FR2939652A1 - Composition, useful for care and/or make up of skin, comprises substituted phenyl compound and solvent comprising isononyl isononanoate, dimethyl isosorbide, and amino acid ester in medium comprising oil - Google Patents

Abstract

Cosmetic and/or dermatological composition comprises: (a) at least one N,N'-diphenyl methylene ethylene diaminediacetic acid ester compound (Ia) and its salt; and (b) at least one solvent comprising isononyl isononanoate, dimethyl isosorbide, ester of amino acid (II), in a medium containing at least one oil. Cosmetic and/or dermatological composition comprises: (a) at least one N,N'-diphenyl methylene ethylene diaminediacetic acid ester compound of formula (Ia) and its salt; and (b) at least one solvent comprising isononyl isononanoate, dimethyl isosorbide, and ester of amino acid of formula (R1a(CO)N(R2a)CH(R3a)(CH 2) n(CO)OR4a) (II), in a medium containing at least one oil. R 11-6C linear saturated alkyl or 3-6C branched saturated alkyl, preferably isopropyl; R-2-R 4H (preferred) or -OR 5-; R 5H or 15C linear saturated alkyl or 3-5C branched saturated alkyl; R1a : alkyl or 5-21C alkenyl; R2a : H or 1-3C alkyl; R3a : H, methyl, ethyl or 3-4C alkyl; R4a : 1-10C alkyl, 2-10C alkenyl or sterol residue; and n : 0.1 or 2. [Image].

Description

The present invention relates to cosmetic and / or dermatological compositions in the form of an oil-in-water emulsion comprising at least one N, N'-diarylmethylene ethylenediaminediacetic acid ester and at least one particular surfactant.

The compositions according to the invention are in particular intended for the care and / or the makeup of keratinous substances, and in particular of the skin. Esters of N, N'-diarylmethylene ethylenediaminediacetic acid are described in WO 94/11338 as iron chelators and scavengers against the formation of hydroxyl free radicals, making them useful for protecting keratin materials, and in particular the skin, against the oxidative stress caused by the ultraviolet rays. These derivatives are therefore useful in the prevention of cutaneous photoaging. However, these compounds have the particularity of being solid at room temperature and of being only little or not soluble in the liquid raw materials conventionally used in cosmetics and / or in dermatology. In particular, these compounds are not soluble in water, and are poorly soluble in polyols such as glycerine, propylene glycol, and also poorly soluble in apolar oils such as isododecane, hydrogenated polyisobutene (Parleam home NOF Corporation), cyclopentasiloxane. Therefore, in order to make the most of their activity, it is generally necessary to formulate these compounds with a particular solvent specifically dedicated to their solubilization. Moreover, formulations in the form of oil-in-water emulsions are advantageous in the field of cosmetics and dermatology in that they generally have a very good tolerance to the skin, and sensory and / or organoleptic properties. satisfactory for the consumer (especially in terms of touching). However, the inventors have found that the production of oil-in-water emulsions with anionic surfactants such as fatty acids such as stearic acid causes a chemical degradation of the ester compounds inducing a decrease in the amount of these ester compounds present in the water. emulsion and therefore a loss of effectiveness of the cosmetic product. For these reasons, there remains a need for compositions that are suitable for the formulation of N, N'-diarylmethylene ethylene diamine diacetic acid esters in the form of more efficient oil-in-water emulsions, which do not impair stability. said ester, while maintaining a good skin tolerance. The object of the present invention is precisely to propose a new galenic formulation of N, N'-diarylmethylene ethylenediamine diacetic acid esters making it possible to overcome the abovementioned disadvantages and to maintain the chemical stability of these compounds in a lasting manner over time. . The inventors have discovered, unexpectedly, that the combination of certain esters of N, N'-diarylmethylene ethylenediaminediacetic acid with certain particular surfactants makes it possible to give satisfaction in these terms, and in particular to maintain the chemical stability of said esters. formulated as an oil-water emulsion.

The invention thus relates, in one of its aspects, to a cosmetic and / or dermatological composition in the form of an oil-in-water emulsion comprising: (a) at least one compound of general formula (I): R3 in which: each R 1 and R "1 independently represents a hydrogen atom or a linear saturated alkyl radical comprising from 1 to 6 carbon atoms or a branched saturated alkyl radical containing from 3 to 6 carbon atoms, provided that the two groups R1 and R "1 do not simultaneously represent a hydrogen atom, - R2, R3 and R4 represent, independently of each other, a hydrogen atom or a radical -OR5, and (I) - R5 represents a hydrogen atom or a linear saturated alkyl radical comprising from 1 to 5 carbon atoms or a branched saturated alkyl radical comprising from 3 to 5 carbon atoms, or their salts, (b) an effective amount of at least one solvent said compound of general formula (I), and (c) at least one ionic surfactant selected from alkali salts of acyl (C10-C22) glutamic acids, alkaline salts of palmitoyl sarcosinate, and mixtures thereof. The compound of general formula (I) is advantageously present in the compositions in accordance with the invention in a form solubilized by the presence of at least one of its solvents in an effective amount. Its chemical stability is, in turn, preserved by the presence of at least one particular ionic surfactant as defined above. The combination, in an oil-in-water emulsion, of a N, N'-diarylmethylene ethylenediamine diacetic acid ester according to the invention with such an ionic surfactant makes it possible to obtain cosmetic and / or dermatological compositions remarkably effective for the aforementioned applications. The compositions in accordance with the invention may in particular be intended for treating and / or protecting keratinous substances of human beings, in particular the skin, against aging caused in particular by exposure to the sun (ultraviolet rays).

