FR3149777A1 - Aqueous cosmetic or dermatological composition comprising a merocyanine and a water-soluble UV filter - Google Patents

Abstract

Title: Aqueous cosmetic or dermatological composition comprising a merocyanine and a water-soluble UV filter The present invention relates to an aqueous 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: 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; in an amount of less than 3% by weight relative to the total weight of the composition; and b) at least one water-soluble organic UV filter.

Description

Aqueous cosmetic or dermatological composition comprising a merocyanine and a water-soluble UV filter

The present invention relates to an aqueous cosmetic or dermatological composition comprising at least one merocyanine of formula (3) which will be defined in detail below and at least one water-soluble UV filter.

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 fibres 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.

Furthermore, 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 capacity for solar radiation, the desired photoprotection compounds must also have good cosmetic properties, good solubility in common solvents and in particular in fatty substances such as oils 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.

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.

For the most part, UV filters are carried in oily phase and/or aqueous phase as an active anti-UV agent and are generally offered in a galenic form such as an emulsion or gel.

It is also known that high filter rates are necessary to achieve high levels of filtering efficiency.

However, high levels of UV filters do not lend themselves to easy development of compositions with a stabilised and pleasant texture.

Thus, formulations with high filtering power can generally present uncomfortable or even unpleasant sensory aspects masking the freshness and comfort of the formulas. In particular, the weak point of photoprotective formulations with a high protection index can be a significant feeling of oiliness, and therefore a lack of lightness of the textures obtained, but also a white appearance on application and therefore not invisible on the skin.

Furthermore, the introduction of high-content UV filters generally causes destabilization problems. This instability can sometimes even cause a phase shift of the emulsion and/or a loss of viscosity of the composition, making the formulation ineffective or even unusable.

To overcome the above-mentioned undesirable effects, and in particular to obtain a fresh effect on application and an invisible effect on the skin, aqueous galenics have already been considered. However, these aqueous compositions containing UV filters are generally sticky and therefore uncomfortable.

Consequently, there is a need for an aqueous cosmetic or dermatological composition exhibiting good long UVA filtration efficiency, exhibiting good cosmetic properties, and perfectly stable and homogeneous, i.e. not subject to demixing phenomena.

There is also a need for an aqueous photoprotective composition exhibiting good filtration efficiency across the entire wavelength spectrum between 280 and 400 nm, exhibiting good cosmetic properties, and being perfectly stable and homogeneous, i.e. not subject to demixing phenomena.

There is still a need for an aqueous cosmetic or dermatological composition that has good long UVA filtration efficiency and is also transparent. In addition, there is a need for a cosmetic or dermatological composition that is transparent even after application to the skin.

In particular, there remains a need for an aqueous cosmetic or dermatological composition having good filtration efficiency between 370 nm and 400 nm, and possibly a high level of UV protection over the entire wavelength spectrum between 280 nm and 400 nm, which has good cosmetic properties on application, in particular which is easy to apply, without a greasy or sticky finish on the skin, in particular after drying, and having a pleasant sensory effect materialized in particular by a slip on application.

The aim of the present invention is to propose new cosmetic or dermatological compositions which respond to these problems.

The Applicant has surprisingly discovered that the addition of at least one water-soluble filter, which is not a solvent and must itself be solubilized in water, makes it possible to very significantly increase the solubility of the merocyanines described above in water.

This allows these specific merocyanines to be solubilized in essentially aqueous sunscreen products without the addition of additional solvent.

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 an aqueous cosmetic or dermatological composition comprising:
a) at least one merocyanine of formula (3) which will be defined in detail below in an amount of less than 3% by weight relative to the total weight of the composition; and
b) at least one water-soluble UV filter.

Thus, the solubility of merocyanines in water is improved in the presence of at least one water-soluble UV filter.

The Applicant surprisingly discovered that by using at least one water-soluble UV filter, it was also possible to significantly improve the solubility of these merocyanines in an aqueous phase, even in the presence of additional organic UV filters.

The Applicant has also discovered that the use of at least one such merocyanine in combination with at least one water-soluble UV filter makes it possible to obtain good cosmeticity of the composition comprising the merocyanines, the latter being in particular non-greasy and non-sticky.

Furthermore, the present invention makes it possible to obtain transparent compositions, even after application to the skin.

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 cosmetic 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 cosmetic 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 cosmetic composition as defined above.

The present invention also relates to the use of at least one water-soluble UV filter to solubilize a merocyanine of formula (3) as defined below in 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.

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

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

For the purposes of the present invention, the term "transparent or translucent composition" means a composition having a turbidity value of less than 1000 NTU, preferably less than 800 NTU, even more preferably less than 500 NTU, better still less than 200 NTU, preferably less than 150 NTU, in particular less than 100 NTU. Preferably, the turbidity of the compositions is at least equal to 1 NTU.

NTU (Nephelometric Turbidity Units) are the units of measurement for the turbidity of a composition. Turbidity measurement is performed, for example, with a Hach Company model 2100P turbidimeter, the tubes used for the measurement being referenced AR397A cat 24347-06. Measurements are performed at room temperature (20 °C to 25 °C).

According to a particular embodiment of the invention, the composition is transparent and has a turbidity value of between 1 and 200 NTU, preferably between 1 and 150 NTU, preferably less than 100 NTU.

Preferably, the composition is transparent after its application to the skin, i.e. there is no white mark after spreading the composition on the skin.

Detailed description of the invention 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-:

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 E/E- and E/Z- isomeric geometric forms:

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:
[Table 1]
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:

The E/E form has the following structure:

The filtering merocyanines in accordance with the invention are present in the composition in an amount of less than 3% by weight, preferably in an amount of less than or equal to 2.5% by weight, preferably in an amount of between 0.01% and 2.5% by weight, and even more preferably between 0.5% and 1.5% 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):

And more particularly for compound 25 described in table 1:

WATER-SOLUBLE ORGANIC UV FILTERS

The composition in accordance with the invention comprises at least one water-soluble organic UV filter.

