FR3117825A1 - Cosmetic or dermatological composition comprising a merocyanine, a triazine UV filter, and a polysaccharide modified by hydrophobic chains - Google Patents

Abstract

Cosmetic or dermatological composition comprising a merocyanin, a triazine UV filter, and a polysaccharide modified by hydrophobic chains The present invention relates to a composition, preferably cosmetic or dermatological, comprising: a) at least one merocyanin of formula (1) or (2 ) following: [Formula 1] and [Formula 2] and b) at least one triazine UV filter; and c) at least one polysaccharide modified with hydrophobic chains. The present invention also relates to the use of at least one such merocyanine of formula (1) or (2) to reduce the staining of fabrics, in particular clothes, after washing.

Description

Cosmetic or dermatological composition comprising a merocyanine, a triazine UV filter, and a polysaccharide modified by hydrophobic chains

The present invention relates to a composition, preferably cosmetic or dermatological, comprising at least one merocyanine of formula (1) or (2) which will be defined later in detail, at least one triazine UV screening agent, and at least one modified polysaccharide by hydrophobic chains.

The present invention also relates to the use of at least one such merocyanine of formula (1) or (2) to reduce the staining of fabrics, in particular clothes, after washing.

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

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

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

Many photo-protective 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 combined with metal oxide pigments such as titanium dioxide or zinc oxide.

Numerous cosmetic compositions intended to limit the darkening of the skin, to improve the color and the 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. Certain compositions may also contain UVA filters. This filtering system must cover UVB protection in order to limit and control the neo-synthesis of melanin favoring global pigmentation, but must also cover UVA protection in order to limit and control the oxidation of already existing melanin leading to darkening of skin color.

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

Advantageously, this improvement is particularly sought after on already pigmented skin with the aim of increasing neither the pigmentary melanin load nor the structure of the melanin already present within the skin.

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

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

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

With the aim of seeking other merocyanines having better solubility in the usual solvents and better photostability, application WO2013/011094 has proposed merocyanines comprising polar groups consisting of hydroxyl and ether functions which show a good long UVA filtration efficiency. However, the oil solubility of these particular merocyanins is not yet fully satisfactory, and often requires a tedious formulation process. Furthermore, the large amounts of solvent needed to solubilize this type of merocyanin can lead to cosmetic inconveniences such as the sticky and greasy effect on application.

Moreover, sunscreens, and in particular those which protect against UVA rays, are well known to those skilled in the art as leaving yellow traces on clothing, these yellow traces being very difficult to remove by washing.

The Applicant has discovered, surprisingly, that when the merocyanins of formula (1) or (2) defined below are used as UVA filters, these leave few traces after washing, and that these fade in time. This discovery is the basis of the present invention.

Thus, in accordance with one of the objects of the present invention, there is now proposed a composition, in particular cosmetic or dermatological, comprising at least one merocyanine of formula (1) or (2) which will be defined in detail later, at least a triazine UV filter, and at least one polysaccharide modified by hydrophobic chains. This composition makes it possible in particular to obtain a sunscreen product which does not have the disadvantage of irreversibly staining clothing or other fabrics. Furthermore, this composition has good cosmetic properties, and in particular it is fresh and light on application. It also provides a good level of photo-protection over a broad spectrum (UVA + UVB).

The present invention also relates to the use of at least one merocyanine of formula (1) or (2) which will be defined later in detail to reduce the staining of fabrics, in particular clothing.

The present invention also relates to a non-therapeutic cosmetic process for 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 the uniformity of the complexion comprising the application to the surface of the keratin material of at least one composition such as previously defined.

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

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

The composition according to the invention is intended for topical application and therefore contains a physiologically acceptable medium. Here, 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 hair, 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 “included between” and “ranging from … to …”.

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

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

“Organic UVA filter” means 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 range of wavelengths between 280 and 320 nm.

The level of sun protection is defined by the sun protection factor (SPF) which is expressed mathematically by the ratio of the exposure time necessary to reach the erythematogenous threshold with the UV filter to the time necessary to reach the erythematogenous threshold without UV filter. .

It can be evaluated in vivo, in particular according to the ISO 24444 method.

It can also be determined according to the “ in vitro ” method described by BL Diffey in J. Soc. Cosmetic. Chem. 40, 127-133, (1989).

To characterize protection against UV-A, the PPD (Persistent Pigment Darkening) method, which measures the color of the skin observed 2 to 4 hours after exposure of the skin to UV-A, is particularly recommended and used. This method has been adopted since 1996 by the Japanese Cosmetic Industry Association (JCIA) as the official test procedure for UV-A labeling of products and is frequently used by test laboratories in Europe and the United States (Japan Cosmetic Industry Association Technical Bulletin; Measurement Standards for UVA protection efficacy; Issued November 21, 1995 and effective of January 1, 1996).

MEROCYANINS

The composition in accordance with the invention comprises at least one UVA screening agent of merocyanine type as defined below.

According to the present invention, these merocyanine compounds correspond to the following formulas (1) or (2):
[Formula 1]
And
[Formula 2]
in which :
R ₁ and R ₂ , independent of each other, are hydrogen; a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, these groups possibly being substituted by at least one hydroxyl group or alternatively interrupted by at least one –O -; or alternatively R ₁ and R ₂ form together with the nitrogen atom which connects them a ring -(CH ₂ ) _n - which can be optionally interrupted by -O- or -NH-;
R ₃ is a -(C=O)OR ₆ group; or a -(CO)NHR ₆ group;
R ₆ 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 -} cycloalkenyl group. C ₂₂ , said groups possibly being substituted by one or more OH;
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ form a -(CH ₂ ) _n - ring which may be substituted by a C ₁ -C ₄ alkyl group and/or interrupted by one or more -O- or by -NH-;
n is a number between 2 and 7;
R ₇ and R _8, independent of each other, are hydrogen; a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, it being possible for the said groups to be interrupted by one or more O and/or substituted by one or more OH; 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-;
or alternatively R ₇ and R ₈ form together with the nitrogen which connects them a ring -(CH ₂ ) _n - which can be interrupted by one or more -O-;
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ form a ring -(CH ₂ ) _n - potentially substituted by a C ₁ -C ₄ alkyl and/or interrupted by an -O- or -NH-;
A is -O-; or –NH;
R ₁₁ 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; or a C ₁ -C ₂₂ alkyl group or a C ₂ -C ₂₂ alkenyl group which is substituted by a C ₃ -C ₂₂ cycloalkyl group or a C ₃ -C ₂₂ cycloalkenyl group, said C ₃ cycloalkyl group -C ₂₂ or C ₃ -C ₂₂ cycloalkenyl group which may be interrupted by one or more -O-.

Preferably, the compounds of formulas (1) or (2) have the following characteristics:
(I) at least one of the R ₁ , R ₂ or R ₆ groups is substituted by a hydroxyl;
(II) if one of R ₁ denotes hydroxyethyl, R ₂ does not denote hydrogen, methyl or ethyl or hydroxyethyl; and if R ₁ denotes hydrogen, R ₂ is not 1-hydroxy-3-methyl-but-2-yl;
(III) if R ₆ is substituted by one or more OH, one of R ₁ or R ₂ is a C ₄ -C ₂₂ alkyl group; or alternatively R ₁ and R ₂ together with the nitrogen to which they are bonded form a piperidyl or morpholinyl radical;
(IV) at least one of the radicals R ₇ , R ₈ , or R ₁₁ is interrupted by one or more -O-.

The preferred compounds are those of formulas (1) or (2) where:
R ₁ and R ₂ , independent of each other, are hydrogen; a C ₄ -C ₁₂ alkyl group; or a C ₃ -C ₁₂ hydroxyalkyl group; or at least one of R ₁ or R ₂ is C ₃ -C ₁₂ hydroxyalkyl; And
R ₃ , R ₄ and R ₅ have the same meanings indicated previously.

The preferred compounds are also those of formulas (1) where:
R6 is a C ₁ -C ₁₂ alkyl group, which may potentially be substituted by one or more hydroxyl.