Thus, according to another of its aspects, the present invention relates to a non-therapeutic treatment method of care and / or makeup of keratinous substances, in particular the skin, comprising at least the step of applying to said keratin materials, and especially on the skin, at least one composition as defined above.

ESTER OF THE N, N'-DIARYLMETHYLENE ETHYLENE DIAMINEDIACETIC ACID The esters of N, N'-diarylmethylene ethylenediaminediacetic acid considered according to the invention are compounds of general formula (I): in which: each group R 1 and R I independently represents a hydrogen atom or a linear saturated alkyl radical comprising from 1 to 6 carbon atoms or a branched saturated alkyl radical comprising from 3 to 6 carbon atoms, provided that the two groups R 1 and R "1 do not not simultaneously represent a hydrogen atom, - R2, R3 and R4 represent, independently of each other, a hydrogen atom or a radical -OR5, and - R5 represents a hydrogen atom or a linear saturated alkyl radical 10 comprising 1 to 5 carbon atoms or a branched saturated alkyl radical comprising from 3 to 5 carbon atoms. These compounds can be obtained by any method known to those skilled in the art and, for example, according to the preparation methods described in WO 94/11338. According to a first embodiment, it is more particularly N, N'-diarylmethylene ethylenediaminediacetic acid esters of general formula (Ia): R 3 in which: (I) - RI represents a linear saturated alkyl radical comprising 1 to 6 carbon atoms or a branched saturated alkyl radical comprising from 3 to 6 carbon atoms, - R2, R3 and R4 represent, independently of each other, a hydrogen atom or a radical -OR5, and - R5 represents a hydrogen atom or a linear saturated alkyl radical comprising from 1 to 5 carbon atoms or a branched saturated alkyl radical comprising from 3 to 5 carbon atoms. According to one embodiment, R2, R3 and R4 represent a hydrogen atom. According to another embodiment, R1 denotes an isopropyl radical.

It may especially be the compound of general formula (Ia) in which R2, R3 and R4 represent a hydrogen atom and R1 denotes an isopropyl radical, that is to say the diisopropyl ester of the acid. N, N'-bis- (benzyl) ethylenediamine-N-N'-diacetic of formula: This compound is more particularly described in Example 16 of WO 94/11338. According to a second embodiment, it may also be esters of N, N'-diarylmethylene ethylenediaminediacetic acid of general formula (Ib): R 3 in which: R 1 represents a linear saturated alkyl radical comprising from 1 to 6 carbon atoms or a branched saturated alkyl radical comprising from 3 to 6 carbon atoms, - R2, R3 and R4 represent, independently of each other, a hydrogen atom or a radical -OR5, and - R5 represents an atom hydrogen or a linear saturated alkyl radical comprising from 1 to 5 carbon atoms or a branched saturated alkyl radical comprising from 3 to 5 carbon atoms. The compounds of formula (Ib) are novel compounds not described in the prior art. The invention also relates to such compounds.

As the compound of formula (Ib), mention may be made of isopropyl monoester of N, N'-bis (benzyl) ethylenediamine-N-N'-diacetic acid. The compounds of formula (Ib) can be obtained according to scheme I of synthesis by reacting a dibenzylated ethylenediamine (A) with a molar equivalent of tert-butyl bromoacetate in the presence of a base such as, for example, potassium carbonate in a polar solvent such as for example dimethylformamide, then reacting a molar equivalent of the bromoacetate derived from the alcohol R1OH. The intermediate diester (B) obtained is then selectively hydrolyzed to its tert-butyl part in an acid medium (for example, hydrochloric or trifluoroacetic acid) to yield the half-ester of formula (Ib).

R3 R3 O R2 Br ~ O R4 O

## STR2 ## wherein R 3 is R 3, R 3 is hydrogen, R 3 is R 3, R 3 is R 3, R 3 is hydrogen, R 3 is R 3 described above include conventional non-toxic salts of said compounds such as those formed from organic or inorganic acids. By way of example, mention may be made of the salts of mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and boric acid. Mention may also be made of organic acid salts, which may comprise one or more carboxylic acid, sulphonic acid or phosphonic acid groups. It may be linear, branched or cyclic aliphatic acids or aromatic acids. These acids may furthermore comprise one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. These include propionic acid, acetic acid, trifluoroacetic acid, terephthalic acid, citric acid and tartaric acid. The preferred salts are those obtained from hydrochloric, sulfuric, acetic, trifluoroacetic, tartaric and citric acids. The amount of N, N'-diarylmethylene ethylenediaminediacetate derivatives to be used in a composition according to the invention depends on the desired cosmetic effect and can therefore vary to a large extent. Those skilled in the art can easily, on the basis of their general knowledge, determine the appropriate quantities. The compositions in accordance with the invention may comprise from 0.2 to 10% by weight, preferably from 0.5 to 5% by weight, in particular from 0.8 to 3% by weight, and for example at least 1% by weight. weight of compound of general formula (I), (Ia) or (Ib), in particular of formula (Ia), relative to the total weight of said composition.

