EP4262719A1 - Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester - Google Patents

Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester

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Publication number
EP4262719A1
EP4262719A1 EP21836527.8A EP21836527A EP4262719A1 EP 4262719 A1 EP4262719 A1 EP 4262719A1 EP 21836527 A EP21836527 A EP 21836527A EP 4262719 A1 EP4262719 A1 EP 4262719A1
Authority
EP
European Patent Office
Prior art keywords
group
formula
composition according
compounds
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21836527.8A
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German (de)
French (fr)
Inventor
Flavie GILLANT
Angélina ROUDOT
Amélie FRIOT-DARDERES
Julie Grumelard
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LOreal SA
Original Assignee
LOreal SA
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Publication of EP4262719A1 publication Critical patent/EP4262719A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/362—Polycarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester
  • the present invention relates to a composition, preferably a cosmetic or dermatological composition, comprising at least one merocyanine of formula (1 ) or (2) that will be defined below in detail and at least one oily phase comprising at least one ester of a di- or tricarboxylic acid and of C1-C24 alcohols.
  • 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.
  • the invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
  • the invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
  • UVA rays with wavelengths of between 320 and 400 nm penetrate more deeply into the skin than UVB rays. UVA rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even of short duration, under normal conditions can result in damage to the collagen fibres and the elastin, which is reflected by a modification of the microrelief of the skin, the appearance of wrinkles and uneven pigmentation (liver spots, heterogeneity of the complexion).
  • UVA and UVB radiation Protection against UVA and UVB radiation is therefore necessary.
  • An effective photoprotective product must protect against both UVA and UVB radiation.
  • photoprotective compositions have been proposed to date to overcome the effects induced by UVA and/or UVB radiation. They generally contain organic UV-screening agents and/or inorganic UV-screening agents, which function according to their own chemical nature and according to their own properties by absorption, reflection or scattering of the UV radiation. They generally contain mixtures of liposoluble organic screening agents and/or of water-soluble UV-screening agents combined with metal oxide pigments such as titanium dioxide or zinc oxide.
  • compositions intended to limit darkening of the skin, and to improve the colour and uniformity of the complexion have been proposed to date. It is well known in the field of antisun products that such compositions can be obtained by using UV-screening agents, and in particular UVB- screening agents. Some compositions may also contain UVA-screening agents. This screening system must cover UVB protection for the purpose of limiting and controlling the neosynthesis of melanin promoting overall pigmentation, but must also cover UVA protection in order to limit and control the oxidation of the already existing melanin resulting in darkening of the skin colour.
  • compositions containing a particular combination of UV-screening agents that would be specially suitable for photoprotection of the skin and particularly for an improvement in the quality of the skin both in terms of the colour and in terms of its mechanical elasticity properties.
  • this improvement is particularly desired on skin that is already pigmented, for the purpose of not increasing either the pigmentary melanin load or the structure of the melanin already present within the skin.
  • the majority of organic UV-screening agents consist of aromatic compounds which absorb in the wavelength range between 280 and 370 nm.
  • the desired photoprotective compounds must also have good cosmetic properties, good solubility in the usual solvents and in particular in fatty substances such as oils, and also good photostability alone or in combination with other UV-screening agents. They must also be colourless or at least have a colour that is cosmetically acceptable for consumers.
  • compositions in particular a cosmetic or dermatological composition, comprising at least one merocyanine of formula (1 ) or (2) that will be defined below in detail and at least one oily phase comprising at least one ester of C2-C22 di- or tricarboxylic acids and of C1-C24 alcohols.
  • esters of C2- C22 di- or tricarboxylic acids and of C1-C24 alcohols it was possible to substantially improve the solubility of these merocyanines in an oily phase, even in the presence of additional organic UV-screening agents.
  • 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.
  • the invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
  • the invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
  • composition according to the invention is intended for topical application and thus contains a physiologically acceptable medium.
  • physiologically acceptable medium means here a medium that is compatible with keratin materials.
  • the term “keratin material” notably means the skin, the scalp, keratin fibres such as the eyelashes, the eyebrows, head hair, bodily hair, the nails, and mucous membranes such as the lips, and more particularly the skin and the mucous membranes (of the body, face, area around the eyes, eyelids, lips, preferably of the body, face and lips).
  • the term "preventing” or “prevention” is intended to mean reducing the risk of occurrence or slowing down the occurrence of a given phenomenon, namely, according to the present invention, the signs of ageing of a keratin material.
  • the merocyanine compounds in accordance with the invention correspond to formula (1 ) or (2) below:
  • Ri and R2 independently of each other, are hydrogen; a C1-C22 alkyl group, a C2-C22 alkenyl group, or a C2-C22 alkynyl group, these groups possibly being substituted with at least one hydroxyl group or else interrupted with at least one -O-; or else R1 and R2 form, together with the nitrogen atom which links them, a -(CH2)n- ring which may be optionally interrupted with -0- or -NH-;
  • Re is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being substituted with one or more OH;
  • R4 and R5 are hydrogens; or R4 and R5 form a -(CH2)n- ring which may be substituted with a C1-C4 alkyl group and/or interrupted with one or more -0- or with -NH-; n is a number between 2 and 7;
  • R7 and Rs independently of each other, are hydrogen; a C1-C22 alkyl group, a C2- C22 alkenyl group, a C2-C22 alkynyl group, said groups possibly being interrupted with one or more 0 and/or substituted with one or more OH; a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more -O-; or else R7 and Rs form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with one or more -O-;
  • R9 and R10 are hydrogen; or R9 and R10 form a -(CH2)n- ring potentially substituted with a C1-C4 alkyl and/or interrupted with an -0- or -NH-;
  • A is -O-; or -NH;
  • R11 is a C1-C22 alkyl group; a C2-C22 alkenyl group; a C2-C22 alkynyl group; a C3- C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more O; or a C1-C22 alkyl group or a C2-C22 alkenyl group which is substituted with a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said C3-C22 cycloalkyl group or C3-C22 cycloalkenyl group possibly being interrupted with one or more -O-.
  • the compounds of formula (1 ) or (2) have the following characteristics:
  • R1 denotes a hydroxyethyl
  • R2 does not denote a hydrogen, a methyl or an ethyl or a hydroxyethyl
  • R1 denotes hydrogen
  • R2 is not 1- hydroxy-3-methylbut-2-yl
  • Re is substituted with one or more OH, one from among R1 and R2 is a C4-C22 alkyl group; or else R1 and R2 form, together with the nitrogen to which they are bonded, a piperidyl or morpholinyl radical;
  • the preferred compounds are those of formula (1 ) or (2) in which:
  • R1 and R2 independently of each other, are hydrogen; a C4-C12 alkyl group; or a C3-C12 hydroxyalkyl group; or at least one of R1 or R2 is a C3-C12 hydroxyalkyl; and
  • R3, R4 and R5 have the same meanings indicated previously.
  • the preferred compounds are also those of formula (1 ) in which: Re is a C1-C12 alkyl group, which may be potentially substituted with one or more hydroxyls.
  • Re is a C1-C12 alkyl group, which may be substituted with one or more hydroxyls; one of the radicals R1 or R2 is a C4-C22 alkyl group; or else R1 and R2 form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with - 0- and/or -NH-; and
  • R4 and R5 and n have the same meanings indicated previously.
  • R11 is a -(CH2)m-O-R-i2 radical, in which
  • R12 is a C1-C12 alkyl group; or a C-i-Ce alkoxy-C-i-Ce alkyl group; m is a number from 1 to 5; and
  • R7, Rs, R9, R10 and A have the same meanings indicated previously.
  • R1 and R2 on the one hand, and R7 and Rs, 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 formula (1 ) and (2) in which:
  • R4 and R5 and R9 and R10 respectively form a carbon-based ring which contains 6 carbon atoms.
  • R1 and R2 independently of each other, are a hydrogen; or a C1-C22 alkyl group; or a C1-C22 hydroxyalkyl group; or R1 and R2 form, together with the nitrogen to which they are bonded, a piperidyl or morpholinyl radical;
  • Re is a C1-C22 alkyl group, which may be substituted with one or more -OH; R4 and R5 are a hydrogen; or R4 and R5 are linked together to form a carbon-based ring which contains 6 carbon atoms.
  • R1 and R2 independently of each other, are a hydrogen; or a C1-C22 hydroxyalkyl group; in which at least one of the radicals R1 and R2 is a C1-C22 hydroxyalkyl group;
  • Re is a C1-C22 alkyl group
  • R4 and R5 are hydrogens; or R4 and R5 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
  • R7 and Rs independently of each other, are a hydrogen or a C-i-Ce alkyl group, which may be interrupted with one or more -O-;
  • A is -0- or -NH
  • R11 is a C1-C22 alkyl
  • R9 and R10 are a hydrogen; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
  • R7 and Re form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
  • A is -O- or -NH
  • R11 is a C1-C22 alkyl group, which may be interrupted with one or more -O-;
  • R9 and R10 are hydrogens; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
  • R11 is a -(CH2)m-O-Ri2 radical, in which R12 is a C1-C4 alkyl group; or a C1-C4 alkoxy-Ci-C4 alkyl group; m is a number from 1 to 3; and
  • R7 and Rs independently of each other, are a hydrogen; a C1-C12 alkyl group, which may be interrupted with one or more O; or R7 and Rs form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
  • R9 and R10 are hydrogens or together form a carbon-based ring which contains 6 carbon atoms
  • A is -O- or -NH.
  • the merocyanine compounds of the invention may be for example in the E/E, E/Z or Z/Z geometric isomer form.
  • alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl chains may be linear or branched, monocyclic or polycyclic chains.
  • a C1-C22 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- bis(tert-amyl)phenoxy]propyl, ethoxycarbonylmethyl-2-(2- hydroxyethoxy)ethyl or 2-fury lethy I .
  • a hydroxy-substituted alkyl group is, for example, a hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxydecyl.
  • a C2-C22 alkenyl group is, for example, a linear C2-C12 alkenyl chain or preferentially a branched C3-C12 alkenyl chain.
  • a C2-C22 alkenyl is, for example, a 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)-thu
  • a C3-C12 cycloalkyl group is, for example, a cyclopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or, preferentially, a cyclohexyl.
  • Examples of merocyanines according to the present invention are listed in Table 1 :
  • A is -0- or -NH
  • R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0.
  • the merocyanine compounds of the invention may be in the E/E- or E/Z geometric isomer forms thereof:
  • A is -O-;
  • R is a C1-C22 alkyl, which may be interrupted with one or more 0.
  • the E/Z form has the following structure:
  • the E/E form has the following structure:
  • the screening merocyanines in accordance with the invention may be present in the compositions according to the invention in a concentration ranging from 0.1 % to 15% by weight, and preferentially from 0.2% to 10% by weight and even better still from 0.5% to 5% by weight relative to the total weight of the composition.
  • the compounds of formulae (1 ) and (2) and especially of formula (3) may be prepared according to known processes, as described, for example, in J. Org. Chem. USSR (English Translation) 26(8), page 1562f (1990); J. Heterocycl. Chem. 33(3), pages 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11 , pages 1537-1543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, pages 397-404 (1982); Chem. Heterocycl. Comp. (English Translation) 24(8), 914-919 (1988) and in Synthetic Communications Vol. 33, No. 3, 2003, pages 367-371.