The most preferred compounds are also those of formula (1), where:
R ₆ is a C ₁ -C ₁₂ alkyl group, which may be substituted by one or more hydroxyl.
one of the R ₁ or R ₂ radicals is a C ₄ -C ₂₂ alkyl group; or alternatively R ₁ and R ₂ together with the nitrogen which connects them form a ring -(CH ₂ ) _n - which can be interrupted by -O- and/or -NH-; And
R ₄ and R ₅ and n have the same meanings indicated above.

The preferred compounds are those of formula (2) where:
R ₁₁ is a -(CH ₂ ) _m -OR ₁₂ radical; Or
R ₁₂ is a C ₁ -C ₁₂ alkyl group; or a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group;
m is a number from 1 to 5; And
R ₇ , R ₈ , R ₉ , R ₁₀ and A have the same meanings indicated above.

Even more preferred compounds are those of formula (1) or (2), where:
R ₁ and R ₂ on the one hand, and R ₇ and R ₈ on the other hand, respectively form together with the nitrogen atom to which they are respectively bonded a piperidyl radical or a morpholinyl radical.

The preferred compounds are also those of formulas (1) and (2), where:
R ₄ and R ₅ and R ₉ and R ₁₀ respectively form a carbon ring which contains 6 carbon atoms.

The most preferred compounds are those of formula (1), where:
R ₁ and R ₂ independently of each other are hydrogen; or a C ₁ -C ₂₂ alkyl group; or a C ₁ -C ₂₂ hydroxyalkyl group; or R ₁ and R ₂ together with the nitrogen to which they are attached form a piperidyl or morpholinyl radical;
R ₃ is a -(C=O)OR ₆ group; or a -(CO)NHR ₆ group;
R ₆ is a C ₁ -C ₂₂ alkyl group, which may be substituted by one or more –OH;
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ are linked together to form a carbon ring which contains 6 carbon atoms.

The most preferred compounds are those of formula (1), where:
R ₁ and R ₂ independently of each other are hydrogen; or a C ₁ -C ₂₂ hydroxyalkyl group; where at least one of the R ₁ and R ₂ radicals is a C ₁ -C ₂₂ hydroxyalkyl group;
R ₃ is a -(C=O)OR ₆ group; or a -(C=O)NHR ₆ group;
R ₆ is a C ₁ -C ₂₂ alkyl group; And
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ are bonded together to form a carbon ring which contains 6 carbon atoms.

The most preferred compounds are those of formula (2), where:
R ₇ and R ₈ independently of each other are hydrogen or a C ₁ -C ₈ alkyl group, which may be by one or more -O-;
A is -O- or -NH;
R ₁₁ is C ₁ -C ₂₂ alkyl; And
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ are bonded together to form a carbon ring which contains 6 carbon atoms.

The most preferred compounds are those of formula (2), where:
R ₇ and R ₈ together with the nitrogen atom to which they are bonded form a morpholinyl or piperidyl radical;
A is -O- or -NH;
R ₁₁ is a C ₁ -C ₂₂ alkyl group which may be interrupted by one or more -O-; And
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ are bonded together to form a carbon ring which contains 6 carbon atoms.

Even more preferred compounds are those of formula (2), where:
R ₁₁ is a -(CH ₂ ) _m -OR ₁₂ radical, where
R ₁₂ is a C ₁ -C ₄ alkyl group; or a C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl group;
m is a number from 1 to 3;
R ₇ and R ₈ independently of each other are hydrogen; a C ₁ -C ₁₂ alkyl group, which may be interrupted by one or more O; or R ₇ and R ₈ together with the nitrogen atom to which they are attached form a morpholinyl or piperidyl radical;
R ₉ and R ₁₀ are hydrogen or together form a carbon ring which contains 6 carbon atoms; And
A is -O- or -NH.

The merocyanine compounds of the invention may, for example, be in the isomeric geometric form E/E-, E/Z- or Z/Z.

The alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl chains can be linear or branched, monocyclic or polycyclic chains.

A C ₁ -C ₂₂ alkyl group is for example a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl , 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl or dodecyl.

A substituted alkyl group is for example a methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-tert-octylphenoxyethyl, 3-(2,4 -di-tert-amylphenoxy)-propyl, ethoxycarbonylmethyl-2-(2-hydroxyethoxy)ethyl or 2-furylethyl.

A hydroxy-substituted alkyl group is for example a hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxydecyl.

A C ₂ -C ₂₂ alkenyl group is for example a linear chain C ₂ -C ₁₂ alkenyl or preferably a branched C ₃ -C ₁₂ alkenyl. A C ₂ -C ₂₂ alkenyl is for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3- methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien- 1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2 ,4-norcaradien-3-yl or the different isomers of hexenyl, octenyl, noenyl, decenyl or dodecenyl.

A C ₃ -C ₁₂ cycloalkyl group is for example a cyclopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or preferably a cyclohexyl.

Examples of merocyanines according to the present invention are listed in Table 1:
Table 1 Compound Structure Compound Structure 1
2 3 4 5
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47

According to a particularly preferred form of the invention, a family of merocyanines corresponding to the following formula (3) as well as their isomeric geometric forms, in particular E/E- or E/Z-, will be used:
[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 , said groups possibly being interrupted by one or more O.

The merocyanine compounds of the invention may be in their E/E-, E/Z- isomeric geometric forms:
[form 4]
[form 5]

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

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

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

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

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

The E/Z shape has the following structure:
[form 6]

The E/E form has the following structure:
[form 7]

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

The compounds of formula (1) and (2) and in particular of formula (3) can be prepared according to known methods, as described for example in J.Org.Chem. USSR (English Translation) 26(8), p. 1562f (1990); J. Heterocycl. Chem. 33(3), p. 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11, p. 1537-1543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, p. 397-404 (1982); Chem.Heterocycl.Comp. (English Translation) 24(8), 914-919 (1988) and in Synthetic Communications Vol. 33, No. 3, 2003, p 367-371.

The synthesis of the compounds used in the present invention is also described in US2003/0181483A1, WO 0234710, Eur. J.Org. Chem. 2003, 2250-2253, J. Med. Chem. 1996, 39, 1112-1124 and J. Org. Chem., Vol. 37, No. 8, 1972, 1141-1145 as follows:
[form 8]

Vinylogenic CH-acid compounds are reacted with amide acetals.

In J. Heterocyclic Chem., 27, 1990, 1143-1151 aminoacrylic acid esters or aminoacrylnitriles are reacted with ethoxymethylenecyanoacetates in ethanol to form the corresponding compounds of the present invention.

The compounds of formula (1) or (2) where R ₄ and R ₅ on the one hand, or R ₉ and R ₁₀ on the other hand, together form a carbocyclic ring containing 6 carbon atoms, respectively, 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 references cited therein.

Triazine UV filters

Among the triazine UV filters in accordance with the invention, mention may be made of 3,3'-(1,4-Phenylene)bis(5,6-diphenyl-1,2,4-triazine), with INCI name Phenylene Bis- Diphenyl triazine with the following chemical formula:
[form 9]

Mention may also be made of 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, and Diethylhexyl Butamido Triazone sold under the trade name commercial “UVASORB HEB ®” by SIGMA 3V.

