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    • 专利摘要:
    The invention relates to a block polymer comprising: a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C from a monomer CH2 = C (R1) -COOR2 with R1 = H or methyl, R2 = C4 to C12 cycloalkyl group; and a second block having a glass transition temperature (Tg) less than or equal to 20 ° C from a vinylphosphonic acid and a monomer CH2 = C (R1) -COOR3 with R1 = H or methyl, R3 = group unsubstituted C1 to C6 alkyl, linear or branched, with the exception of tert-butyl, or methoxyethyl. The invention also relates to a cosmetic composition comprising such a block polymer, as well as a process for the care or makeup of keratin materials using said sequenced polymer associated with an additional compound selected from polyamine compounds having several primary amine groups and / or or secondary amine, amino alkoxysilanes, salts of divalent or trivalent metal ions, clays, metal oxides. The process makes it possible to obtain a film-forming deposit having good resistance to water, oil and sebum. The film is also non-sticky and non-transferable.
    公开号:FR3045614A1
    申请号:FR1563117
    申请日:2015-12-22
    公开日:2017-06-23
    发明作者:Bertrand Lion；Laurent Sabatie
    申请人:LOreal SA；
    IPC主号:
    专利说明:

    The present invention relates to a phosphonic acid group block polymer, a composition comprising such a polymer and the use of this polymer in the cosmetic field.
    It is known from application EP-A-1882709 of block polymers, in particular based on isobornyl (meth) acrylate, isobutyl acrylate and acrylic acid, which are of interest in the cosmetic field for their film-forming properties, of good quality. holding and shine. However, it is desirable to improve the cosmetic properties of such block polymers, in particular the non-transfer and non-sticking properties, in particular during the contact of the film-forming deposit with the fingers. It is also desirable to improve the holding properties of the film in contact with oils or sebum.
    The inventors have discovered particular phosphonic acid group ethylenic block polymers which make it possible to obtain a film having improved holding properties, in particular the properties of non-sticking and non-transfer during contact of the film with the fingers.
    This particular phosphonic block polymer is easily transportable in a hydrocarbon oil such as isododecane.
    When this phosphonic polymer is associated with an additional compound selected from amine compounds having several primary amine and / or secondary amine groups, amino alkoxysilanes, salts of divalent or trivalent metal ions, clays, metal oxides, it forms a film-forming deposit with good properties of resistance to water, oil (especially olive oil) and sebum. The film also has the property of not sticking or transferring to the touch of the finger. The deposit obtained has good holding properties.
    These good film-forming properties are also obtained when the polymer is associated with a non-volatile oil (often used in make-up products).
    This phosphonic block polymer associated with said additional compound forms a film-forming deposit suitable for the makeup of the skin or lips or eyelashes such as foundations, lipsticks, mascaras, or even for fixing the hair.
    More specifically, the subject of the present invention is a block polymer comprising: at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C. and obtained from at least one (meth) monomer acrylate of formula CH 2 = C (R 1) -COOR 2 in which is H or a methyl radical and R 2 is a C 4 to C 12 cycloalkyl group; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one vinylphosphonic acid monomer of formula (I) defined below and at least one a (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which is H or a methyl radical and R 3 represents either a linear or branched C 1 -C 6 unsubstituted alkyl group, with the exception of the tert-butyl group, or a methoxyethyl group.
    Such a sequenced polymer is hereinafter referred to as a phosphonic polymer. The invention also relates to a composition comprising, in a physiologically acceptable medium, a phosphonic polymer as described above. The subject of the invention is also a process, especially a cosmetic one, for treating, in particular skincare or makeup, keratin materials, comprising the topical application to keratin materials of a composition, in particular a cosmetic composition, comprising a phosphonic polymer such as as previously described. The subject of the invention is in particular a process, in particular a cosmetic, treatment method, in particular for the care or make-up of the skin or the lips, comprising the topical application on the skin or the lips of a composition, in particular a cosmetic composition. , comprising a phosphonic polymer as described above.
    According to one embodiment of the process according to the invention, the topical application is carried out on the keratin materials of a composition obtained by mixing (extemporaneous) a composition comprising a phosphonic polymer as described above and an additional component selected from polyamino compounds having several primary amine and / or secondary amine groups, amino alkoxysilanes, divalent or trivalent metal ion salts, clays, metal oxides, or a composition containing it and comprising a physiologically acceptable, the composition (s) used being anhydrous when the additional component is an amino alkoxysilane.
    According to one embodiment of the process according to the invention, the mixture of the composition comprising the phosphonic polymer and of the additional component, or of the composition containing it, is carried out in a time of between 1 minute and 24 hours before its application on the keratin materials, and preferably between 5 and 30 minutes.
    According to a first embodiment of the method according to the invention, the topical application on the keratin materials is carried out a composition resulting from mixing (extemporaneous) a composition comprising a phosphonic polymer as described above and an additional component such as as defined below, or a composition containing it and comprising a physiologically acceptable medium, as defined below.
    According to a second embodiment of the process according to the invention, the sequential application on the keratin materials of a composition comprising a phosphonic polymer as described above and of an additional component as defined below, or of a composition containing it and comprising a physiologically acceptable medium, as defined below. The subject of the invention is also a composition, in particular a cosmetic composition, obtained by mixing a composition comprising, in a physiologically acceptable medium, said phosphonic polymer and an additional component as defined above or a composition containing it and comprising a physiologically acceptable medium, the composition being anhydrous when the additional compound is an amino alkoxysilane. The invention also relates to a kit comprising a first composition comprising said phosphonic polymer as described above and a second composition comprising an additional component as defined above and comprising a physiologically acceptable medium, the first and second compositions being each packaged in a separate conditioning package, the compositions being anhydrous when the additional compound is an amino alkoxysilane. The packaging assembly of the compositions is in a known manner any packaging adapted to store the cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).
    Such a kit makes it possible to implement the process for treating keratin materials according to the invention.
    The method according to the invention is suitable for the care or makeup of keratin materials such as skin, lips, eyelashes, nails.
    The block polymer according to the invention comprises: at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C. and obtained from at least one (meth) acrylate monomer of formula CH 2 = C ( R 1) -COOR 2 wherein H is methyl or R 2 is C 4 -C 12 cycloalkyl; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one vinylphosphonic acid monomer of formula (I) defined below and at least one a (meth) acrylate monomer having the formula CH 2 = C (R 1) -COOR 3 in which R 1 represents H or a methyl radical and R 3 represents a linear or branched C 1 to C 6 unsubstituted alkyl group, with the exception of the tert-butyl group.
    The indicated glass transition temperatures of the first and second sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:
    where ojj is the mass fraction of the monomer i in the sequence under consideration and Tg is the glass transition temperature of the homopolymer of the monomer i.
    Unless otherwise indicated, the Tg values for the first and second sequences in the present application are theoretical Tg. The difference between the glass transition temperatures of the first and second blocks is generally greater than 20 ° C., preferably greater than 40 ° C., and better still greater than 60 ° C.
    In the present invention, the expression "between ... and ..." is intended to denote an interval of values whose mentioned limits are excluded, and "from ... to ..." and "from from ... to ... ", an interval of values whose terminals are included.
    The block polymer used according to the invention has a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C, for example a Tg ranging from 40 to 150 ° C, and obtained from at least one (meth) acrylate monomer of formula CH2 = C (R1) -COOR2 wherein R1 is H or methyl and R2 is C4 to C12 cycloalkyl.
    Preferably, said first block has a Tg greater than or equal to 60 ° C, ranging for example from 60 ° C to 140 ° C, in particular ranging from 80 ° C to 120 ° C.