By "water-soluble organic filter" is meant any organic filter capable of being completely dissolved in molecular form in a liquid aqueous phase, or of being dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.

Among the water-soluble organic UVA filters that can be used according to the present invention, mention may be made of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) and its various salts, described in particular in patent applications FR-A-2528420 and FR-A-2639347. Mention may in particular be made of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as that manufactured under the name “MEXORYL® SX” by the company NOVEAL,

These filters correspond to the following general formula (I):

in which, F denotes a hydrogen atom, an alkali metal or a radical NH(R ₁ ) ₃ ⁺ in which the radicals R ₁ , which may be identical or different, denote a hydrogen atom, a C ₁ to C ₄ alkyl or hydroxyalkyl radical, or a group Mn+, Mn+ denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn+ preferably denoting a metal cation chosen from Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ and Zr ⁴⁺ . It is understood that the compounds of formula (I) above can give rise to the "cis-trans" isomer around one or more double bond(s) and that all the isomers fall within the scope of the present invention.

Among the water-soluble organic UVA filters which can be used according to the present invention, mention may also be made of compounds comprising at least two benzoazolyl groups with sulfonic groups such as those described in patent application EP-A-0669323.

They are described and prepared according to the syntheses indicated in US patent 2,463,264 as well as in patent application EP-A-0669323.

The compounds comprising at least two benzoazolyl groups in accordance with the invention correspond to the following general formula (II):
(II)
in which,
- Z represents an organic residue of valence (l + n) comprising one or more double bonds placed in such a way that it completes the double bond system of at least two benzoazolyl groups as defined inside the brackets to form a fully conjugated set;
- X' denotes S, O or NR ⁶ ;
- R ¹ denotes a hydrogen atom, a C ₁ to C ₁₈ alkyl, a C ₁ to C ₄ alkoxy, a C ₅ to C ₁₅ aryl, a C ₂ to C ₁₈ acyloxy, an SO ₃ Y or COOY group;
- the radicals R ² , R ³ , R ⁴ and R ⁵ , identical or different, denote a nitro group or a radical R ¹ ;
- R ⁶ denotes a hydrogen atom, a C ₁ to C ₄ alkyl or a C ₁ to C ₄ hydroxyalkyl;
- Y denotes a hydrogen atom, Li, Na, K, NH ₄ , 1/2Ca, 1/2Mg, 1/3Al or a cation resulting from the neutralization of a free acid group by an organic nitrogen base;
- m is 0 or 1;
- n is a number from 2 to 6;
- l is a number from 1 to 4;
- provided that l + n does not exceed the value 6.

Among these compounds, 1,4-bis-benzimidazolyl-phenylen-3,3',5,5'-tetrasulfonic acid (INCI name: Disodium Phenyl Dibenzimidazole Tetra-sulfonate) or one of its salts of the following structure (III) sold in particular under the name "NEO HELIOPAN® AP" by the company Symrise will be particularly preferred:
(III)

Preferably, the water-soluble filter capable of absorbing UVA is benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid) such as that manufactured under the name "MEXORYL SX" by NOVEAL.

The water-soluble organic UVB filters that can be used according to the present invention are notably chosen from water-soluble cinnamic derivatives such as ferulic acid or 3-methoxy-4-hydroxycinnamic acid; water-soluble benzylidene camphor compounds; water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic compounds (PABA); water-soluble salicylic compounds, and mixtures thereof.

Examples of water-soluble organic UVB filters include phenyl benzimidazole compounds, such as 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid) sold in particular under the trade name “EUSOLEX 232 ^® ” by MERCK.

The composition according to the invention may also comprise at least one mixed water-soluble filter capable of absorbing UVA and UVB rays.

When the water-soluble UV filter is of the sulfonic acid type, it is preferably associated with an organic base, such as an alkanolamine, or a mineral base, such as sodium hydroxide or potassium hydroxide.

By "alkanolamine" is meant a _C2 - _C10 compound comprising at least one primary, secondary or tertiary amine function and at least one alcohol function, generally primary. As suitable alkanolamine, mention may be made of 2-amino-2-(hydroxymethyl)-1,3-propanediol (INCI name: TROMETHAMINE) and triethanolamine.

The water-soluble organic UV filter(s) may be present in the compositions according to the invention in a concentration ranging from 0.1% to 19% by weight, and preferably from 0.5% to 12% by weight, and even better from 3% to 10% by weight relative to the total weight of the composition.

ADDITIONAL UV FILTERS

The composition in accordance with the invention may comprise at least one additional UV filter other than the merocyanines of formula (3) and water-soluble organic UV filters as described above.

The additional UV filter(s) may be chosen from lipophilic organic UV filters, water-dispersible organic UV filters and inorganic UV filters.

According to a particular embodiment, the additional UV filter(s) may be chosen from water-dispersible organic UV filters and inorganic UV filters.

Lipophilic organic UV filters

By "lipophilic organic filter" we mean any organic 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.

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

Preferably, the lipophilic organic filter(s) are chosen from salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.

Examples of lipophilic organic photoprotective agents include those designated below by their INCI name and/or chemical name.