According to a particular embodiment of the invention, the composition comprises at least one triazine derivative chosen from the 1,3,5-triazine derivatives of formula (10) below:
[form 10]
in which the identical or different radicals A ₁ , A ₂ and A ₃ are chosen from the groups of formula (11) to (18):
[form 11]
[form 12]
[form 13]
[form 14]
[form 15]
[form 16]
[form 17]
[form 18]
in which :
- X _a (each of Xa may be the same or different) represents oxygen or -NH-;
- R _a (each of R _a may be identical or different) is chosen from hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more linear or branched C ₁ -C ₁₈ alkyl or linear or branched C ₁ -C ₁₈ hydroxyalkyl radicals; a linear or branched C ₁ -C ₁₈ , preferably C ₆ -C ₁₂ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and whose terminal OH group is methylated; a radical of formula (19), (20) or (21) below:
[form 19]
[form 20]
[form 21]
in which :
- R ₈ is hydrogen or a methyl radical;
- R ₉ is a C ₁ -C ₉ alkyl radical;
- q is an integer ranging from 0 to 3;
- r is an integer ranging from 1 to 10;
- A is a C ₄ -C ₈ alkyl radical or a C ₅ -C ₈ cycloalkyl radical;
- B is chosen from: a linear or branched C ₁ -C ₈ alkyl radical; a C ₅ -C ₈ cycloalkyl radical; an aryl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals;
- R ₁ denotes a C ₃ -C ₁₈ alkyl radical; a C ₂ -C ₁₈ alkenyl radical; a residue of formula -CH ₂ -CH(OH)-CH ₂ -OT ₁ where T ₁ is a hydrogen atom or a C ₁ -C ₈ alkyl radical; a remainder of the following formula (22):
[form 22]
in which :
- R ₁₃ denotes a covalent bond; a linear or branched C ₁ -C ₄ alkyl radical or else a radical of formula -C _m1 H _2m1 -O- where m ₁ is an integer equal to 1; 2; 3; 4;
- p ₁ is an integer equal to 0; 1; 2; 3; 4; 5;
- the radicals R ₁₀ , R ₁₁ and R ₁₂ , which are identical or different, denote a C ₁ -C ₁₈ alkyl radical; a C ₁ -C ₁₈ alkoxy radical or a radical of formula (23):
[form 23]
where R ₁₄ is a C ₁ -C ₅ alkyl radical.
- R ₂ denotes a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ alkoxy radical;
- R ₃ and R ₄ , identical or different, denote a linear or branched C ₁ -C ₂₀ alkyl radical;
- R ₅ represents a hydrogen atom or a phenyl radical optionally substituted by a halogen or by a C ₁ -C ₄ alkyl radical or by a C ₁ -C ₄ alkoxy radical;
- R ₆ is a linear or branched C ₁ -C ₈ alkyl radical, C ₁ -C ₃ alkoxy, it being understood that, in the latter case, two adjacent R ₆ of the same aromatic ring can together form an alkylidene dioxy group in which the alkylidene group contains 1 to 2 carbon atoms, OH, NHCOCH ₃ or NH ₂ ,
- R ₇ denotes a hydrogen atom, a C ₁ -C ₁₀ alkyl radical, a radical of formula -(CH ₂ CHR ₅ -O) _n1 R ₈ where n ₁ is a number from 1 to 16, or else a radical of structure -CH ₂ -CH-(OH)-CH ₂ OT ₁ with R ₈ and T ₁ having the same meaning indicated above;
- Z represents oxygen, sulfur, -NH- or -NR ₃ - with R ₃ representing a linear or branched C ₁ -C ₂₀ alkyl radical;
- p is 0, 1, 2 or 3;
A ₁ can also be a halogen, an –N(R ₃ ) ₂ radical, the two R ₃ being able to form together a cycle of 4 or 5 carbon atoms, or an –OR ₃ group, R ₃ having the same definition as above.

A first more particularly preferred family of 1,3,5-triazine derivatives, of formula (10), in particular described in document EP-A-0 517 104, corresponds to the 1,3,5-triazines of formula (10) in which the A ₁ , A ₂ and A ₃ are of formula (11) and have the following characteristics:
- one of the X _a -R _a radicals represents the –NH-R _a radical with R _a chosen from: a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical;
- the other 2 X _a -R _a represent the –OR _a radical with R _a , identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more alkyl or hydroxyalkyl radicals; a linear or branched C ₁ -C ₁₈ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical.

A second more particularly preferred family of compounds of formula (10) is that consisting of the 1,3,5-triazine derivatives described in document EP-A-0 570 838, which corresponds to the 1,3,5-triazines of formula (10) in which the A ₁ , A ₂ and A ₃ are of formula (11) and have all of the following characteristics:
- one or two X _a -R _a represents the –NH-R _a radical, with R _a chosen from: a linear or branched C ₁ -C ₁₈ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical;
the other two or more X _a -R _a being the –OR _a radical with R _a , identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more alkyl or hydroxyalkyl radicals; a linear or branched C ₁ -C ₁₈ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical.

A particularly preferred 1,3,5-triazine of this second family is 2-[(p-(tertiobutylamido)anilino]-4,6-bis-[(p-(2'-ethylhexyl-1'-oxycarbonyl)anilino ]-1,3,5-triazine or “Diethylhexyl Butamido Triazone” sold under the trade name “UVASORB HEB” by SIGMA 3V and corresponding to the following formula:
[form 24]
in which R′ denotes a 2-ethylhexyl radical and R denotes a tert-butyl radical.

A third preferred family of compounds of formula (8) which can be used in the context of the present invention, and which is described in particular in document US Pat. No. 4,724,137, which corresponds to the 1,3,5-triazines of formula (10) in which the A ₁ , A ₂ and A ₃ are of formula (11) and have the following characteristics:
- X _a are identical and represent oxygen;
- R _a , which are identical or different and represent a C ₆ -C ₁₂ alkyl radical or a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and whose terminal OH group is methylated.

A particularly preferred 1,3,5-triazine of this third family is 2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)anilino]-1,3,5-triazine or "Ethylhexyl Triazone" sold in particular under the trade name of "UVINUL T 150" by the BASF Company and corresponds to the following formula:
[form 25]
in which R' denotes a 2-ethyl hexyl radical.

A fourth preferred family of compounds that can be used in the context of the present invention, and which is described in particular in patent application EP-A-0775698, is that of the 1,3,5-triazines corresponding to formula (10) in which the A ₁ and A ₂ are of formula (12) and A ₃ is of formula (18) and have all of the following characteristics: R ₁ , which are identical or different, denote a C ₃ -C ₁₈ alkyl radical; a C ₂ -C ₁₈ alkenyl radical or else a residue of formula -CH ₂ -CH(OH)-CH ₂ -OT ₁ where T ₁ is a hydrogen atom or a C ₁ -C ₈ alkyl radical; R ₇ denotes a hydrogen atom, a C ₁ -C ₁₀ alkyl radical.

A particularly preferred 1,3,5-triazine of this fourth family is 2,4-bis{[4-2-ethyl-hexyloxy)]-2-hydroxy]-phenyl}-6-(4-methoxy-phenyl) -1,3,5-triazine or "Anisotriazine" sold under the trade name "TINOSORB S" by CIBA SPECIALTY CHEMICALS and has the following formula:
[form 26]
in which R′ denotes a 2-ethylhexyl radical.

A fifth preferred family of compounds that can be used in the context of the present invention, and which is described in particular in patent applications EP507691, EP507692, EP790243 and EP944624 and whose technical content is fully integrated into the present description is that of 1,3 ,5-triazines corresponding to formula (10) in which the A1, A2 and A3 are of formulas (16) to (20) cited above.

By way of examples of these compounds of formula which can be used, mention may be made of:
- 2,4,6-tris-(diisobutyl 4'-amino benzalmalonate)-s-triazine,
- 2,4,6-tris-(4'-amino benzalmalonate di(2-ethylhexyl))-s-triazine,
- 2,4,6-tris-(4'-amino benzalmalonate di(2-ethylhexyl))-6-chloro-s-triazine,
- 2,4,6-tris-(4'-amino benzalmalonate of di(2-ethylhexyl))-6-(4'-aminobenzoate of 2-ethylhexyl)-s-triazine,
- 2,4,6-tris-(diisobutyl 4'-amino benzalmalonate)-6-butoxy-s-triazine,
- 2,4,6-tris-(4'-amino benzalmalonate diisobutyl)-6-(2-ethylhexylamino)-s-triazine,
- 2,4-bis-(4'-aminobenzylidenecamphor)-6-(2-ethylhexyl-amino)-s-triazine,
- 2,4-bis-(4'-aminobenzylidenecamphor)-6-(4'-amino benzalmalonate diisobutyl)-s-triazine,
- 2,4,6-tris(4'-amino diethyl benzalmalonate)-s-triazine,
- 2,4,6-tris(4'-amino benzalmalonate diisopropyl)-s-triazine,
- 2,4,6-tris(4'-amino dimethyl benzalmalonate)-s-triazine,
- 2,4,6-tris (ethyl α-cyano-4-aminocinnamate)-s-triazine.
- 2,4,6-tris [(3'-benzotriazol-2-yl-2'-hydroxy-5'-methyl) phenylamino]-s-triazine,
- 2,4,6-tris[(3'-benzotriazol-2-yl-2'-hydroxy-5'-ter-octyl)phenylamino]-s-triazine.

