WO2003011243A1 - Emulsion inverse contenant de la dhea - Google Patents
Emulsion inverse contenant de la dhea Download PDFInfo
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- WO2003011243A1 WO2003011243A1 PCT/FR2002/002569 FR0202569W WO03011243A1 WO 2003011243 A1 WO2003011243 A1 WO 2003011243A1 FR 0202569 W FR0202569 W FR 0202569W WO 03011243 A1 WO03011243 A1 WO 03011243A1
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- 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
- A61K8/63—Steroids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P15/00—Drugs for genital or sexual disorders; Contraceptives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P15/00—Drugs for genital or sexual disorders; Contraceptives
- A61P15/02—Drugs for genital or sexual disorders; Contraceptives for disorders of the vagina
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
Definitions
- the invention relates to a new composition of reverse emulsion type containing DHEA and / or its precursors or chemical and / or biological derivatives, and its uses in cosmetics and in dermatology.
- Human skin is made up of two compartments, namely a deep compartment, the dermis, and a superficial compartment, the epidermis.
- the dermis provides the epidermis with solid support. It is also its nourishing element. It is mainly made up of fibroblasts and an extracellular matrix itself composed mainly of collagen, elastin and a substance, called the fundamental substance. There are also leukocytes, mast cells or tissue macrophages. It also contains blood vessels and nerve fibers.
- the epidermis is in contact with the external environment. Its role is to protect the body from dehydration and external aggressions, whether chemical, mechanical, physical or infectious.
- the natural human epidermis is mainly composed of three types of cells which are the keratinocytes, very majority, the melanocytes and the Langerhans cells. Each of these cell types contributes by its own functions to the essential role played in the body by the skin.
- Epidermal lipids are synthesized mainly in the living epidermis. They are essentially made up of phospholipids, sphingolipids, cholesterol, free fatty acids, triglycerides, cholesterol esters and alkanes. During cell differentiation, the phospholipids, the role of which is to develop the fluid structure of the cell membranes of the living layers of the epidermis, are gradually replaced by a mixture composed mainly of fatty acids, ' cholesterol and sphingolipids, essential constituents of the stratum corneum of the epidermis.
- the lipids of the inter-corneocyte cement of the skin are organized in lamellar bi-layers or sheets and participate in the cohesion of the stratum corneum in order to maintain the integrity of the barrier and its protective, anti-penetration and anti-irritation in particular.
- an activation of the metabolism in the living cells of the epidermis, or an increase in cell proliferation in the living layers, will result in an increase in the content of the epidermis in phospholipids (sphingomyelin I phosphatidylinositol or phospholipids membranes, respectively) and will result in an increase in the size or number of living cells, i.e. thickening of the epidermis.
- phospholipids sphingomyelin I phosphatidylinositol or phospholipids membranes, respectively
- Atrophy of the epidermis has also been identified as one of the histological signs of photoaging (Gilchrest B.A., Skin and Aging Processes, 1989, CRC Press).
- This process is also present in other mucous membranes, especially during vulvar or vaginal atrophy.
- DHEA or dehydroepiandrosterone also known as 3-beta-hydroxyandrosterone-5-en-17-one or dehydroisoandrosterone or trans- dehydroandrosterone or prasterone, is a natural steroid produced mainly by the adrenal cortex.
- Exogenous DHEA administered topically or orally, is known for its ability to promote keratinization of the epidermis (JP-07196467) and to treat dry skin by increasing endogenous production and the secretion of sebum and thereby strengthening l barrier effect of the skin (US4,496,556).
- the use of DHEA to remedy atrophy of the dermis by inhibiting the loss of collagen and connective tissue has also been described in patent US Pat. No. 5,843,932.
- the Applicant has demonstrated the ability of DHEA to combat the papery appearance of the skin (FR-2803513), to modulate the pigmentation of the skin and of the hair (EP-1092423) and to combat atrophy of the epidermis.
- DHEA has the difficulty of being very poorly soluble in the cosmetic or pharmaceutical solvents commonly used such as water, polar or non-polar oils.
- DHEA dissolves only with difficulty in aqueous media, which limits its formulation in cosmetic or dermatological compositions applied topically or orally. It therefore tends to recrystallize.
- DHEA indeed presents several polymorphic forms whose type and distribution can be poorly controlled, because dependent on environmental conditions and on the manner of preparing the active principle (Chang et al, J. Pharm. Sci. 84: 1169-1179 ( 1995)). There are between three and five anhydrous polymorphic forms and at least three hydrated forms. These polymorphic forms can only be distinguished by analytical techniques such as X-ray diffraction, infrared spectroscopy and DSC (differential scanning calorimetry) (WO-00/54763). Depending on the source of DHEA supply, there may be a variable polymorphic distribution of the raw material, which can potentially lead to significant variations in therapeutic bioavailability and efficacy.
- reverse emulsion by reverse emulsion is understood to mean an emulsion of the hydrophilic phase dispersed type in the lipophilic phase
- reverse emulsion is understood to mean an emulsion of the hydrophilic phase dispersed type in the lipophilic phase
- hydrophilic solubilizers such as propylene glycol
- solubilizers such as propylene glycol was also not obvious since it had been shown in humans of skin intolerance phenomena, for example in healthy humans (Motoyoshi et al. Cosmet and toiletries, 99, 83-89, 1984) where propylene glycol appeared as an irritant in high concentrations but only under occlusion.
- FR-2777194 describes a cosmetic or dermatological composition of the water-in oil type containing 10 to 50% of a saturated liquid hydrocarbon branched in C20 to C40 or of a mixture of such- 'hydrocarbons, 1 to 47% of a natural phospholipid or a mixture of natural phospholipids and 50 to 80% water. Even if DHEA is mentioned generically in an extensive list of active compounds, no concrete data is provided.
- the phospholipids exhibit limited chemical stability with respect to oxidation phenomena which did not encourage the person skilled in the art to use this document in his search for stable formulations based on DHEA or the like.
- composition making it possible to respond to one or more of the following aspects: having good cold and heat stability, in particular as regards the maintenance of the size of the globules and the absence of phase shift. , have good resistance to oxidation phenomena, allow good stability and bioavailability of DHEA and / or its precursors or chemical and / or biological derivatives, have good skin tolerance. It is also useful to be able to have a composition allowing a high dispersed volume fraction. It is also useful for the preparation of such compositions to benefit from an advantageous method of preparation.
