US20030124161A1

US20030124161A1 - Cosmetic and/or dermatological use of a composition containing at least one oxidation-sensitive hydrophilic active principle and at least one N-vinylimidazole polymer or copolymer

Info

Publication number: US20030124161A1
Application number: US10/305,114
Authority: US
Inventors: Bruno Biatry; Eric Lheureux
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2001-11-28
Filing date: 2002-11-27
Publication date: 2003-07-03
Also published as: DE60222223D1; BR0205152A; FR2832630B1; CN1421196A; US20030125378A1; ES2292705T3; KR20030043766A; DE60222223T2; CN1200687C; JP3606859B2; TW200303760A; BR0205119A; JP2003160426A; CN1421194A; KR20030043767A; CN1230148C; EP1316302B1; JP3606857B2; KR20030043763A; JP2003160431A

Abstract

The invention relates to the use of a composition containing, preferably in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the active principle and the polymer or copolymer both being present in the aqueous phase, for promoting the synthesis of epidermal ceramides and/or for improving the barrier function of the skin, among other uses.

Description

FIELD OF THE INVENTION

The present invention relates to the cosmetic and/or dermatological use of a composition comprising at least one oxidation-sensitive hydrophilic active principle and at least one N-vinylimidazole polymer or copolymer in a physiologically acceptable medium comprising an aqueous phase.

BACKGROUND OF THE INVENTION

It is known to introduce, into cosmetic compositions, various active principles intended to contribute specific treatments to the skin and/or hair. However, some of these active principles exhibit the disadvantage of being unstable in an aqueous medium and of easily decomposing on contact with water, in particular because of oxidation phenomena. They thus rapidly lose their activity over time and this instability conflicts with the desired effectiveness.

Attempts have thus been made for a long time to formulate ascorbic acid or vitamin C because of its numerous beneficial properties. In particular, ascorbic acid stimulates the synthesis of the connective tissue and in particular of collagen, strengthens the defences of the cutaneous tissue against external attacks, such as ultraviolet radiation and pollution, compensates for vitamin E deficiency of the skin, depigments the skin and has a role in combating free radicals. These last two properties make it an excellent candidate as cosmetic or dermatological active principle for combating ageing of the skin or for preventing ageing of the skin. Unfortunately, because of its chemical structure (of α-ketolactone), ascorbic acid is highly sensitive to certain environmental parameters and in particular to oxidation phenomena. There thus ensues rapid decomposition of formulated ascorbic acid in the presence of these parameters and in particular in the presence of oxygen, light or metal ions, as a function of the temperature or under certain pH conditions (Pharm. Acta. Helv., 1969, 44, 611-667; STP Pharma, 1985, 4, 281-286).

Several solutions have thus been envisaged in the prior art for reducing and/or slowing down the decomposition of ascorbic acid.

Provision has thus been made to use ascorbic acid in the form of a chemical derivative (magnesium ascorbyl phosphate or esters of fatty acids and ascorbic acid), but the bioavailability of these derivatives is very low (J. Am. Acad. Dermatol., 1996, 34, 29-33).

The instability of ascorbic acid with respect to oxygen can be improved by using specific packagings, such as twin compartments under an inert atmosphere, as disclosed in Patent U.S. Pat. No. 5,935,584, or alternatively by the use of two-phase emulsions, one phase of which is composed of a dry powder comprising ascorbic acid and the second phase of which is a liquid phase. The mixing of the two phases has to be carried out at the time of use (WO 98/43598). These solutions have disadvantages with regard to the cost and the complexity of the manufacturing operations and significant restrictions with regard to use.

Another solution provided in the prior art consists in using a high concentration of glycols or polyols in order to reduce the solubility of oxygen in the formulation, thus protecting the ascorbic acid (WO 96/24325, EP 0 755 674, U.S. Pat. No. 5,981,578). The polyols can optionally be incorporated in liposomes, as disclosed in Patent U.S. Pat. No. 6,020,367. However, these solutions exhibit the disadvantage of resulting in sticky formulations, the cosmetic quality of which is difficult to improve. Furthermore, the presence of a high concentration of these compounds can lead to phenomena of irritation.

Ascorbic acid can also be formulated in anhydrous media, such as silicones (U.S. Pat. No. 6,194,452), which are capable of creating an anhydrous barrier around ascorbic acid. A major disadvantage of such solutions results from the lack of freshness on application.

The need thus remains for a composition employable in particular in the cosmetics field, in which a hydrophilic active principle which is unstable in an oxidizing medium is stabilized, which is comfortable on application, which does not lead to any skin irritation after application and which is compatible with the constraints of an industrial implementation of its manufacturing process.

Ascorbic acid is capable of improving the lipid profile of reconstructed epidermides by modifying lipogenesis and causes in particular an increase in the synthesis of ceramides (J. Invest. Dermatol., 109, 1997, p. 348-355). In the same way, this effect has also been demonstrated for ascorbic acid derivatives, such as magnesium ascorbyl phosphate or ascorbyl glucoside. Studies have also shown that the barrier function of reconstructed epidermides is improved after treatment with ascorbic acid (EP-1 145 706, EP-1 145 710).

The advantage of using these derivatives in order to maintain and to strengthen the integrity of the lipids of the skin, and thus of overcoming problems of moisturizing, is then understood.

