EP3723708A1 - Composition cosmetique comprenant un derive de pullulan - Google Patents
Composition cosmetique comprenant un derive de pullulanInfo
- Publication number
- EP3723708A1 EP3723708A1 EP18833098.9A EP18833098A EP3723708A1 EP 3723708 A1 EP3723708 A1 EP 3723708A1 EP 18833098 A EP18833098 A EP 18833098A EP 3723708 A1 EP3723708 A1 EP 3723708A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- vinyl
- composition according
- powders
- silicone
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/87—Application Devices; Containers; Packaging
Definitions
- the present invention relates to a new cosmetic composition, and to its use in the field of care or makeup.
- the invention more particularly relates to a novel composition comprising a mixture of ingredients based on trialkylsiloxysilylcarbamoyl pullulan, at least one silicone polymer, a mattifying filler and at least one volatile oil.
- the invention also provides compositions and methods for making up and / or caring for keratinous substances or for the skin, comprising a step of applying a composition according to the invention to form a film.
- Mascaras comprising a composition according to the invention are also objects of the invention.
- a makeup kit comprising such a composition is also part of the invention.
- Cosmetic compositions for the make-up and / or care of the skin or of keratin materials such as eyelashes or eyebrows must meet a complex set of specifications comprising a multitude of criteria. For example, the stability and stability of the product over time, the comfort during its application and over time once applied. These criteria are difficult to meet simultaneously: for example, increasing the strength of a makeup product very frequently leads to a decrease in comfort felt by the user, related to drying out, feeling of stickiness, or heaviness of the deposit on keratinous substances, skin or lips.
- waxes can be used to thicken the film and give a more viscous texture to the composition when it is applied. The disadvantage of waxes is to make the film more rigid and sticky which produces a feeling of discomfort to the application and throughout the day.
- An object of the invention is to maintain the hold (adhesion) of makeup and / or care products over a long period of time, that is to say for at least 24 hours, advantageously 36 hours, while maintaining their flexibility and their comfort of application.
- the pullulan is known from the application US 2003/0082221 for its use as a non-sticking film-forming agent in the cometic field.
- Pullulan is a natural polysaccharide, a polymer consisting of maltotriose units, a triholoside of glucose, also known as alpha-1,4-; alpha-l, 6-glucan. Pullulan is produced from starch by the mushroom Aureobasidium pullulans.
- Silicone derivatives of pullulan of the trialkylsiloxysilylcarbamoyl pullulan type are commonly used in make-up products.
- Application KR2015100201 describes, for example, very soft water-in-oil emulsions based on urethane polymer, one or more species selected from a silicone resin, trimethylsiloxysilylcarbamoyl pullulan and an acrylic silicone copolymer, and a silicone gum or a silicone polymer .
- the application W02014181747 US2016 / 113860 also describes cosmetic compositions based on trimethylsiloxysilylcarbamoyl pullulan, easy to apply and having a good resistance without sticky effect, as well as a good retention effect.
- This document is not relevant because it uses a volatile silicone oil consisting of decamethylcyclopentasiloxane, while the invention described below uses mainly or exclusively a volatile hydrocarbon oil.
- JP 2005/325088 Shiseido uses a volatile silicone oil consisting of decamethylcyclopentasiloxane, while the invention described below mainly or exclusively uses a hydrocarbon volatile oil.
- JP 2004/244333 does not contain silicone polymer in contrast to the present invention, further combined with a volatile hydrocarbon oil.
- the document FR 2910285 (L'OREAL) relates to a cosmetic kit comprising a catalyst or a peroxide with a compound X and a compound Y capable of reacting together in the presence of the catalyst and formulated according to 2 different compositions, totally remote from the present invention .
- One of the objectives of the present invention is to provide a new cosmetic composition for the makeup and / or care of the skin, lips or keratin materials forming during its application a long-lasting film, in particular greater than 24 hours, and comfort of application.
- the inventors have discovered that the combination of a trialkylsiloxysilylcarbamoyl pullulan compound with a silicone polymer and a mattifying filler in the presence of at least one volatile oil leads to a synergistic effect to obtain cosmetic compositions. which leave on the skin, lips or keratin materials a film whose soft and light texture produces a feeling of softness without cardboard effect, non-greasy and non-sticky, while having a significantly improved adhesion (hold), and therefore a resistance with water, sebum, perspiration and friction greater than that of the compositions of the prior art.
- the inventors have unexpectedly shown that it is quite possible to reduce the amount of waxes to a maximum of 5% by weight of the composition and even more advantageously to exclude the waxes from said compositions, and thus to limit the disadvantages known to those skilled in the art, which are including feelings of heaviness and discomfort at the time and after application of the composition. It is thus possible to obtain low-content compositions, and better still without waxes, whose holding properties and application comfort are particularly remarkable.