- the Applicant has surprisingly developed a formulation of the glycol in oil type which makes it possible to overcome the various problems linked to the aspects mentioned above, in particular making it possible to have good stability of the composition as such. but also to allow good stability and bioavailability of DHEA and / or its precursors or chemical and / or biological derivatives which it contains.
- the composition according to the invention also has the advantage of having good skin tolerance and of allowing a high dispersed volume fraction.
- the invention therefore relates to a composition containing DHEA and / or its precursors or derivatives, chemical and / or biological, characterized in that the composition is a reverse emulsion containing a dispersed hydrophilic phase glycolic or hydroglycolic, a lipophilic continuous phase and an HLB emulsifier between 2 and 7.
- HLB Hydrophilic / Lipophilic Ratio or "Hydrophilic / Lipophilic Balance (HLB)" which corresponds to the balance between the dimension and the strength of the hydrophilic group and the dimension and the strength of the lipophilic group of the emulsifier .
- the invention also makes it possible to overcome the problems caused by the polymorphism of DHEA and also to obtain good bioavailability of the active ingredient in the skin, DHEA being used in a solubilized form.
- solubilized form is meant a dispersion in the molecular state in a liquid, no crystallization of the active agent being visible to the naked eye or even under a cross-polarized optical microscope.
- the present invention therefore consists in making reverse emulsions, containing a hydrophilic glycolic or hydroglycolic phase, perfectly stable (size of the globules and viscosity), even with a high dispersed volume fraction, showing no significant recrystallization of DHEA, and / or its precursors. or chemical and / or biological derivatives.
- DHEA precursors is meant its immediate biological precursors or substrates, as well as its chemical precursors.
- biological precursors are ⁇ 5-pregnenolone, 17 ⁇ -hydroxy pregnenolone without this list being limiting.
- chemical precursors are sapogenins such as diosgenin (or spirost-5-en-3-beta-ol), hecogenin, hecogenin acetate, smilagenin and sarsapogenin, as well as natural extracts thereof. containing, in particular fenugreek and extracts of Dioscorea such as the wild yam root or "ild Yam", without this list being exhaustive.
- DHEA derivatives is understood to mean both its metabolic derivatives and its chemical derivatives.
- metabolic derivatives there may be mentioned in particular 7- -OH- DHEA, 7- ⁇ -OH-DHEA, 7-keto-DHEA, ⁇ 5 -androstene-3,17-diol and ⁇ 4- androstene-3, 17-dione, without this list being exhaustive.
- esters such as the esters of hydroxycarboxylic acids and of DHEA described in US5736537 or the other esters such as salicylate, acetate, valerate and enanthate of DHEA.
- esters such as the esters of hydroxycarboxylic acids and of DHEA described in US5736537 or the other esters such as salicylate, acetate, valerate and enanthate of DHEA.
- Other chemical derivatives of DHEA suitable for carrying out the present invention are the derivatives of formula (1):
- Ri and R 2 are independently chosen from: • a C ⁇ -C 12 alkyl group, saturated or unsaturated, linear, branched or cyclic which may optionally contain one or more heteroatoms, and optionally substituted by one or more groups chosen from -OR 'and / or -SR and / or -COOR 'and / or - NR'R' and / or halogen and / or sulfate and / or phosphate and / or aryl and / or heterocycle, said heterocycle can advantageously be chosen from an indole, a pyrimidine, piperidine, morpholine, pyran, furan, piperazine, pyridine;
- an alkylcarbonyl group the CC 24 alkyl part of which is saturated or unsaturated, linear, branched or cyclic, and optionally substituted by one or more groups chosen from -OR 'and / or -SR' and / or -COOR 'and / or -NR'R 'and / or halogen and / or sulfate and / or phosphate and / or aryl and / or heterocycle, said heterocycle possibly advantageously being chosen from an indole, a pyrimidine, a piperidine, a morpholine, a pyran, a furan, a piperazine, a pyridine;
- an arylcarbonyl group preferably a phenylcarbonyl, or an arylalkylcarbonyl group, preferably a benzylcarbonyl, optionally substituted by one or more groups -OR 'and / or -SR' and / or -COOR 'and / or -NR'R' and / or halogen and / or aryl and / or heterocycle;
- R ' is chosen from a hydrogen atom, a C 1 -C 12 , preferably CC 6 , saturated or unsaturated, linear, branched or cyclic alkyl group which may optionally contain one or more heteroatoms, optionally functionalized by one or more groups -OR ", -COOR", halogen, -NR “R”; or by an aryl group, preferably a phenyl, optionally functionalized by one or more groups - OR ", -COOR", halogen or -NR'R ";
- R represents a hydrogen atom, an alkyl chain, preferably CC 6 , saturated or unsaturated, linear, branched or cyclic, it being understood that in each of the groups -NR'R 'and -NR" R ", the substituents R ', respectively R ", are the same or different.
- the diesters of 7-OH-DHEA and more preferably 3-O-acetyl-7-benzoyloxy- dehydroepiandrosterone which is available in particular from the company GATTEFOSSE under the trade name 3-acetoxy-7-benzoate DHEA.
- the composition according to the invention is preferably suitable for topical application to the skin, the integuments and / or the mucous membranes. It generally contains a physiologically acceptable medium and an amount of DHEA-based compound sufficient to obtain the desired effect.
- the weight proportion of DHEA, and / or its precursors or chemical and / or biological derivatives, relative to the total weight of the composition can thus be between 0.001% and 20% (weight / weight), for example between 0.1 and 20%, in particular between 0.2% and 10%, in particular between 0.2 and 4%, for example between 0.2 and 2%.
- the glycols to be considered in the present invention can be defined as alkylene or polyalkylene glycol.
- alkylene and polyalkylene glycols C1 to C6
- alkylene glycols C1 to C6
- ethylene glycol polyethylene glycol (2 to 20 monomers
- propylene glycol dipropylene glycol
- butylene glycol pentylene glycol
- Phexylene glycol They can be oxyethylenated or not (2 to 50 EO).
- the preferred ones according to the invention are hexylene glycol, propylene glycol and dipropylene glycol.
- the glycols which can be used according to the invention will advantageously have as solubility parameter a ⁇ p of less than 10, it being understood that the 3 Hansen solubility parameters: ⁇ d, ⁇ p and ⁇ h characterize, for a given constituent, the energies corresponding respectively to polar, dispersive interactions and of the hydrogen bonding type existing between the molecules of this constituent, ⁇ p characterizing more particularly the Debye interaction forces between dipoles and being a function of the number of oxygen atoms in the formula of the given constituent (S. paint Technology, 30 , 195, 1967, "The three dimensional solubility parameter-Key to paint component affinities").
