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WO2022208027A1 - Cosmetic composition comprising at least one polyhydroxyalkanoate - Google Patents

Cosmetic composition comprising at least one polyhydroxyalkanoate Download PDF

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Publication number
WO2022208027A1
WO2022208027A1 PCT/FR2022/050603 FR2022050603W WO2022208027A1 WO 2022208027 A1 WO2022208027 A1 WO 2022208027A1 FR 2022050603 W FR2022050603 W FR 2022050603W WO 2022208027 A1 WO2022208027 A1 WO 2022208027A1
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WO
WIPO (PCT)
Prior art keywords
formula
polyhydroxyalkanoate copolymer
polymeric units
cosmetic composition
weight
Prior art date
Application number
PCT/FR2022/050603
Other languages
French (fr)
Inventor
Philippe GUARILOFF
Florence Quevauviller
Anthony Courtois
Bertrand Thollas
Original Assignee
Chanel Parfums Beaute
Polymaris Biotechnology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chanel Parfums Beaute, Polymaris Biotechnology filed Critical Chanel Parfums Beaute
Priority to EP22718740.8A priority Critical patent/EP4312969A1/en
Publication of WO2022208027A1 publication Critical patent/WO2022208027A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85Polyesters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments

Definitions

  • the present disclosure relates to the field of cosmetic formulation and more particularly cosmetic compositions comprising biopolymers belonging to the polyhydroxyalkanoate family, and conferring increased persistence of at least one cosmetic effect, in particular of makeup and/or of care provided after application of the composition, as well as good adhesion of the composition after application to the keratin materials.
  • biopolymers make it possible to give said cosmetic composition long-lasting properties as well as homogeneity on application, thanks to their film-forming property.
  • Cosmetic makeup or care compositions are commonly used to provide an aesthetic appearance when applied to the skin and the lips, this effect having to last over time. In particular, they must resist the various external factors likely to modify their aesthetic effect, such as sweat, tears, sebum or saliva.
  • cosmetic makeup or care compositions it is sought to have good color and gloss retention over time, and good transfer resistance.
  • good hold over time of the make-up and its non-transfer are also sought, while preserving the dullness despite the formation of sebum or sweat during the day.
  • resistance to sebum and sweat are also essential, as well as the excellent homogeneity and resistance of the deposited film, which significantly influence the level of ultraviolet protection obtained.
  • film-forming polymers used in a cosmetic composition must be soluble in the phase of the formula which contains the ingredients which must be fixed to the surface of the skin. They must also have an affinity for the skin and promote the adhesion of the makeup during the application of the cosmetic composition to the skin. They must also be pleasant to apply and their deposit must provide a feeling of comfort to the user, while retaining satisfactory aesthetic properties. Finally, they should be easily removed when cleansing the skin.
  • silicone derivatives such as, for example, MQ resins, for example trimethylsiloxysilicates (or T resins), polysilsesquioxanes such as polypropylsilsesquioxane, or even dendrimer polymers such as acrylate/polythmethylsiloxymethacrylate.
  • these film-forming polymers have a certain number of drawbacks.
  • they are mostly synthetic in nature and are not or only slightly biodegradable. It would therefore be desirable to seek technical solutions that are more respectful of the environment.
  • synthetic polymers are likely to contain impurities, such as unreacted monomeric units, or traces of nanoparticles, making them incompatible with cosmetic use.
  • they are sometimes difficult to formulate and to stabilize in cosmetic compositions comprising natural ingredients such as plant extracts.
  • natural ingredients are increasingly used in cosmetic formulations, and can for example be particularly interesting to provide hydration or anti-aging functions.
  • the present invention therefore aims to propose a solution to its various problems, and to propose the implementation of new biocompatible and biodegradable film-forming polymers, in cosmetic compositions.
  • the present invention therefore relates to a cosmetic makeup and/or care composition for the skin and/or lips, providing a makeup or care deposit having improved persistence over time, thus allowing better hold in the skin. time of its color and/or its dullness. More specifically, the present disclosure relates to a cosmetic composition using, as film-forming ingredient, at least one polyhydroxyalkanoate copolymer.
  • the present invention thus relates, according to a first aspect, to a cosmetic composition
  • a cosmetic composition comprising at least one polyhydroxyalkanoate copolymer, characterized in that said polyhydroxyalkanoate copolymer consists of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1) such as: Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0-CH(R2)- (CH2) m -C0-]- in which :
  • R1 represents an n-propyl group
  • R2 represents an n-pentyl group
  • n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1).
  • Document WO2020/128050 proposes, for example, film-forming PHAs consisting of a mixture of at least three distinct polymeric units.
  • This document illustrates, by way of comparisons, PHAs consisting of a repetition of only two polymeric units, and these do not give satisfaction in terms of cosmetic properties (solubility in oils) and therefore cannot be used as film formers.
  • the comparative PHAs illustrated in document WO2020/128050 consist of polymeric units (A1) and (B1) in accordance with the present application, but in proportions very far from the proportions envisaged in the present invention. It is therefore indeed the choice of the polymeric units (A1) and (B1) claimed, in specific proportions, which made it possible to obtain satisfactory cosmetic properties allowing their use as a film-forming agent.
  • the polymers which are the subject of the present application consisting of a repetition of specific polymeric units (A1) and (B1), in well-defined proportions, made it possible to obtain a compound easily soluble in various cosmetic solvents such as isododecane (unlike film-forming PHAs consisting of a mixture of at least three distinct polymeric units as described in document WO2020/128050).
  • the films obtained are stable over time, and in particular are resistant to sebum.
  • the polyhydroxyalkanoate copolymer consists of: - 3 to 5 mol% of polymeric units (A1) and
  • the composition comprises at least one polyhydroxyalkanoate copolymer consisting of:
  • the cosmetic composition according to the invention comprises at least one polyhydroxyalkanoate copolymer consisting of a repetition, successive or not, of polymeric units (A1) and polymeric units (B1) as described above, and having a weight average molecular weight (Mw) between 20,000 to 100,000 g/mol.
  • the polyhydroxyalkanoate copolymer is present in the cosmetic composition in a content of between 0.5% to 30% by weight, preferably 1% to 20% by weight, and very preferably 2% to 8% by weight, by relative to the total weight of the composition.
  • the invention relates to the use of at least one polyhydroxyalkanoate copolymer as a film-forming agent in a cosmetic composition, said polyhydroxyalkanoate copolymer consisting of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1) such as: Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0- CH(R2)-(CH2) m -C0-]- in which:
  • R1 represents an n-propyl group
  • R2 represents an n-pentyl group
  • n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1); said polyhydroxyalkanoate copolymer being obtained by a fermentation process from a bacterium registered under the Budapest Treaty at the National Collection of Cultures of Microorganisms on February 24, 2021 under the deposit number I-5658; and being present in a content of between 2 and 20% by weight, relative to the total weight of said cosmetic composition.
  • film-forming polymer is meant, within the meaning of the present application, a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on the keratin materials, and in particular a cohesive film whose cohesion and mechanical properties are such that it can be isolated from said support.
  • the cosmetic composition according to the invention may be in the form of a single or multiple emulsion of the water-in-oil or oil-in-water type, a microemulsion, a nanoemulsion, a powder, an anhydrous composition, a suspension, a lotion, a cream, an aqueous or hydroalcoholic gel, a foam, a serum, a solution or an aerosol dispersion, or a dispersion of lipid vesicles, or of droplets obtained by coacervation or by microfluidics.
  • Said cosmetic composition may also comprise, in addition to the polyhydroxyalkanoate copolymer according to the invention, at least one additive customary in the cosmetics field, such as for example at least one compound chosen from an emollient or humectant agent, a gelling agent and / or thickener, a surfactant, an oil, a wax, a dye, a pigment, a nacre, a filler such as feel agents, a preservative, an antioxidant agent, an active agent, an organic or inorganic powder, a volatile and/or non-volatile solvent, a solubilizer, a chelating agent, a sequestrant, an ionic salt capable in particular of adjusting the pH of the composition or its ionic strength, a sunscreen which may be organic and/or inorganic and a perfume.
  • at least one additive customary in the cosmetics field such as for example at least one compound chosen from an emollient or humectant agent, a gelling agent and / or
  • the cosmetic composition may also comprise another film-forming polymer in addition to the at least one polyhydroxyalkanoate copolymer according to the invention, said other film-forming agent preferably being environmentally friendly. , especially biodegradable.
  • said composition may contain one or more emollient(s) or humectant(s), which may be chosen, for example, from glycerin, polyols, glycols, water-soluble silicones such as that sold under the name KF6011 (Shin Etsu) and water-soluble jojoba, such as that sold under the name Resplanta jojoba (Res pharma).
  • emollient(s) or humectant(s) which may be chosen, for example, from glycerin, polyols, glycols, water-soluble silicones such as that sold under the name KF6011 (Shin Etsu) and water-soluble jojoba, such as that sold under the name Resplanta jojoba (Res pharma).
  • Said emollient or humectant may be present in the composition at a content of the order of 0 to 30%, preferably 2 to 10% by weight, relative to the total weight of the composition.
  • One or more gelling agent(s) and/or thickener(s) for the aqueous phase can also be incorporated into the composition according to the invention.
  • They are chosen for example from cellulosic derivatives, polysaccharides including in particular gums of plant origin (guar, carob, alginates, carrageenans, pectin), of microbial origin (xanthan), clays (laponite), hydrophilic gelling agents, and lipophilic gelling agents.
  • the hydrophilic gelling agents can in particular be chosen from:
  • lipophilic gelling agent denotes, in the context of the present application, a substance capable of solidifying or gelatinizing the oil present in the composition of the invention.
  • the lipophilic gelling agent is chosen for example from sucrose polyesters. Mention may be made of the esters of sucrose and of fatty acids, and preferably the esters of sucrose, of stearic acid and of acetic acid, such as sucrose tetrastearate triacetate.
  • the gelling agents can be introduced in a content ranging from 0.05 to 40% by weight, relative to the total weight of the composition, preferably from 0.1 to 20% and better from 0.5 to 15% by weight.
  • One or more surfactant(s), preferably nonionic, may form part of the composition according to the invention and will be present in a content of the order of 0 to 8%, preferably 0, 5 to 3% by weight, relative to the total weight of the composition.
  • the compositions according to the present application may also contain at least one or more oils or organic solvent.
  • oil or organic solvent is meant a non-aqueous body which is liquid at ambient temperature and atmospheric pressure.
  • the oil can be volatile or non-volatile.
  • volatile organic oil or solvent is understood to mean, in the sense of the invention, any non-aqueous medium capable of evaporating on contact with keratin materials in less than one hour, at ambient temperature and atmospheric pressure.
  • volatile organic solvent(s) and volatile oils of the invention are volatile organic solvents and cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa at 40,000 Pa (10 3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa ( 0.01 to 10 mm Hg).
  • non-volatile oil means an oil remaining on the keratin materials at room temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 10 -3 mm Hg (0.13 Pa).
  • the oil may be present in the composition in a content ranging from 0.05 to 30%, preferably 0.1 to 15% by weight relative to the total weight of the composition.
  • the composition according to the invention may comprise volatile oils and/or non-volatile oils, and mixtures thereof.
  • the volatile oils (or organic solvents) can be hydrocarbon oils, silicone oils, linear(s), cyclic(s) or branched(s), or mixtures thereof.
  • hydrocarbon oil means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and phosphorus atoms.
  • the volatile hydrocarbon-based oils can be chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, and in particular branched C 8 -Ci 6 alkanes of natural or petroleum origin, such as C 8 -Ci 6 isoalkanes such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, branched C 8 -Ci 6 esters, iso-hexyl neopentanoate, and mixtures thereof.
  • volatile oils it is also possible to use volatile silicones, such as for example volatile linear or cyclic silicone oils, in particular those having a viscosity of 6 centistokes (6.10 -6 m 2 /s), and having in particular from 3 to 6 silicon atoms, these silicones optionally comprising one or more alkyl or alkoxy groups having 1 or 2 carbon atoms.
  • volatile linear or cyclic silicone oils in particular those having a viscosity of 6 centistokes (6.10 -6 m 2 /s), and having in particular from 3 to 6 silicon atoms, these silicones optionally comprising one or more alkyl or alkoxy groups having 1 or 2 carbon atoms.
  • volatile silicone oil which can be used in the invention, mention may in particular be made of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
  • compositions in accordance with the invention may also comprise at least one non-volatile organic oil or solvent, which may in particular be chosen from non-volatile hydrocarbon-based and/or silicone oils.
  • non-volatile hydrocarbon oil mention may in particular be made of: - hydrocarbon oils of plant origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C4 at C24, the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oil, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bankoulier, passionflower, muscat rose, camellia; or alternatively caprylic/capric acid triglycerides;
  • triglycerides consisting of esters of fatty acids and
  • - synthetic ethers having 10 to 40 carbon atoms; - linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as sesam, squalane, and mixtures thereof;
  • esters such as triglycerides, or pelargonic acid derivatives
  • - synthetic esters such as oils of formula R1COOR2 in which R1 represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms at provided that R1 + R2 is 10, such as Purcellin's oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as is
  • - higher fatty acids such as oleic acid, linoleic acid, linolenic acid; and their mixtures.
  • the nonvolatile silicone oils which can be used in the compositions in accordance with the invention may be nonvolatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendent and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
  • PDMS nonvolatile polydimethylsiloxanes
  • phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones,
  • the content of non-volatile oil or organic solvent in the composition in accordance with the invention ranges from 0.01 to 30% by weight, in particular from 0.1 to 25% by weight, and better still from 0.1 to 20% relative to the total weight of the composition.
  • the composition according to the invention may also comprise at least one wax.
  • wax designates a fatty substance with reversible liquid/solid change, having a melting point above 55° C. and generally below 110° C., which is liquid under the conditions of preparation of the composition and which has an organization anisotropic crystalline in the solid state.