  • the compounds of formula (1 ) or (2) in which R4 and R5, on the one hand, or R9 and R10, on the other hand, together form a carbocyclic ring containing 6 carbon atoms, respectively, may be prepared according to the protocols described in patent application WO 2007/071582, in IP.com Journal (2009), 9(5A), 29-30 IPCOM000182396D under the title “Process for producing 3- amino-2-cyclohexan-1-ylidene compounds” and in US-A-4,749,643 on col. 13, line 66 - col. 14, line 57 and the references cited in this regard.
  • the compounds of formula (3) such as compound 2-ethoxyethyl (2Z)-cyano ⁇ 3-[(3-methoxypropyl)amino]cyclohex-2-en-1 - ylidenejethanoate (25) can be synthesized according to the synthesis scheme described in the publication by B. Winkler et al., Tetrahedron Letters, 55 (2014) 1749-1751 , which is intitled « A cyclic merocyanine UV- A absorber : mechanism of formation and crystal structure » and shown below, for the compounds of formula (3) : [formula 8 bis]
  • composition in accordance with the invention comprises at least one ester of C2-C22 di- or tricarboxylic acid and of C1-C24 alcohols.
  • the C2-C22 di- or tricarboxylic acids are in particular chosen from citric acid, malic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, tartaric acid, isocitric acid, and mixtures thereof.
  • the acids are preferably citric acid and adipic acid, and even more preferentially the acid is citric acid.
  • the C1-C24 alcohols are not oxyalkylenated. They may be aliphatic, cyclic or aromatic, having from 1 to 24 carbon atoms. They are in particular chosen from phenol, benzyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, methanol, ethanol, propanol, n-butanol, t-butanol, pentanol and hexanol.
  • the alcohol(s) is/are C-i-Ce alcohol(s) and can be chosen from methanol, ethanol, propanol, n-butanol, t-butanol, pentanol, hexanol, and even more preferentially the alcohol is ethanol.
  • ester(s) of C2-C22 di- or tricarboxylic acid and of C1-C24 alcohols can be mono- or polyesterified.
  • Monoesterified is understood to mean that only one of the two or three carboxylic acid functions is esterified.
  • Polyesterified is understood to mean that at least two carboxylic acid functions are esterified.
  • the di- or tricarboxylic acid can be esterified with a number of different alcohols. It is preferably esterified with just one alcohol.
  • the composition comprises at least one ester of C3-C22 tricarboxylic acid and of C1-C24, preferably C-i-Ce, alcohols. This/these ester(s) can be mono-, di- or triesterified.
  • Monoesterified is understood to mean that only one of the three carboxylic acid functions is esterified. Diesterified is understood to mean that two of the three carboxylic acid functions are esterified. Triesterified is understood to mean that all three carboxylic acid functions are esterified.
  • ester(s) of C3- C22 tricarboxylic acid and of C-i-Ce alcohols are triesterified.
  • ester(s) of C3- C22 tricarboxylic acid and of C-i-Ce alcohols are chosen from the compounds of formula (9) below:
  • R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon- based group having from 1 to 6 carbon atoms;
  • R represents a hydrogen atom or a hydroxyl radical.
  • R1, R2 and R3 represent, independently of each other, a hydrogen atom or a linear or branched, substituted or unsubstituted, preferably unsubstituted, C-i-Ce alkyl radical, and in particular a radical chosen from methyl, ethyl, propyl, n-butyl, t-butyl, pentyl and hexyl radicals.
  • R1, R2 and R3 are chosen, independently of each other, from a hydrogen atom and methyl, ethyl, propyl, n-butyl and t-butyl radicals.
  • the radicals R1, R2 and R3 are identical and are chosen from C-i-Ce, preferably C1-C4, alkyl radicals and even more preferentially are ethyl radicals.
  • R represents a hydroxyl radical.
  • the ester of tricarboxylic acid and of C-i-Ce alcohols has the following formula:
  • esters of di- or tricarboxylic acid and of C1 -C24 alcohols as defined above are generally present in the composition according to the invention in concentrations ranging from 0.1 % to 98% by weight, more particularly from 0.5% to 50% by weight, preferably from 1 % to 20% by weight, and even more preferentially from 1 % to 15% by weight, better still from 1 % to 10% by weight, relative to the total weight of the composition.
  • the composition according to the invention comprises : a) at least one merocyanine corresponding to formula (3) below, and also the geometric isomer forms, notably the E/E- or E/Z-geometric isomer forms, thereof:
  • A is -O- or -NH;
  • R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0 ; and b) at least one ester of tricarboxylic acid and of C-i-Ce alcohols having the following formula:
  • R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon- based group having from 1 to 6 carbon atoms;
  • R represents a hydrogen atom or a hydroxyl radical.
  • the composition according to the invention comprises : a) at least one merocyanine corresponding to formula (3) below, and also the geometric isomer forms, notably the E/E- or E/Z-geometric isomer forms, thereof:
  • A is -0- or -NH
  • R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0 ; and b) the ester of tricarboxylic acid and of C-i-Ce alcohols has the following formula: [Formula 10]
  • the composition comprises at least one polymer comprising monomer units of formulae (A) and (B) defined below:
  • R1 is chosen from alkyl or alkylene radicals, and at least 60% by weight of the Ri groups are radicals chosen from stearyl and behenyl radicals, the percentage by weight relating to the sum of all the Ri groups present in the polymer, and the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the Ri group ranges from 1 :30 to 1 :1 , and the sum of the total of units A and B is at least 95% by weight relative to the total weight of the polymer.
  • Ri is constituted of alkyl radicals, preferably of C16-C22 alkyl radicals, and more preferentially of stearyl (Cis) radicals or of behenyl (C22) radicals.
  • At least 70% by weight of the groups R1 are stearyl or behenyl radicals, preferentially at least 80% by weight and more preferentially at least 90% by weight.
  • all the R1 groups are behenyl radicals.
  • all the R1 groups are stearyl radicals.
  • said weight ratio ranges from 1 :15 to 1 :1 and preferentially ranges from 1 :10 to 1 :4.
  • the polymer units present in the polymer consist of the units (A) and (B) previously described.
  • the polymer has a number-average molecular weight Mn ranging from 2000 to 9000 g/mol, preferably ranging from 5000 to 9000 g/mol.
  • the numberaverage molecular weight may be measured via the gel permeation chromatography method, for example according to the method described in the example hereinbelow.
  • the polymer has a melting point ranging from 40°C to 70°C and preferentially ranging from 45°C to 67°C.
  • the melting point is measured by differential scanning calorimetry (DSC), for example according to the method described in the example hereinbelow.
  • the polymer when the polymer is such that at least 60% by weight of the groups R1 are stearyl radicals, then the polymer preferably has a melting point ranging from 40 to 60°C, and preferentially ranging from 45 to 55°C.
  • the polymer when the polymer is such that at least 60% by weight of the groups R1 are behenyl radicals, then the polymer has a melting point ranging from 60°C to 70°C, and preferentially ranging from 63°C to 67°C.
  • the polymerization may be performed according to known methods, such as solution polymerization or emulsion polymerization.
  • the polymerization is, for example, described in document US 2007/0264204.
  • the acrylic polymer(s) as defined previously can be present in the composition according to the invention in a content of active material ranging from 0.05% to 10% by weight, relative to the total weight of the composition, preferably ranging from 0.1 % to 5% by weight and better still ranging from 0.2% to 3% by weight.
  • composition in accordance with the invention comprises at least one oily phase.
  • oil phase means a phase comprising at least one oil and all of the liposoluble and lipophilic ingredients and the fatty substances used for the formulation of the compositions of the invention.
  • oil is intended to mean any fatty substance that is in liquid form at ambient temperature (20-25°C) and atmospheric pressure (760 mmHg).
  • the oily phase may comprise, in addition to the merocyanine screening agent(s) and optionally the lipophilic additional screening agents and the ester(s) of di- or tricarboxylic acid according to the invention, at least one volatile or non-volatile hydrocarbon-based oil and/or one volatile and/or nonvolatile silicone oil and/or one volatile and/or non-volatile fluoro oil.
  • silicon oil is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group.
  • hydrocarbon-based oil is intended to mean an oil mainly containing hydrogen and carbon atoms and optionally one or more heteroatoms, in particular nitrogen and oxygen.
  • these oils may in particular contain one or more carboxy, ester, ether, hydroxyl functions.
  • fluoro oil is intended to mean an oil comprising at least one fluorine atom.
  • volatile oil is intended to mean an oil that is capable of evaporating on contact with the skin or the keratin fibre in less than one hour, at ambient temperature and atmospheric pressure.
  • volatile oil(s) of the invention are volatile cosmetic oils, which are liquid at ambient temperature, having a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10 -3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
  • non-volatile oil is understood to mean an oil which remains on the skin or the keratin fibre, at ambient temperature and atmospheric pressure, for at least several hours and which has in particular a vapour pressure of less than 10’ 3 mmHg (0.13 Pa).
  • non-volatile hydrocarbon-based oils that may be used according to the invention, mention may notably be made of:
  • hydrocarbon-based oils of plant origin such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C4 to C24, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheatgerm oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil and musk rose oil; or else caprylic/capric acid triglycerides, such as those sold by
  • synthetic esters such as the oils of formula RCOOR' in which R represents a linear or branched fatty acid residue comprising from 1 to 40 carbon atoms and R' represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms, with the proviso that R + R' > 10, for instance Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by the company Witco orTegosoft TN® by the company Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under the name X- Tend 226® by the company ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononan
  • fatty alcohols that are liquid at ambient temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol or 2-undecylpentadecanol;
  • C12-C22 higher fatty acids such as oleic acid, linoleic acid or linolenic acid
  • carbonates such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC® by the company Cognis; and mixtures thereof.
  • non-volatile hydrocarbon-based oils that may be used according to the invention, preference will be given more particularly to glyceride triesters and in particular to caprylic/capric acid triglycerides, synthetic esters and in particular diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2-ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol.
  • the non-volatile hydrocarbon-based oils are chosen from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate and dicaprylyl carbonate.
  • hydrocarbon-based oils that may be used according to the invention, mention may be made in particular of hydrocarbon-based oils containing from 8 to 16 carbon atoms and in particular of branched Cs-C alkanes, such as Cs-C isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2, 2, 4,4,6- pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched Cs-C esters, isohexyl neopentanoate, and mixtures thereof.
  • Cs-C isoalkanes of petroleum origin also known as isoparaffins
  • isododecane also known as 2, 2, 4,4,6- pentamethylheptane
  • isodecane or isohexadecane the oils sold under the Isopar or Permethyl trade names
  • volatile hydrocarbon-based oils for instance petroleum distillates, in particular those sold under the name Shell Solt® by the company Shell, may also be used.
  • the volatile solvent is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof.
  • the non-volatile silicone oils may be notably chosen from non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes including alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, these groups each containing from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxysilicates.