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

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

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

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

Benzophenone compounds:
Benzophenone-3 or Oxybenzone, sold under the trade name “UVINUL® M 40” by the company BASF,
Diethylamino hydroxybenzoyl hexyl benzoate sold under the trade name “UVINUL® A Plus” or in mixture with ethylhexyl methoxycinnamate under the trade name “UVINUL® A Plus B” by the company BASF,

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

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

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol, in particular in solid form as the product sold under the trade name “MIXXIM BB/100 ®” by the company FAIRMOUNT CHEMICAL,

Triazine compounds:
- 3,3'-(1,4-Phenylene)bis(5,6-diphenyl-1,2,4-triazine), INCI name Phenylene Bis-Diphenyl triazine,
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name “Parsol Shield ®” by the company DSM Nutritional Products and under the trade name “TINOSORB® S” by the company BASF,
- Ethylhexyl Triazone sold in particular under the trade name “UVINUL® T 150” by the company BASF,
- Diethylhexyl Butamido Triazone sold under the trade name “UVASORB® HEB” by the company 3V SIGMA,
- symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups described in patent US6,225,467, application WO2004/085412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM IPCOM000031257 Journal, INC WEST HENRIETTA, NY, US (September 20, 2004),

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

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

Water-dispersible organic UV filters

The term "water-dispersible organic filter" means any organic filter capable of forming in a liquid aqueous phase a homogeneous suspension of particles with a volume average size of less than 100 microns. The volume average size is determined by laser diffraction granulometry.

Among the water-dispersible organic filters, the following filters can be mentioned.

Benzophenone compounds:
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 (volume 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,

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol
in the form of an aqueous dispersion of micronized particles having a mean particle size by volume 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 mean degree of polymerization of the unit (C ₆ H ₁₀ O ₅ ) and varies from 1.4 to 1.6 such as the aqueous dispersions described in patent GB-A-2 303 549, in particular the product sold under the trade name "TINOSORB® M" by the company BASF, or
in the form of an aqueous dispersion of micronized particles having a volume 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, in particular the product marketed under the name Tinosorb WPGL by the company BASF,

Triazine compounds:
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its water-dispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer, under the trade name TINOSORB® S LiteAqua by the company BASF,
- symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups used in micronized form (average particle size of 0.02 to 3 µm) obtainable for example according to the micronization process described in applications GB-A-2 303 549 and EP-A-893119, and in particular in aqueous dispersion form, in particular 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine marketed under the name TINOSORB® A2B by the company BASF and which is included in patent applications WO06/035000, WO06/034982, WO06/034991, WO06/035007, WO2006/034992, WO2006/034985,

Benzoxazole compounds:
2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole, CAS number 904-39-2.

Inorganic UV filters

The inorganic UV filters that can be 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 are notably described in Annex VI updated on 09/22/2021 of the European Cosmetic Products Regulation number 1223/2009, but are not limited to this list.

They 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 CRODA, TAYCA, and MERCK.

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

Mention may also be made of TiO2 pigments doped with at least one transition metal such as iron, zinc, manganese and more particularly manganese. Preferably, said doped pigments are in the form of an oily dispersion. The oil present in the oily dispersion is preferably chosen from triglycerides including those of capric/caprylic acids. The oily dispersion of titanium oxide particles may additionally comprise one or more dispersing agents such as, for example, a sorbitan ester such as sorbitan isostearate, 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 TiO2 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 or the product sold under the trade name “OPTISOL™ OTP-1” by the company CRODA.

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

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

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

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

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, as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone or coated with alumina, silica and glycerin.

When the composition according to the invention comprises inorganic UV filters, titanium oxide pigments, coated or uncoated, are particularly preferred.

According to a particular embodiment, the total quantity of additional UV filters present in the composition is less than or equal to 20% by weight, preferably less than or equal to 10% by weight, and even more preferably less than or equal to 5% by weight of the total weight of the composition.

According to a preferred embodiment, the total amount of additional UV filters present in the composition is between 0.1% and 20% by weight, preferably between 0.5% and 10% by weight, and even more preferably between 1% and 5% by weight of the total weight of the composition.

According to a particular embodiment, the only UV filters present in the composition are the water-soluble organic filters and the merocyanines of formula (3).

For the purposes of the present invention, the term “total quantity of additional UV filters” means the sum of the concentrations of active material of each of the UV filters present in the composition other than the merocyanines of formula (3) and the water-soluble organic UV filters as described above.

AQUEOUS PHASE

The composition in accordance with the invention comprises 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.

The aqueous phase may comprise at least one other organic solvent soluble in water, at 25°C, chosen for example from:
- C1-C4 monoalkanols. The term “C1-C4 monoalkanol” means any saturated, linear or branched alkane compound having from 1 to 4 carbon atoms and a single hydroxyl function (OH). The C1-C4 monoalkanol(s) present in the compositions of the invention may be chosen from methanol, ethanol, propanol, isopropanol, butanol or mixtures thereof. Ethanol will be chosen more particularly;
- polyols having in particular from 2 to 20 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, caprylyl glycol, 1,3-propanediol, pentylene glycol, ethylene glycol, or diethylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, sorbitol, simple sugars, water-soluble polyalkylene glycols; preferably, polyols having from 2 to 8 carbon atoms; and mixtures thereof.

According to a particular embodiment, the composition according to the invention comprises at least one C1-C4 monoalkanol, and more particularly ethanol.

The monoalkanols are generally present at concentrations ranging from 0.2% to 90% by weight, more preferably from 0.5% to 50%, and more preferably from 1% to 15% by weight relative to the total weight of the composition.

According to another particular embodiment, the composition according to the invention comprises at least one polyol, in particular as described above. Preferably, it comprises at least 1% by weight of polyol(s) relative to the total weight of the composition, preferably at least 5% by weight of polyol(s) relative to the total weight of the composition, preferably from 5% to 20% by weight, preferably from 10% to 15% by weight.

Preferably, the composition according to the invention comprises as polyol glycerin, butylene glycol, propylene glycol or dipropylene glycol and their mixtures.

The composition according to the invention is aqueous. For the purposes of the present invention, the term “aqueous” means a composition comprising 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 according to the invention is essentially aqueous, i.e. it is free of fatty phase.

According to a particular embodiment of the invention, the composition has a pH of between 3 and 8. Advantageously, the pH of the composition is between 5 and 7.5.