  • Wax can be polar or apolar
  • polar wax is meant a wax comprising at least one heteroatom such as oxygen, nitrogen, silicon or phosphorus.
  • the polar wax can be chosen from the group comprising beeswax, carnauba wax, candelilla wax, cottonseed wax, rice bran wax, bay wax, Chinese insect wax, montan wax, lanolin and its alcoholic, acetylated, esterified, polyethoxylated derivatives, kapok wax, sugar cane wax, hexyl laurate, jojoba wax, wax shellac, polyethoxylated cholesterol ether, synthetic beeswax, or a mixture thereof. Mention may also be made of plant ester waxes such as, for example, by way of illustration, jojoba esters, alkyl esters or hydrogenated alkyl esters.
  • apolar wax is meant a hydrocarbon wax and/or a silicone wax.
  • non-polar hydrocarbon wax means a wax comprising only carbon and hydrogen atoms and not comprising heteroatoms such as oxygen, nitrogen, silicon or phosphorus.
  • Apolar silicone wax means a wax comprising a silicon heteroatom.
  • the wax if it is present in the cosmetic composition of the invention, represents a content of between 0.5 to 20% by weight, preferably from 1% to 10% by weight, relative to the total weight of the composition. .
  • the composition according to the invention may comprise an aqueous phase comprising water and optionally at least one water-soluble solvent.
  • water-soluble solvent denotes a compound that is liquid at ambient temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure).
  • water-soluble solvents which can be used in the compositions in accordance with the invention, mention may be made, by way of indication and not of limitation, of mono-alcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, ketones C 3 -C and C2-C4 aldehydes.
  • One or more active agent(s), of natural or synthetic origin, having a biological activity for example chosen from vitamins, trace elements, allantoin, vegetable proteins, vegetable extracts , moisturizers, anti-aging agents, antioxidants, radiance-promoting agents and mixtures thereof.
  • the active agent is chosen from vanilla planifolia fruit water, niacinamide, hyaluronic acid and its derivatives, a yeast extract and mixtures thereof.
  • compositions in accordance with the invention may also comprise at least one dyestuff such as pulverulent materials, fat-soluble dyes, water-soluble dyes.
  • the pulverulent dyestuffs can be chosen from pigments and nacres.
  • the pigments can be white or colored, inorganic and/or organic, coated or not. Mention may be made, among the mineral pigments, of titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxides, bismuth oxychloride, as well as iron or chromium oxides, manganese violet , ultramarine blue, chromium hydrate and ferric blue.
  • the organic pigments mention may be made of carbon black, D & C type pigments, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
  • the nacres can be chosen from white pearlescent pigments such as mica covered with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
  • the fat-soluble dyes are, for example, Sudan red, D&C Red 17,
  • compositions in accordance with the invention may also comprise at least one filler.
  • the fillers can be chosen from those well known to those skilled in the art and commonly used in cosmetic compositions.
  • the fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders such as Nylon ⁇ marketed under the name Orgasol ⁇ by the company Atochem, poly-13-alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon ⁇ , lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile such as those marketed under the name Expancel ⁇ by the company Nobel Industrie, acrylic powders such as those marketed under the name Polytrap ⁇ by Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (Tospearls ⁇ from Toshiba, for example), precipitated calcium carbonate, carbonate and magnesium hydrogen carbon
  • a compound capable of swelling with heat and in particular heat-expandable particles such as unexpanded microspheres of vinylidene chloride/acrylonitrile/methyl methacrylate copolymer or of acrylonitrile homopolymer copolymer such as for example those marketed respectively under the references Expancel® 820 DU 40 and Expancel® 007WU by the company AKZO NOBEL. Mention may also be made of Advancell® marketed by Sekuisi Plastic or Thermoexpandable microspheres® from Matsumoto.
  • the fillers can represent from 0.1 to 25%, in particular from 0.2 to 20% by weight relative to the total weight of the composition.
  • compositions in accordance with the invention may also comprise at least one fiber.
  • fiber it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber falls.
  • the L/D ratio (or aspect ratio) is chosen in the range going from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150.
  • the fibers that can be used in the composition of the invention can be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or organized, for example braided, hollow or solid. Their section can be arbitrary and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. Their shape can be linear, curved, sinusoidal or curly. In particular, their ends are blunted and or polished to avoid injury.
  • non-rigid fibers such as polyamide fibers (Nylon®) or rigid fibers such as polyimide-amide fibers such as those sold under the names KERMEL®, KERMEL TECH® by the company RHODIA or poly-(p-phenyleneterephthalamide) (or aramid) in particular sold under the name Kevlar® by the company DUPONT DE NEMOURS.
  • the fibers may be present in the composition according to the invention in a content ranging from 0.01% to 10% by weight, relative to the total weight of the composition, in particular from 0.1% to 5% by weight, and more particularly from 0.3% to 3% by weight
  • Other additives usually used in cosmetics may also be present in the composition according to the invention, in particular preservatives, antioxidants, organic and/or inorganic UV filters, or perfumes which are well known in the technical field.
  • the person skilled in the art is able to choose, among all of these possible additives, both the nature and the quantity of those which will be added to the composition, so that the latter retains all of its properties. Of course, those skilled in the art will take care to choose any additional additives and/or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or substantially not, altered by the addition envisaged.
  • the cosmetic composition may be intended for a cosmetic product chosen in particular from lipsticks, glosses, fluid and compact foundations, nail varnishes, eye shadows, mascaras, pencils eyelashes or eyebrows, care creams, serums, products for sun protection, toiletries such as shower gels, etc.
  • the biopolymer can be obtained in a known manner by biosynthesis with the microorganism registered with the National Collection of Microorganism Culture under the Budapest Treaty under the number CNCM I-5658, deposit made in the name of the company Polymaris Biotechnology, located at Brest - France.
  • the present invention therefore does not expressly cover these strains but only the use of the polyhydroxyalkanoates secreted by them for the production of cosmetic compositions.
  • the polyhydroxyalkanoate used in the context of the cosmetic compositions according to the invention can be obtained by fermentation of the bacterium registered under the Budapest Treaty at the National Collection of Microorganism Cultures on February 24, 2021 under the deposit number I-5658 in a suitable culture medium, conventionally agitated and aerated.
  • the fermentation to produce the polyhydroxyalkanoate is carried out under conditions of agitation and aeration of the medium at a temperature of between 20° C. and 37° C., preferably at 30° C., the medium having a pH of between 6.5 and 9 preferably close to 7.5, and being adjusted if necessary during fermentation.
  • the duration of the fermentation is between 24 and 120 hours, preferably between 36 and 72 hours.
  • mineral salts are added during the fermentation of the bacteria.
  • the polyhydroxyalkanoate isolation and purification methods are obtained by conventional means well known to those skilled in the art, such as centrifugation, filtration, ultrafiltration, extraction, evaporation and dialysis.
  • the polyhydroxyalkanoate copolymer produced by the bacterium registered under the number CNCM I-5658 is characterized by the presence of two polymeric units consisting of 4% by mole of polymeric units (A1) , in which n is equal to 1 and R1 represents an n-propyl group, and in 96% by mole of polymeric unit (B1) in which m is equal to 1 and R2 represents an n-pentyl group.
  • Example 1 preparation and isolation of the polyhydroxyalkanoate produced by the bacterium registered under the deposit number CNCM I-5658
  • the operations are carried out according to good microbiology practices under sterile conditions.
  • the various media are also sterilized either by heat treatment (121° C. for 20 minutes) or by 0.2 ⁇ m filtration.
  • a 2 mL cryotube of the CNCM i-5658 strain is inoculated into an Erlenmeyer flask containing 50 mL of medium allowing the culture of marine microorganisms (marine medium broth E2216, Difco, France). The culture is incubated at 30° C. with shaking for 12 to 18 hours.
  • the culture obtained is then inoculated into an Erlenmeyer flask containing 1.45 L of mineral medium suitable for its growth (medium M1 - Table 1) at 30° C. with stirring for 8 hours.
  • the culture is inoculated in a fermenter containing 13.5 L of mineral culture medium suitable for its growth and the biosynthesis of the biopolymer (medium M2 - Table 2).
  • the culture is maintained at 30°C with stirring for at least 30 hours.
  • the pH is regulated at 7.2 by 10 N NaOH or 2N H2SO4.
  • the oxygenation and the agitation of the culture are also regulated to allow the growth of the cells and the accumulation of the biopolymer.
  • the cellular biomass containing the biopolymers is concentrated by centrifugation.
  • the biomass is eliminated by centrifugation (8000 rpm X 20 min) and the supernatant containing the biopolymer is recovered.
  • the latter can be filtered in order to improve the quality of the final biopolymer.
  • the biopolymer concentrated in solution in dichloromethane is finally precipitated by adding a cold ethanol solution (10:1) then dried in a ventilated oven at 40 ⁇ until complete evaporation of the solvent.
  • Example 2 physico-chemical characterization of the polyhydroxyalkanoate biopolymer obtained in example 1
  • the molecular weight is determined by steric exclusion chromatography with a refractometer (RI) for detection.
  • the molecular weight is determined by comparing the retention time of the polymer with the retention time of polystyrene standards via a calibration line.
  • the analysis makes it possible to determine the average molecular weight (Mw in Dalton), the average molecular weight by number (Mn in Dalton) in PS (polystyrene) equivalent, as well as the polydispersity index.
  • composition of the biopolymer is determined by gas phase chromatography fitted with a flame ionization detector (FID) and confirmed by 1 H, 13 C, HMBC and HMQC NMR analysis.
  • FID flame ionization detector
  • a copolymer was thus obtained consisting of 96% by weight of poly(hydroxy-3-octanoate) and 4% by weight of poly(hydroxy-3-hexanoate)
  • Example 3 Evaluation of the film-forming properties of the copolymer of Example 2
  • a solution of the polymer whose film-forming properties are to be evaluated is prepared in a volatile solvent capable of dissolving it.
  • the polymer represents 30 to 50% by mass of the solution.
  • a solution obtained in step 1 is deposited in the bottom of a Petri dish.
  • the choice of the Petri dish makes it possible to come as close as possible to the actual conditions of use of a cosmetic composition, the constituent material of the Petri dish having a surface energy similar to that of human skin.
  • untreated skin has approximately a surface energy of 38 mN/m and skin washed with soap has a surface energy of the order of 25 to 29 mN/m (H. Schott, Contact angles and wettability of human skin, J. Pharm Soi.
  • a plastic Petri dish made of conventional polystryrene material is present it has a surface energy of the order of 39 mN/m.
  • the Petri dish is placed in a ventilated oven at 45°C in order to evaporate the volatile solvent, and obtain a dry film deposit of approximately 1 g, then the quality of the polymer film deposited is characterized. at the bottom of the Petri dish according to 3 assessment criteria:
  • a score of 1 is assigned to a film qualified as transparent (no deformation of the image and its contrast by observing it through the film), 0 for an opaque film
  • a score of 0, 1, or 2 is assigned, the score of 2 characterizing a regular deposit in thickness and covering the entire surface, and the score of 0 characterizing a film that is heavily cracked or has aggregates
  • a score from 4 to 0 is assigned on the basis of the following characteristics; 4 - very adhesive, does not peel off within 48 hours; 3 - adhesive, partially peels off under stress; 2 - adhesive initially, partially peels off in the
  • the copolymer of example 2 obtained by a biosynthetic process, clean and respectful of the environment has evaluation criteria similar to the polymer of the prior art. It is therefore an excellent candidate for replacing the synthetic film-forming polymers of the prior art, and thus making it possible to obtain cosmetic compositions having the same level of quality and performance, while being more respectful of the environment with in particular excellent biodegradability.
  • Example 2 The properties of the polymer of Example 2 were then compared to a copolymer according to document WO2020/128050 consisting of 60% by weight of poly(hydroxy-3- decanoate), 37% by weight of poly(hydroxy-3-octanoate) and 3% by weight of poly(hydroxy-3-hexanoate).
  • the comparative polymer according to document WO2020/128050 is not soluble in isododecane, unlike the copolymer according to the invention.
  • the sebum resistance of the two polymers was compared according to the following protocol:
  • the boxes are slightly shaken to allow a good distribution of the film on the box and left for 30 minutes at room temperature to allow this good distribution.
  • the boxes are placed in an oven at 45°C for 2 hours to allow the evaporation of the latter.
  • 4 mL of biophytosebum are distributed on the latter at ambient temperature.
  • a foundation base was prepared in the form of a water-in-oil emulsion having the composition presented in the following table 4: [0108] [Table 4]
  • aqueous phase comprising the water, glycerin, sorbitol, pentylene glycol and preservative and put it under Rayneri stirring
  • the foundation base obtained is fluid and homogeneous, it is easy to apply without fluffing.
  • the film formed on the skin is uniform.
  • the fluid foundation was prepared according to the following protocol: grind the pigments (iron oxides and titanium dioxide) in the fatty phase comprising methyl trimethicone, dimethicone, and isononyl isononanoate.
  • the mixture obtained was heated to 40° O and the PEG-10 dimethicone, the copolymer of Example 2 and the talc were added.
  • the aqueous phase comprising phenoxyethanol, butylene glycol and demineralised water is added for 2 min with vigorous stirring (Raynerie with a flocculator at 3000 revolutions/min), then the mixture is maintained under moderate stirring. for 5 mins.
  • the foundation is fluid, the emulsion has good stability, it spreads easily and evenly, without leaving a sticky impression.

