FR3141059A1 - Cosmetic or dermatological composition comprising a merocyanine and a gamma-butyrolactone and/or a gamma-butyrolactam - Google Patents

Abstract

Cosmetic or dermatological composition comprising a merocyanine and a gamma-butyrolactone and/or a gamma-butyrolactam The present invention relates to a composition, in particular cosmetic or dermatological, 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 C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkinyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups being able to be interrupted by one or more O; And b) at least one compound chosen from suitably selected gamma-butyrolactones and gamma-butyrolactams. 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 as defined above.

Description

Cosmetic or dermatological composition comprising a merocyanine and a gamma-butyrolactone and/or a gamma-butyrolactam

The present invention relates to a cosmetic or dermatological composition comprising at least one merocyanine of formula (3) which will be defined in detail below and at least one compound chosen from suitably selected gamma-butyrolactones and gamma-butyrolactams.

The present invention also relates to a non-therapeutic cosmetic process for caring for and/or making up 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 uniformity of the complexion comprising the application to the surface of the keratin material of at least one composition as defined above.

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.

It is known that radiation with wavelengths between 280 nm and 400 nm allows the tanning of human epidermis and that radiation with wavelengths between 280 and 320 nm, known as UV-B rays, harms the development of natural tanning. 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 wavelengths 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 for short periods, under normal conditions can lead to a degradation of collagen and elastin fibers, which results in a change in the micro-relief of the skin, the appearance of wrinkles and irregular pigmentation (brown spots, uneven skin tone).

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

Many 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 function 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 associated with metal oxide pigments such as titanium dioxide or zinc oxide.

Many cosmetic compositions intended to limit the 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 sunscreen 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 the darkening of the skin color.

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

Advantageously, this improvement is particularly sought after on already pigmented skin in order to not increase either the pigment load in melanin or the structure of the melanin already present in 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 filtering power of solar radiation, the desired photo-protection compounds must also have good cosmetic properties, good solubility in common solvents and in particular in fatty substances such as oils or in water, as well as good photostability 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 drawbacks known to date of these compositions is that these filtering systems have insufficient efficiency against UV radiation and particularly against long UVA radiation with wavelengths beyond 370 nm in order to control photo-induced pigmentation and its development by a system filtering UV over the entire UV spectrum.

Among all the compounds that have been recommended for this purpose, 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 04/03/2004. These compounds have very good filtration properties in long UVA radiation but have a poorly satisfactory solubility in the usual solvents, both in aqueous phase and in fatty phase, and an unsatisfactory photo-stability for certain merocyanines.

In order to search for other merocyanines having better solubility in common solvents and better photostability, application WO2013/011094 proposed merocyanines comprising polar groups consisting of hydroxyl and ether functions which show good long UVA filtration efficiency. However, the solubility of these particular merocyanines 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 lead to cosmetic inconveniences such as a sticky and greasy effect on application.

There is therefore a need to improve the solubility of these merocyanines in cosmetic compositions, particularly photoprotective formulations, both in aqueous and oily phases, while obtaining good cosmeticity.

The Applicant has surprisingly discovered that by using a gamma-butyrolactone derivative such as, for example, gamma-valerolactone or a gamma-butyrolactam derivative such as, for example, 2-pyrrolidone, 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate, 2-pyrrolidone-5-carboxylic acid and tert-butyl(S) 2-pyrrolidone-5-carbonate, it was possible to significantly improve the solubility of these merocyanines both in an aqueous phase and in a fatty phase. This discovery is the basis of the present invention.

Thus, in accordance with one of the objects of the present invention, there is now provided a cosmetic or dermatological composition comprising at least one merocyanine of formula (3) and at least one gamma-butyrolactone derivative and/or one gamma-butyrolactam derivative which will be defined in detail below.

Furthermore, there is also a need to improve the solubility of merocyanines in the presence of organic filters. Indeed, the addition of additional filters can destabilize compositions comprising a merocyanine.

The Applicant has surprisingly discovered that by using a gamma-butyrolactone derivative such as, for example, gamma-valerolactone or a gamma-butyrolactam derivative such as, for example, 2-pyrrolidone, 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate, 2-pyrrolidone-5-carboxylic acid (PCA), tert-butyl(S) 2-pyrrolidone-5-carbonate (PCA ester) and 1-butyl-5-oxopyrrolidone-3-carboxylic acid, it was possible to significantly improve the solubility of these merocyanines in an aqueous phase or in a fatty phase, even in the presence of additional organic UV filters.

The Applicant has also discovered that the use of a gamma-butyrolactone derivative such as, for example, gamma-valerolactone or a gamma-butyrolactam derivative such as, for example, 2-pyrrolidone, 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate, 2-pyrrolidone-5-carboxylic acid (PCA), tert-butyl(S) 2-pyrrolidone-5-carbonate (PCA ester) and 1-butyl-5-oxopyrrolidone-3-carboxylic acid makes it possible to obtain good cosmeticity of the composition comprising the merocyanines, the latter being in particular non-greasy and non-sticky.

The present invention also relates to a non-therapeutic cosmetic process for caring for and/or making up 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 uniformity of the complexion comprising the application to the surface of the keratin material of at least one composition as defined above.

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.

The present invention also relates to the use of a gamma-butyrolactone derivative such as, for example, gamma-valerolactone or a gamma-butyrolactam derivative such as, for example, 2-pyrrolidone, 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate, 2-pyrrolidone-5-carboxylic acid (PCA), tert-butyl(S) 2-pyrrolidone-5-carbonate (PCA ester) and 1-butyl-5-oxopyrrolidone-3-carboxylic acid for solubilizing a merocyanine of formula (3) as defined below, in particular for solubilizing these molecules in the fatty phase and/or in the aqueous phase.

Other features, aspects and advantages of the invention will become apparent upon 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, the term “physiologically acceptable medium” means a medium compatible with keratin materials.

In the context of the present invention, the term “keratin material” is understood to mean in particular the skin, the scalp, the keratin fibers such as the eyelashes, the eyebrows, the hair, and the body hairs, the nails, the mucous membranes such as the lips, and more particularly the skin and the 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 than 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 keratin material.