- the volume fraction of the hydrophilic phase dispersed in the emulsion according to the invention ranges from 10 to 90% relative to the total volume of the emulsion. It can be exclusively glycolic or hydroglycolic, it being understood that DHEA, and / or its precursors or chemical and / or biological derivatives, are preferably dissolved therein.
- the volume proportion of glycols (relative to the total volume of the dispersed phase) is between 10 and 100%, for example between 30 and 100%, in particular between 60 and 1.00%, and preferably between 80 and 100%.
- .5 glycols preferably between 30 and 50% of .5 glycols (proportion relative to the total volume of the dispersed phase) will be used.
- the invention thus also relates, in a particular way, to a composition as defined above, characterized in that the water activity a w of the hydrophilic phase is less than 0.85.
- the water activity a w of a medium containing water is the ratio of the water vapor pressure of the product "P H2 o product” and the vapor pressure of pure water “pure PH2O At the same temperature. It can also be expressed as the ratio of the number of water molecules "N H2 o” to the number of total molecules "NH 2 O + Ncorps issous", which takes into account those of the dissolved bodies "N CO ⁇ s dissolved”. 0 It is given by the following formulas:
- a cosmetic or dermatological composition has a water activity of around 0.95 to 0.99.
- a water activity of less than 0.85 represents a significant decrease.
- Emulsifiers are natural or synthetic substances formed from a hydrophilic or polar part and from a lipophilic part or nonpolar. These are amphiphilic molecules since they have a double polarity. Emulsifiers are characterized by their HLB; if the HLB is high, the hydrophilic fraction is predominant, if the HLB is low, the lipophilic part predominates.
- polymeric emulsifiers are preferably included, which are characterized by a high molar mass and a non-linear structure which allows greater anchoring at the water / oil interface than that obtained with emulsifiers of the monomer type.
- the emulsifiers which it is possible to use according to the invention, alone or as a mixture, are those making it possible to make inverse emulsions and having an HLB of less than 7.
- the preferred emulsifiers are organopolysiloxanes such as: - E1) Poly Alkyl methicone Copolyols (Polyalkyl methylsiloxane oxyalkylenated optionally crosslinked) containing: Alkyl chains from C6 to C20, saturated or not, linear or branched a Polyoxyethylenated unit of 1 to 50 EO (Ethylene Oxide) and / or
- the organopolysiloxanes of the composition of the invention contain in particular one or more oxyalkylenated and in particular oxyethylenated (OE) groups, for example from 1 to 40 oxyalkylenated units, preferably from 1 to 20, better still from 10 to 20, more preferably from 12 to 20 and even better from 12 to 18 oxyalkylene units, which can form polyoxyalkylene and in particular polyoxyethylene chains.
- OE oxyethylenated
- These groups can be pendant or at the end of the chain.
- the silicon atoms carrying these groups are advantageously about 1 to 10 and better , from 1 to 6.
- the silicone structure forming the polymer backbone of the organopolysiloxane with oxyalkylenated group (s) is advantageously a polydimethylsiloxane (PDMS) structure in which optionally a part of the methyl groups is substituted by C2 to C30 and preferably C8 to C24, and better still from C10 to C20 or phenyl, either at the end of the chain or pendant.
- PDMS polydimethylsiloxane
- silicone emulsifiers such as alkyldimethicone copolyols such as Abil EM-90 or the mixture of dimethicone copolyol and cyclomethicone, sold by the company Dow Corning under the name 3225C Formulation Aid, will therefore be used as emulsifiers of type E1 or E2.
- laurylmethicone copolyol sold under the name of Emulsifier 10 by Dow Corning, or mixtures based on a silicone polymer such as cetyl dimethicone copolyol with polyglyceryW isostearate and hexyl laurate sold under the name of Abil WE09 by Goldschmidt, ⁇ bil EM 97 from Goldschmidt (Dimethicone copolyol & cyclomethicone), Wacker SPG 128 VP from Wacker (cyclomethicone and octyldimethicone methoxy glycosyl), or Silwax WD-IS (Dimethicone copolyol iso-stearate)
- a silicone polymer such as cetyl dimethicone copolyol with polyglyceryW isostearate and hexyl laurate sold under the name of Abil WE09 by Goldschmidt, ⁇ bil EM 97 from Goldschmidt (
- siloxanes for example Lambent Silwax S (Dimethiconol stearate),
- esters of alkoxylated carboxylic acids such as polyhydroxy alkyl esters of PEG, for example Arlacel P 135 from Uniqema (PEG-30 dipolyhydroxystearate).
- HLB emulsifiers between 2 and 7 will be used, preferably a WL silicone W / O emulsifier between 2 and 7, preferably a polymeric HLB silicone W / emulsifier between 2 and 7.
- the reverse emulsion of the invention may alternatively be produced and stabilized advantageously with the following emulsifiers or combinations of emulsifying nature.
- the organopolysiloxane with oxyalkylenated group (s) may comprise one or more silicone skeleton (s) linked together by one or more oxyalkylenated and preferably oxyethylenated groups as defined above, or by one or more alkylene groups, the number of alkylene groups ranging from 1 to 30 and preferably from 1 to 20. Preferably, it comprises at least two polymeric backbones linked together.
- the silicone backbone (s) of the organopolysiloxanes of the composition according to the invention contain from 26 to 80 silicon atoms.
- the elastomeric organopolysiloxanes used in the composition according to the invention are partially or completely crosslinked and of three-dimensional structure. Included in a lipophilic phase, they transform, depending on the rate of lipophilic phase used, from a spongy product when used in the presence of low lipophilic phase contents, into a homogeneous gel in the presence of quantities of phase lipophilic higher. The gelling of the lipophilic phase by these elastomers can be total or partial.
- elastomeric organopolysiloxanes can be in the form of a powder, the particles constituting this powder generally having a size ranging from 0.1 to 500 ⁇ m, preferably from 3 to 200 ⁇ m and better still from 3 to 50 ⁇ m, and possibly being spherical, flat or amorphous with, preferably, a spherical shape. They can also be in the form of an anhydrous gel containing the elastomeric organopolysiloxane dispersed in an oily phase.
- the organopolysiloxanes of the composition of the invention are, for example, that sold under the reference KSG 21 by the company Shin Etsu or the product of Example 3 (synthetic example) of US Pat. No. 5,412,004.
- Oligomers and polymers consisting of a polyolefin apolar part and at least one polar part. They can have a block or comb type structure.