    The monomers present in the first block of the polymer and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C., and in particular as described above.
    According to a preferred embodiment, the first block of the polymer is obtained from at least one acrylate monomer of formula CH 2 CHCH-COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer. formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 cycloalkyl group at
    Ci2.
    The first block of the polymer can be obtained exclusively with said acrylate monomer and said methacrylate monomer.
    The acrylate monomer and the methacrylate monomer are preferably used in acrylate / methacrylate mass proportions of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular between 45:55 and 55:45.
    The proportion of the first block in the block polymer is preferably 60 to 80% by weight of the polymer, more preferably 65 to 75%.
    According to a preferred embodiment, the first block of the polymer is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.
    The first block of the polymer may further comprise an additional monomer selected from linear or branched C 1 -C 22 alkyl (meth) acrylates (i.e., including a C 3 -C 22 alkyl group). such as, for example, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, behenyl acrylate, behenyl methacrylate, stearyl acrylate, stearyl methacrylate .
    Said additional monomer may be present in a content ranging from 0.1 to 15% by weight, relative to the total weight of the monomers of the first block of said block polymer, and preferably ranging from 0.1 to 5%.
    According to one embodiment, the first sequence of said sequenced polymer contains no additional monomer.
    The block polymer used according to the invention has a second block having a glass transition temperature (Tg) of less than or equal to 20 ° C., for example a Tg ranging from -100 to 20 ° C., and is obtained from from at least one vinyl phosphonic acid monomer of formula (I) defined below and at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which is H or a methyl radical and R 3 represents a non-alkyl group substituted C1 to C6, linear or branched, with the exception of tert-butyl, or methoxyethyl.
    Preferably, said second block has a Tg of less than or equal to 10 ° C., in particular ranging from -80 ° C. to 15 ° C. and better still less than or equal to 0 ° C., for example ranging from -100 ° C. to 0 ° C. , especially ranging from -30 ° C to 0 ° C.
    The monomers present in the second block of the polymer and their proportions are preferably chosen so that the glass transition temperature of the second block is less than or equal to 20 ° C., and in particular as described above.
    The vinyl phosphonic acid monomer has the following formula (I):
    wherein: R1 is H or -CH3; X is a covalent bond and n is an integer from 0 to 14; or X denotes a group -COO- and n denotes an integer ranging from 2 to 6.
    Advantageously, for the monomer of formula (I), X denotes a covalent bond and n is an integer ranging from 0 to 6 or X denotes a -COO- group and n is an integer ranging from 2 to 4.
    Preferentially, for the monomer of formula (I):
    R1 = H X denotes a covalent bond and n is an integer from 0 to 4.
    As an example of a monomer of formula (I), mention may be made of: vinylphosphonic acid; 3-butenylphosphonic acid; 4-pentenylphosphonic acid; 10-undecenyl phosphonic acid; 11-dodecenylphosphonic acid; the 2-phosphonoethyl ester of 2-propenoic acid; the 2-phosphonoethyl ester of 2-methyl-2-propenoic acid.
    Preferably, the monomer (I) is vinylphosphonic acid.
    Monomers having a Tg of less than or equal to 20 ° C are preferred isobutyl acrylate, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate or mixtures thereof in any proportion.
    The second block of the polymer can be obtained exclusively with the vinyl phosphonic acid monomer (I) and said acrylate monomer.
    The vinylphosphonic acid monomer (I) and the acrylate monomer are preferably used in mass proportions of acrylate / vinylphosphonic acid monomer (I) ranging from 1 to 10, preferably ranging from 2 to 9, in particular ranging from 3 to 8, or still ranging from 4 to 7.
    The proportion of the second block in the block polymer is preferably from 20 to 40% by weight of the polymer, and more preferably from 25 to 35%.
    According to a preferred embodiment, the second block of the polymer is obtained by polymerization of vinylphosphonic acid and isobutyl acrylate.
    The second block of the polymer may further comprise an additional silicone monomer of formula (N) (hereinafter referred to as silicone monomer):
    in which: - Rs denotes a hydrogen atom or a methyl group; preferably methyl; R 9 denotes a linear or branched divalent hydrocarbon group, preferably linear, having from 1 to 10 carbon atoms, preferably having from 2 to 4 carbon atoms, and optionally containing one or two ether bonds -O-; preferably an ethylene, propylene or butylene group; - R- o denotes a linear or branched alkyl group having 1 to 10 carbon atoms, especially 2 to 8 carbon atoms; preferably methyl, ethyl, propyl, butyl or pentyl; n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200, and preferably ranging from 5 to 100.
    The monomer (II) is a polydimethylsiloxane end-group mono (meth) acryloyloxy.
    In particular, monomethacryloyloxypropyl polydimethylsiloxanes may be used, such as those sold under the names MCR-M07, MCR-M17, MCR-M11 and MCR-M22 by Gelest Inc or the silicone macromonomers sold under the names X-22-2475 and X-22. -2426, X-22-174DX by Shin Etsu.
    The monomer (II) may be present in the second block of the sequenced polymer in a content ranging from 0.1 to 15% by weight, relative to the total weight of the monomers of the second block of said block polymer, and preferably ranging from , 1 to 5%.
    According to one embodiment, the second sequence of said sequenced polymer does not contain additional monomer.
    Preferably, the polymer used according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in the first block and vinyl phosphonic acid and isobutyl acrylate monomers in the second block.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio ranging from 30: 70 to 70: 30 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion of 40: 60 and 60:40 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio ranging from 30: 70 to 70: 30 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion of 40: 60 and 60:40 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second sequence, the first sequence representing between 65 and 75% by weight of the polymer, and in particular 70% by weight.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a weight ratio ranging from 30: 70 to 70: 30 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second block, the first block representing between 65 and 75% by weight of the polymer, and in particular 70% by weight, and vinylphosphonic acid representing from 3 to 7% by weight of the polymer.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion of 40: 60 and 60:40 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second block, the first block representing between 65 and 75% by weight of the polymer, and in particular 70% by weight, and vinylphosphonic acid representing from 3 to 7% by weight of the polymer.
    Preferably, the polymer comprises at least or even consists of isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45: 55 to 55:45 in the first block and isobutyl acrylate and vinyl acid monomers. phosphonic in the second block, the first block representing between 65 and 75% by weight of the polymer, and in particular 70% by weight, and the vinyl phosphonic acid representing from 3 to 7% by weight of the polymer.
    Said first and second polymer blocks may advantageously be interconnected by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
    The intermediate segment is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer makes it possible to "compatibilize" these blocks.
    Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.
    Preferably, the intermediate sequence is derived essentially from constituent monomers of the first sequence and the second sequence.
    By "essentially" is meant at least 85%, preferably at least 90%, better at 95% and even better at 100%.
    Advantageously, the intermediate block has a glass transition temperature Tg between the glass transition temperatures of the first and second blocks.
    The block polymer used according to the invention is advantageously a film-forming polymer. By "film-forming" polymer is meant 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. The polydispersity index of the sequenced polymer is advantageously greater than 2. The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn.
    The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).
    The weight average mass (Mw) of the sequenced polymer is preferably less than or equal to 300,000, for example from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol.
    The number average mass (Mn) of the sequenced polymer is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 50,000 g / mol.