- compositions of the invention produce a so-called “matte” makeup effect, this mattness being particularly advantageous for application to keratinite fibers, in particular eyelashes or eyebrows.
- keratin materials is intended for human keratinous fibers such as eyelashes, eyebrows or hair, and artificial keratinous fibers such as false eyelashes.
- a make-up composition intended to be applied to these keratinous fibers is also called "mascara”.
- film-forming polymer means a polymer capable of forming a continuous film on a support.
- the word polymer may designate a homopolymer or a copolymer.
- copolymer is meant a polymer comprising at least two different monomers or two blocks, which may be of the same chemical family but of different structure.
- silicone polymer or "crosslinked silicone polymer”, or “crosslinked silicone polymer” refer to the same family of ingredients in this specification.
- an “oil”, within the meaning of the present invention, may be defined as a compound which is not soluble in water (solubility less than 0.05 mg / l at 20 ° C.) and liquid at ambient temperature (25 ° C.) of which the melting point, the softening point or the glass transition point at atmospheric pressure is less than or equal to 30 ° C, preferably less than or equal to 25 ° C.
- the volatility may be defined in the context of the invention for example by a vapor pressure measurable by an empirical method at 25 ° C, and whose value will be between 0.13 Pa and 40 000 Pa, for example between 1 Pa and 20 Pa. 000 Pa, between 10 Pa and 8000 Pa, or even between 15 and 150 Pa.
- the vapor pressure will be measured according to one of the most suitable methods for the compound of interest, which methods are included in the guidelines of Test No. 104 of the OECD (2006 version). It is alternatively possible to choose a volatile oil having a boiling point at atmospheric pressure of less than 250 ° C., in a variant of less than 230 ° C. and in another variant of between 150 ° C. and 220 ° C.
- the volatile oil may also be defined as a compound having a flash point ranging from 35 ° C to 100 ° C, in particular between 40 ° C and 80 ° C.
- Isododecane which is considered in the present application as a volatile oil, has a boiling point at 105 Pa of between 175 ° C. and 195 ° C., a flash point of 45 ° C. and a vapor pressure of 20 ° C. C is equal to 100 Pa. Its solubility in water at 20 ° C is less than or equal to 1 ⁇ 10-2 mg / L.
- Cyclopentadimethylsiloxane considered as another volatile oil, has a solubility in water at 25 ° C equal to 1.7 10-2 mg / L, a flash point of 77 ° C, a boiling point at 105 Pa equal to 205 ° C, and a vapor pressure equal to 26 Pa at Aspects of the invention
- the subject of the invention is a cosmetic composition
- a cosmetic composition comprising:
- the compound trialkylsiloxysilylcarbamoyl pullulan (i) can represent from 0.5 to 30% by weight of the composition, in a variant of 1 to 15%, and according to another variant of 1 to 5%, by weight of the total weight of the composition .
- the silicone polymer may represent from 0.1 to 30% by weight of the composition, alternatively from 0.5 to 15%, and according to another variant from 1 to 10% by weight of the total weight of the composition.
- the mattifying filler (iii) may represent from 0.5 to 30% by weight of the composition, alternatively from 0.5 to 15%, according to another variant of 2 to 10% by weight and
- the volatile hydrocarbon oil (iv) may represent from 10 to 70% by weight of the composition, in a variant of 15 to 65%, and according to another variation of from 20 to 60%, by weight of the total weight of the composition.
- the volatile hydrocarbon oil represents the balance at 100% by weight of the composition comprising the ingredients (i) to (iv).
- the cosmetic composition comprises, as a percentage by weight of the composition:
- the ratio by weight of components (i), (ii) and (iii) is in the range 1/1/1 to 1/5/10, and even more particularly in the range 1/1/3 to 1/2/4. According to an even more particular embodiment, it is of the order of 1/2/2. According to these particular embodiments of the invention, the composition has the advantage, once applied to the skin, the lips or the keratin fibers, eyelashes and eyebrows in particular, to form a high-strength film producing a matt effect. quite surprising and a sensation of remarkable comfort.
- the compound trialkylsiloxysilylcarbamoyl pullulan (i) is described in application US 2003/0082221 and also in the application KR2015100201 and also in the application WO2014181747 relating to cosmetic compositions, including mascara, based on trimethylsiloxysilylcarbamoyl pullulan, easy to apply and showing good performance, no sticky effect, and a good retention effect.
