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    • 专利摘要:
    Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium The invention relates to a composition comprising: a) a polyhydroxyalkanoate copolymer comprising, the following polymeric units A, B and C: - [- O-CH (R1) -CH2-CO -] - unit A - [- O-CH (R2) -CH2-CO -] - unit B - [- O-CH (R3) -CH2-CO -] - unit Cin which: in which R1 denotes a linear alkyl radical having 5 to 9 carbon atoms; R2 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical R1 - 2; R3 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical R1 - 4; b) an oily medium comprising a non-silicone oil chosen from ester oils, carbonate oils, non-polar hydrocarbon oils having from 8 to 14 carbon atoms.
    公开号:FR3090365A1
    申请号:FR1873652
    申请日:2018-12-20
    公开日:2020-06-26
    发明作者:Julien PORTAIL；Romain GARCON
    申请人:LOreal SA；
    IPC主号:
    专利说明:

    Description
    Title of the invention: Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium
    The present invention relates to a cosmetic composition comprising a polyhydroxyalkanoate in an oily medium, as well as a process for the treatment of keratin materials using such a composition.
    It is known to use in cosmetics film-forming polymers which can be transported in organic media such as hydrocarbon oils. The polymers are in particular used as a film-forming agent in make-up products such as mascaras, eyeliners, eye shadows or lipsticks.
    Document FR-A-2964663 describes a cosmetic composition comprising pigments coated with a C3-C21 polyhydroxyalkanoate such as poly (hydroxybutyrate-co-hydroxyvalerate).
    Document WO2011 / 154508 describes a cosmetic composition comprising an ester derivative of 4-carboxy-2-pyrolidinone and a film-forming polymer which can be a polyhydroxyalkanoate such as polyhydroxybutyrate, polyhydroxyvalerate and polyhydroxybutyrate-co-polyhydroxy valerate.
    Document US-A-2015/274972 describes a cosmetic composition comprising a cosmetic composition comprising a thermoplastic resin, such as a polyhydroxyalkanoate, in aqueous dispersion and a silicone elastomer.
    There is therefore a need to have a composition comprising a solubilized polyhydroxyalkanoate making it possible to obtain a film having good cosmetic properties, in particular good resistance to oils and to sebum, as well as good mattness.
    The Applicant has discovered that particular polyhydroxyalkanoate copolymers, as defined below, can be easily used in the oily media selected, thus making it possible to obtain homogeneous compositions due to the good solubilization of the copolymer in the oily medium. The composition has good stability, especially after storage for one month at room temperature (25 ° C). The composition, in particular after its application to keratin materials, makes it possible to obtain a film having good cosmetic properties, in particular good resistance to oils and sebum, as well as a matt appearance.
    An object of the present invention is therefore a composition comprising:
    a) a polyhydroxyalkanoate copolymer comprising, preferably consisting of, the following polymeric units A, B and C:
    - [-O-CH (R1) -CH 2 -CO -] - unit A
    - [-O-CH (R2) -CH 2 -CO -] - unit B
    - [-O-CH (R3) -CH 2 -CO -] - unit C in which:
    RI denotes a linear alkyl radical having from 5 to 9 carbon atoms;
    R2 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical RI - 2;
    R3 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical RI - 4;
    the molar percentage in unit A being greater than the molar percentage in unit B and greater than the molar percentage in unit C;
    b) an oily medium comprising a non-silicone oil chosen from:
    ester oils, carbonate oils, apolar branched hydrocarbon oils having 8 to 14 carbon atoms, in admixture with a monoalcohol having 2 to 6 carbon atoms according to a weight ratio monoalcohol / apolar branched hydrocarbon oil ranging from 1/99 at 10/90; and when the polymer is such that the alkyl group RI comprises from 6 to 9 carbon atoms, the non-silicone oil is also chosen from non-polar hydrocarbon oils having from 8 to 14 carbon atoms in the absence of monoalcohol having from 2 with 6 carbon atoms;
    when the polymer is such that the alkyl group RI contains 9 carbon atoms, the non-silicone oil is also chosen from hydrogenated polyisobutylenes. The invention also relates to a non-therapeutic cosmetic method for treating keratin materials, comprising the application to keratin materials of a composition as defined above. The treatment process is in particular a process for caring for or making up keratin materials.
    The polyhydroxyalkanoate copolymer of the composition according to the invention comprises units A, B and C as defined above.
    Preferably, in the copolymer, the unit A is present in a molar percentage ranging from 40 to 97.5%, the unit B is present in a molar percentage ranging from 2 to 40%, and the unit C is present in a molar percentage ranging from 0.5 to 20% relative to all of the units A, B and C.
    According to a first embodiment of the composition according to the invention, the copolymer comprises units A having an alkyl radical RI comprising 5 carbon atoms, units B having an alkyl radical having 3 carbon atoms and units C having an alkyl radical having 1 carbon atom. Advantageously, the copolymer comprises from 85 to 97.5% by mole of unit A; from 2 to 10% by mole of unit B; from 0.5 to 7% by mole of unit C.
    According to a second embodiment of the composition according to the invention, the copolymer comprises units A having an alkyl radical RI comprising 6 carbon atoms, units B having an alkyl radical having 4 carbon atoms and units C having an alkyl radical having 2 carbon atoms. Advantageously, the copolymer comprises from 60 to 94.5% by mole of unit A; from 5 to 35% by mole of unit B; from 0.5 to 7% by mole of unit C.
