7 , X, Y and U are such as defined for formula (VIII) and m 1 , m 2 , n and p are such as defined for formula (V).
• the silicone may also contain urethane and/or urea groups no longer in the skeleton but in side branches.
• the polymer may comprise at least one moiety of the following formula:
• the polymers containing at least one moiety of formula (X) contain siloxane units and urea or urethane groups, and they may be used as texturizing copolymer in the compositions of the invention.
• the siloxane polymers may have a single urea or urethane group per branch or may have branches with two urea or urethane groups, or even contain a mixture of branches with one urea or urethane group and branches with two urea or urethane groups.
• They may be obtained from branched polysiloxanes, containing one or two amino groups per branch, by reacting these polysiloxanes with monoisocyanates.
• the “/” symbol indicates that the segments may be of different lengths and in a random order
• R represents a linear aliphatic group having preferably 1 to 6 carbon atoms and still better 1 to 3 carbon atoms.
• Such branched polymers may be formed by reacting a siloxane polymer having at least three amino groups per polymer molecule with a compound having a single monofunctional group (for example, an acid, an isocyanate or isothiocyanate), thus causing this monofunctional group to react with one of the amino groups and to form the groups capable of establishing hydrogen interactions.
• the amino groups may be on side chains extending from the main chain of the siloxane polymer such that the groups capable of establishing hydrogen interactions are formed on these side chains, or else the amino groups may be at the ends of the main chain such that the groups capable of hydrogen interaction will be terminal groups of the polymer.
• reaction of a diamine siloxane and of a diisocyanate in a silicone solvent so as to produce a gel directly.
• the reaction may be carried out in a silicone fluid, the resulting product being dissolved in the silicone fluid at elevated temperature, the temperature of the system then being lowered to form the gel.
• the polymers preferred for incorporation into the compositions according to the present invention are urea-siloxane copolymers that are linear and that contain urea groups as groups capable of establishing hydrogen interactions in the skeleton of the polymer.
• Ph is a phenyl group and n is a number from 0 to 300, in particular from 0 to 100, for example 50.
• This polymer is obtained by reacting the following polysiloxane having amino groups:
• Branched silicone polyurethanes or polyureas may also be obtained by using, instead of the diisocyanate OCN—Y—NCO, a triisocyanate of the following formula:
• Such a polymer comprises, for example, a moiety according to the formula:
• X 1 and X 2 which are identical or different, have the meaning given for X in formula (I)
• n is such as defined in formula (I)
• Y and T are such as defined in formula (I)
• R 14 to R 21 are groups chosen in the same group as R 4 to R 7
• m 1 and m 2 are numbers in the interval ranging from 1 to 1,000
• p is an integral number ranging from 2 to 500.
• silicone polyurethane or polyurea or hydrocarbon polyurethane or polyurea copolymers may be used in the invention by carrying out the reaction of synthesis of the polymer in the presence of a difunctional ⁇ , ⁇ sequence of non-silicone nature, for example a polyester, a polyether or a polyolefin.
• the copolymers of the invention may have siloxane moieties in the main chain of the polymer and groups capable of establishing hydrogen interactions either in the main chain of the polymer or at the ends thereof, or on side chains or branches of the main chain. This may correspond to the following five arrangements:
• the continuous line is the main chain of the siloxane polymer and the squares represent the groups capable of establishing hydrogen interactions.
• the groups capable of establishing hydrogen interactions are disposed at the ends of the main chain.
• two groups capable of establishing hydrogen interactions are disposed at each of the ends of the main chain.
• the groups capable of establishing hydrogen interactions are disposed in the interior of the main chain, in repetitive moieties.
• Cases (4) and (5) correspond to copolymers in which the groups capable of establishing hydrogen interactions are disposed on branches of the main chain of a first series of moieties that are copolymerized with moieties not containing groups capable of establishing hydrogen interactions.
• the polymers and copolymers used in the composition of the invention advantageously have a solid-liquid transition temperature of 45° C. to 190° C.
• they Preferably they have a solid-liquid transition temperature ranging from 70° C. to 130° C. and better from 80° C. to 105° C.
• the oil-type structuring agent may also be chosen from among the non-polymeric molecular organic gelling agents, also referred to as organo gelling agents, which are compounds whose molecules are capable of establishing physical interactions between one another, leading to auto-aggregation of the molecules with formation of a supra-molecular 3D network, which is responsible for the gelling of the oil or oils (also referred to as liquid fatty phase).
• organo gelling agents which are compounds whose molecules are capable of establishing physical interactions between one another, leading to auto-aggregation of the molecules with formation of a supra-molecular 3D network, which is responsible for the gelling of the oil or oils (also referred to as liquid fatty phase).
• the supra-molecular network may result from the formation of a network of fibrils (due to stacks or aggregations of molecules of organo gelling agent), immobilizing the molecules of the liquid fatty phase.
• each molecule of an organo gelling agent may establish several types of physical interactions with a neighboring molecule.
• the molecules of organo gelling agents according to the invention advantageously contain at least one group capable of establishing hydrogen bonds and better at least two groups capable of establishing hydrogen bonds, at least one aromatic ring and better at least two aromatic rings, at least one or more ethylenically unsaturated bonds and/or at least one or more asymmetric carbons.
• the groups capable of forming hydrogen bonds are chosen from among the hydroxyl, carbonyl, amine, carboxylic acid, amide, urea, benzyl groups and associations thereof.
• the organo gelling agent or agents according to the invention are soluble in the liquid fatty phase after heating until a transparent homogeneous liquid phase is obtained. They may be solid or liquid at room temperature and atmospheric pressure.
• the molecular organo gelling agent or agents that can be used in the composition according to the invention are in particular those described in the document “Specialist Surfactants”, edited by D. Robb, 1997, pp. 209-263, Chapter 8 by P. Terech, European Applications EP A 1068854 and EP A 1086945, or else in Application WO A 02/47031.
• organo gelling agents there may be cited in particular the amides of carboxylic acids, particularly the tricarboxylic acids, such as the cyclohexanetricarboxamides (see European Patent Application EP A 1068854), the diamides having hydrocarbon chains that each contain 1 to 22 carbon atoms, for example 6 to 18 carbon atoms, the said chains being non-substituted or substituted with at least one substituent chosen from among the ester, urea and fluoro groups (see Application EP A 1086945) and especially the diamides resulting from the reaction of diaminocyclohexane, in particular of diaminocyclohexane in trans form, and of an acid chloride such as, for example, N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane, the amides of N-acylamino acids, such as the diamides resulting from the action of an N-acylamino acid with amines
• organo gelling agents there may also be used compounds of bis-urea type of the following general formula:
• R1 is a linear or branched C 1 to C 4 alkyl radical and the * symbolize the points of attachment of group A to each of the two nitrogen atoms of the rest of the compound of general formula (I), and
• n is between 0 and 100, especially between 1 and 80, even 2 to 20; and R2 and R6 are, independently of one another, carbon radicals, especially linear or branched hydrocarbons (alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may comprise 1 to 4 hetero atoms, especially O;
• n is between 0 and 100, especially between 1 and 80, even 2 to 20; and R′2 and R′6 are, independently of one another, carbon radicals, especially linear or branched hydrocarbons (alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may comprise 1 to 4 hetero atoms, especially O. and
• group A may be of formula:
• R1 may be a methyl group, thus leading to a group A of formula:
• the compounds according to the invention may be in the form of a mixture associated with the fact that A may be a mixture of 2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4 isomer)/2,6 isomer) varying from 95/5 to 80/20.
• At least one of the radicals R and/or R′ must be of formula (III):
• L is preferably a divalent carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkylene), comprising 1 to 18 carbon atoms, which may comprise 1 to 4 hetero atoms chosen from among N, O and S.
• the carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms.
• L is chosen from among the methylene, ethylene, propylene, butylene radicals and especially n-butylene or octylene.
• the radical L may also be branched, for example of the —CH 2 —CH(CH 3 )— type, which leads to the following radical of formula III):
• the radical Ra may be a carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S.
• the carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms; in particular the hetero atoms may form one or more —SiO— (or —OSi)— groups.
• Ra may be methyl, ethyl, propyl or butyl.
• the radical Ra may also be a silicone radical of formula:
• R2 to R6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R2 to R6 may be chosen from among methyl, ethyl, propyl, butyl; and in particular a radical:
• n 1 to 100; and even more particularly a radical:
• the radicals Rb and Rc may be carbon radicals, especially saturated or unsaturated, linear, branched and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S.
• alkyl saturated or unsaturated, linear, branched and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S.
• the carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms; in particular the hetero atoms may form one or more —SiO— (or —OSi)— groups.
• Rb and/or Rc may be methyl, ethyl, propyl or butyl;
• n is between 0 and 100, especially between 1 and 80, even 2 to 20; and R′2 to R′6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R′2 to R′6 may be chosen from among methyl, ethyl, propyl, butyl.
• radicals R and/or R′ are preferably chosen from among the following radicals:
• L is preferably a linear or branched C1-C8 alkylene radical, especially methylene, ethylene, propylene, butylene and especially n-butylene, octylene or of formula —CH 2 —CH(CH 3 )—.
• R and R′ are both of formula (III).
• one of the radicals R or R′ represents a saturated or unsaturated, linear, branched and/or cyclic C 1 to C 30 alkyl radical, possibly comprising 1 to 3 hetero atoms chosen from among O, S, F and N.
• radical R or R′ may be a group chosen from among:
• R or R′ represents a saturated or unsaturated, preferably non-cyclic, branched, especially singly branched alkyl radical comprising 3 to 16 carbon atoms, especially 4 to 12, even 4 to 8 carbon atoms, and possibly comprising 1 to 3 hetero atoms chosen from among O, S, F and/or N, preferably O and/or N.
• R or R′ may be tert-butyl or 2-ethylhexyl radicals or of formula:
• the ratio between n R and n R′ is preferably between 5/95 and 95/5, for example between 10/90 and 90/10, in particular between 40/60 and 85/15, especially between 50/50 and 80/20, even between 60/40 and 75/25; where n R is the number of moles of NH 2 —R amine and n R′ is the number of moles of NH 2 —R′ amine used to prepare the compound of formula (I).
• the compounds according to the invention may have the form of salts and/or isomers of compounds of formula (I).
• the compounds of general formula (I) according to the invention may be prepared as described in Application FR 2910809.