SOLVENT OF THE ESTER OF THE N, N'-DIARYLMETHYLENE ETHYLENEDIAMINEDIACETIO ACID The compositions in accordance with the invention comprise at least one N, N'-diarylmethylene ethylenediamine diacetic acid ester of the formula (I), (Ia) or ( Ib) in combination with at least one effective amount of one of its solvents. As a suitable solvent, mention may notably be made of ethanol, hydrogenated isoparaffin, squalane, isopropyl palmitate, octyl-2-dodecanol, 2-ethylhexyl salicylate, dipropylene glycol and myristate. isopropyl, hexylene glycol, phenyltrimethicone, apricot oil, isononyl isononanoate, dimethyl isosorbide, amino acid esters of formula (II): R'1 (CO) N (R) 2) CH (R '3) (CH 2) n (CO) OR' 4 (II) in which: n is an integer equal to 0, 1 or 2; R '1 represents a C 5 alkyl or alkenyl radical; at C21, linear or branched, R'2 represents a hydrogen atom or a C1-C3 alkyl group; R'3 represents a radical chosen from the group formed by a hydrogen atom, a methyl group, a ethyl group, a linear or branched C3 or C4 alkyl radical, and - R'4 represents a linear or branched C 1 to C 10 alkyl radical, or a linear or branched C 2 to C 10 alkenyl radical, or a sterol residue; and one of their mixtures. It will preferably be a solvent selected from isononyl isononanoate, dimethyl isosorbide, amino acid esters of formula (II) as defined above, and a mixture thereof. According to a first embodiment, the solvent is isononyl isononanoate. According to a second embodiment, the solvent is dimethyl isosorbide. According to a third embodiment, the solvent is an amino acid ester of formula (II) as indicated above. The amino acid esters which are suitable for the invention, as well as their synthesis process, are described, for example, in the patent applications EP 1 044 676 and EP 0 928 608 of the company AJINOMOTO Co. In the amino acid esters of the formula (II), the group R'1 (CO) - is preferably an acyl group of an acid preferably selected from the group formed by capric acid, lauric acid, myristic acid, palmitic acid , stearic acid, behenic acid, linoleic acid, linolenic acid, oleic acid, isostearic acid, 2-ethylhexanoic acid, coconut oil fatty acids, fatty acids of palm kernel oil. These fatty acids may furthermore have a hydroxyl group. Even more preferably, it will be lauric acid. The -N (R '2) CH (R' 3) (CH 2) - (CO) - portion of the amino acid ester is preferably selected from the following amino acids: glycine, alanine, valine, leucine, isoleucine, serine threonine, proline, hydroxyproline, 13-alanine, aminobutyric acid, aminoca-proic acid, sarcosine, or N-methyl-13-alanine.

Even more preferably, it will be sarcosine. The part of the amino acid esters corresponding to the group OR '4 can be obtained from the alcohols chosen from the group formed by methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, isobutanol, 3-methyl-1-butanol, 2 1-methyl-1-butanol, fusel oil, pentanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, lauryl alcohol, myristic alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleic alcohol, behenyl alcohol, jojoba alcohol, 2-hexadecyl alcohol, 2-octyldodecanol alcohol and isostearyl alcohol. These amino acid esters can in particular be obtained from natural sources of amino acids. In this case, the amino acids come from hydrolysis of natural plant proteins (oats, wheat, soybean, palm, coconut) and then necessarily lead to mixtures of amino acids which will then be esterified and then N-acylated. The preparation of such amino acids is more particularly described in patent application FR 2 796 550 which is incorporated herein by reference. The amino acid ester more particularly preferred for use in the present invention is isopropyl N-lauroylsarcosinate of formula CH3- (CH2) 1000N (CH3) -CH2-COO-CH (CH3) 2.

As isopropyl N-lauroylsarcosinate, mention may be made, for example, of the product sold by the company Ajinomoto under the reference ELDEW SL-205. In the context of the present invention, it is understood by the effective amount of solvent or solvent mixture according to the invention a sufficient quantity of this solvent or mixture of solvents to solubilize the N, N'-diarylmethylene acid ester. ethylenediaminediacetic formula (I), (Ia) or (Ib), and thus prevent any recrystallization phenomenon, especially during storage. For obvious reasons, the amount of solvent according to the invention which is sufficient to solubilize the N, N'-diarylmethylene ethylenediamine diacetic acid ester is likely to vary to a large extent depending in particular on the chemical nature and / or the amount of said N, N'-diarylmethylene ethylenediaminediacetic acid ester to be solubilized and the nature of the solvent or solvent mixture used. The adjustment of the amount of solvent according to the invention is within the skill of the skilled person. It is clear that in the embodiments in which this solvent is represented by one of the abovementioned solvents or one of their mixture, the joint presence of another solvent is conceivable, provided, of course, that this additional compound does not bear damage to the solubility ensured by the solvent required according to the invention.

By way of illustration, the solvent according to the invention may be present in an amount ranging from 0.05 to 25% by weight, more preferably from 0.5 to 12.5% by weight, and more particularly from 2.5 to 5% by weight. % by weight relative to the total weight of the composition. According to one embodiment, the solvent according to the invention and the compound of general formula (I), (Ia) or (Ib) may be present in a mass ratio [solvent / compound of general formula (I), (Ia ) or (Ib)] at least equal to 1.5, in particular ranging from 1.5 to 15, and preferably ranging from 1.5 to 10. When the solvent is isononyl isononanoate, the weight ratio [isonononoate isononyl / compound of general formula (I), (Ia) or (Ib)] may be especially at least equal to 5.25, for example ranging from 5.25 to 8, and preferably ranging from 5.25 to 6.5. When the solvent is dimethyl isosorbide, the weight ratio [dimethyl isosorbide / compound of general formula (I), (Ia) or (Ib)] may especially be at least equal to 1.6, for example ranging from 1.6 to 10, preferably from 1.6 to 6.