    According to a third embodiment of the composition according to the invention, the copolymer comprises units A having an alkyl radical RI comprising 9 carbon atoms, units B having an alkyl radical having 7 carbon atoms, and units C having an alkyl radical having 5 carbon atoms. Advantageously, the copolymer comprises from 40 to 50 mol% of unit A; 30 to 40% by mole of unit B; from 10 to 20% by mole of unit C.
    The copolymer preferably has a number average molecular weight ranging from 50,000 to 150,000.
    The molecular weight can in particular be measured by steric exclusion chromatography. A method is described below in the examples.
    The copolymer may be present in the composition according to the invention in a content ranging from 0.1 to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 25% by weight .
    Advantageously, the composition may comprise the non-silicone oil of the oily medium in a content ranging from 2 to 99.9% by weight, relative to the total weight of the composition, preferably ranging from 5 to 90% by weight , preferably ranging from 10 to 80% by weight, preferably ranging from 20 to 80% by weight.
    The copolymer can be obtained in known manner by biosynthesis, for example with microorganisms belonging to the genus Pseudomonas, such as Pseudomonas resinovorans, Pseudomomonas putida, Pseudomonas fluoréscens, Pseudomonas aeruginosa, Pseudomonas citronellolis, Pseudomonas mendocina and Pseudomon Pseudomon putida; and with a carbon source which can be a C 2 -C 20, preferably C 6 -C 18 carboxylic acid, such as acetic acid, propionic acid, butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, dodecanoic acid; a saccharide such as fructose, maltose, lactose, xylose, arabinose, etc.); an n-alkane such as hexane, octane, dodecane; an n-alcohol such as methanol, ethanol, octanol, glycerol; methane, carbon dioxide.
    Biosynthesis can optionally be carried out in the presence of an inhibitor of the β-oxidation pathway such as acrylic acid, methacrylic acid, propionic acid, cinnamic acid, salicylic acid, l pentenoic acid, 2-butynoic acid, 2-octynoic acid, phenylpropionic acid, and preferably acrylic acid.
    One can also use for biosynthesis nutrients such as water-soluble salts based on nitrogen, phosphorus, sulfur, magnesium, sodium, potassium, iron.
    One can use the appropriate known conditions of temperature, pH, dissolved oxygen (DO) for the culture of microorganisms.
    The microorganisms can be cultivated according to any known method of culture, such as in a bioreactor in continuous, discontinuous mode, in powered or unpowered mode.
    The biosynthesis of the polymers used according to the invention is described in particular in the article "Biosynthesis and Properties of Medium-Chain-Length Polyhydroxyalkanoates with Enriched Content of the Dominant Monomer", Xun Juan et al; Biomacromolecules 2012, 13, 2926-2932 and in application WO2011 / 069244.
    The oily medium of the composition according to the invention comprises a non-silicone oil as described above.
    By "oil" means a non-aqueous compound, immiscible with water, liquid at room temperature () and atmospheric pressure (Hg).
    By hydrocarbon oil is meant an oil consisting of carbon and hydrogen atoms.
    The hydrocarbon oil having 8 to 16 carbon atoms can be chosen from:
    branched C 8 -C 6 alkanes such as C 8 -C 6 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane , isohexadecane, and for example the oils sold under the trade names of Isopars' or Permyls, linear C8-C16 alkanes, such as n-dodecane (C12) and n-tetradecane (C14) 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 (Cl 1) and n-tridecane (Cl3) obtained in Examples 1 and 2 of application W02008 / 155059 from the Cognis Company, and their mixtures.
    By ester oil is meant an oily compound having one or more ester groups in its chemical structure.
    The ester oil can be chosen from:
    oils of vegetable origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which can have varying chain lengths from C 4 to C 24 , the latter possibly being linear or branched, saturated or unsaturated ; these oils are in particular triglycerides of heptanoic acid or octanoic acid. The oils of vegetable origin can be chosen from the oils of wheat germ, sunflower, grapeseed, sesame, peanut, corn, apricot, castor, shea, avocado, d olive, soya, sweet almond, palm, rapeseed, cotton, coconut, hazelnut, walnut, rice, flax, macadamia, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, black currant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose, argan; shea butter; or the triglycerides of caprylic / capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel, the monoester oils of formula R4COOR5 in which R4 represents a chain hydrocarbon containing from 5 to 19 carbon atoms and R 5 represents a notably branched hydrocarbon chain containing from 4 to 20 carbon atoms provided that R4 + R 5 is 3 9 carbon atoms and preferably <29 carbon atoms, such as for example Γ cetearyl octanoate (Purcellin oil), isopropyl myristate, isopropyl palmitate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate , 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyl-dodecyl myristate, ethyl 2 hexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate, octyl octanoate, esters of lactic acid ic and C10-20 alcohol such as isostearyl lactate, 2-octyl-dodecyl lactate, myristyl lactate, C12-C13 alkyl lactate (Cosmacol® Eli from Sasol), lactate cetyl, lauryl lactate, diesters of malic acid and C10-C20 alcohol such as diisostearyl malate, dialkyl malate (C12-C13) (Cosmacol® EMI from Sasol), malate of dibutyloctyl, diethylhexyl malate, dioctyldodecyl malate, pentaerythritol and C8-C22 carboxylic acid esters (in particular tetraesters, diesters) such as pentaerythrityl tetraoctanoate, pentaerythrytetra tetrytheart tentaerythearate pentaerythrityl, the tetracaprylate / tétracaprate, pentaerythrityl tétracocoate, pentaerythrityl tétraethylhexanoate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrastearate, pentaerythrityl tétraisostérate, pentaerythrityl tetralaurate, pentaerythrityl tétramy pentaerythrityl ristate, pentaerythrityl tetraoleate, pentaerythrityl distearate;