In addition to this activity with regard to the synthesis of lipids, a prodifferentiating effect on keratinocytes of ascorbic acid has recently been demonstrated (Histochem. Cell. Biol., 116(6), 2001, p.287-297). This effect has the consequence of overcoming the detrimental change in this mechanism for the differentiation of keratinocytes which results in an accumulation of squamae at the surface of the skin. This phenomenon modifies the interactions between the surface of the skin and light and is responsible for a faded and rough appearance of the skin.

Ascorbic acid and its derivatives can therefore advantageously be used to combat a faded complexion and to maintain the radiance of the skin.

OBJECTS OF THE INVENTION

One object of the present invention is to provide a composition comprising an oxidation-sensitive active principle preferably selected from the group consisting of ascorbic acid and its derivatives, which exhibits good cosmetic properties, both with regard to touch and with regard to tolerance, the preservation of which over time does not require specific precautions, and which retains the activity of the said active principle in improving the synthesis of ceramides and the barrier function of the skin and in improving the differentiation of keratinocytes, among other benefits and attributes.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have discovered that the use of non-crosslinked N-vinylimidazole polymers or copolymers in compositions in which the aqueous phase includes an oxidation-sensitive active principle, such as ascorbic acid or one of its derivatives, makes it possible to achieve the abovementioned aim.

In the prior art, some compounds having an imidazole structure have been disclosed for their stabilizing properties. Thus, in Patent Application EP 0 586 106, several imidazole-based molecules are used to stabilize certain retinoids against chemical decomposition. Furthermore, polymeric emulsifiers composed of N-vinylimidazole, of alkyl acrylates and of vinyl acetates are disclosed in Patent U.S. Pat. No. 4,057,622. They are used for the purpose of replacing known emulsifiers in order to overcome their disadvantages, in particular with regard to smell, and to stabilize water-in-oil emulsions. Finally, N-vinylimidazole/N-vinylcaprolactam/N-vinylpyrrolidone copolymers are disclosed in Patent U.S. Pat. No. 6,191,188. They are used in the manufacture of hair-strengthening compositions.

To the knowledge of the inventors, polymers or copolymers comprising N-vinylimidazole units have never been used in combination with hydrophilic active principles sensitive to decomposition by oxidation for the purpose of improving their stability in an aqueous medium. This is true in particular in the case of ascorbic acid.

An embodiment of the present invention is therefore the cosmetic and/or dermatological use, for promoting the synthesis of ceramides and/or improving the barrier function of the skin, of a composition comprising, in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the active principle and the polymer or copolymer both being in the aqueous phase. The polymer or copolymer is preferably present in an amount sufficient to stabilize the said oxidation-sensitive hydrophilic active principle.

Another embodiment of the present invention is the cosmetic and/or dermatological use, for combating roughness of the skin and/or maintaining and/or improving the radiance of the complexion, of a composition comprising, in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the active principle and the polymer or copolymer both being in the aqueous phase.

Another embodiment of the invention is the use of a combination composed of at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and of at least one non-crosslinked N-vinylimidazole polymer or copolymer in the aqueous phase of a cosmetic composition as agent for promoting the synthesis of ceramides and/or improving the barrier function of the skin.

Another embodiment of the invention is the use of a combination composed of at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and of at least one non-crosslinked N-vinylimidazole polymer or copolymer in the aqueous phase of a cosmetic composition as agent for combating roughness of the skin and/or maintaining and/or improving the radiance of the complexion.

According to the invention, the term “hydrophilic active principle” is understood to mean a compound having a solubility in water of at least 0.25% at ambient temperature (25° C.).

According to the invention, the term “oxidation-sensitive hydrophilic active principle” is understood to mean any active principle of natural or synthetic origin capable of undergoing decomposition by an oxidation mechanism. This oxidation phenomenon can have several causes, in particular the presence of oxygen, of light or of metal ions, a high temperature or certain pH conditions.

Mention may be made, by way of example and without implied limitation, of: ascorbic acid and its derivatives, such as salts or esters thereof, particularly the 5,6-di-O-dimethylsilylascorbate (sold by Exsymol under the reference PRO-AA), the potassium salt of dl-α-tocopheryl dl-ascorbyl phosphate (sold by Senju Pharmaceutical under the reference SEPIVITAL EPC), magnesium ascorbyl phosphate or sodium ascorbyl phosphate (sold by Roche under the reference Stay-C 50). Preferred principles meet the hydrophilic and oxidation sensitive descriptions above and in addition bring about at least one of the effects described above such as promoting the synthesis of ceramides, etc.

In a particularly advantageous aspect, the oxidation-sensitive hydrophilic active principle is ascorbic acid.

The principle is preferably present in an amount sufficient to bring about its intended effect, such as, for example, in an amount of 0.5, 1, 5, 25, etc. grams per 100 g of composition.

According to the invention, the term “non-crosslinked N-vinylimidazole polymer or copolymer” is understood to mean any polymer comprising N-vinylimidazole units and not comprising a crosslinking agent. Copolymers suitable for the implementation of the invention are copolymers combining N-vinylimidazole with N-vinylpyrrolidone and/or N-vinylcaprolactam subunits.

In an advantageous aspect of the invention, the copolymer has a molar fraction of N-vinylimidazole units of between 0.1 and 1, more preferably between 0.4 and 0.9, inclusive.

According to an advantageous aspect of the invention, the molar ratio of the N-vinylimidazole unit equivalent to the oxidation-sensitive hydrophilic active principle varies between 0.004 and 16 and preferably between 0.01 and 1, inclusive.

Use will preferably be made of an N-vinylimidazole/N-vinylpyrrolidone copolymer.