- the polyolefin apolar part comprises at least 40 carbon atoms and preferably from 60 to 700 carbon atoms. It is important that this part includes at least 40 carbon atoms to achieve the object of the invention. If there are less than 40 carbon atoms, you don't get a very stable system.
- This apolar part can be chosen from polyolefins such as oligomers, polymers and / or copolymers of ethylene, ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl -1 -butene, 3-methy 1-1 -butene, 1-hexene, 1-heptene, 1-octene, 1-dececene, 1-undecene, 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene and 1- octadecene. These polyolefins are hydrogenated or not.
- the oligomers or polymers derived from polyolefins used in the composition of the invention comprise at least one polar part.
- This polar part gives the polyolefin derivatives amphiphilic properties.
- these oligomers or polymers lower the interfacial tension (water / oil, that is to say between aqueous phase and oily phase) by at least 10 mN / m when they are present at a concentration of 0.01% in weight relative to the total weight of the oily phase.
- the polyolefin with succinic termination described below and marketed under the name L2724 by the company Lubrizol at a concentration of 0.01% by weight relative to the total weight of the oily phase, lowers the interfacial tension by 15 mN / m at the interface of an aqueous phase consisting of a 1% aqueous solution of MgSO4, and an oily phase comprising a mixture of oils (isohexadecane / hydrogenated polyisobutene / volatile silicone in a ratio 8/6/4 ).
- the polar part of the oligomeric or polymeric emulsifiers of the invention can be anionic, cationic, nonionic, zwitterionic or amphoteric. It consists, for example, of polyalkylene glycols or polyalkylene imines, or alternatively of acids or dicarboxylic acids, their anhydrides or their derivatives, and their mixtures. Oligomeric or polymeric emulsifiers with a polar carboxylic acid part may for example be obtained from the reaction between a polyolefin and at least one carboxylic acid or anhydride chosen from the group comprising maleic acid, maleic anhydride, fumaric acid, aciditaconic, citraconic acid, mesaconic acid, aconitic acid.
- the polar part is constituted by succinic acid or anhydride, their ester or amide derivatives, the corresponding alkali, alkaline earth or organic ion salts, or alternatively by polyoxyethylene.
- the emulsifiers derived from polyoxyethylene can for example be chosen from polyisoprene-polyoxyethylene diblock polymers, poly (ethylene-co-propylene) -polyoxyethylene polymers and mixtures thereof. These polymers are described in the publication by Allgaier, Poppe, Willner, Richter (Macromolecules, 1997, vol. 30, p.1582-1586).
- the emulsifiers derived from succinic acid or anhydride can be chosen in particular from the polyolefin derivatives of succinic acid or anhydride described in patents US-4,234,435, US-4,708,753, US-5, 129,972, US-4,931, 110 , GB-2,156,799 and US-4,919,179 incorporated here for reference.
- the polyolefin part can consist for example of polyisobutylene, hydrogenated or not, of molecular weight ranging from 400 to 5000.
- the succinic part can be esterified, amidified in the salt form, it is ie it can be modified by alcohols, amines, alkanolamines or polyols, or can also be in the form of alkali or alkaline earth metal salts, of ammonium or of organic base such as the salts diethanolamine and triethanolamine.
- Esterified or amidated succinically terminated polyolefins are reaction products of (a) a succinically terminated polyolefin, and (b) an amine or an alcohol, to form an amide or an ester.
- amine used here includes all types of amines including alkanolamines.
- the alcohols may, for example, be primary, secondary or tertiary mono-amines, these amines possibly being aliphatic, cycloaliphatic, aromatic, heterocyclic, saturated or unsaturated.
- the alcohols can be mono- or poly-alcohols.
- Mono-alcohols include primary, secondary or tertiary aliphatic alcohols, and phenols.
- the polyalcohols can for example be chosen from aliphatic, cycloaliphatic, aromatic and heterocyclic polyalcohols.
- Polyolefins with modified succinic termination (esterified or amidified) and their preparation process are described in particular in document US Pat. No. 4,708,753 which is incorporated here for reference.
- polystyrene resin As polyolefins with succinic termination, mention may in particular be made of polyisobutylenes with modified succinic termination, such as the products sold under the names L2724 and L2721 by the company Lubrizol.
- polymeric emulsifier which can be used in the invention is the product of the reaction of maleic anhydride with polyisobutylene, such as the product marketed under the name Glissopal SA by BASF.
- the amount of oligomer (s) or emulsifying polymer (s) in the composition of the invention can range, for example, from 0.1 to 10% by weight of active material, preferably from 0.5 to 5 % by weight and better still from 1 to 3% by weight relative to the total weight of the composition.
- oligomers or polymers derived from polyolefins can be used. According to a preferred embodiment of the invention, the oligomers or polymers derived from polyolefins are the only emulsifiers used in the composition according to the invention.
- Alkylpolyglycosides having an HLB of less than 7, associated with an oxyalkylenated polydimethylsiloxane preferably contains from 14 to 22 carbon atoms and can in particular be an unsaturated straight chain or a branched chain, and more particularly the oleyl or isostearyl chain.
- the alkylpolyglycosides used according to the present invention can be more particularly represented by the following general formula (I):
- R represents an unsaturated linear alkyl radical or a branched alkyl radical, comprising from 14 to 24 carbon atoms
- G represents a reduced sugar comprising from 5 to 6 carbon atoms
- x denotes a value ranging from 1 to 15.
- Alkylpolyglycosides preferred according to the present invention are compounds of formula (I) in which R denotes more particularly an alkyl radical containing from 16 to 22 carbon atoms, G denotes glucose, fructose or galactose, x is a value ranging from 1 to 4 and more particularly from 1 to 2.
- R is an unsaturated linear alkyl radical (that is to say alkylene radical) or a branched alkyl radical.
- the unsaturated alkyl radical can comprise one or more ethylenic unsaturations, and in particular one or two ethylenic unsaturations.
- the radical R has 18 carbon atoms and denotes in particular an oleyl radical (unsaturated radical in C18) or isostearyl (radical saturated in C18), G denotes glucose and x is a value ranging from 1 to 2.
- the alkylpolyglycoside used in the emulsion of the invention is preferably chosen from the group comprising isostearyl-glucoside, oleyl-glucoside and their mixtures.
- the oxyalkylenated polydimethylsiloxanes considered are those described in paragraph E1 above.
- the composition according to the invention will contain in particular, expressed as a percentage by weight, from 0.5 to 8% of emulsifier, for example from 0.5 to 5%, preferably between 3 and 5%, relative to the total weight of the composition.