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Abstract

The present disclosure falls within the field of cosmetic formulations and more particularly cosmetic compositions comprising biopolymers belonging to the polyhydroxyalkanoate family, and having an increased persistence of at least one cosmetic and/or care effect provided after application of the composition, and also good adhesion of the composition after application to keratin materials. A subject of the present invention is a cosmetic composition comprising at least one polyhydroxyalkanoate copolymer characterized in that said polyhydroxyalkanoate copolymer consists of a repetition of polymer units of formula (A1) and of polymer units of formula (B1) such as: Formula (A1): -[-O-CH(R1)-(CH2)n-CO-]- Formula (B1): -[-O-CH(R2)-(CH2)m-CO-]- in which: R1 is an n-propyl group, R2 is an n-pentyl group; n and m are equal to 1, said polyhydroxyalkanoate copolymer comprising 2 to 10 mol% of polymer units of formula (A1) and 98 to 90 mol% of polymer units of formula (B1). According to another aspect, the invention relates to the use of a polyhydroxyalkanoate copolymer consisting of a repetition of polymer units of formulae (A1) and (B1), as previously defined, as a film-forming agent in cosmetic compositions.

Description

Description Description
Titre : Composition cosmétique comprenant au moins un polyhydroxyalcanoate Title: Cosmetic composition comprising at least one polyhydroxyalkanoate
Domaine technique [0001] La présente divulgation relève du domaine de la formulation cosmétique et plus particulièrement des compositions cosmétiques comprenant des biopolymères appartenant à la famille des polyhydroxyalcanoate, et conférant une persistance accrue d’au moins un effet cosmétique, notamment de maquillage et/ou de soin apporté après application de la composition, ainsi qu’une bonne adhésion de la composition après application sur les matières kératiniques. Technical field [0001] The present disclosure relates to the field of cosmetic formulation and more particularly cosmetic compositions comprising biopolymers belonging to the polyhydroxyalkanoate family, and conferring increased persistence of at least one cosmetic effect, in particular of makeup and/or of care provided after application of the composition, as well as good adhesion of the composition after application to the keratin materials.
[0002] De tels biopolymères permettent de conférer à ladite composition cosmétique des propriétés de longue tenue ainsi qu’une homogénéité à l’application, grâce à leur propriété filmogène. [0002] Such biopolymers make it possible to give said cosmetic composition long-lasting properties as well as homogeneity on application, thanks to their film-forming property.
Technique antérieure [0003] Les compositions cosmétiques de maquillage ou de soin sont couramment employées pour apporter un aspect esthétique lors de l'application sur la peau et les lèvres, cet effet devant perdurer au cours du temps. Elles doivent notamment résister aux différents facteurs extérieurs susceptibles de modifier leur effet esthétique, comme la sueur, les larmes, le sébum ou la salive. En particulier, dans le cas des rouges à lèvres, on cherche à avoir une bonne tenue dans le temps de la couleur et de la brillance, et une bonne résistance au transfert. Pour les fonds de teint, les fards à paupières et les poudres, on recherche également une bonne tenue dans le temps du maquillage et son non-transfert, tout en préservant la matité malgré la formation de sébum ou de sueur au cours de la journée. Enfin, pour les produits de protection solaire, la résistance au sébum et à la sueur sont également essentiels, de même que l’excellente homogénéité et la tenue du film déposé, lesquels influent significativement sur le niveau de protection aux ultra-violets obtenu. PRIOR ART [0003] Cosmetic makeup or care compositions are commonly used to provide an aesthetic appearance when applied to the skin and the lips, this effect having to last over time. In particular, they must resist the various external factors likely to modify their aesthetic effect, such as sweat, tears, sebum or saliva. In particular, in the case of lipsticks, it is sought to have good color and gloss retention over time, and good transfer resistance. For foundations, eyeshadows and powders, good hold over time of the make-up and its non-transfer are also sought, while preserving the dullness despite the formation of sebum or sweat during the day. Finally, for sun protection products, resistance to sebum and sweat are also essential, as well as the excellent homogeneity and resistance of the deposited film, which significantly influence the level of ultraviolet protection obtained.
[0004] Il est connu, afin de limiter le transfert de couleur des compositions cosmétiques et d’améliorer la tenue de leur teinte, d'incorporer dans les formules des polymères dits filmogènes. Les polymères filmogènes mis en oeuvre dans une composition cosmétique doivent être solubles dans la phase de la formule qui contient les ingrédients devant être fixés à la surface de la peau. Ils doivent également présenter une affinité pour la peau et favoriser l’adhérence du maquillage lors de l’application de la composition cosmétique sur la peau. Ils doivent également être agréables à appliquer et leur dépôt doit procurer une sensation de confort à l’utilisatrice, tout en conservant des propriétés esthétiques satisfaisantes. Enfin, ils doivent être facilement éliminés lors du nettoyage de la peau. [0004] It is known, in order to limit the color transfer of cosmetic compositions and to improve their color retention, to incorporate so-called film-forming polymers into the formulas. The film-forming polymers used in a cosmetic composition must be soluble in the phase of the formula which contains the ingredients which must be fixed to the surface of the skin. They must also have an affinity for the skin and promote the adhesion of the makeup during the application of the cosmetic composition to the skin. They must also be pleasant to apply and their deposit must provide a feeling of comfort to the user, while retaining satisfactory aesthetic properties. Finally, they should be easily removed when cleansing the skin.
[0005] Il existe de nombreux polymères filmogènes commercialement disponibles, bien connus de l’homme de l’art et couramment utilisés dans le domaine de la cosmétique. A titre d’exemple illustratif, on peut notamment mentionner les dérivés de silicone tels que, par exemple, les résines MQ, par exemple les trimethylsiloxysilicates (ou résines T), les polysilsesquioxanes telles que le polypropylsilsesquioxane, ou bien encore les polymères dendrimères tels que l’acrylate/polythmethylsiloxymethacrylate. [0005] There are many film-forming polymers commercially available, well known to those skilled in the art and commonly used in the field of cosmetics. By way of illustrative example, mention may in particular be made of silicone derivatives such as, for example, MQ resins, for example trimethylsiloxysilicates (or T resins), polysilsesquioxanes such as polypropylsilsesquioxane, or even dendrimer polymers such as acrylate/polythmethylsiloxymethacrylate.
[0006] Toutefois, ces polymères filmogènes présentent un certain nombre d’inconvénients. En premier lieu, ils sont pour la plupart de nature synthétique et ne sont pas ou peu biodégradables. Il serait donc souhaitable de rechercher des solutions techniques plus respectueuses de l’environnement. De plus, les polymères de synthèse sont susceptibles de contenir des impuretés, telles que des unités monomériques n’ayant pas réagi, ou des traces de nanoparticules, les rendant incompatibles à une utilisation cosmétique. Enfin, ils sont parfois difficiles à formuler et à stabiliser dans des compositions cosmétiques comprenant des ingrédients naturels tels que des extraits de plantes. Or, les ingrédients naturels sont de plus en plus utilisés dans les formulations cosmétiques, et peuvent par exemple être particulièrement intéressants pour apporter des fonctions d’hydratation ou d’anti-âge. [0007] La présente invention vise donc à proposer une solution à ses différents problèmes, et à proposer la mise en oeuvre de nouveaux polymères filmogènes biocompatibles et biodégradables, dans des compositions cosmétiques. [0006] However, these film-forming polymers have a certain number of drawbacks. First, they are mostly synthetic in nature and are not or only slightly biodegradable. It would therefore be desirable to seek technical solutions that are more respectful of the environment. In addition, synthetic polymers are likely to contain impurities, such as unreacted monomeric units, or traces of nanoparticles, making them incompatible with cosmetic use. Finally, they are sometimes difficult to formulate and to stabilize in cosmetic compositions comprising natural ingredients such as plant extracts. However, natural ingredients are increasingly used in cosmetic formulations, and can for example be particularly interesting to provide hydration or anti-aging functions. The present invention therefore aims to propose a solution to its various problems, and to propose the implementation of new biocompatible and biodegradable film-forming polymers, in cosmetic compositions.
Description détaillée de l’invention Detailed description of the invention
[0008] La présente invention concerne donc une composition cosmétique de maquillage et/ou de soin de la peau et/ou des lèvres, procurant un dépôt de maquillage ou de soin présentant une persistance dans le temps améliorée, permettant ainsi une meilleure tenue dans le temps de sa couleur et ou de sa matité. Plus spécifiquement la présente divulgation concerne une composition cosmétique mettant en oeuvre, en tant qu’ingrédient filmogène, au moins un copolymère de polyhydroxyalcanoate. [0009] La présente invention a ainsi pour objet, selon un premier aspect, une composition cosmétique comprenant au moins un copolymère de polyhydroxyalcanoate, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate consiste en une répétition d’unités polymériques de formule (A1) et d’unités polymériques de formule (B1) telles que : Formule (A1) : -[-0-CH(R1)-(CH2)n-C0-]- Formule (B1 ) : -[-0-CH(R2)-(CH2)m-C0-]- dans lesquelles : [0008] The present invention therefore relates to a cosmetic makeup and/or care composition for the skin and/or lips, providing a makeup or care deposit having improved persistence over time, thus allowing better hold in the skin. time of its color and/or its dullness. More specifically, the present disclosure relates to a cosmetic composition using, as film-forming ingredient, at least one polyhydroxyalkanoate copolymer. The present invention thus relates, according to a first aspect, to a cosmetic composition comprising at least one polyhydroxyalkanoate copolymer, characterized in that said polyhydroxyalkanoate copolymer consists of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1) such as: Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0-CH(R2)- (CH2) m -C0-]- in which :
R1 représente un groupe n-propyle R2 représente un groupe n-pentyle ; n et m sont égal à 1 ledit copolymère de polyhydroxyalcanoate comprenant 2 à 10% en moles, d’unités polymériques de formule (A1 ) et 98 à 90% en moles d’unités polymériques de formule (B1 ). R1 represents an n-propyl group R2 represents an n-pentyl group; n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1).
[0010] Il est en effet du mérite de la demanderesse d’avoir mis en évidence que le choix d’unités polymériques (A1) et (B1) spécifiques, dans des proportions bien définies, permettait l’obtention de propriétés filmogènes particulièrement satisfaisantes, et améliorées par rapport à d’autres PHA connus. [0010] It is indeed to the credit of the applicant to have demonstrated that the choice of specific polymeric units (A1) and (B1), in well-defined proportions, made it possible to obtain particularly satisfactory film-forming properties, and improved compared to other known PHAs.
[0011] Le document W02020/128050 propose par exemple des PHA filmogènes constitués d’un mélange d’au moins trois unités polymériques distinctes. Ce document illustre, à titre de comparatifs, des PHA constitués d’une répétition de deux unités polymériques seulement, et ceux-ci de donnent pas satisfaction en termes de propriétés cosmétiques (solubilité dans les huiles) et par conséquent ne peuvent être utilisés comme filmogènes. Les PHA comparatifs illustrés dans le document W02020/128050 sont constitués d’unités polymériques (A1 ) et (B1 ) conformes à la présente demande, mais dans des proportions très éloignées des proportions envisagées dans la présente invention. C’est donc bien le choix des unités polymériques (A1 ) et (B1 ) revendiquées, dans des proportions spécifiques, qui a permis l’obtention de propriétés cosmétiques satisfaisantes permettant leur utilisation comme agent filmogènes. [0011] Document WO2020/128050 proposes, for example, film-forming PHAs consisting of a mixture of at least three distinct polymeric units. This document illustrates, by way of comparisons, PHAs consisting of a repetition of only two polymeric units, and these do not give satisfaction in terms of cosmetic properties (solubility in oils) and therefore cannot be used as film formers. . The comparative PHAs illustrated in document WO2020/128050 consist of polymeric units (A1) and (B1) in accordance with the present application, but in proportions very far from the proportions envisaged in the present invention. It is therefore indeed the choice of the polymeric units (A1) and (B1) claimed, in specific proportions, which made it possible to obtain satisfactory cosmetic properties allowing their use as a film-forming agent.
[0012] La demanderesse a notamment mis en évidence que les polymères objets de la présente demande, consistant une répétition d’unités polymériques (A1 ) et (B1 ) spécifiques, dans des proportions bien définies, permettait l’obtention d’un composé aisément soluble dans divers solvants cosmétiques tel que l’isododécane (contrairement aux PHA filmogènes constitués d’un mélange d’au moins trois unités polymériques distinctes tels que décrits dans le document W02020/128050). Les films obtenus sont stables dans le temps, et en particulier, résistent au sébum. The applicant has in particular demonstrated that the polymers which are the subject of the present application, consisting of a repetition of specific polymeric units (A1) and (B1), in well-defined proportions, made it possible to obtain a compound easily soluble in various cosmetic solvents such as isododecane (unlike film-forming PHAs consisting of a mixture of at least three distinct polymeric units as described in document WO2020/128050). The films obtained are stable over time, and in particular are resistant to sebum.
[0013] D’une façon préférée, le copolymère de polyhydroxyalcanoate consiste en : - 3 à 5% en moles, d’unités polymériques (A1 ) et [0013] Preferably, the polyhydroxyalkanoate copolymer consists of: - 3 to 5 mol% of polymeric units (A1) and
- 97 et 95% en moles d’unités polymériques (B1). - 97 and 95% in moles of polymeric units (B1).
[0014] Selon un autre mode de réalisation de l’invention, la composition comprend au moins un copolymère de polyhydroxyalcanoate consistant en : According to another embodiment of the invention, the composition comprises at least one polyhydroxyalkanoate copolymer consisting of:
- 4% en mole d’unités polymériques (A1), et - 96% en mole d’unités polymériques (B1). [0015] La composition cosmétique selon l’invention comprend au moins un copolymère de polyhydroxyalcanoate consistant en une répétition, successive ou non, d’unités polymériques (A1) et d’unités polymériques (B1) telles que décrites précédemment, et présentant un poids moléculaire moyen (Mw) compris entre 20 000 à 100 000 g/mol. [0016] Le copolymère de polyhydroxyalcanoate est présent dans la composition cosmétique en une teneur comprise entre 0,5 % à 30% en poids, de préférence 1% à 20% en poids, et très préférentiellement 2% à 8% en poids, par rapport au poids total de la composition. - 4% by mole of polymeric units (A1), and - 96% by mole of polymeric units (B1). The cosmetic composition according to the invention comprises at least one polyhydroxyalkanoate copolymer consisting of a repetition, successive or not, of polymeric units (A1) and polymeric units (B1) as described above, and having a weight average molecular weight (Mw) between 20,000 to 100,000 g/mol. The polyhydroxyalkanoate copolymer is present in the cosmetic composition in a content of between 0.5% to 30% by weight, preferably 1% to 20% by weight, and very preferably 2% to 8% by weight, by relative to the total weight of the composition.