The weight-average molar mass of the N-vinylimidazole polymers will advantageously be between 1000 and 1×10 ⁷and preferably between 5000 and 5×10⁶.

Use may be made, to this end, of the vinylpyrrolidone/vinylimidazole (50/50) copolymer having a weight-average molar mass of 1200000 sold under the reference LUVITEC VPI 55K72W by BASF or the vinylpyrrolidone/vinylimidazole (50/50) copolymer having a weight-average molar mass of 10000 sold under the reference LUVITEC VPI 55K18P by BASF.

The at least one polymer or copolymer is preferably present in the composition according to the invention in an amount sufficient to produce the desired effect, that is to say in an amount sufficient to stabilize the oxidation-sensitive hydrophilic active principle. Preferably, the copolymer is present at a concentration of between 0.1 and 5% by weight with respect to the total weight of the aqueous phase and more particularly at a concentration of between 0.1 and 2% by weight with respect to the total weight of the aqueous phase. The amount preferably is a stabilizing amount that delays or stops decomposition of the active principle when tested at 45° C. for two months.

The compositions used according to the invention are preferably intended for topical application to the skin and/or its superficial body growths and therefore comprise a physiologically acceptable medium, that is to say a medium compatible with cutaneous tissues, such as the skin, scalp, eyelashes, eyebrows, hair, nails and mucous membranes. This physiologically acceptable medium comprises an aqueous phase and optionally a physiologically acceptable organic solvent chosen, for example, from lower alcohols comprising from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, isopropanol, propanol or butanol; polyethylene glycols having from 6 to 80 ethylene oxide units; or polyols, such as propylene glycol, isoprene glycol, butylene glycol, glycerol or sorbitol.

When the physiologically acceptable medium is an aqueous medium, it generally preferably has a pH which is compatible with the skin, preferably ranging from 3 to 9 and better still from 3.5 to 7.5.

The compositions according to the invention can be provided in any form, including any pharmaceutical dosage form used conventionally for topical application and in particular in the form of aqueous or aqueous/alcoholic solutions, of oil-in-water (O/W) or water-in-oil (W/O) or multiple (triple: W/O/W or O/W/O) emulsions, of aqueous gels or of dispersions of a fatty phase in an aqueous phase using spherules, it being possible for these spherules to be polymeric nanoparticles, such as nanospheres and nanocapsules, or lipid vesicles of ionic and/or nonionic type (liposomes, niosomes or oleosomes). These compositions are prepared according to the usual methods.

In addition, the compositions used according to the invention can be more or less fluid and can have the appearance of a white or coloured cream, of an ointment, of a milk, of a lotion, of a serum, of a paste or of a foam. They can optionally be applied to the skin in the form of an aerosol. They can also be provided in a solid form, for example in the form of a stick.

When the composition according to the invention comprises an oily phase, the latter preferably comprises at least one oil. It can additionally comprise other fatty substances.

Mention may be made, as oils which can be used in the composition of the invention, of, for example:

hydrocarbonaceous oils of animal origin, such as perhydrosqualene;

hydrocarbonaceous oils of vegetable origin, such as liquid triglycerides of fatty acids comprising from 4 to 10 carbon atoms, such as triglycerides of heptanoic acid or octanoic acid, or alternatively, for example, sunflower, maize, soybean, gourd, grape seed, sesame, hazelnut, apricot, macadamia, arara, castor or avocado oils, triglycerides of caprylic/capric acids, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel, jojoba oil, or karite butter oil;

synthetic esters and ethers, in particular of fatty acids, such as the oils of formulae R ¹COOR²and R¹OR²in which R¹represents the residue of a fatty acid comprising from 8 to 29 carbon atoms and R²represents a branched or unbranched hydrocarbonaceous chain comprising from 3 to 30 carbon atoms, such as, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate or heptanoates, octanoates or decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, such as pentaerythrityl tetraisostearate;

linear or branched hydrocarbons of mineral or synthetic origin, such as volatile or nonvolatile liquid paraffins and their derivatives, liquid petrolatum, polydecenes or hydrogenated polyisobutene, such as parleam oil;

fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;

partially hydrocarbon-comprising and/or silicone-comprising fluorinated oils, such as those disclosed in the document JP-A-2-295912;

silicone oils, such as volatile or nonvolatile polymethylsiloxanes (PDMS) comprising a linear or cyclic silicone chain which are liquid or pasty at ambient temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones), such as cyclohexasiloxane; polydimethylsiloxanes comprising pendent alkyl, alkoxy or phenyl groups or alkyl, alkoxy or phenyl groups at the end of the silicone chain, which groups have from 2 to 24 carbon atoms; or phenylated silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, (2-phenylethyl)trimethylsiloxysilicates and polymethylphenylsiloxanes;

their mixtures.

The term “hydrocarbonaceous oil” is understood to mean, in the list of the oils mentioned above, any oil predominantly comprising carbon and hydrogen atoms and optionally ester, ether, fluorinated, carboxylic acid and/or alcohol groups.

The other fatty substances which can be present in the oily phase are, for example, fatty acids comprising from 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid; waxes, such as lanolin, beeswax, carnauba or candelilla wax, paraffin or lignite waxes or microcrystalline waxes, ceresin or ozokerite, or synthetic waxes, such as polyethylene waxes or Fischer-Tropsch waxes; silicone resins, such as trifluoromethyl C _1-4alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, such as the products sold under the names “KSG” by Shin-Etsu, under the names “Trefil”, “BY29” or “EPSX” by Dow Corning or under the names “Gransil” by Grant Industries.