- the trialkylsiloxysilylcarbamoyl pullulan compound comprises alkyl groups comprising from 1 to 6 carbon atoms. These alkyl groups can be linear or branched. According to another particular embodiment, the trialkylsiloxysilylcarbamoyl pullulan of the invention is trimethylsiloxysilylcarbamoyl pullulan.
- composition according to the invention comprises, as a percentage by weight of the composition:
- the silicone polymer (iii) is, according to a particular variant embodiment, an ungelled or gelled crosslinked silicone polymer.
- the crosslinked silicone polymer can be dispersed or gelled with an oil. It is preferred that it be in the form of particles, gelled or dispersed, the average size is between 10 and 200 microns.
- the crosslinked silicone polymer may be referred to as an elastomer by those skilled in the art.
- the terms "crosslinked gelled or dispersed silicone polymer” and “crosslinked gelled or dispersed silicone polymer particles” are used interchangeably. It is meant that “gelled” means “gelled” by an oil.
- crosslinked silicone polymer may denote the crosslinked silicone polymer gelled or dispersed in an oil.
- the crosslinked silicone polymer may be obtained by reaction of an organopolysiloxane containing in particular at least one -Si-H group in the terminal position with an organopolysiloxane comprising at least one ethylenically unsaturated group bonded to a silicon atom, and better still at least two ethylenically unsaturated groups bonded to said silicon atom.
- the ethylenically unsaturated group may be chosen from vinyl, allyl and propenyl groups; it is in particular located at the ends of the organopolysiloxane molecule.
- the crosslinked silicone polymer can be obtained by hydrosilylation reaction of the two organopolysiloxanes mentioned above, in the presence of a catalyst and an oil, under reaction conditions known to those skilled in the art.
- the catalyst may be hexachloroplatinic acid, or a platinum complex.
- a crosslinked silicone polymer obtained by crosslinking dehydrogenation condensation reaction between the two organopolysiloxanes described above may be used in the presence of a catalyst and an oil.
- the oil used for the preparation of the crosslinked silicone polymer may be a nonvolatile oil or a volatile oil identical to one of the volatile oils described below, used in the composition of the product of the invention. Examples are isododecane or decamethylcyclopentasiloxane.
- At least one of the organopolysiloxanes mentioned above mainly comprises dimethylsiloxane units, the other units may be methylphenylsiloxane or dimethylvinylsiloxy for a vinyl organosiloxane, and methylhydrogensiloxane for the organopolysiloxane containing -Si-H groups.
- the organopolysiloxane comprising at least one ethylenically unsaturated group bonded to a silicon atom may be chosen from copolymers of which part of the units comprise vinyl groups or for which at least one vinyl group is in the terminal position of the chain.
- the organopolysiloxane comprising at least one vinyl group can be chosen from methylvinylsiloxane / dimethylsiloxane copolymers, dimethylvinylsiloxy terminated polydimethylsiloxanes, dimethylvinylsiloxy dimethylsiloxane / methylphenylsiloxane copolymers, and trimethylsiloxy terminated dimethylsiloxane / methylvinylsiloxane copolymers.
- the organopolysiloxane containing -Si-H groups and the organopolysiloxane comprising at least two terminal vinyl groups are in particular used in proportions such that the molar ratio between the total amount of hydrogen atoms bonded to silicon atoms and the total amount of the vinyl groups is between 1.5 / 1 and 20/1.
- the organopolysiloxane containing -Si-H groups may be a polydimethylsiloxane or a poly (dimethyl) (methylhydrogen) siloxane, one or the other comprising at least one Si-H bond at the end of the chain.
- the crosslinked silicone polymer is, for example, the reaction product of a polydimethylsiloxane or a poly (dimethyl) (methylhydrogen) siloxane, comprising either at least one Si-H terminal bond, with a polydimethylsiloxane comprising two vinyl groups, in particular located in the terminal position of the chain.
- the silicone polymer is a silicone elastomer having viscoelastic properties.
- the silicone elastomer used in the present invention improves the feel of the composition ("soft focus" effect).
- Said silicone elastomer is according to one embodiment chosen from polydimethylsiloxane (PDMS) (or dimethicone), methyl-polysiloxane (MQ), vinyl-methyl-polysiloxane (VMQ), phenyl-vinyl-methyl-polysiloxane (PVMQ). ), fluoro-vinyl-methyl-polysiloxane (FVMQ), and mixtures thereof.
- PDMS polydimethylsiloxane
- MQ methyl-polysiloxane
- VMQ vinyl-methyl-polysiloxane
- PVMQ phenyl-vinyl-methyl-polysiloxane
- FVMQ fluoro-vinyl-methyl-polysilox
- the crosslinked silicone polymer is, according to a particular embodiment, in the form of a gel in the composition.
