FR3132637A1 - Cosmetic or dermatological composition comprising a merocyanine and a polyionic complex - Google Patents

Abstract

Cosmetic or dermatological composition comprising a merocyanin and a polyionic complex The present invention relates to a cosmetic or dermatological composition comprising: a) at least one merocyanin of the following formula (3): [Formula 3] and b) at least one polyionic complex containing at least a cationic polysaccharide and at least one cross-linking agent chosen from non-polymeric acids having at least three pKa values and their salts.

Description

Cosmetic or dermatological composition comprising a merocyanine and a polyionic complex

The present invention relates to a cosmetic or dermatological composition comprising at least one merocyanine of formula (3) which will be defined below in detail and at least one polyionic complex containing at least one cationic polysaccharide and at least one crosslinking agent chosen from among non-polymeric acids having at least three pKa values and their salts.

The present invention also relates to the use of at least one such merocyanine of formula (3) to reduce the staining of fabrics, in particular clothing, after washing.

It is known that radiation with a wavelength between 280 nm and 400 nm allows the human epidermis to tan and that radiation with a wavelength between 280 and 320 nm, known as UV rays- B harm the development of natural tan. Exposure is also likely to induce an alteration of the biomechanical properties of the epidermis which results in the appearance of wrinkles leading to premature aging of the skin.

It is also known that UV-A rays with a wavelength between 320 and 400 nm penetrate deeper into the skin than UV-B rays. UV-A rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even of short duration, under normal conditions can lead to a degradation of collagen fibers and elastin which results in a modification of the micro-relief of the skin, the appearance of wrinkles and a irregular pigmentation (brown spots, heterogeneity of complexion).

Protection against UVA and UVB radiation is therefore necessary. An effective photoprotection product must protect against both UVA and UVB radiation.

Numerous photoprotective compositions have been proposed to date to remedy the effects induced by UVA and/or UVB radiation. They generally contain organic UV filters and/or inorganic UV filters which operate according to their own chemical nature and according to their own properties by absorption, reflection, or diffusion of UV radiation. They generally contain mixtures of fat-soluble organic filters and/or water-soluble UV filters combined with metal oxide pigments such as titanium dioxide or zinc oxide.

Numerous cosmetic compositions intended to limit darkening of the skin, improve the color and homogeneity of the complexion have been proposed to date. It is well known in the field of solar products that such compositions can be obtained by using UV filters, and in particular UVB filters. Some compositions may also contain UVA filters. This filtering system must cover UVB protection in order to limit and control the neo-synthesis of melanin promoting overall pigmentation, but must also cover UVA protection in order to limit and control the oxidation of already existing melanin leading to darkening of skin color.

However, it is extremely difficult to find a composition containing a particular combination of UV filters which would be specially adapted to the photo-protection of the skin and particularly to an improvement in the quality of the skin both in terms of color and its appearance. mechanical properties of elasticity.

Advantageously, this improvement is particularly sought after on already pigmented skin with the aim of not increasing either the melanin pigment load or the structure of the melanin already present within the skin.

In fact, the majority of organic UV filters consist of aromatic compounds absorbing in the wavelength range between 280 and 370 nm. In addition to their power to filter solar radiation, the desired photoprotection compounds must also have good cosmetic properties, good solubility in common solvents and in particular in fatty substances such as oils, as well as good photo- stability alone or in combination with other UV filters. They must also be colorless or at least have a color that is cosmetically acceptable to the consumer.

One of the main disadvantages known to date of these compositions is that these filtering systems have insufficient effectiveness against UV radiation and particularly against long UVA radiation with wavelengths beyond 370 nm with the aim of controlling pigmentation. photo-induced and its evolution by a UV filtering system over the entire UV spectrum.

Among all the compounds that have been recommended for this effect, an interesting family of UV filters has been proposed which consists of carbonaceous merocyanine derivatives which is described in patent US4195999, application WO2004/006878 and document IP COM Journal 4 ( 4), 16 No. IPCOM000011179D published on 03/04/2004. These compounds have very good filtration properties in long UVA radiation but have a poorly satisfactory solubility in usual solvents and in particular in fatty substances such as oils, and an unsatisfactory photo-stability for certain merocyanines.

With the aim of searching for other merocyanines having better solubility in usual solvents and better photostability, we have proposed in application WO2013/011094, merocyanines comprising polar groups consisting of hydroxyl and ether functions which show a good filtration efficiency of long UVA rays. However, the oil solubility of these particular merocyanins is not yet fully satisfactory, and often requires a tedious formulation process. Furthermore, the large quantities of solvent required to solubilize this type of merocyanine can cause cosmetic inconveniences such as a sticky and greasy effect upon application.

In addition, sun filters, and in particular those which protect against UVA, are well known to those skilled in the art as leaving yellow traces on clothing, these yellow traces being very difficult to eliminate when washing.

The Applicant surprisingly discovered that when the merocyanines of formula (3) defined below are used as UVA filters, they left few traces after washing, and that these faded over time. This discovery is the basis of the present invention.

Furthermore, the use of a film made from a polyionic complex for cosmetic purposes is proposed in, for example, WO 2013/153678 and JP-A-2014-227389. The film disclosed in WO 2013/153678 and JP-A-2014-227389 can provide certain cosmetic effects.

However, a dispersion comprising a polyionic complex is not always stable. In particular, a dispersion comprising a polyionic complex tends to be unstable at a high temperature such as 45°C or higher. If the dispersion is unstable, the polyion complex tends to precipitate and therefore the dispersion can cause phase separation.

In order to improve the stability of a dispersion comprising a polyionic complex, it has been shown that the use of at least one cationic polysaccharide is effective. For example, as the cationic polymer, a cationic polysaccharide can be used. Alternatively, a cationic polysaccharide may be added to a combination of an anionic polymer and a cationic polymer.

Upon further investigation, it was discovered that a cationic polysaccharide can be used alone with at least one cross-linking agent selected from non-polymeric acids having three or more acid groups and their salts to form a gel which is a gel dynamically and ionically cross-linked, which is abbreviated as DIC gel. The DIC gel which is preferably in particulate form can also form insoluble water-resistant films.

The Applicant has discovered that a composition comprising merocyanines of formula (3) defined below and a polyionic complex containing at least one cationic polysaccharide and at least one crosslinking agent chosen from non-polymeric acids having at least three pKa values and their salts have good stability, good solar filtration efficiency, good cosmeticity and good film-forming properties.

Thus, in accordance with one of the objects of the present invention, there is now proposed a composition in particular cosmetic or dermatological comprising at least one merocyanine of formula (3) which will be defined later in detail, and at least one polyionic complex containing at least one cationic polysaccharide and at least one crosslinking agent chosen from non-polymeric acids having at least three pKa values and their salts.

This composition makes it possible in particular to obtain a sunscreen product which has good film-forming properties while not having the disadvantage of irreversibly staining clothing or other fabrics.

Furthermore, the composition according to the invention has good cosmeticity of the composition comprising merocyanines, the latter being in particular non-greasy and non-sticky.

The present invention also relates to the use of at least one merocyanine of formula (3) which will be defined later in detail to reduce the staining of fabrics, in particular clothing.