These fatty substances can be chosen in a way varied by a person skilled in the art in order to prepare a composition having the desired properties, for example of consistency or of texture, without undue hardship.

According to a specific embodiment of the invention, the composition according to the invention is a water-in-oil (W/O) or oil-in-water (O/W) emulsion. The proportion of the oily phase in the emulsion may preferably range from 5 to 80% by weight and preferably from 5 to 50% by weight with respect to the total weight of the composition.

The emulsions generally comprise at least one emulsifier selected from the group consisting of amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture, and optionally a coemulsifier. The emulsifiers are preferably chosen according to the emulsion to be obtained (W/O or O/W). The emulsifier and the coemulsifier are generally preferably present in the composition in a proportion ranging from 0.3 to 30% by weight and preferably from 0.5 to 20% by weight with respect to the total weight of the composition.

Mention may be made, for the W/O emulsions, for example, as emulsifiers, of dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol sold under the name “DC 5225 C” by Dow Corning, and alkyl dimethicone copolyols, such as the laurylmethicone copolyol sold under the name “Dow Corning 5200 Formulation Aid” by Dow Corning and the cetyl dimethicone copolyol sold under the name Abil EM 90 ^Rby Goldschmidt. Use may also be made, as surfactant of W/O emulsions, of a crosslinked solid organopolysiloxane elastomer comprising at least one oxyalkylenated group, such as those obtained according to the procedure of Examples 3, 4 and 8 of the document U.S. Pat. No. 5,412,004 and the examples of the document U.S. Pat. No. 5,811,487, in particular the product of Example 3 (synthetic example) of Patent U.S. Pat. No. 5,412,004, and such as that sold under the reference KSG 21 by Shin Etsu. Use may also be made, as emulsifier, of a polyolefin-derived oligomer or polymer comprising a succinic ending; the latter is preferably a polyolefin comprising an esterified or amidated succinic ending or a salt of such a polyolefin and in particular polyisobutylene comprising an esterified or amidated succinic ending such as the products sold under the names L5603 and L2721 and OS131769 by Lubrizol.

Mention may be made, for the O/W emulsions, for example, as emulsifiers, of nonionic emulsifiers, such as esters of fatty acids and of glycerol which are oxyalkylenated (more particularly polyoxyethylenated); esters of fatty acids and of sorbitan which are oxyalkylenated; esters of fatty acids which are oxyalkylenated (oxyethylenated and/or oxypropylenated); ethers of fatty alcohols which are oxyethylenated (oxyethylenated and/or oxypropylenated); sugar esters, such as sucrose stearate; and their mixtures, such as the mixture of glyceryl stearate and of PEG-40 stearate.

The composition of the invention can also comprise adjuvants known in the cosmetics or dermatological field, such as hydrophilic or lipophilic gelling agents, preservatives, solvents, fragrances, fillers, UV screening agents, bactericides, odour absorbers, colouring materials, plant extracts or salts. The amounts of these various adjuvants are those used in the field under consideration, for example from 0.01 to 20% of the total weight of the composition. These adjuvants, depending on their nature, can be introduced into the fatty phase, into the aqueous phase and/or into the lipid spherules.

Mention may be made, as fillers which can be used in the composition of the invention, for example, of pigments, silica powder; talc; particles of polyamide and in particular those sold under the name Orgasol by Atochem; polyethylene powders; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer which are sold by Dow Coming under the name Polytrap; expanded powders, such as hollow microspheres and in particular the microspheres sold under the name Expancel by Kemanord Plast or under the name Micropearl F 80 ED by Matsumoto; silicone resin microbeads, such as those sold under the name Tospearl by Toshiba Silicone; and their mixtures. These fillers can be present in amounts ranging from 0 to 20% by weight and preferably from 1 to 10% by weight with respect to the total weight of the composition.

According to a preferred embodiment, the compositions in accordance with the invention can additionally comprise at least one organic photoprotective agent and/or at least one inorganic photoprotective agent which is active in the UV-A and/or UV-B regions (absorbers), and which are soluble in water or in fats or else are insoluble in the cosmetic solvents commonly used.

The organic photoprotective agents may be chosen in particular from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives; camphor derivatives; triazine derivatives, such as those disclosed in Patent Applications U.S. Pat. No. 4,367,390, EP 863 145, EP 517 104, EP 570 838, EP 796 851, EP 775 698, EP 878 469, EP 933 376, EP 507 691, EP 507 692, EP 790 243 and EP 944 624; benzophenone derivatives; β,β-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bisbenzoazolyl derivatives as disclosed in Patents EP 669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives as disclosed in Applications U.S. Pat. Nos. 5,237,071, 5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening polymers and screening silicones, such as those disclosed in particular in Application WO 93/04665; dimers derived from α-alkylstyrene, such as those disclosed in Patent Application DE 198 55 649; 4,4-diarylbutadienes as disclosed in Applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981; and their mixtures.

