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
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K31/00—Medicinal preparations containing organic active ingredients
  • A61K31/33—Heterocyclic compounds
  • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
  • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
  • A61K31/47—Quinolines; Isoquinolines
  • A61K31/473—Quinolines; Isoquinolines ortho- or peri-condensed with carbocyclic ring systems, e.g. acridines, phenanthridines
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P17/00—Drugs for dermatological disorders
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
  • C07D221/06—Ring systems of three rings
  • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes
  • A61K2800/434—Luminescent, Fluorescent; Optical brighteners; Photosensitizers
• • 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
  • A61K2800/54—Polymers characterized by specific structures/properties
• • 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
  • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

• composition comprising a monomeric compound with optical effect, method using said composition, monomeric compound, polymer comprising it and use
• the present invention relates to new cosmetic or pharmaceutical compositions, in particular for topical application, and in particular new makeup compositions, comprising organic polymers having specific optical properties, in particular of fluorescence.
• the present invention also relates to new monomeric compounds having optical properties, in particular to fluorescence, as well as the polymers capable of being prepared from these compounds.
• Cosmetic compositions and in particular makeup compositions such as loose or compact powders, foundations, blush or eyeshadows, lipsticks or nail varnishes, generally consist of a suitable vehicle and one or more coloring agents intended to impart a certain color to said compositions before and / or after their application to the skin, mucous membranes, semi-mucous membranes and / or integuments such as the nails, the eyelashes or the hair.
• coloring agents intended to impart a certain color to said compositions before and / or after their application to the skin, mucous membranes, semi-mucous membranes and / or integuments such as the nails, the eyelashes or the hair.
• coloring agents intended to impart a certain color to said compositions before and / or after their application to the skin, mucous membranes, semi-mucous membranes and / or integuments such as the nails, the eyelashes or the hair.
• lacquers mineral pigments, organic pigments and pearlescent pigments.
• the subject of the invention is a cosmetic or pharmaceutical composition
• a cosmetic or pharmaceutical composition comprising, in a physiologically acceptable medium, at least one polymer comprising at least one monomeric compound as defined below.
• Another subject of the invention is a cosmetic method for making up or caring for keratin materials, in particular the skin of the body or of the face, lips, nails, eyelashes, eyebrows and / or hair, comprising application to said materials of such a cosmetic composition.
• the polymers according to the invention can be in solid or liquid form, and confer remarkable optical effects on the compositions which comprise them as well as on the deposited makeup; in particular, they can provide lightening or color effects. These optical effects can advantageously be modulated as a function of the chemical nature and / or of the position of the various substituents present on the optical effect monomer used to form the polymer.
• the group X is an oxygen
• the resulting monomer will rather be blue / white in color
• the group X comprises a nitrogen atom
• the resulting monomer will rather be in the field of orange.
• the polymers according to the invention can provide their good temperature, pH and light stability. It was also found that the polymers according to the invention exhibited good solubility in fatty substances, solubility which could vary and be adjusted, depending on the nature of the monomers. This good lipid solubility can also facilitate their subsequent implementation, in particular in cosmetic compositions which generally comprise an oily phase.
• compositions according to the invention are maintained, when they comprise the polymers according to the invention.
• the polymers according to the invention can exhibit, depending on the nature of the substituents, a wide variety of optical effects, which can range from blue / purple to orange / red, passing through the yellow.
• This makes it possible to have a range of compounds, belonging to the same chemical family, and therefore formulating in a similar manner, which offer diverse colors or remarkable optical properties; this notably facilitates the work of formulators by allowing them to keep an architecture common to all of their compositions, regardless of the polymers with optical property used.
• the monomers according to the invention and the polymers comprising them have good fluorescence properties, and for some of them, optical brightening properties.
• optical brighteners have fluorescence properties; in general, the fluorescent compounds absorb in the ultraviolet and in the visible, and re-emit energy by fluorescence for a wavelength between 380 nm and 830 nm; when this wavelength is between 380 nm and 480 nm, that is to say in the blue of the visible range, the compounds are then optical brighteners.
• the polymers according to the invention have the advantage of being easily removed.
• composition according to the invention therefore comprises, in a physiologically acceptable medium, in particular a cosmetically or pharmaceutically acceptable medium, at least one polymer capable of being obtained by polymerization, in particular radical) of at least one monomer of formula (I).