The present invention also relates to a non-therapeutic cosmetic process for the care and/or makeup of a keratin material comprising the application to the surface of said keratin material of at least one composition according to the invention as defined above. .

It also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the color and/or homogeneity of the complexion comprising the application to the surface of the keratin material of at least one composition such as previously defined.

It also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of aging of a keratin material comprising the application to the surface of the keratin material of at least one composition as defined above.

Other characteristics, aspects and advantages of the invention will appear on reading the detailed description which follows.

The composition according to the invention is intended for topical application and therefore contains a physiologically acceptable medium. Here we mean “physiologically acceptable medium” a medium compatible with keratin materials.

In the context of the present invention, the term “keratin material” is understood in particular to mean skin, scalp, keratin fibers such as eyelashes, eyebrows, hair and body hair, nails, mucous membranes such as lips. , and more particularly the skin and mucous membranes (body, face, eye contour, eyelids, lips, preferably body, face and lips).

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “between” and “ranging from… to…”.

Furthermore, the expressions “at least one” and “at least” used in this description are respectively equivalent to the expressions “one or more” and “greater or equal”.

By “prevent” or “prevention”, according to the invention is meant the fact of reducing the risk of occurrence or slowing down the occurrence of a given phenomenon, namely, according to the present invention, the signs of aging of a material. keratin.

By “organic UVA filter” we mean any organic chemical molecule capable of absorbing at least UVA radiation in the wavelength range between 320 and 400 nm; said molecule can also absorb UVB radiation in the wavelength range between 280 and 320 nm.

By “organic UVB filter”, we mean any organic chemical molecule capable of exclusively absorbing UVB radiation in the wavelength range between 280 and 320 nm.

MEROCYANINS

The composition according to the invention comprises at least one merocyanine type UVA filter as defined below.

According to the present invention, we will use a family of merocyanines corresponding to the following formula (3) as well as their isomeric geometric forms, in particular E/E- or E/Z-:
[Formula 3]

in which :
A is –O- or –NH;
R is a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, a C ₃ -C ₂₂ cycloalkyl group or a C ₃ -C ₂₂ cycloalkenyl group , said groupings being able to be interrupted by one or more O.

The merocyanine compounds of the invention can be in their E/E-, E/Z- isomeric geometric forms:
[formulas 3 and 3bis]

The even more preferential compounds of formula (3) are those where:
A is -O-; R is a C ₁ -C ₂₂ alkyl, which may be interrupted by one or more O.

Among the compounds of formula (3), we will use more particularly those chosen from the following group as well as their isomeric geometric forms, in particular E/E-, E/Z-: 14
ethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 15
(2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanamide 25
2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 27
2-methylpropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 29

2-butoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 31

3-methoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate
37
3-ethoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate

According to a more particularly preferred embodiment of the invention, the compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)-amino]cyclohex-2-en-1-ylidene}ethanoate (25) will be used in its geometric configuration E/E and/or E/Z.

The E/Z form has the following structure:
[formula 25]

The E/E form has the following structure:
[formula 25bis]

The filtering merocyanines in accordance with the invention may be present in the compositions according to the invention in a concentration ranging from 0.1% to 15% by weight, and preferably from 0.2% to 10% by weight and even better. from 0.5% to 5% by weight relative to the total weight of the composition.

The compounds of formula (3) can be prepared according to the protocols described in Pat. Appl. WO 2007/071582, in IP.com Journal (2009), 9(5A), 29-30 IPCOM000182396D under the title “Process for producing 3-amino-2-cyclohexan-1-ylidene compounds” and in US-A-4,749,643 on col, 13, line 66 – col. 14, line 57 and the references cited therein.

In particular, the compounds of formula (3), such as the compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)-amino]cyclohex-2-en-1-ylidene}ethanoate (25) can be synthesized according to the synthesis scheme described in the publication by B. Winkler et al., Tetrahedron Letters, 55 (2014) 1749-1751, which is entitled “A cyclic merocyanine UV-A absorber: mechanism of formation and crystal structure” , and represented below, for the compounds of formula (3):
[formula 4]
And more particularly for compound 25 described in Table 1:
[formula 5]

Polyion complexes

The composition according to the invention comprises at least one polyionic complex containing at least one cationic polysaccharide and at least one crosslinking agent chosen from non-polymeric acids having at least three pKa values and their salts.

Polyion complexes

The composition according to the present invention comprises at least one polyionic complex. Two or more different types of polyion complexes can be used in combination. Thus, a single type of polyion complex or a combination of different types of polyion complexes can be used.

The quantity of polyionic complexes in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more relative to the weight. total composition.

The amount of polyionic complexes in the composition according to the present invention may be 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less relative to the total weight of the composition.

The quantity of polyionic complexes in the composition according to the present invention can be from 0.01% to 25% by weight, preferably from 0.05% to 20% by weight, and more preferably from 0.1% to 15%. in weight relative to the total weight of the composition.

The above would mean that the polyion complex itself is amphiphilic and insoluble in a fatty material such as an oil or in water.

Cationic polysaccharides

The composition according to the present invention comprises at least one cationic polysaccharide. Two or more different types of cationic polysaccharides may be used in combination. Thus, a single type of cationic polysaccharide or a combination of different types of cationic polysaccharides can be used.

The cationic polysaccharide(s) have a positive charge density. The charge density of the cationic polysaccharides may be from 0.01 meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, and more preferably from 0.1 to 10 meq/g.

It may be preferable that the molecular weight of the cationic polysaccharide(s) is 500 or more, preferably 1000 or more, more preferably 2000 or more, and even more preferably 5000 or more.

Unless otherwise stated in the description, “molecular weight” means number average molecular weight.

The cationic polysaccharide(s) may have at least one positively chargeable and/or positively charged group chosen from primary, secondary or tertiary amino groups, quaternary ammonium groups, a guanidine group, a biguanide group, an imidazole group, an imino group and a pyridyl group. The term “amino group” (primary) here refers to the –NH2 group.

According to a particular embodiment of the invention, the composition comprises at least one cationic polysaccharide having at least one quaternary ammonium group.

The cationic polysaccharide(s) may be homopolymers or copolymers. By “copolymers” we mean both copolymers obtained from two types of monomers and those obtained from more than two types of monomers, such as terpolymers obtained from three types of monomers.

The cationic polysaccharide(s) may be chosen from natural and synthetic cationic polysaccharides.

According to a particular embodiment of the invention, the composition comprises at least one cationic cellulosic polymer. Non-limiting examples of cationic cellulosic polymers are as follows.

(1) Cationic cellulose polymers such as cellulose ether derivatives comprising one or more quaternary ammonium groups described for example in French patent No. 1,492,597, such as polymers sold under the names “JR” (JR 400, JR 125, JR 30M) or “LR” (LR 400, LR 30M) by the Dow Chemical Company. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted with a trimethylammonium group.