    the di-esters of formula (II) below R6-OC (= O) -R'6-C (= O) -OR ”6, with R6 and R” 6, identical or different, represent a C4 to C12, and preferably from C5 to CIO, linear or branched, saturated or unsaturated (preferably saturated), optionally having at least one ring, saturated or unsaturated, preferably saturated, and R'6 represents an alkylene chain, saturated or unsaturated, in C1 to C4, preferably from C2 to C4, such as for example an alkylene chain derived from succinate (in this case R'6 is a saturated C2 alkylene chain), maleate (in this case R'6 is an alkylene chain in Unsaturated C2), glutarate (in this case R'6 is a saturated C3 alkylene chain), or adipate (in this case R'6 is a saturated C4 alkylene chain); in particular, R6 and R ”6 are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, ethyl 2-hexyl, octyl, nonyl, isononyl; there may be mentioned preferentially dicaprylyl maleate or di (2-ethyl hexyl) succinate;
    the diesters of formula (III) below R7-C (= O) -O-R'7-OC (= O) -R ”7, with R7 and R” 7, identical or different, represent a C4 to C12 represent a C4 to C12 alkyl chain, and preferably from C5 to CIO, linear or branched, saturated or unsaturated (preferably saturated), and R'7 represents an alkylene chain, saturated or unsaturated, C1 to C4, preferably from C2 to C4. Mention may in particular be made of the 1,3 propanediol dicaprylate (R7 at C7 and R’7 at C3) sold under the name Dub Zenoat by the company Stearinierie Dubois, or dipropyleneglycol dicaprylate
    The carbonate oils can be chosen from carbonates of formula R8-O-CO-O-R9, with R8 and R9, identical or different, represent a C4 to Cl2 alkyl chain, and preferably from C6 to CIO, linear or branched; the carbonate oils can be dicaprylyl carbonate (or dioctyl carbonate), sold under the name Cetiol CC® by the company BASF, di (ethyl-2-hexyl) carbonate, sold under the name TEGOSOFT DEC® by the company Evonik, dipropylheptyl carbonate (Cetiol 4 Ail from BASF), dibutyl carbonate; dineopentyl carbonate; dipentyl carbonate; di neoheptyl carbonate; di-heptyl carbonate; di-isononyl carbonate; or di-nonyl carbonate; and preferably dioctyl carbonate.
    As described above, the oily medium can comprise a monoalcohol of 2 to 6 carbon atoms. This monoalcohol can be chosen from ethanol, propanol, butanol, pentanol, hexanol. Preferably, the monoalcohol is ethanol, butanol1, and preferably ethanol.
    Advantageously, the composition according to the invention comprises a physiologically acceptable medium. In particular, the composition is a cosmetic composition.
    By physiologically acceptable medium is meant a medium compatible with keratin materials of human beings, such as for example the skin, lips, nails, eyelashes, eyebrows, hair.
    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), liable to divert the consumer.
    By keratin materials is meant the skin (body, face, eye area, scalp), hair, eyelashes, eyebrows, body hair, nails, lips.
    The composition according to the invention may comprise a cosmetic additive chosen from water, perfumes, preservatives, fillers, coloring materials, UV filters, oils, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, anti free radicals, polymers, thickeners.
    Advantageously, the composition according to the invention is a makeup composition, in particular a composition for making up the lips, mascara, eyeliner, eyeshadow, foundation.
    The composition according to the invention can be in the form of an anhydrous composition, a water-in-oil emulsion or an oil-in-water emulsion.
    Anhydrous composition is understood to mean a composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water. Where appropriate, such small quantities of water can in particular be supplied by ingredients of the composition which may contain residual quantities.
    The invention is illustrated in more detail in the following examples. The quantities are indicated in percentage by weight.
    Examples
    Example 1:
    A polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054 ™, octanoic acid.
    The culture mode was carried out in batch axenic conditions in 5 L Fernbach flasks (Corning® ref. 431685) containing 2 L of culture medium, stirred at 110 rpm at 30 ° C in an orbital incubator ( orbit diameter of 2.5 cm).
    The synthesis process was carried out using two separate culture media. The first culture medium defined MCI "inoculum" was used for the preparation of the inoculum. The second culture medium defined MC2 "batch" was used for the non-fed discontinuous growth of the microorganism with octanoic acid in the vials of fernbachs.
    The composition in grams per liter of the two media is described in the table below:
    MCI "inoculum" MC2 "batch" (NH ^ zSQa 4.7 5.02 NasHPO4 7H2O 12 2.24 KH PÛ4 2.7 0.5 Glucose 9 3.9 MqSCM; 7ΗζΟ 0.8 1.03 Citric acid 1.6 1.03 Butte Brte (1) 1 / Acid æteteug. / 3.8 Solution M icroétémenîs (2)1.4 B " QS 3 pH-6., 8 Water QSP 1000 §
    (1) The composition of Nutrient Broth in mass percentage is 37.5% of beef extract and 62.5% of peptone. Reference 233000 DIFCO ™.