[0017] Selon un autre aspect, l’invention a pour objet l’utilisation d’au moins un copolymère de polyhydroxyalcanoate en tant qu’agent filmogène dans une composition cosmétique, ledit copolymère de polyhydroxyalcanoate consistant en une répétition d’unités polymériques de formule (A1 ) et d’unités polymériques de formule (B1) telles que : Formule (A1 ) : -[-0-CH(R1)-(CH2)n-C0-]- Formule (B1 ) : -[-0-CH(R2)-(CH2)m-C0-]- dans lesquelles : According to another aspect, the invention relates to the use of at least one polyhydroxyalkanoate copolymer as a film-forming agent in a cosmetic composition, said polyhydroxyalkanoate copolymer consisting of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1) such as: Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0- CH(R2)-(CH2) m -C0-]- in which:
R1 représente un groupe n-propyle R2 représente un groupe n-pentyle ; n et m sont égal à 1 ledit copolymère de polyhydroxyalcanoate comprenant 2 à 10% en moles, d’unités polymériques de formule (A1 ) et 98 à 90% en moles d’unités polymériques de formule (B1 ) ; ledit copolymère de polyhydroxyalcanoate étant obtenu par un procédé de fermentation à partir d’une bactérie enregistrée en vertu du traité de Budapest à la Collection Nationale de Cultures de Microorganismes le 24 février 2021 sous le numéro de dépôt I-5658 ; et étant présent en une teneur comprise entre 2 et 20% en poids, par rapport au poids total de ladite composition cosmétique. R1 represents an n-propyl group R2 represents an n-pentyl group; n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1); said polyhydroxyalkanoate copolymer being obtained by a fermentation process from a bacterium registered under the Budapest Treaty at the National Collection of Cultures of Microorganisms on February 24, 2021 under the deposit number I-5658; and being present in a content of between 2 and 20% by weight, relative to the total weight of said cosmetic composition.
[0018] Par « polymère filmogène », on entend, au sens de la présente demande, un polymère apte à former, à lui seul ou en présence d’un agent auxiliaire de filmification, un film macroscopiquement continu sur un support, notamment sur les matières kératiniques, et en particulier un film cohésif dont la cohésion et les propriétés mécaniques sont telles qu’il peut être isolé dudit support. By "film-forming polymer" is meant, within the meaning of the present application, a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on the keratin materials, and in particular a cohesive film whose cohesion and mechanical properties are such that it can be isolated from said support.
[0019] La composition cosmétique selon l’invention peut se présenter sous la forme d’une émulsion, simple ou multiple et de type eau dans huile ou huile dans eau, d’une microémulsion, d’une nanoémulsion, d’une poudre, d’une composition anhydre, d’une suspension, d’une lotion, d’une crème, d’un gel aqueux ou hydroalcoolique, d’une mousse, d’un sérum, d’une solution ou d’une dispersion pour aérosol, ou d’une dispersion de vésicules lipidiques, ou de gouttelettes obtenues par coacervation ou par microfluidique. The cosmetic composition according to the invention may be in the form of a single or multiple emulsion of the water-in-oil or oil-in-water type, a microemulsion, a nanoemulsion, a powder, an anhydrous composition, a suspension, a lotion, a cream, an aqueous or hydroalcoholic gel, a foam, a serum, a solution or an aerosol dispersion, or a dispersion of lipid vesicles, or of droplets obtained by coacervation or by microfluidics.
[0020] Ladite composition cosmétique peut également comprendre, outre le copolymère de polyhydroxyalcanoate selon l’invention, au moins un additif usuel dans le domaine cosmétique, tel que par exemple au moins un composé choisi parmi un agent émollient ou humectant, un agent gélifiant et/ou épaississant, un agent tensioactif, une huile, une cire, un colorant, un pigment, une nacre, une charge telle que des agents de toucher, un conservateur, un agent antioxydant, un agent actif, une poudre organique ou inorganique, un solvant volatile et/ou non volatile, un solubilisant, un chélatant, un séquestrant, un sel ionique apte notamment à ajuster le pH de la composition ou sa force ionique, un filtre solaire pouvant être organique et/ou inorganique et un parfum. Selon la galénique souhaitée, le bénéfice soin et/ou maquillage recherché et attendu, la composition cosmétique peut également comprendre un autre polymère filmogène en plus du au moins un copolymère de polyhydroxyalcanoate selon l’invention, ledit autre filmogène étant préférentiellement respectueux de l’environnement, en particulier biodégradable. [0020] Said cosmetic composition may also comprise, in addition to the polyhydroxyalkanoate copolymer according to the invention, at least one additive customary in the cosmetics field, such as for example at least one compound chosen from an emollient or humectant agent, a gelling agent and / or thickener, a surfactant, an oil, a wax, a dye, a pigment, a nacre, a filler such as feel agents, a preservative, an antioxidant agent, an active agent, an organic or inorganic powder, a volatile and/or non-volatile solvent, a solubilizer, a chelating agent, a sequestrant, an ionic salt capable in particular of adjusting the pH of the composition or its ionic strength, a sunscreen which may be organic and/or inorganic and a perfume. Depending on the desired galenic, the care and/or makeup benefit sought and expected, the cosmetic composition may also comprise another film-forming polymer in addition to the at least one polyhydroxyalkanoate copolymer according to the invention, said other film-forming agent preferably being environmentally friendly. , especially biodegradable.
[0021] Notamment, ladite composition peut contenir un ou plusieurs agent(s) émollient(s) ou humectant(s), qui peuvent être choisi(s) par exemple parmi la glycérine, les polyols, les glycols, les silicones hydrosolubles tels que celui vendu sous la dénomination KF6011 (Shin Etsu) et le Jojoba hydrosoluble, tel que celui vendu sous la dénomination Resplanta jojoba (Res pharma). In particular, said composition may contain one or more emollient(s) or humectant(s), which may be chosen, for example, from glycerin, polyols, glycols, water-soluble silicones such as that sold under the name KF6011 (Shin Etsu) and water-soluble jojoba, such as that sold under the name Resplanta jojoba (Res pharma).
[0022] Ledit agent émollient ou humectant peut-être présent dans la composition à une teneur de l’ordre de 0 à 30%, de préférence 2 à 10% en poids, par rapport au poids total de la composition. Said emollient or humectant may be present in the composition at a content of the order of 0 to 30%, preferably 2 to 10% by weight, relative to the total weight of the composition.
[0023] Un ou plusieurs agent(s) gélifiants(s) et ou épaississant(s) de la phase aqueuse, peuvent également être incorporés à la composition selon l’invention. Ils sont choisis par exemple parmi les dérivés cellulosiques, les polysaccharides dont notamment les gommes d’origine végétale (guar, caroube, alginates, carraghénanes, pectine), d’origine microbienne (xanthane), les argiles (laponite), les gélifiants hydrophiles, et les gélifiants lipophiles. [0024] Les gélifiants hydrophiles peuvent notamment être choisis parmi : One or more gelling agent(s) and/or thickener(s) for the aqueous phase can also be incorporated into the composition according to the invention. They are chosen for example from cellulosic derivatives, polysaccharides including in particular gums of plant origin (guar, carob, alginates, carrageenans, pectin), of microbial origin (xanthan), clays (laponite), hydrophilic gelling agents, and lipophilic gelling agents. The hydrophilic gelling agents can in particular be chosen from:
- les homo- ou copolymères d'acides acrylique ou méthacrylique ou leurs sels, les copolymères d'acide acrylique et d'acrylamide et leur sel de sodium, les sels de sodium d'acides polyhydroxycarboxyliques, les copolymères acide polyacryliques/acrylates d'alkyl, l'AMPS (Acide polyacrylamidométhyl propane sulfonique) et ses copolymères acrylamide ou de méthacrylates d'alkyle polyoxyéthylénés (réticulés ou non), et leurs mélanges. - les polyuréthanes associatifs ou des solutions ou dispersions de ces polyuréthanes associatifs notamment dans l'eau ou en milieu hydroalcoolique. - homo- or copolymers of acrylic or methacrylic acids or their salts, copolymers of acrylic acid and acrylamide and their sodium salt, sodium salts of polyhydroxycarboxylic acids, polyacrylic acid/alkyl acrylate copolymers , AMPS (Polyacrylamidomethylpropanesulfonic acid) and its acrylamide or polyoxyethylenated alkyl methacrylate copolymers (crosslinked or not), and mixtures thereof. - associative polyurethanes or solutions or dispersions of these associative polyurethanes, in particular in water or in a hydroalcoholic medium.
[0025] Le terme « gélifiant lipophile », désigne, dans le cadre de la présente demande, une substance capable de solidifier ou de gélatiniser l'huile présente dans la composition de l'invention. Le gélifiant lipophile est choisi par exemple parmi les polyesters de saccharose. On peut citer les esters de saccharose et d’acides gras, et de préférence les esters de saccharose, de l’acide stéarique et de l’acide acétique, tels que le triacétate de tétrastéarate de saccharose. The term “lipophilic gelling agent” denotes, in the context of the present application, a substance capable of solidifying or gelatinizing the oil present in the composition of the invention. The lipophilic gelling agent is chosen for example from sucrose polyesters. Mention may be made of the esters of sucrose and of fatty acids, and preferably the esters of sucrose, of stearic acid and of acetic acid, such as sucrose tetrastearate triacetate.
[0026] S’ils sont présents dans la composition, les gélifiants peuvent être introduits en une teneur allant de 0,05 à 40% en poids, par rapport au poids total de la composition, de préférence de 0,1 à 20% et mieux de 0,5 à 15% en poids. If they are present in the composition, the gelling agents can be introduced in a content ranging from 0.05 to 40% by weight, relative to the total weight of the composition, preferably from 0.1 to 20% and better from 0.5 to 15% by weight.
[0027] Un ou plusieurs agent(s) tensioactif(s), de préférence non ionique, peuvent faire partis de la composition selon l’invention et seront présents dans une teneur de l’ordre de 0 à 8%, de préférence 0,5 à 3% en poids, par rapport au poids total de la composition. [0028] Les compositions selon la présente demande peuvent aussi contenir au moins une ou plusieurs huiles ou solvant organique. One or more surfactant(s), preferably nonionic, may form part of the composition according to the invention and will be present in a content of the order of 0 to 8%, preferably 0, 5 to 3% by weight, relative to the total weight of the composition. The compositions according to the present application may also contain at least one or more oils or organic solvent.
[0029] Par huile ou solvant organique, on entend un corps non aqueux liquide à température ambiante et pression atmosphérique. L'huile peut être volatile ou non volatile. By oil or organic solvent is meant a non-aqueous body which is liquid at ambient temperature and atmospheric pressure. The oil can be volatile or non-volatile.
[0030] Par " huile ou solvant organique volatile", on entend au sens de l'invention tout milieu non aqueux susceptible de s'évaporer au contact des matières kératiniques en moins d'une heure, à température ambiante et pression atmosphérique. Le ou les solvants organiques volatils et les huiles volatiles de l'invention sont des solvants organiques et des huiles cosmétiques volatiles, liquides à température ambiante, ayant une pression de vapeur non nulle, à température ambiante et pression atmosphérique, allant de 0,13 Pa à 40 000 Pa (10 3 à 300 mm de Hg), en particulier allant de 1 ,3 Pa à 13 000 Pa (0,01 à 100 mm de Hg), et plus particulièrement allant de 1 ,3 Pa à 1300 Pa (0,01 à 10 mm de Hg). [0030] The term “volatile organic oil or solvent” is understood to mean, in the sense of the invention, any non-aqueous medium capable of evaporating on contact with keratin materials in less than one hour, at ambient temperature and atmospheric pressure. The volatile organic solvent(s) and volatile oils of the invention are volatile organic solvents and cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa at 40,000 Pa (10 3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa ( 0.01 to 10 mm Hg).
[0031] Par "huile non volatile", on entend une huile restant sur les matières kératiniques à température ambiante et pression atmosphérique au moins plusieurs heures et ayant notamment une pression de vapeur inférieure à 10 -3 mm de Hg (0,13Pa). [0032] L'huile peut être présente dans la composition dans une teneur allant de 0,05 à 30% de préférence 0,1 à 15% en poids par rapport au poids total de la composition. La composition selon l'invention peut comprendre des huiles volatiles et/ou des huiles non volatiles, et leurs mélanges. [0033] Les huiles (ou solvants organiques) volatiles peuvent être des huiles hydrocarbonées, des huiles siliconées, linéaire(s), cyclique(s) ou ramifié(s), ou leurs mélanges. [0031] The term "non-volatile oil" means an oil remaining on the keratin materials at room temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 10 -3 mm Hg (0.13 Pa). The oil may be present in the composition in a content ranging from 0.05 to 30%, preferably 0.1 to 15% by weight relative to the total weight of the composition. The composition according to the invention may comprise volatile oils and/or non-volatile oils, and mixtures thereof. The volatile oils (or organic solvents) can be hydrocarbon oils, silicone oils, linear(s), cyclic(s) or branched(s), or mixtures thereof.
