FR2956316A1 - Cosmetic method of non therapeutic treatment or make up of keratin materials comprises topical application of a composition comprising water, ascorbic acid and sulfonic acid compound - Google Patents

Abstract

Cosmetic method of non therapeutic treatment or make up of keratin materials comprises: topical application of a composition (A) comprising water, ascorbic acid and sulfonic acid compound (I) and their salts. Cosmetic method of non therapeutic treatment or make up of keratin materials comprises: topical application of a composition (A) comprising water, ascorbic acid and sulfonic acid compound of formula (R-O-CH 2-S(=O) 2-OH) (I) and their salts. R : H (preferred) or linear saturated 1-2C hydrocarbon group. An independent claim is included for the composition (A) comprising water, ascorbic acid (0.1-10 wt.%) and sulfonic acid compound (I) and their salts. ACTIVITY : Dermatological. MECHANISM OF ACTION : None given.

Description

The present invention relates to a cosmetic process for treating or making up keratin materials, comprising applying to the keratin materials a cosmetic composition comprising ascorbic acid and a particular sulphonic acid compound.

It is known to introduce into cosmetic compositions various active agents intended to provide specific treatments for the skin and / or the hair. However, some of these active agents have the drawback of being unstable in an aqueous medium and of easily degrading in contact with water, in particular because of oxidation phenomena. They lose their activity quickly over time and this instability runs counter to the desired efficiency.

It has long been sought to formulate ascorbic acid or vitamin C, because of its many beneficial properties. In particular, ascorbic acid stimulates the synthesis of connective tissue and especially collagen, reinforces the skin's defenses against external aggressions such as ultraviolet radiation and pollution, compensates for the vitamin E deficiency of the skin, depigments skin and has an anti-free radical function. These last two properties make it an excellent candidate as a cosmetic or dermatological active agent to fight against the aging of the skin or to prevent it. Unfortunately, ascorbic acid is very sensitive to certain parameters of the environment and in particular to oxidation phenomena. It can oxidize rapidly to dehydroascorbic acid, a highly unstable chemical entity that decays due to its chemical structure (alpha, beta bis-ketolactone). This results in rapid degradation of the ascorbic acid formulated in the presence of these parameters, and more particularly in the presence of oxygen, light, metal ions, depending on the temperature, or under certain conditions. pH (Pharm Acta Helv., 1969, 44, 611-667, STP Pharma, 1985, 4, 281-286). This degradation is manifested in particular by the appearance of a color in the composition that can gradually change from yellow to orange then brown, making the composition unacceptable to the user.

Several solutions have therefore been envisaged in the prior art for decreasing and / or delaying the degradation of ascorbic acid.

One of the solutions described in application EP-A-1374852 is to associate with ascorbic acid a copolymer of styrene and hydrolysed maleic anhydride (that is to say an ethylenically unsaturated dicarboxylic acid) to obtain an improvement. notable for the stability of ascorbic acid in an aqueous medium. Nevertheless, despite this improvement in stability, it has been found that such a composition has the disadvantage of yellowing after storage for at least 15 days or even 1 or 2 months at room temperature and at a temperature of 45 ° C. This yellowing of the composition makes it attractive to consumers and hinders the marketing of such a composition.

The object of the present invention is therefore to provide a composition comprising ascorbic acid in aqueous medium having improved stability and having a small variation in the color of the composition, after storage for 2 months at 45 ° C.

In this regard the Applicant has surprisingly and unexpectedly discovered that the stability of such a composition is improved by combining with ascorbic acid a sulfonic acid compound as described below. It is known in the document Jiang, Libing et al; Jinan 3rd Pharm. Fact., Jinan, 250022, Peop. Rep. China Zhongguo Yaoxue Zazhi (Beijing, China) (1990), 25 (6), 352-4 an injectable pharmaceutical composition comprising 20% ascorbic acid and sodium hydroxymethyl sulfonate. More precisely, the subject of the invention is therefore a cosmetic process for the non-therapeutic treatment or make-up of keratin materials such as the skin, the hair, the hairs, the eyelashes, the eyebrows, the nails of a human being, comprising topical application to keratin materials of a composition comprising, in a physiologically acceptable medium containing water, ascorbic acid, and a sulphonic acid compound of formula (I) below: OIIR ~ O ~ SùOH O ( I) in which R denotes a hydrogen atom or a C1-C2 saturated linear hydrocarbon radical, and their salts.