    (2) The composition of the microelement solution in grams per liter is described in the table below:
    FeSOi -7H2O 10.0 g CaO-SHaO 3.0g ZnSCWHsO 2.2g MnSO4-4H2O 0.5 g H38Q3 0.3g C0CI2OH20 0.2g Na2MoO4 2HzO 0:15 g NiCh-GHsO 0.02 g CuSO4-5H2O 1 00 g ælô.5 N QSP 1000 g
    100 ml of inoculum were prepared by suspending a cryotube containing 1 ml of the strain with 100 ml “inoculum” culture media at pH adjusted to 6.8 with 2N NaOH in a 250 ml fembach flask then incubated at 30 ° C at 150 rpm for 24 h. 1.9 l of MC2 "BATCH" culture medium placed in a previously sterilized 5 1 fernbach flask were inoculated at OD = 0.1 with 100 ml of inoculum. After 70 hours at 30 ° C at 110 rpm, the biomass was dried by lyophilization before being extracted with dichloromethane for 24 h. The suspension was clarified by filtration on a GF / A filter (Wattman®), the filtrate containing the copolymer in solution in dichloromethane was concentrated by evaporation and then dried under high vacuum at 40 ° C to constant mass. The crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter dissolved in 10 times its weight of dichloromethane, in 10 volumes of the cold methanol solution. The solid obtained was dried under high vacuum at 40 ° C to constant mass.
    The molecular weight of the polyhydroxyalkanoate obtained was characterized by steric exclusion chromatography, detection Refractive index
    Eluent: THF
    Analytical flow: 1 mL / min
    Injection: 100 pL
    Columns: 1 Agilent PLGel Mixed-D 5μιη column; 300 x 7.5 mm; 1 Agilent PLGel Mixed-C 5μιη column; 300 x 7.5 mm; 1 Agilent Oligopore column; 300 x 7.5 mm at room temperature (25 ° C)
    Detection: Waters 2487 Dual 1 Absorbance Detector, Waters 2414 Refractive Index Detector
    Integrator: refractive index at 45 ° C and 64mV
    Empower (Relative / conventional molar mass GPC module) Empower injection time 40 min
    Standards: High mass polystyrene / EasiVial PS-H 4 mL from Agilent Technologie Part N ° PL2010-0200
    The analysis makes it possible to measure the average molecular weight by weight (Mw in g / mole), the average molecular weight by number (Mn in g / mole), the polydispersity index Ip (Mw / Mn) and the degree of polymerization. DPn.
    The monomeric composition of the polyhydroxyalkanoate obtained was defined by gas chromatography equipped with a flame ionization detector.
    Identification is carried out via the injection of commercial standards and the monomeric composition has been determined by methanolysis and sylylation treatment. To determine the monomeric composition, 7 mg of the polyhydroxyalkanoate polymer has been dissolved in 1.5 ml of chloroform and has been methanolized. in the presence of 1.5 mL of a MeOH / HCl solution (17/2, v / v) at 100 ° C for 4 h. The organic phase was then washed with 1 ml of water and then dried over MgSO4. The sylilation of the methyl esters formed was carried out by adding 100 μL of BSTFA (N, Obis (trimethylsilyl) trifluoroacetamide) and 100 μL of pyridine to the methylated sample. The solution was heated to 70 ° C for 1 h and then evaporated to dryness.
    The sample is then dissolved in 600 μl of dichloromethane and analyzed by chromatography under the following conditions:
    Hewlett Packard 6890 Series device
    Stationary phase column ZB-5 HT from Phenomenex (length: 30 m, diameter: 0.25 mm)
    Temperature: isothermal 60 ° C to 300 ° C in 6 min (heating rate: 10 ° C / min)
    Gas: Helium; flow rate: 0.8 ml / min
    Injector: Temperature: 250 ° C; 50 ml / min
    Flame ionization detector; Temperature: 300 ° C
    Injection: Volume 1 pl
    A copolymer containing 91% by weight of poly (hydroxy-3-octanoate), 6% by weight of poly (hydroxy-3-hexanoate) and 3% by weight of poly (hydroxy-3-butanoate) was thus obtained.
    Mn = 68 100 g / mol
    Mw = 149 100 g / mol
    Ip = 2.2
    DPn = 531
    Example 2
    A polymer was prepared using the microorganism Pseudomonas putida KT2440 ATCC® 47054 ™, octanoic acid and acrylic acid.
    The culture mode was carried out under axenic conditions continuously at a dilution of D = 0.25 h 1 in a 3 L chemostat containing 1.1 L of culture medium. The system was aerated with air at a flow of 3 vvm (vvm = volume of air per volume of fermentation medium per minute) for a set point of dissolved oxygen (OD) at 30% of saturation.
    The production process was carried out using three separate culture media. The first indefinite culture medium (MCI) was used for the preparation of the inoculum. The second defined culture medium (MC2) was used for the non-fed discontinuous growth of the microorganism in the fermenter. The third defined culture medium (MC3) was used for feeding, or maintenance, continuous fermentation containing octanoic acid and acrylic acid (inhibitor of the β-oxidation pathway).
    The media MCI and MC2 are identical to those described in Example 1. The composition in grams per liter of the medium MC3 is described in the table below:
    MC3 "çQQtînu" (NH4) 2S04 5 02 NatzHPCk; 7H2O 2.24 KH2PO4 0.5 Glucose 3 MgSCU 7H2O 1.03 _______Acjcfe cMUUP_______ 1.03 Nutnent Broth (1) < Aude eUmoiaue 3.8 Solution (2) 1.4 Aude acoâw 0.2QSP pH = 6.8 Water ______ Qsa.woo q______
    100 ml of inoculum were prepared by suspending a cryotube containing ImL of the strain with 100 ml of Nutrient Broth at pH adjusted to 7.0 with 2N NaOH in a 250 ml fernbach flask and then were incubated at 30 °. C at 150 all / min for 24 hours.
    The fermenter containing 1 liter of MC2 culture medium at 30 ° C. was inoculated at an optical density of 0.1 to 630 nm (OD 630 = 0.1). The system was kept at 30 ° C with stirring at 700 +/- 200 rpm and regulated in cascade with oxygenation for approximately 16 h and or until the microorganism can reach its growth plateau.