[0034] On entend par "huile hydrocarbonée", une huile contenant principalement des atomes d'hydrogène et de carbone et éventuellement des atomes d'oxygène, d'azote, de soufre, de phosphore. Les huiles hydrocarbonées volatiles peuvent être choisies parmi les huiles hydrocarbonées ayant de 8 à 16 atomes de carbones, et notamment les alcanes ramifiés en C8-Ci6 d’origine naturelle ou pétrolière, comme les isoalcanes en C8-Ci6 tels que l'isododécane (encore appelé 2,2,4,4,6-pentaméthylheptane), l'isodécane, l'isohexadécane, les esters ramifiés en C8-Ci6, le néopentanoate d'iso-hexyle, et leurs mélanges. The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and phosphorus atoms. The volatile hydrocarbon-based oils can be chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, and in particular branched C 8 -Ci 6 alkanes of natural or petroleum origin, such as C 8 -Ci 6 isoalkanes such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, branched C 8 -Ci 6 esters, iso-hexyl neopentanoate, and mixtures thereof.
[0035] Comme huiles volatiles, on peut aussi utiliser les silicones volatiles, comme par exemple les huiles de silicones linéaires ou cycliques volatiles, notamment celles ayant une viscosité 6 centistokes (6.10 -6 m 2 /s), et ayant notamment de 3 à 6 atomes de silicium, ces silicones comportant éventuellement un ou plusieurs groupes alkyles ou alkoxy ayant de 1 ou 2 atomes de carbone. Comme huile de silicone volatile utilisable dans l'invention, on peut citer notamment l'octaméthyl cyclotétrasiloxane, le décaméthyl cyclopentasiloxane, le dodécaméthyl cyclohexasiloxane, l'heptaméthyl hexyltrisiloxane, l'heptaméthyloctyl trisiloxane, l'hexaméthyl disiloxane, l'octaméthyl trisiloxane, le décaméthyl tétrasiloxane, le dodécaméthyl pentasiloxane et leurs mélanges. As volatile oils, it is also possible to use volatile silicones, such as for example volatile linear or cyclic silicone oils, in particular those having a viscosity of 6 centistokes (6.10 -6 m 2 /s), and having in particular from 3 to 6 silicon atoms, these silicones optionally comprising one or more alkyl or alkoxy groups having 1 or 2 carbon atoms. As volatile silicone oil which can be used in the invention, mention may in particular be made of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.
[0036] Chacune des compositions conformes à l'invention peut également comprendre au moins une huile ou solvant organique non volatile, qui peut être en particulier choisie parmi les huiles hydrocarbonées et/ou siliconées non volatiles. Each of the compositions in accordance with the invention may also comprise at least one non-volatile organic oil or solvent, which may in particular be chosen from non-volatile hydrocarbon-based and/or silicone oils.
[0037] Comme huile hydrocarbonée non volatile, on peut notamment citer : - les huiles hydrocarbonées d'origine végétale telles que les triglycérides constitués d'esters d'acides gras et de glycérol dont les acides gras peuvent avoir des longueurs de chaînes variées de C4 à C24, ces derniers pouvant être linéaires ou ramifiés, saturés ou insaturés ; ces huiles sont notamment les huiles de germe de blé, de tournesol, de pépins de raisin, de sésame, de maïs, d'abricot, de ricin, de karité, d'avocat, d'olive, de soja, l'huile d'amande douce, de palme, de colza, de coton, de noisette, de macadamia, de jojoba, de luzerne, de pavot, de potimarron, de sésame, de courge, de colza, de cassis, d'onagre, de millet, d'orge, de quinoa, de seigle, de carthame, de bancoulier, de passiflore, de rosier muscat, de camélia ; ou encore les triglycérides des acides caprylique/caprique; As non-volatile hydrocarbon oil, mention may in particular be made of: - hydrocarbon oils of plant origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C4 at C24, the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oil, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bankoulier, passionflower, muscat rose, camellia; or alternatively caprylic/capric acid triglycerides;
- les éthers de synthèse ayant de 10 à 40 atomes de carbone ; - les hydrocarbures linéaires ou ramifiés, d'origine minérale ou synthétique tels que la vaseline, les polydécènes, le polyisobutène hydrogéné tel que le parléam, le squalane, et leurs mélanges; - synthetic ethers having 10 to 40 carbon atoms; - linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof;
- les esters naturels comme par exemple les triglycérides, ou les dérivés d’acide pélargoniques ; - les esters de synthèse comme les huiles de formule R1COOR2 dans laquelle R1 représente le reste d'un acide gras linéaire ou ramifié comportant de 1 à 40 atomes de carbone et R2 représente une chaîne hydrocarbonée notamment ramifiée contenant de 1 à 40 atomes de carbone à condition que R1 + R2 soit 10, comme par exemple l'huile de Purcellin (octanoate de cétostéaryle), le myristate d'isopropyle, le palmitate d'isopropyle, le benzoate d'alcool en C12 à C15, le laurate d'hexyle, l'adipate de diisopropyle, l'isononanoate d'isononyle, le palmitate de 2-éthylhexyle, l'isostéarate d'isostéarate, des octanoates, décanoates ou ricinoléates d'alcools ou de polyalcools comme le dioctanoate de propylène glycol ; les esters hydroxylés comme le lactate d'isostéaryle, le malate de di- isostéaryle ; et les esters du pentaérythritol; - les alcools gras liquides à température ambiante à chaîne carbonée ramifiée et/ou insaturée ayant de 12 à 26 atomes de carbone comme l'octyl dodécanol, l'alcool isostéarylique, l'alcool oléique, le 2-hexyldécanol, le 2-butyloctanol, le 2- undécylpentadécanol ; - natural esters such as triglycerides, or pelargonic acid derivatives; - synthetic esters such as oils of formula R1COOR2 in which R1 represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms at provided that R1 + R2 is 10, such as Purcellin's oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12 to C15 alcohol benzoate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters; - fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, 2-undecylpentadecanol;
- les acides gras supérieurs tels que l'acide oléique, l'acide linoléique, l'acide linolénique; et leurs mélanges. - higher fatty acids such as oleic acid, linoleic acid, linolenic acid; and their mixtures.
[0038] Les huiles de silicone non volatiles utilisables dans les compositions conformes à l'invention peuvent être les polydiméthylsiloxanes (PDMS) non volatiles, les polydiméthylsiloxanes comportant des groupements alkyle ou alcoxy, pendant et/ou en bout de chaîne siliconée, groupements ayant chacun de 2 à 24 atomes de carbone, les silicones phénylées comme les phényl triméthicones, les phényl diméthicones, les phényl triméthylsiloxy diphénylsiloxanes, les diphényl diméthicones, les diphényl méthyldiphényl trisiloxanes, les 2-phényléthyl triméthylsiloxysilicates. The nonvolatile silicone oils which can be used in the compositions in accordance with the invention may be nonvolatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendent and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
[0039] La teneur en huile ou solvant organique non volatile dans la composition conforme à l'invention va de 0,01 à 30% en poids, en particulier de 0,1 à 25% en poids, et mieux de 0,1 à 20% par rapport au poids total de la composition. The content of non-volatile oil or organic solvent in the composition in accordance with the invention ranges from 0.01 to 30% by weight, in particular from 0.1 to 25% by weight, and better still from 0.1 to 20% relative to the total weight of the composition.
[0040] La composition selon l’invention peut également comprendre au moins une cire. Le terme « cire» désigne une matière grasse à changement réversible liquide/solide, ayant une température de fusion supérieure à 55 ‘O et généralement inférieure à 110 °C, qui est liquide dans les conditions de préparation de la composition et qui présente une organisation cristalline anisotrope à l'état solide. La cire peut être polaire ou apolaire [0041] Par cire polaire, on entend une cire comprenant au moins un hétéroatome tel que l'oxygène, l'azote, le silicium ou le phosphore. The composition according to the invention may also comprise at least one wax. The term “wax” designates a fatty substance with reversible liquid/solid change, having a melting point above 55° C. and generally below 110° C., which is liquid under the conditions of preparation of the composition and which has an organization anisotropic crystalline in the solid state. Wax can be polar or apolar By polar wax is meant a wax comprising at least one heteroatom such as oxygen, nitrogen, silicon or phosphorus.
[0042] En particulier, la cire polaire peut être choisie dans le groupe comprenant la cire d'abeille, la cire de carnauba, la cire de candelilla, la cire de coton, la cire de son de riz, la cire de baie, la cire d'insecte de chine, la cire de montan, la lanoline et ses dérivés alcools, acétylés, estérifiés, polyéthoxylés, la cire de kapok, la cire de canne à sucre, le laurate d'hexyle, la cire de jojoba, la cire shellac, l'éther de cholestérol polyéthoxylé, les cires d’abeille synthétiques, ou un de leurs mélanges. On peut également citer les cires d'esters végétaux tels que par exemple, à titre illustratif, les esters de jojoba, les esters d'alkyle ou d'esters d'alkyle hydrogénés. [0042] In particular, the polar wax can be chosen from the group comprising beeswax, carnauba wax, candelilla wax, cottonseed wax, rice bran wax, bay wax, Chinese insect wax, montan wax, lanolin and its alcoholic, acetylated, esterified, polyethoxylated derivatives, kapok wax, sugar cane wax, hexyl laurate, jojoba wax, wax shellac, polyethoxylated cholesterol ether, synthetic beeswax, or a mixture thereof. Mention may also be made of plant ester waxes such as, for example, by way of illustration, jojoba esters, alkyl esters or hydrogenated alkyl esters.
[0043] Par cire apolaire, on entend une cire hydrocarbonée et/ou une cire siliconée. By apolar wax is meant a hydrocarbon wax and/or a silicone wax.
[0044] On entend par « cire apolaire hydrocarbonée », une cire comprenant uniquement des atomes de carbone et d’hydrogène et ne comprenant pas d’hétéroatomes tels que l'oxygène, l'azote, le silicium ou le phosphore. On entend par « cire apolaire siliconée », une cire comprenant un hétéroatome de silicium. [0044] The term "non-polar hydrocarbon wax" means a wax comprising only carbon and hydrogen atoms and not comprising heteroatoms such as oxygen, nitrogen, silicon or phosphorus. “Apolar silicone wax” means a wax comprising a silicon heteroatom.
[0045] La cire si elle est présente dans la composition cosmétique de l’invention représente une teneur comprise entre 0,5 à 20% en poids, de préférence de 1% à 10% en poids, par rapport au poids total de la composition. The wax, if it is present in the cosmetic composition of the invention, represents a content of between 0.5 to 20% by weight, preferably from 1% to 10% by weight, relative to the total weight of the composition. .
[0046] La composition selon l’invention peut comprendre une phase aqueuse comprenant de l’eau et optionnellement au moins un solvant soluble dans l’eau. Par « solvant soluble dans l’eau », on désigne un composé liquide à température ambiante et miscible à l'eau (miscibilité dans l'eau supérieure à 50 % en poids à 25 °C et pression atmosphérique). Parmi les solvants hydrosolubles pouvant être utilisés dans les compositions conformes à l'invention, on peut citer à titre indicatif et non limitatif, les mono-alcools ayant de 1 à 5 atomes de carbone tels que l'éthanol et l'isopropanol, les cétones en C3-C et les aldéhydes en C2-C4. The composition according to the invention may comprise an aqueous phase comprising water and optionally at least one water-soluble solvent. The term “water-soluble solvent” denotes a compound that is liquid at ambient temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure). Among the water-soluble solvents which can be used in the compositions in accordance with the invention, mention may be made, by way of indication and not of limitation, of mono-alcohols having from 1 to 5 carbon atoms such as ethanol and isopropanol, ketones C 3 -C and C2-C4 aldehydes.
[0047] Un ou plusieurs agent(s) actif(s), d'origine naturelle ou synthétique, ayant une activité biologique, par exemple choisis parmi les vitamines, les oligo-éléments, l'allantoïne, les protéines végétales, les extraits végétaux, les agents hydratants, les agents antiâges, les antioxydants, les agents favorisant l'éclat et des mélanges de ceux-ci. En particulier, l’agent actif est choisi parmi une eau de fruit de vanilla planifolia, le niacinamide, l'acide hyaluronique et ses dérivés, un extrait de levure et des mélanges de ceux-ci. One or more active agent(s), of natural or synthetic origin, having a biological activity, for example chosen from vitamins, trace elements, allantoin, vegetable proteins, vegetable extracts , moisturizers, anti-aging agents, antioxidants, radiance-promoting agents and mixtures thereof. In particular, the active agent is chosen from vanilla planifolia fruit water, niacinamide, hyaluronic acid and its derivatives, a yeast extract and mixtures thereof.
[0048] Les compositions conformes à l'invention peuvent également comprendre au moins une matière colorante comme les matières pulvérulentes, les colorants liposolubles, les colorants hydrosolubles. [0049] Les matières colorantes pulvérulentes peuvent être choisies parmi les pigments et les nacres. The compositions in accordance with the invention may also comprise at least one dyestuff such as pulverulent materials, fat-soluble dyes, water-soluble dyes. The pulverulent dyestuffs can be chosen from pigments and nacres.
[0050] Les pigments peuvent être blancs ou colorés, minéraux et/ou organiques, enrobés ou non. On peut citer, parmi les pigments minéraux, le dioxyde de titane, éventuellement traité en surface, les oxydes de zirconium, de zinc ou de cérium, l’oxychlorure de bismuth, ainsi que les oxydes de fer ou de chrome, le violet de manganèse, le bleu outremer, l'hydrate de chrome et le bleu ferrique. Parmi les pigments organiques, on peut citer le noir de carbone, les pigments de type D & C, et les laques à base de carmin de cochenille, de baryum, strontium, calcium, aluminium. [0051] Les nacres peuvent être choisies parmi les pigments nacrés blancs tels que le mica recouvert de titane ou d'oxychlorure de bismuth, les pigments nacrés colorés tels que le mica titane avec des oxydes de fer, le mica titane avec notamment du bleu ferrique ou de l'oxyde de chrome, le mica titane avec un pigment organique du type précité ainsi que les pigments nacrés à base d'oxychlorure de bismuth. [0052] Les colorants liposolubles sont par exemple le rouge Soudan, le D&C Red 17, leThe pigments can be white or colored, inorganic and/or organic, coated or not. Mention may be made, among the mineral pigments, of titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxides, bismuth oxychloride, as well as iron or chromium oxides, manganese violet , ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum. The nacres can be chosen from white pearlescent pigments such as mica covered with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. The fat-soluble dyes are, for example, Sudan red, D&C Red 17,
D&C Green 6, le 13-carotène, l'huile de soja, le brun Soudan, le D&C Yellow 11 , le D&C Violet 2, le D&C Orange 5, le jaune quinoléine, le rocou. D&C Green 6, 13-Carotene, Soybean Oil, Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, Quinoline Yellow, Annatto.