- the silicone polymer gel comprises gel-crosslinked silicone polymer particles trapping molecules of an oil, which oil can represent between 10 and 95% by weight of the mass of the gel.
- the proportion of oil contained in the gel may vary from 60 to 95% by weight, for example from 80 to 90% by weight.
- Such a crosslinked silicone polymer gel may be manufactured by applying a high shear to crosslinked silicone polymer particles, which have been synthesized from the two organopolysiloxanes previously described, said shear being carried out in the presence of an oil. Shear can be realized in a high-pressure homogenizer, so as to obtain polymer particles gelled by said oil; their size can vary between 10 and 200 microns.
- the gelling agent of the crosslinked silicone polymer particles may be a non-volatile oil, or preferably a volatile oil chosen from volatile hydrocarbon oils, volatile silicone oils or a mixture thereof, these oils being in accordance with the description of the volatile oils mentioned previously or hereafter in the description.
- crosslinked silicone polymer is gelled or dispersed in the composition.
- the present application describes a crosslinked silicone polymer obtained by reaction of a trimethylsiloxy-terminated polymethylhydrogenosiloxane or trimethylsiloxy-terminated poly (dimethyl) (methylhydrogen) siloxane with a polydimethylsiloxane comprising two vinyl groups, for example two terminal vinyl groups (ie polydimethylsiloxane). terminally dimethylvinylsiloxy) in the presence of a platinum catalyst.
- a cross-linked silicone polymer whose INCI name corresponds to polysilicon-11 can be used.
- polysilicon-11 dispersed with isododecane is used.
- composition according to the invention comprises at least one mattifying filler.
- the matifying filler is, according to a particular embodiment, consisting of a solid filler in pulverulent form or powder.
- the term "filler” means a mass of particles of inorganic or organic nature, natural or synthetic, which is in an insoluble form and dispersed in the medium of the composition.
- the so-called "matifying" charge makes it possible to obtain a matt effect once the film has been formed after application.
- This dullness effect is particularly important when trying to avoid a brilliant make-up. This is particularly the case when the composition is applied to the eyelashes or the eyebrows.
- This mattifying load by the effect it produces, also allows, when applying the composition on the skin, to reduce skin imperfections such as wrinkles or fine lines appear gradually with age.
- the mattifying filler may be at least partially composed of particles treated on the surface with a hydrophilic or lipophilic organic agent to facilitate their incorporation into one or the other phase of the composition, in particular to disperse the particles homogeneously in phases. oily and more generally in liquid phases whose viscosity can be high.
- the mattifying filler consists of nonspherical or spherical particles, with regular or irregular contours, or else hemi-spherical or platelet, having a median volume size, denoted D 50 , lower or equal to 25pm, especially less than or equal to 15pm, in particular less than or equal to 10pm.
- median size by volume is meant the dimension given by the statistical size distribution at half of the population, called D 50 measured by the Malvern-Mastersizer Laser Granulometer.
- the mattifying filler (iii) consists of a solid filler in pulverulent form (or powder) chosen from the group consisting of:
- silica and silicate powders amorphous silica microspheres, silica micro-beads
- PMMA polymethyl methacrylate
- powders of vegetable origin such as rice powders, cotton powders, silk powders, talcs, natural and synthetic micas, sericites, borosilicates, and mixtures thereof.
- cellulose powders with irregular contours such as those marketed by the company Daito Kasei under the name Cellulobeads USF;
- crosslinked elastomeric organopolysiloxane powders coated with silicone resin in particular with silsesquioxane resin, such as the INCI name powders Vinyl dimethicone / methicone silsesquioxane crosspolymer PEG-7 glyceryl cocoate, Polyquaternium-7 and methylsilanol tri-PEG-8 glyceryl cocoate "marketed by Miyoshi Kasei under the name MW-SRP-100;
- PMMA powders such as the powder of the INCI name "methylmetacrylate crosspolymer" of the company Sunjin under the name SUNPMMA-X or MAKIBEADS 150 from the company Daito Kasei;
- hydrophobic silica airgel particles of INCI name Silica silylates marketed by Dow Corning under the name Dow Corning VM-2270 Aerogel fine particles;
- micas such as the product sold under the name SUBMICA M by the company SENSIENT;
- one or more polymethyl methacrylate (PMMA) powder (s), one or more mica (s) or their mixture (s) will be used as the matifying filler.
- composition of the invention comprises at least one volatile hydrocarbon oil (iv).
- the volatile oil is likely to evaporate on contact with the skin in less than one hour, at ambient temperature (25 ° C.) and atmospheric pressure (750 mmHg, ie 105 Pa).