MEROCYANINS

According to the present invention, a family of merocyanines corresponding to the following formula (3) will be used 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 _C1 - _C22 alkyl group, a _C2 - _C22 alkenyl group, a _C2 - _C22 alkinyl group, a _C3 - _C22 cycloalkyl group or a _C3 - _C22 cycloalkenyl group, said groups possibly being interrupted by one or more O.

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

Even more preferred compounds of formula (3) are those where:

A is -O-; R is _C1 - _C22 alkyl, which may be interrupted by one or more O's.

Among the compounds of formula (3), those chosen from the following group and their isomeric geometric forms, in particular E/E-, E/Z-, will be used in particular: 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.

Compounds of formula (3), which form a carbocyclic ring containing 6 carbon atoms, 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, 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 of 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 shown below, for compounds of formula (3):

[formula 4]

And more particularly for compound 25 described in table 1:

[formula 5]

GAMMA-BUTYROLACTONES AND/OR GAMMA-BUTYROLACTAMS

The composition in accordance with the invention comprises at least one compound chosen from gamma-butyrolactones and gamma-butyrolactams corresponding to the formula defined below, as well as their acid or base salts, organic or mineral, or their solvates such as hydrates:

[formula 38]

in which:

X represents an oxygen atom or a nitrogen atom carrying a radical R4, with R4 representing a hydrogen atom, a linear or branched C1-C6 alkyl radical,

R1, R2, R3 represent, independently of each other:

- a hydrogen atom,

- a linear or branched C1-C6 alkyl radical, or

- a radical –[O] _n -C(O)-[O] _p -R5, with:

- n is equal to 0 or 1, p is equal to 0 or 1, with n + p equal to 1 or 2,

- R5 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical.

According to a particular embodiment of the invention, X represents an oxygen atom.

According to a particular embodiment of the invention, X represents an oxygen atom or a nitrogen atom carrying a radical R4, with R4 representing a hydrogen atom, a linear or branched C1-C6 alkyl radical, preferably a hydrogen atom or a linear or branched C1-C4 alkyl radical, and even more preferably a hydrogen atom or a linear C1-C4 alkyl radical.

According to a particular embodiment of the invention, R1, R2, R3 represent, independently of each other:

- a hydrogen atom,

- a linear or branched alkyl radical, C1-C6, preferably C1-C4, or

- a radical –[O] _n -C(O)-[O] _p -R5, with:

- n is equal to 0 or 1, p is equal to 0 or 1, with n + p equal to 1,

- R5 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical.

According to a preferred embodiment, n = 0 and p = 1.

According to a particular embodiment of the invention, R4 represents a hydrogen atom or a linear or branched C1-C4 alkyl radical, such as for example a methyl, ethyl, n-propyl, iso-propyl, tert-butyl, iso-butyl, n-butyl radical, preferably a linear C1-C4 alkyl radical, such as for example an n-butyl radical.

According to a preferred embodiment, R5 represents a hydrogen atom or a branched C1-C6 alkyl radical, for example a tert-butyl radical or a 1,3-dimethylbutyl radical.

Acceptable salts of the compounds of formula 38 include conventional non-toxic salts of said compounds such as those formed from organic or inorganic acids. Examples include salts of mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid. Salts of organic acids, which may comprise one or more carboxylic, sulfonic or phosphonic acid groups, may also be mentioned. These may be linear, branched or cyclic aliphatic acids or aromatic acids. These acids may further comprise one or more heteroatoms selected from O and N, for example in the form of hydroxyl groups. Examples include propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid and lactic acid.

Salts of organic or mineral bases such as ammonium salts, alkanolamine salts such as triethanolamine, aminopropanediol, alkali or alkaline earth metal salts such as sodium, potassium, calcium, magnesium.

The preferred salts are those obtained from hydrochloric, sulfuric, acetic, tartaric, citric, lactic acids as well as alkali metal salts such as sodium, potassium, calcium.

According to a particular embodiment of the invention, the composition comprises at least one compound chosen from those defined below, as well as their acid or base salts, organic or mineral, or their solvates such as hydrates, and optionally their optical isomers, stereoisomers, enantiomers and diastereoisomers and their geometric isomers:

gamma-valerolactone of the following formula:

[formula 39]

2-pyrrolidone of the following formula:

[formula 40]

1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate of the following formula:

[formula 41]

2-pyrrolidone-5-carboxylic acid (PCA) of the following formula:

[formula 42]

tert-butyl(S) 2-pyrrolidone-5-carbonate (PCA ester) of the following formula:

[formula 43]

1-butyl-5-oxopyrrolidone-3-carboxylic acid of the following formula:

[formula 43bis]
.

According to a particular embodiment of the invention, the composition comprises at least one gamma-butyrolactone, preferably a gamma-butyrolactone of formula 38 as defined above in which X is an oxygen atom.

According to another particular embodiment of the invention, the composition comprises at least one gamma-butyrolactam, preferably a gamma-butyrolactam of formula 38 as defined above in which X is a nitrogen atom carrying a radical R4.

Compounds of formula 38 can be obtained according to the syntheses as described in patent application FR 2 968 547.

In particular, 4-carboxy 2-pyrrolidinone derivatives having the following formula (I) or one of its salts, optical isomers, stereoisomers, enantiomers and diastereoisomers or one of its geometric isomers:

[formula 44]
(I)

in which:

R1 and R3 represent, independently of one another, a hydrogen atom, a linear or branched C1-C6, preferably C1-C4, alkyl radical,

R4 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical,

R5 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical,

when R ₃ is hydrogen, the compounds may be in their free acid form or in the form of their cosmetically acceptable salts,

can be obtained:

- either by the condensation of a diester of itaconic acid of formula (II) with a primary amine of formula (III), with or without solvent at a temperature between 20°C and 150°C according to the following scheme:
[formula 45]

- either in 2 steps from itaconic acid of formula (IV) by condensation with the primary amine of formula (III) in the presence of a solvent or not to give the intermediate acid of formula (V), followed by an esterification of this acid of formula (V) in the presence of an excess of alcohol of formula (VI) according to the following scheme:

[formula 46]

According to a particular embodiment of the invention, the compound(s) chosen from gamma-butyrolactones and gamma-butyrolactams as defined above are present in the composition in a content ranging from 0.1 to 99%, preferably from 0.1 to 50% by weight, preferably from 1 to 30%, even more preferably from 1 to 10%, better still from 1 to 5% by weight relative to the total weight of the composition.