A particularly preferred 1,3,5-triazine of this fifth family is 2,4,6-tris-(diisobutyl 4'-amino benzalmalonate)-s-triazine which corresponds to the following formula:
[form 27]

The triazine UV screening agent(s) are generally present in the compositions according to the invention in a concentration ranging from 0.1% to 30% by weight, preferably from 0.2% to 20% by weight, and preferentially from 0.5 % to 10% by weight, and even more preferably from 0.5% to 5% by weight relative to the total weight of the composition.
Polysaccharides modified by hydrophobic chains

The composition according to the invention comprises at least one hydrophobic modified polysaccharide, preferably a fructan.

Fructans or fructans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with one or more saccharide residues different from fructose. Fructans can be linear or branched. The fructans can be products obtained directly from a plant or microbial source or else products whose chain length has been modified (increased or reduced) by fractionation, synthesis or hydrolysis, in particular enzymatic. Fructans generally have a degree of polymerization from 2 to about 1000 and preferably from 2 to about 60.

There are 3 groups of fructans. The first group corresponds to products whose fructose units are mostly linked by β-2-1 bonds. These are essentially linear fructans such as inulins.

The second group also corresponds to linear fructoses but the fructose units are essentially linked by β-2-6 bonds. These products are levans.

The third group corresponds to mixed fructans, i.e. having sequences β-2-6 and β-2-1. They are essentially branched fructans like gramineans.

The fructans preferably used in the compositions according to the invention are inulins. Inulin can be obtained for example from chicory, dahlia or Jerusalem artichokes. Preferably, the inulin used in the composition according to the invention is obtained for example from chicory.

The fructans, in particular the inulins, used in the compositions according to the invention are hydrophobic modified. In particular, they are obtained by grafting hydrophobic chains onto the hydrophilic skeleton of the fructan.

The hydrophobic chains capable of being grafted onto the main chain of the fructan can in particular be linear or branched, saturated or unsaturated hydrocarbon chains, having from 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl, alkylene groups; divalent cycloaliphatic groups or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may in particular comprise one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulfonamide functions such as in particular methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene.

In particular, fructan, in particular inulin, has a degree of polymerization of 2 to around 1000 and preferably from 2 to around 60, and a degree of substitution of less than 2 on the basis of a fructose unit.

According to a preferred embodiment, the hydrophobic chains have at least one alkyl carbamate group of formula R-NH-CO-O in which R is an alkyl group having from 1 to 32 carbon atoms or a hydrophobic ester group C4-C32 alkyl ester , i.e. an –OCO-R group, R being C4-C32 alkyl.

Advantageously, the hydrophobic ester group is a C6-C20 alkyl ester group. Preferably, the hydrophobic ester group is a C8-C20 alkyl ester group. Preferably, the hydrophobic ester group is a C10-C20 alkyl ester group. More preferably, the hydrophobic ester group is a C10-C18 alkyl ester group.

According to a more preferred embodiment, the hydrophobic chains are alkylcarbamate groups, in particular C8-C18 alkyl carbamate and more particularly laurylcarbamate.

These hydrophobic groups result in particular from the reaction of the hydroxyl groups of the starting inulin with either an isocyanate R-N=C=O (to form a carbamate group), or an acid R-COOH or acid chloride R-COCl ( to form an ester group).

In particular, by way of non-limiting illustration of the hydrophobic modified inulins which can be used in the compositions according to the invention, mention may be made of stearoyl inulin such as those sold under the names Lifidrem INST by the company Engelhard and Rheopearl INS by the company Ciba ; palmitoyl inulin; undecylenoyl inulin such as those sold under the names Lifidrem INUK and Lifidrem INUM by the company Engelhard; and inulin lauryl carbamate such as that sold under the name INUTEC SL1 by the company CREACHEM.

In particular, the hydrophobic modified fructan is a lauryl carbamate-grafted inulin, in particular derived from the reaction of lauryl isocyanate with an inulin, in particular derived from chicory. By way of example of these compounds, mention may in particular be made of the product sold under the name INUTEC SL1 by the company CREACHEM.

The hydrophobic modified polysaccharide may be present in the composition according to the invention in a content ranging from 0.05% to 10% by weight, preferably from 0.05% to 5% by weight, and more preferably from 0.1% to 2% by weight relative to the total weight of the composition.

OILY PHASE

The composition in accordance with the invention comprises at least one oily phase.

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

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

The oily phase may comprise, in addition to the merocyanine screening agent(s) and the lipophilic complementary screening agents according to the invention, at least one volatile or non-volatile hydrocarbon-based oil and/or a volatile and or non-volatile silicone oil and/or a fluorinated oil. volatile and/or non-volatile.

Within the meaning 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 optionally 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.

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

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

As non-volatile hydrocarbon-based oils which can be used according to the invention, mention may be made in particular of:
(i) hydrocarbon oils of vegetable origin such as triesters of glycerides which are generally triesters of fatty acids and of glycerol whose fatty acids can have chain lengths varying from C ₄ to C ₂₄ , the latter possibly be linear or branched, saturated or unsaturated; these oils are in particular wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soybean oil, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bankoulier, passionflower, muscat rose; or alternatively 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 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 branched containing from 1 to 40 carbon atoms provided that R + R' is ≥ 10, such as Purcellin's oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoate of C ₁₂ -C alcohols ₁₅ 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 as the commercial product sold under the name “X-TEND 226®” by ISP Company, Isopropyl Lanolate, Hexyl Laurate, Diisopropyl Adipate, Isononyl Isononanoate, Oleyl Erucate, 2-Ethyl Palmitate -hexyl, isostearyl isostearate, diisopropyl sebacate such as the product sold under the name n of “Dub Dis” by 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 linear C ₁₂ -C ₁₃ di-alkyl tartrates such as those sold under the name COSMACOL ETI® by the company ENICHEM AUGUSTA INDUSTRIALE as well as linear C ₁₄ -C ₁₅ di-alkyl tartrates such as than 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-based oils that can be used according to the invention, preference will be given more particularly to glyceride triesters and in particular the triglycerides of caprylic/capric acids, synthetic esters and in particular isononyl isononanoate, oleyl erucate, C ₁₂ -C ₁₅ alcohol benzoate, 2-ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol.

As volatile hydrocarbon-based oils that can be used according to the invention, mention may in particular be made of hydrocarbon-based oils having from 8 to 16 carbon atoms, and in particular branched C alkanes₈-VS₁₆like C isoalkanes₈-VS₁₆of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, the oils sold under the trade names Isopars or Permetyls, the C-branched esters₈-VS₁₆, iso-hexyl 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 from 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 application WO2008/155059 from 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-based oils such as petroleum distillates, in particular those sold under the name Shell Solt® by the company SHELL, can also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures.
Silicone oils

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

As volatile silicone oils, mention may be made, for example, of 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 which can be used 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.

Mention may also be made of volatile alkyltrisiloxane linear oils of the following general formula:
[form 28]
where R represents an alkyl group comprising from 2 to 4 carbon atoms and of which one or more hydrogen atoms may be substituted by a fluorine or chlorine atom.

Among the oils of general formula (24), mention may be made of:
3-butyl 1,1,1,3,5,5,5-heptamethyl trisiloxane,
3-propyl 1,1,1,3,5,5,5-heptamethyl trisiloxane, and
3-ethyl 1,1,1,3,5,5,5-heptamethyl trisiloxane,
corresponding to the oils of formula (24) for which R is respectively a butyl group, a propyl group or an ethyl group.
Fluorinated oils

It is also possible to use fluorinated volatile oils, such as nonafluoromethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane and mixtures thereof.

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

Another fatty substance which may be present in the oily phase may be, for example:
- a fatty acid chosen from fatty acids comprising from 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, paraffin or lignite waxes or microcrystalline waxes, ceresin or ozokerite, synthetic waxes such as waxes polyethylene, Fischer-Tropsch waxes;
- a gum chosen from silicone gums (dimethiconol),
- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of an oligomeric glycerol, arachidyl propionate, fatty acid triglycerides and their derivatives,
- and mixtures thereof.