- the ratio (co-emulsifier / emulsifier) ) will advantageously be less than 1.5 and preferably less than 0.75.
- - Alkyl or poly alkyl sorbitan esters polyoxyethylenated or not with between 1 and 5 alkyl chains between C10 and C20 saturated or not, branched or not, and with from 0 to 40 EO (for example: sorbitan monolaurate 20OE or sorbitan monooleate 200 OE (Uniqema Tween 80))
- a co-solvent of DHEA having a lower evaporation temperature at 100 ° C, preferably linear or branched hydrophilic alcohols from C1 to C4, such as ethanol and isopropanol.
- the preparation of the emulsion according to the invention has been found to require little mechanical or thermal energy compared to the preparations of other reverse emulsions already known.
- the composition of the invention may also contain the adjuvants usual in the cosmetic and dermatological fields, such as hydrophilic or lipophilic gelling agents, humectants such as glycerin and sorbitol, hydrophilic or lipophilic active agents, phase thickeners fatty, preservatives antioxidants, electrolytes, solvents, perfumes, fillers, filters, pigments, odor absorbers and coloring matters.
- the amounts of these various adjuvants are those conventionally used in the fields under consideration, and for example from 0.01 to 20% of the total weight of the composition.
- adjuvants depending on their nature, can be introduced into the lipophilic phase or into the hydrophilic phase
- adjuvants as well as their concentrations, must be such that they do not harm the cosmetic or dermatological properties of DHEA and / or its precursors or chemical and / or biological derivatives, in the composition according to the invention.
- oils which can be used for the continuous lipophilic phase in the emulsions according to the invention
- oils and in particular mineral oils (petroleum jelly oil), oils of vegetable origin (avocado oil, soybean oil) can be used.
- oils of animal origin lanolin
- synthetic oils perhydrosqualene
- silicone oils cyclomethicone
- fluorinated oils perfluoropolyethers
- Fatty alcohols such as cetyl alcohol, fatty acids, waxes and gums and in particular silicone gums can also be used as fats.
- non-oxidizable fats are used for the oils of the continuous lipophilic phase, which are preferably chosen from those of silicone type, those of ester type or those of mineral type.
- the lipophilic phase is non-solvent for the. DHEA.
- hydrophilic gelling agents mention may in particular be made of carboxyvinyl polymers (carbomers), acrylic copolymers such as acrylate / alkyl acrylate copolymers, polyacrylamides, polysaccharides, natural gums and clays, and, as lipophilic gelling agents, cite modified clays such as bentones, metal salts of fatty acids and hydrophobic silica.
- isoflavonoids As active agents, isoflavonoids, metalloproteinase inhibitors, carotenoids, anti-glycation compounds, NO-synthase inhibitors, vitamins, desquamating agents, compounds which increase the synthesis of glycosaminoglycans, anti- irritants, compounds • reducing irritation of neurogenic origin, muscle relaxants and depigmentants.
- composition according to the invention has a cosmetically acceptable feel, good skin tolerance, stability (by stability is meant physical stability, that is to say absence of phase shift and maintenance of the size of the globules and not recrystallization of the active) in the cold (at 4 ° C) and in the heat (45 ° C) over a long period, for example over 2 months, with a stable viscosity.
- the invention also relates to a cosmetic or dermatological composition for topical application to the skin, the integuments and / or the mucous membranes, in the form of a reverse emulsion containing a hydrophilic glycolic or dispersed hydroglycolic phase and a continuous lipophilic phase, characterized in that it contains, in a physiologically acceptable medium (that is to say compatible with topical application to the skin, integuments and / or mucous membranes), expressed as a percentage by weight:
- glycols - from 30 to 100% glycols - from 0.5 to 8% of HLB emulsifier between 2 and 7,
- the dispersed hydrophilic phase has a water activity of less than 0.85.
- the invention also extends to a composition which is a triple emulsion of hydrophilic phase / lipophilic phase / hydrophilic phase type comprising an external hydrophilic phase, and a lipophilic phase constituting with an internal hydrophilic phase a reverse emulsion (called primary reverse emulsion in as part of this triple emulsion) according to the invention.
- the present invention relates to a triple emulsion of hydrophilic phase / lipophilic phase / hydrophilic phase type where the internal hydrophilic phase of the triple emulsion has a water activity value less than or equal to 0.85, in particular in order to improve the stability of the active ingredient present in the internal hydrophilic phase.
- the water activity value less than or equal to 0.85 is obtained by incorporating an effective amount of glycol.
- effective quantity is understood to mean a sufficient quantity of polyol to obtain a low water activity value, that is to say a water activity value less than or equal to 0.85.
- the primary reverse emulsion constitutes from 20 to 35% and more particularly approximately 25% by weight of the triple emulsion.
- the triple emulsion is prepared in a conventional manner by preparation of the primary emulsion and incorporation of a determined quantity of the primary emulsion in the external hydrophilic phase.
- the invention also extends to a triple emulsion of hydrophilic phase / lipophilic phase / hydrophilic phase type comprising an external hydrophilic phase, a lipophilic phase constituting with an internal hydrophilic phase a reverse emulsion (called primary reverse emulsion in the context of this emulsion triple) according to the invention comprising a gelled external hydrophilic phase containing:
- At least one emulsifying copolymer consisting of a majority fraction of a monoolefinically unsaturated carboxylic acid monomer in C3-C3 or of its anhydride and of a minority fraction of fatty ester monomer of acrylic acid, and
- the lipophilic phase of the triple emulsion according to the invention contains at least one silicone oil and / or a silicone emulsifier.
- the emulsifying copolymers which can be used in the triple emulsion according to the present invention are prepared by polymerizing a preponderant amount of a monoolefinically unsaturated carboxylic monomer or its anhydride, to a smaller amount of fatty chain acrylic ester monomer.
- the term fatty chain is understood to mean a linear or branched alkyl radical containing from 8 to 30 carbon atoms.
- the amount of carboxylic monomer or its anhydride is preferably from 80 to 98% by weight and more particularly from 90 to 98% by weight, while the acrylic ester monomer is present in amounts ranging from 2 to 20% by weight. weight and more particularly from 1 to 10% by weight, the percentages being calculated relative to the weight of the two monomers.
- the preferred carboxylic monomers are chosen from those corresponding to the following formula (I):
- the particularly preferred carboxylic monomers are chosen from acrylic acid, methacrylic acid or their mixtures.