- the presence of at least one volatile oil in the composition of the invention is essential in that it allows by its rapid evaporation at the moment the application of the composition on a support such as skin or keratin materials, the progressive formation of a film in situ.
- the one formed by the composition also has a soft texture that provides outstanding comfort and a superior hold at 24 hours.
- the hydrocarbon volatile oil (iv) of the invention may, according to an alternative embodiment, be mixed with a silicone oil. It can be of animal, vegetable, mineral or synthetic origin.
- silicon oil means a compound comprising at least one silicon atom, and in particular at least one Si-O group.
- hydrocarbon oil means an oil containing mainly hydrogen and carbon atoms.
- the oils may optionally comprise oxygen, nitrogen, sulfur and / or phosphorus atoms, for example, in the form of hydroxyl or acidic radicals.
- volatile hydrocarbon oils there may be mentioned branched alkanes having from 8 to 16 carbon atoms, such as isoalkanes (also known as isoparaffins) having from 8 to 16 carbon atoms, such as isododecane, isodecane, isohexadecane, branched esters having 8 to 16 carbon atoms such as isohexyl neopentanoate, and mixtures thereof.
- a volatile hydrocarbon oil comprises or consists of isododecane. It is also possible to mention linear alkanes having from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms.
- volatile silicone oils mention may be made of linear silicone oils such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane and dodecamethylpentasiloxane.
- Cyclic silicone volatile oils that may be mentioned include cyclopentasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcydohexasiloxane.
- a volatile hydrocarbon oil (iv) is chosen from isododecane, isohexadecane, and mixtures thereof with a volatile silicone oil, for example cyclopentasiloxane.
- the volatile oil (iv) comprises or consists of isododecane.
- the cosmetic composition comprises, as a percentage by weight of the composition:
- Hsododecane in particular from 10 to 70% by weight of at least isododecane, which may in particular constitute the balance of the mixture of compounds (i) to (iv).
- the composition may comprise one or more additional components or adjuvants which make it possible to improve the composition on criteria such as chemical or microbiological stability, the visual or olfactory appearance, the rheological behavior or even confer on this composition a cosmetic activity, for example of hydration and / or anti-aging, without altering the essential properties at the base of the invention such as holding, dullness or comfort of the film formed by said composition after application on a support.
- additional components or adjuvants which make it possible to improve the composition on criteria such as chemical or microbiological stability, the visual or olfactory appearance, the rheological behavior or even confer on this composition a cosmetic activity, for example of hydration and / or anti-aging, without altering the essential properties at the base of the invention such as holding, dullness or comfort of the film formed by said composition after application on a support.
- the composition may thus also comprise a non-volatile oil, of natural or synthetic, hydrocarbon or silicone origin.
- This non-volatile oil is particularly useful for dispersing the pigments used in the composition of the invention to produce a visual makeup effect.
- the non-volatile oil may be present in an amount of between 0.5 and 15%, in particular between 0.5 and 10% and more preferably between 0.5 and 5%.
- the composition comprises from 0 to 5% by weight of a wax, alternatively up to 2% by weight. According to yet another embodiment of the invention, the composition is free of wax.
- the wax may be for example chosen from.
- nonpolar waxes such as microcrystalline waxes, paraffins, ozokerite, polyethylene waxes, silicone waxes and fluorinated waxes, and
- polar waxes such as, for example, beeswax, rice bran wax, carnauba wax, candellila wax, ouricurry wax, japanese wax, berry wax, Sumac wax, Montan wax, Alfa wax, cork fiber wax, sugar cane wax, orange wax, lemon wax, laurel wax, waxes obtained by hydrogenation of animal or vegetable oils having linear or branched C 8 -C 32 fatty chains, such as jojoba oil, sunflower oil, castor oil, coconut oil, lanolin oil, olive oil esterified with stearyl alcohol, castor oil esterified with cetyl alcohol, and
- the composition may comprise from 0 to 20% of water.
- the composition is anhydrous.
- the anhydrous composition according to the invention makes it possible to obtain, at the time of application, a film which is formed particularly rapidly and whose mechanical properties are remarkable.
- the composition may comprise an aqueous phase dispersed in a continuous phase (water-in-oil emulsion)
- composition of the invention may also comprise a non-silicone film-forming polymer.
- the non-silicone film-forming polymer may be of natural or synthetic origin, and is in particular chosen from:
- polystyrene resins which are hydrogenated or non-hydrogenated, and preferably the polymers or copolymers of C 2 -C 2 2 alkenes, such as polybutenes, polyisobutenes and polydecenes,
- alkylcelluloses and preferably alkylcelluloses bearing a C 2 -C 6 alkyl group, such as ethylcellulose and propylcellulose,
- the non-silicone film-forming polymer represents from 0.5 to 10%, and even more particularly from 1 to 5%, by weight of the total weight of the composition.