When the solvent is an amino acid ester of formula (II), the weight ratio [amino acid ester of formula (II) / compound of general formula (I), (Ia) or (Ib)], may be in particular at least 4.5, for example ranging from 4.5 to 10, preferably ranging from 4.5 to 6. In particular, the weight ratio [isopropyl N-lauroylsarcosinate / diisopropyl ester of the acid N, N'-bis- (benzyl) ethylenediamine-N-N'-diacetic] may be at least 4.5, for example ranging from 4.5 to 10, preferably ranging from 4.5 to 6.

IONIC SURFACTOR The compositions in accordance with the invention further comprise at least one ionic surfactant chosen from the alkaline salts of acyl (C10-C22) glutamic acids, the alkaline salts of palmitoyl sarcosinate, and mixtures thereof. As alkaline salts, there may be mentioned, for example, sodium salts, potassium salts and lithium salts, and preferably sodium salts. According to one embodiment, the compositions in accordance with the invention comprise at least one alkaline salt of glutamic acyl (C10-C22) acids, preferably an alkaline salt of acyl (C12-C20) glutamic acids, and for example a salt. alkali of acyl (C16-C1g) glutamic acids.

It may in particular be one of the alkaline salts of stearoyl glutamic acid, lauroyl glutamic acid, acyl glutamic acid, myristoyl glutamic acid, cocoyl glutamic acid or acylated hydrogenated tallow glutamic acid. Preferably, it will be an ionic surfactant chosen from sodium stearoyl glutamate, disodium stearoyl glutamate, potassium stearoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, potassium lauroyl glutamate and cocoyl. sodium glutamate, hydrogenated tallow acyl glutamate, and mixtures thereof, and preferably sodium stearoyl glutamate. By way of illustration, mention may be made, for example, of sodium steryl glutamate sold by the company Ajinomoto under the reference AMISOFT HS 11 PF. According to another embodiment, the compositions in accordance with the invention comprise at least one alkaline salt of palmitoyl sarcosinate. Preferably, it will be palmitoyl sarcosinate sodium. For obvious reasons, the amount of ionic surfactant according to the invention is likely to vary to a large extent depending in particular on the chemical nature and / or the amount of said N, N'-diarylmethylene ethylenediaminediacetic acid ester. and the nature of the ionic surfactant used. The adjustment of the amount of ionic surfactant according to the invention is within the skill of those skilled in the art. By way of illustration, the ionic surfactant according to the invention may be present in an amount of active material ranging from 0.01% to 20% by weight, more preferably from 0.1% to 10% by weight and even more preferably from 0% to 10% by weight. , 2 to 5% by weight and more particularly still from 0.25 to 2% by weight relative to the total weight of the composition.

EMULSION The compositions according to the invention are in the form of an oil-in-water emulsion. In addition to an ionic surfactant according to the invention, these emulsions may contain at least one additional emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The additional emulsifiers are of course selected appropriately for obtaining an oil-in-water emulsion.

As additional emulsifiers which may be used, mention may be made, for example, of nonionic emulsifiers such as fatty acid esters of oxyalkylenated polyols (more particularly polyoxyethylenated), and for example polyethylene glycol stearates such as PEG-100 stearate. PEG-50 stearate and PEG-40 stearate; and mixtures thereof such as the mixture of glyceryl mono-stearate and of polyethylene glycol stearate (100 OE) marketed under the name SIMULSOL 165 by the company SEPPIC; esters of oxyalkylenated fatty acids and of sorbitan comprising, for example, from 20 to 100%, and for example those sold under the trade names Tween 20 or Tween 60 by the company Ubiqema; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; and mixtures thereof, for example the mixture of glyceryl stearate and PEG-100 stearate, sold under the name Arlacel 165 by Uniqema, or the mixture of glyceryl stearate and PEG-40 stearate.

It is also possible to prepare emulsions without additional emulsifying surfactants or containing less than 0.5% of the total weight of the composition, using suitable compounds, for example polymers having emulsifying properties such as acrylic acid / stearyl methacrylate polymers. such as those marketed under the names Carbopol 1342 and Pemulen by Noveon; or polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Clariant under the name Hostacerin AMPS (CTFA name: ammonium polyacryldimethyltauramide) or as the acrylamide / sodium acrylamido 2-methyl propane sulfonate polymer such as that sold under the name Sepigel 305 by the company Seppic (INCI name: polyacrylamide / C13-C14 isoparaffin / laureth-7), the copolymer (AMPS ethoxylated C12 / C14 alcohol methacrylate) (8 moles OE) (80/20) (Aristoflex LNC from Clariant); ionic or nonionic polymer particles, more particularly anionic polymer particles such as in particular isophthalic acid or sulfoisophthalic acid polymers, and in particular phthalate / sulfoisophthalate / glycol copolymers (for example diethylene glycol / phthalate / isophthalate / 1,4-cyclohexane dimethanol (INCI name: DiglycoUCHDM / I sophthalates / SIP Copolymer) sold under the names Eastman AQ polymer (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the company Eastman Chemical The composition according to the invention can comprise in addition, at least one organic photoprotective agent and / or at least one active inorganic photoprotective agent in the UVA and / or UVB (absorbers) which may be water-soluble or fat-soluble or insoluble in the cosmetic solvents commonly used. a filter system will be used for both UVA and UVB radiations.Solar filters are molecules that absorb UV radiation and thus prevent them from reaching the level of skin cells. They can absorb either UVB or mainly UVA, depending on their nature. There are two main categories of solar filters, either organic or mineral (zinc or titanium oxides). By using them in cosmetic compositions in combination and in sufficient quantity, they make it possible to stop a large part of the UV radiation. However, it is generally accepted that, in order to be effective, these formulas must be used under good conditions of application (sufficient quantity, frequent renewal, homogeneous spreading). These conditions of application are not always respected by the user, which increases the risk that a significant amount of UV radiation reaches the cells of the skin, and therefore generates the biological effects mentioned above. Moreover, in order to obtain an absorption with respect to all the wavelengths of the UV UV + UVA solar spectrum, it is necessary to associate several absorbing molecules in domains of complementary wavelengths. The complementary organic screening agents are chosen in particular from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; derivatives of (3, (3-diphenylacrylate, triazine derivatives, benzotriazole derivatives, benzalmalonate derivatives, in particular those cited in US Patent 5,624,663, benzimidazole derivatives, imidazolines, bis-benzoazolyl derivatives such as described in patents EP 0 669 323 and US 2,463,264, derivatives of p-aminobenzoic acid (PABA), methylene derivatives bis (hydroxyphenyl benzotriazole) as described in US applications 5,237,071, US 5,166,355, GB 2303549, DE 197 26 184 and EP 0 893 119, the benzoxazole derivatives as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10 16 2844, filter polymers and silicone filters such as those described in particular in patent application WO-93/04665, dimers derived from α-alkylstyrene such as those described in patent application DE 19 855649, 4,4-diarylbutadienes as described in applications EP 0 967 200, DE 19 746654, DE 755649, EP-A-1,008,586, EP 1,133,980 and EP 1,133,981; merocyanine derivatives such as those described in applications WO 04/006878, WO 05/058269 and WO 06/032741 and mixtures thereof.