• non-silicone bis-urea compounds may correspond to the following general formula (II):
• R′ is a linear or branched C 1 to C 4 alkyl radical and the * symbolize the points of attachment of the group A to each of the two nitrogen atoms of the rest of the compound of general formula (II), and
• the group represented by A is a group of formula:
• R′ and the * are such as defined in the foregoing.
• R′ may be a methyl group, and the group A is then more particularly a group of formula:
• R may be chosen from among the singly branched radicals of general formula C n H 2n+1 , where n is an integer varying from 6 to 15, particularly from 7 to 9, even equal to 8.
• R of the compound of formula (II) may respectively represent a group:
• R may be chosen from among the singly branched radicals of general formula C m-p H 2m+1 ⁇ 2p X p , where p is equal to 1, 2 or 3, preferably equal to 1, m is an integer varying from 6 to 15, preferably from 10 to 14, in particular from 10 to 12, even equal to 11, and X represents sulfur and/or oxygen atoms, in particular oxygen atoms.
• R may be a radical of formula C m′ H 2m′ X—(C p′ H 2p′ X′) r —C x H 2x+1 , in which X and X′ are, independently of one another, an oxygen or sulfur atom, preferably oxygen, r is equal to 0 or 1, m′, p′ and x are integers such that their sum varies from 6 to 15, in particular from 10 to 12, is even equal to 11, and its being understood that at least one of the carbon chains C m′ H 2m′ , C p′ H 2p′ or C x H 2x+1 is branched.
• the C x H 2x+1 chain is branched, preferably r is equal to 0, preferably m′ is an integer varying from 1 to 10, especially from 2 to 6, in particular equal to 3, and/or preferably x is an integer varying from 4 to 16, especially from 6 to 12, in particular equal to 8.
• R of the compound of formula (I) may respectively represent a group:
• Such compounds may be present in the compositions according to the invention in mixtures with isomers, especially position isomers on group A, especially in proportions of 95/5 or 80/20.
• isomers especially position isomers on group A, especially in proportions of 95/5 or 80/20.
• the presence of one or the other of its radicals in the molecule of general formula (II) proves particularly advantageous for conferring universal character within the meaning of the invention upon the corresponding non-silicone bis-urea derivatives.
• non-silicone bis-urea derivatives following formula (III):
• R 1 is a saturated or unsaturated, branched, non-cyclic C 3 to C 15 carbon radical, possibly containing 1 to 3 hetero atoms chosen from among O, S, F and N and/or a carbonyl, and combinations thereof,
• R 2 is different from R 1 and is chosen from among the linear, branched or cyclic, saturated or unsaturated C 1 -C 24 alkyl radicals, possibly containing 1 to 3 hetero atoms chosen from among O, S, F and N, and possibly substituted by:
• n and m are equal, and more particularly are equal to zero, and R 3 is a radical R′ 3 such as defined below.
• R 3 is a radical R′ 3 such as defined below.
• A preferably represents a group
• R 3 ′ is a linear or branched C 1 to C 4 alkyl radical and * symbolize the point of attachment of the group A to the two nitrogen atoms of the rest of the compound of general formula (III).
• the compound of general formula (III) comprises, by way of A, at least one group chosen from among:
• R 3 ′ and * are such as defined in the foregoing.
• R 3 ′ may be a methyl group, and in this case group A represents a group
• the compounds are such that A is a mixture of 2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4 isomer)/2,6 isomer) varying from 95/5 to 80/20.
• the compound of general formula (III) comprises, by way of R 1 , a branched C 6 -C 15 radical.
• the compound of general formula (III) comprises, by way of R 1 , a compound chosen from among:
• R 2 which is different from R 1 , it may be advantageously chosen from among the following groups:
• the described compounds may be prepared as described in Application FR 2910809.
• fatty-phase rheological agent there may also be used grafted or sequenced block polymers.
• grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer, such as the graft copolymers of acrylic/silicone type, which may be employed in particular when the non-aqueous medium is a silicone.
• grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one polyether.
• the polyorganopolysiloxane block may be in particular a polydimethylsiloxane or else even a poly (C 2 -C 18 ) alkyl methylsiloxane;
• the polyether block may be a poly (C 2 -C 18 ) alkylene, particularly polyoxyethylene and/or polyoxypropylene.
• copolyol dimethicones or copolyol (C 2 -C 18 ) alkyl dimethicones such as those sold under the name “Dow Corning 3225C” by the Dow Corning Company
• the lauryl dimethicones such as those sold under the name “Dow Corning Q2-5200” by the Dow Corning Company.
• grafted or sequenced block copolymers there may also be cited those comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds, which may be conjugated, such as ethylene or the dienes such as butadiene and isoprene, and at least one block of a vinyl and better styrene polymer.
• the ethylenic monomer contains several ethylenic bonds, which may be conjugated, the residual ethylenic unsaturations after polymerization are generally hydrogenated.
• the polymerization of isoprene leads, after hydrogenation, to the formation of ethylene-propylene block
• the polymerization of butadiene leads, after hydrogenation, to the formation of ethylene-butylene block.
• sequenced copolymers especially of “diblock” or “triblock” type of the polystyrene/polyisoprene (SI), polystyrene/polybutadiene (SB) type, such as those sold under the name of ‘LUVITOL HSB’ by BASF, of the polystyrene/copoly(ethylene-propylene) (SEP) type, such as those sold under the name of ‘Kraton’ by Shell Chemical Co or even of the polystyrene/copoly(ethylene-butylene) (SEB) type.
• SI polystyrene/polyisoprene
• SB polystyrene/polybutadiene
• SEP polystyrene/copoly(
• Kraton G1650 SEBS
• Kraton G1651 SEBS
• Kraton G1652 SEBS
• Kraton G1657X SEBS
• Kraton G1701X SEP
• Kraton G1702X SEP
• Kraton G1726X SEB
• Kraton D-1102(SBS) Kraton D-1107(SIS)
• the polymers are generally referred to as hydrogenated or non-hydrogenated diene copolymers.
• Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 may also be used Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 (mixture of triblock and star polymer), Versagel 5960 of Penreco (triblock+star polymer); OS129880, OS129881 and OS84383 of Lubrizol (styrene/methacrylate copolymer).
• grafted or sequenced block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds and at least one block of an acrylic polymer
• poly(methyl methacrylate)/polyisobutylene bisequenced or trisequenced copolymers or the graft copolymers with poly(methyl methacrylate) skeleton and polyisobutylene grafts there may be cited the poly(methyl methacrylate)/polyisobutylene bisequenced or trisequenced copolymers or the graft copolymers with poly(methyl methacrylate) skeleton and polyisobutylene grafts.
• grafted or sequenced block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds and at least one block of a polyether such as a C 2 -C 18 polyalkylene (especially containing polyethylene and/or polyoxypropylene) there may be cited the polyoxyethylene/polybutadiene or polyoxyethylene/polyisobutylene bisequenced or trisequenced copolymers.
• a polyether such as a C 2 -C 18 polyalkylene (especially containing polyethylene and/or polyoxypropylene)
• elastomer there is understood a deformable, flexible solid material having viscoelastic properties, and especially the consistency of a sponge. This elastomer is formed from polymeric chains of high molecular weight, whose mobility is limited by a uniform network of cross-linking points.
• the elastomeric organopolysiloxanes used in the composition according to the invention are preferably partly or completely cross-linked. They have the form of particles.
• the elastomeric organopolysiloxane particles have a size ranging from 0.1 to 500 ⁇ m preferably from 3 to 200 ⁇ m and better from 3 to 50 ⁇ m.
• These particles may have any shape and for example may be spherical, flat or amorphous.
• these elastomeric organopolysiloxanes When they are included in an oil phase, these elastomeric organopolysiloxanes become transformed, depending on the proportion of the oil phase used, into a product of spongy appearance when they are used in the presence of low contents of oil phase, or into a homogeneous gel in the presence of higher quantities of oil phase.
• the gelling of the oil phase by these elastomers may be total or partial.
• the elastomers of the invention may be conveyed in the form of anhydrous gel composed of an elastomeric organopolysiloxane and of an oil phase.
• the oil phase used during the manufacture of the anhydrous elastomeric organopolysiloxane gel contains one or more oils that are liquid at room temperature (25° C.), chosen from among the hydrocarbon oils and/or the silicone oils.
• the oil phase is a silicone liquid phase containing one or more oils chosen from among the linear chain or cyclic polydimethylsiloxanes that are liquid at room temperature, possibly containing an alkyl or aryl chain of pendant type or at the end of the chain, the alkyl chain having 1 to 6 carbon atoms.
• the elastomeric organopolysiloxanes used according to the invention may be obtained by addition and cross-linking reaction, in the presence of a catalyst, preferably a catalyst of platinum type, of at least:
• the first organopolysiloxane (i) is chosen from among the polydimethylsiloxanes; it is preferably an ⁇ - ⁇ -dimethylvinyl polydimethylsiloxane.
• the organopolysiloxane is preferably in a gel obtained according to the following steps:
• the cross-linked organopolysiloxane may be obtained by a polymeric addition reaction of an organohydrogenpolysiloxane of formula (I) with an organopolysiloxane of formula (II) and/or an unsaturated hydrogen chain of formula (III).
• the cross-linked organopolysiloxane is obtained by a polymeric reaction of an organohydrogenpolysiloxane of formula (I) with an organopolysiloxane of formula (II).
• the organohydrogenopolysiloxane of formula (I) comprises at least one structural unit chosen in the group composed of an SiO 2 unit, an HSiO 1.5 unit, an RSiO 1.5 unit, an RHSiO unit, an R 2 SiO unit, an R 3 SiO 0.5 unit and an R 2 HSiO 0.5 unit, wherein the group R in these units is a monovalent hydrocarbon chain containing 1 to 16 carbon atoms and may or may not be substituted, but is different from an unsaturated aliphatic group and possesses on average at least 1.5 hydrogen atoms bonded to a silicon atom.
• the group R in the organohydrogenopolysiloxane of formula (I) may be an alkyl group containing 1 to 16, preferably 10 to 16 carbon atoms.
• This group R may be, for example, a methyl group, an ethyl group, a propyl group, a lauryl group, a myristyl group and a palmityl group.
• the group R in the organohydrogenopolysiloxane of formula (I) may also be an aryl group such as a phenyl or tolyl group.