  • PDMSs non-volatile polydimethylsiloxanes
  • phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphen
  • volatile silicone oils examples include volatile linear or cyclic silicone oils, in particular those with a viscosity ⁇ 8 centistokes (8x1 O’ 6 m 2 /s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms.
  • volatile silicone oils that may be used in the invention, mention may notably be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
  • R represents an alkyl group containing from 2 to 4 carbon atoms and of which one or more hydrogen atoms may be substituted with a fluorine or chlorine atom.
  • oils of general formula (11 ) mention may be made of:
  • Use may also be made of volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof.
  • volatile fluoro oils such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof.
  • An oily phase according to the invention may also comprise other fatty substances, mixed with or dissolved in the oil.
  • Another fatty substance that may be present in the oily phase may be, for example:
  • waxes such as lanolin, beeswax, carnauba or candelilla wax, rice bran wax, paraffin waxes, lignite waxes, microcrystalline waxes, ceresin or ozokerite, or synthetic waxes, such as polyethylene waxes or Fischer-Tropsch waxes;
  • a pasty compound such as polymeric or non-polymeric silicone compounds, esters of a glycerol oligomer, arachidyl propionate, fatty acid triglycerides and derivatives thereof;
  • 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 preferentially from 10% to 80% by weight, relative to the total weight of the composition.
  • 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 that is suitable for use in the invention may comprise, for example, a water chosen from a natural spring water, such as water from La Roche-Posay, water from Vittel, water from Saint Gervais Mont Blanc or waters from Vichy, or a floral water.
  • a natural spring water such as water from La Roche-Posay, water from Vittel, water from Saint Gervais Mont Blanc or waters from Vichy, or a floral water.
  • the water-soluble or water-miscible solvents that are suitable for use in the invention comprise short-chain monoalcohols, for example C1-C4 monoalcohols, 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.
  • C1-C4 monoalcohols 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
  • use may more particularly be made of ethanol, propylene glycol, glycerol, and mixtures thereof.
  • 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 preferentially from 10% to 80% by weight, relative to the total weight of the composition.
  • compositions according to the invention may also contain one or more additional UV-screening agents chosen from hydrophilic, lipophilic or insoluble organic UV-screening agents and/or one or more mineral pigments. It will preferentially be constituted of at least one hydrophilic, lipophilic or insoluble organic UV-screening agent.
  • hydrophilic UV-screening agent is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid aqueous phase or else which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.
  • lipophilic screening agent is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid fatty phase or else which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.
  • insoluble UV-screening agent is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation which has a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in the majority of organic solvents such as liquid paraffin, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® sold by the company Dynamit Nobel.
  • This solubility determined at 70°C, is defined as the amount of product in solution in the solvent at equilibrium with an excess of solid in suspension after returning to ambient temperature. It may be readily evaluated in the laboratory.
  • the additional organic UV-screening agents are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; (3, [3-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent US 5 624 663; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds, as described in patents EP 669 323 and US 2 463 264; p-aminobenzoic (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds, as described in patent applications US 5 237 071 , US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole compounds, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101
  • organic photoprotective agents mention may be made of those denoted hereinbelow under their INCI name.
  • Cinnamic compounds are Cinnamic compounds:
  • Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX® by DSM Nutritional Products,
  • Neo Heliopan E 1000® Isoamyl p-Methoxycinnamate, sold under the trade name Neo Heliopan E 1000® by Symrise,
  • Butyl Methoxydibenzoylmethane sold in particular under the trade name Parsol 1789® by DSM Nutritional Products,
  • Ethylhexyl Dimethyl PABA sold in particular under the name Escalol 507® by ISP,
  • PEG-25 PABA sold under the name llvinul P 25® by BASF.
  • 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.
  • Diphenyl acrylate compounds :
  • Octocrylene sold in particular under the trade name llvinul N 539® by BASF
  • Etocrylene sold in particular under the trade name llvinul N 35® by BASF.
  • 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-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, as a mixture with octyl methoxycinnamate, under the trade name Uvinul A Plus B® by the company BASF,
  • Camphor Benzalkonium Methosulfate manufactured under the name Mexoryl SO® by Chimex,
  • Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name Eusolex 232® by Merck.
  • Neo Heliopan AP® Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name Neo Heliopan AP® by Haarmann and Reimer.
  • 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 with a mean particle size ranging from 0.01 to 5 pm, more preferentially from 0.01 to 2 pm and more particularly from 0.020 to 2 pm, with at least one alkylpolyglycoside surfactant having the structure C n H2n+iO(C6Hio05)xH, in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the (CeH Os) unit and ranges from 1 .4 to 1 .6, as described in patent GB-A-2 303 549, sold in particular under the trade name Tinosorb M® by BASF, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.02 to 2 pm, more preferentially from 0.01 to 1.5
  • Neo Heliopan MA® Menthyl anthranilate, sold under the trade name Neo Heliopan MA® by Symrise.
  • Polyorganosiloxane comprising benzalmalonate functions such as Polysilicone-15, sold under the trade name Parsol SLX® by Hoffmann-La Roche.
  • the preferential organic screening agents are chosen from:
  • the particularly preferred organic screening agents are chosen from:
  • Drometrizole Trisiloxane and mixtures thereof.
  • the inorganic UV-screening agents used in accordance with the present invention are metal oxide pigments. More preferentially, the inorganic UV- screening agents of the invention are metal oxide particles with a mean elementary particle size of less than or equal to 0.5 pm, more preferentially between 0.005 and 0.5 pm, even more preferentially between 0.01 and 0.2 pm, better still between 0.01 and 0.1 pm and more particularly between 0.015 and 0.05 pm.
  • They may be chosen in particular from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof.
  • Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773.
  • Commercial pigments that may be mentioned include the products sold by the companies Sachtleben Pigments, Tayca, Merck and Degussa.
  • the metal oxide pigments may be coated or uncoated.
  • the coated pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
  • coated pigments are more particularly titanium oxides that have been coated:
  • silica such as the product Sunveil® from the company Ikeda
  • alumina and aluminum stearate such as the products Microtitanium Dioxide MT 100 T®, MT 100 TX®, MT 100 Z® and MT-01® from the company Tayca, the products Solaveil CT-10 W® and Solaveil CT 100® from the company Uniqema and the product Eusolex T-AVO® from the company Merck,
  • iron oxide and iron stearate such as the product Microtitanium Dioxide MT 100 F® from the company Tayca,
  • 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, - with silica, alumina and aluminum stearate and treated with a silicone, such as the product STT-30-DS® from the company Titan Kogyo,
  • TiO2 pigments doped with at least one transition metal such as iron, zinc or manganese and more particularly manganese.
  • 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 also comprise one or more dispersants, for instance a sorbitan ester, for instance sorbitan isostearate, or a polyoxyalkylenated fatty acid ester of glycerol, for instance TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate.
  • the oily dispersion of titanium oxide particles includes at least one dispersant chosen from polyoxyalkylenated fatty acid esters of glycerol. Mention may be made more particularly of the oily dispersion of TiO2 particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate having the INCI name: titanium dioxide (and) TRI-PPG-3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for instance the product sold under the trade name Optisol TD50® by the company Croda.
  • the uncoated titanium oxide pigments are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 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 LIFTR®, by the company Tomen under the name ITS® and by the company Tioxide under the name Tioveil AQ®
  • the uncoated zinc oxide pigments are, for example:
  • Nanox® those sold under the name Nanox® by the company Elementis;
  • Nanogard WCD 2025® those sold under the name Nanogard WCD 2025® by the company Nanophase Technologies.
  • coated zinc oxide pigments are for example:
  • Daitopersion Zn-30® and Daitopersion Zn-50® sold 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 polymethylhydrosiloxane);
  • Nanox Gel TN® those sold under the name Nanox Gel TN® by the company Elementis (ZnO dispersed at 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).
  • the uncoated cerium oxide pigments may be, for example, those sold under the name Colloidal Cerium Oxide® by the company Rhone-Poulenc.
  • the uncoated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2002® (FE 45B®), Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ® and Nanogard WCD 2006® (FE 45R®) or by the company Mitsubishi under the name TY-220®.
  • the coated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2008 (FE 45B FN)®, Nanogard WCD 2009® (FE 45B 556®), Nanogard FE 45 BL 345® and Nanogard FE 45 BL® or by the company BASF under the name Transparent Iron Oxide®.
  • metal oxides especially of titanium dioxide and of cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company Ikeda under the name Sunveil A®, and also 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 glycerol, such as the product M 211® sold by the company Sacht
  • coated or uncoated titanium oxide pigments are particularly preferred.
  • the additional UV-screening agents according to the invention can be present in the composition according to the invention in 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.
  • composition in accordance with the present invention may also comprise conventional cosmetic adjuvants chosen in particular from organic solvents, ionic or non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient commonly used in the cosmetic and/or dermatological field.
  • conventional cosmetic adjuvants chosen in particular from organic solvents, ionic or non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants
  • C1-C4 monoalkanols as defined above and in particular short-chain C2-C8 polyols, such as glycerol or diols, such as caprylyl glycol, 1 ,2-pentanediol, propanediol, butanediol, glycols and glycol ethers, such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol
  • carboxyvinyl polymers such as the Carbopols® (Carbomers) and the Pemulens, such as Pemulen TR1® and Pemulen TR2® (acrylate/C10-C30 alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305® (CTFA name: polyacrylamide/Ci3-i4 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80) by the company SEPPIC; 2- acrylamido-2-methylpropanesulfonic acid polymers and copolymers, optionally crosslinked and/or neutralized, such as the poly(2-acrylamido-2- methylpropanesulfonic acid) sold by the company Hoechst under the trade name Hostacerin AMPS®
  • carboxyvinyl polymers such as the
  • acidifying agents examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
  • mineral or organic acids for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide.
  • the cosmetic composition comprises one or more basifying agents chosen from alkanolamines, in particular triethanolamine, and sodium hydroxide.
  • 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 5.5 to 8.
  • active agents for caring for keratin materials such as the skin, the lips, the scalp, the hair, the eyelashes or the nails
  • compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art. They may in particular be in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W), such as a cream, a milk or a cream gel.
  • a simple or complex emulsion O/W, W/O, O/W/O or W/O/W
  • anhydrous composition is intended to mean a composition containing less than 1 % by weight of water, or even less than 0.5% water, and especially 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 aerosol form and may be in the form of a mousse or a spray.
  • the emulsification processes that may be used are of the paddle or impeller, rotor-stator and HPH type.
  • the emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or non-ionic emulsifiers, used alone or as a mixture.
  • the emulsifiers are chosen in an appropriate manner according to the emulsion to be obtained (W/O or O/W emulsion).
  • W/O emulsifying surfactants examples include alkyl esters or ethers of sorbitan, of glycerol, of polyol, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C® by the company Dow Coming, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Coming 5200 Formulation Aid by the company Dow Coming; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R® by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name Abil WE 09® by the company Goldschmid
  • non-silicone emulsifying surfactants in particular alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.
  • Polyol alkyl esters that may in particular be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135® by the company ICI.