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

AQUEOUS PHASE

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

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

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

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

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

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

ADDITIVES

Additional UV filters

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

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

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

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

The complementary organic UV screening agents are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds, dibenzoylmethane compounds, benzylidenecamphor compounds; benzophenone compounds; β,β-diphenylacrylate compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in US Pat. No. 5,624,663; 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; screening polymers and screening silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadiene compounds as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 and 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.

Dibenzoylmethane compounds:
Butyl Methoxydibenzoylmethane sold in particular under the trade name PARSOL 1789 ® by DSM Nutritial Products,
Isopropyl Dibenzoylmethane.

Para-aminobenzoic compounds:
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.

β , β -diphenylacrylate compounds :
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,
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate sold under the trade name "UVINUL A Plus ®" or in a 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 aqueous dispersion.

Benzylidene Camphor Compounds:
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.

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

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

Phenyl benzotriazole compounds:
Drometrizole Trisiloxane sold under the name “Silatrizole®” by RHODIA CHIMIE.

Methylene bis-(hydroxyphenyl benzotriazole) compounds:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol, in particular in solid form such as the product sold under the trade name "MIXXIM BB/100 ®" by 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 of 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 notably sold under the trade name "TINOSORB M®" by BASF or in the form of an aqueous dispersion of micronized particles having an average particle size which varies from 0.02 to 2 μm and more preferentially from 0.01 to 1.5 μm and more particularly from 0.02 to 1 μm in the presence of at least one polyglycerol mono-(C ₈ -C ₂₀ )alkyl ester having a degree of glycerol polymerization of at least 5, such as the aqueous dispersions described in application WO2009/063392.

Anthranil compounds:
Menthyl anthranilate sold under the trade name "NEO HELIOPAN MA®" by Symrise.

Imidazoline compounds:
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate.

Benzalmalonate compounds:
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.

Benzoxazole compounds:
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.

The preferred additional organic filters are chosen from:
Ethylhexyl Methoxycinnamate,
Ethylhexyl Salicylate,
Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazole Sulphonic 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,
Drometrizole Trisiloxane,
Polysilicon-15,
1,1-dicarboxy (2,2'-dimethyl-propyl)-4,4-diphenylbutadiene,
and their mixtures.

The particularly preferred additional organic screening agents are chosen from:
Ethylhexyl Salicylate,
Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene,
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate,
Terephthalylidene Dicamphor Sulfonic Acid,
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 screening agents of the invention are metal oxide particles having an average elementary particle size less than or equal to 0.5 μm, more preferably between 0.005 and 0.5 μm and even more preferably between 0.01 and 0.2 μm, even better between 0.01 and 0.1 μm, and more particularly between 0.015 and 0.05 μm.

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

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 which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

The coated pigments are more particularly coated titanium oxides:
- silica such as the "SUNVEIL®" product from IKEDA,
- silica and iron oxide such as the "SUNVEIL F®" product from 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 ISHIHARA, and "UVT 14/4" from 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 UNIQEMA and the product "Eusolex T-AVO®" from 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 a silicone such as the product "STT-30-DS®" from 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 ISHIHARA, or "UV TITAN M 262®" from SACHTLEBEN PIGMENTS,
- triethanolamine such as the product "STT-65-S" from TITAN KOGYO,
- stearic acid such as the product "TIPAQUE TTO-55 (C)®" from 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,
- TiO ₂ coated with aluminum stearate, alumina and silicone sold under the trade name Solaveil CT-12W-LQ- (WD from CRODA),
- the TiO ₂ coated with lauroyl lysine sold by Daito Kasei Kogyo under the name LL 5 Titanium Dioxyde CR 50,
- TiO ₂ 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. Mention may be made more particularly of the oily dispersion of particles of TiO ₂ doped with manganese in the triglyceride of capric/caprylic acid 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 like the product sold under the trade name OPTISOL TD50 ® by the company CRODA.

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

Examples of coated zinc oxide pigments are:
- those marketed under the name "Oxide zinc CS-5®" by the company Toshibi (ZnO coated with polymethylhydrogensiloxane);
- those marketed under the name "Nanogard Zinc Oxide FN®" by the company Nanophase Technologies (dispersed at 40% in Finsolv TN®, C12-C15 alcohol benzoate);
- 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 copolymer based on perfluoroalkylethyl in dispersion 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 ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer mixture);
- 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 polycondensate of hydroxystearic acid).

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

Uncoated iron oxide pigments are for example sold 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®".

The coated iron oxide pigments are for example sold 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 "OXIDE DE FER TRANSPARENT®".

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the equal weight mixture of silica-coated titanium dioxide and cerium dioxide, 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 of 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 additional UV screening agents 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 also comprise conventional cosmetic adjuvants chosen in particular from organic solvents, ionic or nonionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-aging agents. - mousse, 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 cosmetics and/or dermatological.

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

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 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 the company Hoechst under the trade name “Hostacerin ^AMPS® ” ( CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800® sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropane sulphonic acid and hydroxyethyl acrylate such as SIMULGEL NS® and SEPINOV EMT 10® marketed by the company SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives such as acrylic silicones, silicones polyethers and cationic silicones and mixtures thereof.

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

Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides.

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

In the case of a direct emulsion, the pH of the composition in accordance with the invention is generally between 3 and 12 approximately, preferably between 5 and 11 approximately, and even more particularly from 6 to 8.5.

Among the active agents for the care of keratin materials such as the skin, the lips, the scalp, the hair, the eyelashes or the nails, mention may be made, for example, of vitamins and their derivatives or precursors, alone or in mixtures; antioxidants; anti-radical agents; anti-pollutant agents; self-tanning agents; anti-glycation agents; soothing agents; deodorant agents; essential oils ; NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and/or preventing their degradation; agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; muscle relaxants; cooling agents; tensioning agents; matting agents; depigmenting agents; pro-pigmenting agents; keratolytic agents; desquamating agents; moisturizing agents; anti-inflammatory agents; anti-microbial 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, the hair, the eyelashes, the eyebrows, the nails.

Of course, those skilled in the art will take care to choose the optional additional 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 substantially not, altered by the addition(s) envisaged.

DOSAGE FORMS

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art. They may in particular 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 .

They can also be in anhydrous form, such as, for example, in the form of an oil. The term "anhydrous composition" means a composition containing less than 1% by weight of water, or even less than 0.5% of water, and in particular free of water, the water not being added during the preparation of the composition but corresponding to the residual water provided by the mixed ingredients. They may optionally be packaged in an aerosol and come in the form of a foam or a 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 paddle or propeller, rotor-stator and HHP type.

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

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

The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen appropriately according to the emulsion to be obtained (W/O or O/W).

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

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

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

As 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, mention may be made, for example, as nonionic emulsifying surfactants of polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylene) fatty acid and glycerol esters; oxyalkylenated sorbitan fatty acid esters; polyoxyalkylenated fatty acid esters (in particular polyoxyethylenated and/or polyoxypropylene) 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 oxypropylene) 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 the company Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearylglucoside optionally mixed with cetostearyl alcohol, marketed for example under the name Montanov 68® by the company Seppic, under the name Tegocare CG90® by the company Goldschmidt and under the name Emulgade KE3302® by the company Henkel, as well as arachidyl glucoside, for example under the form of the mixture of arachidic and behenic alcohols and of arachidylglucoside marketed under the name Montanov 202® by the company Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol can be in the form of a self-emulsifying composition, as described for example in document WO- A-92/06778.

When it is an emulsion, the aqueous phase thereof may comprise a 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, of the skin, the lips and the hair, including the scalp, in particular for the protection and/or the care of the skin, the lips and/or the hair, and/or for making up the skin and/or the 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 the scalp, in particular care products, sun protection products and make-up products.

The cosmetic compositions according to the invention can for example be used as a make-up product.

Another object of the present invention consists of a non-therapeutic cosmetic process for caring for and/or making up a keratin material, consisting in applying to the surface of said keratin material at least one composition according to the invention as defined above. -above.