• P is a polymerizable group chosen from one of the following formulas
• R - R ' represents H or a hydrocarbon radical, linear or branched, saturated in C1-6,
• - n is 0 or 1 and m is 0 or 1.
• cyclic radical is understood to mean a monocyclic or polycyclic radical, which therefore presents itself in the form of one or more cycles, saturated and / or unsaturated, optionally substituted (for example cyclohexyl, cyclodecyl , benzyl or fluorenyl), but also a radical which comprises one or more of the said rings (for example p-tertbutylcyclohexyl or 4-hydroxybenzyl).
• saturated and / or unsaturated radical is understood to mean fully saturated radicals, totally unsaturated radicals, including aromatic radicals, as well as radicals comprising one or more double and / or triple bonds, the remainder bonds being simple bonds.
• the radical R2 is preferably a hydrogen atom.
• the radical R3 is preferably a carbon radical, in particular hydrocarbon, cyclic, linear and / or branched, saturated and / or unsaturated, optionally comprising a hydrocarbon ring itself saturated and / or unsaturated, comprising 2 to 18, in particular 3 to 14 , or even 6 to 12 carbon atoms, and can comprise at least one heteroatom, in particular one, two or three nitrogen, sulfur and / or oxygen atoms.
• R3 can be an n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, cyclooctyl, decyl, cyclodecyl radical. dodecyl, cyclododecyl, p-tertbutylcyclohexyl, benzyl, phenyl.
• X'R3 can be a radical -NH- (CH 2 ) n H; -O- (CH 2 ) n H, for example ethoxy or methoxy; -S- (CH 2 ) n H, -SO- (CH 2 ) n H or -SO 2 - (CH 2 ) n H with n being an integer between 1 and 30, in particular between 4 and 12; or alternatively -NH-C6-C18 cycloalkyl, especially -NH-cyclohexyl, -NH-cyclooctyl, -NH-cyclodecyl, -NH-cyclododecyl; or -S-C6-C18 cycloalkyl, -SO-C6-C18 cycloalkyl or -S ⁇ 2 -C6-C18 cycloalkyl; or even a radical chosen from the following:
• G is chosen from saturated linear or branched divalent hydrocarbon-based radicals optionally comprising a saturated hydrocarbon-based ring, comprising in total 2 to 16, in particular 3 to 10 carbon atoms.
• G can be chosen from methylene, ethylene, n-propylene radicals, isopropylene (or methyl-1 ethylene and methyl-2 ethylene), n-butylene, isobutylene, pentylene in particular n-pentylene, hexylene in particular n-hexylene or cyclohexy- lene, heptylene, octylene, cyclooctylene, decylene, cyclodecylene, cyclohexyldimethylene, dodecylene, cyclododecylene.
• the divalent radical X is preferably chosen from -O-, -S-, -NH- or -NR4-, preferably O.
• R4 can be an ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, phenyl or benzyl radical.
• p is equal to 1.
• the polymerizable group P is preferably chosen from one of the following formulas:
• R ' represents H or methyl
• Another subject of the present invention is a monomeric compound of formula (I) below:
• P is a polymerizable group chosen from one of the following formulas
• R - R ' represents H or a hydrocarbon radical, linear or branched, saturated in C1-6,
• - m is 0 or 1;
• R3 is chosen from (i) the alkyl radicals - linear or branched C2-C5 or C7-C24 saturated, optionally substituted and / or optionally interrupted and (ii) saturated cyclic C5-C18 alkyl radicals, optionally substituted and / or optionally interrupted.
• R2 is hydrogen, X 'is O, NH or NR4, and R3 is a linear, branched and / or cyclic, saturated and / or unsaturated carbon radical comprising 2 to 12 carbon atoms; and / or - G is a linear, branched and / or cyclic, saturated and / or unsaturated divalent carbon radical comprising 1 to 8 carbon atoms.
• Another subject of the invention is a polymer comprising at least one such monomeric compound.
• Another object of the invention is the use of at least one such monomeric compound or of such a polymer comprising it, in a composition, to confer on said composition optical effects, in particular of fluorescence or optical brightener.