  • examples of glycerol and/or sorbitan esters that may be mentioned include polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34® by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by the company ICI, and mixtures thereof.
  • non-ionic emulsifying surfactants examples include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids, optionally in combination with an ester of a fatty acid and of glycerol, such as the PEG-100 stearate/glyceryl stearate mixture sold, for example, by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular
  • the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, for example as described in the document WO-A-92/06778.
  • the aqueous phase of this emulsion may comprise a non-ionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
  • the compositions according to the invention find their application in a large number of treatments, in particular cosmetic treatments, for the skin, the lips and the hair, including the scalp, in particular for protecting and/or caring for the skin, the lips and/or the hair, and/or for making up the skin and/or the lips.
  • compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, in particular care products, antisun products and makeup products.
  • the cosmetic compositions according to the invention may be used, for example, as a makeup product.
  • Another subject of the present invention is constituted of a non- therapeutic cosmetic process for caring for and/or making up a keratin material, which consists in applying, to the surface of said keratin material, at least one composition according to the invention as defined above.
  • the cosmetic compositions according to the invention may be used, for example, as a care product and/or antisun product for the face and/or body, with a liquid to semi-liquid consistency, such as milks, more or less smooth creams, cream gels or pastes. They may optionally be packaged in aerosol form and may be in the form of a mousse or a spray.
  • compositions according to the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles by means of pressurizing devices.
  • the devices in accordance with the invention are well known to those skilled in the art and comprise non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. These devices are described in patents US 4 077 441 and US 4 850 517.
  • compositions packaged in aerosol form in accordance with the invention generally contain conventional propellants, for instance hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in amounts ranging from 15% to 50% by weight relative to the total weight of the composition.
  • the invention also relates to a cosmetic assembly comprising: i) a container delimiting one or more compartments, said container being closed by a closing member and optionally being unsealed; and ii) a makeup and/or care composition in accordance with the invention placed inside said compartment(s).
  • the container may be, for example, in the form of a jar or a box.
  • the closing member may be in the form of a lid comprising a cap mounted so as to be able to move by translation or by pivoting relative to the container housing said makeup and/or care composition(s).
  • composition ingredients are given as % by weight of starting materials, relative to the total weight of the composition.
  • the completion of the alkylation reaction can be monitored for example by methods such as TLC, GC or HPLC.
  • the crude product (15) is obtained in the form of a dark brown oil.
  • the sample is prepared by preparing a solution of the polymer at 10 mg/ml in tetrahydrofuran. The sample is placed in an oven at 54°C for 10 minutes and then in an oscillating shaker for 60 minutes to aid dissolution. After visual inspection, the sample appears to be totally dissolved in the solvent.
  • the sample prepared was analysed using two polypore 300x7.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and detection by refractive index.
  • the sample was filtered through a 0.45 pm nylon filter, before being injected into the liguid chromatograph.
  • the standards used for the calibration are the Easi Vial narrow polystyrene (PS) standards from Agilent Technologies.
  • Polystyrene standards ranging from 2 520 000 to 162 daltons were used for the calibration.
  • the system is eguipped with a PSS SECcurity 1260 Rl detector.
  • the polystyrene calibration curve was used to determine the average molecular weight.
  • the recording of the diagrams and the determination of the various molecular weights were performed by the Win GPC Unichrom 81 program.
  • This method describes the general procedure for determining the melting point of polymers by differential scanning calorimetry. This method is based on the standards ASTM E791 and ASTM D 34182 and the DSC calibration is performed according to standard ASTM E 9672.
  • the solvent was then removed by vacuum distillation, 1 g of dilauryl peroxide was then added and the reaction was continued for 60 minutes at 110°C. The step was repeated. The mixture was then cooled to 90°C, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.
  • the solvent was then removed by vacuum distillation, 1 g of dilauryl peroxide was then added and the reaction was continued for 60 minutes at 125°C. The step was repeated. The mixture was then cooled to 90°C, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.
  • solubility of merocyanine in the oily solutions can be evaluated macroscopically and/or microscopically. It is considered that the merocyanine is soluble if, at ambient temperature, the solution appears to the eye to be clear and translucent, and it does not have any visible crystals under a whitelight or polarized-light microscope (objective *20 to *40).
  • the solubility is evaluated macroscopically. It is evaluated at ambient temperature, on the day the solution is prepared and then over time. During this time period, the solutions are stored at ambient temperature or at 4°C.
  • compositions described in Examples 1 and 9 are prepared in the following way: the screening agents and the oils are introduced successively into a container, before being stirred by means of a magnetic stirrer and being heated at from 80 to 90°C for between 10 min and 1 hour, until the merocyanine has dissolved.
  • the aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained.
  • Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained.
  • Phase B2 is then introduced at 75°C, and then phase B3 at 65°C.
  • the emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 min at 65°C.
  • Phase C is then introduced at 55°C and the mixture is left to homogenize for 5 minutes.
  • Phase D is then introduced at 25°C.
  • the aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained.
  • Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained.
  • Phase B2 is then introduced at 65°C.
  • the emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes at 65°C.
  • the emulsion is then cooled to 35°C, while maintaining stirring, and then phase C is introduced (stirring for 10 minutes).
  • Phase D is then added, then phase E, with stirring.
  • phase F is introduced at 25°C.
  • the final emulsion is characterized by drops of 1 pm to 20 pm.
  • aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained.
  • Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained.
  • phase B2 is added and then phase B3 at65°C.
  • the emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes at 65°C.
  • the emulsion is then cooled to 25°C, while maintaining stirring, and then phase C is introduced.
  • the final emulsion is characterized by drops of 1 pm to 20 pm.

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Abstract

The present invention relates to a composition, in particular a cosmetic or dermatological composition, comprising: a) at least one merocyanine corresponding to either of formulae (1) and (2) below or one of the geometric isomer forms, in particular E/E or E/Z geometric isomer forms, thereof: (Formula (1) and Formula (2)) and b) at least one oily phase comprising at least one ester of C2-C22 di- or tricarboxylic acid and of C1-C24 alcohols. 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 as defined above.

Description

Description
Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester
The present invention relates to a composition, preferably a cosmetic or dermatological composition, comprising at least one merocyanine of formula (1 ) or (2) that will be defined below in detail and at least one oily phase comprising at least one ester of a di- or tricarboxylic acid and of C1-C24 alcohols.
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.
The invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
The invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
It is known that radiation with a wavelength of between 280 nm and 400 nm allows tanning of the human epidermis and that radiation with a wavelength of between 280 and 320 nm, known under the name UVB rays, harms the development of a natural tan. Exposure is also liable to induce impairment of the biomechanical properties of the epidermis, which is reflected by the appearance of wrinkles, leading to premature ageing of the skin.
It is also known that UVA rays with wavelengths of between 320 and 400 nm penetrate more deeply into the skin than UVB rays. UVA rays cause immediate and persistent browning of the skin. Daily exposure to UVA rays, even of short duration, under normal conditions can result in damage to the collagen fibres and the elastin, which is reflected by a modification of the microrelief of the skin, the appearance of wrinkles and uneven pigmentation (liver spots, heterogeneity of the complexion).
Protection against UVA and UVB radiation is therefore necessary. An effective photoprotective product must protect against both UVA and UVB radiation.
Many photoprotective compositions have been proposed to date to overcome the effects induced by UVA and/or UVB radiation. They generally contain organic UV-screening agents and/or inorganic UV-screening agents, which function according to their own chemical nature and according to their own properties by absorption, reflection or scattering of the UV radiation. They generally contain mixtures of liposoluble organic screening agents and/or of water-soluble UV-screening agents combined with metal oxide pigments such as titanium dioxide or zinc oxide.
Many cosmetic compositions intended to limit darkening of the skin, and to improve the colour and uniformity of the complexion have been proposed to date. It is well known in the field of antisun products that such compositions can be obtained by using UV-screening agents, and in particular UVB- screening agents. Some compositions may also contain UVA-screening agents. This screening system must cover UVB protection for the purpose of limiting and controlling the neosynthesis of melanin promoting overall pigmentation, but must also cover UVA protection in order to limit and control the oxidation of the already existing melanin resulting in darkening of the skin colour.
However, it is extremely difficult to find a composition containing a particular combination of UV-screening agents that would be specially suitable for photoprotection of the skin and particularly for an improvement in the quality of the skin both in terms of the colour and in terms of its mechanical elasticity properties. Advantageously, this improvement is particularly desired on skin that is already pigmented, for the purpose of not increasing either the pigmentary melanin load or the structure of the melanin already present within the skin.
In fact, the majority of organic UV-screening agents consist of aromatic compounds which absorb in the wavelength range between 280 and 370 nm. In addition to their solar radiation-screening capacity, the desired photoprotective compounds must also have good cosmetic properties, good solubility in the usual solvents and in particular in fatty substances such as oils, and also good photostability alone or in combination with other UV-screening agents. They must also be colourless or at least have a colour that is cosmetically acceptable for consumers.
One of the main drawbacks known to date of these compositions is that these screening systems have insufficient efficiency against UV radiation and particularly against long UVA radiation with a wavelength above 370 nm with the aim of controlling light-induced pigmentation and the evolution thereof by means of a system which screens out UV radiation over the whole of the UV spectrum.
Among all the compounds that have been recommended for this purpose, an advantageous family of UV-screening agents which is constituted of carbonated merocyanine derivatives has been proposed, which is described in patent US 4 195 999, application WO 2004/006878 and document IP COM Journal 4 (4), 16 No. IPCOM000011179D published on 04/03/2004. These compounds have very good screening properties in the long UVA radiation range, but have poorly satisfactory solubility in the usual solvents and in particular in fatty substances such as oils, and an unsatisfactory photostability for some merocyanines.
With the aim of searching for other merocyanines which have better solubility in the usual solvents and better photostability, application WO 2013/011094 has proposed merocyanines comprising polar groups constituted of hydroxyl and ether functions, which show good long UVA- screening efficiency. However, the oil-solubility of these particular merocyanines is still not entirely satisfactory, and often requires a fastidious formulating process. Moreover, the large amounts of solvent that are required in order to dissolve this type of merocyanine may lead to cosmetic unpleasantness such as a tacky and greasy effect on application.
There thus remains the need to improve the solubility of these merocyanines in photoprotective formulations comprising at least one oily phase, while still obtaining good cosmeticity.
The applicant has discovered, surprisingly, that by using esters of di- or tricarboxylic acids and of C1-C24 alcohols, it was possible to substantially improve the solubility of these merocyanines in an oily phase. This discovery forms the basis of the present invention.
Therefore, in accordance with one of the subjects of the present invention, there is now proposed a composition, in particular a cosmetic or dermatological composition, comprising at least one merocyanine of formula (1 ) or (2) that will be defined below in detail and at least one oily phase comprising at least one ester of C2-C22 di- or tricarboxylic acids and of C1-C24 alcohols.
Moreover, there also remains the need to improve the solubility of merocyanines in the presence of organic screening agents. Indeed, the addition of additional screening agents can destabilize compositions comprising a merocyanine.