    Preferably, the sequenced polymer has a polydispersity index greater than 2, for example ranging from 3 to 20, preferably greater than or equal to 4, for example ranging from 4 to 18. The subject of the invention is also a preparation method of a sequenced polymer, comprising mixing, in the same reactor, a polymerization solvent, an initiator, a vinylphosphonic acid monomer of formula (I) as described above, at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which R 1 represents H or a methyl radical and R 3 represents a linear or branched C 1 to C 6 alkyl group, with the exception of the tert-butyl group, at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 2 in which R! represents H or a methyl radical and R2 represents a C4 to C12 cycloalkyl group, according to the following sequence of steps: - is poured into the reactor, a part of the polymerization solvent and a part of the initiator mixture that one heated to a reaction temperature of between 60 and 120 ° C., the at least one monomer (meth) acrylate of formula CH 2 = C (R 1) -COOR 2, which is left to react for a period of time, is then poured in a first casting. a duration T corresponding to a conversion rate of said monomers of 90% maximum, then pouring into the reactor, in a second casting, again the polymerization initiator, vinyl phosphonic acid monomer (I) and said (meth) ) acrylate CH2 = C (R1) -COOR3, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought to room temperature.
    By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, C 6 -C 16 branched alkanes such as C 6 -C 16 isoalkanes such as isododecane, isodecane and isohexadecane. and their mixtures. Preferably, the polymerization solvent is isododecane.
    According to another embodiment, the subject of the invention is a method for preparing a polymer, comprising mixing, in the same reactor, a polymerization solvent, an initiator, a vinyl phosphonic acid monomer (I) such as defined above, at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 3 in which R 1 represents H or a methyl radical and R 3 represents a linear or branched C 1 to C 6 unsubstituted alkyl group in which R 3 represents a linear or branched C 1 to C 12 unsubstituted alkyl group, with the exception of the tert-butyl group, at least one (meth) acrylate monomer of formula CH 2 = C (R 1) -COOR 2 in which R 1 represents H or a methyl radical; and R2 represents a C4 to C12 cycloalkyl group in which R2 represents a C4 to C12 cycloalkyl group, according to the following sequence of steps: a portion of the polymerization solvent and a part of the initiator are metered into the reactor; when heated to a reaction temperature of between 60 and 120 ° C., the vinyl phosphonic acid monomer (I) and said (meth) acrylate of formula CH 2 = C (Ri) are then poured in a first casting; -COOR3que it allows to react for a time T corresponding to a conversion rate of said monomers 90% maximum, then poured into the reactor, in a second casting, again the polymerization initiator, said at least monomer (Meth) acrylate of formula CH 2 = C (R 1) -COOR 2, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature.
    The polymerization temperature is preferably between 85 and 95 ° C, in particular of the order of 90 ° C.
    The reaction time after the second casting is preferably between 3 and 6 hours.
    The monomers used in the context of this process, as well as their proportions may be those described above.
    The polymerization is especially carried out in the presence of a radical initiator, in particular of the peroxide type (for example tert-Butyl peroxy-2-ethylhexanoate: Trigonox 21S, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel) or azo for example (AIBN: azobisisobutyronitrile; V50: 2,2'-azo-bis (2-amidinopropane) dihydrochloride).
    The polymer used according to the invention may be used in a composition comprising a physiologically acceptable medium, in particular in a cosmetic composition.
    By physiologically acceptable medium is meant a medium compatible with keratin materials of human beings, in particular with the skin, the lips, the nails, the eyelashes.
    By cosmetic composition is meant a composition compatible with keratin materials, which has a pleasant color, odor and feel, and which does not generate unacceptable discomfort (tingling, tightness, redness), likely to distract the consumer .
    The phosphonic polymer as defined above may be present in the composition according to the invention in a content ranging from 0.1 to 40% by weight, relative to the total weight of the composition resulting from extemporaneous mixing, preferably 0.5 % to 35% by weight, and preferably ranging from 1% to 30% by weight, and more preferably from 10% to 30% by weight. This is the composition that is applied to keratin materials.
    The additional component used in the process according to the invention is in particular an amine compound chosen from polyamine compounds having several primary amine and / or secondary amine groups or even amino alkoxysilanes. It can therefore be chosen from amino alkoxysilane compounds, diamine compounds and triamine compounds.
    According to a first embodiment of the invention, the polyamine compound is a compound comprising from 2 to 20 carbon atoms, in particular a non-polymeric compound. By non-polymeric compound is meant a compound which is not directly obtained by a polymerization reaction of monomers.
    Polyamino compounds that may be mentioned include N-methyl-1,3-diaminopropane, N-propyl-1,3-diaminopropane, N-isopropyl-1,3-diaminopropane and N-cyclohexyl-1,3-diaminopropane. (3-aminopropylamino) ethanol, 3- (2-aminoethyl) aminopropylamine, bis (3-aminopropyl) amine, methyl bis (3-aminopropyl) amine, N- (3-aminopropyl) -1,4- diaminobutane, N, N-dimethyldipropylene triamine, 1,2-bis (3-aminopropylamino) ethane, N, N'-bis (3-aminopropyl) -1,3-propanediamine, ethylene diamine, 1, 3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylene diamine, tris (2-aminoethyl) amine, spermidine. Preferably, the amine compound is chosen from ethylene diamine, 1,3-propylenediamine and 1,4-butylenediamine. Preferably, the polyamine compound is ethylene diamine.
    The amine compound may also be chosen from aminoalkoxysilanes, such as those of formula (III): R'iSi (OR '2) z (R, 3) x (III) in which: R'i is a hydrocarbon-based chain linear or branched, saturated or unsaturated, cyclic or acyclic CrC 6 substituted by a group chosen from the groups: amine NH 2 or NHR with R = C 1 -C 4 alkyl; an aryl or aryloxy group substituted by an amino group or by a C 1 -C 4 aminoalkyl group; R 1 can be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group (CO), R'i being bonded to the silicon atom directly via a carbon atom, • R'2 and R 3, which are identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, z denotes an integer ranging from 1 to 3, and • x denotes an integer ranging from 0 to 2, with z + x = 3.
    Preferably, R'2 represents an alkyl group comprising from 1 to 4 carbon atoms.
    Preferably, R'2 represents a linear alkyl group comprising from 1 to 4 carbon atoms.
    Preferably, R'2 represents the ethyl group.
    Preferably, R '3 represents an alkyl group comprising from 1 to 4 carbon atoms.
    Preferably, R '3 represents a linear alkyl group comprising from 1 to 4 carbon atoms.
    Preferably, R '3 represents the methyl or ethyl group.
    Preferably R'-ι is an acyclic chain.
    Preferably R '·, is a linear or branched, saturated or unsaturated C 1 -C 8 hydrocarbon-based chain substituted by an NH 2 or NHR amine group (R = C 1 -C 4 alkyl, C 3 -C cycloalkyl or C 1 aromatic). . Preferentially, R't is a linear saturated C-1 -C 5 hydrocarbon-based chain substituted by an NH 2 amine group. More preferably, R 1 is a saturated linear C 2 -C 4 hydrocarbon-based chain substituted with an NH 2 amine group.
    Preferably, R 1 is a saturated linear C 1 -C 8 hydrocarbon-based chain substituted with an amine group NH 2, R 2 represents an alkyl group comprising from 1 to 4 carbon atoms, R 3 represents an alkyl group comprising from 1 to 4 carbon atoms.
    Preferably z is 3.
    Preferably, the aminosilane of formula (III) is chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane. - (m-aminophenoxy) propyltrimethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethylaminomethyl) phenethyltrimethoxysilane.
    Preferably, the aminosilane (III) is chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane.
    Preferably the aminosilane (III) is 3-aminopropyl triethoxysilane (APTES).