• the new monomers, and the polymers comprising them have good optical properties and are capable of being prepared more easily than those of the prior art.
• polymers and the monomeric compounds according to the invention find a very particular use for conferring on a composition optical effects, in particular of fluorescence or optical brightener.
• Some of these compounds can in particular be prepared according to the state of the art, for example according to the teaching of document EP728745, in particular the compounds for which X is N.
• the naphthalic amine is present in slight excess relative to the naphthalic anhydride, in particular at a rate of 1 to 1.5 equivalents, preferably 1, 1 equivalent, for 1 equivalent of anhydride.
• the reaction can be carried out in a solvent chosen by the solvents in which the anhydride is soluble, and in particular toluene, xylene, acetic acid, NMP or ethanol; the reaction is preferably carried out at reflux of the solvent, for example at a temperature of 50-250 ° C, preferably 75-150 ° C.
• the timid formed can be reacted with an alcohol or a thiol.
• R'3 is a halogen (preferably chlorine or bromine)
• R'3 is a halogen (preferably chlorine or bromine)
• an aromatic nucleophilic substitution using for example an alcohol or a thiol, such as ethanol, cyclohexanol or dodecane - thiol.
• the reaction can be carried out in the absence of solvent, or in the presence of an aprotic dipolar solvent such as dichloromethane, THF (tetrahydrofuran), in particular at a temperature of 20-150 ° C.
• the sulfur derivatives can be oxidized under mild conditions so as to lead to the corresponding sulfoxide. By modifying the oxidation conditions, it is also possible to prepare the corresponding sulfone. These sulfides, sulfoxides and sulfones can then be transformed to obtain the desired methacrylates or acrylates.
• the alcoholic derivatives for their part, can be reacted with a (meth) acryloyl halide, in particular a chloride, so as to form the corresponding (meth) acrylate.
• a (meth) acryloyl halide in particular a chloride
• This reaction can be carried out in the presence of a base such as triethanolamine, in a solvent such as tetrahydrofuran or dichloromethane, in particular at a temperature of -30 ° C to 100 ° C, preferably 0 to 80 ° C .
• a base such as triethanolamine
• a solvent such as tetrahydrofuran or dichloromethane
• These monomeric compounds can be used as the first monomer to prepare copolymers comprising them.
• the monomeric compounds with optical effect according to the invention can be used to prepare homopolymers or copolymers comprising only monomeric compounds with optical effect of formula (I), alone or as a mixture, or alternatively of formula (I) in admixture with others, in particular in admixture with those of formula A, B and or C as defined below, these various compounds then being able, for example, to be present each in an amount of 0.5 to 99.5% by weight , in particular 5 to 95% by weight, or even 10 to 90% by weight, even better each at a rate of 30 to 70% by weight, relative to the total weight of the polymer.
• This can in particular make it possible to prepare polymers having a wide palette of optical effect (color in particular, optical brightener or other).
• - Ra2 and Ra3 present on the same cycle or each on a different cycle, represent, independently of one another, a hydrogen, a halogen, or a group of formula -Xa-Ga-Pa (II), under provided that at least one of the radicals Ra2 and / or Ra3 represents a group of formula (II), in which:
• - Pa is a polymerizable group chosen from one of the following formulas
• - X ' represents O, NH or NR "with R” representing a radical chosen from C1-6 alkyl, C6-10 aryl, (C6-10) aryl (C1-6) or C1-6 alkyl radicals ) aryls (C6-10), the alkyl and / or aryl groups possibly also being substituted by one or more groups chosen from OH, halogen, C1-6 alkoxy and C6-10 aryloxy; and
• - m is 0 or 1; n is 0 or 1; p is 0, 1 or 2;
• R20 and R21 are, independently of each other, a hydrogen atom, a linear or branched C1-8 alkyl radical, a cyclopentyl, cyclohexyl, cycloctyl, cyclodecyl, cyclododecyl, benzyl, naphthyl or phenyl.
• the copolymers according to the invention can be random, alternating or grafted, or block, for example diblock or triblock, comprising said monomeric compounds with optical effect according to the invention and additional comonomers.