According to a particular embodiment of the invention, the mass ratio of the total quantity of compounds chosen from gamma-butyrolactones and gamma-butyrolactams of formula (38) to the total quantity of merocyanines of formula (3) is greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a first preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (39), with a mass ratio of the amount of compound (39) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a second preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (40), with a mass ratio of the amount of compound (40) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a third preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (41), with a mass ratio of the amount of compound (41) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a fourth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (42), with a mass ratio of the amount of compound (42) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a fifth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (43), with a mass ratio of the amount of compound (43) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to a sixth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (43bis), with a mass ratio of the amount of compound (43bis) to the amount of compound (25) greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1.

According to another particular embodiment of the invention, the mass ratio of the total quantity of compounds chosen from gamma-butyrolactones and gamma-butyrolactams of formula (38) to the total quantity of merocyanines of formula (3) is less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a first preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (39), with a mass ratio of the quantity of compound (39) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a second preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (40), with a mass ratio of the quantity of compound (40) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a third preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (41), with a mass ratio of the quantity of compound (41) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a fourth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (42), with a mass ratio of the quantity of compound (42) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a fifth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (43), with a mass ratio of the quantity of compound (43) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

According to a sixth preferred embodiment, the composition in accordance with the invention comprises as merocyanine of formula (3) the compound (25) and as compound chosen from gamma-butyrolactones and gamma-butyrolactams the compound of formula (43bis), with a mass ratio of the quantity of compound (43bis) to the quantity of compound (25) less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1.

FATTY PHASE

The composition in accordance with the invention may comprise at least one fatty phase.

For the purposes of the invention, the term “fatty phase” means a phase comprising at least one fatty substance, in particular liquid, solid or pasty, and all of the liposoluble and lipophilic ingredients used for the formulation of the compositions of the invention.

According to a particular embodiment, the composition according to the invention comprises at least one oil.

Oil is any fatty substance in liquid form at room temperature (20 – 25°C) and atmospheric pressure (760 mm Hg).

The fatty phase may comprise in particular at least one volatile or non-volatile hydrocarbon oil and/or one volatile and/or non-volatile silicone oil and/or one volatile and/or non-volatile fluorinated oil.

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 keratin fiber in less than one 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 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 of less than 10 ^-3 mm Hg (0.13 Pa).

Hydrocarbon oils

The composition in accordance with the invention comprises at least one ester of C2-C22 di or tricarboxylic acid and C1-C24 alcohols.

The _C2 - _C22 di- or tricarboxylic acids are in particular chosen from citric acid, malic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, tartaric acid, isocitric acid and mixtures thereof. Preferably the acids are citric acid and adipic acid, and even more preferably it is citric acid.

The C1-C24 alcohols are not oxyalkylenated. They can be aliphatic, cyclic or aromatic, having from 1 to 24 carbon atoms. They are notably chosen from phenol, benzyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, methanol, ethanol, propanol, n-butanol, t-butanol, pentanol, hexanol. Preferably, the alcohol(s) are C1-C6 and can be chosen from methanol, ethanol, propanol, n-butanol, t-butanol, pentanol, hexanol, and even more preferably it is ethanol.

The ester(s) of C2-C22 di- or tricarboxylic acid and C1-C24 alcohols may be mono- or poly-esterified.

By monoesterified we mean that only one of the two or three carboxylic acid functions is esterified. By polyesterified we mean that at least two carboxylic acid functions are esterified.

The di or tricarboxylic acid can be esterified by several different alcohols. Preferably, it is esterified by a single alcohol.

According to a particular embodiment of the invention, the composition comprises at least one ester of C3-C22 tricarboxylic acid and C1-C24 alcohols, preferably C1-C6. This or these esters may be mono-, di- or tri-esterified.

By monoesterified we mean that only one of the three carboxylic acid functions is esterified. By diesterified we mean that two of the three carboxylic acid functions are esterified. By triesterified we mean that all three carboxylic acid functions are esterified.

According to a particular embodiment of the invention, the ester(s) of C3-C22 tricarboxylic acid and C1-C6 alcohols are tri-esterified.

According to a particular embodiment of the invention, the ester(s) of C3-C22 tricarboxylic acid and C1-C6 alcohols are chosen from the compounds of the following formula (47):

(R ₁ O-CO)CH ₂ -C(R)(OC-OR ₂ )-CH ₂ (OC-OR ₃ )

in which:

R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon group having from 1 to 6 carbon atoms;

R represents a hydrogen atom or a hydroxyl radical.

According to a preferred embodiment, R1, R2 and R3 represent, independently of one another, a hydrogen atom or a linear or branched, substituted or unsubstituted, preferably unsubstituted, C1-C6 alkyl radical, and in particular a radical chosen from methyl, ethyl, propyl, n-butyl, t-butyl, pentyl and hexyl radicals. Preferably, R1, R2 and R3 are chosen independently of one another from a hydrogen atom and methyl, ethyl, propyl, n-butyl and t-butyl radicals.

According to a preferred embodiment of the invention, the radicals R1, R2 and R3 are identical and are chosen from C1-C6 alkyl radicals, preferably C1-C4, and even more preferably they are ethyl radicals.

According to a preferred embodiment of the invention, R represents a hydroxyl radical.

According to a particular embodiment of the invention, the ester of tricarboxylic acid and C1-C6 alcohols has the following formula:

[Formula 48]

As an example of a C3-C22 tricarboxylic acid ester and C1-C6 alcohols of formula (48) and INCI name TRIETHYL CITRATE, we will cite that which is marketed under the name CITROFOL AI EXTRA by the company JUNGBUNZLAUER.