[0053] Ces matières colorantes peuvent être présentes en une teneur allant de 0,01 à 30% en poids par rapport au poids total de la composition. [0054] Les compositions conformes à l'invention peuvent également comprendre au moins une charge. These dyestuffs may be present in a content ranging from 0.01 to 30% by weight relative to the total weight of the composition. The compositions in accordance with the invention may also comprise at least one filler.
[0055] Les charges peuvent être choisies parmi celles bien connues de l'homme du métier et couramment utilisées dans les compositions cosmétiques. Les charges peuvent être minérales ou organiques, lamellaires ou sphériques. On peut citer le talc, le mica, la silice, le kaolin, les poudres de polyamide comme le Nylon ©commercialisé sous la dénomination Orgasol © par la société Atochem, de poly-13-alanine et de polyéthylène, les poudres de polymères de tétrafluoroéthylène comme le Téflon © , la lauroyl-lysine, l'amidon, le nitrure de bore, les micro sphères creuses polymériques expansées telles que celles de chlorure de polyvinylidène/acrylonitrile comme celles commercialisées sous la dénomination d'Expancel © par la société Nobel Industrie, les poudres acryliques telles que celles commercialisées sous la dénomination Polytrap © par la société Dow Corning, les particules de polyméthacrylate de méthyle et les microbilles de résine de silicone (Tospearls © de Toshiba, par exemple), le carbonate de calcium précipité, le carbonate et l'hydro- carbonate de magnésium, l'hydroxyapatite, les microsphères de silice creuses (Silica Beads © de MAPRECOS), les microcapsules de verre ou de céramique, les savons métalliques dérivés d'acides organiques carboxyliques ayant de 8 à 22 atomes de carbone, et en particulier de 12 à 18 atomes de carbone, par exemple le stéarate de zinc, de magnésium ou de lithium, le laurate de zinc, le myristate de magnésium. The fillers can be chosen from those well known to those skilled in the art and commonly used in cosmetic compositions. The fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders such as Nylon © marketed under the name Orgasol © by the company Atochem, poly-13-alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon © , lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile such as those marketed under the name Expancel © by the company Nobel Industrie, acrylic powders such as those marketed under the name Polytrap © by Dow Corning, polymethyl methacrylate particles and silicone resin microbeads (Tospearls © from Toshiba, for example), precipitated calcium carbonate, carbonate and magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads © from MAPRECOS), glass or ceramic microcapsules, soaps metallic derivatives of organic carboxylic acids having from 8 to 22 carbon atoms, and in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
[0056] On peut également utiliser un composé susceptible de gonfler à la chaleur et notamment des particules thermoexpansibles telles que les microsphères non expansées de copolymère de chlorure de vinylidène/d'acrylonitrile/méthacrylate de méthyle ou de copolymère d'homopolymère d'acrylonitrile comme par exemple celles commercialisées respectivement sous les références Expancel ® 820 DU 40 et Expancel ® 007WU par la Société AKZO NOBEL. On peut citer également les Advancell® commercialisées par Sekuisi Plastic ou les Thermoexpandable microspheres® de Matsumoto. It is also possible to use a compound capable of swelling with heat and in particular heat-expandable particles such as unexpanded microspheres of vinylidene chloride/acrylonitrile/methyl methacrylate copolymer or of acrylonitrile homopolymer copolymer such as for example those marketed respectively under the references Expancel® 820 DU 40 and Expancel® 007WU by the company AKZO NOBEL. Mention may also be made of Advancell® marketed by Sekuisi Plastic or Thermoexpandable microspheres® from Matsumoto.
[0057] Les charges peuvent représenter de 0,1 à 25% en particulier de 0,2 à 20% en poids par rapport au poids total de la composition. The fillers can represent from 0.1 to 25%, in particular from 0.2 to 20% by weight relative to the total weight of the composition.
[0058] Les compositions conformes à l'invention peuvent également comprendre au moins une fibre. [0059] Par "fibre", il faut comprendre un objet de longueur L et de diamètre D tel que L soit très supérieur à D, D étant le diamètre du cercle dans lequel s'inscrit la section de la fibre. En particulier, le rapport L/D (ou facteur de forme) est choisi dans la gamme allant de 3,5 à 2500, en particulier de 5 à 500, et plus particulièrement de 5 à 150. The compositions in accordance with the invention may also comprise at least one fiber. By "fiber", it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber falls. In particular, the L/D ratio (or aspect ratio) is chosen in the range going from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150.
[0060] Les fibres utilisables dans la composition de l'invention peuvent être des fibres d'origine synthétique ou naturelle, minérale ou organique. Elles peuvent être courtes ou longues, unitaires ou organisées par exemple tressées, creuses ou pleines. Leur section peut être quelconque et notamment de section circulaire ou polygonale (carrée, hexagonale ou octogonale) selon l'application spécifique envisagée. Leur forme peut être linéaire, courbe, sinusoïdale ou frisée. En particulier, leurs extrémités sont épointées et ou polies pour éviter de se blesser. The fibers that can be used in the composition of the invention can be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or organized, for example braided, hollow or solid. Their section can be arbitrary and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. Their shape can be linear, curved, sinusoidal or curly. In particular, their ends are blunted and or polished to avoid injury.
[0061] A titre de fibres utilisables dans la composition selon l'invention, on peut citer les fibres non rigides telles que les fibres de polyamide (Nylon®) ou les fibres rigides telles que les fibres de polyimide-amide comme celles vendues sous les dénominations KERMEL®, KERMEL TECH® par la société RHODIA ou de poly-(p-phénylènetéréphtalamide) (ou d'aramide) notamment vendues sous la dénomination Kevlar® par la société DUPONT DE NEMOURS. As fibers that can be used in the composition according to the invention, mention may be made of non-rigid fibers such as polyamide fibers (Nylon®) or rigid fibers such as polyimide-amide fibers such as those sold under the names KERMEL®, KERMEL TECH® by the company RHODIA or poly-(p-phenyleneterephthalamide) (or aramid) in particular sold under the name Kevlar® by the company DUPONT DE NEMOURS.
[0062] Les fibres peuvent être présentes dans la composition selon l'invention en une teneur allant de 0,01% à 10% en poids, par rapport au poids total de la composition, en particulier de 0,1% à 5% en poids, et plus particulièrement de 0,3% à 3% en poids [0063] D’autres additifs habituellement utilisés en cosmétique peuvent également être présents dans la composition selon l’invention, notamment des conservateurs, des agents antioxydants, des filtres UV organiques et/ou inorganiques, ou des parfums bien connus dans le domaine technique. [0064] L’homme du métier est en mesure de choisir, parmi l’ensemble de ces éventuels additifs, aussi bien la nature que la quantité de ceux qui seront ajoutés à la composition, de telle sorte que celle-ci conserve l’ensemble de ses propriétés. Bien entendu, l'homme du métier veillera à choisir les éventuels additifs complémentaires et/ou leur quantité de telle manière que les propriétés avantageuses de la composition selon l'invention ne soient pas, ou substantiellement pas, altérées par l'adjonction envisagée. The fibers may be present in the composition according to the invention in a content ranging from 0.01% to 10% by weight, relative to the total weight of the composition, in particular from 0.1% to 5% by weight, and more particularly from 0.3% to 3% by weight [0063] Other additives usually used in cosmetics may also be present in the composition according to the invention, in particular preservatives, antioxidants, organic and/or inorganic UV filters, or perfumes which are well known in the technical field. [0064] The person skilled in the art is able to choose, among all of these possible additives, both the nature and the quantity of those which will be added to the composition, so that the latter retains all of its properties. Of course, those skilled in the art will take care to choose any additional additives and/or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or substantially not, altered by the addition envisaged.
[0065] La composition cosmétique peut être à destination d’un produit cosmétique choisi notamment parmi les rouges à lèvres, les gloss, les fonds de teint fluide, compact, les vernis à ongles, les ombres à paupières, les mascaras, les crayons à cils ou à sourcils, les crèmes de soins, les sérums, Is produits à usage de protection solaire, les toiletries telles que les gels douches, etc... The cosmetic composition may be intended for a cosmetic product chosen in particular from lipsticks, glosses, fluid and compact foundations, nail varnishes, eye shadows, mascaras, pencils eyelashes or eyebrows, care creams, serums, products for sun protection, toiletries such as shower gels, etc.
[0066] Le biopolymère peut être obtenu de façon connue par biosynthèse avec le microorganisme enregistré à la Collection Nationale de Culture des Microorganismes sous le traité de Budapest sous le numéro CNCM I-5658, dépôt effectué au nom de la société Polymaris Biotechnology, sise à Brest - France. La présente invention ne couvre donc pas expressément ces souches mais seulement l’utilisation des polyhydroxyalcanoates secrétés par celles-ci pour la réalisation de composition cosmétiques. The biopolymer can be obtained in a known manner by biosynthesis with the microorganism registered with the National Collection of Microorganism Culture under the Budapest Treaty under the number CNCM I-5658, deposit made in the name of the company Polymaris Biotechnology, located at Brest - France. The present invention therefore does not expressly cover these strains but only the use of the polyhydroxyalkanoates secreted by them for the production of cosmetic compositions.
[0067] Le polyhydroxyalcanoate mis en oeuvre dans le cadre des compositions cosmétiques selon l'invention peut être obtenu par fermentation de la bactérie enregistrée en vertu du traité de Budapest à la Collection Nationale de Cultures de Microorganismes le 24 février 2021 sous le numéro de dépôt I-5658 dans un milieu de culture approprié, conventionnellement sous agitation et aéré. La fermentation pour produire le polyhydroxyalcanoate est réalisée dans des conditions d'agitation et d'aération du milieu à une température comprise entre 20 °C et 37°C, préférentiellement à 30 ‘O, le milieu ayant un pH compris entre 6,5 et 9 préférentiellement proche de 7,5, et étant ajusté si nécessaire durant la fermentation. La durée de la fermentation est comprise entre 24 et 120 heures, préférentiellement comprise entre 36 et 72 heures. Selon un mode de réalisation de l'invention, des sels minéraux sont apportés durant la fermentation de la bactérie. A titre illustratif et non limitatif, on peut citer parmi les sels minéraux ceux aptes à fournir au milieu de culture des ions Na+, K+, NH4 +, Ca2+, Mg2+, P04 3 , S0 2 , Cl , C03 ou des éléments essentiels tels que Cu, Mn, Fe et du Zn. [0068] Les méthodes d’isolation et de purification du polyhydroxyalcanoate sont obtenues par des moyens classiques et bien connus de l’homme de l’art, tels que la centrifugation, la filtration, l’ultrafiltration, l’extraction, l’évaporation et la dialyse. The polyhydroxyalkanoate used in the context of the cosmetic compositions according to the invention can be obtained by fermentation of the bacterium registered under the Budapest Treaty at the National Collection of Microorganism Cultures on February 24, 2021 under the deposit number I-5658 in a suitable culture medium, conventionally agitated and aerated. The fermentation to produce the polyhydroxyalkanoate is carried out under conditions of agitation and aeration of the medium at a temperature of between 20° C. and 37° C., preferably at 30° C., the medium having a pH of between 6.5 and 9 preferably close to 7.5, and being adjusted if necessary during fermentation. The duration of the fermentation is between 24 and 120 hours, preferably between 36 and 72 hours. According to one embodiment of the invention, mineral salts are added during the fermentation of the bacteria. By way of non-limiting illustration, mention may be made, among the mineral salts, of those capable of supplying the culture medium with Na + , K + , NH 4 + , Ca 2+ , Mg 2+ , P0 4 3 , S0 2 , Cl , C0 3 or essential elements such as Cu, Mn, Fe and Zn. The polyhydroxyalkanoate isolation and purification methods are obtained by conventional means well known to those skilled in the art, such as centrifugation, filtration, ultrafiltration, extraction, evaporation and dialysis.
[0069] Dans un mode préféré de l’invention, le copolymère de polyhydroxyalcanoate produit par la bactérie enregistrée sous le numéro CNCM I-5658 est caractérisée par la présence de deux unités polymériques consistant en 4% en mole d’unités polymériques (A1), dans laquelle n est égal à 1 et R1 représente un groupe n-propyle, et en 96% en mole d’unité polymérique (B1 ) dans laquelle m est égal à 1 et R2 représente un groupe n- pentyle. In a preferred mode of the invention, the polyhydroxyalkanoate copolymer produced by the bacterium registered under the number CNCM I-5658 is characterized by the presence of two polymeric units consisting of 4% by mole of polymeric units (A1) , in which n is equal to 1 and R1 represents an n-propyl group, and in 96% by mole of polymeric unit (B1) in which m is equal to 1 and R2 represents an n-pentyl group.
[0070] L’invention sera maintenant illustrée par les exemples non limitatifs suivants. The invention will now be illustrated by the following non-limiting examples.
Exemples Examples
[0071] Exemple 1 : préparation et isolation du polyhydroxyalcanoate produit par la bactérie enregistrée sous le numéro de dépôt CNCM I-5658 Example 1: preparation and isolation of the polyhydroxyalkanoate produced by the bacterium registered under the deposit number CNCM I-5658
[0072] a) Méthode de culture de la bactérie enregistrée sous le numéro de dépôt CNCM I- 5658 [0072] a) Method for culturing the bacteria registered under the deposit number CNCM I-5658
[0073] Pour la production du biopolymère, l’ensemble des opérations sont réalisées selon les bonnes pratiques de microbiologie en conditions stériles. Les différents milieux sont également stérilisés soit par traitement thermique (121 °C pendant 20 minutes) ou par filtration 0,2pm. For the production of the biopolymer, all the operations are carried out according to good microbiology practices under sterile conditions. The various media are also sterilized either by heat treatment (121° C. for 20 minutes) or by 0.2 μm filtration.