- the fatty chain acrylic ester monomers are preferably chosen from those corresponding to formula (II) below:
- Ri is chosen from the group formed by hydrogen, the methyl radical and the ethyl radical, and R 2 is a C 3 -C 30 alkyl radical.
- the particularly preferred ester monomers are those for which R 1 is hydrogen or a methyl radical and R 2 is an alkyl radical in
- the emulsifying copolymers can optionally be crosslinked using a crosslinking agent used in an amount ranging from 0.1 to 4%, preferably from 0.2 to 10% by weight relative to the total weight of carboxylic monomers and acrylic ester monomers.
- the particularly preferred emulsifying copolymers are those having a viscosity measured with the BROOKFIELD viscometer in a 2% water solution at 25 ° C, less than or equal to 5000 cps (5 Pa.s) and more preferably of the order of around 3000 cps (3 Pa.s).
- Use is more particularly made of an acrylate / C 10 -C 30 -alkylacrylate copolymer and in particular that sold under the name PEMULEN TR 1 by the company GOODRICH.
- the emulsifying copolymer is used in the triple emulsion according to the invention in a concentration ranging, for example, from 0.05 to 3% and preferably from 0.1 to 1%, and better still from 0.2 to 0.6 % of the total weight of the emulsion.
- the invention also covers the use of the new reverse emulsion as described above in cosmetics and dermatology.
- composition thus finds application in cosmetics, in particular for treating and / or protecting the skin, mucous membranes or keratin fibers, ie the hair and the eyelashes.
- composition according to the invention also finds application in the prevention and / or treatment of the signs of chronological or actinic skin aging as well as in the treatment of certain pathologies.
- the present invention therefore also relates to the cosmetic use of the composition mentioned above for preventing and / or treating chronological or actinic aging, in particular:
- composition for the cosmetic treatment of the scalp, in particular for preventing or treating canities.
- the present invention also relates to the cosmetic use of the composition according to the invention for attenuating pigment spots
- the invention also extends to the use of a composition according to the invention for manufacturing a pharmaceutical preparation, in particular for manufacturing a pharmaceutical preparation intended to prevent or treat atrophy of the skin or mucous membranes, in particular intended to prevent or treat vulvar or vaginal atrophy.
- the invention also covers pharmaceutical preparations and medicaments obtained from the compositions according to the invention.
- Phase B1 DHEA is dissolved in Propylene Glycol.
- Phase B2 The electrolyte (MgS04 or NaCI) is dissolved in water.
- the hydrophobic constituents are mixed and heated to 50 ° C.
- Phase B is incorporated into Phase A with moderate mechanical stirring.
- the DHEA which can be used according to the invention is for example available from the company AKZO NOBEL
- Emulsifier 10 (lauryl methicone copolyol) 5.00% Cyclomethicone 15.00%
- Phase B1 Propylene Glycol 19.00%
- Emulsifier 10 (lauryl methicone copolyol) 3.00% Cyclomethicone 10.00%
- Phase B1 Propylene Glycol 75.00%
- Emulsify 10 (lauryl methicone copolyol) 3.00%
- Emulsify 10 (lauryl methicone copolyol) 3.00%
- Phase B1 Propylene Glycol 49.30% DHEA 1.00%
- a HAAKE VT 510 rheometer was used with an SVDIN measuring mobile. The rheograms were performed at 25 ° C by varying the shear rate over time, and by measuring the stress. The results obtained are collated in the table below:
- ⁇ o By flow threshold ( ⁇ o) is meant the force required (minimum shear stress) to overcome the cohesion forces of the Van der Waals type and cause the flow.
- DHEA is dissolved in Propylene Glycol at 55 ° C.
- Phase A The hydrophobic constituents are mixed and heated to 50 ° C.
- Phase B is incorporated into Phase A with moderate mechanical stirring at 50 ° C.
- Phase C The electrolyte is dissolved in water. Then the ethanol is incorporated. This phase is introduced at room temperature into the emulsion with moderate stirring.
- phase B is introduced into phase A with stirring of the blade or stator rotor type.
- the emulsion is made at a temperature below 40 ° C.
- a slightly viscous, stable composition is then obtained, showing no recrystallization of DHEA after at least 15 days at 4 ° C.
- Example 25 Study of the release and penetration of DHEA in a formulation according to the invention.
- the in vitro penetration release of DHEA and / or its precursors or chemical and / or biological derivatives in compositions according to the invention can be evaluated , on whole human skin.
- the tested formulation is applied for 16 hours on glass diffusion cells (3 mL; 1 cm 2 ).
- Non-dermatomal whole skin was used.
- the skin was fixed on a diffusion cell, the dermis being in contact with a saline solution physiological supplemented to 0.25% (w / w) with an emulsifier (receiving liquid).
- the system was maintained in static mode (no renewal of the receiving liquid as a function of time).
- the excess surface is removed, the receiving liquid and the skin are removed.
- the epidermis (stratum corneum included) is separated from the dermis.
- a total balance of the active ingredient is calculated taking into account the excess and the amounts found in the skin and in the receiving liquid.
- the active ingredient concentrations are determined using an HPLC assay with APCI / MS / MS detection (limit of quantification: 10 ng.mL "1 ).
- Topical applications of the compositions according to the invention are repeated for 2 weeks on the right ear of the internal face mice (except during the weekend).
- the formulations are placed in tubes, these being stored at room temperature. Each tube is identified by a label containing the study number, product name, formulation number, dose and expiry date.
- mice used are female Balb / C Albino Consanguine mice aged 7 - 8 weeks at the start of the study from IFFA CREDO, France, in batches of 8 mice.
- the animals are kept in acclimatization at least 5 days before the start of the study.
- the animals are weighed on D1, when being studied and placed in an individual cage.
- compositions to be tested 20 ⁇ L are applied to the right ear of the mice, internal face, using a multipette (Eppendorf 4780 set to position 2, fitted with its Combitip Eppendorf 0.5 mL tip).
- the treatments are made at the rate of one application per day, 5 days per week for 2 weeks, the duration of the treatment being variable depending on the results of the irritation.
- the animals are observed on D1 before the first treatment, and every other day until the end of the study.
- the ear thickness measurements are made using an oditest and the ear thicknesses and clinical observations are noted.
- the averages of ear thicknesses per batch and the areas under curves are calculated and represented by corresponding graphs and histograms.
- the corresponding statistical analyzes are made on ' Minitab, the tests used are Mann-withney and sample-t.
- composition according to the invention tested and its placebo, applied under the same conditions do not exhibit a significant irritation response. It is therefore considered to be non-irritant.