As non-volatile hydrocarbon oils which can be used according to the invention, we may notably cite:

(i) hydrocarbon oils of vegetable origin such as glyceride triesters which are generally triesters of fatty acids and glycerol whose fatty acids may have chain lengths varying from _C4 to _C24 , the latter being able to be linear or branched, saturated or unsaturated; These oils include wheat germ, sunflower, grape seed, sesame, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose; or caprylic/capric acid triglycerides 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 from 10 to 40 carbon atoms;

(iii) linear or branched hydrocarbons, of mineral or synthetic origin such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof;

(iv) synthetic esters such as oils of formula RCOOR' in which R represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R' represents a hydrocarbon chain, in particular a branched chain, containing from 1 to 40 carbon atoms provided that R + R' is ≥ 10, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C ₁₂ -C ₁₅ alcohol benzoate such as 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 such as the commercial product sold under the name "X-TEND 226®" by the company ISP, lanolate isopropyl, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, 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 glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters; citrates or tartrates such as _C12 - _C13 linear dialkyl tartrates such as those sold under the name COSMACOL ETI® by the company ENICHEM AUGUSTA INDUSTRIALE as well as _C14 - _C15 linear dialkyl tartrates such as those sold under the name COSMACOL ETL® by the same company; acetates;

(v) fatty alcohols which are liquid at room temperature with a branched and/or unsaturated carbon chain having from 12 to 26 carbon atoms such as octyl dodecanol, isostearyl alcohol, oleyl 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 that can be used according to the invention, the following will be particularly preferred: glyceride triesters and in particular caprylic/capric acid triglycerides, synthetic esters and in particular diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, C ₁₂ -C ₁₅ alcohol benzoate, 2-ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol. Preferably, the non-volatile hydrocarbon oils are chosen from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate and dicaprylyl carbonate.

As volatile hydrocarbon oils which can be used according to the invention, mention may in particular be made of hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched C alkanes.₈-C₁₆like C isoalkanes₈-C₁₆of 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, branched C esters₈-C₁₆, isohexyl neopentanoate, and mixtures thereof.

Mention may also be made of the alkanes described in the patent applications of the company Cognis WO 2007/068371, or WO2008/155059 (mixtures of distinct alkanes and different by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil. Mention may be made of the mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ) obtained in examples 1 and 2 of the application WO2008/155059 of the company Cognis. Mention may also be made of 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, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

Silicone oils

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

Examples of volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, in particular those having a
viscosity ≤ 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 from 1 to 10 carbon atoms. As volatile silicone oil usable in the invention, mention may in particular be made of octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

A fatty phase according to the invention may further comprise, mixed with or dissolved in the oil, other fatty substances.

Another fatty substance that may be present in the fatty phase can 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 candelilla wax, rice bran wax, paraffin wax, lignite wax or microcrystalline wax, ceresin or ozokerite, synthetic waxes such as polyethylene waxes, 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, fatty acid triglycerides and their derivatives,

- and their mixtures.

Preferably, the overall fatty phase, including all lipophilic substances other than the lipophilic filters 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 total weight of the composition.

AQUEOUS PHASE

The composition in accordance with the invention may comprise at least one aqueous phase.

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

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

According to a particular form of the invention, the overall aqueous phase, including all the hydrophilic substances other than the hydrophilic filters of the composition capable of being solubilized in this same phase, represents from 1 to 99% by weight, and preferably from 10 to 80% by weight relative to the total weight of the composition.

ADDITIVES

Additional UV filters

The compositions according to the invention may additionally contain one or more complementary UV filters 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" we mean 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 micellar form) in a liquid aqueous phase.

By "lipophilic filter" we mean 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 suspended solid after returning to room temperature. It can easily be evaluated in the laboratory.

The complementary organic UV filters are notably chosen from cinnamic compounds; anthranilate compounds; salicylic compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds notably those cited in patent US5624663; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds as described in patents EP669323 and US 2,463,264; p-aminobenzoic compounds (PABA); 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-diarylbutadienes compounds as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 and mixtures thereof.

Examples of organic photoprotective agents include those designated below by their INCI name.

Cinnamic compounds:

Ethylhexyl Methoxycinnamate sold in particular under the trade name PARSOL MCX ® by DSM Nutritial Products

Isopropyl Methoxycinnamate

Isoamyl p-Methoxycinnamate sold under the trade name NEO HELIOPAN E 1000 ® by Symrise

DEA Methoxycinnamate,

Diisopropyl Methylcinnamate,

Glyceryl Ethylhexanoate Dimethoxycinnamate.

Compounds dibenzoylmethane :

Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 ® by DSM Nutritial Products,

Isopropyl Dibenzoylmethane.

Compounds para-aminobenzoic :

PABA,

Ethyl PABA,

Ethyl Dihydroxypropyl PABA,

Ethylhexyl Dimethyl PABA sold in particular under the name “ESCALOL 507®” by ISP,

Glyceryl PABA,

PEG-25 PABA sold under the name “UVINUL P 25®” by BASF.

Salicylic compounds:

Homosalate sold under the name “Eusolex HMS®” by Rona/EM Industries,

Ethylhexyl Salicylate sold under the name “NEO HELIOPAN OS®” by Symrise,

Dipropylene Glycol Salicylate sold under the name “DIPSAL ®” by SCHER,

TEA Salicylate, sold under the name “NEO HELIOPAN TS®” by Symrise.

Compounds β , β - diphenylacrylate :

Octocrylene sold in particular under the trade name “UVINUL N 539®” by BASF,

Etocrylene, sold in particular under the trade name “UVINUL N 35®” by BASF.

Benzophenone compounds:

Benzophenone-1 sold under the trade name “UVINUL 400®” by BASF,

Benzophenone-2 sold under the trade name “UVINUL D 50®” by BASF,

Benzophenone-3 or Oxybenzone, sold under the trade name “UVINUL M 40®” by BASF,

Benzophenone-4 sold under the trade name “UVINUL MS 40®” by BASF,

Benzophenone-5,

Benzophenone-6 sold under the trade name “Helisorb 11®” by Norquay,

Benzophenone-8 sold under the trade name “Spectra-Sorb UV-24®” by American Cyanamid,

Benzophenone-9 sold under the trade name “UVINUL DS 49®” by BASF,

Benzophenone-12,

2-(4-diethylamino-2-hydroxybenzoyl)-benzoate de n-hexyl sold under the trade name “UVINUL A Plus ®” or in mixture with octylmethoxycinnamate 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 of an aqueous dispersion.