• the group R may also be a monovalent hydrocarbon chain comprising a cycloalkyl group such as cyclohexyl or else a hydrocarbon chain substituted by one, two or more groups chosen from among a halogen atom such as chlorine, bromine, fluorine and a cyano group, for example an ⁇ -trifluoropropyl or chloromethyl group.
• a halogen atom such as chlorine, bromine, fluorine and a cyano group, for example an ⁇ -trifluoropropyl or chloromethyl group.
• the group R preferably represents at least 30 mol % of methyl groups and from 5 to 50 mol %, preferably from 10 to 40 mol % of hydrocarbon chains containing 10 to 16 carbon atoms.
• the hydrocarbon chain may then advantageously contain at least one lauryl group, and even the majority of the groups R may be lauryl groups.
• the organohydrogenopolysiloxane of formula (I) may be linear, branched or cyclic.
• the organohydrogenopolysiloxane of formula (I) preferably contains 2 to 50 and even more preferably 2 to 10 hydrogen atoms bonded to a silicon atom (Si—H).
• the content of hydrogen atoms bonded to a silicon atom in this compound of formula (I) traditionally varies from 0.5 to 50 mol %, and even more preferably from 1 to 20 mol % relative to the total sum of the hydrogen atoms and of all the organic groups bonded to a silicon atom.
• the organopolysiloxane of formula (II) comprises at least one structural unit chosen in the group composed of an SiO 2 unit, a (CH 2 ⁇ CH)SiO 1.5 unit, an RSiO 1.5 unit, an R(CH 2 ⁇ CH)SiO unit, an R 2 SiO unit, an R 3 SiO 05 unit and an R 2 (CH 2 ⁇ CH)SiO 0.5 unit, wherein the group R is such as defined in formula (I) and possesses on average at least 1.5 vinyl groups bonded to a silicon atom.
• This compound preferably contains 2 to 50 vinyl groups bonded to a silicon atom.
• the mean number of vinyl groups bonded to a silicon atom preferably varies from 2 to 10 and even more preferably from 2 to 5.
• At least 30 mol % of the groups R are methyl groups and 5 to 50 mol %, preferably from 10 to 40 mol % of the groups R are a hydrocarbon chain containing 10 to 16 carbon atoms.
• the organopolysiloxane of formula (II) may be linear, branched or cyclic.
• the content of vinyl groups in the compound of formula (II) preferably varies between 0.5 and 50 mol %, and even more preferably from 1 to 20 mol % relative to all the organic groups bonded to a silicon atom.
• the unsaturated hydrocarbon chain of formula (III) corresponds to the following formula:
• n is an integer varying from 2 to 6 and x is an integer equal to at least 1.
• x is preferably an integer varying from 1 to 20.
• cross-linked organopolysiloxanes there are preferred the cross-linked polyalkyl dimethylsiloxanes.
• polyalkyl dimethylsiloxane there is understood a linear organopolysiloxane of formula (IV)
• Ra is an alkyl group containing 10 to 16 carbon atoms, and preferably it may be a lauryl group
• ya is an integer from 1 to 100
• za is an integer from 1 to 100
• yb is an integer from 1 to 100
• zb is an integer from 1 to 100.
• non-emulsifying elastomers that can be used according to the invention there are preferably used the dimethicone/vinyl dimethicone copolymers (INCI name: Dimethicone/Vinyldimethicone crosspolymer), and the vinyl dimethicone/alkyl dimethicone copolymers, such as the vinyl dimethicone/lauryl dimethicone copolymers (INCI name: Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer).
• dimethicone/vinyl dimethicone copolymers INCI name: Dimethicone/Vinyldimethicone crosspolymer
• vinyl dimethicone/alkyl dimethicone copolymers such as the vinyl dimethicone/lauryl dimethicone copolymers (INCI name: Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer).
• non-emulsifying elastomer there may also be cited spherical non-emulsifying silicone elastomers in the form of elastomeric cross-linked organopolysiloxane powder coated with silicone resin, especially silsesquioxane resin, such as described, for example, in U.S. Pat. No. 5,538,793.
• spherical non-emulsifying silicone elastomers in the form of elastomeric cross-linked organopolysiloxane powder coated with silicone resin, especially silsesquioxane resin, such as described, for example, in U.S. Pat. No. 5,538,793.
• Such elastomers are sold under the trade names ‘KSP-100”, KSP-101”, “KSP-102”, “KSP-103”, “KSP-104”, “KSP-105” by the Shin Etsu Company.
• elastomeric cross-linked organopolysiloxanes in the form of spherical powders may be hybrid silicone powders functionalized by fluoroalkyl groups, especially sold under the trade name “KSP-200” by the Shin Etsu Company; hybrid silicone powders functionalized by phenyl groups, especially sold under the trade name “KSP-300” by the Shin Etsu Company.
• silicone elastomers with MQ groups such as those sold by the Wacker Company under the trade names Belsil RG100, Belsil RPG33 and preferably RG80. These particular elastomers, when they are in association with the resins according to the invention, may make it possible to improve the non-transfer properties of compositions comprising them.
• liquid crystal agents there is understood compounds generating a mesomorphic state, or in other words a state for which melting of the crystals makes it possible to obtain liquids possessing optical properties comparable to those of certain crystals. These compounds are defined more precisely in the Liquid Crystals chapter of Ullmann's Encyclopedia.
• liquid crystal agents are described in particular in the patents or patent applications EP 545409, WO 94109086, EP 709445, GB 2282145, GB 2276883, WO 95132247, WO 95132248, EP 686674, EP 711780.
• liquid crystal agents may react in response to vibrations by a change in viscosity and/or by a change of color.
• the compounds generating a mesomorphic state are compounds with cholesteric function, whose structure is the following:
• R is an alkyl, alkylcarbonyl group comprising 1 to 30 carbon atoms, which may or may not be substituted by cyclic, aromatic, halogen groups, which may or may not be branched.
• liquid crystals satisfying this definition: cholesterol erucyl carbonate, cholesterol methyl carbonate, cholesterol oleyl carbonate, cholesterol para-nonylphenyl carbonate, cholesterol phenyl carbonate, cholesterol acetate, cholesterol benzoate, cholesterol butyrate, cholesterol isobutyrate, cholesterol chloride, cholesterol chloroacetate, cholesterol cinnamate, cholesterol crotanoate, cholesterol decanoate, cholesterol erucate, cholesterol heptanoate, cholesterol hexanoate, cholesterol myristate, cholesterol nonanoate, cholesterol octanoate, cholesterol oleate, cholesterol propionate, cholesterol valerate, dicholesteryl carbonate.
• composition according to the invention may contain a continuous aqueous phase or a continuous oil phase.
• composition of continuous aqueous phase there is understood that the composition has a conductivity, measured at 25° C., greater than or equal to 23 S/cm (microSiemens/cm), the conductivity being measured, for example, by means of an MPC227 conductimeter of Mettler Toledo and an Inlab730 conductivity measuring cell.
• the measuring cell is immersed in the composition, in such a way as to eliminate the air bubbles that tend to form between the 2 electrodes of the cell.
• the conductivity reading is taken as soon as the value of the conductimeter has stabilized. A mean is established over at least 3 successive measurements.
• composition of continuous oil phase there is understood that the composition has a conductivity, measured at 25° C., greater than or equal to 23 ⁇ S/cm (microSiemens/cm), the conductivity being measured, for example, by means of an MPC227 conductimeter of Mettler Toledo and an Inlab730 conductivity measuring cell.
• the measuring cell is immersed in the composition, in such a way as to eliminate the air bubbles that tend to form between the 2 electrodes of the cell.
• the conductivity reading is taken as soon as the value of the conductimeter has stabilized.
• a mean is established over at least 3 successive measurements.
• compositions may contain 1 to 60% of fatty-phase rheological agent.
• the composition may contain 2% to 50% by weight, better 5% to 40% of fatty-phase rheological agent.
• composition comprises a fatty-phase rheological agent
• it contains a continuous oil phase.
• composition according to the invention may comprise at least one wax.
• compositions according to the invention may therefore comprise at least one wax, and mixture 1) described hereinabove.
• wax within the meaning of the present invention there is understood a lipophilic compound, solid at room temperature (25° C.), with reversible change of state between solid and liquid, having a melting point higher than or equal to 30° C. and possibly up to 120° C.
• the melting point of the wax may be measured by means of a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the trade name DSC 30 by the METTLER Company.
• D.S.C. differential scanning calorimeter
• the waxes may be hydrocarbon, fluoro and/or silicone and be of vegetable, mineral, animal and/or synthetic origin.
• the waxes have a melting temperature higher than 25° C. and better higher than 45° C.
• the wax or the mixture of waxes is present in a content at least equal to 7% by weight. Preferably, it is present in a content ranging from 10 to 40% by weight relative to the total weight of the composition, better from 15 to 35% and even better from 16 to 30% by weight.
• hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, carnauba wax, ouricurry wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and the waxy copolymers as well as the esters thereof.
• waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains There may also be cited the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains.
• hydrogenated jojoba oil hydrogenated sunflower seed oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, di-(trimethylol-1,1,1-propane) tetrastearate sold under the trade name “HEST 2T-4S” by the HETERENE Company, di-(trimethylol-1,1,1-propane) tetrabehenate sold under the trade name HEST 2T-4B by the HETERENE Company.
• wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the trade name “PHYTOWAX Olive 18 L 57” or else the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the trade name “PHYTOWAX ricin 16L64 and 22L73” by the SOPHIM Company.
• PHYTOWAX ricin 16L64 and 22L73 such waxes are described in Application FR A 2792190.
• compositions according to the invention may comprise at least one wax referred to as tacky wax, or in other words possessing a tack greater than or equal to 0.7 N.s and a hardness smaller than or equal to 3.5 MPa.
• a tacky wax especially may make it possible to obtain a cosmetic composition that is applied easily on the eyelashes, clings well to the eyelashes and leads to the formation of a smooth, homogeneous and thickening makeup.
• the tacky wax used may possess especially a tack ranging from 0.7 N.s to 30 N.s, in particular greater than or equal to 1 N.s, especially ranging from 1 N.s to 20 N.s, in particular greater than or equal to 2 N.s, especially ranging from 2 N.s to 10 N.s and in particular ranging from 2 N.s to 5N.s.