• the monomeric compounds according to the invention can form all or part of a block, or block, or even of several blocks or blocks. It is thus possible to prepare block copolymers of the type AB, ABA, BAB, ABC where A is a block comprising the monomeric compound or compounds according to the invention, optionally in admixture with additional comonomers, B and C being distinct blocks, comprising additional comonomers, alone or as a mixture, and identical or different from the comonomers present in the sequence A.
• copolymers comprising the monomeric compounds according to the invention can also be of the gradient type.
• the monomeric compounds with an optical effect may be present in an amount of 0.01 to 70% by weight relative to the weight of the final polymer, in particular in an amount of 0.1% to 50% by weight, in particular of 0.5 to 30% by weight, or even 1 to 20% by weight, even better from 2 to 10% by weight, the additional comonomers, alone or in mixture, representing the complement to 100% by weight.
• copolymers according to the invention may comprise, in addition to the monomeric compound or compounds with an optical effect, at least one additional comonomer which is hydrophilic, or a mixture of such comonomers.
• hydrophilic comonomers can be present in an amount of 1 to 99.99% by weight, especially 2-70% by weight, even better 5-50% by weight, or even 10-30% by weight, relative to the total weight of the copolymer .
• hydrophilic monomer will denote either the monomers whose homopolymers are soluble or dispersible in water, or whose ionic form is.
• a homopolymer is said to be water-soluble if it forms a clear solution when it is in solution at 5% by weight in water, at 25 ° C.
• a homopolymer is said to be water-dispersible if, at 5% by weight in water, at 25 ° C, it forms a stable suspension of fine particles, generally spherical.
• the average size of the particles constituting said dispersion is less than 1 ⁇ m and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering.
• a monomer will be called 'hydrophobic' if it is not hydrophilic.
• the hydrophilic additional comonomer (s) has a Tg greater than or equal to 20 ° C., in particular greater than or equal to 50 ° C., but may optionally have a Tg less than or equal to 20 ° C.
• the copolymers according to the invention can comprise at least one additional hydrophobic comonomer, or a mixture of such comonomers.
• additional hydrophobic comonomers can be present in an amount of 1 to 99.99% by weight, in particular 30-98% by weight, even better 50-95% by weight, or even 70-90% by weight, relative to the total weight of the copolymer.
• the hydrophobic comonomer has a Tg greater than or equal to 20 ° C., in particular greater than or equal to 30 ° C., but can optionally have a Tg less than or equal to 20 ° C.
• the Tg (or glass transition temperature) is measured according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry") on a calorimeter, over a temperature range between -100 ° C. and + 150 ° C at a heating rate of 10 ° C / min in 150 ⁇ l aluminum crucibles.
• DSC differential enthalpy analysis
• the following monomers may be mentioned, alone or as a mixture:
• ethylenic hydrocarbons having 2 to 10 carbons such as ethylene, isoprene, or butadiene;
• alkyl group from 1 to 18 carbon atoms, in which there are optionally intercalated one or more heteroatoms chosen from O, N, S and P; said alkyl group possibly also being optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms (CI, Br, I and F), and Si groups (R4R5).
• R 4 and R 5 identical or different represent an alkyl group with or a phenyl group; in particular R'3 can be a methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, dodecyl, cyclohexyl, t-butylcyclohexyl or stearyl group; ethyl-2-perfluorohexyl; or hydroxyalkyl group having 1 to 4 such as 2-hydroxyethyl, 2-hydroxybutyl and 2-hydroxypropyl; or an alkoxy (C1-4) alkyl (CM) group such as methoxyethyl, ethoxyethyl and methoxypropyl,
• CM alkoxy (C1-4) alkyl
• a C 3 to C 12 cycloalkyl group such as the isobomyl group
• a C 3 to C 2 o aryl group such as the phenyl group, a C 4 to C 30 aralkyl group (C 1 to C 8 alkyl group) such as 2-phenylethyl, t-butylbenzyl or benzyl,
• heterocyclic group of 4 to 12 members containing one or more heteroatoms chosen from O, N and S, the ring being aromatic or not,
• heterocycloalkyl group (alkyl of 1 to 4 C), such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl groups which may be optionally substituted by one or more substituents chosen from hydroxyl groups, atoms of 'halogen, and C1-4 alkyl groups, linear or branched in which there is (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S and P, said alkyl groups being able, in addition, to be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms (Cl, Br, I and F), and Si groups (R 4 R 5 ), where R 4 and R 5, which are identical or different, represent a C1 to C6 alkyl group, or a phenyl group, - R 3 can also be a group - (C 2 H 4 ⁇ )
• R6 / H, C C CO-N ⁇ R7 in which R 8 denotes H or methyl; and R 7 and R ⁇ , identical or different, represent:
• R6 and / or R7 may be a methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, do-decyl, cyclohexyl, t-butylcyclohexyl or stearyl group;
• a C 4 to C 30 aralkyl group such as 2-phenylethyl, t-butylbenzyl or benzyl,
• heterocycloalkyl group (alkyl of 1 to 4 C), such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl groups which may be optionally substituted by one or more substituents chosen from hydroxyl groups, atoms of 'halogen, and C1-C4 alkyl groups, linear or branched in which is (are) optionally intercalated ⁇ ) one or more heteroatoms chosen from O, N, S and P, said alkyl groups being able, in addition, to be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms (Cl, Br, I and F), and Si groups (R 4 R 5 ), where R 4 and R 5, which are identical or different, represent a group C1 to C6 alkyl, or a phenyl group.