Compounds benzylidene camphor:

3-Benzylidene camphor manufactured under the name “MEXORYL SD®” by CHIMEX,

4-Methylbenzylidene camphor sold under the name “EUSOLEX 6300®” by MERCK,

Benzylidene Camphor Sulfonic Acid manufactured under the name “MEXORYL SL®” by CHIMEX,

Camphor Benzalkonium Methosulfate manufactured under the name “MEXORYL SO®” by CHIMEX,

Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name “MEXORYL SX®” by CHIMEX,

Polyacrylamidomethyl Benzylidene Camphor manufactured under the name “MEXORYL SW®” by CHIMEX.

Compounds phenyl benzimidazole :

Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name “EUSOLEX 232®” by MERCK.

Bis-compounds benzoazolyl :

Disodium Phenyl Dibenzimidazole Tetra-sulfonate sold under the trade name “NEO HELIOPAN AP®” by Haarmann and REIMER.

Compounds phenyl benzotriazole :

Drometrizole Trisiloxane sold under the name “Silatrizole®” by RHODIA CHIMIE.

Methylene bis-( hydroxyphenyl benzotriazole ) :

Methylene bis-Benzotriazolyl Tetramethylbutylphenol in particular in solid form such as the product sold under the trade name "MIXXIM BB/100 ®" by 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 BASF or under 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 polymerization of glycerol of at least 5 such as the aqueous dispersions described in application WO2009/063392.

Triazine compounds:

- 3,3'-(1,4-Phenylene)bis(5,6-diphenyl-1,2,4-triazine), INCI name Phenylene Bis-Diphenyl triazine, with the following chemical formula:

[formula 49]

- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name “TINOSORB S®” by BASF,

- Ethylhexyl Triazone sold in particular under the trade name “UVINUL T 150®” by BASF,

- Diethylhexyl Butamido Triazone sold under the trade name “UVASORB HEB ®” by SIGMA 3V,

- dineopentyl 2,4,6-tris-(4'-amino benzalmalonate)-s-triazine,

- diisobutyl 2,4,6-tris-(4'-amino benzalmalonate)-s-triazine,

- n-butyl 2,4-bis-(4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,

- 2,4-bis-(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine,

- symmetrical triazine filters substituted by 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(di-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine 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 the form of an aqueous dispersion,

- triazine silicones substituted by two aminobenzoate groups as described in patent EP0841341, in particular 2,4-bis-(n-butyl 4’-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyloxy]disiloxanyl}propyl)amino]-s-triazine.

Compounds anthranilic :

Menthyl anthranilate sold under the trade name “NEO HELIOPAN MA®” by Symrise.

Imidazoline compounds:

Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate.

Compounds benzalmalonate :

Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name “PARSOL SLX ®” by HOFFMANN LA ROCHE.

4,4-Diarylbutadiene compounds:

-1,1-dicarboxy(2,2'-dimethyl-propyl)-4,4-diphenylbutadiene.

Compounds benzoxazole :

2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazine sold as Uvasorb K2A® by Sigma 3V.

Preferred organic filters are chosen from:

Ethylhexyl Methoxycinnamate,

Ethylhexyl Salicylate,

Homosalate,

Butyl Methoxydibenzoylmethane,

Octocrylene,

Phenylbenzimidazole Sulfonic Acid,

Benzophenone-3,

Benzophenone-4,

Benzophenone-5,

n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-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-(4'-amino dineopentyl benzalmalonate)-s-triazine,

2,4,6-tris-(4'-amino diisobutyl benzalmalonate)-s-triazine,

2,4-bis-(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,

2,4-bis-(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s-triazine,

2,4-bis-(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyloxy]disiloxanyl}propyl)amino]-s-triazine,

2,4,6-tris-(di-phenyl)-triazine,

2,4,6-tris-(ter-phenyl)-triazine

Drometrizole Trisiloxane,

Polysilicone-15,

1,1-dicarboxy(2,2'-dimethyl-propyl)-4,4-diphenylbutadiene,

2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazine,

and their mixtures.

Particularly preferred organic filters are chosen from:

Ethylhexyl Salicylate,

Homosalate,

Butyl Methoxydibenzoylmethane,

Octocrylene,

n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate,

Terephthalylidene Dicamphor Sulfonic Acid,

Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,

Ethylhexyl Triazone,

Diethylhexyl Butamido Triazone,

2,4-bis-(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyloxy]disiloxanyl}propyl)amino]-s-triazine,

Drometrizole Trisiloxane,

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 of 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 can be chosen in particular from titanium, zinc, iron, zirconium, cerium oxides or their mixtures.

Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. As commercial pigments, mention may be made of the products sold by the companies SACHTLEBEN PIGMENTS, TAYCA, MERCK and DEGUSSA.

Metal oxide pigments can be coated or uncoated.

Coated pigments are pigments that 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 aluminium salts of fatty acids, metal alkoxides (titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

Coated pigments are more particularly coated titanium oxides:

- silica such as the product "SUNVEIL®" from the company IKEDA,

- silica and iron oxide such as the product "SUNVEIL F®" from the company IKEDA,

- silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA®" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE,

- alumina such as the products "TIPAQUE TTO-55 (B)®" and "TIPAQUE TTO-55 (A)®" from the company ISHIHARA, and "UVT 14/4" from the company SACHTLEBEN PIGMENTS,

- alumina and aluminum stearate such as the products "MICROTITANIUM DIOXIDE MT 100 T®, MT 100 TX®, MT 100 Z®, MT-01®" from the company TAYCA, the products "Solaveil CT-10 W®" and "Solaveil CT 100®" from the company UNIQEMA and the product "Eusolex T-AVO®" from the company MERCK,

- silica, alumina and alginic acid such as the product "MT-100 AQ®" from the company TAYCA,

- alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE MT 100 S®" from the company TAYCA,

- iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F®" from the company TAYCA,

- zinc oxide and zinc stearate such as the product "BR 351®" from the company TAYCA,

- silica and alumina and treated with a silicone such as the products "MICROTITANIUM DIOXIDE MT 600 SAS®", "MICROTITANIUM DIOXIDE MT 500 SAS®" or "MICROTITANIUM DIOXIDE MT 100 SAS®" from the company TAYCA,

- silica, alumina, aluminum stearate and treated with silicone such as the product "STT-30-DS®" from the company TITAN KOGYO,

- silica and treated with a silicone such as the product "UV-TITAN X 195®" from the company SACHTLEBEN PIGMENTS,

- alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)®" from the company ISHIHARA, or "UV TITAN M 262®" from the company SACHTLEBEN PIGMENTS,

- triethanolamine such as the product "STT-65-S" from the company TITAN KOGYO,

- stearic acid such as the product "TIPAQUE TTO-55 (C)®" from the company ISHIHARA,

- sodium hexametaphosphate such as the product "MICROTITANIUM DIOXIDE MT 150 W®" from the company TAYCA.