• the tack of the wax is determined by measuring the evolution of force (compression force or stretching force) as a function of time at 20° C. by means of the texturometer sold under the trade name “TA-TX2i®” by the RHEO Company, equipped with an acrylic polymer traveler in the form of a cone having an angle of 45°.
• the measurement protocol is the following:
• the wax is melted at a temperature equal to the melting point of the wax +10° C.
• the molten wax is cast in a receptacle of 25 mm diameter and 20 mm depth.
• the wax is recrystallized at room temperature (25° C.) for 24 hours, in such a way that the surface of the wax is plane and smooth, then the wax is kept for at least 1 hour at 20° C. before the measurement of the tack is carried out.
• the traveler of the texturometer is displaced at a speed of 0.5 mm/s, then penetrates into the wax as far as a penetration depth of 2 mm.
• the traveler is maintained in fixed position for 1 second (corresponding to the relaxation time) then is withdrawn at a speed of 0.5 mm/s.
• the tack corresponds to the integral of the curve of force as a function of time for the part of the curve corresponding to the negative values of force (stretching force).
• the value of the tack is expressed in N.s.
• the tacky wax that may be used generally has a hardness of smaller than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa, even better ranging from 0.1 MPa to 2.5 MPa.
• the hardness is measured according to the protocol described in the foregoing.
• tacky wax there may be used a C20-C40 alkyl(hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms) alone or in a mixture, in particular a C20-C40 alkyl 12-(12′-hydroxystearyloxy) stearate of formula (II):
• m is an integer ranging from 18 to 38, or a mixture of compounds of formula (II).
• Such a wax is sold in particular under the trade names “Kester Wax K 82 P®” and “Kester Wax K 80 P®” by the KOSTER KEUNEN Company.
• the waxes cited above generally have a starting melting point lower than 45° C.
• microcrystalline wax sold under the reference SP18 by the STRAHL and PITSCH Company, which wax has a hardness of approximately 0.46 MPa and a tack value of approximately 1 N.s.
• the wax or waxes may be present in the form of an aqueous microdispersion of wax.
• aqueous microdispersion of wax there is understood an aqueous dispersion of wax particles in which the size of the said wax particles is smaller than or equal to approximately 1 ⁇ M.
• microdispersions of wax are stable dispersions of colloidal particles of wax, and are described in particular in “Microemulsions Theory and Practice”, L.M. Prince Ed., Academic Press (1977) pages 21-32.
• these wax microdispersions may be obtained by melting the wax in the presence of a surfactant and possibly a portion of water, then progressively adding hot water with agitation. There is observed the intermediate formation of an emulsion of water-in-oil type, followed by a phase inversion that finally yields a microemulsion of the oil-in-water type. Upon cooling, there is obtained a stable microdispersion of solid colloidal particles of wax.
• the wax microdispersions may also be obtained by agitation of the mixture of wax, surfactant and water using agitation means such as ultrasound, high-pressure homogenizer, turbines.
• the particles of the wax microdispersion preferably have mean dimensions smaller than 1 ⁇ m (in particular ranging from 0.02 ⁇ m to 0.99 ⁇ m), preferably smaller than 0.5 ⁇ m (in particular ranging from 0.06 ⁇ m to 0.5 ⁇ m).
• These particles are composed substantially of a wax or of a mixture of waxes. Nevertheless, they may comprise a minority proportion of fatty oil and/or paste additives, a surfactant and/or a common fat-soluble additive/active substance.
• composition according to the invention may comprise at least one hydrophilic gelling agent, also referred to as hydrophilic thickening agent hereinafter.
• thickening agents may be used alone or in association. These thickening agents may be chosen in particular from among the gums and the cellulose polymers.
• hydrophilic thickening agent there is understood a thickening agent that is soluble or dispersible in water.
• hydrophilic thickening agents there may be cited in particular the water-soluble or water-dispersible thickening polymers. These may be chosen in particular from among:
• the hydrophilic thickening agent may be chosen from among the associative polymers.
• associative polymer within the meaning of the present invention there is understood any amphiphilic polymer containing in its structure at least one fatty chain and at least one hydrophilic portion.
• the associative polymers according to the present invention may be anionic, cationic, non-ionic or amphoteric.
• associative anionic polymers there may be cited those containing at least one hydrophilic moiety and at least one fatty-chain allyl ether moiety, more particularly from among those whose hydrophilic moiety is composed of an ethylenically unsaturated anionic monomer, more particularly of a vinyl carboxylic acid and very particularly of an acrylic acid, a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether moiety corresponds to the monomer of the following formula (I):
• R′ denotes H or CH 3
• B denotes the ethyleneoxy radical
• n is zero or denotes an integer ranging from 1 to 100
• R denotes a hydrocarbon radical chosen from among the alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals comprising 8 to 30 carbon atoms, preferably 10 to 24, and still more particularly 12 to 18 carbon atoms.
• Anionic amphiphilic polymers of this type are described and prepared according to an emulsion polymerization method in EP Patent 0216479.
• anionic polymers there may also be cited the anionic polymers containing at least one hydrophilic moiety of olefinically unsaturated carboxylic acid type, and at least one hydrophobic moiety exclusively of the type (C 10 -C 30 ) alkyl ester of unsaturated carboxylic acid.
• cationic associative polymers there may be cited the quaternized cellulose derivatives and the polyacrylates with amino side groups.
• the non-ionic associative polymers may be chosen from among:
• the associative polymer is chosen from among the associative polyurethanes.
• the associative polyurethanes are non-ionic sequenced copolymers containing, in the chain, both hydrophilic sequences, most often of polyoxyethylene nature, and hydrophobic sequences, which may be aliphatic chains alone and/or cycloaliphatic and/or aromatic chains.
• these polymers contain at least two lipophilic hydrocarbon chains having C 6 to C 30 carbon atoms, separated by a hydrophilic sequence, wherein the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence.
• the polymer may contain a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.
• the associative polyurethanes may be sequenced in triblock or multiblock form. The hydrophobic sequences may therefore be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (multisequenced copolymer, for example).
• the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylene chain containing 50 to 1,000 oxyethylene groups.
• the associative polyurethanes contain a urethane bond between the hydrophilic sequences, thus explaining the origin of the name.
• associative polymers that can be used in the invention there may be cited the polymer C 16 —OC 120 —C 16 of the SERVO DELDEN Company (under the name SER AD FX1100, a molecule with urethane function and weight-average molecular weight of 1300), OE being one oxyethylene moiety.
• Rheolate 205 with urea function sold by the RHEOX Company or else Rheolate 208 or 204 or even Rheolate FX 1100 by Elementis.
• These associative polyurethanes are sold in pure form.
• the product DW 1206B of ROHM & HAAS with C 20 alkyl chain and urethane bond, sold as 20% dry material in water, may also be used.
• composition according to the invention may comprise at least one filler.
• the filler or fillers may be present in a content ranging from 0.01% to 50% by weight relative to the total weight of the composition, preferably ranging from 0.01 to 30% by weight.
• fillers there must be understood particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers are used in particular to modify the rheology or the texture of the composition.
• the fillers may be mineral or organic of any platelet, spherical or oblong shape, regardless of the crystallographic form (for example layered, cubic, hexagonal, orthorhombic, etc.).
• talc talc
• mica silica
• kaolin polyamide powders
• polyamide powders Nylon® (Orgasol® of Atochem)
• the powders of polymethyl methacrylate the powders of acrylic polymers, poly- ⁇ -alanine and polyethylene
• lauroyl lysine powders starch powders
• the powders of cellulose, boron nitride the hollow microspheres of organic polymers, especially the polymeric hollow microspheres of polyvinylidine chloride/acrylonitrile, such as Expancel® (Nobel Industrie), of acrylic acid copolymers (Polytrap of the Dow Corning Company) and the microbeads of silicone resin (
• the inventors have shown a synergic effect of the association of the resins according to the invention with at least one filler made it possible to improve the matt property and the staying power of the matt property over time in skin care or makeup compositions compared with a composition comprising the same filler without the resins according to the invention.
• the association of resins according to the invention with at least one filler of mineral nature, possibly in association with at least one organic filler makes it possible to obtain a product whose finish is gentle and whose cosmetic properties are stable in time, especially throughout the entire day.
• the product also glides on the skin during application, without a sensation of rubbing, and imparts a soft feel to the said skin.
• mineral fillers there may be cited in particular talc, mica, silica, kaolin, boron nitride, precipitated calcium carbonate, magnesium carbonate and bicarbonate, hydroxyapatite, the microspheres of hollow silica (Silica Beads® of Maprecos), the microcapsules of glass or ceramic, clay, quartz, the powder of natural diamond or mixtures thereof.
• silica powder there may be cited:
• the silicas such as the hollow silica microspheres, in particular the SB700® of Miyoshi Kasei.
• the composition according to the invention additionally comprises at least one other filler.
• the said at least one other filler may be mineral or organic. It may therefore be a mixture of mineral and organic fillers.
• composition according to the invention may contain a mineral filler and one other mineral filler, the said mineral fillers being such as defined hereinabove, and possibly at least one organic filler such as defined below.
• composition according to the invention may contain one mineral filler and one organic filler.
• organic fillers there may be cited in particular the polyamide powders (Nylon® or Orgasol® of Arkema), the powders of acrylic polymers, especially the powders of polymethyl methacrylate, polymethyl methacrylate/ethylene glycol dimethacrylate, allyl polymethacrylate/ethylene glycol dimethacrylate, ethylene glycol dimethacrylate/lauryl methacrylate copolymer, the powders of cellulose, poly- ⁇ -alanine and polyethylene, the powders of tetrafluoroethylene polymers (Teflon®), Iauroyl lysine, starch, the polymeric hollow microspheres such as those of polyvinylidine chloride/acrylonitrile, such as Expancel® (Nobel Industrie), of acrylic acid copolymers (Polytrap of the Dow Corning Company) and the microbeads of silicone resin (Tospearls® of Toshiba, for example), the particles of elastomeric polyorganosiloxanes
• elastomeric silicone powder there may be cited the powders sold under the trade names “Trefil® Powder E-505C”, “Trefil® Powder E-506C” by the DOW CORNING Company.
• the organic filler corresponds to the polyamide powders.
• composition according to the invention comprises mineral fillers and other fillers of organic type, they may be advantageously in the same composition in a ratio of mineral fillers/organic fillers greater than or equal to 1.