The applicant has discovered, surprisingly, that by using esters of C2- C22 di- or tricarboxylic acids and of C1-C24 alcohols, it was possible to substantially improve the solubility of these merocyanines in an oily phase, even in the presence of additional organic UV-screening agents.
The applicant has also discovered that the use of these solvents made it possible to obtain good cosmeticity of the composition comprising the merocyanines, said composition being in particular non-greasy and non-tacky.
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. The invention also relates to a non-therapeutic cosmetic process for limiting the darkening of the skin and/or improving the colour and/or uniformity of the complexion, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
The invention also relates to a non-therapeutic cosmetic process for preventing and/or treating the signs of ageing of a keratin material, comprising the application, to the surface of the keratin material, of at least one composition as defined previously.
Other characteristics, aspects and advantages of the invention will become apparent on reading the detailed description which follows.
The composition according to the invention is intended for topical application and thus contains a physiologically acceptable medium. The term “physiologically acceptable medium” means here a medium that is compatible with keratin materials.
In the context of the present invention, the term “keratin material” notably means the skin, the scalp, keratin fibres such as the eyelashes, the eyebrows, head hair, bodily hair, the nails, and mucous membranes such as the lips, and more particularly the skin and the mucous membranes (of the body, face, area around the eyes, eyelids, lips, preferably of the body, face and lips).
In the text which follows, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”.
Moreover, the expressions “at least one” and “at least” used in the present description are equivalent to the expressions “one or more” and “greater than or equal to”, respectively.
According to the invention, the term "preventing" or "prevention" is intended to mean reducing the risk of occurrence or slowing down the occurrence of a given phenomenon, namely, according to the present invention, the signs of ageing of a keratin material. MEROCYANINES
According to the present invention, the merocyanine compounds in accordance with the invention correspond to formula (1 ) or (2) below:
[Formula 1 ] in which:
Ri and R2, independently of each other, are hydrogen; a C1-C22 alkyl group, a C2-C22 alkenyl group, or a C2-C22 alkynyl group, these groups possibly being substituted with at least one hydroxyl group or else interrupted with at least one -O-; or else R1 and R2 form, together with the nitrogen atom which links them, a -(CH2)n- ring which may be optionally interrupted with -0- or -NH-;
R3 is a -(C=O)ORe group; or a -(CO)NHRe group;
Re is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being substituted with one or more OH;
R4 and R5 are hydrogens; or R4 and R5 form a -(CH2)n- ring which may be substituted with a C1-C4 alkyl group and/or interrupted with one or more -0- or with -NH-; n is a number between 2 and 7;
R7 and Rs, independently of each other, are hydrogen; a C1-C22 alkyl group, a C2- C22 alkenyl group, a C2-C22 alkynyl group, said groups possibly being interrupted with one or more 0 and/or substituted with one or more OH; a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more -O-; or else R7 and Rs form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with one or more -O-;
R9 and R10 are hydrogen; or R9 and R10 form a -(CH2)n- ring potentially substituted with a C1-C4 alkyl and/or interrupted with an -0- or -NH-;
A is -O-; or -NH;
R11 is a C1-C22 alkyl group; a C2-C22 alkenyl group; a C2-C22 alkynyl group; a C3- C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more O; or a C1-C22 alkyl group or a C2-C22 alkenyl group which is substituted with a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said C3-C22 cycloalkyl group or C3-C22 cycloalkenyl group possibly being interrupted with one or more -O-.
Preferably, the compounds of formula (1 ) or (2) have the following characteristics:
(I) at least one of the groups R1, R2 or Re is substituted with a hydroxyl;
(II) if one of the R1 denotes a hydroxyethyl, R2 does not denote a hydrogen, a methyl or an ethyl or a hydroxyethyl; and if R1 denotes hydrogen, R2 is not 1- hydroxy-3-methylbut-2-yl;
(III)if Re is substituted with one or more OH, one from among R1 and R2 is a C4-C22 alkyl group; or else R1 and R2 form, together with the nitrogen to which they are bonded, a piperidyl or morpholinyl radical;
(IV) at least one from among the radicals R7, Rs and Rn is interrupted with one or more -0-
The preferred compounds are those of formula (1 ) or (2) in which:
R1 and R2, independently of each other, are hydrogen; a C4-C12 alkyl group; or a C3-C12 hydroxyalkyl group; or at least one of R1 or R2 is a C3-C12 hydroxyalkyl; and
R3, R4 and R5 have the same meanings indicated previously.
The preferred compounds are also those of formula (1 ) in which: Re is a C1-C12 alkyl group, which may be potentially substituted with one or more hydroxyls.
The compounds which are the most preferential are also those of formula (1 ), in which:
Re is a C1-C12 alkyl group, which may be substituted with one or more hydroxyls; one of the radicals R1 or R2 is a C4-C22 alkyl group; or else R1 and R2 form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with - 0- and/or -NH-; and
R4 and R5 and n have the same meanings indicated previously.
The preferred compounds are those of formula (2) in which:
R11 is a -(CH2)m-O-R-i2 radical, in which
R12 is a C1-C12 alkyl group; or a C-i-Ce alkoxy-C-i-Ce alkyl group; m is a number from 1 to 5; and
R7, Rs, R9, R10 and A have the same meanings indicated previously.
The compounds that are even more preferential are those of formula (1 ) or (2), in which:
R1 and R2, on the one hand, and R7 and Rs, 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 formula (1 ) and (2) in which:
R4 and R5 and R9 and R10 respectively form a carbon-based ring which contains 6 carbon atoms.
The compounds which are the most preferential are those of formula (1 ), in which:
R1 and R2, independently of each other, are a hydrogen; or a C1-C22 alkyl group; or a C1-C22 hydroxyalkyl group; or R1 and R2 form, together with the nitrogen to which they are bonded, a piperidyl or morpholinyl radical;
R3 is a -(C=O)ORe group; or a -(CO)NHRe group;
Re is a C1-C22 alkyl group, which may be substituted with one or more -OH; R4 and R5 are a hydrogen; or R4 and R5 are linked together to form a carbon-based ring which contains 6 carbon atoms.
The compounds which are the most preferential are those of formula (1 ), in which:
R1 and R2, independently of each other, are a hydrogen; or a C1-C22 hydroxyalkyl group; in which at least one of the radicals R1 and R2 is a C1-C22 hydroxyalkyl group;
R3 is a -(C=O)ORe group; or a -(C=O)NHRe group;
Re is a C1-C22 alkyl group; and
R4 and R5 are hydrogens; or R4 and R5 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
The compounds which are the most preferential are those of formula (2), in which:
R7 and Rs, independently of each other, are a hydrogen or a C-i-Ce alkyl group, which may be interrupted with one or more -O-;
A is -0- or -NH;
R11 is a C1-C22 alkyl; and
R9 and R10 are a hydrogen; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
The compounds which are the most preferential are those of formula (2), in which:
R7 and Re form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
A is -O- or -NH;
R11 is a C1-C22 alkyl group, which may be interrupted with one or more -O-; and
R9 and R10 are hydrogens; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
The compounds which are even more preferential are those of formula (2), in which:
R11 is a -(CH2)m-O-Ri2 radical, in which R12 is a C1-C4 alkyl group; or a C1-C4 alkoxy-Ci-C4 alkyl group; m is a number from 1 to 3; and
R7 and Rs, independently of each other, are a hydrogen; a C1-C12 alkyl group, which may be interrupted with one or more O; or R7 and Rs form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
R9 and R10 are hydrogens or together form a carbon-based ring which contains 6 carbon atoms; and
A is -O- or -NH.
The merocyanine compounds of the invention may be for example in the E/E, E/Z or Z/Z geometric isomer form.
The alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl chains may be linear or branched, monocyclic or polycyclic chains.
A C1-C22 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- bis(tert-amyl)phenoxy]propyl, ethoxycarbonylmethyl-2-(2- hydroxyethoxy)ethyl or 2-fury lethy I .
A hydroxy-substituted alkyl group is, for example, a hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxydecyl.
A C2-C22 alkenyl group is, for example, a linear C2-C12 alkenyl chain or preferentially a branched C3-C12 alkenyl chain. A C2-C22 alkenyl is, for example, a 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 various isomers of hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
A C3-C12 cycloalkyl group is, for example, a cyclopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or, preferentially, a cyclohexyl. Examples of merocyanines according to the present invention are listed in Table 1 :
[Table 1]
According to a particularly preferred form of the invention, use will be made of a family of merocyanines corresponding to formula (3) below, and also the geometric isomer forms, in particular the E/E or E/Z geometric isomer forms, thereof:
[Formula 3] in which:
A is -0- or -NH;
R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0.
The merocyanine compounds of the invention may be in the E/E- or E/Z geometric isomer forms thereof:
[formula 4]
[formula 5] 1
The compounds of formula (3) that are even more preferential are those in which:
A is -O-; R is a C1-C22 alkyl, which may be interrupted with one or more 0.
Among the compounds of formula (3), use will be made more particularly of those chosen from the following group and also the geometric isomer forms, in particular the E/E or E/Z geometric isomer forms, thereof: [Table 2]
According to a more particularly preferred embodiment of the invention, use will be made of the compound 2-ethoxyethyl (2Z)-cyano{3-[(3- methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate (25) in its E/E and/or E/Z geometric configuration.
The E/Z form has the following structure:
[formula 6]
The E/E form has the following structure:
[formula 7]
The screening merocyanines in accordance with the invention may be present in the compositions according to the invention in a concentration ranging from 0.1 % to 15% by weight, and preferentially from 0.2% to 10% by weight and even better still from 0.5% to 5% by weight relative to the total weight of the composition.
The compounds of formulae (1 ) and (2) and especially of formula (3) may be prepared according to known processes, as described, for example, in J. Org. Chem. USSR (English Translation) 26(8), page 1562f (1990); J. Heterocycl. Chem. 33(3), pages 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11 , pages 1537-1543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, pages 397-404 (1982); Chem. Heterocycl. Comp. (English Translation) 24(8), 914-919 (1988) and in Synthetic Communications Vol. 33, No. 3, 2003, pages 367-371.
The synthesis of the compounds used in the present invention is also described in US 2003/0181483A1 , WO 02/34710, 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:
[formula 8]
CH-acid vinylogenic compounds are reacted with amide acetals.
In J. Heterocyclic Chem., 27, 1990, 1143-1151 , aminoacrylic acid esters or aminoacrylonitriles are reacted with ethoxym ethylenecyanoacetates in ethanol to form the corresponding compounds of the present invention. The compounds of formula (1 ) or (2) in which R4 and R5, on the one hand, or R9 and R10, on the other hand, together form a carbocyclic ring containing 6 carbon atoms, respectively, may be prepared according to the protocols described in patent application WO 2007/071582, in IP.com Journal (2009), 9(5A), 29-30 IPCOM000182396D under the title “Process for producing 3- amino-2-cyclohexan-1-ylidene compounds” and in US-A-4,749,643 on col. 13, line 66 - col. 14, line 57 and the references cited in this regard.