- TiO ₂ treated with octyl trimethyl silane sold under the trade name "T 805®" by the company DEGUSSA SILICES,

- TiO ₂ treated with a polydimethylsiloxane sold under the trade name "70250 Cardre UF TiO2SI3®" by the company CARDRE,

- anatase/rutile TiO ₂ treated with a polydimethylhydrogensiloxane sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC®" by the company COLOR TECHNIQUES,

- TiO ₂ coated with triethylhexanoin, aluminum stearate, alumina sold under the trade name Solaveil CT-200-LQ-(WD) from CRODA,

- _TiO2 coated with aluminum stearate, alumina and silicone sold under the trade name Solaveil CT-12W-LQ-(WD from CRODA),

- TiO ₂ coated with lauroyl lysine sold by Daito Kasei Kogyo under the name LL 5 Titanium Dioxide CR 50,

- _TiO2 coated with C9-15 fluoroalcohol phosphate and aluminum hydroxide sold by Daito Kasei Kogyo under the name PFX-5 TiO2 CR-50.

Mention may also be made of TiO ₂ 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, a polyoxyalkylenated fatty acid and glycerol ester 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 polyoxyalkylenated fatty acid and glycerol esters. More particularly, mention may be made of the oily dispersion of manganese-doped TiO ₂ particles in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 MYRISTYLETHER CITRATE and POLYGLYCERYL-3-POLYRICINOLEATE and SORBITAN ISOSTERATE with the INCI name: TITANIUM DIOXIDE (and) TRI-PPG-3 MYRISTYLETHER CITRATE (and) POLYGLYCERYL-3 RICINOLEATE (and) SORBITAN ISOSTEARATE as the product sold under the trade name OPTISOL TD50 ® by the company CRODA.

Uncoated titanium oxide pigments are, for example, sold by TAYCA under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B®", by DEGUSSA under the name "P 25", by WACKHER under the name "Transparent titanium oxide PW®", by MIYOSHI KASEI under the name "UFTR®", by TOMEN under the name "ITS®" and by TIOXIDE under the name "TIOVEIL AQ".

Uncoated zinc oxide pigments are, for example:

- those marketed under the name “Z-cote” by the company Sunsmart;

- those marketed under the name “Nanox®” by the company Elementis;

- those marketed under the name “Nanogard WCD 2025®” by the company Nanophase Technologies.

Coated zinc oxide pigments include for example:

- those marketed under the name “Oxide zinc CS-5®” by the company Toshibi (ZnO coated with polymethylhydrogenesiloxane);

- those marketed under the name "Nanogard Zinc Oxide FN®" by the company Nanophase Technologies (in 40% dispersion in Finsolv TN®, benzoate of C12-C15 alcohols);

- those marketed under the name "DAITOPERSION Zn-30®" and "DAITOPERSION Zn-50®" by the company Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of zinc oxides coated with silica and polymethylhydrogensiloxane);

- those marketed under the name "NFD Ultrafine ZnO®" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and perfluoroalkylethyl copolymer dispersed in cyclopentasiloxane);

- those marketed under the name "SPD-Z1®" by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);

- those marketed under the name "Escalol Z100®" by the company ISP (ZnO treated with alumina and dispersed in the mixture of ethylhexyl methoxycinnamate / PVP-hexadecene copolymer / methicone);

- those marketed under the name "Fuji ZnO-SMS-10®" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);

- those marketed under the name "Nanox Gel TN®" by the company Elementis (ZnO dispersed at 55% in C12-C15 alcohol benzoate with hydroxystearic acid polycondensate).

Uncoated cerium oxide pigments may be, for example, those sold under the name "COLLOIDAL CERIUM OXIDE®" by the company RHONE POULENC.

Uncoated iron oxide pigments are sold, for example, by the company ARNAUD under the names "NANOGARD WCD 2002® (FE 45B®)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ®, "NANOGARD WCD 2006 ® (FE 45R®)", or by the company MITSUBISHI under the name "TY-220®".

Coated iron oxide pigments are sold, for example, by the company ARNAUD under the names "NANOGARD WCD 2008 (FE 45B FN)®", "NANOGARD WCD 2009® (FE 45B 556®)", "NANOGARD FE 45 BL 345®", "NANOGARD FE 45 BL®", or by the company BASF under the name "TRANSPARENT IRON OXIDE".

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company IKEDA under the name "SUNVEIL A®", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product "M 261®" sold by the company SACHTLEBEN PIGMENTS or coated with alumina, silica and glycerin such as the product "M 211®" sold by the company SACHTLEBEN PIGMENTS.

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 in accordance with the present invention may further comprise conventional cosmetic adjuvants, in particular chosen from organic solvents, ionic or non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foaming agents, 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 and/or dermatological field.

Among the organic solvents, mention may be made of short-chain monoalcohols, for example C ₁ -C ₄ such as ethanol and isopropanol, short-chain polyols C ₂ -C ₈ , 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, hexylene glycol, dipropylene glycol or diethylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, sorbitol, and mixtures thereof.

According to a preferred embodiment, it is possible to use more particularly ethanol, propylene glycol, glycerin, and their mixtures.