• Examples of (meth) acrylamide monomers are (meth) acrylamide, N-ethyl (meth) acrylamide, N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethyl (meth) acrylamide, the N, N-dibutylacrylamide, N-octylacrylamide, N-dodecylacrylamide, undecylacrylamide, and N (2-hydroxypropylmethacrylamide).
• alkyl group a linear or branched alkyl group, from 1 to 18 carbon atoms, in which there are optionally intercalated one or more heteroatoms chosen from O, N, S and P; said alkyl group possibly also being optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms (Cl, Br, I and F), and Si groups (R4R 5 ), where R4 and R 5 identical or different represent an alkyl group -C 6 or phenyl;
• a C 3 to C 12 cycloalkyl group such as isobornyl, cyclohexane,
• aryl group such as phenyl
• aralkyl group such as 2-phenylethyl; benzyl,
• heterocyclic group of 4 to 12 members containing one or more heteroatoms chosen from O, N and S, the ring being aromatic or not,
• heterocycloalkyl group (alkyl of 1 to 4 C), such as furfurylmethyl or tetrahydrofurfurylmethyl, said cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl groups which may be optionally substituted by one or more substituents chosen from hydroxyl groups, atoms of 'halogen, and alkyl groups of 1 to 4 C linear or branched in which there are (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S and P, said alkyl groups being able, in addition, to be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms (Cl, Br, I and F) and Si (Rs) groups where R 4 and R 5, which are identical or different, represent a C 1 to C 6 alkyl group , or a phenyl group.
• R 4 and R 5 which are identical or different, represent a C 1 to C 6 al
• vinyl monomers are vinylcyclohexane, and styrene.
• vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate.
• vinyl ethers mention may be made of vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.
• the ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric or sulfonic acid or anhydride function, such as for example acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamide-dopropanesulfonic acid, vinyl benzoic acid, vinyl phosphoric acid and the salts thereof,
• ethylenically unsaturated monomers comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and the salts thereof.
• the salts can be formed by neutralization of the anionic groups using a mineral base, such as LiOH, NaOH, KOH, Ca (OH) 2 , NH 4 OH or Zn (OH) 2 ; or with an organic base such as a primary, secondary or tertiary alkylamine, in particular triethylamine or butylamine.
• a mineral base such as LiOH, NaOH, KOH, Ca (OH) 2 , NH 4 OH or Zn (OH) 2
• an organic base such as a primary, secondary or tertiary alkylamine, in particular triethylamine or butylamine.
• This primary, secondary or tertiary alkylamine can comprise one or more nitrogen and / or oxygen atoms and can therefore comprise, for example, one or more alcohol functions; mention may in particular be made of ramino-2-methyl-2-propanol, triethanolamine and dimethylamino-2-propanol. Mention may also be made of lysine
• mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid.
• the additional comonomer (s) may be present in an amount of 30% to 99.99% by weight relative to the weight of the final polymer, in particular in one amount from 50% to 99.9% by weight, in particular from 70% to 99.5% by weight, or even from 80 to 99% by weight, even better from 90 to 98% by weight.
