FR2870738A1 - Composition, useful e.g. in cosmetic process for skin care for hydration of skin, comprises microspheres comprising an atellocollagen and polyholoside; salt of alkaline-earth metal or transition metal; hydroxyacid; and amino acid - Google Patents

Abstract

Composition (A) in a medium comprises microspheres (I) comprising an atellocollagen and a polyholoside; salt of alkaline-earth metal (II) or transition metal (III); a hydroxyacid (IV); and an amino acid (V). An independent claim is also included for cosmetic process for skin care, comprising topical application of (A) on the skin.

Description

The present invention relates to a composition comprising, in a

  physiologically acceptable medium:

  (a) microspheres whose wall comprises atellocollagen and at least one polyholoside, (b) at least one alkaline earth or transition metal salt, (c) at least one hydroxy acid, and (d) at least one amino acid.

  It also relates to a cosmetic process for the care, in particular hydration, of the skin, comprising the topical application thereto of the above-mentioned composition.

  Human skin consists of two compartments namely a superficial compartment, the epidermis, and a deep compartment, the dermis.

  The natural human epidermis is composed mainly of three types of cells, which are the keratinocytes, a very large majority, melanocytes and Langerhans cells.

  Each of these cell types contributes by its own functions to the essential role played in the body by the skin. In particular, the keratinocytes undergo a continuous and oriented maturation process which, keratinocytes found in the basal layer of the epidermis, results in the formation of corneocytes, which are completely keratinized dead cells consisting of end-stage keratinocytes of their differentiation. . This differentiation process leads to the formation of bilayer lipids in the stratum corneum. It also makes it possible to produce the constituents of the NMF (Natural Moisturizing Factor) composed of small hydrosoluble molecules with a high hygroscopic power and playing a moisturizing role. The NMFs also act as plasticizers, and thus contribute to the suppleness of the skin. The stratum corneum thus formed plays a key role in barrier function and hydration.

  It is known that the skin tends to dry out due to its exposure to the air and the sun. However, it is important that the skin is well hydrated and does not suffer loss of water that may cause wilting, drying or even peeling of the skin.

  Also, it is common to incorporate in the cosmetic compositions moisturizers, that is to say hygroscopic substances that cause rehydration of the skin by capturing the atmospheric water and by retaining water from the skin. Examples of these moisturizers are the constituents of the NMF mentioned above.

  The NMF consists mainly of amino acids (65%), organic acids (21%), ions (8%), urea (4%) and sugars (2%).

  Thus, it is also known to use hydroxyl acids and their salts, and in particular lactic acid and sodium lactate to improve the suppleness and elasticity of the skin (M. Rieger, Cosmetics & Toiletries, 1992, vol. 107, pp. 89-90.). Urea has also been used for this purpose (FR-2 181 659). There are also commercially available mixtures of NMF constituents that can be used in the cosmetic field, such as the products sold under the trade names Hydrasoft by the company VINCI ENCE and Hydrosmyl LS4513 by the company COGNIS.

  Nevertheless, it remains the need to have moisturizing compositions capable of providing the skin, in a continuous manner during the day, an association of compounds close to the NMF.

  However, the Applicant has discovered that the inclusion of certain constituents of the NMF in particular spheres, biodegradable, having a good affinity with the skin, allows a prolonged release of these constituents to continuously stimulate skin enzymes and boost cell metabolism, thus allowing the skin to maintain optimal hydration throughout the day.

  The subject of the present invention is therefore a composition containing, in a physiologically acceptable medium: (a) microspheres whose wall comprises atellocollagen and at least one polyholoside, (b) at least one alkaline earth metal salt or transition, (c) at least one hydroxy acid, and (d) at least one amino acid.

  The constituents of this composition will now be described in more detail.

  Microspheres The microspheres that can be used according to the invention can be those described in application EP-0 381 543 of BIOETICA.

  It can thus be microspheres prepared from atellocollagen and a polysaccharide such as a glycosaminoglycan, according to a process comprising: (a) mixing a solution, generally a slightly acidic aqueous solution, atellocollagen with a solution, usually a basic aqueous solution, of polyholoside, to obtain a mixed solution, (b) emulsification of this mixed solution with a hydrophobic liquid phase (such as pentaerythrityl tetraisostearate) to obtain an emulsion E / H or HIE, and (c) crosslinking the atellocollagen and the polyholoside with a crosslinking agent such as an acid dichloride or an acid anhydride.