By way of illustration, mention may be made, as photoprotective agents which are active in the UV-A and/or UV-B regions, denoted below under their INCI names, of:

p-aminobenzoic acid (PABA) derivatives, in particular PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA (sold in particular under the name “Escalol 507” by ISP), glyceryl PABA or PEG-25 PABA (sold under the name “Uvinul P25” by BASF),

salicylic derivatives, in particular homosalate (sold under the name “Eusolex HMS” by Rona/EM Industries), ethylhexyl salicylate (sold under the name “Neo Heliopan OS” by Haarmann and Reimer), dipropylene glycol salicylate (sold under the name “Dipsal” by Scher), or TEA salicylate (sold under the name “Neo Heliopan TS” by Haarmann and Reimer),

dibenzoylmethane derivatives, in particular butyl methoxydibenzoylmethane (sold in particular under the trade name “Parsol 1789” by Hoffmmann-LaRoche), or isopropyl dibenzoylmethane,

cinnamic derivatives, in particular ethylhexyl methoxycinnamate (sold in particular under the trade name “Parsol MCX” by Hoffmmann-LaRoche), isopropyl methoxycinnamate, isoamyl methoxycinnamate (sold under the trade name “Neo Heliopan E 1000” by Haarmann and Reimer), cinoxate, DEA methoxycinnamate, diisopropyl methyl cinnamate, or glyceryl ethylhexanoate dimethoxycinnamate,

β,β-diphenylacrylate derivatives, in particular octocrylene (sold in particular under the trade name “Uvinul N539” by BASF) or etocrylene (sold in particular under the trade name “Uvinul N35” by BASF),

benzophenone, in particular benzophenone-1 (sold under the trade name “Uvinul 400” by BASF), benzophenone-2 (sold under the trade name “Uvinul D50” by BASF), benzophenone-3 or oxybenzone (sold under the trade name “Uvinul M40” by BASF), benzophenone-4 (sold under the trade name “Uvinul MS40” by BASF), benzophenone-5, benzophenone-6 (sold under the trade name “Helisorb 11” by Norquay), benzophenone-8 (sold under the trade name “Spectra-Sorb UV-24” by American Cyanamid), benzophenone-9 (sold under the trade name “Uvinul DS-49” by BASF), benzophenone-12, or n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

benzylidene camphor derivatives, in particular 3-benzylidene camphor (manufactured under the name “Mexoryl SD” by Chimex), 4-methylbenzylidene camphor (sold under the name “Eusolex 6300” by Merck), benzylidene camphor sulphonic acid (manufactured under the name “Mexoryl SL” by Chimex), camphor benzalkonium methosulphate (manufactured under the name “Mexoryl SO” by Chimex), terephthalylidene dicamphor sulphonic acid (manufactured under the name “Mexoryl SX” by Chimex), or polyacrylamidomethyl benzylidene camphor (manufactured under the name “Mesoryl SW” by Chimex),

benzimidazole derivatives, in particular phenylbenzimidazole sulphonic acid (sold in particular under the trade name “Eusolex 232” by Merck), or disodium phenyl dibenzimidazole tetrasulphonate (sold under the trade name “Neo Heliopan AP” by Haarmann and Reimer),

triazine derivatives, in particular anisotriazine (sold under the trade name “Tinosorb S” by Ciba Specialty Chemicals), ethylhexyl triazone (sold in particular under the trade name “Uvinul T150” by BASF), diethylhexyl butamido triazone (sold under the trade name “Uvasorb HEB” by Sigma 3V) or 2,4,6-tris(diisobutyl 4′-amino-benzalmalonate)-s-triazine,

benzotriazole derivatives, in particular drometrizole trisiloxane (sold under the name “Silatrizole” by Rhodia Chimie) or methylene bisbenzotriazolyl tetramethylbutylphenol (sold in the solid form under the trade name “Mixxim BB/100” by Fairmount Chemical or in the micronized form in aqueous dispersion under the trade name “Tinosorb M” by Ciba Specialty Chemicals),

anthranilic derivatives, in particular menthyl anthranilate (sold under the trade name “Neo Heliopan MA” by Haarmann and Reimer),

imidazoline derivatives, in particular ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate,

benzalmalonate derivatives, in particular polyorganosiloxane comprising benzalmalonate functional groups (sold under the trade name “Parsol SLX” by Hoffmmann-LaRoche),

4,4-diarylbutadiene derivatives, in particular 1,1′-dicarboxy (2,2′-dimethyl-propyl)-4,4-diphenylbutadiene,

and their mixtures.

The organic photoprotective agents which are more particularly preferred are selected from the group consisting of ethylhexyl salicylate, ethylhexyl methoxycinnamate, octocrylene, phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 4-methylbenzylidene camphor, terephthalylidene dicamphor sulphonic acid, disodium phenyl dibenzimidazole tetrasulphonate, 2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine, anisotriazine, ethylhexyl triazone, diethylhexyl butamido triazone, methylene bisbenzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane, 1,1′-dicarboxy (2,2′-dimethylpropyl)-4,4-diphenylbutadiene, and their mixtures.

The inorganic photoprotective agents may be selected from the group consisting of pigments or alternatively nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) formed from coated or uncoated metal oxides, such as, for example, titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide nanopigments, which are all UV photoprotective agents well known per se. Conventional coating agents are, furthermore, alumina and/or aluminium stearate. Such nanopigments formed from coated or uncoated metal oxides are disclosed in particular in Patent Applications EP 518 772 and EP 518 773.

The photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.1 to 20% by weight with respect to the total weight of the composition and preferably ranging from 0.2 to 15% by weight with respect to the total weight of the composition.

In another advantageous aspect of the invention, the composition used can additionally comprise at least one other active principle in addition to the principle described above which acts on the barrier function of the skin or which promotes moisturizing of the skin and/or one desquamating agent.