• the filler may be chosen from among the fillers referred to as “sebum absorbent”.
• the sebum absorbent filler may be a mineral powder or an organic powder; it may be chosen from among silica, the polyamide powders (Nylon®), the powders of acrylic polymers, especially of polymethyl methacrylate, of polymethyl methacrylate/ethylene glycol dimethacrylate, of allyl polymethacrylate/ethylene glycol dimethacrylate, of ethylene glycol dimethacrylate/lauryl methacrylate copolymer; polymeric hollow microspheres of polyvinylidine chloride/acrylonitrile, the powders of elastomeric silicone, especially obtained by polymerization of organopolysiloxane having at least two hydrogen atoms each bonded to a silicon atom and of an organopolysiloxane comprising at least two groups with ethylenic unsaturation (especially two vinyl groups) in the presence of a platinum catalyst.
• the polyamide powders Nylon®
• the powders of acrylic polymers especially of polymethyl methacrylate, of polymethyl me
• the sebum-absorbent powder may be a powder coated with a hydrophobic treatment agent.
• the hydrophobic treatment agent may be chosen from among the fatty acids, such as stearic acid; the metal soaps, such as aluminum dimyristate, the aluminum salt of hydrogenated suet glutamate; the amino acids; the N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, and mixtures thereof.
• the N-acyl amino acids may comprise an acyl group having 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.
• the salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium, potassium salts.
• the amino acid may be, for example, lysine, glutamic acid, alanine.
• alkyl mentioned in the compounds cited in the foregoing denotes in particular an alkyl group having 1 to 30 carbon atoms, preferably having 5 to 16 carbon atoms.
• silica powder there may be cited:
• polymeric hollow microspheres of polyvinylidine chloride/acrylonitrile there may be cited those sold under the trade name Expancel® by the Nobel Industrie Company.
• elastomeric silicone powder there may be cited the powders sold under the trade names “Trefil® Powder E-505C”, “Trefil® Powder E-506C” by the DOW CORNING Company.
• the solid particles such as the pulverulent coloring materials (pigments and nacres) and the fillers may be surface-treated completely or partly with a compound of silicone nature, a compound of fluoro nature, a compound of fluorosilicone nature, a fatty acid or amino acid or one of the mixtures thereof.
• the skin makeup or care compositions and especially the foundations may comprise solid particles surface-treated completely or partly with a compound of fluoro nature, especially to improve the staying power of the color and of the matt property.
• the hydrophobic treatment agent may be chosen from among the silicones such as the methicones, the dimethicones, the perfluoroalkylsilanes, the perfluoroalkyl silazanes, triethoxy caprylylsilane, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone; the fatty acids such as stearic acid, the metal soaps such as aluminum dimyristate, the aluminum salt of hydrogenated suet glutamate; the perfluoroalkyl phosphates, the polyoxides of hexafluoropropylene, the polyorganosiloxanes comprising perfluoroalkyl perfluoro polyether groups, the silicone-grafted acrylic polymers (especially described in Patent Application JP A 05-339125, the contents of which are incorporated by reference); the amino acids; the N-acyl amino acids or their salts; lecithin, isopropyl tris
• the N-acyl amino acids may comprise an acyl group having 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.
• the salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium, potassium salts.
• the amino acid may be, for example, lysine, glutamic acid, alanine.
• the fluoro surface agents may be chosen from among the perfluoroalkyl phosphates, the perfluoro polyethers, polytetrafluopolyethylene (PTFE) and the perfluoroalkanes.
• perfluoro polyethers are described in particular in Patent Application EP A 486135, and are sold under the trade names FOMBLIN by the MONTEFLUOS Company.
• Perfluoroalkyl phosphates are described in particular in Patent Application JP H05-86984.
• the perfluoroalkyl diethanolamine phosphates sold by Asahi Glass under the reference AsahiGuard AG530 may be used.
• linear perfluoroalkanes there may be cited the perfluorocycloalkanes, the perfluoro(alkylcycloalkanes), the perfluoropolycycloalkanes, the perfluoro aromatic hydrocarbons (the perfluoroarenes) and the perfluoro organohydrocarbon compounds containing at least one hetero atom.
• perfluoroalkanes there may be cited the series of linear alkanes such as perfluorooctane, perfluorononane or perfluorodecane.
• perfluorocycloalkanes and the perfluoro(alkylcycloalcanes) there may be cited perfluorodecalin sold under the trade name of “FLUTEC PP5 GMP” by the RHODIA Company, perfluoro(methyldecalin), the perfluoro(C3-C5 alkyl-cyclohexanes) such as perfluoro(butylcyclohexane).
• perfluoropolycycloalkanes there may be cited the derivatives of bicyclo [3.3.1] nonane such as perfluorotrimethylbicyclo [3.3.1] nonane, the derivatives of adamantane, such as perfluorodimethyladamantane, and the perfluoro derivatives of hydrogenated phenanthrene, such as tetracosafluoro-tetradecahydrophenanthrene.
• perfluorearenes there may be cited the perfluoro derivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1-naphthalene.
• composition according to the invention may comprise at least one film-forming polymer.
• compositions according to the invention may therefore comprise at least one film-forming polymer and mixture 1) described hereinabove.
• film-forming polymer a polymer capable of forming, on its own or in the presence of an auxiliary filmifying agent, a macroscopically continuous film that adheres to horny tissues, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that the said film may be isolated and manipulated in isolation, for example when the said film is formed by casting on a non-sticking surface, such as a Teflon-coated or silicone-coated surface.
• the film-forming polymer or polymers used, in association with the mixtures of MQ and propyl T resins, may be conveyed in the oil phase (fat-soluble or fat-dispersible polymers) or conveyed in an aqueous phase (water soluble polymers or latex).
• the composition may contain an aqueous phase, and the film-forming polymer may be present in this aqueous phase.
• the film-forming polymer may be present in this aqueous phase.
• it will preferably be a polymer in aqueous dispersion or a water-soluble polymer.
• film-forming polymers that can be used in the composition of the present invention there may be cited the synthetic polymers of radical type or of polycondensate type, the polymers of natural origin and mixtures thereof.
• water-soluble film-forming polymers there may be cited:
• the film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase, known generally under the name of latex or pseudolatex.
• aqueous dispersion of film-forming polymer there may be used the acrylic dispersions sold under the trade names: Neocryl XK-90®, Neocryl A-10700, Neocryl A-10900, Neocryl BT-62®, Neocryl A-1079®, and Neocryl A-523® by the AVECIA-NEORESINS Company; Dow Latex 432® by the DOW CHEMICAL Company; Daitosol 5000 AD® or Daitosol 5000 SJ® by the DAITO KASEY KOGYO Company; Syntran 5760® by the Interpolymer Allianz Company, Opt® by the Rohm and Haas Company, the aqueous dispersions of acrylic or styrene/acrylic polymers sold under the trade
• the composition according to the invention comprises, by way of hydrophilic film-forming polymers, at least the association of a cationic polymer and an anionic polymer.
• the cationic polymer may be chosen from among the ether derivatives of quaternary cellulose, the copolymers of cellulose with a water-soluble monomer of quaternary ammonium, the cyclopolymers, the cationic polysaccharides, the silicone-containing cationic polymers, the quaternized or non-quaternized copolymers of vinylpyrrolidone and dialkylaminoalkyl acrylate or methacrylate, the quaternary polymers of vinylpyrrolidone and vinylimidazole, the polyamidoamines and mixtures thereof.
• the cationic polymer is a hydroxy(C 1 -C 4 )alkyl cellulose containing quaternary ammonium groups.
• the most particularly preferred anionic polymers are chosen from among the non-cross-(linked anionic polymers such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold under the trade name GANTREZ ES 425 by the ISP Company, the acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers sold under the trade name ULTRAHOLD STRONG by the BASF Company, the copolymers of methacrylic acid and methyl methacrylate sold under the trade name EUDRAGIT L by the ROHM PHARMA Company, the vinyl acetate/vinyl tert-butyl benzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the trade name Resin 28-29-30 by the NATIONAL STARCH Company, the copolymers of methacrylic acid and ethyl acrylate sold under
• the anionic polymer is a sodium polymethacrylate.
• the composition may contain an oil phase, and the film-forming polymer may be present in this oil phase.
• the polymer may then be in dispersion or in solution.
• non-aqueous dispersions of fat-dispersible film-forming polymer in the form of non-aqueous dispersions of polymer particles in one or more silicone and/or hydrocarbon oils and capable of being stabilized at their surface by at least one stabilizing agent, especially a sequenced, grafted or statistical polymer
• the acrylic dispersions in isododecane such as Mexomere PAP® of the CHIMEX Co.
• the dispersions of particles of a graft ethylene preferably acrylic polymer in a liquid fatty phase, the ethylene polymer being advantageously dispersed in the absence of additional surface stabilizer of the particles such as described in particular in the document of WO 04/055081.
• film-forming polymers that can be used in the composition of the present invention, there may be cited the synthetic polymers of radical type or polycondensate type, the polymers of natural origin, and mixtures thereof.
• radical film-forming polymer there is understood a polymer obtained by polymerization of monomers having unsaturation, especially ethylenic, each monomer being capable of homopolymerization (unlike the polycondensates).
• the film-forming polymers of radical type may be in particular vinyl polymers or copolymers, especially acrylic polymers.
• the vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.
• monomer carrying acid groups there may be used ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid.
• ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid.
• (meth)acrylic acid and crotonic acid Preferably there are used (meth)acrylic acid and crotonic acid, and more preferably (meth)acrylic acid.
• esters of acid monomers are advantageously chosen from among the esters of (meth)acrylic acid (also referred to as the (meth)acrylates), especially alkyl(meth)acrylates, in particular C1-C30 alkyl, preferably C1-C20, aryl(meth)acrylates, in particular C6-C10 aryl, hydroxyalkyl(meth)acrylates), in particular C2-C6 hydroxyalkyl.
• alkyl(meth)acrylates in particular C1-C30 alkyl, preferably C1-C20, aryl(meth)acrylates, in particular C6-C10 aryl, hydroxyalkyl(meth)acrylates), in particular C2-C6 hydroxyalkyl.
• alkyl(meth)acrylates there may be cited methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.
• hydroxyalkyl(meth)acrylates there may be cited hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.