• the additional comonomers are chosen more particularly from, alone or as a mixture, C1-C18 alkyl (meth) acrylates or C3-C12 cycloalkyl, and in particular from methyl acrylate, methyl methacrylate, isobornyl acrylate, isobomyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, dodecyl acrylate , dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate.
• Said polymers can be prepared according to methods known to those skilled in the art, in particular by radical polymerization; controlled radical polymerization, for example with xanthans, dithiocarbamates or dithioesters; by polymerization using nitroxide type precursors; by radical atom transfer polymerization (ATRP); by group transfer polymerization.
• radical polymerization controlled radical polymerization, for example with xanthans, dithiocarbamates or dithioesters
• ATRP radical atom transfer polymerization
• group transfer polymerization by group transfer polymerization.
• the polymerization can be carried out in the presence of a polymerization initiator, which can be a radical initiator, and in particular which can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, ter -butyl peroxy-2-ethylhexanoate; or among diazotized compounds such as azobisisobutyronitrile or azobisdimethylvaleronitrile.
• a polymerization initiator which can be a radical initiator, and in particular which can be chosen from organic peroxide compounds such as dilauroyl peroxide, dibenzoyl peroxide, ter -butyl peroxy-2-ethylhexanoate; or among diazotized compounds such as azobisisobutyronitrile or azobisdimethylvaleronitrile.
• the reaction can also be initiated using photoinitiators or by UV-type radiation, by neutrons or by plasma.
• the monomeric compounds with an optical effect preferably have an absorption wavelength between 200 and 550 nm, especially between 220 and 520 nm, or even between 240 and 500 nm.
• They preferably have an emission wavelength between 350 and 750 nm, in particular between 390 and 700 nm, or even between 420 and 670 nm.
• the weight average molecular weight (Mw) of the copolymers according to the invention is preferably between 5000 and 600,000 g / mol, in particular between 10,000 and 300,000 g / mol, and even better between 20,000 and 150,000 g / mol.
• the average molecular weights by weight (Mw) and number (Mn) are determined by liquid gel permeation chromatography (GPC), eluent THF, calibration curve established with linear polystyrene standards, refractometric and UV detector.
• the polymers according to the invention can be present, alone or as a mixture, in the compositions according to the invention in an amount of 0.01 to 60% by weight, preferably 0.1 to 50% by weight, in particular 1 to 25% by weight, or even 3 to 15% by weight, and even better 5 to 12% by weight, relative to the total weight of the composition.
• the polymers according to the invention are soluble or dispersible in at least one of the phases of the composition which comprises them.
• compositions according to the invention comprise, in addition to said polymers, a physiologically acceptable medium, in particular cosmetically, dermatologically or pharmaceutically acceptable, that is to say a medium compatible with keratin materials such as the skin of the skin. face or body, hair, eyelashes, eyebrows and nails.
• a physiologically acceptable medium in particular cosmetically, dermatologically or pharmaceutically acceptable, that is to say a medium compatible with keratin materials such as the skin of the skin. face or body, hair, eyelashes, eyebrows and nails.
• the composition can thus comprise, a hydrophilic medium comprising water or a mixture of water and organic solvent (s) hydrophilic (s) such as alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or even C ethers 2 and hydrophilic C 2 -C 4 aldehydes.
• a hydrophilic medium comprising water or a mixture of water and organic solvent (s) hydrophilic (s) such as alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pen
• the water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably 10% to 80% by weight.
• the composition can also be anhydrous.
• the composition can also comprise a fatty phase which can comprise fatty substances liquid at ambient temperature (25 ° C. in general) and / or fatty substances solid at ambient temperature such as waxes, pasty fatty substances, gums and their mixtures. These fatty substances can be of animal, vegetable, mineral or synthetic origin. This fatty phase can, in addition, contain lipophilic organic solvents.
• oils As fatty substances liquid at room temperature, often called oils, which can be used in the invention, mention may be made of: hydrocarbon oils of animal origin such as perhydrosqualene; vegetable hydrocarbon oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms such as heptanoic or octanoic acid triglycerides, or even sunflower, corn, soybean, grape seed, sesame oils, apricot, macadamia, castor, avocado, caprylic / capric acid triglycerides, jojoba oil, shea butter; linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petroleum jelly, polydeneces, hydrogenated polyisobutene such as parlameam; synthetic esters and ethers, in particular of fatty acids such as, for example, Purcellin oil, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2-
• oils can be present in a content ranging from 0.01 to 90%, and better still from 0.1 to 85% by weight, relative to the total weight of the composition.