- Example 27 Measurement of the activation of lipogenesis by the formulations according to the invention.
- the animals are kept in individual cages throughout the duration of the study and have permanent access to water and food (Hamster RJ: AURA (IOPS Han).
- the temperature of the rooms is 22 +/- 2 ° C with a hygrometry of 55 +/- 15%.
- the manipulations carried out on animals are in accordance with the legislation in force on the use and protection of laboratory animals.
- Hamsters receive a daily dose of the formulations to be tested, placebos , negative controls or positive controls, topically for 10 days on the inner side of the right ear.
- the cartilage of the right and left ears is removed using a scalpel and skin biopsies with a diameter of 8 mm are carried out for lipid composition and histology analyzes.
- the different study groups are made up of 10 animals: 5 animals are intended for studying the lipid composition of the sebaceous glands by thin layer chromatography; 5 animals are intended for histological analysis.
- the skin taken from each animal is put into survival in 12-well culture plates containing DMEM medium supplemented with fetal bovine serum (10%), in the presence of antibiotics and antifungals.
- Radiolabeled acetate is added to the cultures and these are kept in an incubator at 37 ° C for a period of 6 hours.
- the biopsies are then collected and rinsed with PBS.
- the radiolabelled lipids are extracted into different mixtures of solvents according to the Blye & Dyer procedure and taken up in 400 ⁇ l of a dichloromethane / methanol mixture (2/1).
- the samples are then deposited in groups of 20 on 10x20 silica plates for HPTLC using a deposition robot (Camag-ATSIV).
- the formulation according to the invention allows the induction of lipogenesis in a dose-dependent manner on the treated skin while maintaining good skin tolerance.
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Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020047001627A KR100569639B1 (ko) | 2001-08-02 | 2002-07-18 | Dhea를 함유하는 역에멀젼 |
EP02791424A EP1414405B1 (fr) | 2001-08-02 | 2002-07-18 | Emulsion inverse contenant de la dhea |
MXPA04001007A MXPA04001007A (es) | 2001-08-02 | 2002-07-18 | Emulsion inversa que contiene dihidroepiandrosterona. |
DE60221020T DE60221020T2 (de) | 2001-08-02 | 2002-07-18 | Inverse emulsion mit dhea |
AU2002334011A AU2002334011B2 (en) | 2001-08-02 | 2002-07-18 | Invert emulsion containing DHEA |
CA002455358A CA2455358A1 (fr) | 2001-08-02 | 2002-07-18 | Emulsion inverse contenant de la dhea |
BR0211735-5A BR0211735A (pt) | 2001-08-02 | 2002-07-18 | Composições, composição cosmética ou dermatológica, uso cosmético de uma composição e uso de uma composição |
JP2003516475A JP2005500342A (ja) | 2001-08-02 | 2002-07-18 | Dheaを含む逆エマルション |
HU0401181A HUP0401181A3 (en) | 2001-08-02 | 2002-07-18 | Invert emulsion containing dhea |
US10/767,814 US20040219123A1 (en) | 2001-08-02 | 2004-01-30 | Invert emulsions comprising DHEA |
US12/168,356 US20090069279A1 (en) | 2001-08-02 | 2008-07-07 | Invert emulsions containing dhea |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0110398A FR2828100B1 (fr) | 2001-08-02 | 2001-08-02 | Composition de type emulsion inverse contenant de la dhea et/ou ses precurseurs ou derives, et ses utilisations en cosmetique et en dermatologie |
FR01/10398 | 2001-08-02 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/767,814 Continuation US20040219123A1 (en) | 2001-08-02 | 2004-01-30 | Invert emulsions comprising DHEA |
Publications (1)
Publication Number | Publication Date |
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WO2003011243A1 true WO2003011243A1 (fr) | 2003-02-13 |
Family
ID=8866242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/002569 WO2003011243A1 (fr) | 2001-08-02 | 2002-07-18 | Emulsion inverse contenant de la dhea |
Country Status (19)
Country | Link |
---|---|
US (2) | US20040219123A1 (fr) |
EP (1) | EP1414405B1 (fr) |
JP (1) | JP2005500342A (fr) |
KR (1) | KR100569639B1 (fr) |
CN (1) | CN1564676A (fr) |
AR (1) | AR034962A1 (fr) |
AT (1) | ATE366102T1 (fr) |
AU (1) | AU2002334011B2 (fr) |
BR (1) | BR0211735A (fr) |
CA (1) | CA2455358A1 (fr) |
DE (1) | DE60221020T2 (fr) |
ES (1) | ES2288566T3 (fr) |
FR (1) | FR2828100B1 (fr) |
HU (1) | HUP0401181A3 (fr) |
MX (1) | MXPA04001007A (fr) |
PL (1) | PL367698A1 (fr) |
RU (1) | RU2270665C2 (fr) |
WO (1) | WO2003011243A1 (fr) |
ZA (1) | ZA200400770B (fr) |
Cited By (5)
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---|---|---|---|---|
FR2830015A1 (fr) * | 2001-09-27 | 2003-03-28 | Berkem Sa | Compositions a base de derives de steroides |
FR2871699A1 (fr) * | 2004-06-17 | 2005-12-23 | Galderma Sa | Composition de type emulsion inverse contenant du calcitrol et du 17-propionate de clobetasol, et ses utilisations en cosmetiques et en dermatologie |
EP2251004A3 (fr) * | 2005-11-10 | 2012-02-01 | Galderma Research & Development | Composition pharmaceutique ou cosmétique, et procédé de solubilisation mixte pour préparer la composition |
US8268806B2 (en) | 2007-08-10 | 2012-09-18 | Endorecherche, Inc. | Pharmaceutical compositions |
US8835413B2 (en) | 2004-10-20 | 2014-09-16 | Endorecherche, Inc. | Sex steroid precursors alone or in combination with a selective estrogen receptor modulator and/or with estrogens and/or a type 5 cGMP phosphodiesterase inhibitor for the prevention and treatment of vaginal dryness and sexual dysfunction in postmenopausal women |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040223935A1 (en) * | 2003-04-09 | 2004-11-11 | L'oreal | Cosmetic composition containing a fatty acid glyceride, an alcohol and a silicone emulsifier |