The term “desquamating agent” is understood to mean any compound capable of acting:

either directly on desquamation by promoting exfoliation, such as β-hydroxy acids, in particular salicylic acid and its derivatives (including 5-(n-octanoyl)salicylic acid); α-hydroxy acids, such as glycolic acid, citric acid, lactic acid, tartaric acid, malic acid or mandelic acid; urea; gentisic acid; oligofucoses; cinnamic acid; Saphora japonica extract; or resveratrol;

or on the enzymes involved in desquamation or decomposition of the corneodesmosomes, such as glycosidases, stratum corneum chymotryptic enzyme (SCCE) or indeed even other proteases (trypsin, chymotrypsin-like). Mention may be made of agents which chelate inorganic salts: EDTA; N-acyl-N,N′,N′-ethylene-diaminetriacetic acid; aminosulphonic compounds and in particular N-(2-hydroxyethyl)piperazine-N′-2-ethanesulphonic acid (HEPES); 2-oxothiazolidine-4-carboxylic acid (procysteine) derivatives; derivatives of α-amino acids of glycine type (as disclosed in EP-0 852 949, and sodium methylglycinediacetate, sold by BASF under the trade name Trilon M ); honey; or sugar derivatives, such as O-octanoyl-6-D-maltose and N-acetylglucosamine.

Mention may be made, among the active principles which act on the barrier function of the skin or which promote moisturizing of the skin, of, for example:

either compounds which act on the barrier function, for the purpose of keeping the stratum corneum moisturized, or occlusive compounds, in particular ceramides, sphingoid-based compounds, lecithins, glycosphingolipids, phospholipids, cholesterol and its derivatives, phytosterols (stigmasterol, β-sitosterol or campesterol), essential fatty acids, 1,2-diacylglycerol, 4-chromanone, pentacyclic triterpenes, such as ursolic acid, petroleum jelly and lanolin;

or compounds which directly increase the water content of the stratum corneum, such as threalose and its derivatives, hyaluronic acid and its derivatives, glycerol, pentanediol, sodium pidolate, serine, xylitol, sodium lactate, glyceryl polyacrylate, ectoin and its derivatives, chitosan, oligo- and polysaccharides, cyclic carbonates, N-lauroylpyrrolidonecarboxylic acid and N-α-benzoyl-L-arginine;

or compounds which activate the sebaceous glands, such as steroid derivatives (including DHEA) and vitamin D and its derivatives.

The composition according to the invention can be applied to the skin or mucous membranes. It can thus be used in a cosmetic treatment process for the purpose of promoting the synthesis of ceramides and/or of improving the barrier function of the skin or mucous membranes, comprising the application of the composition according to the invention to the skin or mucous membranes.

The present invention also relates to a process for the cosmetic treatment of the skin, comprising the application of the composition according to the invention to the skin for the purpose of maintaining the radiance of the complexion and/or of preventing and/or treating roughness of the skin.

The present invention additionally relates to a cosmetic process for moisturizing the skin or mucous membranes, comprising the application of a composition according to the invention to the skin or mucous membranes.

Another aspect of the invention relates to a process for the cosmetic treatment of dry skin, comprising the application of a composition according to the invention to the skin.

In an alternative form, the composition according to the invention can be used for the manufacture of a dermatological preparation comprising an aqueous phase which is intended to promote the synthesis of ceramides and/or to improve the barrier function of the skin.

The examples which follow serve to illustrate the invention without, however, exhibiting a limiting nature. The compounds are, depending on the situation, cited according to chemical names or according to CTFA (International Cosmetic Ingredient Dictionary and Handbook) names.

EXAMPLES

Example 1

Accelerated Storage Test. [0092]

The aim of this test is to study the decomposition of an oxidation-sensitive hydrophilic active principle after storing for two months at 45° C. Various solutions were prepared and their compositions are collated in the following table:

TABLE I


	Solution A
Compositions (in water)	(Control)	Solution B	Solution C	Solution D

Ascorbic acid	15%	15%	15%	15%
Polymer 1	—	1%	—	—
Polymer 2	—	—	1%	—
Polymer 3	—	—	—	1%

All the solutions are brought to pH 6 with 8.9 mol/l KOH. [0094]
The percentages of the polymers are given as active material. [0095]
Polymer 1: Vinylpyrrolidone/vinylimidazole (50/50) copolymer sold under the reference Luvitec VPI 55K72W of BASF (Weight-average molecular mass 1.2×10[0096] ⁶).
Polymer 2: Vinylpyrrolidone/vinylimidazole (50/50) copolymer sold under the reference Luvitec VPI 55K18P of BASF (Weight-average molecular mass 10 000). [0097]
Polymer 3: Polyvinylpyrrolidone sold under the reference Kollidon 12PF of BASF (Weight-average molecular mass 3 000). [0098]
The degree of decomposition measured is given by the ratio:[0099]
(C₀-C_{2 months})/C₀
with C[0100] ₀concentration of ascorbic acid at t=0 and C_{2 months}the concentration of ascorbic acid at t=2 months, under the conditions indicated in the above table.
The concentration of ascorbic acid is determined by the HPLC technique (LaChrom Merck system). The analytical conditions are as follows: [0101]
Column: Lichrosphere100 RP18 (250 mm) [0102]
Eluent: 0.1M phosphate buffer, pH 2.1 [0103]
Flow rate: 1 ml/min [0104]
Detection at 257 nm [0105]
Dilution of the sample such that the concentration of ascorbic acid is between 0.05 and 1 mg/ml. [0106]
The results obtained are collated in the following Table II: [0107]

TABLE II

Degree of decomposition after 2 months at 45° C.