    Preferably, the amine compound is chosen from 3-aminopropyltriethoxysilane (APTES), N-methyl-1,3-diaminopropane, N-propyl-1,3-diaminopropane, N-isopropyl-1,3-diaminopropane, N-cyclohexyl-1,3-diaminopropane, 2- (3-aminopropylamino) ethanol, 3- (2-aminoethyl) aminopropylamine, bis (3-aminopropyl) amine, methyl bis (3-aminopropyl) amine, N (3-aminopropyl) -1,4-diaminobutane, Ν, Ν-dimethyldipropylene triamine, 1,2-bis (3-aminopropylamino) ethane, N, N'-bis (3-aminopropyl) -1,3 propane diamine, ethylene diamine, lysine.
    The polyamine compound may also be chosen from amino polymers, in particular having a weight average molecular weight ranging from 500 to 1,000,000, preferably ranging from 500 to 500,000, and preferably ranging from 500 to 100,000.
    Amine polymers that may be used include poly (C 2 -C 5 alkyleneimines), and in particular polyethyleneimines and polypropyleneimines, especially poly (ethylene imines) (for example that sold under the reference 46,852-3 by the company Aldrich Chemical ); poly (allylamine) (for example that sold under the reference 47,913-6 by Aldrich Chemical); polyvinylamines and their copolymers, especially with vinylamides; mention may especially be made of vinylamine / vinylformamide copolymers such as those sold under the name Lupamine® 9030 by the company BASF; polyamino acids having NH 2 groups such as polylysine, for example that sold by JNC Corporation (formerly Chisso); dextran amino, such as that sold by CarboMer Inc; polyvinyl amino alcohol such as that sold by CarboMer Inc., copolymers based on acrylamidopropylamine; chitosan;
    Polydimethylsiloxanes comprising primary amino groups at the end of the chain or on side chains, for example terminal or lateral aminopropyl groups, for example those of formula (A) or (B) or (C):
    H2NCH2CH2CH2-Si (CH3) 2-0- [Si (CH3) 2-O] n-Si (CH3) 2C4Hg (C) in the formula (A): the value of n is such that the weight average molecular weight of the silicone is between 500 and 55,000. As an example of aminosilicone (A), mention may be made of those sold under the names "DMS-A11", "DMS-A12", "DMS-A15", "DMS-A21", "DMS-A31", "DMS-A32," DMS-A35 "by GELEST," reference 481688 "from Aldrich. in the formula (B), the values of n and m are such that the weight average molecular weight of the silcone is between 1000 and 55 000. Examples of silicone (B) include those sold under the names "AMS -132 "," AMS-152 "," AMS-162 "," AMS-163 "," AMS-191 "," AMS-1203 "by the company GELEST. in the formula (C), the value of n is such that the weight average molecular weight of the silicone is between 500 and 3000. Examples of silicone (C) include those sold under the names "MCR-A11 "MCR-A12" by the company GELEST. the amodimethicones of formula (D):
    wherein R, R 'and R ", which may be identical or different, each represents a C 1 -C 4 alkyl or hydroxyl group, A represents a C 3 alkylene group and m and n are such that the weight average molecular weight of the compound is between 5,000 and 5,000. and about 500,000.
    Polyether amines, especially known under the reference JEFFAMINE from the company HUNSTMAN; and especially :
    Polyethylene glycol and / or polypropylene glycol α, ω-diamine (end-amine functional) such as those sold under the names JEFFAMINE D-230, D-400, D-2000, D-4000, ED-600, ED-9000 , ED-2003.
    Poly (α-diamine) polytetrahydrofuran (or polytetramethylene glycol), α, β-diamine polybutadienes;
    Polyamidoamine dendrimers (PANAM) with terminal amine functions.
    Poly (meth) acrylates or poly (meth) acrylamides bearing primary or secondary secondary amine functions such as poly (3-aminopropyl) methacrylamide, poly (2-aminoethyl) methacrylate.
    As aminated polymer, polydimethylsiloxanes comprising primary amine groups at the end of the chain or on side chains are preferably used. Preferentially, the polydimethylsiloxanes comprising aminopropyl end groups comprising end-chain.
    Advantageously, the polyamino compounds used in the process according to the invention are chosen from ethylene diamine, the polydimethylsiloxanes comprising primary amine groups at the end of the chain or on side chains.
    Preferably, the amine compounds used in the process according to the invention are chosen from polydimethylsiloxanes comprising primary amines at the end of the chain or on side chains, 3-aminopropyltriethoxysilane (APTES). More preferably, the polydimethylsiloxanes comprising end-of-the-chain aminopropyl end groups, 3-aminopropyltriethoxysilane (APTES) are used.
    Advantageously, the amine compound used in the process according to the invention is used in a molar ratio amino group of the amine compound / phosphonic acid group of the phosphonic polymer ranging from 0.01 to 10, preferably ranging from 0.1 to 5. , preferably ranging from 0.1 to 2, and more preferably ranging from 0.1 to 1.
    The polyamine compound in contact with the phosphonic polymer reacts with the phosphonic acid functions to form a crosslinked polymer, for example as follows:
    Scheme I
    Such a crosslinked polymer is new and is therefore also the object of the present invention.
    The crosslinked polymer is thus capable of being obtained by reacting said polyamine compound with the vinyl phosphonic acid block polymer described above. Some or all of the anhydride groups react with the N H or NH 2 group of the polyamine compound and form a unit having an amide group and a carboxylic acid group as described in Scheme I.
    The amino alkoxysilane (II) compound in contact with the phosphonic polymer in an anhydrous medium reacts with the phosphonic acid functions to form a unit of the following formula:
    Scheme II
    Such an amino-alkoxysilane block polymer obtained by reacting the phosphonic block polymer with the amino alkoxysilane compound (II) is novel and therefore also the object of the present invention. The invention also relates to an anhydrous composition comprising such an amino-alkoxysilane block polymer and a physiologically acceptable medium. The invention therefore also relates to a polymer obtained by the reaction of said phosphonic block polymer an amine compound as defined above, the reaction taking place in anhydrous medium when the amino compound is an amino alkoxysilane. Other particular additional components may be used in the process according to the invention to help improve the film-forming properties of the polymer according to the invention. Such additional components are especially the salts of divalent or trivalent metal ions, the clays, the metal oxides described below.
    The composition according to the invention may comprise salts of divalent or trivalent metal ions, in particular chosen from ion salts derived from Al (III), Ca (II), Cu (II), Fe (II), Fe (III), Mg (II), Mn (II), Zn (II) and mixtures thereof. The ions from Ca (II), Mg (II) are preferred.
    The salts of these metal ions are well known, for example with anions such as gluconate, chloride, sulfate, hydroxide, acetate, stearate. For example, the following salts may be used: calcium gluconate, calcium chloride, magnesium chloride, copper chloride, magnesium gluconate, iron sulfate, iron gluconate, aluminum sulfate, sodium stearate.
    The said salts of divalent or trivalent metal ions may be present in the composition according to the invention in a content ranging from 0.1 to 20% by weight, preferably from 0.1 to 15% by weight, relative to total weight of the composition.
    Alternatively, the divalent or trivalent metal ion salt can be applied sequentially in the process of the invention
    The composition according to the invention may comprise a clay.
    Clays are already well known products per se, which are described for example in the book "Clay Mineralogy, S. Caillere, S. Hénin, M. Rautureau, 2nd Edition 1982, Masson", whose teaching is here included for reference.
    Among the clays, there may be mentioned, for example, clays of the family of smectites such as laponite and montmorillonite, of the family of kaolinites such as kaolinite, dickite, nacrite, optionally modified clays of the family. halloysite, dombassite, antigorite, benthiérine, pyrophyllite, montmorillonites, beidellite, vermiculites, talc, stevensite, hectorites, bentonites, saponites, chlorites , sepiolite and illite.