• composition according to the invention can also comprise one or more organic solvents, physiologically acceptable.
• solvents can generally be present in a content ranging from 0.1 to 90%, preferably from 0.5 to 85%, more preferably from 10 to 80% by weight, relative to the total weight of the composition, and better still from 30 to 50%. Mention may in particular be made, in addition to the hydrophilic organic solvents mentioned above, ketones which are liquid at room temperature such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; propylene glycol ethers which are liquid at room temperature such as propylene glycol mono-methyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol mono n-butyl ether; short chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate d isopentyl;
• wax within the meaning of the present invention is meant a lipophilic compound, solid at room temperature (25 ° C.), with reversible solid / liquid state change, having a melting point greater than or equal to 25 ° C. up to 'at 120 ° C.
• melting By bringing the wax to the liquid state (melting), it is possible to make it miscible with the oils possibly present and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, one obtains recrystallization of the wax from the oils in the mixture.
• the melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER.
• DSC differential scanning calorimeter
• the waxes can be hydrocarbon, fluorinated and / or silicone and be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting point greater than 30 ° C and better still greater than 45 ° C.
• wax which can be used in the composition of the invention mention may be made of beeswax, Carnauba or Candellila wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene or Fischer Tropsch waxes, silicone waxes such as alkyl or alkoxy-dimethicone having from 16 to 45 carbon atoms.
• the gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and the pasty bodies are generally hydrocarbon compounds such as lanolines and their derivatives or PDMS.
• the composition may contain from 0.1 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.
• composition according to the invention can also comprise, in a particular phase, pigments and / or nacres and / or fillers usually used in cosmetic compositions.
• composition can also comprise other coloring materials chosen from water-soluble dyes and / or liposoluble dyes well known to those skilled in the art.
• pigments should be understood to mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.
• fillers it is necessary to understand colorless or white, mineral or synthetic particles, lamellar or non-lamellar, intended to give body or rigidity to the composition, and / or softness, mattness and uniformity in makeup.
• the pigments can be present in the composition in an amount of 0.01 to 25% by weight of the final composition, and preferably at a rate of 3 to 10% by weight. They can be white or colored, mineral or organic. Mention may be made of titanium, zirconium or cerium oxides, as well as oxides of zinc, iron or chromium, ferric blue, chromium hydrate, carbon black, overseas (polysulphides of aluminosilicates), manganese pyrophosphate and certain metallic powders such as those of silver or aluminum. Mention may also be made of the D&C pigments and the lacquers commonly used to give the lips and the skin a makeup effect, which are calcium, barium, aluminum, strontium or zirconium salts.
• the nacres can be present in the composition in an amount of 0.01 to 20% by weight, preferably at a rate of the order of 3 to 10% by weight.
• liposoluble or water-soluble which may be present in the composition, alone or as a mixture, at a rate of 0.001 to 15% by weight, preferably 0.01 to 5% by weight and in particular from 0.1 to 2% by weight, relative to the total weight of the composition, there may be mentioned the disodium salt of culvert, the disodium salt of alizarin green, quinoline yellow, the trisodium salt of amaranth, the disodium salt of tartrazine, the salt monosodium rhodamine, disodium fuchsin salt, xanthophyll, methylene blue, cochineal carmine, halo-acid, azo, anthraquinone dyes, copper or iron sulfate, Sudan brown, Sudan red and annatto, as well as beet juice and carotene.
• the disodium salt of culvert the disodium salt of alizarin green, quinoline yellow
• the trisodium salt of amaranth the dis
• composition according to the invention may also further comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.02% at 30% by weight.
• the fillers can be mineral or organic in any form, platelet, spherical or oblong.
• talc Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®), poly- ⁇ -alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), of acrylic acid copolymers (Polytrap® of the company Dow Corning) and mi - silicone resin beads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbon, hydroxyapatite, hollow silica microspheres (Silica Beads® of Maprecos), glass or ceramic microcapsules, metallic soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon
• the composition may further comprise an additional polymer such as a film-forming polymer.