[0074] Un cryotube de 2 mL de la souche CNCM i-5658 est inoculé dans un erlenmeyer contenant 50 mL de milieu permettant la culture de microorganismes marin (milieu marine broth E2216, Difco, France). La culture est incubée à 30°C sous agitation pendant 12 à 18 heures. A 2 mL cryotube of the CNCM i-5658 strain is inoculated into an Erlenmeyer flask containing 50 mL of medium allowing the culture of marine microorganisms (marine medium broth E2216, Difco, France). The culture is incubated at 30° C. with shaking for 12 to 18 hours.
[0075] La culture obtenue est ensuite inoculée dans un erlenmeyer contenant 1 ,45 L de milieu minéral adapté à sa croissance (milieu M1 - Tableau 1) à 30 ‘O sous agitation pendant 8 heures. The culture obtained is then inoculated into an Erlenmeyer flask containing 1.45 L of mineral medium suitable for its growth (medium M1 - Table 1) at 30° C. with stirring for 8 hours.
[0076] Enfin, la culture est inoculée en fermenteur contenant 13,5 L de milieu minéral de culture adaptée à sa croissance et la biosynthèse du biopolymère (milieu M2 - Tableau 2). La culture est maintenue à 30 ‘O sous agitation pendant au minimum 30 heures. Finally, the culture is inoculated in a fermenter containing 13.5 L of mineral culture medium suitable for its growth and the biosynthesis of the biopolymer (medium M2 - Table 2). The culture is maintained at 30°C with stirring for at least 30 hours.
[0077] Pendant les 28 premières heures de culture, il est ajouté toutes les deux heures 15 mL d’une solution d’acide octanoïque tamponnée à pH 6 avec du NaOH 10N. During the first 28 hours of culture, 15 mL of an octanoic acid solution buffered at pH 6 with 10N NaOH is added every two hours.
[0078] Le pH est régulé à 7,2 par du NaOH 10 N ou du H2S04 2N. The pH is regulated at 7.2 by 10 N NaOH or 2N H2SO4.
[0079] L’oxygénation et l’agitation de la culture sont également régulés pour permettre la croissance des cellules et l’accumulation du biopolymère. [0080] A la fin de la fermentation, la biomasse cellulaire contenant les biopolymères est concentrée par centrifugation. The oxygenation and the agitation of the culture are also regulated to allow the growth of the cells and the accumulation of the biopolymer. At the end of the fermentation, the cellular biomass containing the biopolymers is concentrated by centrifugation.
[0081] Cette biomasse est ensuite séchée afin d’éliminer toute l’eau et jusqu’à obtention d’une masse constante. [0082] [Tableau 1] - Composition du milieu M1
Figure imgf000016_0001
This biomass is then dried in order to eliminate all the water and until a constant mass is obtained. [0082] [Table 1] - Composition of medium M1
Figure imgf000016_0001
[0083] [Tableau 2] - Composition du milieu M2
Figure imgf000016_0002
[0083] [Table 2] - Composition of medium M2
Figure imgf000016_0002
[0084] b) Purification du biopolymère de polyhydroxyalcanoate [0085] L’extraction du biopolymère polyhydroxyalcanoate est réalisée par ajout de dichlorométhane à raison de 10 % de biomasse sèche par volume de solvant à température ambiante et sous agitation pendant 18 heures. b) Purification of the polyhydroxyalkanoate biopolymer The extraction of the polyhydroxyalkanoate biopolymer is carried out by adding dichloromethane at a rate of 10% of dry biomass per volume of solvent at room temperature and with stirring for 18 hours.
[0086] La biomasse est éliminée par centrifugation (8000 rpm X 20 min) et le surnageant contenant le biopolymère est récupéré. The biomass is eliminated by centrifugation (8000 rpm X 20 min) and the supernatant containing the biopolymer is recovered.
[0087] Ce dernier peut être filtré afin d’améliorer la qualité du biopolymère final. The latter can be filtered in order to improve the quality of the final biopolymer.
[0088] Il est concentré par élimination du dichlorométhane à l’aide d’un évaporateur rotatif. It is concentrated by elimination of the dichloromethane using a rotary evaporator.
[0089] Le biopolymère concentré en solution dans le dichlorométhane est enfin précipité par ajout d’une solution d’éthanol à froid (10 :1) puis séché dans une étuve ventilée à 40 'Ό jusqu’à évaporation complète du solvant. The biopolymer concentrated in solution in dichloromethane is finally precipitated by adding a cold ethanol solution (10:1) then dried in a ventilated oven at 40 Ό until complete evaporation of the solvent.
[0090] Exemple 2 : caractérisation physico-chimique du biopolymère polyhydroxyalcanoate obtenu dans l’exemple 1 Example 2: physico-chemical characterization of the polyhydroxyalkanoate biopolymer obtained in example 1
[0091] Le poids moléculaire est déterminé par chromatographie d’exclusion stérique avec pour détection un réfractomètre (RI). The molecular weight is determined by steric exclusion chromatography with a refractometer (RI) for detection.
[0092] Le poids moléculaire est déterminé par comparaison du temps de rétention du polymère avec le temps de rétention de standards Polystyrène via une droite d’étalonnage. The molecular weight is determined by comparing the retention time of the polymer with the retention time of polystyrene standards via a calibration line.
[0093] L’analyse permet de déterminer le poids moléculaire moyen (Mw en Dalton), le poids moléculaires moyen en nombre (Mn en Dalton) en équivalent PS (polystyrène), ainsi que l’indice de polydispersité. The analysis makes it possible to determine the average molecular weight (Mw in Dalton), the average molecular weight by number (Mn in Dalton) in PS (polystyrene) equivalent, as well as the polydispersity index.
[0094] La composition du biopolymère est déterminée par chromatographie en phase gazeuse munie d’un détecteur à ionisation de flamme (FID) et confirmée par analyse RMN 1 H, 13C, HMBC et HMQC. The composition of the biopolymer is determined by gas phase chromatography fitted with a flame ionization detector (FID) and confirmed by 1 H, 13 C, HMBC and HMQC NMR analysis.
[0095] On a ainsi obtenu un copolymère consistant en 96% en poids de poly(hydroxy-3- octanoate) et 4% en poids de poly(hydroxy-3-hexanoate) A copolymer was thus obtained consisting of 96% by weight of poly(hydroxy-3-octanoate) and 4% by weight of poly(hydroxy-3-hexanoate)
Exemple 3 : Evaluation des propriétés filmogènes du copolymère de l’exemple 2Example 3: Evaluation of the film-forming properties of the copolymer of Example 2
[0096] Dans une première étape, on prépare une solution du polymère dont on souhaite évaluer les propriétés filmogènes dans un solvant volatile apte à le solubiliser. Le polymère représente 30 à 50% en masse de la solution. Dans une seconde étape on dépose une solution obtenue à l’étape 1 dans le fond d’une boîte de Pétri. Le choix de la boîte de Pétri permet de se rapprocher au plus près des conditions réelles d’utilisation d’une composition cosmétique, le matériau constitutif de la boite de Pétri présentant une énergie de surface similaire à celle de la peau humaine. Ainsi la peau non traitée présente approximativement une énergie de surface de 38 mN/m et une peau lavée au savon, une énergie de surface de l’ordre de 25 à 29 mN/m (H. Schott, Contact angles and wettability of human skin, J. Pharm Soi. 60 (1971) 1893-1895), une boîte de Pétri plastique en matériau classique polystryrène présente quant à elle une énergie de surface de l’ordre de 39 mN/m. Dans une troisième étape, on place la boîte de Pétri dans une étuve ventilée à 45 ‘O afin d’évaporer le solvant volatile, et obtenir un dépôt de film sec d’environ 1 g, puis on caractérise la qualité du film de polymère déposé au fond de la boîte de Pétri selon 3 critères d’appréciation:In a first step, a solution of the polymer whose film-forming properties are to be evaluated is prepared in a volatile solvent capable of dissolving it. The polymer represents 30 to 50% by mass of the solution. In a second step, a solution obtained in step 1 is deposited in the bottom of a Petri dish. The choice of the Petri dish makes it possible to come as close as possible to the actual conditions of use of a cosmetic composition, the constituent material of the Petri dish having a surface energy similar to that of human skin. Thus, untreated skin has approximately a surface energy of 38 mN/m and skin washed with soap has a surface energy of the order of 25 to 29 mN/m (H. Schott, Contact angles and wettability of human skin, J. Pharm Soi. 60 (1971) 1893-1895), a plastic Petri dish made of conventional polystryrene material is present it has a surface energy of the order of 39 mN/m. In a third step, the Petri dish is placed in a ventilated oven at 45°C in order to evaporate the volatile solvent, and obtain a dry film deposit of approximately 1 g, then the quality of the polymer film deposited is characterized. at the bottom of the Petri dish according to 3 assessment criteria:
- la transparence du film : une note de 1 est attribuée à un film qualifié de transparent (pas de déformation de l’image et de son contraste par son observation au travers du film), 0 pour un film opaque ; - la régularité du film : une note de 0, 1 , ou 2 est attribuée, la note de 2 caractérisant un dépôt régulier en épaisseur et couvrant l’ensemble de la surface, et la note de 0 caractérisant un film fortement craquelé ou présentant des agrégats ; - the transparency of the film: a score of 1 is assigned to a film qualified as transparent (no deformation of the image and its contrast by observing it through the film), 0 for an opaque film; - the regularity of the film: a score of 0, 1, or 2 is assigned, the score of 2 characterizing a regular deposit in thickness and covering the entire surface, and the score of 0 characterizing a film that is heavily cracked or has aggregates;
- l’adhésion du film : une note de 4 à 0 est attribuée sur la base des caractéristiques suivantes ; 4 - très adhésif, ne se décolle pas dans les 48h ; 3 - adhésif, se décolle partiellement sous la contrainte ; 2 - adhésif initialement, se décolle partiellement dans les- adhesion of the film: a score from 4 to 0 is assigned on the basis of the following characteristics; 4 - very adhesive, does not peel off within 48 hours; 3 - adhesive, partially peels off under stress; 2 - adhesive initially, partially peels off in the
48h ; 1 - faible adhésif, se décolle totalement dans les 48h ; 0 - pas d’adhésion initial.48 hours; 1 - weak adhesive, peels off completely within 48 hours; 0 - no initial membership.
Plus la note du polymère testé est haute, meilleure sont ces qualités filmogènes : The higher the grade of the polymer tested, the better these film-forming qualities:
[0097] Le polymère obtenu dans l’exemple 2 est ainsi évalué et ses propriétés filmogènes sont comparées à celles obtenues selon le même protocole pour le Belsil TMS 803 (nom INCI : Trimethyl silicate) commercialisé par la société AES, un filmogène de l’état de l’art couramment utilisé dans le domaine cosmétique. Les résultats sont présentés dans le Tableau 3. The polymer obtained in example 2 is thus evaluated and its film-forming properties are compared with those obtained according to the same protocol for Belsil TMS 803 (INCI name: Trimethyl silicate) marketed by the company AES, a film former of state of the art commonly used in the cosmetic field. The results are shown in Table 3.
[0098] [Tableau 3] - Evaluation des propriétés filmogènes :
Figure imgf000018_0001
[0098] [Table 3] - Evaluation of the film-forming properties:
Figure imgf000018_0001
Ό099] On constate que le copolymère de l’exemple 2 obtenu par un procédé de biosynthèse, propre et respectueux de l’environnement présente des critères d’évaluation similaire au polymère de l’art antérieur. Il est donc un excellent candidat pour substituer les polymères filmogènes synthétiques de l’art antérieur, et permettre ainsi d’obtenir des compositions cosmétiques présentant le même niveau de qualité et de performance, tout en étant plus respectueux de l’environnement avec notamment une excellente biodégradabilité. Ό099] It is noted that the copolymer of example 2 obtained by a biosynthetic process, clean and respectful of the environment, has evaluation criteria similar to the polymer of the prior art. It is therefore an excellent candidate for replacing the synthetic film-forming polymers of the prior art, and thus making it possible to obtain cosmetic compositions having the same level of quality and performance, while being more respectful of the environment with in particular excellent biodegradability.
[0100] On a ensuite comparé les propriétés du polymère de l’exemple 2 à un copolymère selon le document W02020/128050 consistant en 60% en poids de poly(hydroxy-3- décanoate), 37% en poids de poly(hydroxy-3-octanoate) et 3% en poids de poly(hydroxy- 3-hexanoate). The properties of the polymer of Example 2 were then compared to a copolymer according to document WO2020/128050 consisting of 60% by weight of poly(hydroxy-3- decanoate), 37% by weight of poly(hydroxy-3-octanoate) and 3% by weight of poly(hydroxy-3-hexanoate).