According to a particular embodiment, the cosmetic composition according to the invention may comprise an acidifying agent and/or an alkalizing agent.

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, sodium hydroxide and potassium hydroxide.

HYDROPHILIC GELLING AGENTS

The composition according to the invention may comprise at least one hydrophilic gelling agent (or hydrophilic thickening agent).

For the purposes of the present invention, the term “hydrophilic gelling agent” (or “hydrophilic thickening agent”) means a compound capable of gelling the aqueous phase of the compositions according to the invention.

In particular, in the context of the present application, the term “thickening agent” is understood to mean in particular an agent making it possible to increase by at least 10 times, preferably by at least 15 times, preferably by at least 20 times, the viscosity of a mixture comprising said agent at 1% by weight, triethanolamine at 0.9% by weight and water, at a temperature of 25°C.

According to a particular embodiment of the invention, the hydrophilic gelling agent(s) are polymeric.

The hydrophilic gelling agent(s) may be selected from anionic synthetic thickening polymers, nonionic thickening polysaccharides, sulfated thickening polysaccharides and carboxylated branched thickening polysaccharides.

The term “carboxylated” means comprising at least one carboxylic acid function.

Preferably, the composition according to the invention is substantially free (i.e. contains less than 0.4%, preferably less than 0.3%, preferably less than 0.2%, and better still less than 0.1% by weight relative to the total weight of the composition), preferably is totally free, of thickening agent chosen from clays, mica, modified starches such as phosphate starches, and gellan gum.

Anionic synthetic thickening polymers

The composition according to the invention may comprise an anionic synthetic thickening polymer.

Preferably, the anionic synthetic thickening polymer is non-aromatic; that is, it does not contain any aromatic monomer.

Among the anionic synthetic thickening polymers which may be used, mention may be made of crosslinked homopolymers or copolymers of acrylic or methacrylic acid, homopolymers of 2-acrylamido-2-methyl-propanesulfonic acid, crosslinked or not, or their salts, and copolymers of acrylamido-2-methyl propanesulfonic acid or its salts and one or more nonionic monomers, crosslinked or not, alone or in mixtures.

A first family of suitable thickening polymers is represented by crosslinked homopolymers of acrylic acid. Among the homopolymers of this type, mention may be made of those crosslinked by an allyl ether of alcohol of the sugar series, such as for example the products sold under the names CARBOPOL 980, 981, 954, 2984 and 5984 by the company LUBRIZOL or the products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3V.

Such acrylic homopolymers may be present in the composition in a particulate or non-particulate form. When they are in a particulate form, their average size in the hydrated state is preferably less than or equal to 10 µm, and even more preferably less than or equal to 5 µm. Their average size in the dry or non-hydrated state is preferably less than or equal to 2 µm, preferably less than or equal to 1 µm.

Preferably, the acrylic acid homopolymer is present in non-particulate form.

Preferably, an at least partially neutralized acrylic acid homopolymer is used. The homopolymer used according to the invention is in particular chosen from sodium polyacrylates and potassium polyacrylates. Sodium polyacrylate is preferably used.

Examples of these acrylic polymers which are already neutralized before their implementation include:
- sodium polyacrylates such as those marketed under the name Cosmedia SP® containing 90% dry matter and 10% water, or Cosmedia SPL® in inverse emulsion containing approximately 60% dry active matter, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company BASF;
- partially neutralized sodium polyacrylates, in particular in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by the company BASF; and
- their mixtures.

It is also possible to use a polymer of acrylic acid that has not been previously neutralized, which is then partially or completely neutralized before implementation by any appropriate means and in particular by adding any base such as sodium hydroxide, potash, an alkanolamine such as triethanolamine. In this way, sodium polyacrylates are obtained in particular. Potassium polyacrylates are also suitable for the present invention.

A second family of suitable thickening polymers is represented by crosslinked copolymers of (meth)acrylic acid and C1-C30 alkyl acrylate.

Preferably, these copolymers are crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate.

The (meth)acrylic acid monomer is preferably present in amounts ranging from 20 to 80% by weight, and more particularly from 25 to 70% by weight, and even more particularly from 35 to 60% by weight relative to the total weight of the copolymer.

The C1-C6 alkyl acrylate monomer is preferably present in amounts ranging from 15 to 80% by weight, and more particularly from 25 to 75% by weight, and even more particularly from 40 to 65% by weight relative to the total weight of the copolymer. Among these monomers, mention may be made of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, styrene, acrylamide, N,N-dimethylacrylamide, tert-butylacrylamide, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate.

Such a copolymer is typically partially or completely crosslinked by at least one conventional crosslinking agent. The crosslinking agents are in particular polyunsaturated compounds. These compounds are in particular polyalkenyl ethers of sucrose or polyols, diallylphthalates, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methylene bis-acrylamide, trimethylol propane tri(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, zinc (meth)acrylate, castor oil derivatives or polyols manufactured from unsaturated carboxylic acids. As crosslinking agent, it is also possible to use unsaturated monomeric compounds comprising a reactive group capable of reacting with an unsaturation to form a crosslinked copolymer. The content of crosslinking agent generally varies from 0.01 to 5% by weight, and preferably from 0.03 to 3% by weight, and even more particularly from 0.05 to 1% by weight relative to the total weight of the copolymer.

The crosslinked copolymer of (meth)acrylic acid and C1-C6 alkyl acrylate preferred according to the invention is chosen from crosslinked copolymers of methacrylic acid and C1-C6 alkyl acrylate, crosslinked copolymers of acrylic acid and C1-C6 alkyl acrylate, and more particularly a crosslinked copolymer of methacrylic acid and ethyl acrylate.

According to a particularly preferred form, the copolymer of the invention may be in particular in the form of a dispersion in water. The number-average size of the copolymer particles in the dispersion is generally between 10 and 500 nm, and preferably between 20 and 200 nm, and more preferably from 50 to 150 nm.