    The feeding of the fermenter with MC3 media was initiated when the microorganism reached its growth plateau, the racking was carried out in order to keep the mass of initial fermentation medium. Once the equilibrium state reached in continuous culture, a fraction of the racking was centrifuged in order to separate the biomass from the fermentation medium. The biomass was dried by lyophilization, then extracted with dichloromethane for 24 h. The suspension obtained was clarified by filtration on a GL / A filter (Wattman®). The filtrate obtained, comprising the copolymer in solution in dichloromethane, was concentrated by evaporation and then dried under high vacuum at 40 ° C to constant mass. The crude polyhydroxyalkanoate was purified by precipitation of a solution of the latter dissolved in 10 times its weight of dichloromethane, in 10 volumes of the cold methanol solution. The solid obtained was dried under high vacuum at 40 ° C to constant mass.
    A copolymer was thus obtained comprising 96% by weight of poly (hydroxy-3-octanoate), 3% by weight of poly (hydroxy-3-hexanoate) and 1% by weight of poly (hydroxy-3-butanoate).
    Mn = 67,900 g / mol:
    Mw = 142,000 g / mol:
    Ip = 2.1, DPn = 611 Example 3: A polymer was prepared according to the procedure of Example 2 using nonanoic acid (instead of octanoic acid). :
    A copolymer was thus obtained comprising 86% by weight of poly (hydroxy-3-nonanoate), 9% by weight of poly (hydroxy-3-heptanoate and 5% by weight of poly (hydroxy-3-pentanoate)
    Mn = 65,900 g / mol
    Mw = 143,600 g / mol Ip = 2.2 DPn = 531
    Example 4:
    A polymer was prepared according to the procedure of Example 2 using nonanoic acid (in place of octanoic acid) and without acrylic acid.
    A copolymer was thus obtained comprising 68% by weight of poly (hydroxy-3-nonanoate), 27% by weight of poly (hydroxy-3-heptanoate) and 5% by weight of poly (hydroxy-3-pentanoate).
    Mn = 55,800 g / mol
    Mw = 124,500 g / mol
    Ip = 2.2
    DPn = 469
    Example 5:
    A polymer was prepared according to the procedure of Example 2 using dodecanoic acid (instead of octanoic acid).
    A copolymer was obtained comprising 44% by weight of poly (hydroxy-3-dodecanoate) and 38% by weight of poly (hydroxy-3-decanoate), and 18% by weight of poly (hydroxy-3-octanoate).
    Mn = 67,400 g / mol
    Mw = 129,800 g / mol
    Ip = 1.9
    DPn = 484
    Example 6 (outside the invention):
    A copolymer was prepared using the microorganism Pseudomonas resinovorans ATCC® 14235 ™, hexanoic acid and acrylic acid according to the procedure of Example 2.
    The composition of the microelement solution used in grams per liter is described in the table below:
    ZnSCMJHsO 0.1s M1CÎ2-4H2Ô 0.03 g hhBCh 0.3g CoCb6H2O 0.2 q Na2MoO4-2H2O 0.03 g NiCbOHsO 0.02 g CuS04-5'H2O 0.01 gqs 1000 g
    A copolymer was thus obtained comprising 95% by weight of poly (hydroxy-3-hexanoate) and 5% by weight of poly (hydroxy-3-octanoate).
    Mn = 107,200 g / mol
    Mw = 219 100 g / mol
    Ip = 2 DPn = 1227
    Example 7 (outside the invention):
    A polymer was prepared according to the procedure of Example 2 using heptanoic acid (in place of octanoic acid).
    A copolymer was thus obtained comprising 96% by weight of poly (hydroxy-3-heptanoate) and 4% by weight of poly (hydroxy-3-pentanoate).
    Mn = 83,600 g / mol
    Mw = 184,200 g / mol
    Ip = 2.2
    DPn = 845
    Example 8: solubility test in oils
    The solubility in various oils described in the table below was evaluated of the polymers of Examples 1 to 7 as well as 3 commercial polymers A to C described below.
    1 g of polymer was introduced into a flask in 9 g of oil, the mixture was heated to 70 ° C. with stirring for 1 h, then the flask was placed at room temperature for 24 h and observed at 1. 'the naked eye the solubility of the polymer in the mixture.
    We also did the test with 3 commercial polymers outside the invention:
    Polymer A: poly (hydroxy-3-butanoate) sold under the reference 363502 Aldrich by the company Sigma-Aldrich
    Polymer B: Poly (hydroxy-3-butanoate) -co- (hydroxy-3-valerate), the hydroxy3-valerate motif being present at 12 mol%, sold under the reference 403121 Aldrich by the company Sigma-Aldrich
    Polymer C: Poly (hydroxy-3-butanoate) -co- (hydroxy-3-valerate), the hydroxy3-valerate motif being present at 8 mol%, sold under the reference 403105 Aldrich by the company Sigma-Aldrich
    The following results were obtained
    Ex1 Ex2 hX 3 Ex 4 Ex 5 Ex 6 Ex 7 AT B L * b.Qdsdecans. - - -b -i- 4 * - - - -ethanol 97/3 -K 4- -E- - --Ç ^ LQlUT - - 4 ' 4- - 44Eætew - - - - 4- - - - - - Eafteo /ethanol 97/3 - - 4- - : - d Mrafe T 4--i- 4-- -- HufeOo. -l · · 4- 4- -i- 4- - - - - - limit of -F~ arbonate ί '·silicone L5 - - -- - - - - -
    Cetiol UT: undecane / tridecane mixture from BASF
    Parleam: hydrogenated polyisobutene from NOF Corporation
    Silicone L5: dodecamethylpentasiloxane + means that the polymer is soluble in the oil tested: the mixture is homogeneous, clear and stable for one month at room temperature.