The cosmetic compositions according to the invention can for example be used as care and/or sunscreen products for the face and/or the body of liquid to semi-liquid consistency, such as milks, more or less smooth creams, gel-creams, pastes. They may optionally be packaged in an aerosol and come in the form of a foam or a 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 the 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 propellant. The latter are described in US patents 4,077,441 and US 4,850,517.

The compositions packaged as an aerosol in accordance with the invention generally contain conventional propellants such as, for example, the hydrofluorinated compounds dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, trichlorofluoromethane. They are preferably present in 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 receptacle delimiting one or more compartment(s), said receptacle being closed by a closing element and possibly not being sealed; And
ii) a make-up 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 closure element may be in the form of a lid comprising a mounted cap that can be moved by translation or by pivoting relative to the container housing the said make-up and/or care composition(s).

EXAMPLES

The following examples serve to illustrate the invention without however being limiting. In these examples, the amounts of the composition ingredients are given in % by weight of raw material relative to the total weight of the composition.

Example A1: Preparation of Compound (14)
[form XIV]

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 of 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-amyl alcohol Example A1.5 3-methoxypropylamine toluene Example A1.6 3-methoxypropylamine dimethylformamide Example A1.7 3-methoxypropylamine solvent free Example A1.8 N-morpholine isopropanol

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

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

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

Melting point: 92.7°C.

Example A2: Preparation of Compound (15)
[form XV]

101.00 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one is 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 of 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-amyl alcohol 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 as 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)
[form XXVII]

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-amyl alcohol 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 as 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)
[form XXV]

148.4 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one is 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 indicated 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-amyl alcohol Example A4.5 3-methoxypropylamine toluene Example A4.6 3-methoxypropylamine dimethylformamide Example A4.7 3-methoxypropylamine solvent free

Examples of formulations

Mode of preparation of the compositions

The aqueous phase A is prepared by mixing the raw materials by heating to 70°C until a homogeneous phase is obtained. Proceed in the same way for phase B by heating to 80°C until a homogeneous phase is obtained. The emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes. Switch off the heating. Introduce phase C, then phase D, and leave to homogenize for 10 minutes. Then add phase E. Finally, introduce phase F at 25°C. The final emulsion is characterized by drops of 1 µm to 20 µm.

Protocol for evaluating the staining power of UVA filters

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

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

For the evaluation of the reduction in staining, we are interested in the ΔE, which measures the total color variation between an area stained by the formula and an unstained area of the fabric washed, then dried. The lower ΔE, the lower the staining of the fabrics by the product.

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

In this formula, ΔL represents the difference between the value of L of the unstained area and the value of L of the stained area after 24 hours after washing the fabric, Δa represents the difference between the value of a of the unstained area and the value of a of the stained area after 24 hours following the washing of the fabric and Δb represents the difference between the value of b of the unstained area and the value of b of the stained area after 24 hours following the washing of the fabric.

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

Comparative Example 1 - Compositions 1 to 5

The following compositions 1 to 5 were prepared according to the protocol detailed above. Phase Ingredient 1
(reference) 2
(invention) 3
(invention) AT WATER 30 30 30 AT Curator(s) QS QS QS AT INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 0.3 AT SODIUM STEAROYL GLUTAMATE
(EUMULGIN SG from BASF) 0.3 0.3 0.3 B ISOPROPYL LAUROYL SARCOSINATE
(ELDEW SL-205 from AJINOMOTO) 10 10 10 B DIISOPROPYL SEBACATE 2.5 2.5 7 B PEG-8 10 10 10 B BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(TINOSORB S from BASF) 3 3 3 B BUTYL METHOXYDIBENZOYLMETHANE
(PARSOl 1789 from DSM) 0 0 0 B METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE
(compound 25) 0 3 3 B DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A+ from BASF) 0 0 0 B CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 1.4 VS WATER QSP 100 QSP 100 QSP 100 D CARBOMER 0.1 0.1 0.1 D AMMONIUM ACRYLOYLDIMETHYLTAURATE/VP COPOLYMER
(ARISTOFLEX AVC from CLARIANT) 0.35 0.35 0.35 D ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER
(PEMULEN TR-2 POLYMER from LUBRIZOL) 0.1 0.1 0.1 E POTASSIUM HYDROXIDE 0.016 0.016 0.016 F Charge(s) 1.5 1.5 1.5 G ALCOHOL DENAT. 15 15 15 Phase Ingredient 4
(comparative) 5
(comparative) AT WATER 30 30 AT Curator(s) QS QS AT INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 AT SODIUM STEAROYL GLUTAMATE
(EUMULGIN SG from BASF) 0.3 0.3 B ISOPROPYL LAUROYL SARCOSINATE
(ELDEW SL-205 from AJINOMOTO) 10 10 B DIISOPROPYL SEBACATE 2.5 2.5 B PEG-8 10 10 B BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL TRIAZINE
(TINOSORB S from BASF) 3 3 B BUTYL METHOXYDIBENZOYLMETHANE
(PARSOl 1789 from DSM) 0 3 B METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE
(compound 25) 0 0 B DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A+ from BASF) 3 0 B CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 VS WATER QSP 100 QSP 100 D CARBOMER 0.1 0.1 D AMMONIUM ACRYLOYLDIMETHYLTAURATE/VP COPOLYMER
(ARISTOFLEX AVC from CLARIANT) 0.35 0.35 D ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER
(PEMULEN TR-2 POLYMER from LUBRIZOL) 0.1 0.1 E POTASSIUM HYDROXIDE 0.016 0.016 F Expenses 1.5 1.5 G ALCOHOL DENAT. 15 15

The results obtained with compositions 1 to 5 are described in the table below. Composition 1
(reference) 2
(invention) 3
(invention) 4
(comparative) 5
(comparative) ΔE after washing 1.20 ± 0.08 0.77 ± 0.18 0.99 ± 0.10 2.53 ± 0.39 1.96 ± 0.32

These results show that compositions 2 and 3 according to the invention in which METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE (compound 25) is used as a UVA filter leave fewer traces after washing than reference composition 1 which does not contain UVA filters or than comparative compositions 4 and 5 in which DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE (for example Uvinul A+ from BASF) or BUTYL METHOXYDIBENZOYLMETHANE (for example Parsol 1789 from DSM) is used as UVA filter.

Comparative Example 2 - Compositions 6 to 9

The following compositions 6 to 9 were prepared according to the protocol detailed above. Phase Ingredient 6
(reference) 7
(invention) AT WATER 30 30 AT Conservatives QS QS AT INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 AT SODIUM STEAROYL GLUTAMATE
(EUMULGIN SG from BASF) 0.3 0.3 B ISOPROPYL LAUROYL SARCOSINATE
(ELDEW SL-205 from AJINOMOTO) 10 10 B DIISOPROPYL SEBACATE 2.5 2.5 B PEG-8 10 10 B ETHYLHEXYL TRAZONE
(UVINUL T150 from BASF) 3 3 B BUTYL METHOXYDIBENZOYL METHANE
(PARSOl 1789 from DSM) 0 0 B METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE(compound 25) 0 3 B DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A+ from BASF) 0 0 B CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 VS WATER QSP 100 QSP 100 D CARBOMER 0.1 0.1 D AMMONIUM ACRYLOYLDIMETHYLTAURATE/VP COPOLYMER
(ARISTOFLEX AVC from CLARIANT) 0.35 0.35 D ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER
(PEMULEN TR-2 POLYMER from LUBRIZOL) 0.1 0.1 E POTASSIUM HYDROXIDE 0.016 0.016 F Expenses 1.5 1.5 G ALCOHOL DENAT. 15 15 Phase Ingredient 8
(comparative) 9
(comparative) AT WATER 30 30 AT Conservatives QS QS AT INULIN LAURYL CARBAMATE
(INUTEC SL1 from CREACHEM) 0.3 0.3 AT SODIUM STEAROYL GLUTAMATE
(EUMULGIN SG from BASF) 0.3 0.3 B ISOPROPYL LAUROYL SARCOSINATE
(ELDEW SL-205 from AJINOMOTO) 10 10 B DIISOPROPYL SEBACATE 2.5 2.5 B PEG-8 10 10 B ETHYLHEXYL TRAZONE
(UVINUL T150 from BASF) 3 3 B BUTYL METHOXYDIBENZOYL METHANE
(PARSOl 1789 from DSM) 0 3 B METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE(compound 25) 0 0 B DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE
(UVINUL A+ from BASF) 3 0 B CETEARYL ALCOHOL (and) CETEARYL GLUCOSIDE
(MONTANOV 68 from SEPPIC) 1.4 1.4 VS WATER QSP 100 QSP 100 D CARBOMER 0.1 0.1 D AMMONIUM ACRYLOYLDIMETHYLTAURATE/VP COPOLYMER
(ARISTOFLEX AVC from CLARIANT) 0.35 0.35 D ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER
(PEMULEN TR-2 POLYMER from LUBRIZOL) 0.1 0.1 E POTASSIUM HYDROXIDE 0.016 0.016 F Expenses 1.5 1.5 G ALCOHOL DENAT. 15 15