(in %)

under air, amber glass under nitrogen, aluminium

bottle flask

Solution A 43 19.4

Solution B 10.8 1

Solution C 23.4 4.5

Solution D 35.8 15.7
It is found, from Table II, that the stability of ascorbic acid is improved in the presence of Polymer 1 and Polymer 2 of the invention, even in the presence of atmospheric oxygen, in comparison with the control. It is also found that the N-vinylpyrrolidone homopolymer alone is not sufficient to effectively stabilize the ascorbic acid solution. [0108]
As the polymers mentioned are hydrophilic, it will be sufficient to add them to an aqueous ascorbic acid solution to stabilize the ascorbic acid. [0109]

Example 2

Effect of the Composition According to the Invention on the Differentiation of Keratinocytes [0110]
Principle of the Method: [0111]
The study consists in evaluating the effect of the combination of ascorbic acid and of a polymer or copolymer according to the invention on the differentiation of keratinocytes by measuring the transglutaminase activity (TGk) of cultured human epidermal keratinocytes. The TGk is a marker of the terminal differentiation of the keratinocyte and of the formation of the cornified envelope (corneocyte). [0112]
Human epidermal keratinocytes used at the 3rd passage are inoculated in a 96-well plate at a density of 10 000 cells per well and are cultured in complete SFM medium (Gibco 170005034, EGF and pituitary extract). After preincubating for 24 hours, the cells are brought into contact with the product (tested at 30 μM) for 48 hours. The cells are subsequently washed and then sonicated on ice in Tris/EDTA, pH 8 buffer. The membrane enzyme is extracted in the presence of Triton X100. The TGk activity is quantitatively determined by measuring the covalent addition of tritiated putrescine to casein to a final concentration of 2 μCi/ml. The casein is precipitated with 20% trichloroacetic acid comprising 1 mM of putrescine. The precipitates are collected on Skatron filters and collector. The precipitates are washed in 5% TCA medium comprising 0.1 mM of putrescine and ethanol. The dry filters are counted by liquid scintillation. The proteins are quantitatively determined on each sample using a Dc Protein Assay kit (BioRad). The TGk activities are reported in μg of protein. [0113]
Retinol (10[0114] ⁻⁶M) and a calcium-poor medium were used as references for antidifferentiating effect.
Intergroup comparisons were carried out by variance analysis (ANOVA) using Dunnett's multiple comparison test. [0115]
Results: [0116]
The results show that the combination of ascorbic acid and of an N-vinylimidazole/N-vinylpyrrolidone copolymer leads to a significant increase in the TGk activity present in cultures of keratinocytes and thus to a prodifferentiating activity with respect to the keratinocytes. Furthermore, this compound had no cytotoxicity under the conditions of the test. [0117]

Example 3

O/W Fluid [0118]

The following composition is prepared in a way conventional to persons skilled in the art.



Methyl glucose sesquistearate	2	g
Stearyl alcohol and ceteareth-20	2	g
Cyclohexasiloxane	10	g
Propyl paraben	0.1	g
Prunus armeniaca (apricot) kernel oil	6	g
Shorea robusta seed butter	2	g
Water	13.85	g
Methylparaben	0.25	g
PEG-20 methyl glucose sesquistearate	2	g
Ascorbic acid	5	g
Potassium hydroxide (50% solution)	2.97	g
Vinylpyrrolidone/vinylimidazole copolymer	1	g
Water	41.03	g
Polyacrylamide and C_13-14isoparaffin and Laureth-7	1	g
Xanthan gum	0.25	g
Chlorohexidine digluconate	0.05	g
Water	10.5	g

A soft and fresh fluid is obtained, which fluid improves the appearance of the skin by virtue of better moisturizing and in which fluid ascorbic acid has good stability. [0120]

Example 4

O/W Cream [0121]

The following composition is prepared in a way conventional to a person skilled in the art.



Phase A:
Glyceryl stearate and PEG-100 stearate	2.1	g
Polysorbate 60	0.9	g
Cetyl alcohol	2.6	g
Hydrogenated polyisobutene	12	g
Cyclomethicone	8	g
Phase B:
Water	59.23	g
Glycerol	2	g
Ascorbic acid	5	g
Potassium hydroxide (50% solution)	3.07	g
Vinylpyrrolidone/vinylimidazole copolymer	1	g
Xanthan gum	0.1	g
Carbomer	0.4	g
Phase C:
Triethanolamine	0.3	g
Water	3	g

	Preservatives	0	.3	g

A soft and fresh fluid is obtained, which fluid provides better moisturizing and in which fluid ascorbic acid has good stability. [0123]
The above description of the invention, as illustrated by non-limiting examples, allows one of ordinary skill in the art to make and use a method for promoting the synthesis of ceramides and/or improving the barrier function of the skin with a composition comprising, preferably in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the said active principle and the said polymer or copolymer both being present in the aqueous phase by simple application to the skin of the described composition. Also fully described in such terms as to allow one of ordinary skill to make and use it is a method for maintaining and/or improving the radiance of the complexion with application of a composition comprising, preferably in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the said active principle and the said polymer or copolymer both being in the aqueous phase. Similarly fully described is a method for preventing and/or combating roughness of the skin using such a composition. Also fully described in terms allowing one of ordinary skill to make and use it is the use of at least one oxidation-sensitive principle selected from the group consisting of ascorbic acid and its derivatives and of at least one non-crosslinked N-vinylimidazole polymer or copolymer for the preparation of a dermatological composition comprising an aqueous phase which is intended to promote the synthesis of ceramides and/or to improve the barrier function of the skin, and a process for moisturizing the skin and/or treating dry skin and/or maintaining and/or improving the radiance of the complexion, comprising the application to the skin of a composition comprising, preferably in a physiologically acceptable medium, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the active principle and the polymer or copolymer both being present in the aqueous phase. [0124]
French Patent Application 0115375 is hereby incorporated by reference, as are all documents, references, texts, patents, applications, standards, etc. mentioned above. Where a numerical range or limit stated herein, all values therebetween are incorporated as if specifically written out. [0125]
Also incorporated herein by reference are the following U.S. applications, all filed Nov. 27, 2002, where the present application is listed for information only:[0126]
U.S. Ser. No. ______ (Atty. Docket 230634US0) [0127]
U.S. Ser. No. ______ (Atty. Docket 230608US0) [0128]
U.S. Ser. No. ______ (Atty. Docket 230616US0) [0129]
U.S. Ser. No. ______ (Atty. Docket 230614US0) [0130]
U.S. Ser. No. ______ (Atty. Docket 230615US0) [0131]