• aryl(meth)acrylates there may be cited benzyl acrylate and phenyl acrylate.
• esters of (meth)acrylic acid are the alkyl(meth)acrylates.
• the alkyl group of the esters may be either fluorinated or pefluorinated, meaning that part or all of the hydrogen atoms of the alkyl group have been substituted by fluorine atoms.
• amides of acid monomers there may be cited, for example, the (meth)acrylamides, and especially the N-alkyl(meth)acrylamides, in particular C2-C12 alkyl.
• the N-alkyl (meth)acrylamides there may be cited N-ethyl acrylamide, N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecyl acrylamide.
• the vinyl film-forming polymers may also result from the homopolymerization or the copolymerization of monomers chosen from among the vinyl esters and the styrene monomers.
• these monomers may be polymerized with acid monomers and/or their esters and/or their amides, such as those mentioned in the foregoing.
• vinyl esters there may be cited vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
• styrene monomers there may be cited styrene and alpha-methylstyrene.
• the film-forming polycondensates there may be cited the polyurethanes, the polyesters, the amide polyesters, the polyamides and the epoxy ester resins, the polyureas.
• the polyurethanes may be chosen among the anionic, cationic, non-ionic or amphoteric polyurethanes, the polyurethane acrylics, the polyurethane polyvinylpyrrolidones, the polyester polyurethanes, the polyether polyurethanes, the polyureas, the polyurea polyurethanes and mixtures thereof.
• the polyesters may be obtained in known manner by polycondensation of dicarboxylic acids with polyols, especially diols.
• the dicarboxylic acid may be aliphatic, alicyclic or aromatic.
• such acids there may be cited: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid.
• These dicarboxylic acid monomers may be used alone or in combination of at least two dicar
• the diol may be chosen from among the aliphatic, alicyclic, aromatic diols. Preferably there is used a diol chosen from among: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol. As other polyols there may be used glycerol, pentaerythritol, sorbitol, trimethylol propane.
• the amide polyesters may be obtained in a manner analogous to that for the polyesters, by polycondensation of diacids with diamines or amino alcohols.
• diamine there may be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine.
• amino alcohol there may be used monoethanolamine.
• the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents (it is then said that the film-forming polymer is a fat-soluble polymer).
• the liquid fatty phase comprises a volatile oil, if necessary in a mixture with a non-volatile oil.
• fat-soluble polymer there may be cited the copolymers of vinyl ester (the vinyl group being bonded directly to the oxygen atom of the ester group and the vinyl ester having a linear or branched, saturated hydrocarbon radical with 1 to 19 carbon atoms, bonded to the carbonyl of the ester group) and of at least one other monomer, which may be a vinyl ester (different from the already present vinyl ester), an ⁇ -olefin (having 8 to 28 carbon atoms), an alkyl vinyl ether (whose alkyl group contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical with 1 to 19 carbon atoms, bonded to the carbonyl of the ester group).
• vinyl ester different from the already present vinyl ester
• an ⁇ -olefin having 8 to 28 carbon atoms
• alkyl vinyl ether whose alkyl group contains 2 to 18 carbon atoms
• copolymers may be cross-linked by means of cross-linking agents, which may be either of the vinyl type or of the allyl or methallyl type, such as tetrallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.
• cross-linking agents may be either of the vinyl type or of the allyl or methallyl type, such as tetrallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.
• copolymers there may be cited the following copolymers: vinyl acetate/allyl stearate, vinyl acetate//vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/octadecene-1, vinyl acetate/dodecene-1, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2,2-dimethyl octanoate/vinyl laurate, allyl 2,2-dimethyl pentanoate/vinyl laurate, vinyl dimethyl propionate/vinyl stearate, allyl dimethyl propionate/vinyl stearate, vinyl prop
• fat-soluble film-forming polymers there may be cited the copolymers of vinyl ester and at least one other monomer, which may be a vinyl ester, especially vinyl neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an ⁇ -olefin, an alkyl vinyl ether, or an allyl or a methallyl ester.
• a vinyl ester especially vinyl neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an ⁇ -olefin, an alkyl vinyl ether, or an allyl or a methallyl ester.
• fat-soluble film-forming polymers there may also be cited fat-soluble copolymers, and in particular those resulting from copolymerization of vinyl esters having 9 to 22 carbon atoms or acrylates or alkyl methacrylates, the alkyl radicals having 10 to 20 carbon atoms.
• Such fat-soluble copolymers may be chosen from among the copolymers of: vinyl polystearate, vinyl polystearate cross-linked by means of divinylbenzene, diallyl ether, or diallyl phthalate, the copolymers of stearyl poly(meth)acrylate, vinyl polylaurate, lauryl poly(meth)acrylate, these poly(meth)acrylates being capable of being cross-linked by means of ethylene glycol dimethacrylate or tetraethylene glycol.
• the fat-soluble polymers defined in the foregoing are known and are described especially in the Application FR A 2232303; they may have a weight-average molecular weight ranging from 2,000 to 500,000, and preferably from 4,000 to 200,000.
• fat-soluble film-forming polymers that can be used in the invention there may also be cited polyalkylenes and especially C2-C20 alkene copolymers such as polybutene, the alkyl celluloses with a C1 to C8 saturated or unsaturated, linear or branched alkyl radical such as ethyl cellulose and propyl cellulose, the copolymers of vinylpyrrolidone (VP) and especially the copolymers of vinylpyrrolidone and C2 to C40 alkene, and better C3 to C20.
• C2-C20 alkene copolymers such as polybutene
• the alkyl celluloses with a C1 to C8 saturated or unsaturated, linear or branched alkyl radical such as ethyl cellulose and propyl cellulose
• the copolymers of vinylpyrrolidone (VP) and especially the copolymers of vinylpyrrolidone and C2 to C40 alkene and better C3 to C20.
• VP copolymers that can be used in the invention there may be cited the copolymer of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP); VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene, VP/acrylic acid/lauryl methacrylate.
• PVP polyvinylpyrrolidone
• silicone resins generally soluble or swellable in silicone oils, that are cross-linked polyorganosiloxane polymers.
• siloxysilicate resins there may be cited the trimethylsiloxysilicate resins (TMS), such as those sold under the reference SR1000 by the General Electric Company or under the reference TMS 803 by the Wacker Company.
• TMS trimethylsiloxysilicate resins
• SR1000 by the General Electric Company
• TMS 803 by the Wacker Company
• TMS 803 by the Wacker Company
• trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the trade name KF-7312J by the Shin-Etsu Company, or “DC 749”, “DC 593” by the Dow Corning Company.
• copolymers of silicone resins such as those cited hereinabove with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers sold by the Dow Corning Company under the reference BIO-PSA and described in the document U.S. Pat. No. 5,162,410, or else the silicone copolymers obtained by the reaction of a silicone resin, such as those described hereinabove, and a diorganosiloxane such as those described in the document WO 2004/073626.
• acrylic/silicone graft copolymers having a vinyl, methacrylic or acrylic polymeric skeleton and organosiloxane or polyorganoxilane pendant grafts.
• acrylic/silicone graft copolymers having a vinyl, methacrylic or acrylic polymeric skeleton and organosiloxane or polyorganoxilane pendant grafts.
• Such polymers are described in particular in U.S. Pat. Nos. 4,693,935, 4,981,903 and 4,981,902.
• these polymers comprise monomers A, C and optionally B, for which:
• X is a vinyl group that can be copolymerized with monomers A and B;
• Examples of monomers A are lower to intermediate esters of methacrylic acid and C1-12 alcohols with linear or branched chain, of styrene, vinyl esters, vinyl chloride, vinylidine chloride or acryloyl monomers.
• Examples of monomers B are polar acrylic or methacrylic monomers having at least one hydroxy, amino, ester or ionic group (such as the quaternary ammoniums, the carboxylate salt or the acids such as the carboxylic acids, the acrylic acids, sulfonic acid or salts thereof).
• Monomer C is defined above.
• acrylic/silicone graft copolymers there may be cited those sold by 3M under the reference 3M Silicones “Plus” VS70 Dry Polymer®, with the INCI name: Polysilicone-6, or else KP-561® sold by SHIN-ETSU with the INCI name: Acrylates/Stearyl Acrylate/Dimethicone Methacrylate Copolymer, KP-562® sold by SHIN-ETSU with the INCI name: Acrylates/Behenyl Acrylate/Dimethicone Acrylate Copolymer.
• the film-forming polymer is a film-forming linear sequenced ethylene polymer, which preferably comprises at least one first sequence and at least one second sequence having different glass transition temperatures (Tg), the said first and second sequences being bonded together by an intermediate sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.
• Tg glass transition temperatures
• the first and second sequences of the sequenced polymer are incompatible with one another.
• Such polymers are described, for example, in the documents EP 1411069 or WO04/028488.
• the film-forming polymer may be chosen from among the block or static polymers and/or copolymers composed in particular of polyurethanes, polyacrylics, silicones, fluoro polymers, butyl rubbers, ethylene copolymers, natural rubbers and polyvinyl alcohols and mixtures thereof.
• the monomers of the block or static copolymers comprising at least one association of monomers whose polymer results in a glass transition temperature lower than room temperature (25° C.) may be chosen in particular from among butadiene, ethylene, propylene, acrylic, methacrylic, isoprene, isobutene, a silicone and mixtures thereof.
• composition according to the invention also may comprise at least one film-forming polymer, chosen from among the vinyl polymers comprising at least one moiety derived from carbosiloxane dendrimer.
• the vinyl polymer may have in particular a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer structure.
• carbosiloxane dendrimer structure represents a molecular structure possessing branched groups having high molecular weights, the said structure having high regularity in the radial direction starting from the bond to the skeleton.
• Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Kokai 9-171 154, a Japanese Patent Application laid open to public inspection.
• the vinyl polymer contains moieties derived from carbosiloxane dendrimers that can be represented by the following general formula:
• R 1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms
• R 1 is the same as defined hereinabove
• R 2 represents an alkylene group possessing 2 to 10 carbon atoms
• R 3 represents an alkyl group possessing 1 to 10 carbon atoms
• i is an integral number from 1 to 10, representing the generation of the said silylalkyl group
• a i is an integral number from 0 to 3
• Y represents a radical-polymerizable organic group chosen from the group constituted by an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulas:
• R 4 represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group possessing 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 possessing 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 possessing 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred
• R 1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms, where the alkyl group is preferably represented by a methyl group, an ethyl group, a propyl group, butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, and where the aryl group is preferably represented by a phenyl group and a naphthyl group, in which the methyl and phenyl groups are particularly preferred, and the methyl group is preferred above all.