• film-forming polymer means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
• film-forming polymers capable of being used in the composition of the present invention mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures, in particular acrylic polymers, polyurethanes , polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.
• composition according to the invention may also include ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, hair loss agents, dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, hair loss agents, dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, hair loss agents, dandruff agents, propellants, ceramides, or mixtures
• the composition according to the invention may be in the form of a suspension, a dispersion in particular of oil in water by means of vesicles; an oily solution possibly thickened or even gelled; an oil-in-water, water-in-oil, or multiple emulsion; a gel or foam; an oily or emulsified gel; a dispersion of vesicles, in particular lipid vesicles; a biphasic or multiphase lotion; a spray; loose, compact or poured powder; an anhydrous paste.
• This composition may have the appearance of a lotion, a cream, an ointment, a flexible paste, an ointment, a cast or molded solid and in particular in stick or in a cup, or alternatively of compacted solid.
• the cosmetic composition according to the invention may be in the form of a product for caring for and / or making up the skin of the body or of the face, lips, nails, eyelashes, eyebrows and / or hair, a sun or self-tanning product, a hair product for the care, treatment, shaping, makeup or coloring of the hair.
• a makeup composition in particular a product for the complexion such as a foundation, a blusher or an eyeshadow; a lip product such as lipstick or lip care; a concealer; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip or eye pencil; a nail product such as nail polish or nail care; a body makeup product; a hair makeup product (mascara or hair spray).
• a composition for protecting or caring for the skin of the face, neck, hands or body in particular an anti-wrinkle composition, a hydrating or treating composition; an anti-sun or artificial tanning composition.
• It can also be in the form of a hair product, in particular for coloring, maintaining the hairstyle, shaping the hair, caring for, treating or cleaning the hair, such as shampoos, gels, styling lotions, brushing lotions, fixing and styling compositions such as lacquers or spray.
• a hair product in particular for coloring, maintaining the hairstyle, shaping the hair, caring for, treating or cleaning the hair, such as shampoos, gels, styling lotions, brushing lotions, fixing and styling compositions such as lacquers or spray.
• a subject of the invention is also a cosmetic process for making up or caring for keratin materials, in particular the skin of the body or of the face, lips, nails, eyelashes, eyebrows and / or hair, comprising application to said materials of a cosmetic composition as defined above.
• Wavelength measurement method emission and absorption
• Wavelength measurement is performed using a Varian Cary fluorimeter
• this measurement is carried out as follows: 20 mg of product are placed in a 50 ml cylinder. In order to dissolve the product, said cylinder is made up to 50 ml, using an appropriate solvent, for example dichloromethane (DCM), chloroform or dimethylsulfoxide (DMSO). The resulting solution is mixed and 250 microliters are taken, which is placed in a 50 ml cylinder, and then made up again with the solvent to 50 ml.
• DCM dichloromethane
• DMSO dimethylsulfoxide
• the whole is mixed and a sample of the solution is taken which is placed in a closed tank, quartz and 10 mm thick, which is then placed in the measurement chamber.
• a homopolymer is prepared from a monomer according to the invention.
• a homopolymer is prepared from a monomer according to the invention.
• a random copolymer is prepared comprising a monomer according to the invention.
• the reaction mixture is heated to 90 ° C; stirring and heating are continued for 4 hours and then cooled to room temperature.
• the resulting polymer is purified by precipitation.
• 100 g of random polymer are obtained comprising (% by weight): 70% of isobornyl acrylate, 20% ethylhexyl acrylate and 10% of monomer according to the invention.
• a random copolymer is prepared comprising a monomer according to the invention.
• An anhydrous foundation comprising (% by weight): - polyethylene wax 12%
• Example 8 A random copolymer comprising a monomer according to the invention is prepared.
• Trigonox 21 S t-butyl peroxy-2-ethylhexanoate
• a statistical polymer comprising (% by weight): 54% methyl methacrylate, 34% methyl acrylate, 10% acrylic acid and 2% of monomer according to the invention.
• a nail varnish is prepared comprising: - 5% by weight of polymer according to Example 8 - qs 100% organic solvents.

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