Claims

1. A method for promoting the synthesis of ceramides and/or improving the barrier function of the skin, for maintaining and/or improving the radiance of the complexion, for treating dry skin, for moisturizing the skin, or for preventing and/or combating roughness of the skin, comprising applying to the skin a composition comprising, in a physiologically acceptable medium comprising an aqueous phase, at least one oxidation-sensitive hydrophilic active principle selected from the group consisting of ascorbic acid and its derivatives and at least one non-crosslinked N-vinylimidazole polymer or copolymer, the at least one active principle and the at least one polymer or copolymer both being present in the aqueous phase.

2. The method according to claim 1, wherein said method is for maintaining and/or improving the radiance of the complexion.

3. The method according to claim 1, wherein said method is for preventing and/or combating roughness of the skin.

4. The method according to claim 1, wherein said ascorbic acid derivatives are selected from the group consisting of ascorbic acid esters and ascorbic acid salts.

5. The method according to claim 1, wherein the hydrophilic active principle is selected from the group consisting of 5,6-di-O-dimethylsilylascorbate, dl-α-tocopheryl dl-ascorbyl phosphate potassium salt, magnesium ascorbyl phosphate and sodium ascorbyl phosphate.

6. The method according to claim 1, wherein the hydrophilic active principle is ascorbic acid.

7. The method according to claim 1, wherein the composition comprises a non-crosslinked copolymer that is a combination of the N-vinylimidazole with N-vinylpyrrolidone and/or N-vinylcaprolactam subunits.

8. The method according to claim 1, wherein the composition comprises a non-crosslinked copolymer that is an N-vinylimidazole/N-vinylpyrrolidone copolymer.

9. The method according to claim 1, wherein the composition comprises a non-crosslinked copolymer selected from the group consisting of a vinylpyrrolidone/vinylimidazole (50/50) copolymer having a weight-average molar mass of 1 200 000 and a vinylpyrrolidone/vinylimidazole (50/50) copolymer having a weight-average molar mass of 10 000.

10. The method according to claim 1, wherein the molar ratio of N-vinylimidazole unit equivalent to the oxidation-sensitive hydrophilic active principle is 0.004 to 16.

11. The method according to claim 10, wherein the molar ratio of the N-vinylimidazole unit equivalent to the oxidation-sensitive hydrophilic active principle varies between 0.01 and 1.

12. The method according to claim 1, wherein the polymer or copolymer is present at a concentration of 0.1 to 5% by weight of the aqueous phase.

13. The method according to claim 12, wherein the polymer or copolymer is present at a concentration of 0.1 to 2% by weight of the aqueous phase.

14. The method according to claim 1, wherein the polymer or copolymer has a molar fraction of N-vinylimidazole units of 0.1 to 1.

15. The method according to claim 14, wherein the polymer or copolymer has a molar fraction of N-vinylimidazole units of 0.4 to 0.9.

16. The method according to claim 1, wherein the composition further comprises another agent in addition to the oxidation-sensitive hydrophilic active principle, which agent acts on the barrier function of the skin or which promotes moisturizing of the skin and/or desquamating.

17. The method according to claim 16, the composition further comprising an agent selected from the group consisting of ceramides, sphingoid, lecithins, glycosphingolipids, phospholipids, cholesterol and its derivatives, phytosterols, essential fatty acids, 1,2-diacylglycerol, 4-chromanone, pentacyclic triterpenes, petroleum jelly, lanolin, threalose and its derivatives, hyaluronic acid and its derivatives, glycerol, pentanediol, sodium pidolate, serine, xylitol, sodium lactate, glyceryl polyacrylate, ectoin and its derivatives, chitosan, oligo- and polysaccharides, cyclic carbonates, N-lauroylpyrrolidonecarboxylic acid, N-α-benzoyl-L-arginine, DHEA and steroid derivatives, and vitamin D and its derivatives.

18. The method according to claim 16, the composition further comprising an agent selected from the group consisting of β-hydroxy acids; α-hydroxy acids; urea; gentisic acid; oligofucoses; cinnamic acid; Saphora japonica extract; resveratrol; EDTA; N-acyl-N,N′,N′-ethylenediaminetriacetic acid; aminosulphonic compounds; 2-oxothiazolidine-4-carboxylic acid (procysteine) derivatives; derivatives of α-amino acids of glycine; honey; and sugar derivatives.

19. The method of claim 1, for promoting the synthesis of ceramides and/or improving the barrier function of the skin.