(2) Cationic cellulosic polymers such as cellulosic copolymers and cellulosic derivatives grafted with at least one water-soluble quaternary ammonium monomer, and described for example in US patent 4,131,576, such as hydroxyalkylcelluloses, for example hydroxymethyl-, hydroxyethyl- and hydroxypropylcelluloses grafted in particular with at least one group chosen from methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium, and dimethyldiallylammonium. The commercial products corresponding to these polymers include, for example, the products sold under the names “Celquat® L 200” and “Celquat® H 100” by the company Akzo Novel.

(3) Cationic cellulose polymers having at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms. It may be preferable for the cationic cellulosic polymers to be quaternized hydroxyethyl celluloses modified by at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the quaternary ammonium group can preferably contain from 8 to 30 carbon atoms, in particular from 10 to 30 carbon atoms. Aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group comprising at least one C8-C30 hydrocarbon group. As examples of quaternized alkylhydroxyethylcelluloses with C8-C30 fatty chains, mention may be made of the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B (C12 alkyl) and Quatrisoft LM-X 529-8 (Alkyl C18) or Softcat Polymer SL100, Softcat SX-1300X, Softcat SX-1300H, Softcat SL-5, Softcat SL-30, Softcat SL-60, Softcat SK-MH, Softcat SX-400X, Softcat SX- 400H, SoftCat SK-L, Softcat SK-M and Softcat SK-H, marketed by the company Dow Chemical, and the products Crodacel QM, Crodacel, QL (C12 alkyl) and Crodacel QS (C18 alkyl) marketed by the company Croda.

According to a preferred embodiment of the invention, the composition comprises at least one cationic polysaccharide chosen from polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67.

The amount of cationic polysaccharides in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.07% by weight or more, relative to the total weight of the composition.

The amount of cationic polysaccharides in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition.

The quantity of cationic polysaccharides in the composition according to the present invention may be from 0.01% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.05% to 1% by weight. weight, better from 0.07% to 1% by weight relative to the total weight of the composition.

Cross-linking agents

The composition according to the present invention comprises at least one crosslinking agent chosen from non-polymeric acids having three or more acid groups and their salts. Two or more different types of acids having three or more acid groups and/or their salts may be used in combination. Thus, a single type of acid having three or more acid groups and/or its salts or a combination of different types of acids having three or more acid groups and/or their salts can be used. At least one of the acid groups of each of these acids may be in the form of a salt. All the acidic groups of these acids can be in the form of salts. The term "salt" in the present invention means a salt formed by addition of one or more suitable bases to the acid having three or more acid groups, which can be obtained from a reaction between the acid having three or several acid groups with the base(s) according to methods known to those skilled in the art. As salt, mention may be made of metal salts, for example alkali metal salts such as Na and K, and alkaline earth metal salts such as Mg and Ca, and ammonium salts.

The crosslinking agent(s) are chosen from non-polymeric acids having three or more acid groups, preferably from non-polymeric organic acids having three or more acid groups. The term "non-polymeric" here means that the crosslinking agent is not obtained by polymerization of two or more monomers. Consequently, the non-polymeric acid, in particular the non-polymeric organic acid, does not correspond to an acid obtained by polymerization of two or more monomers such as polycarboxylic acid. Preferably, the molecular weight of the non-polymeric acid, especially the non-polymeric organic acid, having three or more acid groups, is 1000 or less, preferably 800 or less, and more preferably 600 or less.

The non-polymeric acid(s) having three or more acid groups, or a salt thereof, may be hydrophilic or water-soluble.

The non-polymeric acid(s) having three or more acidic groups may have three or more acidic groups selected from carboxylic, sulfuric, sulfonic, phosphonic, phosphoric, phenolic hydroxyl, and a mixture thereof. The non-polymeric acid(s) having three or more acid groups and their salts may be chosen from tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, hexacarboxylic acids, their salts and mixtures thereof.

The non-polymeric acid(s) having three or more acid groups and their salts may be chosen from citric acid, aconitic acid, phytic acid, EDTA, glycyrrhizin, inositol triphosphate, inositol pentakisphosphate , tripolyphosphate, adenosine triphosphate, and their salts. Preferably, the non-polymeric acid(s) having three or more acid groups and their salts are chosen from citric acid, phytic acid, and their salts.

The amount of non-polymeric acids having three or more acid groups and their salts in the composition according to the present invention may be 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more, better still 0.1% by weight or more, relative to the total weight of the composition.

The amount of non-polymeric acids having three or more acid groups and their salts in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less. , relative to the total weight of the composition.

The amount of non-polymeric acids having three acid groups and their salts in the composition according to the present invention can be from 0.001% to 10% by weight, preferably from 0.005% to 5%. by weight, and more preferably from 0.01% to 1% by weight, better still from 0.1% to 1% by weight relative to the total weight of the composition.

OILY PHASE

The composition according to the invention may comprise at least one oily phase.

For the purposes of the invention, the term “oily phase” means a phase comprising at least one oil and all of the liposoluble and lipophilic ingredients and fatty substances used for the formulation of the compositions of the invention.

By oil we mean any fatty substance in liquid form at room temperature (20 – 25°C) and at atmospheric pressure (760 mm Hg).

The oily phase may comprise, in addition to the merocyanine filter(s) and optionally the complementary lipophilic filters, at least one volatile or non-volatile hydrocarbon oil and/or a volatile and or non-volatile silicone oil and/or a volatile and or non-volatile fluorinated oil. volatile.

For the purposes of the present invention, the term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

The term “hydrocarbon oil” means an oil containing mainly hydrogen and carbon atoms and possibly one or more heteroatoms, in particular nitrogen and oxygen. Thus these oils may in particular contain one or more carboxy, ester, ether or hydroxy functions.

The term “fluorinated oil” means an oil comprising at least one fluorine atom.

For the purposes of the invention, the term “volatile oil” means an oil capable of evaporating on contact with the skin or the keratin fiber in less than an hour, at room temperature and atmospheric pressure. The volatile oil(s) of the invention are volatile cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40,000 Pa (10 ^{- 3} to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm of Hg).

By "non-volatile oil" is meant an oil remaining on the skin or keratin fiber at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure less than 10 ^-3 mm Hg (0.13 Pa) .

Hydrocarbon oils

As non-volatile hydrocarbon oils which can be used according to the invention, the following may be cited in particular:
(i) hydrocarbon oils of plant origin such as glyceride triesters which are generally triesters of fatty acids and glycerol whose fatty acids can have chain lengths varying from C ₄ to C ₂₄ , the latter being able to be linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oil. sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, cancholy, passionflower, muscat rose; or even the triglycerides of caprylic/capric acids such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
(ii) synthetic ethers having 10 to 40 carbon atoms;
(iii) linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parulam, squalane, and their mixtures;
(iv) synthetic esters such as oils of formula RCOOR' in which R represents the remainder of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R' represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms provided that R + R' is ³ 10, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C ₁₂ -C alcohol benzoate ₁₅ like the product sold under the trade name “Finsolv TN®” or “Witconol TN®” by the company WITCO or “TEGOSOFT TN ®” by the company EVONIK GOLDSCHMIDT, 2-ethylphenyl benzoate like the commercial product sold under the name “X-TEND 226®” by the company ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethyl palmitate -hexyl, isostearyl isostearate, diisopropyl sebacate such as the product sold under the name “Dub Dis” by the company Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene dioctanoate glycol; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters; citrates or tartrates such as linear C ₁₂ -C ₁₃ di-alkyl tartrates such as those sold under the name COSMACOL ETI® by the Company ENICHEM AUGUSTA INDUSTRIALE as well as linear C ₁₄ -C ₁₅ di-alkyl tartrates such than those sold under the name COSMACOL ETL® by the same company; acetates;
(v) fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2- butyloctanol, 2-undecylpentadecanol;
(vi) higher C12-C22 fatty acids, such as oleic acid, linoleic acid, linolenic acid;
(vii) carbonates such as dicaprylyl carbonate such as the product sold under the name “Cetiol CC®” by the company Cognis;
and their mixtures.