    The clays present in the composition of the invention may be natural or synthetic. Natural clay is a sedimentary rock composed for the most part of specific minerals, usually silicates of aluminum. Kaolin is a natural clay.
    The clays can also be chemically modified by various compounds such as acrylic acids, polysaccharides (for example carboxymethylcellulose) or organic cations.
    In the context of the present invention, the clays which are cosmetically compatible with and acceptable for the skin and / or the scalp are preferably used. According to a particular embodiment of the present invention, the clay used is chosen from kaolinite, montmorillonites, saponites, laponites, bentonites, and in particular hectorites, and illites. Clays mixtures and natural clays are still more particularly used. As natural clay, mention may be made of green clays, particularly rich in illite; clays rich in montmorillonite, known as Terre de Sommière, or as bentonites, or white clays rich in kaolinite. As bentonites, mention may in particular be made of those sold under the names "BENTONE 38 VCG", "BENTONE GEL CAO V", "BENTONE 27 V" and "BENTONE GEL MIO V" "BENTONE GEL ISD V" by the company ELEMENTIS.
    Montmorillonites and smectites are hydrated aluminum and / or magnesium silicates. By way of example, mention may be made of montmorillonite sold under the name GEL White H by ROCKWOOD ADDITIVES, the purified smectite marketed under the name VEEGUM GRANULES by VANDERBILT. Mention may also be made of montmorillonite sold under the name Kunipia G4 by Kunimine and Sepiolite Pangel S9 marketed by TOLSA.
    Examples of kaolinites include kaolins sold under the names COSLIN C 100 by the company BASF PERSONAL CARE INGREDIENTS or KAOLIN SUPREME by the company IMERYS.
    Talcs are hydrated magnesium silicates, most often aluminum silicate. The crystalline structure of the talc consists of repeated layers of a brucite sandwich between silica layers. By way of examples, mention may be made of micronized magnesium silicate with a 5 micron particle size distribution marketed under the name MICRO ACE P3 by the company NIPPON TALC or talcs marketed under the names ROSE TALC and TALC SG-2000 by the company NIPPON TALC, , J 68 BC by the company US COSMETICS (MIYOSHI), LYZENAC 00 and LUZENAC PHARMA M by the company LUZENAC, and TALC JA-46R by the company ASADA MILLING. As saponite, which belongs to the family of montmorillonites, mention may be made of synthetic saponite, in particular that sold by Kunimine under the name SUMECTON®. As an example of synthetic laponite, mention may be made of the XLG laponite marketed by Rockwood. The clay may be present in the composition according to the invention in an amount ranging from 0.1 to 50% by weight, especially from 1 to 30% by weight and in particular from 1 to 20% by weight relative to the total weight. of the composition.
    The metal oxides may be chosen from titanium dioxide, iron oxides, zirconium oxides, zinc oxides, cerium oxides and chromium oxides. Iron oxides or titanium dioxide are preferably used. The metal oxide may be present in the composition according to the invention in an amount ranging from 0.1 to 50% by weight, especially from 1 to 30% by weight and in particular from 1 to 20% by weight relative to the weight. total of the composition.
    The composition used according to the invention is generally suitable for topical application to keratin materials, and therefore generally comprises a physiologically acceptable medium, that is to say a medium compatible with keratin materials such as the skin and / or its dander . It is preferably a cosmetically acceptable medium, that is to say which has a pleasant color, odor and feel and that does not generate unacceptable discomfort (tingling, tightness, redness), likely to divert the consumer from using this composition.
    According to a preferred embodiment of the invention, the composition comprising the phosphonic polymer may contain a hydrocarbon oil. The hydrocarbon oil is a liquid oil at room temperature (25 ° C).
    Hydrocarbon oil is understood to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups. The hydrocarbon oil may be volatile or non-volatile. The hydrocarbon-based oil may be chosen from: hydrocarbon-based oils having 8 to 14 carbon atoms, and in particular: C 8 -C 14 branched alkanes, such as C 8 -C 14 isoalkanes of petroleum origin (also called isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names Isopars' or permetyls, - linear alkanes, for example such as the n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97, as well as their mixtures, the undecane-tridecane mixture, the mixtures of n-undecane (C11 ) and n-tridecane (C13) obtained in Examples 1 and 2 of Application WO2008 / 155059 from Cognis, and mixtures thereof. short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate; plant origin such as triglycerides consisting of esters of fatty acids and of glycerol whose fatty acids may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or alternatively caprylic / capric acid triglycerides, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, synthetic ethers having from 10 to 40 carbon atoms. carbon; linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof; synthetic esters, such as oils; of the formula R 1 CO 2, in which represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R 2 represents a hydrocarbon chain, especially a branched hydrocarbon chain, containing from 1 to 40 carbon atoms, provided that R! R 2 is> 10, such as for example purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoates, hexyl laurate, adipate of diisopropyl, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl myristate dodecyl, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters, branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol and oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.
    Advantageously, the hydrocarbon oil is apolar (thus formed only of carbon and hydrogen atoms). The hydrocarbon oil is preferably chosen from hydrocarbon oils having 8 to 14 carbon atoms, in particular apolar oils, described above.
    Preferentially, the hydrocarbon oil is isododecane.
    The composition comprising the polymer may contain, in addition to the hydrocarbon oil, a silicone oil. The term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The silicone oil can be volatile or non-volatile.
    The term "volatile oil", an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular, having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 100 mm Hg), 10 mmHg).
    The term "non-volatile oil" means an oil having a vapor pressure of less than 0.13 Pa.
    As volatile silicone oils, mention may be made of volatile linear or cyclic silicone oils, especially those having a viscosity <8 centistokes (cSt) (8 × 10 -6 m 2 / s), and having, in particular, from 2 to 10 atoms silicon, and in particular from 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having from 1 to 10 carbon atoms. As the volatile silicone oil that may be used in the invention, mention may be made, in particular, of dimethicones of viscosity 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.
    Non-volatile silicone oils that may be mentioned are non-volatile, linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
    Advantageously, the composition may comprise a hydrocarbon oil in a content ranging from 60 to 100% by weight of the total weight of the oils present in the composition and from 0 to 40% by weight of silicone oil. According to a preferred embodiment of the invention, the composition contains as oil only a hydrocarbon oil.
    The composition according to the invention may comprise a cosmetic additive chosen from perfumes, preservatives, fillers, UV filters, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, anti-inflammatory agents and free radicals, polymers, thickeners, dyestuffs.
    The composition according to the invention may also comprise a dyestuff such as pulverulent dyestuffs, liposoluble dyes and water-soluble dyes. This dyestuff may be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition.
    The pulverulent dyestuffs may be chosen from pigments and nacres.
    The pigments may be white or colored, mineral and / or organic, coated or uncoated. Among the inorganic pigments, titanium dioxide, optionally surface-treated, oxides of zirconium, zinc or cerium, as well as oxides of iron or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments, mention may be made of carbon black, D type pigments &amp; C, and lacquers based on carmine cochineal, barium, strontium, calcium, aluminum.
    The nacres may be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
    Liposoluble dyes are, for example, Sudan Red, D &amp; C Red 17, D &amp; C Green 6, β-carotene, soybean oil, Sudan Brown, D &amp; C Yellow 11, D &amp; C Violet 2, D &amp; C orange 5, yellow quinoline, annatto. The water-soluble dyes are, for example, beet juice, methylene blue.
    Advantageously, the composition according to the invention is a skin care composition.