Among the crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate, mention may be made of the product sold under the name VISCOATEX 538C by the company COATEX which is a crosslinked copolymer of (meth)acrylic acid and C1-C4 ethyl acrylate in aqueous dispersion at 38% active material, or the product sold under the name ACULYN 33 by the company ROHM & HAAS which is a crosslinked copolymer of acrylic acid and ethyl acrylate in aqueous dispersion at 28% active material. More particularly, mention may be made of the crosslinked methacrylic acid/ethyl acrylate copolymer in the form of a 30% aqueous dispersion manufactured and sold under the name CARBOPOL AQUA SF-1 by the company LUBRIZOL.

A third family of suitable thickening polymers is represented by homopolymers of 2-acrylamido-2-methyl-propanesulfonic acid (AMPS®), crosslinked or not, or their salts. These homopolymers can be crosslinked or not crosslinked.

Such a homopolymer may have a number average molecular weight ranging from 1,000 to 20,000,000 g/mole, preferably ranging from 20,000 to 5,000,000, and more preferably still from 100,000 to 1,500,000 g/mole.

In particular, 2-acrylamido-2-methylpropanesulfonic acid and its partially or completely neutralized forms are used.

When the polymers are crosslinked, the crosslinking agents can be chosen from the polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization. Examples of crosslinking agents which may be mentioned are divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di(meth)acrylate, trimethylol propane triacrylate, methylene bis acrylamide, methylene bis methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallyl ethylenediamine, tetraallyloxy ethane, trimethylol propane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, as well as allyl esters of phosphoric acid derivatives and/or vinylphosphonic, or mixtures of these compounds.

According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The crosslinking rate generally ranges from 0.01 to 10 mol%, and more particularly from 0.2 to 2 mol% relative to the polymer.

The homopolymer only contains monomers with a sulfonic group and, if it is crosslinked, one or more crosslinking agents.

Preferred 2-acrylamido-2-methylpropanesulfonic acid homopolymers are generally characterized by comprising, randomly distributed:
(a) from 90 to 99.9% by weight of units of the following general formula (1):
(1)
in which X ⁺ denotes a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, at most 10 mol% of the X ⁺ cations being able to be H ⁺ protons;
b) from 0.01 to 10% by weight of crosslinking units originating from at least one monomer having at least two olefinic double bonds, the proportions by weight being defined relative to the total weight of the polymer.

The more particularly preferred homopolymers according to the invention comprise from 98 to 99.5% by weight of units of formula (1) and from 0.2 to 2% by weight of crosslinking units.

Polymers of this type include, in particular, the crosslinked and neutralized homopolymer of 2-acrylamido 2-methylpropane sulfonic acid, marketed by the company Clariant under the trade name “Hostacerin AMPS®” (CTFA name: ammonium polyacryldimethyltauramide).

The polymer may also be an amphiphilic homopolymer (or hydrophobically modified homopolymer) chosen from random amphiphilic polymers of 2-acrylamido-2-methylpropanesulfonic acid modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, such as those described in document WO-A-00/31154, which are grafted homopolymers.

A fourth family of suitable thickening polymers is represented by copolymers of acrylamido-2-methyl propane sulfonic acid or its salts and one or more nonionic monomers. They can be crosslinked or non-crosslinked.

When the polymers are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for crosslinking polymers obtained by radical polymerization. Such agents are described above.

According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The crosslinking rate generally ranges from 0.01 to 10 mol%, and more particularly from 0.2 to 2 mol% relative to the polymer.

The copolymers according to the invention are obtained from AMPS® and one or more hydrophilic or hydrophobic ethylenically unsaturated nonionic monomers and, if they are crosslinked, one or more crosslinking agents such as those defined above.

The 2-acrylamido-2-methylpropanesulfonic acid monomer of the copolymer contained in the composition according to the invention is in free form or is partially or totally neutralized by a mineral base (soda, potash, ammonia) or an organic base such as mono-, di-, or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine as well as the mixture of these compounds.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is partially or completely salified in the form of an ammonium or sodium salt.

Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is fully salified, preferably in the form of ammonium or sodium salt.

AMPS® copolymers contain one or more nonionic monomers selected from water-soluble ethylenically unsaturated monomers, hydrophobic monomers, or mixtures thereof.

Among the non-ionic water-soluble monomers, we can cite for example:
- (meth)acrylamide,
- N-vinylacetamide and N-methyl N-vinylacetamide,
- N-vinylformamide and N-methyl N-vinylformamide,
- maleic anhydride,
- vinylamine,
- N-vinyllactams comprising a cyclic alkyl group having from 4 to 9 carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam and N-vinylcaprolactam,
- vinyl alcohol of formula CH ₂ =CHOH,
- water-soluble vinyl monomers of the following formula (2):
(2)
in which:
- R ₁₅ is selected from H, -CH ₃ , -C ₂ H ₅ or -C ₃ H ₇
- X ₂ is chosen from alkyl oxides of the type –OR ₁₆ where R ₁₆ is a linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbons, optionally substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether.

Examples include glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, and ethylene glycol, diethylene glycol or polyalkylene glycol (meth)acrylates.

Preferably, the water-soluble monomer is chosen from acrylamide, vinylpyrrolidone, hydroxyalkyl(meth)acrylates, more particularly vinylpyrrolidone.