  The microspheres thus formed can then be washed and then separated, for example by decantation, and optionally dried. They generally have an average size of between 1 and 3000 μm, preferably between 1 and 50 μm, better still, close to 20 μm. Used in dehydrated form, these microspheres make it possible to absorb a large quantity (more than a hundred times their volume) of water containing the constituents according to the present invention, and to release them progressively as they are degraded by skin enzymes. Their swelling also helps, by re-inflating the skin, to smooth fine lines.

  Atellocollagen can be obtained by enzymatic digestion of native collagen. The polyholoside may be selected from chondroitin-4-sulfate, chondroitin-6-sulfate, dermatan sulfate, heparan sulfate, keratan sulfate, dextran, dextran sulfate and mixtures thereof.

  The polyholoside can represent from 15 to 50% of the weight of the collocollagen.

  Microspheres of this type are available in particular from the company COLETICA under the trade names Spheres Marine Filling CLOR102A.

  The microspheres may represent from 0.01 to 5% of the total weight of the composition.

  Metal salt The metal salt that can be used in the composition according to the invention is chosen from alkaline earth metal salts, such as magnesium and calcium, and transition metal salts, for example from manganese, zinc and copper salts. or iron, with organic or inorganic acids.

  These salts can thus be salts of inorganic acids chosen from hydrochloric, sulfuric and phosphoric acids, or organic acids chosen from acetic, propionic, succinic, fumaric, lactic, glycolic, gluconic, citric and tartaric acids.

  Gluconates of alkaline earth or transition metals, particularly zinc, calcium and / or manganese, are preferred for use in the present invention.

  The metal salt (s) may be from 0.00001 to 5% of the total weight of the composition.

  Hydroxy acids The hydroxy acid used in the composition according to the invention may be chosen from α-hydroxy acids and β-hydroxy acids.

  Examples of α-hydroxy acids are citric, lactic, glycolic, tartaric, mandelic and malic acids. Examples of G3-hydroxy acids are salicylic acid and its derivatives such as noctanoyl-5-salicylic acid.

  Lactic acid is preferred for use in the present invention.

  Amino acids The amino acids that may be used in the composition according to the invention may be chosen in particular from: alanine, arginine, aspartic acid, citrulline, glutamic acid, urocanic acid, glycine, histidine, leucine, lysine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and their salts and mixtures.

  An example of a commercially available raw material comprising a mixture of amino acids that can be used in the composition according to the invention is the product sold by COGNIS under the trade name Hydrosmyl LS 4513, which comprises in particular a mixture of arginine and serine, citrulline, alanine, threonine, glutamic acid and lysine hydrochloride.

  The amino acid (s) may represent from 0.005 to 5% of the total weight of the composition.

  The composition according to the invention is suitable for topical application to the skin and therefore generally comprises a physiologically acceptable medium, that is to say compatible with the skin and / or its integuments. It is preferably a cosmetically acceptable medium, that is to say which has a pleasant color, odor and feel and does not generate unacceptable discomfort (tingling, tightness, redness), likely to divert the consumer of this composition.

  The composition according to the invention may be in any of the galenical forms conventionally used for topical application and in particular in the form of dispersions of the lotion or aqueous gel type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersion. a fatty phase in an aqueous phase (O / W) or conversely (W / O), or suspensions or emulsions of soft, semi-solid or solid consistency of the cream type, or multiple emulsions (W / O) / E or H / E / H), microemulsions, vesicular dispersions of ionic and / or nonionic type, or wax / aqueous phase dispersions. These compositions are prepared according to the usual methods.

  It can be a care product or facial cleanser, or a makeup product such as a foundation.

  According to a preferred embodiment of the invention, the composition is in the form of an O / W emulsion.

  This composition may also contain various adjuvants commonly used in the cosmetics field, such as emulsifiers including esters of fatty acids and glyceryl, esters of fatty acids and of polyethylene glycol (comprising from 20 to 100 oxide units). ethylene) and sucrose esters; fillers, especially nylon in the form of microbeads or fibers, polymethyl methacrylate beads or silica; pigments; dyes; conservatives; sequestering agents such as EDTA and its salts; perfumes; and thickeners and gelling agents, in particular xanthan gum, acrylamide homo- and copolymers and acrylamido methylpropanesulfonic acid (AMPS) homopolymers and copolymers.