• the vinyl polymer that contains a carbosiloxane dendrimer structure may be the product of polymerization of
• Y represents a radical-polymerizable organic group
• R 1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms
• R 1 is the same as defined hereinabove
• R 2 represents an alkylene group possessing 2 to 10 carbon atoms
• R 3 represents an alkyl group possessing 1 to 10 carbon atoms
• i is an integral number from 1 to 10, representing the generation of the said silylalkyl group
• a i is an integral number from 0 to 3
• the said radical-polymerizable organic group contained in component (B) is chosen from the group constituted by an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulas:
• R 4 represents a hydrogen atom or an alkyl group
• R 5 represents an alkylene group possessing 1 to 10 carbon atoms
• R 6 represents a hydrogen atom or an alkyl group
• R 7 represents an alkyl group possessing 1 to 10 carbon atoms
• R 8 represents an alkylene group possessing 1 to 10 carbon atoms
• b is an integral number from 0 to 4 and c is equal to 0 or 1. In the case that c is equal to 0, —(R 8 ) c -represents a bond.
• the monomer of vinyl type that is component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group.
• This monomer of vinyl type methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower analogous alkyl methacrylate; glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate or a higher analogous methacrylate; vinyl acetate, vinyl propionate,
• Multifunctional monomers of vinyl type may also be used. What follows represents examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl methacrylate, tris-(2-hydroxyethyl) isocyanurate dimethacrylate, tris-(2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups possessing divinylbenzene groups at both ends, or analogous silicone compounds possessing unsaturated groups.
• the carbosiloxane dendrimer which is component (B), is represented by the following formula:
• radical-polymerizable organic group Y an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.
• R 1 represents an alkyl group or an aryl group possessing 1 to 10 carbon atoms, where the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group; and the aryl group may be a phenyl group or a naphthyl group.
• the methyl and phenyl groups are particularly preferred, the methyl group being preferred above all.
• R 2 represents an alkylene group possessing 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group or an analogous linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group or an analogous branched alkylene group.
• the ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are preferred above all.
• R 3 represents an alkyl group possessing 1 to 10 carbon atoms, such as the methyl, ethyl, propyl, butyl and isopropyl groups.
• R 1 is the same as defined hereinabove.
• a i is an integral number from 0 to 3 and i is an integral number from 1 to 10, indicating 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 hereinabove, R 12 represents a hydrogen atom or is identical to R 1 ; a 1 is identical to a i .
• the mean total number of OR 3 groups in a molecule is in 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 hereinabove; a 1 and a 2 represent the a i of the indicated generation.
• the mean total number of OR 3 groups in a molecule is in the range from 0 to 25.
• the carbosiloxane dendrimer may be 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 hereinabove; a 1 , a 2 and a 3 represent the a i of the indicated generation.
• the mean total number of OR 3 groups in a molecule is in the range from 0 to 79.
• a carbosiloxane dendrimer containing a radical-polymerizable organic group may be represented by the following mean structural formulas:
• the carbosiloxane dendrimer may be manufactured according to the method for manufacturing a branched siloxane silalkylene described in Japanese Patent Hei 9-171154. For example, it may be produced by subjecting to a hydrosilylation reaction an organosilicon compound that contains a hydrogen atom bonded 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 carried out in the presence of a chloroplatinic acid, of a complex of vinylsiloxane and platinum or of an analogous catalyst of a transition metal.
• the polymerization ratio between components (A) and (B), in terms of weight ratio between (A) and (B), may be in a range of 0/100 to 99.9/0.1, and preferably in a range of 1/99 to 99/1.
• a ratio of 0/100 between components (A) and (B) means that the compound becomes a homopolymer of component (B).
• the vinyl polymer contains a carbosiloxane dendrimer structure and this polymer may be obtained by copolymerization of components (A) and (B) or by polymerization of component (B) alone.
• the polymerization may be a radical polymerization or an ionic polymerization, but radical polymerization is preferred.
• the polymerization may be carried out by causing a reaction between components (A) and (B) in a solution during a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50° C. to 150° C.
• An appropriate solvent for this purpose is hexane, octane, decane, cyclohexane or an analogous aliphatic hydrocarbon; benzene, toluene, xylene or an analogous aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane or analogous ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or analogous ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate or analogous esters; methanol, ethanol, isopropanol, butanol or analogous alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane
• a radical initiator may be any compound known in the art for traditional 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 analogous compounds of azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or an analogous organic peroxide.
• These radical initiators may be used alone or in a combination of two or more.
• the radical initiators may be used in a quantity of 0.1 to 5 parts by weight per 100 parts by weight of 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 possessing a mercaptopropyl group or an analogous compound of mercapto type; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane or an analogous halogen compound.
• the residual vinyl monomer that has not reacted may be eliminated after the polymerization under conditions of heating under vacuum.
• the number-average molecular weight of the vinyl polymer containing a carbosiloxane dendrimer may be chosen in a range between 3,000 and 2,000,000, preferably between 5,000 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 constituted by dilution of a dispersion or of a powder in solvents.
• the vinyl polymer may be a dispersion, in a liquid such as a silicone oil, an organic oil, an alcohol or water, of a polymer of vinyl type having a carbosiloxane dendrimer structure in its side molecular chain.
• the vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain is the same as that described hereinabove.
• the liquid may be a silicone oil, an organic oil, an alcohol or water.
• the silicone oil may be a dimethylpolysiloxane having the two molecular ends capped by trimethylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3,3,3-trifluoropropylsiloxane and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, or analogous non-reactive linear silicone oils, as well as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane
• the organic oils may be paraffin oil, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecylmyristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol, cetostearic alcohol, oleic alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower seed oil, soy oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef suet, lard, polypropylene glycol monooleate, neopentyl glycol 2-eth
• the alcohol may be any type whatsoever that is appropriate for use in conjunction with a raw material for cosmetic products.
• it may be methanol, ethanol, butanol, isopropanol or analogous lower alcohols.
• a solution or a dispersion of alcohol should have a viscosity in the range of 10 to 10 9 mPa at 25° C. To improve the sensory properties of use in a cosmetic product, the viscosity should be in the range of 100 to 5 ⁇ 10 8 mPa ⁇ s.
• the solutions and the dispersions may be easily prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure with a silicone oil, an organic oil, an alcohol or water.
• the liquids may be present in the step of polymerization of the polymer of vinyl type having a carbosiloxane dendrimer structure.
• the residual vinyl monomer that has not reacted should be completely eliminated by heat treatment of the solution or of the dispersion under atmospheric 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 sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef suet trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide or an analogous cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyal
• the solvents and the dispersions may be combined with iron oxide appropriate for use with cosmetic products, or an analogous pigment, as well as zinc oxide, titanium dioxide, silicon oxide, mica, talc or analogous inorganic oxides in the form of powder.
• a mean diameter of the particles of polymer of vinyl type may be in a range between 0.001 and 100 microns, preferably between 0.01 and 50 microns. In fact, outside the recommended range, a cosmetic product mixed in the emulsion will not have a sufficiently good sensation on the skin or to the touch, and will not have sufficient spreading properties or a pleasant sensation.
• the vinyl polymer contained in the dispersion or solution may have a concentration in a range between 0.1 and 95% by weight, preferably between 5 and 85% by weight. However, to facilitate the manipulation and preparation of the mixture, the range should preferably be between 10 and 75% by weight.
• the vinyl polymer may be one of the polymers described in the examples of Patent Application EP0963751 or, for example, the product TIB-4-200 sold by Dow Corning.
• the vinyl polymer additionally comprises at least one fluoro organic group.
• the fluoro organic groups may be obtained by substituting, with fluorine atoms, all or part of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and other alkyl groups having 1 to 20 carbon atoms, as well as of alkyloxyalkylene groups having 6 to 22 carbon atoms.
• the groups represented by the formula: —(CH 2 ) x —(CF 2 ) y —R 13 are suggested by way of example of fluoroalkyl groups, obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups.
• the index “x” is 0, 1, 2 or 3 and “y” is an integer from 1 to 20.
• R 13 is an atom or a group chosen from among a hydrogen atom, a fluorine atom, —CH(CF 3 ) 2 — or CF(CF 3 ) 2 .
• Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulas presented below.
• fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups.
• the index “m” is 0 or 1
• “n” is 0, 1, 2, 3, 4 or 5
• R 14 is a fluorine atom or CF 3 .
• fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxyfluoroalkylene groups represented by the formulas presented below.
• the number-average molecular weight of the vinyl polymer used in the present invention may be between 3,000 and 2,000,000, and more preferably between 5,000 and 800,000.
• This type of fluoro vinyl polymer may be obtained by addition
• Y is a radical-polymerizable organic group and R 1 and X i are as hereinabove, and by subjecting them to copolymerization.
• the vinyl monomers (A) containing fluoro organic groups in the molecule are preferably monomers represented by the general formula: —(CH 2 ) ⁇ CR 15 COOR f .
• R 15 is a hydrogen atom or a methyl group
• R f is a fluoro organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above.
• the compounds represented by the formulas presented below are suggested by way of specific examples of component (A). In the formulas presented below, “z” is an integer from 1 to 4.
• the vinyl polymers represented by the formulas presented below are preferable.
• the vinyl polymers represented by the formulas presented below are particularly preferable.
• the vinyl monomers (B) that do not contain fluoro organic groups in the molecule may be any molecules whatsoever having radical-polymerizable vinyl groups, which molecules are exemplified for example by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, cyclohexyl acrylate, cyclohexyl acrylate, cyclo
• vinyl monomers (B) the polyfunctional vinyl monomers that are exemplified for example by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl acrylate, tri
• the weight ratio of compound (A) to compound (B) must be in the range from 0.1:99.9 to 100:0, and preferably in the range of 1:99 to 100:0.
• Carbosiloxane dendrimer (C) is represented by general formula (III) indicated hereinabove.
• Y is a radical-polymerizable organic group, whose type is not subject to any special limitations whatsoever, provided it is an organic group capable of undergoing a radical addition reaction.