    The composition according to the invention may be a makeup composition such as a foundation, a lipstick or a liner.
    According to one embodiment, the composition according to the invention is a make-up composition and comprises a volatile oil and a non-volatile oil as described above. In particular, the makeup composition may comprise a hydrocarbon volatile oil and a non-volatile hydrocarbon oil.
    According to one embodiment, the composition used according to the invention is an anhydrous composition. By anhydrous composition is meant a composition containing less than 2% by weight of water, or even less than 0.5% of water, and especially free of water. If necessary, such small amounts of water may in particular be brought by ingredients of the composition which may contain residual amounts.
    In particular, when the amino compound is an amino alkoxysilane (III) as defined above, the composition containing it and the compositions used in the process are anhydrous compositions. Advantageously, these compositions additionally contain a C2-C5 monoalcohol such as ethanol or isopropanol, especially in a content ranging from 0.1 to 5% by weight, relative to the total weight of the composition. now be described with reference to the following examples given for illustrative and non-limiting.
    Example 1 Isobornyl Methacrylate / Isobornyl Acrylate (35/35) Copolymer-Isobutyl Copper / Vinyl Phosphonic Acid Copolymer (25/5)
    150 g of isododecane were added to a 1 liter reactor and the solvent was heated by increasing the temperature from 25 ° C to 90 ° C in 1 hour.
    105 g of isobornyl methacrylate, 105 g and of isobornyl acrylate and 1.8 g of 2,5-bis (2-ethylhexanoylperoxy) initiator were then added over 1 hour while maintaining the temperature at 90 ° C. -2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel). The mixture was kept at 90 ° C for 1 hour 30 minutes.
    75 g of isobutyl acrylate, 15 g of vinylphosphonic acid, 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane and 20 g of toluene were then introduced in the course of 30 minutes. g of ethanol.
    The mixture was held for 3 hours at 90 ° C, then was diluted with 150 g of isododecane and then concentrated by distillation to remove unreacted monomers.
    Finally, a 50% by weight solution of the polymer in isododecane was obtained.
    The resulting polymer has a number average molecular weight (Mn) of 20,800 and a weight average molecular weight (Mw) of 312,2000; with an Ip = 15.
    Examples 2 to 5: Cosmetic Evaluation of Makeup Composition
    The makeup compositions (lipstick gloss) described below containing the polymer of Example 1 with or without Disteardimonium Hectorite were prepared and then the composition was applied to an equivalent elastomeric skin support by depositing 100 μm wet thickness and allowed to dry at room temperature (25 ° C) for 24 hours.
    The state of the film obtained was then observed.
    The elastomer support was also manually deformed and the state of the film after this deformation was observed to determine its resistance to deformation.
    The strength of the obtained film was evaluated by separately applying 0.5 ml of water, 0.5 ml of olive oil and 0.5 ml of sebum; after 5 minutes of contact, the surface of the film was rubbed with a cotton pad and then the condition of the film (degraded or non-degraded aspect of the film) was observed.
    It was also evaluated the stickiness of the film and its ability to transfer or not by touching the film with the finger The assessment was made as follows: +++: Cosmetic property evaluated high performance ++: evaluated cosmetic property moderately efficient +: evaluated cosmetic property not performing o: cosmetic property evaluated not performing
    The following results were obtained:
    The results obtained show that the deposit resulting from the application of the polymer 1 alone (Example 2) forms a homogeneous film which is non-sticky and does not transfer to the finger but which breaks up under mechanical stress and which has a low resistance to contact with it. olive oil and sebum. The deposit resulting from the application of the polymer 1 mixed with Disteardimonium Hectorite (Example 3) forms a homogeneous film, which fragments under mechanical stress, and the resistance of the film in contact with olive oil and sebum is clearly improved.
    When the composition comprises 2-octyl dodecanol (non-volatile oil), the deposit obtained resulting from the application of the polymer 1 alone (Example 4) forms a homogeneous non-fragmented film after mechanical stressing but which is a little sticky and not enough. transfer, and little resistant to contact with olive oil and sebum. While the deposit resulting from the application of the polymer 1 mixed with Disteardimonium Hectorite (Example 5) shows an improvement in the properties of non-sticking, non-transfer and resistance of the film in contact with olive oil and sebum .
    Thus, the addition of Disteardimonium Hectorite contributes to improving the cosmetic properties of the film obtained.
    The lipstick compositions of Examples 3 and 5 applied to the lips thus make it possible to obtain a makeup which is non-tacky, non-transferable and resistant to water, oil and sebum, thus having good strength.
    Examples 6 and 7: Cosmetic Evaluation of Makeup Composition
    The makeup compositions (lipstick gloss) described hereinafter containing the polymer of Example 1 with or without 3-aminopropyl-terminated polydimethylsiloxane were prepared and the cosmetic properties were evaluated according to the protocols described in Examples 2 to Previous 5
    The following results were obtained:
    The deposit resulting from the application of the polymer 1 mixed with the 3-aminopropyl-terminated Polydimethylsiloxane (Example 6) forms a homogeneous film, which fragments under mechanical stress, and the resistance of the film in contact with the olive oil and sebum is significantly improved (compared with Example 2).
    When the composition comprises 2-octyl dodecanol (non-volatile oil), the deposit resulting from the application of the polymer 1 mixed with the 3-aminopropyl-terminated Polydimethylsiloxane (Example 7) has an improvement in the properties of non-tacky, non-transferable and resistance of the wire in contact with olive oil and sebum.
    Thus, the addition of the 3-aminopropyl-terminated Polydimethylsiloxane contributes to improving the cosmetic properties of the resulting film (as compared with Example 4).
    The lipstick compositions of Examples 6 and 7 applied to the lips thus make it possible to obtain a makeup which is non-tacky, non-transferable and resistant to water, oil and sebum, thus having good strength.
    Examples 8 and 9: Cosmetic Evaluation of Makeup Composition
    The makeup compositions described below containing the polymer of Example 1 with or without APTES were prepared, and the cosmetic properties were evaluated according to the protocols described in Examples 2 to 5 above.
    The following results were obtained:
    The deposit resulting from the application of the polymer 1 mixed with the APTES (Example 8) forms a homogeneous film, which fragments under mechanical stress, and the resistance of the film in contact with olive oil and sebum is clearly improved (compared with Example 2).
    When the composition comprises 2-octyl dodecanol (non-volatile oil), the deposit resulting from the application of the polymer 1 mixed with the APTES (Example 9) has an improvement in the properties of non-tacky, non-transferable and resistant to film in contact with water, olive oil and sebum.
    Thus, the addition of the APTES contributes to improving the cosmetic properties of the film obtained (as compared with Example 4).
    The lipstick compositions of Examples 8 and 9 applied to the lips thus make it possible to obtain a makeup which is non-tacky, non-transferable and resistant to water, oil and sebum, thus having good strength.
    权利要求:
    Claims (33)
    [1" id="c-fr-0001]
    A block polymer comprising: at least one first block having a glass transition temperature (Tg) greater than or equal to 40 ° C and obtained from at least one (meth) acrylate monomer of formula CH 2 = C (R 1) COOR 2 wherein R 1 is H or methyl and R 2 is C 4 -C 12 cycloalkyl; and at least one second block having a glass transition temperature (Tg) less than or equal to 20 ° C and is obtained from at least one vinylphosphonic acid monomer of formula (I) and at least one monomer (meth) ) acrylate of formula CH 2 = C (R 1) -COOR 3 in which R! is H or methyl and R3 is either unsubstituted C1-C6 alkyl, linear or branched, with the exception of tert-butyl or methoxyethyl; said vinyl phosphonic acid monomer of formula (I) being: wherein:

    R1 is H or -CH3; X is a covalent bond and n is an integer from 0 to 14; or X denotes a group -COO- and n denotes an integer ranging from 2 to 6.