As AMPS® copolymers in accordance with the invention with hydrophilic monomers, we can cite for example:
- copolymers of acrylamido-2-methyl propane sulfonic acid and vinylpyrrolidone such as in particular the commercial product ARISTOFLEX AVC sold by CLARIANT;
- crosslinked acrylamide/sodium acrylamido-2-methyl propane sulfonate copolymers, such as that used in the commercial product SEPIGEL 305® (INCI name: Polyacrylamide/C ₁₃ -C ₁₄ Isoparaffin/ Laureth-7) or that used in the commercial product sold under the name SIMULGEL 600® (INCI name: Acrylamide / Sodium Acryloyldimethyltaurate / Isohexadecane / Polysorbate-80) by the company SEPPIC;
- copolymers of AMPS® and hydroxyethyl acrylate, such as for example the AMPS® sodium/hydroxyethyl acrylate copolymer such as that used in the commercial product sold under the name SIMULGEL NS® by the company SEPPIC (INCI name: Hydroxyethyl acrylate/Sodium Acryloyldimethyltaurate copolymer (and) Squalane (and) Polysorbate 60);
- hydrophobically modified AMPS® copolymers such as the copolymer known under the INCI name: AMMONIUM ACRYLOYLDIMETHYLTAURATE / STEARETH-25 METHACRYLATE CROSSPOLYMER sold under the trade name ARISTOFLEX HMS by the company CLARIANT.

The concentration of anionic synthetic thickening polymer (i.e. active material) generally ranges from 0.05 to 35% by weight relative to the total weight of the composition, and preferably from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, preferably from 0.25 to 5% by weight, and even more particularly from 0.3 to 3% by weight.

Thickening polysaccharides

The composition according to the invention may also comprise a thickening polymer chosen from nonionic thickening polysaccharides, sulfated thickening polysaccharides and carboxylated branched thickening polysaccharides.

Among the nonionic thickening polysaccharides, we can notably cite nonionic cellulose thickening polysaccharides.

Preferably, the celluloses which can be used in the compositions according to the present invention are chosen from celluloses not comprising a hydrophobic chain and non-ionic celluloses comprising one or more hydrophobic chains.

Preferably, the celluloses used according to the invention are cellulose ethers. Even more preferably, these celluloses are nonionic hydroxyalkylcelluloses, and in particular hydroxyethylcelluloses or hydroxypropylcelluloses. They may or may not contain a fatty chain. Among the nonionic celluloses not comprising a fatty chain, mention may be made of hydroxyethylcelluloses, hydroxypropylcelluloses and hydroxypropylmethylcelluloses. A particularly suitable hydroxyethylcellulose is Cellosize HEC QP-4400 H offered by Amerchol (INCI name: HYDROXYETHYLCELLULOSE).

The celluloses modified by groups comprising one or more non-ionic fatty chains which can be used according to the present invention are in particular:
- nonionic hydroxyethylcelluloses modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, such as the product NATROSOL PLUS GRADE 330 CS® (C16 alkyls) sold by the company ASHLAND corresponding to the INCI name “CETYLHYDROXYETHYLCELLULOSE”, or the product BERMOCOLL EHM 100® sold by the company AKZO NOBEL,
- those modified by polyalkylene glycol ether groups of alkyl phenol, such as the product AMERCELL POLYMER HM-1500® (polyethylene glycol (15) ether of nonyl phenol) sold by the company AMERCHOL corresponding to the INCI name “NONOXYNYL HYDROXYETHYLCELLULOSE”.

Among the sulfated thickening polysaccharides, mention may be made in particular of sulfated polysaccharides devoid of rhamnose. These sulfated polysaccharides are preferably carrageenans.

Carrageenans are polysaccharides that constitute the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinaceae, Hypneaceae, Furcellariaceae and Polyideaceae. They comprise long galactan chains, anionic polyelectrolytes. Their molecular mass can be greater than 10 ⁶ . These linear polymers, formed by disaccharide units, are composed of two D-galactopyranose units linked alternately by α- and β- bonds. They are highly sulfated polysaccharides (20-50%) and the α-D-galactopyranosyl residues can be in 3',6'-anhydro form.

Initially, carrageenans were subdivided into two families according to their solubility in potassium chloride (KCl). The KCl-soluble fractions were designated by the prefixes "Kappa", while the terms "Lambda" were reserved for the insoluble ones. Later, the classifications were based on the number and position of sulfate groups as well as the presence of 3',6'-anhydro bridges on the β-D-galactopyranosyl residues. This resulted in the four major families: κ, λ, β and ω.

The different types of carrageenans do not exist in a pure state, but in the form of hybrids. Thus in the natural state, κ and ί-carrageenans occur in a Kappa-iota hybrid form but one of the two structures can predominate over the other. The κ-ί hybrid state of a structure can be elucidated by using specific enzymes, which make it possible to enrich or decrease the content of one of the two forms. Carrageenans can coexist with their precursors. Carrageenans from different families of belonging can coexist in a hybrid structure.

The composition according to the invention preferably comprises one or more sulfated polysaccharides of lambda carrageenan type. The sulfated polysaccharide of lambda carrageenan type may be chemically modified or not. Preferably, the sulfated polysaccharide of lambda carrageenan type is not chemically modified. Preferably, the molecular weight (MW) of the polysaccharide is between 100,000 and 1,000,000, and more preferably between 250,000 and 800,000. As sulfated polysaccharide of lambda carrageenan type, mention may be made of SATIAGUM UTC 10 or SATIAGUM VPC 410 from the company CARGILL and WELGEENAN ED 1039 from the company EUROGUM.

Among the carboxylated branched thickening polysaccharides, mention may be made in particular of anionic branched polysaccharides based on glucose, mannose, acetylated mannose, pyruvic acid and glucuronic acid. Such a polysaccharide is preferably xanthan.