Among the non-volatile hydrocarbon oils which can be used according to the invention, we will more particularly prefer glyceride triesters and in particular the triglycerides of caprylic/capric acids, synthetic esters and in particular isononyl isononanoate, oleyl erucate, C ₁₂ -C ₁₅ alcohol benzoate, 2-ethylphenyl benzoate and fatty alcohols in particular octyldodecanol.

As volatile hydrocarbon oils which can be used according to the invention, mention may in particular be made of hydrocarbon oils having 8 to 16 carbon atoms, and in particular branched C alkanes.₈-VS₁₆like C isoalkanes₈-VS₁₆of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, oils sold under the trade names Isopars or Permetyls, C-branched esters₈-VS₁₆, iso-hexyl neopentanoate, and mixtures thereof.

We can also cite the alkanes described in the patent applications of the company Cognis WO 2007/068371, or WO2008/155059 (mixtures of distinct alkanes different from at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from coconut or palm oil. we can cite the mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ) obtained in Examples 1 and 2 of application WO2008/155059 from the Cognis Company. We can also cite n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97®, as well as their mixtures.

Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Solt® by the company SHELL, can also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms and their mixtures.

Silicone oils

The non-volatile silicone oils can be chosen in particular from non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and/or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, silicones phenyls such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

As volatile silicone oils, mention may be made, for example, of linear or cyclic volatile silicone oils, in particular those having a viscosity of 8 centistokes (8 10 ^-6 m ² /s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil which can be used in the invention, mention may be made in particular of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

We can also cite linear volatile alkyltrisiloxane oils of the following general formula:
[formula 9]
where R represents an alkyl group comprising 2 to 4 carbon atoms and one or more hydrogen atoms of which may be substituted by a fluorine or chlorine atom.

Among the oils of general formula (9), we can cite:
3-butyl 1,1,1,3,5,5,5-heptamethyl trisiloxane,
3-propyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, and
3-ethyl 1,1,1,3,5,5,5-heptamethyl trisiloxane,
corresponding to the oils of formula (9) for which R is respectively a butyl group, a propyl group or an ethyl group.

Fluorinated oils

Fluorinated volatile oils can also be used, such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof.

An oily phase according to the invention may further comprise, mixed with or solubilized in the oil, other fatty substances.

Another fatty substance which may be present in the oily phase may be, for example:
- a fatty acid chosen from fatty acids containing 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid and oleic acid;
- a wax chosen from waxes such as lanolin, beeswax, Carnauba or Candellila wax, paraffin waxes, lignite waxes or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as waxes polyethylene, Fischer-Tropsch waxes;
- a gum chosen from silicone gums (dimethiconol),
- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, triglycerides of fatty acids and their derivatives,
- and their mixtures.

Preferably, the overall oily phase, including all the lipophilic substances of the composition capable of being solubilized in this same phase, represents from 5 to 95% by weight, and preferably from 10 to 80% by weight relative to the weight. total composition.

AQUEOUS PHASE

The composition according to the invention may additionally comprise at least one aqueous phase.

The aqueous phase contains water, and optionally other organic solvents soluble or miscible in water.

An aqueous phase suitable for the invention may comprise, for example, water chosen from natural spring water, such as water from La Roche-Posay, water from Vittel, water from Saint Gervais Mont Blanc, or Vichy waters, or floral water.

The water-soluble or miscible solvents suitable for the invention include short-chain monoalcohols, for example C ₁ -C ₄ , such as ethanol and isopropanol; diols or polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, and mixtures thereof.

According to a preferred embodiment, ethanol, propylene glycol, glycerin, and their mixtures can be used more particularly.

According to a particular form of the invention, the overall aqueous phase, including all the hydrophilic substances of the composition capable of being dissolved in this same phase, represents from 5 to 95% by weight, and preferably from 10 to 80% by weight. weight relative to the total weight of the composition.

ADDITIVES Complementary UV filters

The compositions according to the invention may additionally contain one or more complementary UV filters, different from merocyanine derivatives and triazine derivatives as described above, chosen from hydrophilic, lipophilic or insoluble organic UV filters and/or one or more mineral pigments. Preferably, it will consist of at least one hydrophilic, lipophilic or insoluble organic UV filter.

By "hydrophilic UV filter" is meant any organic or inorganic cosmetic or dermatological compound filtering UV radiation capable of being completely dissolved in the molecular state in a liquid aqueous phase or of being solubilized in colloidal form (for example in the form micellar) in a liquid aqueous phase.

By "lipophilic filter" is meant any organic or inorganic cosmetic or dermatological compound filtering UV radiation capable of being completely dissolved in the molecular state in a liquid fatty phase or of being solubilized in colloidal form (for example in micellar form ) in a liquid fatty phase.

By “insoluble UV filter” is meant any organic or inorganic cosmetic or dermatological compound filtering UV radiation having a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in most organic solvents such as paraffin oil, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® marketed by the company DYNAMIT NOBEL. This solubility, achieved at 70°C, is defined as the quantity of product in solution in the solvent at equilibrium with an excess of solid in suspension after return to ambient temperature. It can easily be evaluated in the laboratory.

The complementary organic UV filters are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent US5624663; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds as described in patents EP669323 and US 2,463,264; ; methylene bis-(hydroxyphenyl benzotriazole) compounds as described in applications US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole compounds as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and filter silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadiene compounds as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 and their mixtures.

As examples of organic photoprotective agents, we can cite those designated below under their INCI name.