Examples of complementary organic photoprotective agents are those referred to below under their INCI name:

Cinnamic derivatives: Ethylhexyl Methoxycinnamate sold in particular under the trade name Parsol MCX by DSM Nutritional Products, Inc., Isopropyl Methoxycinnamate, Isoamyl Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 by SYMRISE, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate,

Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name ESCALOL 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name Uvinul P25 by BASF, Salicylic derivatives Homosalate sold under the name Eusolex HMS by Rona / EM Industries, Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by

Dipropylene glycol salicylate sold under the name DIPSAL by SCHER, TEA Salicylate, sold under the name NEO HELIOPAN TS by SYMRISE,

Derivatives of (3, (3-diphenylacrylate: Octocrylene sold in particular under the trade name UVINUL N539 by BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by BASF,

Derivatives of benzophenone: 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, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate sold under the trade name UVINUL A + by BASF,

Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by MERCK, SYMRISE, Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name Mexoryl SO by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX, Derivatives of phenyl benzimidazole: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name EUSOLEX 232 by MERCK, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name NEO HELIOPAN AP by SYMRISE, Derivatives of phenyl benzotriazole: Drometrizole Trisiloxane sold under the name Silatrizole by Rhodia Chimie, methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form under the name commercial MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trademark TINOSORB M by CIBA SPECIALTY CHEMICALS,

Triazine derivatives: - Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name TINOSORB S by CIBA GEIGY, - Ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF, - Diethylhexyl butamido triazone sold under the trade name UVASORB 30 HEB by SIGMA 3V 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine - 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, - 2 , 4bis (n-butyl 4'-aminobenzoate) -6- (aminopropyltrisiloxane) -s-triazine, 2,4bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s- triazine, the symmetrical triazine filters described in US Pat. No. 6,225,467, WO 2004/085412 (see compounds 6 and 9) or the Symetrical Triazine Derivatives IP.COM Journal, IP.COM INC. WEST HENRIETTA, NY, US (20). September 2004) including 2,4,6-tris- (biphenyl) -1,3,5-triazines (in particular 2,4,6-tris (biphenyl-4-yl-1,3,5-triazine and 2.4, 6-tris (terphenyl) -1,3,5-triazine which is incorporated in patent applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006 / 034,985,

Anthranilic Derivatives: Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by Haarmann and REIMER, Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

Benzalmalonate Derivatives: A benzalmalonate-functional polyorganosiloxane such as Polysilicone-15 sold under the trade name PARSOL SLX by DSM Nutritional Products, Inc.,

4,4-Diarylbutadiene derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene,

Benzoxazole derivatives: 2,4-bis- [5 - 1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine sold as Uvasorb K2A by Sigma 3V, Merocyanine Derivatives: Octyl-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate, and mixtures thereof

The preferred organic screening agents are chosen from ethylhexyl methoxycinnamate, ethylhexyl salicylate, homosalate, octocrylene, phenylbenzimidazo, sulphonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. hexyl, 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Methylene bis-Benzotriazolyl Tetramethylbutylphenol, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Ethylhexyl Triazone, Diethylhexylbutamido Triazone, 2,4,6-Tris (4'- dineopentyl amino benzalmalonate) -s-triazine, 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, 2,4bis (n-butyl 4'-aminobenzoate) -6- (aminopropyltrisiloxane) -s-triazine, 2,4bis (dineopentyl 4'-aminobenzalmalonate) -6- (n-butyl 4-aminobenzoate) -s-triazine, 2,4,6-tris (4-biphenyl) 1,3,5-triazine, 2,4,6-tris (terphenyl) -1,3,5-triazine, Drometrizole Trisiloxane, Polysilicone-15, 1,1-Dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene, 2,4-bis- [5 - 1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] (6-ethylhexyl) -imino-1,3,5-triazine, Octyl-5-N, N-diethylamino-2-phenysulfonyl-2,4-pentadienoate, and mixtures thereof.