- composition according to the invention may also comprise a coloring material in particular chosen from pigments and pearlescent agents.
- the pigments may be in pulverulent or powder form and, alternatively, have an average diameter not exceeding 200 ⁇ m, and in another variant, not exceeding 150 ⁇ m.
- pigments white or colored particles, mineral or organic, coated or not, insoluble in an aqueous phase, intended to color and / or opacify the composition containing them.
- pigments that may be used in the composition of the invention, mention may be made of titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, as well as iron or chromium oxides, and manganese violet. ultramarine blue, chromium hydrate, ferric blue, carbon black, and mixtures thereof. It can also be a pigment having a structure that can be for example of the type sericite / brown iron oxide / titanium dioxide / silica. It may also be pigments having a structure which may be, for example, silica microspheres type containing iron oxide.
- the pigments of the invention are iron oxides and / or titanium dioxides.
- the pigment particles may be surface-treated by deposition of an agent on the surface of the colorant by solvent evaporation, chemical reaction, or creation of covalent bonds between the surfactant and the treated particle.
- the agent is a silicone or an amino acid.
- the pigment may be coated with a layer of silicone, in particular with a layer of methicone, dimethicone (also called polydimethylsiloxane (PDMS)), hydrogenated dimethicone, a dimethicone-methicone copolymer, an acrylate-dimethicone copolymer, and still more particularly by a dimethicone layer.
- the pigment is chosen from iron oxides and / or titanium dioxides coated in a dimethicone layer.
- the composition of the invention represents from 5% to 20% by weight, and in a variant of 5 to 15% by weight, relative to the total weight of the composition.
- composition of the invention may also comprise at least one gelling compound different from the silicone or non-silicone polymers mentioned previously.
- This gelling agent which makes it possible to structure the fatty phase based on volatile oil is in particular chosen from natural or synthetic clays; modified natural micas such as aluminum, magnesium and potassium fluorosilicate; dextrin and fatty acid esters such as dextrin palmitate or dextrin myristate; tri-esters of C 8 -C 30 fatty acids and mono- or poly-glyceryl such as glyceryl tri (hydroxystearate) (INCI name: Trihydroxystearin).
- the gelling compound of the invention is chosen from a natural or synthetic clay chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.
- the clay is chosen from hectorites.
- hectorites modified with a quaternary alkylammonium chloride are used, said ammonium being substituted by at least one, and in particular at least two radicals.
- the gelling compound may represent from 0.05 to 10%, and alternatively from 0.1 to 5%, by weight of the total weight of the composition.
- composition of the invention may also comprise any additive usually used in cosmetics such as antioxidants, preservatives, perfumes, cosmetic active agents, for example emollients, moisturizers, vitamins, sunscreens, and mixtures thereof.
- additives such as antioxidants, preservatives, perfumes, cosmetic active agents, for example emollients, moisturizers, vitamins, sunscreens, and mixtures thereof.
- the composition of the invention may be in any cosmetic form conventionally used for applications on keratinous fibers, the skin, such as solid, liquid or even liquid forms under pressure. It may especially be formulated in the form of a cream, a gel, an anhydrous product.
- composition of the invention may be prepared according to conventional methods for compositions comprising a volatile oil.
- the composition according to the invention is more particularly a mascara intended for the makeup of keratinous fibers, in particular eyelashes and eyebrows.
- the process for preparing said composition may optionally comprise a grinding step in order to obtain a powder formed of fine solid particles. This grinding step can be carried out in a tricylindrar mill such as an EXAKT 50i mill from the company EXAKT TECHNOLOGIES.
- composition according to the invention is formulated in the form of an anhydrous mascara comprising the compounds (i), (ii), (iii) and (iv) mentioned above.
- the invention also relates to a process for the makeup and / or care of keratinous materials comprising a step of applying the keratin materials, in particular the eyelashes, the eyebrows, the skin or the lips, to a composition according to the invention.
- Another object of the invention is a film consisting of a composition according to the invention having in particular a thickness ranging from 150 to 800 .mu.m. Once dry, the film formed on the support is essentially free of volatile oil (iv).
- a further object of the invention relates to the use of a composition according to the invention for the makeup and / or care of keratin materials, skin or lips, and more particularly in semi-permanent mascaras, complexion and lipsticks.
- the present invention also covers semi-permanent mascaras, long-lasting foundations comprising a composition according to the invention.
- These make-up products combine staying, comfort and flexibility for at least 24 hours.