The results obtained with compositions 6 to 9 are described in the table below. Composition 6
(reference) 7
(invention) 8
(comparative) 9
(comparative) ΔE after washing 0.60 ± 0.19 0.71 ± 0.09 1.06 ± 0.27 1.19 ± 0.17

These results show that the composition 7 according to the invention in which the METHOXYPROPYLAMINO CYCLOHEXENYLIDENE ETHOXYETHYLCYANOACETATE (compound 25) is used as UVA filter and the reference composition 6 which does not contain UVA filters leave less traces after washing than the compositions comparatives 8 and 9 in which DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE (for example Uvinul A+ from BASF) or BUTYL METHOXYDIBENZOYLMETHANE (for example Parsol 1789 from DSM) is used as UVA filter.

Claims (27)

Composition, in particular cosmetic or dermatological, comprising:
a) at least one merocyanine corresponding to one of the following formulas (1) or (2) or one of its geometric isomeric forms, in particular E/E or E/Z:
[Formula 1]
And
[Formula 2]

in which :
R ₁ and R ₂ , independent of each other, are hydrogen; a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, these groups possibly being substituted by at least one hydroxyl group or alternatively interrupted by at least one –O -; or alternatively R ₁ and R ₂ form together with the nitrogen atom which connects them a ring -(CH ₂ ) _n - which can be optionally interrupted by -O- or -NH-;
R ₃ is a -(C=O)OR ₆ group; or a -(CO)NHR ₆ group;
R ₆ 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 -} cycloalkenyl group. C ₂₂ , said groups possibly being substituted by one or more OH;
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ form a -(CH ₂ ) _n - ring which may be substituted by a C ₁ -C ₄ alkyl group and/or interrupted by one or more -O- or by -NH-;
n is a number between 2 and 7;
R ₇ and R _8, independent of each other, are hydrogen; a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkinyl group, it being possible for the said groups to be interrupted by one or more O and/or substituted by one or more OH; 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-;
or alternatively R ₇ and R ₈ form together with the nitrogen which connects them a ring -(CH ₂ ) _n - which can be interrupted by one or more -O-;
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ form a ring -(CH ₂ ) _n - potentially substituted by a C ₁ -C ₄ alkyl and/or interrupted by an -O- or -NH-;
A is -O-; or –NH;
R ₁₁ 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; or a C ₁ -C ₂₂ alkyl group or a C ₂ -C ₂₂ alkenyl group which is substituted by a C ₃ -C ₂₂ cycloalkyl group or a C ₃ -C ₂₂ cycloalkenyl group, said C ₃ cycloalkyl group -C ₂₂ or C ₃ -C ₂₂ cycloalkenyl group which may be interrupted by one or more -O-; And
b) at least one triazine UV filter; And
c) at least one polysaccharide modified by hydrophobic chains. Composition according to Claim 1, in which the compounds of formula (1) are chosen from those for which:
R ₆ is a C ₁ -C ₁₂ alkyl group, which may be substituted by one or more hydroxyl;
one of the R ₁ or R ₂ radicals is a C ₄ -C ₂₂ alkyl group; or alternatively R ₁ and R ₂ together with the nitrogen which connects them form a ring -(CH ₂ ) _n - which can be interrupted by -O- and/or -NH-; And
R ₄ and R ₅ and n have the same meanings as in claim 1. Composition according to either of Claims 1 and 2, in which the compounds of formula (2) are chosen from those for which:
R ₁₁ is a -(CH ₂ ) _m -OR ₁₂ radical, where
R ₁₂ is a C ₁ -C ₁₂ alkyl group; or a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group;
m is a number from 1 to 5; And
R ₇ , R ₈ , R ₉ , R ₁₀ and A have the same meanings as in claim 1. Composition according to any one of Claims 1 to 3, in which the compounds of formula (1) or (2) are chosen from those for which:
R ₁ and R ₂ on the one hand, and R ₇ and R ₈ on the other hand, respectively form together with the nitrogen atom to which they are respectively bonded a piperidyl radical or a morpholinyl radical. Composition according to any one of Claims 1 to 4, in which the compounds of formula (1) or (2) are chosen from those for which:
R ₄ and R ₅ and R ₉ and R ₁₀ respectively form a carbon ring which contains 6 carbon atoms. Composition according to any one of Claims 1 to 5, in which the compounds of formula (1) are chosen from those for which:
R ₁ and R ₂ independently of each other are hydrogen; or a C ₁ -C ₂₂ alkyl group; or a C ₁ -C ₂₂ hydroxyalkyl group; or R ₁ and R ₂ form together with the nitrogen to which they are attached a piperidyl or morpholinyl radical;
R ₃ is a -(C=O)OR ₆ group; or a -(CO)NHR ₆ group;
R ₆ is a C ₁ -C ₂₂ alkyl group, which may be substituted by one or more –OH;
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ are linked together to form a carbon ring which contains 6 carbon atoms. Composition according to any one of Claims 1 to 6, in which the compounds of formula (1) are chosen from those for which:
R ₁ and R ₂ independently of each other are hydrogen; or a C ₁ -C ₂₂ hydroxyalkyl group; where at least one of the R ₁ and R ₂ radicals is a C ₁ -C ₂₂ hydroxyalkyl group;
R ₃ is a -(C=O)OR ₆ group; or a -(C=O)NHR ₆ group;
R ₆ is a C ₁ -C ₁₂ alkyl group;
R ₄ and R ₅ are hydrogen; or R ₄ and R ₅ are bonded together to form a carbon ring which contains 6 carbon atoms. Composition according to any one of Claims 1 to 7, in which the compounds of formula (2) are chosen from those for which:
R ₇ and R _8, independently of one another, are hydrogen or a C ₁ -C ₈ alkyl group, which may be interrupted by one or more -O-;
A is -O- or -NH;
R ₁₁ is C ₁ -C ₂₂ alkyl; And
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ are bonded together to form a carbon ring which contains 6 carbon atoms. Composition according to any one of Claims 1 to 8, in which the compounds of formula (2) are chosen from those for which:
R ₇ and R ₈ together with the nitrogen atom to which they are bonded form a morpholinyl or piperidyl radical;
A is -O-; or –NH;
R ₁₁ is a C ₁ -C ₂₂ alkyl group which may be interrupted by one or more -O-; And
R ₉ and R ₁₀ are hydrogen; or R ₉ and R ₁₀ are bonded together to form a carbon ring which contains 6 carbon atoms. Composition according to any one of Claims 1 to 9, in which the compounds of formula (2) are chosen from those for which:
R ₁₁ is a -(CH ₂ ) _m -OR ₁₂ radical, where
R ₁₂ is a C ₁ -C ₄ alkyl group; or a C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl group;
m is a number from 1 to 3;
R ₇ and R ₈ independently of each other are hydrogen; a C ₁ -C ₁₂ alkyl group, which may be interrupted by one or more O; or R ₇ and R ₈ together with the nitrogen atom to which they are attached form a morpholinyl or piperidyl radical;
R ₉ and R ₁₀ are hydrogen or together form a carbon ring which contains 6 carbon atoms; And
A is -O- or -NH. Composition according to any one of Claims 1 to 10, in which the compounds of formula (1) or (2) are chosen from the following compounds, as well as their geometric isomers, in particular E/E or E/Z:
Table 1 Compound Structure Compound Structure 1
2 3 4 5
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Composition according to any one of Claims 1 to 11, in which the compounds of formula (1) or (2) are chosen from those 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. Composition according to Claim 12, 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 either of Claims 12 and 13, in which the merocyanine of formula (3) is 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene }ethanoate (25) in its E/Z geometric configuration with the following structure:

and/or in its geometric configuration E/E with the following structure:
Composition according to any one of Claims 1 to 14, comprising at least one triazine UV screening agent chosen from the 1,3,5-triazine derivatives of formula (10) below:
[form 10]

in which the identical or different radicals A ₁ , A ₂ and A ₃ are chosen from the groups of formula (11) to (18):
[form 11]