[0101] Le polymère comparatif selon document W02020/128050 n’est pas soluble dans l’isododécane, contrairement au copolymère selon l’invention. En outre, la résistance au sébum des deux polymères a été comparée selon le protocole suivant : The comparative polymer according to document WO2020/128050 is not soluble in isododecane, unlike the copolymer according to the invention. In addition, the sebum resistance of the two polymers was compared according to the following protocol:
[0102] Les deux polymères ont été dissous dans du cyclohexane à une concentration de 33 %. Pour permettre une bonne solubilité, les solutions ont été mises à chauffer à 45 ‘O en étuve pendant 2 heures. Après 2 heures, les solutions sont limpides et mises à refroidir à température ambiante. [0103] 3,3 ml de solution de chaque copolymère à 33% ont été coulées sur les boites deThe two polymers were dissolved in cyclohexane at a concentration of 33%. To allow good solubility, the solutions were heated at 45°C in an oven for 2 hours. After 2 hours, the solutions are clear and allowed to cool to room temperature. [0103] 3.3 ml of solution of each copolymer at 33% were poured onto the boxes of
Pétri. Les boites sont légèrement agitées pour permettre une bonne répartition du film sur la boite et laissées 30 minutes à température ambiante pour permettre cette bonne répartition. Les boites sont mises en étuve à 45 °C pendant 2 h afin de permettre l’évaporation de ce dernier. [0104] Afin d’avoir une bonne homogénéité du sébum sur le film de PHA, 4 mL de biophytosebum sont répartis sur ce dernier à température ambiante. Petri. The boxes are slightly shaken to allow a good distribution of the film on the box and left for 30 minutes at room temperature to allow this good distribution. The boxes are placed in an oven at 45°C for 2 hours to allow the evaporation of the latter. In order to have a good homogeneity of the sebum on the film of PHA, 4 mL of biophytosebum are distributed on the latter at ambient temperature.
[0105] Au bout de 2 heures, le film comparatif selon document W02020/128050 commence à se « fripper » tandis que celui de l’exemple 2 reste intact. [0105] After 2 hours, the comparative film according to document W02020/128050 begins to “crease” while that of example 2 remains intact.
[0106] Après 24h de contact, le film comparatif selon document W02020/128050 est complètement déstructuré alors que le film obtenu à partir du polymère selon l’exemple 2 reste intègre et lisse. [0106] After 24 hours of contact, the comparative film according to document W02020/128050 is completely destructured, whereas the film obtained from the polymer according to Example 2 remains intact and smooth.
Exemple 4 : Composition cosmétique de base de teint Example 4: Cosmetic foundation base composition
[0107] On a préparé une base de teint sous forme d’émulsion eau-dans-huile ayant la composition présentée dans le tableau 4 suivant : [0108] [Tableau 4]
Figure imgf000020_0001
[0107] A foundation base was prepared in the form of a water-in-oil emulsion having the composition presented in the following table 4: [0108] [Table 4]
Figure imgf000020_0001
1 -peser la phase aqueuse comprenant l’eau, la glycérine, le sorbitol, le pentylène glycol et le conservateur et la mettre sous agitation Rayneri, 1 - weigh the aqueous phase comprising the water, glycerin, sorbitol, pentylene glycol and preservative and put it under Rayneri stirring,
2- ajouter le copolymère de l’Exemple 2 sous agitation 10 min à 250 rpm jusqu’à formation du gel, 2- add the copolymer of Example 2 with stirring for 10 min at 250 rpm until the gel forms,
3- mélanger le CITHROL, le KSG-210 et le CETIOL ULTIMATE sous agitation dans un rotor stator à 245 rpm pendant 5min, 3- mix CITHROL, KSG-210 and CETIOL ULTIMATE with stirring in a rotor stator at 245 rpm for 5 min,
4- ajouter les pigments sous agitation dans un rotor stator à 350 rpm dans la phase grasse - introduire la phase aqueuse (1+2) dans ce mélange (3+4) dans un rotor stator à 245 rpm pendant 5min pour former l’émulsion. 4- add the pigments with stirring in a rotor stator at 350 rpm in the fatty phase - introduce the aqueous phase (1+2) into this mixture (3+4) in a rotor stator at 245 rpm for 5 min to form the emulsion .
[0110] La base de teint obtenue est fluide et homogène, elle s’applique facilement sans pelucher. Le film formé sur la peau est uniforme. The foundation base obtained is fluid and homogeneous, it is easy to apply without fluffing. The film formed on the skin is uniform.
[0111] Exemple 5 : Composition cosmétique de Fond de teint fluide :
Figure imgf000021_0001
Example 5: Cosmetic composition of fluid foundation:
Figure imgf000021_0001
On a préparé le fond de teint fluide selon le protocole suivant : broyer les pigments (oxydes de fer et dioxyde de titane) dans la phase grasse comprenant la methyle trimethicone, la dimethicone, et l’isononyl isononanoate. On a chauffé à 40 'O le mélange obtenu et ajouter le PEG-10 dimethicone, le copolymere de l’exemple 2 et le talc. Lorsque cette phase est homogène, on ajoute sous forte agitation (Raynerie avec une floculeuse à 3000 tours / min) pendant 2 min, la phase aqueuse comprenant le phenoxyéthanol, le butylène glycol et l’eau déminéralisée, puis on maintient le mélange sous agitation modérée pendant 5 mn. The fluid foundation was prepared according to the following protocol: grind the pigments (iron oxides and titanium dioxide) in the fatty phase comprising methyl trimethicone, dimethicone, and isononyl isononanoate. The mixture obtained was heated to 40° O and the PEG-10 dimethicone, the copolymer of Example 2 and the talc were added. When this phase is homogeneous, the aqueous phase comprising phenoxyethanol, butylene glycol and demineralised water is added for 2 min with vigorous stirring (Raynerie with a flocculator at 3000 revolutions/min), then the mixture is maintained under moderate stirring. for 5 mins.
[0112] Le fond de teint est fluide, l’émulsion présente une bonne stabilité, il s’étale facilement et de façon homogène, sans laisser d’impression collante. Référence à du matériel biologique déposé The foundation is fluid, the emulsion has good stability, it spreads easily and evenly, without leaving a sticky impression. Reference to deposited biological material
[0113] Dans la présente demande, il est fait référence à (aux) matériel(s) biologique(s) suivant(s) et aux souches variantes ou mutantes dérivées : In the present application, reference is made to the following biological material(s) and to the derived variant or mutant strains:
-référence d’identification « 939 » et numéro d’enregistrement « I-5658 » déposée à la Collection Nationale de Cultures de Micro-organismes (CNCM), en France, le 24 février 2021 , par Polymaris Biotechnology dont l’adresse est 160 rue Pierre Rivoalon, 29200 Brest,- identification reference "939" and registration number "I-5658" deposited at the National Collection of Microorganism Cultures (CNCM), in France, on February 24, 2021, by Polymaris Biotechnology whose address is 160 rue Pierre Rivoalon, 29200 Brest,
France. France.

Claims

Revendications Claims
[Revendication 1] Composition cosmétique comprenant au moins un copolymère de polyhydroxyalcanoate, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate consiste en une répétition d’unités polymériques de formule (A1) et d’unités polymériques de formule (B1 ) telles que : [Claim 1] Cosmetic composition comprising at least one polyhydroxyalkanoate copolymer, characterized in that the said polyhydroxyalkanoate copolymer consists of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1) such as:
Formule (A1) : -[-0-CH(R1)-(CH2)n-C0-]- Formule (B1) : -[-0-CH(R2)-(CH2)m-C0-]- dans lesquelles : Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0-CH(R2)-(CH2) m -C0-]- in which :
R1 représente un groupe n-propyle R2 représente un groupe n-pentyle ; n et m sont égal à 1 ledit copolymère de polyhydroxyalcanoate comprenant 2 à 10% en moles, d’unités polymériques de formule (A1 ) et 98 à 90% en moles d’unités polymériques de formule (B1 ). R1 represents an n-propyl group R2 represents an n-pentyl group; n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1).
[Revendication 2] Composition cosmétique selon la revendication précédente, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate consiste en : [Claim 2] Cosmetic composition according to the preceding claim, characterized in that the said polyhydroxyalkanoate copolymer consists of:
- 3 à 5% en moles d’unités polymériques (A1) et - 3 to 5% in moles of polymeric units (A1) and
- 97 et 95% en moles d’unités polymériques (B1) - 97 and 95% in moles of polymeric units (B1)
[Revendication 3] Composition cosmétique selon l’une des revendications précédentes, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate consiste en : - 4% en mole d’unités polymériques (A1 ), et [Claim 3] Cosmetic composition according to one of the preceding claims, characterized in that the said polyhydroxyalkanoate copolymer consists of: - 4% by mole of polymeric units (A1), and
- 96% en mole d’unités polymériques (B1). - 96% by mole of polymeric units (B1).
[Revendication 4] Composition cosmétique selon l’une des revendications précédentes, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate présente un poids moléculaire moyen (Mw) compris entre 20 000 à 100 000 g/mol. [Revendication 5] Composition cosmétique selon l’une des revendications précédentes, caractérisée en ce que ledit copolymère de polyhydroxyalcanoate est présent en une teneur comprise entre 0,[Claim 4] Cosmetic composition according to one of the preceding claims, characterized in that the said polyhydroxyalkanoate copolymer has an average molecular weight (Mw) of between 20,000 and 100,000 g/mol. [Claim 5] Cosmetic composition according to one of the preceding claims, characterized in that the said polyhydroxyalkanoate copolymer is present in a content of between 0,
5 % à 30% en poids, de préférence 1% à 20% en poids, et très préférentiellement 2% à 8% en poids, par rapport au poids total de la composition. 5% to 30% by weight, preferably 1% to 20% by weight, and very preferably 2% to 8% by weight, relative to the total weight of the composition.
[Revendication 6] Composition cosmétique selon l’une des revendications précédentes caractérisée en ce que ledit copolymère de polyhydroxyalcanoate est obtenu selon un procédé de fermentation en présence d’une bactérie enregistrée en vertu du traité de Budapest à la Collection Nationale de Cultures de Microorganismes le 24 février 2021 sous le numéro de dépôt I-5658. [Claim 6] Cosmetic composition according to one of the preceding claims, characterized in that the said polyhydroxyalkanoate copolymer is obtained according to a fermentation process in the presence of a bacterium registered under the Budapest Treaty at the National Collection of Microorganism Cultures on February 24, 2021 under filing number I-5658.
[Revendication 7] Composition cosmétique selon l’une des revendications précédentes, caractérisée en ce qu’elle se présente sous la forme d’une émulsion, d’une microémulsion, d’une nanoémulsion, d’une poudre, d’une composition anhydre, d’une suspension, d’une lotion, d’une crème, d’un gel aqueux ou hydroalcoolique, d’une mousse, d’un sérum, d’une solution ou d’une dispersion pour aérosol, ou d’une dispersion de vésicules lipidiques, ou de gouttelettes obtenues par coacervation ou par microfluidique. [Claim 7] Cosmetic composition according to one of the preceding claims, characterized in that it is in the form of an emulsion, a microemulsion, a nanoemulsion, a powder, an anhydrous , suspension, lotion, cream, aqueous or hydroalcoholic gel, foam, serum, aerosol solution or dispersion, or dispersion of lipid vesicles, or of droplets obtained by coacervation or by microfluidics.
[Revendication 8] Composition cosmétique selon l’une des revendications précédentes, caractérisée en ce qu’elle comprend au moins un composé choisi parmi un agent émollient ou humectant, un agent gélifiant et/ou épaississant, un agent tensioactif, une huile, une cire, un colorant, un pigment, une nacre, une charge, un conservateur, un agent antioxydant, un agent actif, une poudre organique ou inorganique, un solvant volatile et/ou non volatile, un solubilisant, un chélatant, un séquestrant, un sel ionique, un filtre solaire et un parfum. [Claim 8] Cosmetic composition according to one of the preceding claims, characterized in that it comprises at least one compound chosen from an emollient or humectant, a gelling and/or thickening agent, a surfactant, an oil, a wax , a dye, a pigment, a nacre, a filler, a preservative, an antioxidant agent, an active agent, an organic or inorganic powder, a volatile and/or non-volatile solvent, a solubilizer, a chelating agent, a sequestrant, a salt ionic, a sunscreen and a perfume.
[Revendication 9] Utilisation d’au moins un copolymère de polyhydroxyalcanoate en tant qu’agent filmogène dans une composition cosmétique, ledit copolymère de polyhydroxyalcanoate consistant en une répétition d’unités polymériques de formule (A1) et d’unités polymériques de formule (B1) telles que : [Claim 9] Use of at least one polyhydroxyalkanoate copolymer as a film-forming agent in a cosmetic composition, said polyhydroxyalkanoate copolymer consisting of a repetition of polymeric units of formula (A1) and polymeric units of formula (B1 ) as :
Formule (A1) : -[-0-CH(R1)-(CH2)n-C0-]- Formule (B1) : -[-0-CH(R2)-(CH2)m-C0-]- dans lesquelles : R1 représente un groupe n-propyle R2 représente un groupe n-pentyle ; n et m sont égal à 1 ledit copolymère de polyhydroxyalcanoate comprenant 2 à 10% en moles, d’unités polymériques de formule (A1 ) et 98 à 90% en moles d’unités polymériques de formule (B1 ) ; ledit copolymère de polyhydroxyalcanoate étant obtenu par un procédé de fermentation à partir d’une bactérie enregistrée en vertu du traité de Budapest à la Collection Nationale de Cultures de Microorganismes le 24 février 2021 sous le numéro de dépôt I-5658 ; et étant présent en une teneur comprise entre 2 et 20% en poids, par rapport au poids total de ladite composition cosmétique.. Formula (A1): -[-0-CH(R1)-(CH2) n -C0-]- Formula (B1): -[-0-CH(R2)-(CH2) m -C0-]- in which : R1 represents an n-propyl group R2 represents an n-pentyl group; n and m are equal to 1 said polyhydroxyalkanoate copolymer comprising 2 to 10% by moles of polymeric units of formula (A1) and 98 to 90% by moles of polymeric units of formula (B1); said polyhydroxyalkanoate copolymer being obtained by a fermentation process from a bacterium registered under the Budapest Treaty at the National Collection of Cultures of Microorganisms on February 24, 2021 under the deposit number I-5658; and being present in a content of between 2 and 20% by weight, relative to the total weight of said cosmetic composition.
PCT/FR2022/050603 2021-03-31 2022-03-30 Cosmetic composition comprising at least one polyhydroxyalkanoate WO2022208027A1 (en)

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