- a mascara has a hold of at least 24 hours, or even up to 36h, and withstands a day, a night and a shower.
- a final subject of the invention relates to a make-up kit comprising a composition according to the invention, packaged in a reservoir, as well as means for sampling and applying said composition to the keratinous fibers, the skin and / or the lips .
- the reservoir can be a bottle, a bucket or a pot.
- the sampling and application means may comprise a brush, a brush, a sponge or a cellular foam.
- the invention also comprises other embodiments or variants that will be apparent from the additional description which follows, which relates to the preparation of compositions according to the invention given by way of illustration. and which in no way limit the scope of the invention.
- the examples are, however, an integral part of the invention.
- An anhydrous mascara is prepared according to the formula below (% by weight of the final composition).
- the raw materials used are as follows:
- Trimethylsiloxysilylcarbamoyl pullulan TSPL-30-ID F® from Shin-Etsu Silicone
- the silicone polymer is dispersed in the isododecane with trimethylsiloxysilylcarbamoylpullulan using an ULTRA TURRAX stirrer at room temperature.
- the pigments previously crushed using a three-cylinder are added to the mixture and finally the PMMA.
- the composition obtained is a mascara.
- This mascara is applied to the eyelashes using an applicator. Evaporation of the isododecane allows the formation of a film on the keratin fibers. The film has a supple texture producing a feeling of comfort. Makeup rendering is a matte effect.
- the mascara can be kept for more than 24 hours, and can withstand showering.
- Example 1 is reproduced by replacing the PMMA with mica in the same proportions as a mattifying filler.
- An anhydrous mascara is prepared according to the formula below (% by weight of the final composition).
- the method of manufacturing the composition is identical.
- composition obtained according to this same method is applied to the eyebrows to produce a makeup effect.
- the formed film presents a matte rendering.
- the holding of the formula is superior to 24h.
- a comparative or control mascara is prepared according to the following formula:
- Example 1 the silicone polymer is replaced by its weight in isododecane in the comparative or control mascara composition.
- compositions according to the invention are stable at T0, the pigments do not sediment.
- composition of the comparative example is totally unstable at TO (total sedimentation of the pigments) because of a very low viscosity compared to that of the two compositions of the invention.
- the comparative formula has a slightly less matt effect than the two compositions of the invention.
- the film recovered in the mold is wound around cylinder of different diameter: 0 5mm, 10mm, 20mm, 30mm, 40mm, 50mm starting from the largest diameter to the smallest.
- cylinder of different diameter 0 5mm, 10mm, 20mm, 30mm, 40mm, 50mm starting from the largest diameter to the smallest.
- the two compositions according to the invention are more flexible than the comparative composition. This particularly interesting property provides comfort to the application of the same film on the skin.
- the two compositions of the invention have a stability significantly greater than the comparative composition.
- the superior flexibility measured on the compositions of the invention provides a feeling of flexibility and comfort when a composition according to the invention is applied to the eyelashes or eyebrows.
- the mascaras formed by the compositions according to the invention have a duration of use of up to 36 hours.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1762272A FR3075054B1 (fr) | 2017-12-15 | 2017-12-15 | Composition cosmetique comprenant un derive de pullulan |
PCT/FR2018/053256 WO2019115949A1 (fr) | 2017-12-15 | 2018-12-13 | Composition cosmetique comprenant un derive de pullulan |
Publications (1)
Publication Number | Publication Date |
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EP3723708A1 true EP3723708A1 (fr) | 2020-10-21 |