In particular, the compounds of formula (3), such as compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1 - ylidenejethanoate (25) can be synthesized according to the synthesis scheme described in the publication by B. Winkler et al., Tetrahedron Letters, 55 (2014) 1749-1751 , which is intitled « A cyclic merocyanine UV- A absorber : mechanism of formation and crystal structure », and shown below, for the compounds of formula (3) : [formula 8 bis]
And more particularly, for compound 25 described in table 1 : [formula 8 ter]
DI- OR TRICARBOXYLIC ACID ESTERS
The composition in accordance with the invention comprises at least one ester of C2-C22 di- or tricarboxylic acid and of C1-C24 alcohols.
The C2-C22 di- or tricarboxylic acids are in particular chosen from citric acid, malic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, tartaric acid, isocitric acid, and mixtures thereof. The acids are preferably citric acid and adipic acid, and even more preferentially the acid is citric acid.
The C1-C24 alcohols are not oxyalkylenated. They may be aliphatic, cyclic or aromatic, having from 1 to 24 carbon atoms. They are in particular chosen from phenol, benzyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, methanol, ethanol, propanol, n-butanol, t-butanol, pentanol and hexanol. Preferably, the alcohol(s) is/are C-i-Ce alcohol(s) and can be chosen from methanol, ethanol, propanol, n-butanol, t-butanol, pentanol, hexanol, and even more preferentially the alcohol is ethanol.
The ester(s) of C2-C22 di- or tricarboxylic acid and of C1-C24 alcohols can be mono- or polyesterified.
Monoesterified is understood to mean that only one of the two or three carboxylic acid functions is esterified. Polyesterified is understood to mean that at least two carboxylic acid functions are esterified.
The di- or tricarboxylic acid can be esterified with a number of different alcohols. It is preferably esterified with just one alcohol. According to a particular embodiment of the invention, the composition comprises at least one ester of C3-C22 tricarboxylic acid and of C1-C24, preferably C-i-Ce, alcohols. This/these ester(s) can be mono-, di- or triesterified.
Monoesterified is understood to mean that only one of the three carboxylic acid functions is esterified. Diesterified is understood to mean that two of the three carboxylic acid functions are esterified. Triesterified is understood to mean that all three carboxylic acid functions are esterified.
According to a particular embodiment of the invention, the ester(s) of C3- C22 tricarboxylic acid and of C-i-Ce alcohols are triesterified.
According to a particular embodiment of the invention, the ester(s) of C3- C22 tricarboxylic acid and of C-i-Ce alcohols are chosen from the compounds of formula (9) below:
(RIO-CO)CH2-C(R)(OC-OR2)-CH2(OC-OR3) in which:
R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon- based group having from 1 to 6 carbon atoms;
R represents a hydrogen atom or a hydroxyl radical.
According to a preferred embodiment, R1, R2 and R3 represent, independently of each other, a hydrogen atom or a linear or branched, substituted or unsubstituted, preferably unsubstituted, C-i-Ce alkyl radical, and in particular a radical chosen from methyl, ethyl, propyl, n-butyl, t-butyl, pentyl and hexyl radicals. Preferably, R1, R2 and R3 are chosen, independently of each other, from a hydrogen atom and methyl, ethyl, propyl, n-butyl and t-butyl radicals.
According to a preferred embodiment of the invention, the radicals R1, R2 and R3 are identical and are chosen from C-i-Ce, preferably C1-C4, alkyl radicals and even more preferentially are ethyl radicals.
According to a preferred embodiment of the invention, R represents a hydroxyl radical. According to a particular embodiment of the invention, the ester of tricarboxylic acid and of C-i-Ce alcohols has the following formula:
[Formula 10]
As an example of an ester of C3-C22 tricarboxylic acid and of C1 -C6 alcohols of formula (10) and having the INCI name TRIETHYL CITRATE, mention will be made of the product sold under the name CITROFOL Al EXTRA by Jungbunzlauer.
The esters of di- or tricarboxylic acid and of C1 -C24 alcohols as defined above are generally present in the composition according to the invention in concentrations ranging from 0.1 % to 98% by weight, more particularly from 0.5% to 50% by weight, preferably from 1 % to 20% by weight, and even more preferentially from 1 % to 15% by weight, better still from 1 % to 10% by weight, relative to the total weight of the composition.
According to one particular embodiment, the composition according to the invention comprises : a) at least one merocyanine corresponding to formula (3) below, and also the geometric isomer forms, notably the E/E- or E/Z-geometric isomer forms, thereof:
[Formule 3] in which :
A is -O- or -NH; R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0 ; and b) at least one ester of tricarboxylic acid and of C-i-Ce alcohols having the following formula:
(RIO-CO)CH2-C(R)(OC-OR2)-CH2(OC-OR3) in which:
R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon- based group having from 1 to 6 carbon atoms;
R represents a hydrogen atom or a hydroxyl radical.
According to a preferred embodiment, the composition according to the invention comprises : a) at least one merocyanine corresponding to formula (3) below, and also the geometric isomer forms, notably the E/E- or E/Z-geometric isomer forms, thereof:
[Formule 3] in which :
A is -0- or -NH;
R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0 ; and b) the ester of tricarboxylic acid and of C-i-Ce alcohols has the following formula: [Formula 10]
ADDITIONAL ACRYLIC POLYMER According to a particular embodiment of the invention, the composition comprises at least one polymer comprising monomer units of formulae (A) and (B) defined below:
[formula A] [formula B] in which:
R1 , independently at each instance, is chosen from alkyl or alkylene radicals, and at least 60% by weight of the Ri groups are radicals chosen from stearyl and behenyl radicals, the percentage by weight relating to the sum of all the Ri groups present in the polymer, and the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the Ri group ranges from 1 :30 to 1 :1 , and the sum of the total of units A and B is at least 95% by weight relative to the total weight of the polymer. Preferably, Ri is constituted of alkyl radicals, preferably of C16-C22 alkyl radicals, and more preferentially of stearyl (Cis) radicals or of behenyl (C22) radicals.
Preferably, at least 70% by weight of the groups R1 are stearyl or behenyl radicals, preferentially at least 80% by weight and more preferentially at least 90% by weight.
According to a preferred embodiment, all the R1 groups are behenyl radicals.
According to another preferred embodiment, all the R1 groups are stearyl radicals.
Preferably, said weight ratio ranges from 1 :15 to 1 :1 and preferentially ranges from 1 :10 to 1 :4.
Advantageously, the polymer units present in the polymer consist of the units (A) and (B) previously described.
The polymer has a number-average molecular weight Mn ranging from 2000 to 9000 g/mol, preferably ranging from 5000 to 9000 g/mol. The numberaverage molecular weight may be measured via the gel permeation chromatography method, for example according to the method described in the example hereinbelow.
Preferably, the polymer has a melting point ranging from 40°C to 70°C and preferentially ranging from 45°C to 67°C. The melting point is measured by differential scanning calorimetry (DSC), for example according to the method described in the example hereinbelow.
According to a first embodiment, when the polymer is such that at least 60% by weight of the groups R1 are stearyl radicals, then the polymer preferably has a melting point ranging from 40 to 60°C, and preferentially ranging from 45 to 55°C.
According to a second embodiment, when the polymer is such that at least 60% by weight of the groups R1 are behenyl radicals, then the polymer has a melting point ranging from 60°C to 70°C, and preferentially ranging from 63°C to 67°C.
The polymer used according to the invention can be prepared by polymerization of a monomer of formula CH2=CH-C00-R-I, RI having the meaning previously described, and of 2- hydroxyethyl acrylate.
The polymerization may be performed according to known methods, such as solution polymerization or emulsion polymerization.
The polymerization is, for example, described in document US 2007/0264204.
The acrylic polymer(s) as defined previously can be present in the composition according to the invention in a content of active material ranging from 0.05% to 10% by weight, relative to the total weight of the composition, preferably ranging from 0.1 % to 5% by weight and better still ranging from 0.2% to 3% by weight.
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 of the liposoluble and lipophilic ingredients and the fatty substances used for the formulation of the compositions of the invention.
The term "oil" is intended to mean any fatty substance that is in liquid form at ambient temperature (20-25°C) and atmospheric pressure (760 mmHg).
The oily phase may comprise, in addition to the merocyanine screening agent(s) and optionally the lipophilic additional screening agents and the ester(s) of di- or tricarboxylic acid according to the invention, at least one volatile or non-volatile hydrocarbon-based oil and/or one volatile and/or nonvolatile silicone oil and/or one volatile and/or non-volatile fluoro oil.
For the purposes of the present invention, the term "silicone oil" is understood to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group.
The term "hydrocarbon-based oil" is intended to mean an oil mainly containing 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, hydroxyl functions.
The term "fluoro oil" is intended to mean an oil comprising at least one fluorine atom.
For the purposes of the invention, the term "volatile oil" is intended to mean an oil that is capable of evaporating on contact with the skin or the keratin fibre in less than one hour, at ambient temperature and atmospheric pressure. The volatile oil(s) of the invention are volatile cosmetic oils, which are liquid at ambient temperature, having a non-zero vapour pressure, at ambient temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
The term "non-volatile oil" is understood to mean an oil which remains on the skin or the keratin fibre, at ambient temperature and atmospheric pressure, for at least several hours and which has in particular a vapour pressure of less than 10’3 mmHg (0.13 Pa).
Hydrocarbon-based oils
As non-volatile hydrocarbon-based oils that may be used according to the invention, mention may notably be made of:
(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C4 to C24, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheatgerm oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil and musk rose oil; or else caprylic/capric acid triglycerides, such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;
(ii) synthetic ethers containing from 10 to 40 carbon atoms; (iii) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene, such as Parleam, squalane and mixtures thereof;
(iv) synthetic esters, such as the oils of formula RCOOR' in which R represents a linear or branched fatty acid residue comprising from 1 to 40 carbon atoms and R' represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms, with the proviso that R + R' > 10, for instance Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by the company Witco orTegosoft TN® by the company Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under the name X- Tend 226® by the company ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate such as the product sold under the name Dub Dis by the company Stearineries Dubois, alcohol or polyalcohol octanoates, decanoates or ricinoleates, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as linear C12-C13 dialkyl tartrates, such as those sold under the name Cosmacol ETI® by the company Enichem Augusta Industriale, and also linear C14-C15 dialkyl tartrates such as those sold under the name Cosmacol ETL® by the same company; acetates;
(v) fatty alcohols that are liquid at ambient temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2- butyloctanol or 2-undecylpentadecanol;
(vi) C12-C22 higher fatty acids, such as oleic acid, linoleic acid or linolenic acid;
(vii) carbonates, such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC® by the company Cognis; and mixtures thereof.
Among the non-volatile hydrocarbon-based oils that may be used according to the invention, preference will be given more particularly to glyceride triesters and in particular to caprylic/capric acid triglycerides, synthetic esters and in particular diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2-ethylphenyl benzoate and fatty alcohols, in particular octyldodecanol. Preferably, the non-volatile hydrocarbon-based oils are chosen from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate and dicaprylyl carbonate.