Cinnamic compounds:
Ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL® MCX by the company DSM Nutritional Products;
Isoamyl p-Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 ® by the company Symrise,

Dibenzoylmethane compounds:
Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL® 1789 by the company DSM Nutritional Products,

Salicylic compounds:
Homosalate sold under the name “Parsol® HMS” by the company DSM Nutritional Products,
Ethylhexyl Salicylate sold under the name “NEO HELIOPAN® OS” by the company Symrise,

Compounds β , β -diphenylacrylate:
Octocrylene sold in particular under the trade name “UVINUL® N 539 T” by the company BASF,

Benzophenone compounds:
Benzophenone-3 or Oxybenzone, sold under the trade name “UVINUL® M 40” by the company BASF,
Diethylamino hydroxybenzoyl hexyl benzoate sold under the trade name “UVINUL® A Plus” or mixed with ethylhexyl methoxycinnamate under the trade name “UVINUL® A Plus B” by the company BASF,
1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (CAS 919803-06-8) as described in application WO2007/ 071584; this compound being advantageously used in micronized form (average size of 0.02 to 2 µm) which can be obtained for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in the form aqueous dispersion,

Benzylidene camphor compounds:
4-Methylbenzylidene camphor sold under the name “EUSOLEX® 6300” by the company MERCK,
Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name “MEXORYL® SX” by the company NOVEAL,

Phenyl benzimidazole compounds:
Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name “EUSOLEX® 232” by the company MERCK,

Bis-benzoazolyl compounds :
Disodium Phenyl Dibenzimidazole Tetra-sulfonate sold under the trade name “NEO HELIOPAN® AP” by the company Symrise,

Phenyl benzotriazole compounds:
Drometrizole Trisiloxane manufactured under the name “MEXORYL® XL” by the company NOVEAL,

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol in particular in solid form such as the product sold under the trade name “MIXXIM BB/100 ®” by the company FAIRMOUNT CHEMICAL or
in the form of an aqueous dispersion of micronized particles having an average particle size which varies from 0.01 to 5 μm and more preferably from 0.01 to 2 μm and more particularly from 0.020 to 2 μm with at least one alkylpolyglycoside surfactant of structure C _n H _2n+1 O(C ₆ H ₁₀ O ₅ ) _x H in which n is an integer from 8 to 16 and x is the average degree of polymerization of the unit (C ₆ H ₁₀ O ₅ ) and varies from 1, 4 to 1.6 as described in patent GB-A-2 303 549 in particular sold under the trade name “TINOSORB® M” by the company BASF or
in the form of an aqueous dispersion of micronized particles having an average particle size which varies from 0.02 to 2 μm and more preferably from 0.01 to 1.5 μm and more particularly from 0.02 to 1 μm in the presence of 'at least one mono-(C ₈ -C ₂₀ ) alkyl ester of polyglycerol having a degree of glycerol polymerization of at least 5 such as the aqueous dispersions described in application WO2009/063392, in particular the product marketed under the name Tinosorb WPGL by the company BASF,

Triazine compounds:
- 3,3'-(1,4-Phenylene)bis(5,6-diphenyl-1,2,4-triazine), INCI name Phenylene Bis-Diphenyl triazine,
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name “TINOSORB® S” by the company BASF, and in its water-dispersible form under the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name TINOSORB® S LiteAqua by the company BASF,
- Ethylhexyl Triazone sold in particular under the trade name “UVINUL® T 150” by the company BASF,
- Diethylhexyl Butamido Triazone sold under the trade name “UVASORB® HEB” by the company 3V SIGMA,
- symmetrical triazine filters substituted with naphthalenyl groups or polyphenyl groups described in patent US6,225,467, application WO2004/085412 (see compounds 6 and 9) or the document “Symetrical Triazine Derivatives” IP.COM IPCOM000031257 Journal, INC WEST HENRIETTA, NY, US (September 20, 2004) in particular 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine marketed under the name TINOSORB® A2B by the company BASF and which is included in patent applications WO06/035000, WO06/034982, WO06/034991, WO06/035007, WO2006/034992, WO2006/034985, these compounds being advantageously used in micronized form (average particle size of 0.02 to 3 µm) which can be obtained for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119 and in particular in aqueous dispersion form,

Anthranilic compounds:
Menthyl anthranilate sold under the commercial trade name “NEO HELIOPAN® MA” by the company Symrise,

Benzalmalonate compounds:
Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name “PARSOL SLX ®” by the company HOFFMANN LA ROCHE,

Benzoxazole compounds:
The INCI name filter 2,2'-(1,4-Phenylene)bis(1,3-benzoxazole offered under the name DBO by the company DSM.

Preferential organic filters are chosen from:
Ethylhexyl Methoxycinnamate,
Ethylhexyl Salicylate,
Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3,
Diethylamino hydroxybenzoyl hexyl benzoate,
4-Methylbenzylidene camphor,
Terephthalylidene Dicamphor Sulfonic Acid,
Disodium Phenyl Dibenzimidazole Tetra-sulfonate,
Methylene bis-Benzotriazolyl Tetramethylbutylphenol,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2,4,6-tris-(bi-phenyl)-triazine,
2,4,6-tris-(ter-phenyl)-triazine,
Drometrizole Trisiloxane,
Polysilicone-15,
Bis-(diethylaminohydroxybenzoyl benzoyl) piperazine,
and their mixtures.

Particularly preferred organic filters are chosen from:
Ethylhexyl Salicylate,
Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene,
Diethylamino hydroxybenzoyl hexyl benzoate,
Terephthalylidene Dicamphor Sulfonic Acid,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
Bis-(diethylaminohydroxybenzoyl benzoyl) piperazine,
Drometrizole Trisiloxane,
2,4,6-tris-(bi-phenyl)-triazine,
and their mixtures.

The 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 elementary particle size less than or equal to 0.5 µm, more preferably between 0.005 and 0.5 µm and even more preferably between 0.01 and 0.2 µm, even better between 0.01 and 0.1 µm, and more particularly between 0.015 and 0.05 µm. They are notably described in Annex VI updated on 09/22/2021 of the European cosmetic products regulation number 1223/2009, but are not limited to this list.

They may in particular be chosen from oxides of titanium, zinc, iron, zirconium, cerium or mixtures thereof.

Such metal oxide pigments, coated or uncoated, are in particular described in patent application EP-A-0 518 773. As commercial pigments, we can mention the products sold by the companies CRODA, TAYCA, and MERCK.

Metal oxide pigments can be coated or uncoated.

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 (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly coated titanium oxides:
- hydrated silica such as the product “MT-100WP” from the company TAYCA,
- silica and iron oxide such as the product “SUNVEIL F®” from the company IKEDA,
- silica and alumina such as the products “MT-500SA®” and “MT-100SA®” from the company TAYCA, “TIOVEIL™ AQ-N” from the company CRODA,
- alumina such as the “TTO-55 (A)®” products from the company ISHIHARA,
- alumina and aluminum stearate such as the products “MT-100TV®, MT-100Z®, MT-01®” from the company TAYCA, the product “Solaveil™ CT100” from the company CRODA and the product “ Eusolex T-AVO®" from the MERCK company,
- silica, alumina and alginic acid such as the product “MT-100AQ®” from the company TAYCA,
- alumina and aluminum laurate,
- iron oxide and iron stearate,
- zinc oxide and zinc stearate,
- silica and alumina and treated with a silicone such as the products "MTY-500SAS®" or "MICROTITANIUM DIOXIDE MT-100SAS®" from the company TAYCA,
- silica, alumina, aluminum stearate and treated with a silicone,
- silica and treated with a silicone,
- alumina and treated with a silicone such as the "TTO-55(S)®" products from the company ISHIHARA,
- triethanolamine,
- stearic acid such as the product “TTO-55 (C)®” from the company ISHIHARA,
- sodium hexametaphosphate,
- TiO2 treated with octyl trimethyl silane,
- TiO2 treated with a polydimethylsiloxane,
- anatase/rutile TiO2 treated with a polydimethylhydrogensiloxane,
- TiO2 coated with triethylhexanoin, aluminum stearate, alumina sold under the trade name “Solaveil™ CT-200” from CRODA,
- TiO2 coated with aluminum stearate, alumina and silicone sold under the trade name “Solaveil™ CT-12W” from CRODA,
- TiO2 coated with lauroyl lysine,
- TiO2 coated with C9-C15 fluoroalcohol phosphate and aluminum hydroxide.