    - means that the polymer is not soluble in the oil tested: the mixture is not homogeneous and the polymer precipitates or the mixture is cloudy
    The solubility test for the polymer of Example 2 was completed with other oils described in the table below. The following results were obtained:
    ex 2 Mate -- ώώάώ - 1 -ol§7 / 3
    Example 11: Evaluation of film-forming and cosmetic properties
    A polymer solution (example polymer at 10% by weight in isododecane) was deposited to be evaluated on a contrast card (for example that sold under the reference byko-charts by the company BYK-gardner) with a film puller (speed: 50 mm / s
    - 100 μm thick of the wet deposit) and the film deposited was dried for 24 hours at room temperature (25 ° C.). The dry film has a thickness of about 10 µm.
    The gloss of the film was measured using a gloss meter (three Refo 3 / Refo 3D angles from De Lange, Labomat distributor) on the black part of the contrast card at an angle of 20 °.
    The resistance of the film obtained was evaluated by separately depositing on the dry film 2 drops (1 drop = 10 μl) of olive oil and 2 drops of sebum on the black part of the contrast card. The drops were left in contact with the dry film for 5 minutes and 30 minutes respectively and then the drop of oil was wiped off and the appearance of the area of the film which was in contact with the oil was observed. If the film has been damaged by the drop deposited, the polymer film is considered not to be resistant to olive oil and / or sebum.
    The tackiness of the polymer film was assessed by touching the dry film with your finger. The following results were obtained:
    Property PolymerExample 1 PolymerExample 2 PolymerExample 3 Polymer Example 4 PolymerExample 5 Resistance to olive oil Good resistance Good resistance Good resistance Good resistance Good resistance Sebum resistance Good resistance Sounds resistance Good resistance Good resistance Good resistance Shine Mast film · - Matte film Matte film Matte film Matte film Tights Not sticky Not sticky Not sticky Not sticky Not sticky
    The results obtained show that the 5 polymers according to the invention are film-forming and the film obtained is non-sticky, of matt appearance and has good resistance to oil and sebum.
    Example 12: Cosmetic evaluation of makeup compositions
    A makeup composition (lipstick) described below was prepared:
    Polymer at the end _____.........,: ...; _____.......... : . : ...; _____: _____: _____. 20%
    Pigment paste. 40% by weight of DG Red 7 pigment in the isodecard ..................................... ......................................-...-, 5%
    Isododecane _________________________________......______________....________________________________... qs 100%
    The composition was prepared with each polymer of Examples 1 to 5.
    Each composition was applied to an equivalent elastomeric skin support, depositing a thickness of 100 μm wet and allowed to dry at room temperature (25 ° C.) for 24 hours.
    The resistance of the film obtained was evaluated by separately applying 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, making 25 passes of cotton on the surface, and then the condition of the film was observed (whether or not the film was degraded).
    We also assessed the film's resistance to tape:
    A piece of scotch tape was applied to the dry film (Scotch® Magic ™ 810 from 3M; 1 = 19 mm L = 5 cm). We put a weight of about 1070 g (surface 65 * 55mm) on the piece of tape for 30 seconds. The tape was then removed which was then placed on an object slide to observe the adherent surface of the applied tape and see if it contains traces of the dry polymer film. The following results were obtained.
    Property Polymer Example! PolymerFree 2 PolymerExample 3 Polymer Example 4 PolymerExample 5 Resistance to olive oil Good resistance Good resistance Good resistance Good resistance Good resistance Sebum resistance Good resistance Good resistance Good resistance Good resistance Good resistance Scotch test Good resistance Good resistance Good resistance Good; resistance Good resistance
    The results obtained show that the compositions according to the invention exhibit good resistance to oil and sebum and good resistance (resistance to scotch tape). The lipstick composition applied to the lips thus makes it possible to obtain makeup that is resistant to oil and sebum and therefore exhibits good hold.