As volatile hydrocarbon-based oils that may be used according to the invention, mention may be made in particular of hydrocarbon-based oils containing from 8 to 16 carbon atoms and in particular of branched Cs-C alkanes, such as Cs-C isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2, 2, 4,4,6- pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched Cs-C esters, isohexyl neopentanoate, and mixtures thereof.
Mention may also be made of the alkanes described in the Cognis patent applications WO 2007/068371 or WO 2008/155059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, which are themselves obtained from coconut kernel or palm oil. Mention may be made of the mixtures of n-undecane (Cn) and n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155059 from the company Cognis. Mention may also be made of n-dodecane (C12) and n-tetradecane (Cu) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97®, and also mixtures thereof.
Other volatile hydrocarbon-based oils, for instance petroleum distillates, in particular those sold under the name Shell Solt® by the company Shell, may also be used. According to one embodiment, the volatile solvent is chosen from volatile hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures thereof.
Silicone oils
The non-volatile silicone oils may be notably chosen from non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes including alkyl or alkoxy groups which are pendent and/or at the end of the silicone chain, these groups each containing from 2 to 24 carbon atoms, or phenyl silicones, such as phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxysilicates.
Examples of volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, in particular those with a viscosity < 8 centistokes (8x1 O’6 m2/s) and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
Mention may also be made of the volatile linear alkyltrisiloxane oils of general formula below:
[formula 11 ] wherein R represents an alkyl group containing from 2 to 4 carbon atoms and of which one or more hydrogen atoms may be substituted with a fluorine or chlorine atom.
Among the oils of general formula (11 ), mention may be made of:
3-buty 1-1 ,1 ,1 ,3,5,5,5-heptamethyltrisiloxane,
3-propyl-1 ,1 ,1 ,3,5,5,5-heptamethyltrisiloxane, and
3-ethy 1-1 ,1 ,1 ,3,5,5,5-heptamethyltrisiloxane, corresponding to the oils of formula (9) for which R is, respectively, a butyl group, a propyl group or an ethyl group.
Fluoro oils
Use may also be made of volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof.
An oily phase according to the invention may also comprise other fatty substances, mixed with or dissolved in the oil.
Another fatty substance that may be present in the oily phase may be, for example:
- a fatty acid chosen from fatty acids including 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, rice bran wax, paraffin waxes, lignite waxes, microcrystalline waxes, ceresin or ozokerite, or synthetic waxes, such as polyethylene waxes or Fischer-Tropsch waxes;
- a gum chosen from silicone gums (dimethiconol);
- a pasty compound, such as polymeric or non-polymeric silicone compounds, esters of a glycerol oligomer, arachidyl propionate, fatty acid triglycerides and derivatives thereof;
- and mixtures thereof.
Preferentially, 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 preferentially from 10% to 80% by weight, relative to the total weight of the composition.
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 that is suitable for use in the invention may comprise, for example, a water chosen from a natural spring water, such as water from La Roche-Posay, water from Vittel, water from Saint Gervais Mont Blanc or waters from Vichy, or a floral water.
The water-soluble or water-miscible solvents that are suitable for use in the invention comprise short-chain monoalcohols, for example C1-C4 monoalcohols, 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, use may more particularly be made of ethanol, propylene glycol, glycerol, and mixtures thereof.
According to one 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 preferentially from 10% to 80% by weight, relative to the total weight of the composition.
ADDITIVES
Additional UV-screeninq agents
The compositions according to the invention may also contain one or more additional UV-screening agents chosen from hydrophilic, lipophilic or insoluble organic UV-screening agents and/or one or more mineral pigments. It will preferentially be constituted of at least one hydrophilic, lipophilic or insoluble organic UV-screening agent.
The term "hydrophilic UV-screening agent" is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid aqueous phase or else which can be dissolved in colloidal form (for example in micellar form) in a liquid aqueous phase.
The term "lipophilic screening agent" is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation, which can be fully dissolved in molecular form in a liquid fatty phase or else which can be dissolved in colloidal form (for example in micellar form) in a liquid fatty phase.
The term "insoluble UV-screening agent" is intended to mean any cosmetic or dermatological organic or inorganic compound for screening out UV radiation which has a solubility in water of less than 0.5% by weight and a solubility of less than 0.5% by weight in the majority of organic solvents such as liquid paraffin, fatty alcohol benzoates and fatty acid triglycerides, for example Miglyol 812® sold by the company Dynamit Nobel. This solubility, determined at 70°C, is defined as the amount of product in solution in the solvent at equilibrium with an excess of solid in suspension after returning to ambient temperature. It may be readily evaluated in the laboratory.
The additional organic UV-screening agents are chosen in particular from cinnamic compounds; anthranilate compounds; salicylic compounds; dibenzoylmethane compounds; benzylidenecamphor compounds; benzophenone compounds; (3, [3-diphenylacrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, in particular those cited in patent US 5 624 663; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds, as described in patents EP 669 323 and US 2 463 264; p-aminobenzoic (PABA) compounds; methylenebis(hydroxyphenylbenzotriazole) compounds, as described in patent applications US 5 237 071 , US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole compounds, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones, such as those described in particular in patent application WO 93/04665; a-alkylstyrene-based dimers, such as those described in patent application DE 198 55 649; 4,4- diarylbutadiene compounds, as described in patent applications EP 0967200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981 , and mixtures thereof.
As examples of organic photoprotective agents, mention may be made of those denoted hereinbelow under their INCI name.
Cinnamic compounds:
Ethylhexyl methoxycinnamate sold in particular under the trade name Parsol MCX® by DSM Nutritional 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 Nutritional 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 llvinul 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. Diphenyl acrylate compounds:
Octocrylene, sold in particular under the trade name llvinul N 539® by BASF, Etocrylene, sold in particular under the trade name llvinul 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, as a mixture with octyl methoxycinnamate, under the trade name Uvinul A Plus B® by the company BASF,
1 , 1'-(1 ,4-Piperazinediyl)bis[1 -[2-[4-(diethylamino)-2- hydroxybenzoyl]phenyl]methanone] (CAS 919803-06-8), as described in patent application WO 2007/071 584; this compound advantageously being used in micronized form (mean size of 0.02 to 2 pm), which may be obtained, for example, according to the micronization process described in patent applications GB-A-2 303 549 and EP-A-893 119, and in particular in the form of an aqueous dispersion.
Benzylidenecamphor 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.
Phenylbenzimidazole compounds:
Phenylbenzimidazole Sulfonic Acid, sold in particular under the trade name Eusolex 232® by Merck.
Bisbenzazolyl compounds:
Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name Neo Heliopan AP® by Haarmann and Reimer.
Phenylbenzotriazole compounds:
Drometrizole Trisiloxane, sold under the name Silatrizole® by Rhodia Chimie.
Methylenebis(hydroxyphenylbenzotriazole) 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 with a mean particle size ranging from 0.01 to 5 pm, more preferentially from 0.01 to 2 pm and more particularly from 0.020 to 2 pm, with at least one alkylpolyglycoside surfactant having the structure CnH2n+iO(C6Hio05)xH, in which n is an integer from 8 to 16 and x is the mean degree of polymerization of the (CeH Os) unit and ranges from 1 .4 to 1 .6, as described in patent GB-A-2 303 549, sold in particular under the trade name Tinosorb M® by BASF, or in the form of an aqueous dispersion of micronized particles with a mean particle size ranging from 0.02 to 2 pm, more preferentially from 0.01 to 1.5 pm and more particularly from 0.02 to 1 pm, in the presence of at least one polyglyceryl mono(C8-C2o)alkyl ester with a degree of glycerol polymerization of at least 5, such as the aqueous dispersions described in patent application WO 2009/063392.
Triazine compounds:
- 3,3'-(1 ,4-Phenylene)bis(5,6-diphenyl-1 ,2,4-triazine), with the INCI name Phenylene bis-diphenyltriazine, and having the following chemical structure:
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, sold under the trade name Tinosorb S® by BASF,
- Ethylhexyl Triazone sold in particular under the trade name llvinul T 150® by BASF,
- Diethylhexyl Butamido Triazone, sold under the trade name Uvasorb HEB® by Sigma 3V,
- 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine,
- 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine,
- 2,4-bis(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,
- 2,4-bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s- triazine,
- symmetrical triazine screening agents substituted with naphthalenyl groups or polyphenyl groups described in patent US 6 225 467, patent application WO 2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives", IP.COM IPCOM000031257 Journal, INC West Henrietta, NY, US (20 September 2004), in particular 2,4,6-tris(diphenyl)triazine and 2,4,6- tris(terphenyl)triazine, which is also mentioned in patent applications WO 06/035000, WO 06/034982, WO 06/034991 , WO 06/035007, WO 2006/034992 and WO 2006/034985, these compounds advantageously being used in micronized form (mean particle size of 0.02 to 3 pm), which may be obtained, for example, according to the micronization process described in patent applications GB-A-2 303 549 and EP-A-893 119, and in particular in aqueous dispersion form,
- silicone triazines substituted with two aminobenzoate groups, as described in patent EP 0 841 341 , in particular 2, 4-bis(n-butyl 4'-aminobenzalmalonate)-6-[(3- {1 ,3,3,3-tetramethyl-1 -[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine.
Anthranilic compounds:
Menthyl anthranilate, sold under the trade name Neo Heliopan MA® by Symrise.
Imidazoline compounds:
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate.
Benzalmalonate compounds:
Polyorganosiloxane comprising 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'-dimethylpropyl)-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 under the name Uvasorb K2A® by Sigma 3V.
The preferential organic screening agents are chosen from:
Ethylhexyl Methoxycinnamate,
Ethylhexyl Salicylate,
Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3, Benzophenone-4,
Benzophenone-5, n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidene camphor,
Terephthalylidene Dicamphor Sulfonic Acid,
Disodium Phenyl Dibenzimidazole Tetrasulfonate,
Methylene bis-Benzotriazolyl Tetramethylbutylphenol,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2.4.6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine,
2.4.6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine,
2.4-Bis(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,
2.4-Bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s- triazine,
2.4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-1 -
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,
2.4.6-T ris(diphenyl)triazine,
2,4,6-T ris(terphenyl)triazine,
Drometrizole Trisiloxane,
Polysilicone-15,
1 , 1 -Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene,
2.4-Bis[5-(1-dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2- ethylhexyl)imino-1 ,3,5-triazine, and mixtures thereof.
The particularly preferred organic screening agents are chosen from:
Ethylhexyl Salicylate, Homosalate,
Butyl Methoxydibenzoylmethane,
Octocrylene, n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
Terephthalylidene Dicamphor Sulfonic Acid,
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-1 -
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,
Drometrizole Trisiloxane, and mixtures thereof.
The inorganic UV-screening agents used in accordance with the present invention are metal oxide pigments. More preferentially, the inorganic UV- screening agents of the invention are metal oxide particles with a mean elementary particle size of less than or equal to 0.5 pm, more preferentially between 0.005 and 0.5 pm, even more preferentially between 0.01 and 0.2 pm, better still between 0.01 and 0.1 pm and more particularly between 0.015 and 0.05 pm.
They may be chosen in particular from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof.
Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0 518 773. Commercial pigments that may be mentioned include the products sold by the companies Sachtleben Pigments, Tayca, Merck and Degussa.