• Organic groups containing acryl and methacryl, organic groups containing alkenaryl, or alkenyl groups with 2 to 10 carbon atoms represented by the general formulas presented below are suggested by way of specific examples.
• R 4 and R 6 are hydrogen atoms or methyl groups
• R 7 is an alkyl group with 1 to 10 carbon atoms.
• the index “b” is an integer from 0 to 4
• “c” is 0 or 1.
• Y, R 1 , R 2 and R 3 are such as hereinabove and R 12 is a hydrogen atom or such as R 1 described hereinabove.
• the index “a 1 ” is an integer from 0 to 3, the mean total of “a 1 ” per molecule being from 0 to 7).
• the carbosiloxane dendrimers of this component with a generation number of 2 are represented by the general formula:
• Component (C) is exemplified by carbosiloxane dendrimers represented by the formulas of mean composition represented below.
• the carbosiloxane dendrimers of component (C) may be prepared by using the method of preparation of branched siloxane/silalkylene copolymers described in the document EP1055674. For example, they may be prepared by subjecting organic silicone compounds containing alkenyl groups and silicone compounds comprising hydrogen atoms bonded to the silicon, represented by the general formula:
• 3-methacyloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane and 4-vinylphenyltris(dimethylsiloxy)silane are used by way of silicon compounds represented by the above formula.
• Vinyltris(dimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane and 5-hexenyltris(trimethylsiloxy)silane are used as organic silicon compounds containing alkenyl groups.
• the copolymerization ratio of component (C), in terms of its weight ratio relative to the total of compound (A) and of compound (B), must be in the range of 0.1:99.9 to 99.9:0.1, and preferably in the range of 1:99 to 99:1, and even more preferably in the range of 5:95 to 95:5.
• Amino groups may be introduced into the side chains of the vinyl polymer by using, included in component (B), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, then carrying out a modification with potassium monochloroacetate, ammonium monochloroacetate, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halo fatty acids; otherwise it is possible to introduce carboxylic acid groups into the side chains of the vinyl polymer by using, included in component (B), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid and similar compounds, then neutralizing the product with trie
• the fluoro vinyl polymer may be one of the polymers described in the examples of Patent Application WO03/045337 or, for example, the product TIB-4-100 sold by Dow Corning.
• film-forming polymers there also may be cited as film-forming polymers, two-component systems such as the compounds X and Y defined hereinafter, capable of polymerizing in situ, at atmospheric pressure and room temperature, and of forming films advantageously biocompatible, non-sticking, slightly opalescent and even peelable.
• two-component systems such as the compounds X and Y defined hereinafter, capable of polymerizing in situ, at atmospheric pressure and room temperature, and of forming films advantageously biocompatible, non-sticking, slightly opalescent and even peelable.
• Such systems are especially described in part in Patents WO 01/96450 and GB 2407496 of Dow Corning.
• the compounds X and the compounds Y are silicones.
• the compounds X and Y may or may not be amines.
• At least one of the compounds X and Y is a polymer whose main chain is formed predominantly by organosiloxane units.
• silicone compounds cited hereinafter some may exhibit both film-forming and adhesive properties, depending, for example, on their proportion of silicone or depending on whether they are used in a mixture with a particular additive. Consequently, it is possible to modulate the film-forming properties or the adhesive properties of such compounds depending on the envisioned use, and this is the case in particular for the reactive elastomeric silicones referred to as “room temperature vulcanization”.
• the compounds X and Y may react together at a temperature varying between room temperature and 180° C.
• the compounds X and Y are capable of reacting together at room temperature (20 ⁇ 5° C.) and atmospheric pressure, or advantageously in the presence of a catalyst, via a hydrosilylation reaction or a condensation reaction, or a cross-linking reaction in the presence of a peroxide.
• the compounds X and Y react by hydrosilylation in the presence of a catalyst.
• the compounds X and Y are chosen from among the silicone compounds capable of reacting by hydrosilylation in the presence of a catalyst; in particular, the compound X is chosen from among the polyorganosiloxanes comprising units of formula (I) described below and the compound Y is chosen from among the organosiloxanes comprising alkylhydrogenosiloxanes of formula (III) described below.
• the compound X is a polydimethylsiloxane containing terminal vinyl groups
• the compound Y is a polymethylhydrogenosiloxane
• R′ is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group.
• R represents an alkyl radical comprising 1 to 10 carbon atoms or else a phenyl group, and preferably a methyl radical, and R′ is a vinyl group.
• the hydrosilylation reaction is carried out in the presence of a catalyst, which may be present with one or the other of the compounds X or Y or may be present in isolated manner.
• this catalyst may be present in the composition in an encapsulated form, if the two components X and Y, whose interaction it must bring about, are present in this same composition in a non-encapsulated form or, conversely, it may be present in the composition in a non-encapsulated form if at least one of the compounds X and Y is present in the composition in an encapsulated form.
• the catalyst is preferably based on platinum or tin.
• the catalyst may be present in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.
• the compounds X and/or Y may be associated with polymerization inhibitors or retarders, and more particularly with catalyst inhibitors.
• polymerization inhibitors or retarders and more particularly with catalyst inhibitors.
• catalyst inhibitors there may be cited the cyclic polymethylvinylsiloxanes, and in particular tetravinyl tetramethyl cyclotetrasiloxane, the acetylenic alcohols, preferably volatile, such as methylisobutynol.
• ionic salts such as sodium acetate
• the compound X may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.
• the compound Y may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.
• composition according to the invention may comprise a plasticizing agent favoring the formation of a film with the film-forming polymer.
• a plasticizing agent may be chosen from among all the compounds known to those skilled in the art as being capable of fulfilling the sought function.
• composition according to the invention may comprise at least one ionic surfactant.
• compositions according to the invention may therefore comprise at least one ionic surfactant and mixture 1) described hereinabove.
• the surfactant may be lipophilic and/or hydrophilic, used alone or in combination.
• the surfactant may be chosen from among the anionic, cationic, amphoteric surfactants.
• the surfactant may be present in the composition according to the invention and in a content ranging from 0.1% to 10% by weight relative to the total weight of the composition, and preferably ranging from 0.5% to 8% by weight, and preferentially ranging from 0.5% to 7% by weight.
• ionic surfactant is an anionic surfactant, it is chosen from among:
• compositions according to the invention may also contain one or more amphoteric surfactants such as the N-acyl amino acids, such as the N-alkyl aminoacetates and disodium cocoamphodiacetate and the amine oxides such as stearamine oxide, the betaines, the N-alkylamido betaines and their derivatives, the sultaines, the alkyl polyaminocarboxylates, the alkylamphoacetates, or even the silicone surfactants such as the dimethicone copolyol phosphates such as that sold under the trade name PECOSIL PS100® by the PHOENIX CHEMICAL Company and mixtures thereof.
• amphoteric surfactants such as the N-acyl amino acids, such as the N-alkyl aminoacetates and disodium cocoamphodiacetate and the amine oxides such as stearamine oxide, the betaines, the N-alkylamido betaines and their derivatives, the sultaines, the
• compositions according to the invention also comprise an elastomer of amphiphilic silicone containing polyalkylene, in particular polyoxyethylene and/or polyoxypropylene hydrophilic groups, sequences or grafts, or polyglycerol hydrophilic groups, sequences or grafts, which are capable in addition of possessing alkyl side groups, in particular lauryl side groups, especially an elastomer of polyglycerol silicone.
• an elastomer of amphiphilic silicone containing polyalkylene in particular polyoxyethylene and/or polyoxypropylene hydrophilic groups, sequences or grafts, or polyglycerol hydrophilic groups, sequences or grafts, which are capable in addition of possessing alkyl side groups, in particular lauryl side groups, especially an elastomer of polyglycerol silicone.
• an elastomeric cross-linked organopolysiloxane that may be obtained by cross-linking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and polyglycerol compounds having ethylenically unsaturated groups, especially in the presence of platinum catalyst.
• polyglycerol silicone elastomers there may be used those sold under the trade names “KSG-710,” “KSG-810,” “KSG-820,” “KSG-830,” “KSG-840” by the Shin-Etsu Company.
• the composition may comprise fibers.
• fiber there is to be understood an object of length L and of diameter D such that L is greater than D, D being the diameter of the circle in which the cross section of the fiber is inscribed.
• the L/D ratio (or form factor) is chosen in the interval ranging from 3.5 to 2,500, preferably from 5 to 500, and better from 5 to 150.
• the fibers that can be used in the composition of the invention may be fibers of synthetic or natural, mineral or organic origin. They may be short or long, individual or organized, for example, in braids, hollow or solid. They may have any shape and in particular be of circular or polygonal (square, hexagonal or octagonal) cross section depending on the specific application envisioned. In particular, their ends are blunted or polished to avoid causing injury.
• the fibers have a length ranging from 1 ⁇ m to 10 mm, preferably from 0.1 mm to 5 mm and better from 0.3 mm to 3 mm.
• Their cross section may be contained in a circle of diameter ranging from 2 nm to 500 ⁇ m, preferably ranging from 100 nm to 100 ⁇ m and better from 1 ⁇ m to 50 ⁇ m.
• the weight or titer of the fibers is often expressed in denier or decitex and represents the weight in grams for 9 km of filament.
• the fibers according to the invention have a titer chosen in the interval ranging from 0.01 to 10 denier, preferably from 0.1 to 2 denier and better from 0.3 to 0.7 denier.
• the fibers may be present in the composition in a content ranging from 0.1% to 30% by weight relative to the total weight of the composition, preferably ranging from 0.1% to 20% by weight, and preferentially ranging from 0.1% to 10% by weight.
• ingredients described below may be used alone or in association with the resins of the invention or as additives to supplement other aforementioned ingredients in association with the said resins according to the invention.
• compositions according to the invention may additionally comprise an amphiphilic silicone elastomer, preferably chosen from among the polyoxyalkylene and polyglycerol silicone elastomers.
• polyoxyalkylene silicone elastomers there may be cited those described in U.S. Pat. Nos. 5,236,986, 5,412,004, 5,837,793, 5,811,487.
• polyoxyalkylene silicone elastomers there may be used:

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• 2008
  • 2008-12-02 FR FR0858195A patent/FR2939033B1/fr not_active Expired - Fee Related
• 2009
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