As thickeners, mention may be made of 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, the 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 the company Seppic; 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 Hoechst under the trade name “Hostacerin AMPS ^® ” (CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800® marketed by 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 SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; water-soluble silicone derivatives or water-dispersible such as acrylic silicones, polyether silicones and cationic silicones and their mixtures.

Among the acidifying agents, we can cite, for example, 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.

Examples of alkalizing agents include ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and 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.

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; antioxidant agents; anti-radical agents; anti-polluting 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; myorelaxant agents; refreshing agents; tightening 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.

The person 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) mentioned 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 not substantially, altered by the addition(s) envisaged.

DOSAGE FORMS

The compositions in accordance with the invention may be aqueous or anhydrous.

When the compositions are aqueous, they contain at least one aqueous phase.

They can then be in purely aqueous form, that is to say they comprise a quantity of fatty phase of less than 10% by weight, preferably less than 5% by weight, and even more preferably less than 2% by weight relative to the total weight of the composition. Advantageously, the composition in accordance with the invention is essentially aqueous, that is to say it is free of fatty phase.

The compositions according to the invention may also be 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.

In the case where the composition in accordance with the invention is aqueous, and it is possible to measure its pH, this is generally between approximately 3 and 12, preferably between approximately 5 and 9, and even more particularly from 5.5 to 8.

The compositions may also be in anhydrous form, such as in the form of an oil, a glycolic solution or an alcoholic solution. An “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 the preparation of the composition but corresponding to the residual water provided by the mixed ingredients. They may optionally be packaged as an aerosol and in the form of a 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 of the blade 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 concentrated phase then 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 drop sizes down to 100 nm.

Emulsions generally contain at least one emulsifier selected 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).

Examples of W/O emulsifying surfactants include 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 company Dow Corning; 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 company Goldschmidt. One or more co-emulsifiers may also be added, which, advantageously, may be chosen from the group comprising polyol alkyl esters.

We can also cite non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, glycerol, polyol or sugars.

Examples of polyol alkyl esters include polyethylene glycol esters such as PEG-30 Dipolyhydroxystearate such as the product marketed under the name Arlacel P135® by the company ICI.

As glycerol and/or sorbitan esters, mention may be made, for example, of polyglycerol isostearate, such as the product marketed 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 mixtures thereof.

For O/W emulsions, examples of nonionic emulsifying surfactants that may be mentioned include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) fatty acid and glycerol esters; oxyalkylenated sorbitan fatty acid esters; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) fatty acid esters, optionally in combination with a fatty acid and glycerol ester such as the PEG-100 Stearate/Glyceryl Stearate mixture marketed for example by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed for example by 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 Seppic, under the name Tegocare CG90® by Goldschmidt and under the name Emulgade KE3302® by Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohols and arachidylglucoside marketed under the name Montanov 202® by Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may 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 nonionic 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 treatments, 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 the 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 a makeup product.

Another subject of the present invention consists of 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 above.

Another object of the invention consists of the use of at least one compound chosen from gamma-butyrolactones and gamma-butyrolactams to solubilize a merocyanine of formula (3) as defined above.

According to a particular embodiment, the compounds chosen from gamma-butyrolactones and gamma-butyrolactams make it possible to solubilize the merocyanines in accordance with the invention in the fatty phase and/or in the aqueous phase.

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 aerosol and be in the form of mousse 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 in accordance with 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 US patents 4,077,441 and US 4,850,517.

The compositions packaged in aerosol form 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 amounts 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 assembly comprising:

(i) a container delimiting one or more compartment(s), 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 mounted hood movable by translation or by pivoting relative to the container housing said makeup and/or care composition(s).

EXAMPLES

The following examples serve to illustrate the invention without, however, being limiting in nature.

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 followed 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 silica gel column (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 formulations

Examples of solubilization 1 to 7

Solubility assessment protocol i you

The solubility of merocyanine in oily and/or aqueous solutions can be assessed macroscopically and/or microscopically. Merocyanine is considered soluble if, at room temperature, the solution appears clear and translucent to the eye, and does not show visible crystals under a microscope in white or polarized light (x20 to x40 objective).

In the following examples, solubility is evaluated macroscopically. It is evaluated at room temperature, on the day the solution is prepared and then over time. During this time, the solutions are stored at room temperature.

In Examples 1 to 7, the quantities of the composition ingredients are given in % by weight of raw materials relative to the total weight of the composition.

Examples comparatives 1 and 2 : solubilization in the presence of gamma- valerolactone

The following solutions were prepared according to the above method. Ingredients 1
(excluding invention) 2
(invention) Compound (25) 20 20 Gamma-valerolactone
marketed by All Organic Treasures GMBH - 80 Propylene carbonate
marketed by Merck KGaA 80 - Solubility at t ₀ soluble soluble Solubility at room temperature at 24 hours insoluble soluble

Method of preparation:

The compositions described in Examples 1 and 2 are prepared as follows: mix all the ingredients, heat to around 55°C and stir regularly by hand until a clear mixture is obtained (1 to 5 minutes). Leave to stir for 12 hours at room temperature. The solubility of the compositions is then observed according to the protocol as defined below.

Examples comparatives 3 and 4 : solubilization in the presence of 2- pyrrolidone

The following solutions were prepared using the procedure below. Ingredients 3
(excluding invention) 4
(invention) Compound (25) 20 20 2-pyrrolidone
marketed by
Sigma Aldrich - 80 Propylene carbonate
marketed by
Merck KGaA 80 - Solubility at t ₀ soluble soluble Solubility at room temperature at 24 hours insoluble soluble

Method of preparation:

The compositions described in Examples 3 and 4 are prepared as follows: mix all the ingredients, heat to around 55°C and stir regularly by hand until a clear mixture is obtained (1 to 5 minutes). Leave to stir for 12 hours at room temperature. The solubility of the compositions is then observed according to the protocol as defined below.