    [2" id="c-fr-0002]
    2. Polymer according to the preceding claim, characterized in that the first block is obtained from at least one acrylate monomer of formula CH 2 CHCH-COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group and at least one a methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C4 to C12 cycloalkyl group; and optionally an additional monomer chosen from linear or branched C4-C22 alkyl (meth) acrylates.
    [3" id="c-fr-0003]
    3. Polymer according to the preceding claim, characterized in that for the first sequence said acrylate monomer and said methacrylate monomer are in acrylate / methacrylate mass proportions of between 30:70 and 70:30, preferably between 40: 60 and 60: 40, especially between 45: 55 and 55:45.
    [4" id="c-fr-0004]
    4. Polymer according to one of claims 2 or 3, characterized in that the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.
    [5" id="c-fr-0005]
    5. Polymer according to any one of the preceding claims, characterized in that the proportion of the first block ranges from 60 to 80% by weight of the polymer, more preferably from 65 to 75%.
    [6" id="c-fr-0006]
    6. Polymer according to any one of the preceding claims, characterized in that for the monomer (I): X denotes a covalent bond and n is an integer ranging from 0 to 6 or X denotes a group -COO- and n is an integer ranging from 2 to 4.
    [7" id="c-fr-0007]
    7. Polymer according to one of the preceding claims, characterized in that for the monomer (I), R1 = H and X denotes a covalent bond and n is an integer ranging from 0 to 4.
    [8" id="c-fr-0008]
    8. Polymer according to one of the preceding claims, characterized in that the monomer (I) is chosen from: vinyl phosphonic acid; 3-butenylphosphonic acid; 4-pentenylphosphonic acid; 10-undecenyl phosphonic acid; 11-dodecenylphosphonic acid; the 2-phosphonoethyl ester of 2-methyl-2-propenoic acid; the 2-phosphonoethyl ester of 2-propenoic acid; and preferably vinyl phosphonic acid.
    [9" id="c-fr-0009]
    9. Polymer according to one of the preceding claims, characterized in that the second block comprises a monomer selected from isobutyl acrylate, ethyl acrylate, n-butyl acrylate, acrylate and the like. methoxyethyl, or mixtures thereof, and preferably isobutyl acrylate.
    [10" id="c-fr-0010]
    10. Polymer according to any one of the preceding claims, characterized in that for the second block the vinylphosphonic acid monomer (I) and said monomer (meth) acrylate are in proportions by mass (meth) acrylate / vinylphosphonic acid (I). ) ranging from 1 to 10, preferably ranging from 2 to 9, in particular ranging from 3 to 8, or even from 4 to 7.
    [11" id="c-fr-0011]
    11. Polymer according to one of the preceding claims, characterized in that the proportion of the second block ranges from 20 to 40% by weight of the polymer, more preferably from 25 to 35% by weight.
    [12" id="c-fr-0012]
    12. Polymer according to one of the preceding claims, characterized in that it comprises an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block, in particular is a random polymer.
    [13" id="c-fr-0013]
    13. Polymer according to one of the preceding claims, characterized in that it has a polydispersity index is greater than 2, preferably ranging from 3 to 20.
    [14" id="c-fr-0014]
    14. Composition comprising in a physiologically acceptable medium a block polymer according to one of claims 1 to 13.
    [15" id="c-fr-0015]
    15. Composition according to the preceding claim, characterized in that the block polymer is present in a content ranging from 0.1 to 40% by weight, relative to the total weight of the composition from extemporaneous mixing, preferably from 0, 5% to 35% by weight, and preferably ranging from 1% to 30% by weight, and more preferably ranging from 10% to 30% by weight.
    [16" id="c-fr-0016]
    16. A cosmetic process for treating keratin materials comprising topically applying to the keratin materials a composition according to claim 14 or 15.
    [17" id="c-fr-0017]
    17. Method according to the preceding claim, characterized in that the topical application is carried out on the keratin materials of a composition obtained by mixing the composition according to one of claims 14 or 15 and an additional component. selected from: (i) an amino compound selected from polyamine compounds having multiple primary amine and / or secondary amine groups and amino alkoxysilanes, (ii) salts of divalent or trivalent metal ions, (iii) clays (iv ) the metal oxides or a composition containing it and comprising a physiologically acceptable medium, the composition (s) used being anhydrous when the additional component is an amino alkoxysilane.
    [18" id="c-fr-0018]
    18. Process according to the preceding claim, characterized in that the polyamine compound comprises from 2 to 20 carbon atoms.
    [19" id="c-fr-0019]
    19. Method according to any one of claims 17 or 18, characterized in that the polyamine compound is selected from N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2- (3-aminopropylamino) ethanol, 3- (2-aminoethyl) aminopropylamine, bis (3-aminopropyl) amine, methyl bis (3 aminopropyl) amine, N- (3-aminopropyl) -1,4-diaminobutane, N, N-dimethyldipropylene triamine, 1,2-bis (3-aminopropylamino) ethane, N, N'-bis (3-aminopropyl) -aminopropyl) -1,3-propanediamine, ethylene diamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylene diamine, tris (2-aminoethyl) amine, spermidine ;
    [20" id="c-fr-0020]
    20. Process according to Claim 17, characterized in that the amino alkoxysilane is of formula (III):

    (III) in which: R 'i is a linear or branched, saturated or unsaturated, cyclic or acyclic C 1 -C 6 hydrocarbon-based chain substituted with a group chosen from the following groups: - amine NH 2 or NHR with R = C 1 -C 4 alkyl an aryl or aryloxy group substituted by an amino group or by a C 1 -C 4 aminoalkyl group; R'i may be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group (CO), R'i being bonded to the silicon atom directly via a carbon atom, • R'2 and R'3, which may be identical or different, represent a linear or branched alkyl group comprising from 1 to 6 carbon atoms, • z denotes an integer ranging from 1 to 3, and • x denotes an integer ranging from 0 to 2, with z + x = 3; and preferably is 3-aminopropyltriethoxysilane.
    [21" id="c-fr-0021]
    21. The method of claim 17, characterized in that the polyamine compound is selected from amino polymers, especially having a weight average molecular weight ranging from 500 to 1,000,000, preferably from 500 to 500,000, and preferably ranging from 500 to 100,000.
    [22" id="c-fr-0022]
    22. Process according to the preceding claim, characterized in that the polyamine compound is an aminated polymer chosen from poly (C2-C5) alkylene imines), and in particular polyethyleneimines and polypropyleneimines, especially poly (ethyleneimine). ; poly (allylamine); polyvinylamines and their copolymers, especially with vinylamides; vinylamine / vinylformamide copolymers; polyamino acids having NH 2 groups such as polylysine; dextran amino; polyvinyl amino alcohol, copolymers based on acrylamidopropylamine; chitosan; polydimethylsiloxanes comprising primary amino groups at the end of the chain or on side chains, for example terminal or lateral aminopropyl groups, for example those of formula (A) or (B) or (C):

    (AT)

    (B) H2NCH2CH2CH2-Si (CH3) 2-O- [Si (CH3) 2-O] n-Si (CH3) 2C4H9 (C) with: in formula (A): the value of n is such that the weight Molecular weight average molecular weight of the silicone is between 500 and 55,000. In the formula (B), the values of n and m are such that the weight average molecular weight of the silicone is between 1,000 and 55,000. formula (C), the value of n is such that the weight average molecular weight of the silicone is between 500 and 3000; the amodimethicones of formula (D):

    wherein R, R 'and R ", which may be identical or different, each represents a C 1 -C 4 alkyl hydroxyl group, A represents a C 3 alkylene group and m and n are such that the weight average molecular weight of the compound is between About 5 000 and 500 000. Polyethers diamines and in particular polyethylene glycol and / or polypropylene glycol α, ω-diamine, polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine, polyamidoamine dendrimers with amine functions poly (meth) acrylates or poly (meth) acrylamides bearing primary or secondary secondary amine functions such as poly (3-aminopropyl) methacrylamide, poly (2-aminoethyl) methacrylate, and preferably polydimethylsiloxanes comprising groups primary amines at the end of the chain or on side chains, preferably the polydimethylsiloxanes comprising at the end of the chain amine terminal groups; inopropyl.