The composition used in the process according to the invention comprises ascorbic acid which may be present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, and preferably ranging from 1 at 6% by weight. The invention also relates to a composition comprising, in a physiologically acceptable medium containing water, from 0.005% to 5% by weight, relative to the total weight of the composition, of ascorbic acid, and a compound sulfonic acid of formula (I) below: OIIR ~ O ~ SùOH 0 (I) wherein R denotes a hydrogen atom or a saturated linear hydrocarbon radical C1-C2, and their salts.

Preferentially, for the compound of formula (I) described above, R denotes a hydrogen atom. The salts of the compounds of formula (I) may in particular be alkali metal or alkaline earth metal salts or ammonium salts. For example, the sodium, potassium, lithium, magnesium, calcium and zinc salts may be mentioned. Preferably, the sodium salts are used.

As compounds of formula (I), mention may be made of hydroxymethylsulfonic acid, sodium hydroxymethylsulphonate (known compound having CAS No. 870-72-4), methoxymethylsulfonic acid, and ethoxymethylsulfonic acid. Hydroxymethylsulphonic acid or sodium hydroxymethylsulphonate is preferably used. More preferably, sodium hydroxymethylsulphonate is used.

The compounds of formula (I) for which R denotes a saturated linear hydrocarbon radical C1-C2 are described in particular in the application WO2003 / 106379. The sulphonic acid compound of formula (I) described above may be present in the composition according to the invention in a content ranging from 0.005% to 5% by weight, relative to the total weight of the composition, and preferably of 0.05% by weight. % to 1% by weight. The composition according to the invention comprises a physiologically acceptable medium. In particular the composition is suitable for topical application to the skin. The physiologically acceptable medium is in particular a cosmetically or dermatologically acceptable medium, that is to say without odor, color or unpleasant appearance, and which does not generate tingling, tightness or redness unacceptable to the user. By physiologically acceptable medium is meant a medium compatible with human keratin materials such as skin, mucous membranes, nails, scalp and / or hair.

The composition used according to the invention may be intended for a cosmetic or pharmaceutical application, particularly dermatological. Preferably the composition according to the invention is intended for a cosmetic application. It can be used for the care or makeup of keratin materials.

The composition according to the invention comprises water which may be present in a content ranging from 5% to 80% by weight, relative to the total weight of the composition, and preferably ranging from 35% to 75% by weight. .

The composition may also comprise a polyol which is miscible with water at an amobal temperature (25 ° C.), in particular chosen from polyols having in particular from 2 to 20 carbon atoms, preferably having from 2 to 10 carbon atoms. and preferably having from 2 to 6 carbon atoms, such as glycerine, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as monoalkyl, di- or tripropylene glycol alkyl (C1-C4) ethers, mono-, di- or alkyl (C1-C4) ethers; triethylene glycol; and their mixtures.

The composition according to the invention may comprise a polyol which is miscible with water at room temperature in a content ranging from 1% to 20% by weight, relative to the total weight of the composition, and preferably ranging from 3% to at 15% by weight.

The composition may include an oil. The term "oil" means a fatty substance that is liquid at room temperature (25 ° C.). As oils which can be used in the composition of the invention, mention may be made, for example, of: hydrocarbon-based oils of animal origin, such as perhydrosqualene and squalane; hydrocarbon-based oils of plant origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, such as the triglycerides of heptanoic or octanoic acids, or else, for example, sunflower, corn, soya, squash, grape seed, sesame, hazelnut, apricots, macadamia, arara, sunflower, castor oil, avocado, caprylic / capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the tradenames Miglyol 810, 812 and 818 by Dynamit Nobel, jojoba oil, shea butter oil; esters and synthetic ethers, in particular of fatty acids, such as the formula oils R'COOR2 and R'OR2 in which R 'represents the residue of a fatty acid containing from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or unbranched, containing from 3 to 30 carbon atoms, for example purcellin oil, isononyl isononanoate, isopropyl myristate or 2-ethyl palmitate. hexyl, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, 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 (Prisorine 3631); linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam oil; fatty alcohols having from 8 to 26 carbon atoms, such as cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol; partially fluorinated hydrocarbon oils and / or silicone oils such as those described in document JP-A-2-295912; silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane and cyclopentasiloxane; polydimethylsiloxanes (or dimethicones) comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl-dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; - their mixtures.