Xanthan is a heteropolysaccharide produced on an industrial scale by aerobic fermentation of the bacterium Xanthomonas campestris . Its structure consists of a main chain of β-D-glucoses linked in β(1,4), similar to cellulose. Every second glucose molecule carries a trisaccharide side chain composed of an α-D-mannose, a β-D-glucuronic acid and a terminal β-D-mannose. The internal mannose residue is generally acetylated on carbon 6. About 30% of the terminal mannose residues carry a pyruvate group linked in chelated form between carbons 4 and 6. The charged glucuronic acids and pyruvic acids are ionizable, and therefore responsible for the anionic nature of xanthan (negative charge up to pH 1). The content of pyruvate and acetate residues varies depending on the bacterial strain, the fermentation process, the post-fermentation conditions and the purification steps. These groups can be neutralized in commercial products with Na+, K+ or Ca2+ ions (SATIA Company, 1986). The neutralized form can be converted to the acid form by ion exchange or by dialysis of an acid solution.

Xanthan gums have a molecular weight between 1,000,000 and 50,000,000 and a viscosity between 0.6 and 1.65 Pa.s for an aqueous composition containing 1% xanthan gum (measured at 25°C using a Brookfield viscometer, type LVT at 60 rpm).

Xanthan gums are represented, for example, by the products sold under the names Rhodicare® by the company PMC OUVRIE, under the name SATIAXANE™ by the company Cargill Texturizing Solutions (for the food, cosmetic and pharmaceutical industries), under the name NOVAXAN™ by the company ADM, and under the names Kelzan® and Keltrol® by the company CP-Kelco.

The concentration of thickening polysaccharides used in the compositions according to the present invention ranges from 0.01 to 20%, preferably from 0.02 to 10%, preferably from 0.03 to 8%, preferably from 0.05 to 5%, and even more preferably from 0.1 to 3% by weight relative to the total weight of the composition.

According to a preferred embodiment, the composition according to the invention comprises a thickening agent chosen from crosslinked homopolymers of acrylic acid, crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate, copolymers of acrylamido-2-methyl propane sulfonic acid with one or more nonionic monomers, crosslinked and preferably neutralized homopolymers of 2-acrylamido 2-methylpropane sulfonic acid, hydroxyethylcelluloses, carrageenans and xanthan gum.

According to a preferred embodiment, the composition according to the invention comprises a thickening agent chosen from crosslinked homopolymers of acrylic acid, crosslinked and preferably neutralized homopolymers of 2-acrylamido 2-methylpropane sulfonic acid, hydroxyethylcelluloses, carrageenans and xanthan gum.

The composition according to the invention may also comprise a mixture of several thickening polymers, typically at least two or more thickening polymers. The composition may typically comprise at least one anionic synthetic thickening polymer and at least one thickening agent selected from nonionic thickening polysaccharides, sulfated thickening polysaccharides, carboxylated branched thickening polysaccharides and mixtures thereof.

According to a particular embodiment of the invention, the total concentration of thickening agent(s) used in the composition ranges from 0.01 to 50%, preferably from 0.1 to 20%, preferably from 0.2 to 10%, preferably from 0.3 to 8%, and even more preferably from 0.5 to 3% by weight relative to the total weight of the composition.

ADDITIVES

The composition in accordance with the present invention may further comprise conventional cosmetic adjuvants, notably chosen from softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foaming agents, perfumes, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, or any other ingredient usually used in the cosmetic and/or dermatological field.

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 are aqueous, that is to say they contain at least one aqueous phase.

The compositions in accordance with the invention are in 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 1% 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 be in the form of an aqueous solution or an aqueous gel. According to a preferred embodiment, the composition is in the form of an aqueous gel.

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.

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 hydrophilic organic UV filter to solubilize a merocyanine of formula (3) as defined above.

According to the invention, the water-soluble organic UV filter(s) make it possible to solubilize the merocyanines in accordance with the invention in aqueous phase.

EXAMPLES

The present invention will now be described more specifically by way of examples, which are in no way limiting of the scope of the invention. However, the examples serve to support specific features, variations, and preferred embodiments of the invention.

A/ Examples of synthesis of merocyanines of formula (3)

Example A1: Preparation of compound (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)

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)

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)

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

B/ Examples of formulations

In these examples, the quantities of the ingredients present in the compositions are given in % by weight of active ingredients relative to the total weight of the composition.

Solubility assessment protocol

The solubility of merocyanine in 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, after 24 hours. During this time, the solutions are stored at room temperature.

Example 1: solubilization in the presence of 2-phenyl-1H-benzimidazole-5-sulfonic acid and/or one of its salts

The following solutions were prepared using the procedure below.

Ingredients 1
(excluding invention) 2
(excluding invention) 3
(invention) Compound (25) 0.1 0.1 0.1 PHENYLBENZIMIDAZOLE SULFONIC ACID
(EUSOLEX® 232 from MERCK) - - 1 TRIETHANOLAMINE - 0.5 0.5 (qs pH 7) WATER / AQUA qsp 100 qsp 100 qsp 100 Solubility at room temperature at 24 hours insoluble insoluble soluble

The different ingredients are mixed in a beaker, then stirring is maintained using a magnetic stirrer at room temperature for 2 hours. The preparations thus obtained are then kept at room temperature for 24 hours before the macroscopic evaluation of the solubility of merocyanine.

These results show that compound 25, insoluble in water, solubilizes in the presence of 2-phenyl-1H-benzimidazole-5-sulfonic acid and/or one of its salts.

Example 2: solubilization in the presence of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) and/or one of its salts

The following solutions were prepared using the procedure below.

Ingredients 4
(excluding invention) 5
(excluding invention) 6
(invention) Compound (25) 0.1 0.1 0.1 TEREPHTHALYLIDENE DICAMPHOR SULFONIC ACID
(MEXORYL® SX from NOVEAL) - - 1 TRIETHANOLAMINE
- 0.7 0.7 (qs pH 7) WATER / AQUA qsp 100 qsp 100 qsp 100 Solubility at room temperature at 24 hours insoluble insoluble soluble

The different ingredients are mixed in a beaker, then stirring is maintained using a magnetic stirrer at room temperature for 2 hours. The preparations thus obtained are then kept at room temperature for 24 hours before the macroscopic evaluation of the solubility of merocyanine.