FR2873573B1 (fr) * | 2004-08-02 | 2006-11-17 | Oreal | Emulsion eau-dans-huile comprenant une huile non-volatile non-siliconee, un tensioactif cationique, une polyolefine a partie's) polaire(s), et un alkylmonoglycoside ou alkylpolyglycoside |
EP1917954B1 (fr) * | 2006-10-13 | 2018-02-21 | Cognis IP Management GmbH | Emulsions métastables de type huile-dans-eau |
WO2009088109A1 (fr) * | 2008-01-04 | 2009-07-16 | Biospectrum, Inc. | Composition contenant de la diosgénine pour le blanchiment de la peau |
EP2986634B1 (fr) | 2013-04-19 | 2019-11-20 | University of Houston System | Formulations de dhea co-cristallines |
RU2640188C1 (ru) * | 2016-10-28 | 2017-12-26 | Рамиль Рафаилевич Рахматуллин | Средство для биологического омоложения |
US10722465B1 (en) | 2017-12-08 | 2020-07-28 | Quicksilber Scientific, Inc. | Transparent colloidal vitamin supplement |
US11344497B1 (en) | 2017-12-08 | 2022-05-31 | Quicksilver Scientific, Inc. | Mitochondrial performance enhancement nanoemulsion |
US11291702B1 (en) | 2019-04-15 | 2022-04-05 | Quicksilver Scientific, Inc. | Liver activation nanoemulsion, solid binding composition, and toxin excretion enhancement method |
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- 2002-07-18 PL PL02367698A patent/PL367698A1/xx not_active Application Discontinuation
- 2002-07-18 RU RU2004106024/15A patent/RU2270665C2/ru not_active IP Right Cessation
- 2002-07-18 DE DE60221020T patent/DE60221020T2/de not_active Expired - Lifetime
- 2002-07-18 JP JP2003516475A patent/JP2005500342A/ja active Pending
- 2002-07-18 AT AT02791424T patent/ATE366102T1/de not_active IP Right Cessation
- 2002-07-18 CA CA002455358A patent/CA2455358A1/fr not_active Abandoned
- 2002-07-18 MX MXPA04001007A patent/MXPA04001007A/es active IP Right Grant
- 2002-07-18 BR BR0211735-5A patent/BR0211735A/pt not_active IP Right Cessation
- 2002-07-18 AU AU2002334011A patent/AU2002334011B2/en not_active Ceased
- 2002-07-18 KR KR1020047001627A patent/KR100569639B1/ko not_active IP Right Cessation
- 2002-07-18 HU HU0401181A patent/HUP0401181A3/hu unknown
- 2002-07-18 EP EP02791424A patent/EP1414405B1/fr not_active Expired - Lifetime
- 2002-07-18 ES ES02791424T patent/ES2288566T3/es not_active Expired - Lifetime
- 2002-07-18 WO PCT/FR2002/002569 patent/WO2003011243A1/fr active IP Right Grant
- 2002-07-18 CN CNA028196287A patent/CN1564676A/zh active Pending
- 2002-08-01 AR ARP020102916A patent/AR034962A1/es not_active Application Discontinuation
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2004
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- 2004-01-30 ZA ZA200400770A patent/ZA200400770B/xx unknown
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2830015A1 (fr) * | 2001-09-27 | 2003-03-28 | Berkem Sa | Compositions a base de derives de steroides |
FR2871699A1 (fr) * | 2004-06-17 | 2005-12-23 | Galderma Sa | Composition de type emulsion inverse contenant du calcitrol et du 17-propionate de clobetasol, et ses utilisations en cosmetiques et en dermatologie |
WO2006005843A1 (fr) * | 2004-06-17 | 2006-01-19 | Galderma S.A. | Composition de type emulsion inverse contenant du calcitriol et du 17 proprionate de clobetasol, et ses utilisations en cosmetique et en dermatologie |
US8835413B2 (en) | 2004-10-20 | 2014-09-16 | Endorecherche, Inc. | Sex steroid precursors alone or in combination with a selective estrogen receptor modulator and/or with estrogens and/or a type 5 cGMP phosphodiesterase inhibitor for the prevention and treatment of vaginal dryness and sexual dysfunction in postmenopausal women |
US10076525B2 (en) | 2004-10-20 | 2018-09-18 | Endorecherche, Inc. | Sex steroid precursors alone or in combination with selective estrogen receptor modulators for the prevention and treatment of dyspareunia in postmenopausal women |
US10478443B2 (en) | 2004-10-20 | 2019-11-19 | Endorecherche, Inc. | Sex steroid precursors alone or in combination with selective estrogen receptor modulators for the prevention and treatment of sexual dysfunction in postmenopausal women |
EP2251004A3 (fr) * | 2005-11-10 | 2012-02-01 | Galderma Research & Development | Composition pharmaceutique ou cosmétique, et procédé de solubilisation mixte pour préparer la composition |
US8268806B2 (en) | 2007-08-10 | 2012-09-18 | Endorecherche, Inc. | Pharmaceutical compositions |
US8629129B2 (en) | 2007-08-10 | 2014-01-14 | Endorecherche, Inc. | Pharmaceutical compositions |
US8957054B2 (en) | 2007-08-10 | 2015-02-17 | Endorecherche, Inc. | Pharmaceutical compositions |
US10881650B2 (en) | 2007-08-10 | 2021-01-05 | Endorecherche, Inc. | Pharmaceutical compositions |
Also Published As
Publication number | Publication date |
---|---|
CA2455358A1 (fr) | 2003-02-13 |
BR0211735A (pt) | 2004-09-21 |
EP1414405B1 (fr) | 2007-07-04 |
PL367698A1 (en) | 2005-03-07 |
HUP0401181A3 (en) | 2009-01-28 |
RU2004106024A (ru) | 2005-04-10 |
FR2828100A1 (fr) | 2003-02-07 |
EP1414405A1 (fr) | 2004-05-06 |
HUP0401181A2 (hu) | 2004-12-28 |
MXPA04001007A (es) | 2004-07-08 |
ZA200400770B (en) | 2004-12-15 |
ATE366102T1 (de) | 2007-07-15 |
DE60221020D1 (de) | 2007-08-16 |
RU2270665C2 (ru) | 2006-02-27 |
CN1564676A (zh) | 2005-01-12 |
FR2828100B1 (fr) | 2004-09-24 |
KR100569639B1 (ko) | 2006-04-10 |
US20090069279A1 (en) | 2009-03-12 |
KR20040030911A (ko) | 2004-04-09 |
JP2005500342A (ja) | 2005-01-06 |
ES2288566T3 (es) | 2008-01-16 |
US20040219123A1 (en) | 2004-11-04 |
AU2002334011B2 (en) | 2005-04-07 |
DE60221020T2 (de) | 2008-03-06 |
AR034962A1 (es) | 2004-03-24 |
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