We can also cite TiO2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric/caprylic acids. The oily dispersion of titanium oxide particles may additionally comprise one or more dispersing agents such as for example a sorbitan ester such as sorbitan isostearate, an ester of fatty acid and polyoxyalkylenated glycerol such as TRI-PPG3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3 POLYRICINOLEATE. Preferably, the oily dispersion of titanium oxide particles comprises at least one dispersing agent chosen from fatty acid esters and polyoxyalkylenated glycerol. Mention may be made more particularly of the oily dispersion of TiO2 particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE or the product sold under the trade name “OPTISOL™ OTP-1” by the company CRODA.

Uncoated titanium oxide pigments are for example sold by the company TAYCA under the trade names “MT-500B” or “MT-600B®”, by the company Evonik under the name “DEGUSSA P 25”.

Uncoated zinc oxide pigments are, for example:
- those marketed under the name “Z-COTE®” by the company BASF;
- those marketed under the name “NanoArc® Zinc Oxide” by the company Nanophase Technologies.

Coated zinc oxide pigments are for example:
- ZnO coated with polymethylhydrogensiloxane;
- CRODA’s “Solaveil™ CZ-100” dispersed in C12-15 alkyl benzonate (INCI: Zinc Oxide (and) C12-15 Alkyl Benzoate (and) Polyhydroxystearic Acid (and) Isostearic Acid);
- those marketed under the name and “DAITOPERSION Zn-60VA®” by the company Daito Kasei (dispersions in C9-12 alkane with a dispersing agent);
- those marketed under the name "SPD-Z5®" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane).

Uncoated cerium oxide pigments can for example be those sold under the name RHODIGARD® W185 by the company Solvay.

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and cerium dioxide, including the equal weight mixture of titanium dioxide and cerium dioxide coated with silica, as well as the mixture of titanium dioxide and cerium dioxide. zinc coated with alumina, silica and silicone or coated with alumina, silica and glycerin.

According to the invention, titanium oxide pigments, coated or uncoated, are particularly preferred.

The complementary UV filters according to the invention may be present in the composition according to the invention at a content ranging from 0.1% to 60% by weight, and in particular from 5% to 30% by weight relative to the total weight of the composition.

Other additives

The composition according to the present invention may further comprise conventional cosmetic adjuvants chosen in particular from organic solvents, ionic or non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-inflammatory agents. -foam, perfumes, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalizing or acidifying agents or any other ingredient usually used in the cosmetic field and/or dermatological.

Among the organic solvents, mention may be made of alcohols other than C ₁ -C ₄ mono-alkanols as defined above and in particular short-chain C ₂ -C ₈ polyols, such as glycerin, diols such as caprylyl glycol, 1,2-pentanediol, propanediol, butanediol, glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

As thickeners, we can cite carboxyvinyl polymers such as Carbopols® (Carbomers) and Pemulen such as Pemulen TR1® and Pemulen TR2® (Acrylate/C10-C30-alkylacrylate copolymer); polyacrylamides such as for example crosslinked copolymers sold under the names Sepigel 305® (CTFA name: polyacrylamide/C ₁₃ - ₁₄ isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by Seppic company; polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and/or neutralized, such as poly(2-acrylamido 2-methylpropane sulfonic acid) marketed by the company Hoechst under the trade name “Hostacerin AMPS ^® ” ( CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800® marketed by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido 2-methylpropane sulfonic acid and hydroxyethyl acrylate such as SIMULGEL NS® and SEPINOV EMT 10® marketed by the company SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as Xanthan gum; water-soluble or water-dispersible silicone derivatives such as acrylic silicones, silicones polyethers and cationic silicones and their mixtures.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the alkalizing agents we can cite, by way of example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides.

Preferably, the cosmetic composition comprises one or more alkalizing agents chosen from alkanolamines, in particular triethanolamine, and sodium hydroxide.

In the case of a direct emulsion, the pH of the composition according to the invention is generally between approximately 3 and 12, preferably between approximately 5 and 11, and even more particularly between 5.5 and 8.

Among the active ingredients for the care of keratin materials such as the skin, lips, scalp, hair, eyelashes or nails, we can cite for example vitamins and their derivatives or precursors, alone or in mixtures; anti-oxidant agents; anti-free radical agents; anti-pollutant agents; self-tanning agents; anti-glycation agents; soothing agents; deodorant agents; essential oils ; NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and/or preventing their degradation; agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; muscle relaxants; refreshing agents; tensor agents; mattifying agents; depigmenting agents; pro-pigmenting agents; keratolytic agents; desquamating agents; moisturizing agents; anti-inflammatory agents; antimicrobial agents; slimming agents; agents acting on the energy metabolism of cells; insect repellents; substance P or CRGP antagonists; anti-hair loss agents; anti-wrinkle agents; anti-aging agents.

Those skilled in the art will choose the said active ingredient(s) according to the desired effect on the skin, hair, eyelashes, eyebrows and nails.

Of course, those skilled in the art will take care to choose the possible complementary compound(s) cited above and/or their quantities in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially not altered by the planned addition(s).

DOSAGE FORMS

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art. They can be presented in particular in the form of an emulsion, simple or complex (O/W, W/O, O/W/O or W/O/W) such as a cream, a milk or a cream gel. .

They can also be in anhydrous form, for example in the form of an oil. The term “anhydrous composition” means a composition containing less than 1% by weight of water, or even less than 0.5% of water, and in particular free of water, the water not being added during preparation. of the composition but corresponding to the residual water provided by the mixed ingredients.

The compositions according to the invention can also be presented in aqueous form, with a quantity of oily phase preferably less than 1% by weight, even more preferably less than 0.5% by weight, and in particular free of oily phase.

They can optionally be packaged in an aerosol and come in the form of foam or spray.

In the case of compositions in the form of oil-in-water or water-in-oil emulsions, the emulsification processes that can be used are pale or propeller, rotor-stator and HHP type.

To obtain stable emulsions with a low polymer content (oil/polymer ratio >25), it is possible to make the dispersion in the concentrated phase then to dilute the dispersion with the rest of the aqueous phase.

It is also possible, by HHP (between 50 and 800 bars), to obtain stable dispersions with droplet sizes down to 100 nm.

The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or non-ionic emulsifiers, used alone or in a mixture. The emulsifiers are chosen appropriately depending on the emulsion to be obtained (W/O or O/W).

As an example of W/O emulsifying surfactants, mention may be made of alkyl esters or ethers of sorbitan, glycerol, polyol, glycerol or sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C®" by the company Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the name " Dow Corning 5200 Formulation Aid" by the Dow Corning Company; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R® by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE O9 ® by the Goldschmidt company. One or more co-emulsifiers can also be added, which, advantageously, can be chosen from the group comprising alkylated polyol esters.

Mention may also be made of non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, glycerol, polyol or sugars.