    [23" id="c-fr-0023]
    23. The method of claim 17, characterized in that the additional component is an amine compound selected from polydimethylsiloxanes comprising primary amino groups at the end of the chain or on side chains and 3-aminopropyltriethoxysilane; and preferably from polydimethylsiloxanes comprising at the end end aminopropyl end groups and 3-aminopropyltriethoxysilane.
    [24" id="c-fr-0024]
    24. Process according to any one of Claims 17 to 23, characterized in that the amine compound is used in a molar ratio amino group of the amine compound / phosphonic acid of the polymer ranging from 0.01 to 10, preferably ranging from 0.1 to 5, preferentially ranging from 0.1 to 2, and more preferably ranging from 0.1 to 1.
    [25" id="c-fr-0025]
    25. Method according to one of claims 17 and 20, characterized in that when the composition (s) used (s) contains an amino alkoxysilane, it comprises a C2-C5 monohydric alcohol, preferably ethanol or isopropanol, in particular in a content ranging from 0.1 to 5% by weight, relative to the total weight of the composition
    [26" id="c-fr-0026]
    26. Process according to Claim 17, characterized in that the additional component is a clay chosen from clays of the smectite family such as laponite and montmorillonite, of the kaolinite family, such as kaolinite or dickite. nacrite, optionally modified clays from the family of halloysite, dombassite, antigorite, benthiérine, pyrophyllite, montmorillonites, beidellite, vermiculites, talc, stevensite, hectorites, bentonites, saponites, chlorites, sepiolite and illite; and preferably selected from kaolinite, smectites such as laponite and montmorillonite, bentonite and saponite.
    [27" id="c-fr-0027]
    27. The method of claim 17, characterized in that the additional component is a salt of divalent or trivalent metal ions selected from ion salts derived from Al (III), Ca (II), Cu (II) Fe (II), Fe (III), Mg (II), Mn (II), Zn (II) and mixtures thereof.
    [28" id="c-fr-0028]
    28. The method of claim 17, characterized in that the additional component is a metal oxide selected from titanium dioxide, iron oxides, zirconium oxides, zinc oxides, cerium oxides, oxides of chromium.
    [29" id="c-fr-0029]
    29. A method according to any one of claims 17 to 28, characterized in that the mixture of the composition comprising the phosphonic polymer and additional component, or the composition containing it, is carried out in a time of between 1 minute and 24 hours before its application on keratin materials, and preferably between 5 and 30 minutes.
    [30" id="c-fr-0030]
    30. Method according to any one of claims 17 to 29, characterized in that the composition applied to the keratin materials comprises an oil.
    [31" id="c-fr-0031]
    31. Composition obtained by mixing a composition according to claim 14 or 15 and an additional component as defined in one of claims 17 to 23 and 26 to 28, or a composition containing it and comprising a medium. physiologically acceptable.
    [32" id="c-fr-0032]
    32. Kit comprising a first composition according to claim 14 or 15 and a second composition comprising an additional compound as defined in one of claims 17 to 23 and 26 to 28 and comprising a physiologically acceptable medium, the first and second compositions being each packaged in a separate packaging set
    [33" id="c-fr-0033]
    33. Polymer obtained by the reaction of a block polymer according to one of claims 1 to 13 with an amino compound as defined according to one of claims 17 to 24, the reaction taking place in an anhydrous medium when the amine compound is an amino alkoxysilane.
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    同族专利:
    公开号 | 公开日
    EP3394127A1|2018-10-31|
    WO2017108600A1|2017-06-29|
    FR3045614B1|2018-01-26|
    KR20180095055A|2018-08-24|
    EP3394127B1|2019-11-27|
    CN108431063A|2018-08-21|
    US20180369128A1|2018-12-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2871470A1|2004-06-11|2005-12-16|Oreal|Gradient copolymer comprising two different monomers acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate or methyl methacrylate) useful as e.g. make up product and lip care product|
    WO2009050122A1|2007-10-12|2009-04-23|Basf Se|Copolymers of vinyl phosphonic acid as an additive in cross-link curing paint formulations|FR3103704A1|2019-11-29|2021-06-04|L'oreal|Composition comprising a UV filter, an ethylenic polymer with a phosphonic acid group and a hydrocarbon oil|
    FR3103705A1|2019-11-29|2021-06-04|L'oreal|A composition comprising a UV filter, a block polymer containing a phosphonic acid group and a hydrocarbon oil|FR2873702B1|2004-07-29|2006-12-22|Oreal|HYPERBRANCH COPOLYMER COMPRISING SELECTED MONOMERS, COMPOSITION COMPRISING SAME, AND COSMETIC PROCESS|
    FR2904320B1|2006-07-27|2008-09-05|Oreal|POLYMER SEQUENCES, AND PROCESS FOR THEIR PREPARATION|
    FR2943909B1|2009-04-07|2012-11-09|Oreal|METHOD FOR MAKING LACQUERS|
    TWI653988B|2012-11-09|2019-03-21|Howard University|Block copolymer for tooth enamel protection|
    FR3022909B1|2014-06-25|2016-10-21|Oreal|PHOSPHONIC COPOLYMER AND COSMETIC USE FOR TREATING SKIN WRINKLES|FR3064911B1|2017-04-07|2020-04-17|L'oreal|HAIR COLORING METHOD COMPRISING A SEQUENCE POLYMER WITH PHOSPHONIC ACID GROUPS AND A PIGMENT|
    法律状态:
    2016-11-11| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-11-15| PLFP| Fee payment|Year of fee payment: 5 |
    2021-09-10| ST| Notification of lapse|Effective date: 20210806 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1563117A|FR3045614B1|2015-12-22|2015-12-22|SEQUENCE POLYMER WITH PHOSPHONIC ACID GROUPS AND COSMETIC APPLICATIONS|
    FR1563117|2015-12-22|FR1563117A| FR3045614B1|2015-12-22|2015-12-22|SEQUENCE POLYMER WITH PHOSPHONIC ACID GROUPS AND COSMETIC APPLICATIONS|
    KR1020187020642A| KR20180095055A|2015-12-22|2016-12-16|Block polymers having phosphonic acid groups and their use for cosmetic use|
    US16/063,502| US20180369128A1|2015-12-22|2016-12-16|Block polymer bearing phosphonic acid groups and cosmetic uses thereof|
    PCT/EP2016/081353| WO2017108600A1|2015-12-22|2016-12-16|Block polymer bearing phosphonic acid groups and cosmetic uses thereof|
    CN201680074775.0A| CN108431063A|2015-12-22|2016-12-16|Block polymer with phosphonyl group and its cosmetic use|
    EP16822644.7A| EP3394127B1|2015-12-22|2016-12-16|Block polymer bearing phosphonic acid groups and cosmetic uses thereof|
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