These results show that compound 25, insoluble in water, solubilizes in the presence of benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) and/or one of its salts.

Example 3: solubilization in the presence of 1,4-bis-benzimidazolyl-phenylen-3,3’,5,5’-tetrasulfonic acid and/or one of its salts

The following solutions were prepared using the procedure below.

Ingredients 1
(excluding invention) 2
(excluding invention) 3
(invention) Compound (25) 0.1 0.1 0.1 DISODIUM PHENYL DIBENZIMIDAZOLE TETRA-SULFONATE
(NEO HELIOPAN® AP from Symrise) - - 1 TRIETHANOLAMINE
- 0.5 0.5 (qs pH 7) WATER / AQUA qsp 100 qsp 100 qsp 100 Solubility at room temperature at 24 hours insoluble insoluble soluble

The different ingredients are mixed in a beaker, then stirring is maintained using a magnetic stirrer at room temperature for 2 hours. The preparations thus obtained are then kept at room temperature for 24 hours before the macroscopic evaluation of the solubility of merocyanine.

These results show that compound 25, insoluble in water, solubilizes in the presence of 1,4-bis-benzimidazolyl-phenylen-3,3',5,5'-tetrasulfonic acid and/or one of its salts.

Example 4: Clear aqueous serum

The following composition is prepared. Phase Composition Mass percentage A1 CAPRYLYL GLYCOL 0.3 A1 PROPANEDIOL 3 A1 POLYSORBATE 20 1 A1 PEG-8 10 A1 METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE 1 A2 WATER / AQUA 70.18 A2 TEREPHTHALYLIDENE DICAMPHOR SULFONIC ACID 1 A2 DISODIUM PHENYL DIBENZIMIDAZOLE TETRASULFONATE 1 A2 PHENYLBENZIMIDAZOLE SULFONIC ACID 1 A2 TRIETHANOLAMINE (qs pH 7) 1.52 B ALCOHOL DENAT. 10

Method of preparation

Prepare phase A1 with magnetic stirring at 50°C and phase A2 with magnetic stirring at room temperature, then slowly add phase A2 to phase A1 with stirring until a clear mixture is obtained. Allow to return to room temperature then add phase B with stirring.

Claims (13)

Aqueous 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:

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;
in an amount less than 3% by weight relative to the total weight of the composition; and
b) at least one water-soluble organic UV filter. Composition according to claim 1 in which the compound(s) of formula (3) are those where A is -O-; R is a C ₁ -C ₂₂ alkyl, which may be interrupted by one or more O. Composition according to any one of claims 1 and 2 in which the merocyanines of formula (3) are chosen from the following compounds, as well as their E/E or E/Z isomeric geometric forms:
14
ethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 15
(2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanamide 25
2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 27
2-methylpropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate 29

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

3-methoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate
37
3-ethoxypropyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate Composition according to any one of claims 1 to 3 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:

and/or in its geometric configuration E/E of the following structure:
. Composition according to any one of claims 1 to 4 in which the quantity of merocyanine corresponding to the following formula (3), as well as their isomeric geometric forms, in particular E/E or E/Z is less than or equal to 2.5% by weight, preferably between 0.01% and 2.5% by weight, and even more preferably between 0.5% and 1.5% of the total weight of the composition. Composition according to any one of claims 1 to 5, in which the water-soluble organic UV filter(s) are chosen from 2-phenyl-1H-benzimidazole-5-sulfonic acid; benzene acid (INCI name: PHENYLBENZIMIDAZOLE SULFONIC ACID); benzene 1,4-di(3-methylidene-10-camphorsulfonic acid) (INCI name: TEREPHTHALYLIDENE DICAMPHOR SULFONIC ACID); 1,4-bis-benzimidazolyl-phenylen-3,3',5,5'-tetrasulfonic acid (INCI name: DISODIUM PHENYL DIBENZIMIDAZOLE TETRA-SULFONATE); and their salts. Composition according to any one of claims 1 to 6 in which the water-soluble organic UV filter(s) are present in a concentration ranging from 0.1% to 19% by weight, and preferably from 0.5% to 12% by weight, and even better from 3% to 10% by weight relative to the total weight of the composition. Composition according to any one of claims 1 to 7 comprising at least one additional UV filter chosen from lipophilic organic UV filters, water-dispersible organic UV filters and inorganic UV filters, preferably chosen from water-dispersible organic UV filters and inorganic UV filters. Composition according to claim 8, in which the lipophilic organic UV filter(s) are chosen from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds; methylene bis-(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; filter polymers and filter silicones; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes and mixtures thereof; preferably salicylic compounds, dibenzoylmethane compounds, benzylidenecamphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof. Composition according to any one of claims 8 and 9, in which the water-dispersible organic UV filter(s) are chosen from Methylene bis-Benzotriazolyl Tetramethylbutylphenol 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; Methylene bis-Benzotriazolyl Tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having an average particle size ranging 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; Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in its water-dispersible form with the INCI name Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (and) Acrylates/C12-22 Alkyl Methacrylate Copolymer; symmetrical triazine filters substituted by naphthalenyl groups or polyphenyl groups used in micronized form (average particle size of 0.02 to 3 µm), and in particular in aqueous dispersion form, in particular 2,4,6-tris(bi-phenyl)-triazine and 2,4,6-tris(ter-phenyl)-triazine. Composition according to any one of claims 8 to 10 in which the inorganic UV filter(s) are chosen from titanium oxide pigments, coated or uncoated. Composition according to any one of claims 1 to 11 in which the total quantity of additional UV filters is less than or equal to 20% by weight, preferably less than or equal to 10% by weight, and even more preferably less than or equal to 5% by weight of the total weight of the composition. Composition according to any one of claims 1 to 12 in which the only UV filters present in the composition are the water-soluble organic filters and the merocyanines of formula (3).