The organic filters in accordance with the invention may represent from 0.1 to 30%, preferably from 1 to 25%, of the total weight of the composition.

The complementary inorganic UV filters used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV filters of the invention are metal oxide particles having an average element particle size of less than or equal to 500 nm, more preferably between 5 nm and 500 nm, and even more preferentially between 10 nm. and 100 nm, and preferably between 15 and 50 nm. They may be chosen in particular from oxides of titanium, zinc, iron, zirconium, cerium or their mixtures and more particularly titanium oxides. Such metal oxide pigments, coated or uncoated are in particular described in the patent application EP-A-0 518 773. As commercial pigments can be mentioned the products sold Kemira, Tayca, Merck and Degussa. The metal oxide pigments may be coated or uncoated. The coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (of titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly titanium oxides coated with: silica, such as the SUNVEIL product from the company IKEDA, silica and iron oxide, such as the SUNVEIL F product from IKEDA, silica and alumina, such as the products MICROTITANIUM DIOXIDE TM 500 SA and MICROTITANIUM DIOXIDE MT 100 = SA from the company TAYCA, TIOVEIL from the company TIOXIDE, 19-alumina such as the products TIPAQUE TTO-55 (B) and TIPAQUE TTO- 55 (A) from ISHIHARA, and UVT 14/4 from KEMIRA, - alumina and aluminum stearate such as MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT 100 Z, MT-01 products. from the company TAYCA, Solaveil products CT-10 W and Solaveil CT 100 from the company UNIQEMA and the product Eusolex T-AVO from the company Merck, - silica, alumina and alginic acid such as the product MT- 100 AQ from TAYCA, - alumina and aluminum laurate such that the MICROTITANIUM DIOXIDE MT 100 S product from the company TAYCA, iron oxide and iron stearate such as the MICROTITANIUM DIOXIDE MT 100 F product from TAYCA, zinc oxide and zinc stearate, that the product BR 351 from the company TAYCA, silica and alumina and treated with a silicone such as MICROTITANIUM DIOXIDE MT 600 SAS products, MICROTITANIUM DIOXIDE MT 500 SAS or MICROTITANIUM DIOXIDE MT 100 SAS from TAYCA, - silica, alumina, aluminum stearate and treated with a silicone such as the product STT-30-DS from the company TITAN KOGYO, of silica and treated with a silicone such as the product UV-TITAN X 195 from the company KEMIRA, - alumina and treated with a silicone such as TIPAQUE products TTO-55 (S) from the company ISHIHARA, or UV TITAN M 262 from the company KEMIRA, - triethanolamine such as the product STT- 65-S of the company TITAN KOGYO, - ac stearic acid such as the product TIPAQUE TTO-55 from the company ISHIHARA, 30 - sodium hexametaphosphate such as MICROTITANIUM DIOXIDE MT 150 W from TAYCA, - TiO2 treated with octyl trimethyl silane sold under the name commercial T 805 by the company DEGUSSA SILICES, - TiO2 treated with a polydimethylsiloxane sold under the trade name 70250 Cardre UF TiO2SI3 by CARDRE, - the anatase / rutile TiO2 treated with a polydimethylhydrogensiloxane sold under the trade name MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC by the company COLOR TECHNIQUES. Uncoated titanium oxide pigments are for example sold by Tayca under the trade names MICROTITANIUM DIOXIDE MT 500 B or MICROTITANIUM DIOXIDE MT600 B, by DEGUSSA under the name P 25, by the company WACKHER under the name Oxide of transparent titanium PW, by the company MIYOSHI KASEI under the name UFTR, by TOMEN under the name ITS and by the company TIOXIDE under the name TIOVEIL AQ.

The uncoated zinc oxide pigments are, for example, those sold under the name Z-cote by the company Sunsmart. The coated zinc oxide pigments are for example: those sold under the name Oxide zinc CS-5 by the company Toshibi (ZnO coated with polymethylhydrogen siloxane); those marketed under the name DAITOPERSION ZN-30 and DAITOPERSION Zn-50 by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of ultrafine zinc oxides coated with silica and polymethylhydrogensiloxane); those marketed under the name NFD Ultrafine ZnO by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name SPD-Z1 by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name Escalol Z100 by ISP (ZnO treated with alumina and dispersed in the ethylhexyl methoxycinnamate / PVP-hexadecene / methicone copolymer mixture); those marketed under the name Fuji ZnO-SMS-10 by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane). The uncoated cerium oxide pigments may for example be those sold under the name COLLOIDAL CERIUM OXIDE by the company RHONE 5 POULENC. Uncoated iron oxide pigments are for example sold by MITSUBISHI under the name TY-220. The coated iron oxide pigments are for example sold by BASF under the name OXIDE DE FER TRANSPARENT. Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and cerium dioxide, including the titanium dioxide / cerium-coated cerium-aluminum alloy mixture sold by the company IKEDA under the trademark SUNVEIL A as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product M 261 sold by KEMIRA or coated with alumina, silica and glycerin such as M 211 product sold by KEMIRA company. According to the invention, titanium oxide pigments, coated or uncoated, are particularly preferred. The inorganic filters according to the invention may represent from 0.5 to 40%, preferably from 1 to 30%, of the total weight of the composition.

The following examples are given by way of illustration of the invention and should not be interpreted as limiting its scope.