The term "hydrocarbon-based oil" in the list of oils mentioned above, any oil predominantly comprising carbon and hydrogen atoms, and optionally ester, ether, fluoro, carboxylic acid and / or alcohol groups.

The oil may be present in a content ranging from 5 to 50% by weight, relative to the total weight of the composition, and preferably ranging from 10 to 30% by weight. The composition may also comprise a cosmetic additive especially chosen from fillers, surfactants, cosmetic or dermatological active agents, UV filters, film-forming polymers, gelling agents, preservatives, perfumes, pigments.

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

The composition used according to the invention may be in any galenical form normally used in the cosmetic and dermatological fields; it may especially be in the form of an aqueous solution, hydroalcoholic, optionally gelled, a dispersion of the lotion type possibly two-phase, an oil-water or water-in-oil or multiple emulsion, an aqueous gel, d an oil dispersion in an aqueous phase using spherules, these spherules possibly being polymeric nanoparticles such as nanospheres and nanocapsules or, better still, lipid vesicles of ionic and / or nonionic type. Advantageously, the composition is an oil-in-water emulsion.

When the composition is an emulsion, the proportion of the fatty phase can range from 5 to 80% by weight, and preferably from 5 to 50% by weight relative to the total weight of the composition. The oils and emulsifiers used in the composition in emulsion form are chosen from those conventionally used in the field considered. The emulsifier is present in the composition in a proportion ranging from 0.3 to 30% by weight. and preferably from 0.5 to 20% by weight relative to the total weight of the composition.

This composition may be more or less fluid and have the appearance of a white or colored cream, an ointment, a milk, a lotion, a serum, a paste, a mousse . It can optionally be applied to the skin in the form of an aerosol. It can also be in solid form, and for example in the form of a stick.

The following examples illustrate the invention.

Comparative Examples 1 to 3: There was prepared: a) an oil-in-water emulsion A according to the invention comprising ascorbic acid and sodium hydroxymethyl sulfonate;

b) an oil-in-water emulsion B not forming part of the invention, similar to emulsion B in which the sodium hydroxymethyl sulphonate has been replaced by the styrene / maleic acid copolymer, sodium salt with 40% by weight in water (SMA1000HNa® marketed by the company CRAY VALLEY) c) an oil-in-water emulsion B not forming part of the invention, similar to emulsion A but not containing hydroxymethyl sodium sulphonate (compensated by 1% of water added) The emulsions produced are as follows, the contents being expressed in percentages by weight: Phase Ingredients A (invention) BC (excluding inven- (excepting) vention) Al sesquistearate methyl 2,00 2 2 glucose (Glucamate SS from Noveon) Mixture of stearyl alcohol 2.00 2 2 and cetyl stearyl alcohol oxyethylen-20 EO (Promulgen G from Noveon) Cyclohexasiloxane 10.00 10 10 Propylparaben 0,10 0,10 0,10 A2 Apricot fines oil 6,00 6 6 Sh butter orea 2.00 2 2 BI water 38.93 38.93 38.93 methylparaben 0.25 0.25 0.25 Pentasodium salt of acid 0.05 0.05 0.05 ethylene diamine tetramethylene phosphonic hydroxymethyl sulfonate of sodium 2 0 B2 water 5,00 5 5 methyl sesquistearate 2,00 2 2 oxyethylenated glucose (Glucanate SSE 20 from Noveon) C Potassium hydroxide 3.15 3.15 3.15 water 10.00 10 Ascorbic acid 5,00 5 D acrylate-1,00 mmol / sodium acrylamido 2-methyl propane sulphonate copolymer in 40% inverse emulsion in isoparaffin / water (Sepigel 305 from Septopus) E Gum of Xanthane 0.25 0.25 0.25 water 8.00 8 8 F Chlorhexic digluconate 0.30 0.30 0.30 dine water 3.97 3.97 4.97 Styrene / acid copolymer 1% MA therefore maleic acid, sodium salt 2.5% salt 40% by weight sodium at 40% in water (SMA1000HNa® by weight sold by the company CRAY VALLEY) 100.00 100 100 Procedure.

Heat phase B1 to 75 ° C. Heat the B2 phase to 60 ° C. Pour phase B2 into phase B1 and keep at 60 ° C with stirring. Prepare phase E. Heat Al phase at 65-75 ° C.