As alkylated polyol esters, mention may in particular be made of polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as the product marketed under the name Arlacel P135® by the company ICI.

As esters of glycerol and/or sorbitan, mention may be made, for example, of polyglycerol isostearate, such as the product sold under the name Isolan GI 34® by the company Goldschmidt; sorbitan isostearate, such as the product marketed under the name Arlacel 987® by the company ICI; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986® by the company ICI, and their mixtures.

For O/W emulsions, for example, polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) fatty acid and glycerol esters may be cited as nonionic emulsifying surfactants; oxyalkylenated fatty acid and sorbitan esters; esters of polyoxyalkylenated fatty acids (in particular polyoxyethylenated and/or polyoxypropylenated) optionally in association with a fatty acid and glycerol ester such as the PEG-100 Stearate/Glyceryl Stearate mixture sold for example by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and/or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkyl polyglucosides (APG) such as decylglucoside and laurylglucoside marketed for example by the company Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearylglucoside optionally mixed with cetostearyl alcohol, marketed for example under the name Montanov 68® by the company Seppic, under the name Tegocare CG90® by the company Goldschmidt and under the name Emulgade KE3302® by the company Henkel, as well as arachidyl glucoside, for example under the name form of the mixture of arachidic and behenic alcohols and arachidylglucoside marketed under the name Montanov 202® by the company Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self-emulsifying composition, as described for example in document WO- A-92/06778.

When it is an emulsion, the aqueous phase thereof may comprise a non-ionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).

The compositions according to the invention find their application in a large number of treatments, in particular cosmetic, of the skin, lips and hair, including the scalp, in particular for the protection and/or care of the skin, lips and/or hair, and/or for makeup of the skin and/or lips.

Another object of the present invention consists of the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and/or scalp, in particular care products, sun protection products and makeup products.

The cosmetic compositions according to the invention can for example be used as makeup products.

Another object of the present invention is constituted by a non-therapeutic cosmetic process for the care and/or makeup of a keratin material consisting of applying to the surface of said keratin material at least one composition according to the invention as defined below. -above.

The cosmetic compositions according to the invention can for example be used as a care and/or sun protection product for the face and/or body of liquid to semi-liquid consistency, such as milks, more or less creamy creams, gel-creams, pastes. They can optionally be packaged in an aerosol and come in the form of foam or spray.

The compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles by means of pressurization devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant as well as aerosol pumps using compressed air as a propellant. The latter are described in patents US 4,077,441 and US 4,850,517.

The compositions packaged in aerosol in accordance with the invention generally contain conventional propellants such as, for example, the hydrofluorinated compounds dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane. They are preferably present in quantities ranging from 15 to 50% by weight relative to the total weight of the composition.

TOGETHER

According to another aspect, the invention also relates to a cosmetic set comprising:
i) a container delimiting one or more compartments (d), said container being closed by a closing element and possibly being non-watertight; And
ii) a makeup and/or care composition in accordance with the invention placed inside said compartment(s).

The container can for example be in the form of a pot or a box.

The closing element may be in the form of a cover comprising a cover mounted movable by translation or by pivoting relative to the container housing said makeup and/or care composition(s).

EXAMPLES

The examples which follow serve to illustrate the invention without, however, being limiting in nature. In these examples, the quantities of the composition ingredients are given in weight% relative to the total weight of the composition.

Example A1: Preparation of compound (14)
[formula 14]

122.23 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 75.45 grams of ethyl cyanoacetate in approximately equimolar proportions in the presence of a base and optionally a solvent.

The base/solvent combinations shown in the following table are used. Example Base Solvent Example A1.1 DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) dimethylacetamide Example A1.2 Triethylamine isopropanol Example A1.3 3-methoxypropylamine isopropanol Example A1.4 3-methoxypropylamine tert-amylalcohol Example A1.5 3-methoxypropylamine toluene Example A1.6 3-methoxypropylamine dimethylformamide Example A1.7 3-methoxypropylamine solvent free Example A1.8 N-morpholine isopropanol

The completion of the alkylation reaction can be monitored for example by methods such as TLC, GC or HPLC.

162.30 grams of compound (14) are obtained in the form of a brown oil.

After crystallization, the product is obtained in the form of yellowish crystals.

Melting point: 92.7°C.

Example A2: Preparation of compound (15)
[formula 15]

101.00 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 86.00 grams of 2-cyano-N-(3- methoxy-propyl)-acetamide in approximately equimolar proportions in the presence of a base and optionally a solvent.

The base/solvent combinations shown in the following table are used.
Example
Base
Solvent Example A2.1 DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) dimethylacetamide Example A2.2 Triethylamine isopropanol Example A2.3 3-methoxypropylamine isopropanol Example A2.4 3-methoxypropylamine tert-amylalcohol Example A2.5 3-methoxypropylamine toluene Example A2.6 3-methoxypropylamine dimethylformamide Example A2.7 3-methoxypropylamine solvent free

The crude product (15) is obtained in the form of a dark brown oil.

After chromatography on a column in silica gel (eluent: toluene/methanol 99/1), 81.8 grams of product are obtained in the form of yellowish crystals.

Melting point: 84.7-85.3°C.

Example A3: Preparation of compound (27)
[formula 27]

13.09 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 10.12 grams of isobutyl cyanoacetate in the presence of a base and optionally a solvent.

The base/solvent combinations shown in the following table are used. Example Base Solvent Example A3.1 DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) dimethylacetamide Example A3.2 Triethylamine isopropanol Example A3.3 3-methoxypropylamine isopropanol Example A3.4 N-methylmorpholine tert-amylalcohol Example A3.5 3-methoxypropylamine toluene Example A3.6 3-methoxypropylamine dimethylformamide Example A3.7 3-methoxypropylamine solvent free

15.97 grams of crude product (27) are obtained in the form of a dark brown oil.

After chromatography on a silica gel column (eluent: toluene/acetone), 13.46 grams of product are obtained in the form of yellowish crystals.

Melting point: 96.3°C.

Example A4: Preparation of compound (25)
[formula 25]

148.4 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 130.00 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.

The base/solvent combinations shown in the table below are used. Example Base Solvent Example A4.1 DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) dimethylacetamide Example A4.2 Triethylamine isopropanol Example A4.3 3-methoxypropylamine isopropanol Example A4.4 N-methylmorpholine tert-amylalcohol Example A4.5 3-methoxypropylamine toluene Example A4.6 3-methoxypropylamine dimethylformamide Example A4.7 3-methoxypropylamine solvent free

Examples of wording

Method of preparing compositions

The aqueous phase A1 is prepared by mixing all the raw materials by heating at 80°C until a homogeneous phase is obtained. Phase A2 is added to phase A1 when the temperature returns to 25°C. Phase B2 is introduced with stirring into phase B1, previously heated to 50°C, until a homogeneous phase is obtained. Phase B is prepared by mixing all the ingredients while heating at 50°C, until a homogeneous phase is obtained. The emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes at 25°C. Phase C is then introduced, then phase D, and finally phase E with stirring until a smooth formula is obtained.