Example 1: Preparation of trifluoroacetic acid salt of N, N'-bis- (benzyl) ethylenediamine-N-N'-diacetic acid isopropyl monoester Br. Embedded image In a 2-liter reactor equipped with mechanical stirring, the catalyst is used in a 2-liter reactor equipped with mechanical stirring. Benzathine (A) (36.19 g, 150 mmol) was added to 300 ml of dimethylformamide as well as potassium carbonate (20.81 g, 150 mmol). The reaction medium was maintained at a temperature of 0 ° C. and then tert-butylbromoacetate (27.26 g, 150 mmol) diluted beforehand in 500 ml of dimethylformamide was added dropwise over 5 hours. It was stirred for thirty minutes and then isopropyl bromocetate (29.37 g, 150 mmol) was introduced in its entirety. The reaction medium was brought to room temperature and stirring was maintained for 17 hours. After filtration, the filtrate from the reaction was concentrated. The product obtained was taken up in 150 ml of dichloromethane. The formed salts were filtered and the filtrate was concentrated under reduced pressure. This intermediate was solubilized in 50 ml of dichloromethane and a solution of 75% trifluoroacetic acid in dichloromethane was added. After 6 hours when the whole of the mixed di-ester has disappeared (mass monitoring), the reaction medium was concentrated under reduced pressure and co-evaporated twice with toluene.

This crude product was purified on silica sinter with a dichloromethane / methanol eluent system. The percentage of methanol varies from 0% to 8%. At first, the cleanest fractions were pooled and dried. A sticky brown oil was obtained which was taken up in heptane overnight and then the solid obtained was filtered. This solid was recrystallized from a minimum of water: a first fraction (batch 1) of 3.1 g of a white powder was obtained. In a second step, the other fractions were grouped together. A yellow-orange oil was obtained which was recrystallized from isopropyl ether and a few milliliters of heptane. The precipitate was filtered to give a white powder which was washed in water. A second fraction (batch 2) of 3 g of a white powder was obtained. The overall yield is 10%. The product is obtained in the form of trifluoroacetic acid salt (mono-salt). Elemental Analyzes: Calculated: C: 58.6%; H: 6.1%, N: 5.5%; 0: 18.7%; F: 11.1% Measured (lot 1): C: 58.32%; H: 6.10%; N: 5.39%; F: 10.94% Measured (lot 2): C: 58.42%, H: 6.12%, N: 5.45%, F: 11.09% EXAMPLE 2 (Comparative) The following oil-in-water emulsions were produced: - glyceryl stearate Polyethylene glycol stearate (40 0E) - sorbitan tristearate (SPAN 65 V from Croda) - cetyl alcohol - sodium stearoyl glutamate (Amisoft HS 11 PF from Ajinomoto) - stearic acid - hydrogenated polyisobutene (Parléam from NOF) Isopropyl N-lauroylsarcosinate - diisopropyl ester of N, N'-bis (benzyl) ethylenediamine N, N'-diacetic acid - dibutyl pentaerithrityl tetrahydroxycinnamate (Tinogard TT from Ciba) - Cyclopentasiloxane - Propylene glycol - Mixture Methyl, butyl, ethyl, propyl, isobutyl (7/57/22/14) -triethanoamine - Water-R (control) p-hydroxybenzoates 3 3 2 2 0.90 0.90 4 4 0 1.2 1, The content of diisopropyl ester of 5 N, N'-bis acid was then measured. (benzyl) ethylenediamine N, N'-diacetic after 2 months of storage at 4 ° C, at room temperature and at 45 ° C. The diester compound content is measured by reverse phase high performance liquid chromatography using a WATERS / X-Trerra RP18 column (5 m) at 150 nm, and as eluent a 0.02 M acetonitrile / sodium acetate buffer gradient. / 40 and 95/5.

The chromatographic conditions are as follows: Flow rate: 1 ml / ml Volume injected: 20 UL Detection: 210 nm Retention time: approximately 6.7 minutes

The two standard solutions used are as follows: 12 g / ml and 120 g / ml of diisopropyl ester of N, N'-bis (benzyl) ethylenediamine N, N'-diacetic acid in acetonitrile.

Preparation of the sample to be measured (test solution): A mass m of the stored composition is dispersed in a volume V of acetonitrile so as to obtain a concentration of diester compound in the standard range. The calibration line is plotted by plotting on the ordinate the surface values obtained on the chromatograms of the standard solutions and on the abscissa the concentrations of diester compound in the standard solutions. The concentration in the stored composition is deduced from the calibration straight line using the following formula: ## EQU1 ## where C is the concentration of diester compound in the test solution (in mg / ml) - S being the peak area of the diester compound on the test chromatogram - A being the ordinate at the origin of the calibration line of the diester compound, and - B being the slope of the calibration line of the diester compound.

The content T (in%) of the diester compound in the stored composition is determined by the following formula: T = 100 × (C x V) / m, - C being the concentration of diester compound in the test solution (in mg / ml V is the final volume after dispersion of the sample (in ml), and m being the amount of sample of the stored composition.

The results are as follows: Content after 2 months of storage (control) at 4 ° C. 1.0% 1.0% at 45 ° C. 0.8% 0.9% The use of a compliant ionic surfactant With the invention, sodium stearoyl glutamate makes it possible to maintain, at high temperature, the chemical stability of the diisopropyl ester of N, N'-bis (benzyl) ethylenediamine N, N'-diacetic acid in an oil emulsion. -in-water.