Comparative examples 5 and 6: solubilization in the presence of 1-butyl-acid 5 - oxo pyrrolidone- 3 -carboxylic

The following solutions were prepared using the procedure below. Ingredients 5
(excluding invention) 6
(invention) Compound (25) 10 10 1-Butyl-5-oxopyrrolidone-3-carboxylic acid - 10 ISOPROPYL LAUROYL SARCOSINATE
(ELDEW SL-205 from AJINOMOTO) 90 80 Solubility at t ₀ soluble soluble Solubility at room temperature at 48 hours insoluble soluble

Method of preparation:

The compositions described in Examples 5 and 6 are prepared as follows: mix all the ingredients, heat to around 80°C and stir with a magnetic bar until completely dissolved (approximately 1 hour). The solubility of the compositions is then observed macroscopically when hot (point noted t0), after returning to room temperature, and 48 hours after returning to room temperature.

Example 7 : solubilization in the presence of 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate

The following solutions were prepared using the procedure below. Ingredients 7
(invention) Compound (25) 10 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate 90 Solubility at t ₀ soluble Solubility at room temperature at 24 hours soluble

Method of preparation :

The different raw materials are successively introduced into a container before being mixed using a magnetic stirrer and heated to 80 to 90°C for 1 hour, until all the compounds are dissolved.

The mixture is then left to stand to return to room temperature where it is stored.

Examples 8 has 10 : solubilization in the presence of PCA and PCA ester

The following solutions were prepared using the procedure below. Ingredients 8 (excluding invention) 9 (invention) 10 (invention) Compound 25 50 mg 50 mg 50 mg 2-Pyrrolidone 5-carboxylic acid (PCA)
Sigma Aldrich - 20 mg - butyl(S) 2-pyrrolidone 5-carboxylate (PCA ester)
Sigma Aldrich - - 29 mg Water buffered to pH5 with citric acid 5 g 5 g 5 g pH measured 5 2.5 3.2 Absorption at 385 nm 0.66 0.78 1.17

Operating mode and solubility assessment :

Mix all ingredients and leave to stir under mechanical stirring for 24 hours at room temperature.

The mixture is filtered through a 0.2 µm diameter PTFE syringe filter to extract a clear liquid.

Take 30 µL of the liquid and dilute it in 5 mL of ethanol.

Introduce the diluted solution into a 1 cm cuvette and perform a UV/Visible spectrum of the solution.

Device: Perkin Elmer Lambda 19 spectrophotometer.

Results

The results obtained show that the gamma butyrolactones of the invention such as PCA and PCA ester make it possible to solubilize a greater quantity of merocyanine in water.

Claims (13)

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 possibly being interrupted by one or more O; and
(b) at least one compound selected from gamma-butyrolactones and gamma-butyrolactams of formula as defined below, as well as their acid or base salts, organic or mineral, or their solvates such as hydrates:
[formula 38]

in which:
X represents an oxygen atom, a sulfur atom or a nitrogen atom carrying a radical R4, with R4 representing a hydrogen atom, a linear or branched alkyl radical, C1-C6, preferably C1-C4,
R1, R2, R3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C6 alkyl radical, or
- a radical –[O] _n -C(O)-[O] _p -R5, with:
- n is equal to 0 or 1, p is equal to 0 or 1, with n + p equal to 1 or 2,
- R5 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical;
the mass ratio of the total quantity of compounds chosen from gamma-butyrolactones and gamma-butyrolactams of formula (38) to the total quantity of merocyanines of formula (3) is greater than or equal to 0.2/1, preferably greater than 0.5/1, even more preferably greater than 1/1, better still greater than or equal to 2/1, even better still greater than or equal to 4/1, or even greater than or equal to 8/1, more preferably greater than or equal to 9/1, and even better still greater than or equal to 10/1. Composition according to claim 1 in which the mass ratio of the total quantity of compounds chosen from gamma-butyrolactones and gamma-butyrolactams of formula (38) to the total quantity of merocyanines of formula (3) is less than or equal to 50/1, preferably less than or equal to 40/1, even more preferably less than or equal to 30/1, better still less than or equal to 20/1. 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 possibly being interrupted by one or more O; and
(b) the compound selected from gamma-butyrolactones and gamma-butyrolactams of formula as defined below, as well as its acid or base salts, organic or mineral, or its solvates such as hydrates:
[formula 43bis]
. Composition according to any one of claims 1 to 3 in which the merocyanines of formula (3) are chosen from the following compounds, as well as their isomeric geometric forms, in particular E/E or 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 Composition according to any one of claims 1 to 4 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 geometric E/Z configuration of the following structure:
[formula 25]

and/or in its geometric configuration E/E of the following structure:
[formula 25bis]
Composition according to any one of claims 1 to 5 in which, in formula 38, R1, R2, R3 represent, independently of one another:
- a hydrogen atom,
- a linear or branched alkyl radical, C1-C6, preferably C1-C4, or
- a radical –[O] _n -C(O)-[O] _p -R5, with:
- n is equal to 0 or 1, p is equal to 0 or 1, with n + p equal to 1,
- R5 represents a hydrogen atom, a linear or branched C1-C6 alkyl radical. A composition according to any one of claims 1 to 6 wherein, in formula 38, n = 0 and p = 1. Composition according to any one of claims 1, 2 and 4 to 7 comprising at least one gamma-butyrolactone, preferably a gamma-butyrolactone of formula 38 as defined in claims 1, 4 and 5 in which X is an oxygen atom. Composition according to any one of claims 1 to 8 comprising at least one gamma-butyrolactam, preferably a gamma-butyrolactam of formula 38 as defined in claims 1, 4 and 5 in which X is a nitrogen atom carrying a radical R4. 10. Composition according to any one of claims 1, 2 and 4 to 9 comprising at least one compound chosen from gamma-valerolactone, 2-pyrrolidone, 1,3-dimethylbutyl 1-butyl-5-oxopyrrolidine-3-carboxylate, 2-pyrrolidone-5-carboxylic acid (PCA), tert-butyl(S) 2-pyrrolidone-5-carbonate (PCA ester) and 1-butyl-5-oxopyrrolidone-3-carboxylic acid. 11. Composition according to any one of claims 1 to 10 further comprising one or more additional UV filters. 12. 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 cosmetic composition as defined in any one of claims 1 to 11. 13. Use of at least one compound chosen from gamma-butyrolactones and gamma-butyrolactams as defined in any one of claims 1 to 11 for solubilizing a merocyanine as defined in any one of claims 1 to 4, in particular in the fatty phase and/or in the aqueous phase.