Protocol for evaluating the staining power of U filters GO

The product is transferred to a white cotton fabric using a 25 cm² PMMA plate. The quantity deposited is equivalent to 2mg/cm². The fabric is then left to dry for 24 hours in the open air, then machine washed (Color program 40°C – duration 1h30) with liquid detergent. The staining power is evaluated 24 hours and 3 weeks after washing via the measurement of ΔE obtained using a chromameter (KONICA MINOLTA SENSING EUROPE BV).

The results are expressed in the system (L, a, b) in which L represents luminance, a represents the red-green axis (-a = green, +a = red) and b represents the yellow-blue axis ( -b =blue, +b =yellow).

To evaluate the reduction in staining, we are interested in ΔE, which measures the total color variation between an area stained by the formula and an unstained area of the fabric washed, then dried, and after waiting an instant t after machine washing. The lower ΔE, the lower the staining of fabrics by the product.

ΔE is calculated from the variations ΔL, Δa and Δb according to the following formula:

In this formula, ΔL represents the difference between the value of L of the unstained area and the value of L of the stained area after a time t after washing the fabric, Δa represents the difference between the value of a of the unstained area stained and the value of a of the stained area after a time t after washing the fabric and Δb represents the difference between the value of b of the unstained area and the value of b of the stained area after a time t after washing fabric.

3 measurements are taken on each piece of fabric. The operation is repeated on 3 pieces of fabric. The ΔE values given below correspond to the average of the results obtained on the 3 pieces of fabric.

Comparative example - Compositions 1 to 4

The following compositions 1 to 4 were prepared according to the protocol detailed above. Phase Ingredients 1 (reference) 2 (invention) A1 BUTYL METHOXYDIBENZOYLMETHANE 0 0 A1 DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE 0 0 A1 METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE 0 3 A1 DIISOPROPYL SEBACATE 5 5 A1 DICAPRYLYL CARBONATE 5 5 A1 TRIETHYL CITRATE 8 8 A1 C15-19 ALKANE QSP 100 QSP 100 A1 POLY C10-30 ALKYL ACRYLATE 0.2 0.2 A1 ISOSTEARIC ACID 1 1 A1 CETYL PEG/PPG-10/1 DIMETHICONE 1 1 A1 POLYGLYCERYL-6 POLYRICINOLEATE 1 1 A1 DIMETHICON 9 9 A1 Conservatives QS QS A2 DISTEARDIMONIUM HECTORITE (and) PROPYLENE CARBONATE 2 2 B WATER 20 20 B POLYQUATERNIUM-67 0.17 0.17 B PHYTIC ACID 0.07 0.07 VS DIMETHICONE (and) DIMETHICONE/VINYL DIMETHICONE CROSSPOLYMER 2 2 D Load(s) 9.5 9.5 E ALCOHOL DENAT. 8 8 Phase Ingredients 3 (comparative) 4 (comparative) A1 BUTYL METHOXYDIBENZOYLMETHANE 3 0 A1 DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE 0 3 A1 METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE 0 0 A1 DIISOPROPYL SEBACATE 5 5 A1 DICAPRYLYL CARBONATE 5 5 A1 TRIETHYL CITRATE 8 8 A1 C15-19 ALKANE QSP 100 QSP 100 A1 POLY C10-30 ALKYL ACRYLATE 0.2 0.2 A1 ISOSTEARIC ACID 1 1 A1 CETYL PEG/PPG-10/1 DIMETHICONE 1 1 A1 POLYGLYCERYL-6 POLYRICINOLEATE 1 1 A1 DIMETHICON 9 9 A1 Conservatives QS QS A2 DISTEARDIMONIUM HECTORITE (and) PROPYLENE CARBONATE 2 2 B WATER 20 20 B POLYQUATERNIUM-67 0.17 0.17 B PHYTIC ACID 0.07 0.07 VS DIMETHICONE (and) DIMETHICONE/VINYL DIMETHICONE CROSSPOLYMER 2 2 D Load(s) 9.5 9.5 E ALCOHOL DENAT. 8 8

The results obtained with compositions 1 to 4 are described in the table below. Composition 1
(reference) 2
(invention) 3
(comparative) 4
(comparative) ΔE 24h after washing 1.25 ± 0.38 1.17 ± 0.27 2.34 ± 0.40 1.49 ± 0.24 ΔE 3 weeks after washing 0.43 ± 0.14 0.53 ± 0.11 1.98 ± 0.29 1.18 ± 0.26

These results show that composition 2 according to the invention in which METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE (compound 25) is used as a UVA filter leaves traces after washing (after 24 hours and after 3 weeks) equivalent to those left by the reference composition 1 which does not contain UVA filters. Composition 2 leaves fewer traces after washing than comparative compositions 3 and 4 in which BUTYL METHOXYDIBENZOYLMETHANE (for example Parsol 1789 from DSM) or DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE (for example Uvinul A+ from BASF) is used as a UVA filter .

Claims (11)

Cosmetic or dermatological composition comprising:
a) at least one merocyanine corresponding to the following formula (3), as well as their isomeric geometric forms, in particular E/E or E/Z:
[Formula 3]

in which :
A is –O- or –NH;
R is a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, a C ₃ -C ₂₂ cycloalkyl group or a C ₃ -C ₂₂ cycloalkenyl group, said groups being able to be interrupted by one or more O; And
b) at least one polyionic complex containing at least one cationic polysaccharide and at least one crosslinking agent chosen from non-polymeric acids having at least three pKa values and their salts. Composition according to claim 1 in which the merocyanines of formula (3) are chosen from the following compounds, as well as their E/E or E/Z isomeric geometric forms: 14
ethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 15
(2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanamide 25
2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 27
2-methylpropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 29

2-butoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 31

3-methoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate
37
3-ethoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate Composition according to claim 2 in which the merocyanine of formula (3) is 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate (25) in its E/Z geometric configuration with the following structure:
[formula 25]

and/or in its E/E geometric configuration of the following structure:
[form 25Bis]
Composition according to any one of claims 1 to 3 comprising at least one cationic cellulosic polymer. Composition according to any one of claims 1 to 4 comprising at least one cationic polysaccharide containing at least one quaternary ammonium group. Composition according to any one of claims 1 to 5 comprising at least one cationic polysaccharide chosen from polyquaternium-4; polyquaternium-10; polyquaternium-24; and polyquaternium-67, preferably polyquaternium-67. Composition according to any one of claims 1 to 6 comprising at least one crosslinking agent chosen from non-polymeric acids having three or more acid groups and their salts. Composition according to one of Claims 1 to 7 in which the non-polymeric acid(s) having three acid groups are chosen from tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids and hexacarboxylic acids. Composition according to any one of claims 1 to 8 in which the non-polymeric acid(s) having three or more acid groups are chosen from citric acid, aconitic acid, phytic acid, EDTA, glycyrrhizin, inositol triphosphate, inositol pentakisphosphate, tripolyphosphate, adenosine triphosphate, preferably citric acid, phytic acid, and even more preferably phytic acid. Composition according to any one of claims 1 to 9 comprising at least one additional UV filter. Non-therapeutic cosmetic process for the care and/or makeup of a keratin material comprising the application to the surface of said keratin material of at least one composition as defined in any one of claims 1 to 10.