EXAMPLE 3 A sunscreen composition in the form of an oil-in-water emulsion containing the following ingredients is prepared: 0.88 g triethanolamine disodium salt of ethylene diamine tetracetic acid 0.1 g tetrahydroxycinnamate dibutyl pentaerithrityl 0.20 g (Tinogard TT from Ciba) - isopropyl N-lauroylsarcosinate 8 g - Diisopropyl ester of N, N'-bis (benzyl) ethylenediamine-N, N 'diacetic acid 1 g - Alcohol stearyl 1 g - Preservatives (mixture of parabens and phenoxyethanol - PHENONIP 1 g from Clariant) - Preservatives (NIPASTAT paraben mixture from Clariant) 0.25 g - 2-ethylhexyl salicylate 5 g - 4-tert-butyl 4 33% methoxy dibenzoyl methane in water 3 g - terephthalylidene dicamphosulphonic acid 5 g - 2-cyano 3,3-diphenylacrylate, 2-ethyl hexyl 7 g - Drometrizole trisiloxane (Silatrizole from Rhodia) 1.5 g Acrylamide / acrylamido 2-methyl propane sulfonate copolymer sodium gg in 40% inverse emulsion in isohexadecane / water (Simulgel 600 from Seppic) 2 - Styrene / acrylate copolymer particles (Sunspheres Powder from 2 Rohm and Haas) - Cyclopentasiloxane 3 g - Glycerin 5 g - Stearate mixture glyceryl and PEG-100 stearate (ARLACEL 165 FL from Uniqema) 2 g - sodium stearoyl glutamate (Amisoft HS 11 PF from Ajinomoto) 1.3 g - Water qs 100 g5

Claims (14)

REVENDICATIONS1. Cosmetic and / or dermatological composition in the form of an oil-in-water emulsion comprising (a) at least one compound of general formula (Ia): R 3 in which: R 1 represents a linear saturated alkyl radical comprising from 1 to 6 carbon atoms or a branched saturated alkyl radical comprising from 3 to 6 carbon atoms, - R2, R3 and R4 represent, independently of each other, a hydrogen atom or a radical -OR5, and - R5 represents an atom hydrogen or a linear saturated alkyl radical comprising from 1 to 5 carbon atoms or a branched saturated alkyl radical comprising from 3 to 5 carbon atoms, or their salts, (b) an effective amount of at least one solvent of said compound of general formula (Ia), and (c) at least one ionic surfactant selected from alkaline salts of acyl (C10-C22) glutamic acids, alkaline salts of palmitoyl sarcosinate, and mixtures thereof. 20 2. Composition according to the preceding claim, wherein R2, R3 and R4 represent a hydrogen atom. 3. Composition according to any one of the preceding claims, in which R1 denotes an isopropyl radical. 4. A composition according to any one of the preceding claims wherein the compound of general formula (Ia) is N, N'-bis (benzyl) ethylenediamine-N-N'-diacetic acid diisopropyl ester. 5. Composition according to any one of the preceding claims, comprising from 0.2 to 10% by weight, preferably from 0.5 to 5% by weight, in particular from 0.8 to 3% by weight, and for example at least 1% by weight of compound of general formula (Ia) relative to the total weight of said composition. 6. A composition according to any one of the preceding claims, wherein said alkaline salts are selected from sodium salts, potassium salts and lithium salts, and preferably from sodium salts. 7. Composition according to any one of the preceding claims, comprising at least one alkaline salt of acyl (C12-C20) glutamic acids, and preferably an alkaline salt of acyl (C16-C18) glutamic acids. 8. Composition according to the preceding claim, comprising at least one of the alkali salts of stearoyl glutamic acid, lauroyl glutamic acid, acyl C glutamic acid, myristoyl glutamic acid, acid glutamic cocoyl or glutamic hydrogenated tallow acyl acid. 9. Composition according to the preceding claim, comprising at least sodium stearoyl glutamate, disodium stearoyl glutamate, potassium stearoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, potassium lauroyl glutamate, cocoyl glutamate and sodium, hydrogenated tallow acyl glutamate or mixtures thereof, and preferably sodium stearoyl glutamate. 10. Composition according to any one of the preceding claims, comprising at least sodium palmitoyl sarcosinate. 25 11. Composition according to any one of the preceding claims, characterized in that said ionic surfactant is present in an amount of active material ranging from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight, still more preferably from 0.2 to 5% by weight and more particularly from 0.25 to 2% by weight relative to the total weight of the composition. 30 12. Composition according to any one of the preceding claims, in which the solvent is chosen from ethanol, hydrogenated isoparaffin, squalane, isopropyl palmitate, octyl-2-dodecanol, salicylate of 2- ethyl hexyl, dipropylene glycol, isopropyl myristate, hexylene glycol, phenyl trimethicone, apricot oil, isononyl isononanoate, dimethyl isosorbide, and amino acid esters of formula (II): R '1 (CO) N (R' 2) CH (R '3) (CH 2) n (CO) OR' 4 (II) in which: n is an integer equal to 0, 1 or 2, - R ' 1 represents a linear or branched C5 to C21 alkyl or alkenyl radical; R'2 represents a hydrogen atom or a C1-C3 alkyl group; R'3 represents a radical chosen from the group formed by an atom; hydrogen, a methyl group, an ethyl group, a linear or branched C3 or C4 alkyl radical, and - R'4 represents a linear or branched C 1 to C 10 alkyl radical, or an alkenyl radical containing C2 to C10 linear or branched, or a sterol residue; and one of their mixtures. 13. Composition according to the preceding claim wherein the solvent is selected from isononyl isononanoate, dimethyl isosorbide, said amino acid esters of formula (II) and a mixture thereof. 14. Non-therapeutic treatment method of care and / or makeup of keratin materials, especially the skin, comprising at least the step of applying to said keratinous substances, and in particular to the skin, at least one composition as defined in any one of claims 1 to 13.