    权利要求:
    Claims (1)
    [1" id="c-fr-0001]
    Claims [Claim 1] Composition comprising: a) a polyhydroxyalkanoate copolymer comprising, preferably consisting of, the following polymeric units A, B and C: - [- O-CH (R1) -CH 2 -CO -] - unit A - [-O-CH (R2) -CH 2 -CO -] - unit B - [-O-CH (R3) -CH 2 -CO -] - unit C in which: RI denotes a linear alkyl radical having from 5 to 9 carbon atoms; R2 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical RI - 2; R3 denotes a linear alkyl radical having a carbon number corresponding to the number of carbon atoms of the radical RI - 4; the molar percentage in unit A being greater than the molar percentage in unit B and greater than the molar percentage in unit C; b) an oily medium comprising a non-silicone oil chosen from: ester oils, carbonate oils, apolar branched hydrocarbon oils having from 8 to 14 carbon atoms, in admixture with a monoalcohol having from 2 to 6 carbon atoms according to a weight ratio monoalcohol / branched non-polar hydrocarbon oil ranging from 1/99 to 10/90; and when the polymer is such that the alkyl group RI comprises from 6 to 9 carbon atoms, the non-silicone oil is also chosen from non-polar hydrocarbon oils having from 8 to 14 carbon atoms in the absence of monoalcohol having from 2 with 6 carbon atoms; when the polymer is such that the alkyl group RI comprises 9 carbon atoms, the non-silicone oil is also chosen from hydrogenated polyisobutylenes. [Claim 2] Composition according to Claim 1, characterized in that for the copolymer, the unit A is present in a molar percentage ranging from 40 to 97.5%, the unit B is present in a molar percentage ranging from 2 to 40%, and unit C is present in a molar percentage ranging from 0.5 to 20% relative to all of units A, B and C. [Claim 3] Composition according to Claim 1 or 2, characterized in that the copolymer comprises units A having an alkyl radical RI comprising
    5 carbon atoms, B units having an alkyl radical having 3 carbon atoms and C units having an alkyl radical having 1 carbon atom. [Claim 4] Composition according to one of Claims 1 to 3, characterized in that the copolymer comprises from 85 to 97.5% by mole of unit A; from 2 to 10% by mole of unit B; from 0.5 to 7% by mole of unit C. [Claim 5] Composition according to Claim 1 or 2, characterized in that the copolymer comprises units A having an alkyl radical RI comprising 6 carbon atoms, units B having an alkyl radical having 4 carbon atoms and units C having an alkyl radical having 2 carbon atoms. [Claim 6] Composition according to one of claims 1, 2 or 5, characterized in that the copolymer comprises from 60 to 94.5% by mole of unit A; from 5 to 35% by mole of unit B; from 0.5 to 7% by mole of unit C. [Claim 7] Composition according to either of Claims 1 and 2, characterized in that the copolymer comprises units A having an alkyl radical RI comprising 9 carbon atoms, units B having an alkyl radical having 7 carbon atoms, and units C having an alkyl radical having 5 carbon atoms. [Claim 8] Composition according to one of claims 1, 2 or 7, characterized in that the copolymer comprises from 40 to 50% by mole of unit A; 30 to 40% by mole of unit B; from 10 to 20% by mole of unit C. [Claim 9] Composition according to one of the preceding claims, characterized in that the copolymer has a number average molecular weight ranging from 50,000 to 150,000. [Claim 10] Composition according to one of the preceding claims, characterized in that the copolymer is present in a content ranging from 0.1 to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.1 to 25% in weight. [Claim 11] Composition according to one of the preceding claims, characterized in that the apolar hydrocarbon oil having from 8 to 16 carbon atoms is chosen from branched C 8 -C 6 alkanes and linear C 8 -C 16 alkanes. [Claim 12] Composition according to one of Claims 1 to 10, characterized in that the ester oil is chosen from triglycerides consisting of esters of C4-C24 fatty acids and of glycerol; monoester oils of formula R4COOR5 in which R4 represents a hydrocarbon chain containing from 5 to 19 carbon atoms and R 5 represents a hy-
    [Claim 13] [Claim 14] [Claim 15] [Claim 16] Drocarbon in particular branched containing from 4 to 20 carbon atoms provided that R4 + R 5 is 3 9 carbon atoms; esters of lactic acid and C10-20 alcohol; diesters of C10-C20 malic acid and alcohol; esters of pentaerythritol and C8-C22 carboxylic acid; the di-esters of formula (II) R6-OC (= O) -R'6-C (= O) -OR ”6, with R6 and R” 6, identical or different, represent a C4 to C12 alkyl chain , linear or branched, saturated or unsaturated possibly having at least one ring, saturated or not, and R'6 represents an alkylene chain, saturated or unsaturated, from C1 to C4; the diesters of formula (III) R7-C (= O) -O-R'7-OC (= O) -R ”7, with R7 and R” 7, identical or different, represent a C4 to C12 alkyl chain represent a C4 to C12 alkyl chain, linear or branched, saturated or unsaturated, and R'7 represents an alkylene chain, saturated or unsaturated, in C1 to C4. Composition according to one of claims 1 to 10, characterized in that the carbonate oils are chosen from carbonates of formula R8-O-CO-O-R9, with R8 and R9, identical or different, represent a C4 alkyl chain to Cl2.
    Composition according to one of Claims 1 to 10, characterized in that it comprises a monoalcohol of 2 to 6 carbon atoms, preferably chosen from ethanol, butanol-1, and preferably ethanol.
    Composition according to one of the preceding claims, characterized in that it comprises a physiologically acceptable medium.