[form 12]

[form 13]

[form 14]

[form 15]

[form 16]

[form 17]

[form 18]

in which :
- X _a (each of Xa may be the same or different) represents oxygen or -NH-;
- R _a (each of R _a may be identical or different) is chosen from hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more linear or branched C ₁ -C ₁₈ alkyl or linear or branched C ₁ -C ₁₈ hydroxyalkyl radicals; a linear or branched C ₁ -C ₁₈ , preferably C ₆ -C ₁₂ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and whose terminal OH group is methylated; a radical of formula (19), (20) or (21) below:
[form 19]

[form 20]

[form 21]

in which :
- R ₈ is hydrogen or a methyl radical;
- R ₉ is a C ₁ -C ₉ alkyl radical;
- q is an integer ranging from 0 to 3;
- r is an integer ranging from 1 to 10;
- A is a C ₄ -C ₈ alkyl radical or a C ₅ -C ₈ cycloalkyl radical;
- B is chosen from: a linear or branched C ₁ -C ₈ alkyl radical; a C ₅ -C ₈ cycloalkyl radical; an aryl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals;
- R ₁ denotes a C ₃ -C ₁₈ alkyl radical; a C ₂ -C ₁₈ alkenyl radical; a residue of formula -CH ₂ -CH(OH)-CH ₂ -OT ₁ where T ₁ is a hydrogen atom or a C ₁ -C ₈ alkyl radical; a remainder of the following formula (22):
[form 22]

in which :
- R ₁₃ denotes a covalent bond; a linear or branched C ₁ -C ₄ alkyl radical or else a radical of formula -C _m1 H _2m1 -O- where m ₁ is an integer equal to 1; 2; 3; 4;
- p ₁ is an integer equal to 0; 1; 2; 3; 4; 5;
- the radicals R ₁₀ , R ₁₁ and R ₁₂ , which are identical or different, denote a C ₁ -C ₁₈ alkyl radical; a C ₁ -C ₁₈ alkoxy radical or a radical of formula (23):
[form 23]

where R ₁₄ is a C ₁ -C ₅ alkyl radical.
- R ₂ denotes a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ alkoxy radical;
- R ₃ and R ₄ , identical or different, denote a linear or branched C ₁ -C ₂₀ alkyl radical;
- R ₅ represents a hydrogen atom or a phenyl radical optionally substituted by a halogen or by a C ₁ -C ₄ alkyl radical or by a C ₁ -C ₄ alkoxy radical;
- R ₆ is a linear or branched C ₁ -C ₈ alkyl radical, C ₁ -C ₃ alkoxy, it being understood that, in the latter case, two adjacent R ₆ of the same aromatic ring can together form an alkylidene dioxy group in which the alkylidene group contains 1 to 2 carbon atoms, OH, NHCOCH ₃ or NH ₂ ,
- R ₇ denotes a hydrogen atom, a C ₁ -C ₁₀ alkyl radical, a radical of formula -(CH ₂ CHR ₅ -O) _n1 R ₈ where n ₁ is a number from 1 to 16, or else a radical of structure -CH ₂ -CH-(OH)-CH ₂ OT ₁ with R ₈ and T ₁ having the same meaning indicated above;
- Z represents oxygen, sulfur, -NH- or -NR ₃ - with R ₃ representing a linear or branched C ₁ -C ₂₀ alkyl radical;
- p is 0, 1, 2 or 3;
A ₁ can also be a halogen, an –N(R ₃ ) ₂ radical, the two R ₃ being able to form together a cycle of 4 or 5 carbon atoms, or an –OR ₃ group, R ₃ having the same definition as above. Composition according to any one of Claims 1 to 15, comprising at least one triazine filter chosen from the 1,3,5-triazines of formula (10) in which the A ₁ , A ₂ and A ₃ are of formula (11) and having all of the following characteristics:
- one or two X _a -R _a represents the –NH-R _a radical, with R _a chosen from: a linear or branched C ₁ -C ₁₈ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical;
the other two or more X _a -R _a being the –OR _a radical with R _a , identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more alkyl or hydroxyalkyl radicals; a linear or branched C ₁ -C ₁₈ alkyl radical; a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl radicals; a radical of formula (19), (20) or (21) above in which:
- B is a C ₁ -C ₄ alkyl radical;
- R ₉ is the methyl radical. Composition according to any one of claims 1 to 16 comprising 2-[(p-(tertiobutylamido)anilino]-4,6-bis-[(p-(2'-ethylhexyl-1'-oxycarbonyl)anilino]-1 ,3,5-triazine corresponding to the following formula:
[form 24]

in which R′ denotes a 2-ethylhexyl radical and R denotes a tert-butyl radical. Composition according to one of Claims 1 to 17 comprising at least one triazine filter chosen from the 1,3,5-triazines of formula (10) in which the A1, A2 and A3 are of formula (11) and have the following characteristics :
- Xa are identical and represent oxygen;
- Ra, identical or different and represent a C6-C12 alkyl radical or a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and whose terminal OH group is methylated. Composition according to any one of claims 1 to 18 comprising 2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)anilino]-1,3,5-triazine and has the following formula :
[form 25]

in which R' denotes a 2-ethyl hexyl radical. Composition according to one of Claims 1 to 19 comprising at least one triazine filter chosen from the 1,3,5-triazines corresponding to formula (10) in which A ₁ and A ₂ are of formula (12) and A ₃ is of formula (18) and having all of the following characteristics: R ₁ , which are identical or different, denote a C ₃ -C ₁₈ alkyl radical; a C ₂ -C ₁₈ alkenyl radical or else a residue of formula -CH ₂ -CH(OH)-CH ₂ -OT ₁ where T ₁ is a hydrogen atom or a C ₁ -C ₈ alkyl radical; R ₇ denotes a hydrogen atom, a C ₁ -C ₁₀ alkyl radical. Composition according to any one of claims 1 to 20 comprising the 1,3,5-triazine of formula (10) is 2,4-bis{[4-2-ethyl-hexyloxy)]-2-hydroxy]-phenyl }-6-(4-methoxy-phenyl)-1,3,5-triazine corresponding to the following formula:
[form 26]

in which R′ denotes a 2-ethylhexyl radical. Composition according to any one of Claims 1 to 21, in which the polysaccharide(s) are fructans with hydrophobic chains, and preferably inulin. Composition according to any one of Claims 1 to 22, in which the hydrophobic chains of the polysaccharide are linear or branched, saturated or unsaturated hydrocarbon chains, having from 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl, alkylene ; divalent cycloaliphatic groups or organopolysiloxane chains comprising one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulfonamide functions such as in particular methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene. Composition according to any one of Claims 22 or 23, in which the inulin has a degree of polymerization of 2 to approximately 1000 and preferably of 2 to approximately 60, and a degree of substitution lower than 2 on the basis of one unit fructose. Composition according to any one of Claims 1 to 24, in which the hydrophobic chains are alkylcarbamate groups, in particular C8-C18 alkyl carbamate, and more particularly laurylcarbamate. Use of at least one such merocyanine of formula (1) or (2) as defined in any one of Claims 1 to 14 to reduce the staining of fabrics, in particular clothes, after washing. Non-therapeutic cosmetic process for caring for and/or making up a keratin material comprising the application to the surface of the said keratin material of at least one composition as defined in any one of the preceding claims.