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ID=61187518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP18833098.9A Pending EP3723708A1 (fr) | 2017-12-15 | 2018-12-13 | Composition cosmetique comprenant un derive de pullulan |
Country Status (7)
Country | Link |
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US (1) | US11253462B2 (fr) |
EP (1) | EP3723708A1 (fr) |
JP (1) | JP2021506736A (fr) |
KR (1) | KR20200099963A (fr) |
CN (1) | CN110730653B (fr) |
FR (1) | FR3075054B1 (fr) |
WO (1) | WO2019115949A1 (fr) |
Families Citing this family (5)
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CN117064795A (zh) | 2018-05-04 | 2023-11-17 | 强生消费者公司 | 清洁组合物 |
EP4129417A4 (fr) * | 2020-04-01 | 2024-05-01 | Kao Corporation | Procédé d'application de maquillage |
US20230143138A1 (en) * | 2020-04-01 | 2023-05-11 | Kao Corporation | Makeup application method |
US20240335370A1 (en) * | 2021-08-02 | 2024-10-10 | Kao Corporation | Cosmetic composition |
FR3134972B1 (fr) * | 2022-04-28 | 2024-03-15 | Oreal | Kit de maquillage comprenant une composition de maquillage et une composition anhydre de fixation avec une résine trialkylsiloxysilylcarbamoyl pullulane |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0660286B2 (ja) | 1989-02-15 | 1994-08-10 | 信越化学工業株式会社 | 油性ペースト組成物 |
DE19733625A1 (de) * | 1997-07-28 | 1999-02-04 | Lancaster Group Gmbh | Dekorative kosmetische O/W-Emulsion |
US6027738A (en) * | 1997-10-31 | 2000-02-22 | E-L Management Corp. | Anhydrous matte cosmetic |
JP3689588B2 (ja) * | 1998-04-30 | 2005-08-31 | 株式会社資生堂 | 外用組成物 |
ES2290255T3 (es) * | 2001-02-16 | 2008-02-16 | L'oreal | Utilizacion cosmetica de un copolimero de vinilpirrolidona y de un alqueno para modificar el aspecto de la piel y/o de las semimucosas. |
US20030082221A1 (en) | 2001-09-27 | 2003-05-01 | Lavipharm Laboratories Inc. | Pullulan based film forming cosmetic compositions |
JP2004244333A (ja) * | 2003-02-12 | 2004-09-02 | Noevir Co Ltd | 油性化粧料 |
JP2006062995A (ja) * | 2004-08-25 | 2006-03-09 | Shiseido Co Ltd | しわ改善用皮膚外用剤 |
JP4570905B2 (ja) * | 2004-05-17 | 2010-10-27 | 株式会社資生堂 | 皮膚外用剤 |
FR2910285B1 (fr) * | 2006-12-20 | 2014-04-25 | Oreal | Produit cosmetique comprenant des composes silicones et du pmma |
EP2337544A2 (fr) * | 2007-04-30 | 2011-06-29 | Living Proof, Inc. | Utilisation d'inhibiteurs de la métalloprotéinase de la matrice pour les soins de la peau |
EP2025364A1 (fr) * | 2007-08-13 | 2009-02-18 | Procter & Gamble International Operations SA. | Compositions comprenant des particules chargées de colorant |
JP2010132567A (ja) * | 2008-12-02 | 2010-06-17 | Shiseido Co Ltd | 化粧料 |
CA2749153A1 (fr) * | 2009-01-27 | 2010-08-05 | Revlon Consumer Products Corporation | Produit pour les levres longue tenue |
JP2010229094A (ja) * | 2009-03-27 | 2010-10-14 | Shiseido Co Ltd | 凹凸補正用皮膚外用剤 |
JP5777213B2 (ja) * | 2011-10-04 | 2015-09-09 | 株式会社 資生堂 | 睫毛用化粧料 |
JP5795281B2 (ja) * | 2012-04-04 | 2015-10-14 | 信越化学工業株式会社 | 化粧料 |
JP6036530B2 (ja) | 2013-05-09 | 2016-11-30 | 信越化学工業株式会社 | 油性増粘剤、増粘油性組成物及び化粧料 |
KR101666267B1 (ko) * | 2014-02-25 | 2016-10-13 | (주)셀트리온 | 화장 지속성 및 유연감이 우수한 유중수형 메이크업 화장료 조성물 |
FR3059002A1 (fr) | 2016-11-23 | 2018-05-25 | Lvmh Rech | Composition filmogene a base de pullulan, et ses utilisations dans des compositions cosmetiques pour le maquillage et/ou le soin des matieres keratiniques, de la peau et des levres |
-
2017
- 2017-12-15 FR FR1762272A patent/FR3075054B1/fr active Active
-
2018
- 2018-12-13 JP JP2019566582A patent/JP2021506736A/ja active Pending
- 2018-12-13 EP EP18833098.9A patent/EP3723708A1/fr active Pending
- 2018-12-13 US US16/619,035 patent/US11253462B2/en active Active
- 2018-12-13 KR KR1020197036012A patent/KR20200099963A/ko not_active Application Discontinuation
- 2018-12-13 WO PCT/FR2018/053256 patent/WO2019115949A1/fr unknown
- 2018-12-13 CN CN201880038237.5A patent/CN110730653B/zh active Active
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CN110730653A (zh) | 2020-01-24 |
JP2021506736A (ja) | 2021-02-22 |
WO2019115949A1 (fr) | 2019-06-20 |
US11253462B2 (en) | 2022-02-22 |
US20200138692A1 (en) | 2020-05-07 |
FR3075054B1 (fr) | 2020-12-25 |
FR3075054A1 (fr) | 2019-06-21 |
KR20200099963A (ko) | 2020-08-25 |
CN110730653B (zh) | 2023-08-22 |
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