    Non-therapeutic cosmetic method for treating keratin materials, comprising the application to keratin materials of a composition according to one of the preceding claims.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP1184028B2|2009-12-02|Non-transfer cosmetic composition comprising a non-volatile silicone, a non-volatile hydrocarbon oil and an inert particulate phase
    EP1112734B1|2003-07-23|Non-transfer cosmetic composition comprising a non-volatile silicon compound, and a non-volatile hydrocarbon oil incompatible with the silicone compound
    EP1068855B1|2002-04-10|Composition with a liquid fatty phase gelified by a polyamide having ester end-groups
    EP0955039B1|2004-05-19|Topical composition containing an ester of a c24-c28 branched fatty acid or alcohol
    EP0997139B1|2001-09-19|Cosmetic composition containing a film-forming polymer, a poly-alpha-olefin and a liquid fatty phase
    CA2151575C|1999-08-17|Cosmetic composition containing a fatty substance and a polymeric aqueous dispersion and use of said substance
    FR2811552A1|2002-01-18|COMPOSITION, IN PARTICULAR COSMETIC OR PHARMACEUTICAL, IN SOLID FORM
    FR3090365A1|2020-06-26|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium
    EP1864649A2|2007-12-12|Bis-urea type compound, composition comprising it, use and cosmetic treatment method
    FR2843020A1|2004-02-06|Composition for e.g. lipstick comprises fatty acid ester of dextrin as thickener and gelling agent
    CA2262134A1|1999-09-27|Cosmetic composition containing a new pigment
    FR2892303A1|2007-04-27|Cosmetic composition, useful as a skin care and/or make-up product, comprises a liquid fatty phase containing a lipophilic compound e.g. monoalcohol
    EP0850640A1|1998-07-01|Personal care compositon comprising a solid elastomeric organopolysiloxane
    FR2753625A1|1998-03-27|COSMETIC COMPOSITION COMPRISING A PARTICULAR COPOLYMER AND USE OF SAID COPOLYMER IN COSMETICS
    FR2904217A1|2008-02-01|MIXTURE OF PARTIAL ESTERS OF MONOPENTAERYTRITOL, DIPENTAERYTRITOL AND TRIPENTAERYTRITOL, PROCESS FOR THEIR PRODUCTION AND COSMETIC PRODUCT CONTAINING THE SAME
    FR2760357A1|1998-09-11|HOMOGENEOUS OIL COMPOSITION BASED ON SILICONE GUM
    FR2779440A1|1999-12-10|Anhydrous composition with low viscosity, especially for cosmetic use
    FR2796270A1|2001-01-19|Structurized oil composition, used in cosmetics, comprises a liquid oil phase structurized by a polyamide backbone polymer, with a terminal alkyl or alkenyl group| joined by an ester, associated with a liquid amphiphile compound|
    FR3111811A1|2021-12-31|Cosmetic composition comprising a polyhydroxyalkanoate copolymer containing an | saturated hydrocarbon chain, and a surfactant
    FR2819402A1|2002-07-19|Composition useful for making nail varnish sticks comprises liquid phase including volatile organic solvent thickened with specified polymer
    FR3060330A1|2018-06-22|COMPOSITION COMPRISING AT LEAST ONE OIL AND A POLYESTER
    FR3111557A1|2021-12-24|Cosmetic composition comprising a polyhydroxyalkanoate copolymer comprising at least two different polymer units with a | saturated hydrocarbon chain in a fatty medium
    FR3104975A1|2021-06-25|Retinol-based composition
    FR2977156A1|2013-01-04|Cosmetic composition, useful e.g. as a skin care and make up product of skin of the body, face, lips, eyelashes, eyebrows, hair, scalp or nails, comprises polysiloxane having linking group and/or amide compound
    FR2977154A1|2013-01-04|Cosmetic composition, useful e.g. as make up composition e.g. mascara, comprises ureidopyrimidone functionalized wax obtained by reaction between waxes having reactive functional group e.g. hydroxy and linking group, and an amide compound
    同族专利:
    公开号 | 公开日
    US20220008317A1|2022-01-13|
    JP2022514244A|2022-02-10|
    KR20210091260A|2021-07-21|
    EP3897535A1|2021-10-27|
    CN113164348A|2021-07-23|
    FR3090365B1|2021-01-01|
    WO2020128050A1|2020-06-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1980235A1|2007-03-13|2008-10-15|Riken|Biodegradable oil absorbing film|
    WO2008155059A2|2007-06-19|2008-12-24|Cognis Ip Management Gmbh|Hydrocarbon mixtures and use thereof|
    WO2011069244A1|2009-12-07|2011-06-16|Queen's University At Kingston|Medium chain length polyhydroxyalkanoate polymer and method of making same|
    WO2011154508A1|2010-06-09|2011-12-15|L'oreal|Cosmetic composition comprising a polymer and a 4-carboxy-2-pyrrolidinone derivative, cosmetic treatment process and compound|
    FR2964663A1|2010-09-14|2012-03-16|Oreal|COSMETIC COMPOSITION COMPRISING COLORING MATTER, COLORING MATERIAL, AND COSMETIC TREATMENT PROCESS|
    US20150274972A1|2012-10-12|2015-10-01|Alzo International, Inc.|Enhanced water and transfer resistant film forming|
    WO2015123049A1|2014-02-17|2015-08-20|The Procter & Gamble Company|Skin cleansing compositions comprising biodegradable abrasive particles|
    WO2018178899A1|2017-03-30|2018-10-04|Bio-On S.P.A.|Cosmetic composition comprising a biodegradable polyester and an oily phase|
    WO2018017899A1|2016-07-20|2018-01-25|Emory University|Formulations for the suprachoroidal space of an eye and methods|FR3111812A1|2020-06-24|2021-12-31|L'oreal|Cosmetic composition comprising a polyhydroxyalkanoate copolymer grafted in a fatty medium|
    FR3111811A1|2020-06-24|2021-12-31|L'oreal|Cosmetic composition comprising a polyhydroxyalkanoate copolymer containing ansaturated hydrocarbon chain, and a surfactant|
    法律状态:
    2019-11-15| PLFP| Fee payment|Year of fee payment: 2 |
    2020-06-26| PLSC| Publication of the preliminary search report|Effective date: 20200626 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 3 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1873652A|FR3090365B1|2018-12-20|2018-12-20|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium|FR1873652A| FR3090365B1|2018-12-20|2018-12-20|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium|
    PCT/EP2019/086809| WO2020128050A1|2018-12-20|2019-12-20|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium|
    KR1020217018162A| KR20210091260A|2018-12-20|2019-12-20|Cosmetic composition comprising polyhydroxyalkanoate in an oily medium|
    EP19832960.9A| EP3897535A1|2018-12-20|2019-12-20|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium|
    JP2021534127A| JP2022514244A|2018-12-20|2019-12-20|Cosmetic composition containing polyhydroxyalkanoate in an oily medium|
    CN201980079830.9A| CN113164348A|2018-12-20|2019-12-20|Cosmetic composition comprising polyhydroxyalkanoate in an oily medium|
    US17/291,717| US20220008317A1|2018-12-20|2019-12-20|Cosmetic composition comprising a polyhydroxyalkanoate in an oily medium|
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