  This composition may also contain other active ingredients such as vitamins and in particular vitamin E (tocopherol) and its derivatives such as tocopheryl acetate.

  Of course, those skilled in the art will take care to choose this or these optional additional compounds and their amount in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, impaired by the addition envisaged.

  The composition according to the invention may further contain at least one UVA and / or UVB filter. The sunscreens may be chosen from organic screening agents, inorganic screening agents and mixtures thereof.

  The more particularly preferred organic filters are chosen from: anthranilates, in particular menthyl anthranilate; benzophenones, in particular benzophenone-1, benzophenone-3, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone-12, and preferentially benzophenone-3 (oxybenzone), or Benzophenone-4 (Uvinul MS40 available from BASF); benzylidenecamphers, in particular 3-benzylidene camphor, benzylidenecamphosulfonic acid, camphor benzalkonium methosulphate, polyacrylamidomethylbenzylidene camphor, terephthalylidene di-camphorsulfonic acid, and preferentially 4-methylbenzylidene camphor (Eusolex 6300 available). at Merck); benzimidazoles, in particular benzimidazilate (Neo Heliopan AP available from Haarmann and Reimer), or phenylbenzimidazole sulfonic acid (Eusolex 232 available from Merck); benzotriazoles, in particular trisiloxane drometzol, or methylene bis-benzotriazolyltetramethylbutylphenol (Tinosorb M available from Ciba); cinnamates, in particular cinoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, dimethoxycinnamate glyceryl ethylhexanoate, isopropyl methoxycinnamate, isoamyl cinnamate, and preferably ethocrylene (Uvinul N35 available from BASF), octyl methoxycinnamate (Parsol MCX available from Hoffmann La Roche), or octocrylene (Uvinul 539 available from BASF); dibenzoylmethanes, especially butyl methoxydibenzoylmethane (Parsol 1789); imidazolines, in particular ethylhexyl dimethoxybenzylidene dioxoimidazoline; PABAs, in particular ethyl dihydroxypropyl PABA, ethylhexyldimethyl PABA, glyceryl PABA, PABA, PEG-25 PABA, and preferentially diethylhexylbutamido-triazone (Uvasorb HEB available from 3V Sigma), ethylhexyltriazone (Uvinul T150 available from BASF), or ethyl PABA (benzocaine); salicylates, especially dipropylene glycol salicyclate, ethylhexyl salicylate, homosalate, or TEA salicylate; triazines, in particular anisotriazine (Tinosorb S available from Ciba); drometrizole trisiloxane ..

  The inorganic filters are preferably chosen from pigments or even nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium.

  The composition according to the invention makes it possible to improve the hydration of the skin and to smooth it.

  The invention therefore also relates to a cosmetic skin care process, in particular for hydrating it, comprising the topical application thereto of the aforementioned composition.

  The composition according to the invention can be applied to the face and / or the neck, in particular of persons with dry skin.

  The invention will now be illustrated by the following nonlimiting examples. In these examples, the amounts are indicated in weight percent.

  EXAMPLES Example 1 Cream for Dry Skin An HIE emulsion having the composition below was prepared: Stearic acid 1% Oils 21% Preservatives 0.85% Tocopherol at 50% in oil 0.2% Tocopheryl acetate 0, 5% Sequestrant 0.05% Thickener 0.9% Surfactant 5% Glycerin 7% Calcium Gluconate 0.013% Zinc Gluconate 0.013% Manganese Gluconate 0.00006% Lactic Acid 0.06% Microspheres * 0, 1% Blend 54 % of amino acids ** 0.6% Fragrance 0.2% Water qs 100% * Marine Filling Spheres CLOR102A. of COLETICA ** Hydrosmyl LS 4513 from COGNIS This composition can be applied morning and / or evening on the face to moisturize the skin.

  EXAMPLE 2 Cream for Combination Skins An HIE emulsion having the composition below was prepared, in a conventional manner for the person skilled in the art: Oils 12.65% Preservatives 0.75% Tocopheryl acetate 0.5% Sequestering 0, 05 Thickeners 0.7% Glycerin 7% Dipropylene Glycol 2% Heteropolysaccharide 0.05% Alcohol 5% Menthoxypropanediol 0.05% Ceramide 0.15% Cholesterol 0.15% Silica 1.5% Calcium Gluconate 0. 009% Gluconate zinc 0.009 Manganese Gluconate 0.00004% Lactic Acid 0.04% Microspheres * 0.1% 54% Amino Acid Blend ** 0.44% Neutralizer 0.05% Fragrance 0.15% Water qs 100% This composition can be applied morning and / or evening on the face to prevent drying of the skin.