Heat the A2 phase to 60 ° C. Pour phase A2 into phase Al and maintain at 60 ° C. Emulsify by slowly pouring the phases Al + A2 in the phases B1 + B2 at 60 ° C (the high speed is sufficient to heat) for 15 min with stirring. allow to cool to 50 ° C by decreasing the stirring speed.

Add the phases C, D, E and F.

The ascorbic acid degraded during the storage of the compositions causes a coloration of the composition. The more the composition is stable and the less the composition is colored after storage. The stability of the emulsions was therefore evaluated by measuring the color of the compositions tested at t0 = 0 and at t1 = 2 months / 45 ° C.

The compositions were stored for 2 months at 45 ° C in a half-filled vial of 30 ml so that the volume of oxygen in each vial was constant. After this storage time, the color of each composition was measured in the L *, a *, b *, L * systems representing the intensity of the color, a * indicating the green / red color axis and b * the blue / yellow color axis, using a Konika-Minolta CM-2600d spectrophotometer. The measurements of L, a, b were carried out in reflectance with specular excluded, (for a measurement only of the color). Each day, the calibration of white and black was performed before the measurements on the samples.

For color measurements, 24-well plastic plates were used in which a sample of the composition to be evaluated was deposited. The device measures from below the plate to always have the same distance to the sample and therefore good reproducibility. For each for-mule, two measurements were made. The color is given by the average of the 2 measured values of L, a and b.

The color of the composition was measured at t0 = 0 (values L1, a1, b1) then at t0 = 0 and t1 = 2 months / 45 ° C (values L2, a2, b2) and the color difference is measured. AE of the composition according to the following relationship: E _ The following results were obtained: Composition Delta E 1 17.5 2 22.1 3 31.8 The results obtained show that the variation of the color of the emulsions stored for 2 months at 45 ° C is the lowest for the emulsion A according to the invention containing sodium hydroxymethyl sulfonate while it is higher for emulsion B (containing the styrene / maleic acid copolymer, sodium salt) and emulsion C containing no stabilizer. Thus, the presence of sodium hydroxymethyl sulfonate contributes to a better stability of the emulsion according to the invention and to a smaller variation in the color of the emulsion. The composition according to the invention applied daily to the face makes it possible to combat the signs of aging of the skin.

Claims (10)

REVENDICATIONS1. A cosmetic process for the non-therapeutic treatment or makeup of keratin materials comprising the topical application to keratin materials of a composition comprising, in a physiologically acceptable medium containing water, ascorbic acid, and a compound of following formula (I): ## STR2 ## wherein R denotes a hydrogen atom or a saturated linear hydrocarbon radical C1-C2, and their salts. 2. Method according to the preceding claim, characterized in that for the compound of formula (I) R denotes a hydrogen atom. 3. Method according to one of the preceding claims, characterized in that the compound of formula (I) is chosen from hydroxymethylsulfonic acid, sodium hydroxymethylsulfonate, methoxymethyl sulfonic acid, and ethoxymethyl acid. sulfonic acid. 4. Method according to one of the preceding claims, characterized in that the compound of formula (I) is present in a content ranging from 0.005% to 5% by weight, relative to the total weight of the composition, and preferably from 0.05% to 1% by weight. 5. Method according to one of the preceding claims, characterized in that the ascorbic acid present in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, and preferably ranging from 1 to 6% by weight,% by weight. 6. A composition comprising, in a physiologically acceptable medium containing water, from 0.1% to 10% by weight, relative to the total weight of the composition, ascarbic acid, and a compound of formula (I ) wherein R denotes a hydrogen atom or a C1-C2 saturated linear hydrocarbon radical, and their salts. 7. Composition according to the preceding claim, characterized in that for the compound of formula (I), R denotes a hydrogen atom. 8. Composition according to any one of claims 6 or 7, characterized in that the compound of formula (I) is chosen from hydroxymethylsulfonic acid, sodium hydroxymethylsulfonate, methoxymethyl sulfonic acid, and the acid. ethoxymethyl sulfonic acid. 9. Composition according to any one of claims 6 to 8, characterized in that the compound of formula (I) is present in a content ranging from 0.005% to 5% by weight, relative to the total weight of the composition, and preferably from 0.05% to 1% by weight. 10. Composition according to any one of claims 6 to 8, characterized in that it is in the form of an oil-in-water emulsion.