  15 20 * Marine Filling Spheres CLOR102A. Example 3: Evaluation of the Moisturizing Effect The hydrating effect of the compositions according to Examples 1 and 2 was evaluated by means of a corneometer. This device measures the electrical impedance of the skin: the lower it is, the more the skin is hydrated.

  Protocol The compositions were applied at a rate of 2 mg / cm 2 on a panel of 23 subjects with dry skin for the composition of Example 1 and 24 subjects with dry skin for the composition of Example 2, on the inner face of the forearm. The hydration of the treated area was measured using a CM825 SEI-M-0014-CORN 06 corneometer, and compared to the bare skin, at different time intervals: at application (to), after 1h, after 6h and after 24h.

  Results For the composition of Example 1: After one hour of application of the composition, an increase of 32.9% in the hydration of the treated zone was observed. This percentage is still 26.3% after 6 hours and 11.9% after 24 hours.

  For the composition of Example 2: After one hour of application of the composition, an 11% increase in the hydration of the treated zone is observed. This percentage is still 8.3% after 6 hours and 5.6% after 24 hours.

  In comparison, the level of hydration of the untreated skin does not vary significantly during this period of time.

  The compositions according to the invention thus make it possible to improve the hydration of the skin and this effect remains perceptible even 24 hours after its application.

Claims (15)

  1. A composition containing, in a physiologically acceptable medium: (a) microspheres whose wall comprises atellocollagen and at least one polyholoside, (b) at least one alkaline earth or transition metal salt, (c) at least one hydroxy acid, and (d) at least one amino acid.   2. Composition according to claim 1, characterized in that said microspheres are prepared according to a process comprising: (a) mixing a solution of atellocollagen with a solution of polyholoside, to obtain a mixed solution, (b) the setting in emulsion of this mixed solution with a hydrophobic liquid phase to obtain an W / O or HIE emulsion, and (c) the crosslinking of the atellocollagen and the polyholoside by a crosslinking agent.   3. Composition according to claim 1 or 2, characterized in that the polyholoside is selected from chondroitin-4-sulfate, chondroitin-6 sulfate, dermatan sulfate, heparan sulfate, keratan sulfate, dextran, dextran sulphate and their mixtures.   4. Composition according to any one of claims 1 to 3, characterized in that the polysaccharide represents from 15 to 50% of the weight of atellocollagen.   5. Composition according to any one of Claims 1 to 4, characterized in that the alkaline earth metal salt is chosen from magnesium and calcium salts of organic or inorganic acids.   6. Composition according to any one of claims 1 to 4, characterized in that the transition metal salt is selected from manganese salts, zinc, copper and iron of organic or inorganic acids.   7. Composition according to Claim 5 or 6, characterized in that the inorganic acid is chosen from hydrochloric, sulfuric and phosphoric acids.   8. Composition according to claim 5 or 6, characterized in that the organic acid is selected from acetic acid, propionic, succinic, fumaric, lactic, glycolic, gluconic, citric and tartaric.   9. Composition according to any one of claims 1 to 6, characterized in that the alkaline earth metal salt or transition is a zinc gluconate, calcium or manganese.   10. Composition according to any one of claims 1 to 9, characterized in that the hydroxyacid is an α-hydroxy acid selected from citric, lactic, glycolic, tartaric, mandelic and malic acids.   11. Composition according to claim 10, characterized in that the hydroxyacid is lactic acid.   12. Composition according to any one of claims 1 to 9, characterized in that the hydroxyacid is a fi hydroxyacid selected from salicylic acid and noctanoyl-5-salicylic acid.   13. Composition according to any one of claims 1 to 12, characterized in that the amino acid is chosen from: alanine, arginine, aspartic acid, citrulline, glutamic acid, acid urocanic, glycine, histidine, leucine, lysine, ornithine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and their salts.   14. Cosmetic skin care process, comprising the topical application thereto of the composition according to any one of claims 1 to 13.   15. Process according to claim 14, characterized in that it is intended to moisturize the skin.