The metal oxide pigments may be coated or uncoated.
The coated pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal alkoxides (of titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
The coated pigments are more particularly titanium oxides that have been coated:
- with silica, such as the product Sunveil® from the company Ikeda,
- with silica and iron oxide, such as the product Sunveil F® from the company Ikeda,
- with silica and alumina, such as the products Microtitanium Dioxide MT 500 SA® and Microtitanium Dioxide MT 100 SA from the company Tayca and Tioveil from the company Tioxide,
- with alumina, such as the products Tipaque TTO-55 (B)® and Tipaque TTO-55 (A)® from the company Ishihara and UVT 14/4 from the company Sachtleben Pigments,
- with alumina and aluminum stearate, such as the products Microtitanium Dioxide MT 100 T®, MT 100 TX®, MT 100 Z® and MT-01® from the company Tayca, the products Solaveil CT-10 W® and Solaveil CT 100® from the company Uniqema and the product Eusolex T-AVO® from the company Merck,
- with silica, alumina and alginic acid, such as the product MT-100 AQ® from the company Tayca,
- with alumina and aluminum laurate, such as the product Microtitanium Dioxide MT 100 S® from the company Tayca,
- with iron oxide and iron stearate, such as the product Microtitanium Dioxide MT 100 F® from the company Tayca,
- with zinc oxide and zinc stearate, such as the product BR 351® from the company Tayca,
- with 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, - with silica, alumina and aluminum stearate and treated with a silicone, such as the product STT-30-DS® from the company Titan Kogyo,
- with silica and treated with a silicone, such as the product UV-Titan X 195® from the company Sachtleben Pigments,
- with alumina and treated with a silicone, such as the products Tipaque TTO-55 (S)® from the company Ishihara or UV Titan M 262® from the company Sachtleben Pigments,
- with triethanolamine, such as the product STT-65-S from the company Titan Kogyo,
- with stearic acid, such as the product Tipaque TTO-55 (C)® from the company Ishihara,
- with sodium hexametaphosphate, such as the product Microtitanium Dioxide MT 150 W® from the company Tayca,
- TiO2 treated with octyltrimethylsilane, sold under the trade name T 805® by the company Degussa Silices,
- TiO2 treated with a polydimethylsiloxane, sold under the trade name 70250 Cardre UF TiO2SI3® by the company Cardre,
- anatase/rutile TiO2 treated with a polydimethylhydrosiloxane, sold under the trade name Micro Titanium Dioxide USP Grade Hydrophobic® by the company Color Techniques,
- TiO2 coated with triethylhexanoin, with aluminum stearate and with alumina sold under the trade name Solaveil CT-200-LQ-(WD) by Croda,
- TiO2 coated with aluminum stearate, with alumina and with silicone sold under the trade name Solaveil CT-12W-LQ-(WD) by Croda,
- TiO2 coated with lauroyl lysine sold by Daito Kasei Kogyo under the name LL 5 Titanium Dioxide CR 50,
- TiO2 coated with C9-15 fluoroalcohol phosphate and with aluminum hydroxide sold by Daito Kasei Kogyo under the name PFX-5 TiO2 CR-50.
Mention may also be made of TiO2 pigments doped with at least one transition metal such as iron, zinc or 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 also comprise one or more dispersants, for instance a sorbitan ester, for instance sorbitan isostearate, or a polyoxyalkylenated fatty acid ester of glycerol, for instance TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium oxide particles includes at least one dispersant chosen from polyoxyalkylenated fatty acid esters of glycerol. Mention may be made more particularly of the oily dispersion of TiO2 particles doped with manganese in capric/caprylic acid triglyceride in the presence of TRI-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate having the INCI name: titanium dioxide (and) TRI-PPG-3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for instance the product sold under the trade name Optisol TD50® by the company Croda.
The uncoated titanium oxide pigments are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 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 LIFTR®, by the company Tomen under the name ITS® and by the company Tioxide under the name Tioveil AQ®
The uncoated zinc oxide pigments are, for example:
- those sold under the name Z-Cote by the company Sunsmart;
- those sold under the name Nanox® by the company Elementis;
- those sold under the name Nanogard WCD 2025® by the company Nanophase Technologies.
The coated zinc oxide pigments are for example:
- those sold under the name Oxide Zinc CS-5® by the company Toshibi (ZnO coated with polymethylhydrosiloxane); - those sold under the name Nanogard Zinc Oxide FN® by the company Nanophase Technologies (as a 40% dispersion in Finsolv TN®, C12-C15 alkyl benzoate);
- those sold 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 polymethylhydrosiloxane);
- those sold under the name NFD Ultrafine ZnO® by the company Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane);
- those sold under the name SPD-Z1® by the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);
- those sold under the name Escalol Z100® by the company ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture);
- those sold under the name Fuji ZnO-SMS-10® by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane);
- those sold under the name Nanox Gel TN® by the company Elementis (ZnO dispersed at 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate).
The uncoated cerium oxide pigments may be, for example, those sold under the name Colloidal Cerium Oxide® by the company Rhone-Poulenc.
The uncoated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2002® (FE 45B®), Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ® and Nanogard WCD 2006® (FE 45R®) or by the company Mitsubishi under the name TY-220®.
The coated iron oxide pigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2008 (FE 45B FN)®, Nanogard WCD 2009® (FE 45B 556®), Nanogard FE 45 BL 345® and Nanogard FE 45 BL® or by the company BASF under the name Transparent Iron Oxide®.
Mention may also be made of mixtures of metal oxides, especially of titanium dioxide and of cerium dioxide, including the equal-weight mixture of titanium dioxide and cerium dioxide coated with silica, sold by the company Ikeda under the name Sunveil A®, and also 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 glycerol, such as the product M 211® sold by the company Sachtleben Pigments.
According to the invention, coated or uncoated titanium oxide pigments are particularly preferred.
The additional UV-screening agents according to the invention can be present in the composition according to the invention in 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 non-ionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants, basifying or acidifying agents or any other ingredient commonly used in the cosmetic and/or dermatological field.
Mention may be made, among organic solvents, of alcohols other than C1-C4 monoalkanols as defined above and in particular short-chain C2-C8 polyols, such as glycerol or diols, such as caprylyl glycol, 1 ,2-pentanediol, propanediol, butanediol, glycols and glycol ethers, such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
Mention may be made, as thickeners, of carboxyvinyl polymers, such as the Carbopols® (Carbomers) and the Pemulens, such as Pemulen TR1® and Pemulen TR2® (acrylate/C10-C30 alkyl acrylate copolymer); polyacrylamides, for instance the crosslinked copolymers sold under the names Sepigel 305® (CTFA name: polyacrylamide/Ci3-i4 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate 80) by the company SEPPIC; 2- acrylamido-2-methylpropanesulfonic acid polymers and copolymers, optionally crosslinked and/or neutralized, such as the poly(2-acrylamido-2- methylpropanesulfonic acid) sold 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 polyacryloyldimethyl taurate/polysorbate 80/sorbitan oleate); copolymers of 2- acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, such as Simulgel NS® and Sepinov EMT 10®, sold 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, polyether silicones and cationic silicones, and mixtures thereof.
Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide.
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 5.5 to 8.
Among the active agents for caring for 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 derivatives or precursors thereof, alone or as mixtures; antioxidants; free-radical scavengers; anti-pollutants; self-tanning agents; anti-glycation agents; calmatives; deodorant agents; essential oils; NO-synthase inhibitors; agents for stimulating the synthesis of dermal or epidermal macromolecules and/or for preventing degradation thereof; agents for stimulating fibroblast proliferation; agents for stimulating keratinocyte proliferation; muscle relaxants; refreshing agents; tensioning agents; mattifying agents; depigmenting agents; propigmenting agents; keratolytic agents; desquamating agents; moisturizing agents; anti-inflammatories; antimicrobials; thinning agents; agents which act on cell energy metabolism; insect repellents; substance P antagonists or CRGP antagonists; agents for preventing hair loss; antiwrinkle agents; anti-ageing agents.
Those skilled in the art will select said active agent(s) as a function of the effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
Needless to say, those skilled in the art will take care to select the optional additional compound(s) mentioned above and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisioned addition(s).
PRESENTATION FORMS
The compositions according to the invention may be prepared according to the techniques that are well known to those skilled in the art. They may in particular be in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W), such as a cream, a milk or a cream gel.
They may also be in anhydrous form, for instance in the form of an oil. The term "anhydrous composition" is intended to mean a composition containing less than 1 % by weight of water, or even less than 0.5% water, and especially 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 aerosol form and may be in the form of a mousse or a spray. In the case of compositions in the form of oil-in-water or water-in-oil emulsions, the emulsification processes that may be used are of the paddle or impeller, rotor-stator and HPH type.
In order to obtain stable emulsions with a low content of polymer (oil/polymer ratio > 25), it is possible to prepare the dispersion in concentrated phase and then to dilute the dispersion with the remainder of the aqueous phase.
It is also possible, via HPH (between 50 and 800 bar), to obtain stable dispersions with drop sizes that may be as small as 100 nm.
The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or non-ionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen in an appropriate manner according to the emulsion to be obtained (W/O or O/W emulsion).
Examples of W/O emulsifying surfactants that may be mentioned include alkyl esters or ethers of sorbitan, of glycerol, of polyol, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the name DC 5225 C® by the company Dow Coming, and alkyldimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Coming 5200 Formulation Aid by the company Dow Coming; cetyldimethicone copolyol, such as the product sold under the name Abil EM 90R® by the company Goldschmidt, and the mixture of cetyldimethicone copolyol, of polyglyceryl isostearate (4 mol) and of hexyl laurate, sold under the name Abil WE 09® by the company Goldschmidt. One or more coemulsifiers, which may be chosen advantageously from the group comprising polyol alkyl esters, may also be added thereto.
Mention may also be made of non-silicone emulsifying surfactants, in particular alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.
Polyol alkyl esters that may in particular be mentioned include polyethylene glycol esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135® by the company ICI. Examples of glycerol and/or sorbitan esters that may be mentioned include polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34® by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986® by the company ICI, and mixtures thereof.
For the O/W emulsions, examples of non-ionic emulsifying surfactants that may be mentioned include polyoxyalkylenated (more particularly polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids and of glycerol; oxyalkylenated esters of fatty acids and of sorbitan; polyoxyalkylenated (in particular polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids, optionally in combination with an ester of a fatty acid and of glycerol, such as the PEG-100 stearate/glyceryl stearate mixture sold, for example, by the company ICI under the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl glucoside and lauryl glucoside, sold, for example, by the company Henkel under the respective names Plantaren 2000® and Plantaren 1200®, cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, sold, 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, and arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and of arachidyl glucoside sold under the name Montanov 202® by the company SEPPIC. According to one particular embodiment of the invention, the mixture of the alkyl polyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, for example as described in the document WO-A-92/06778.
When it is an emulsion, the aqueous phase of this emulsion may comprise a non-ionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008). The compositions according to the invention find their application in a large number of treatments, in particular cosmetic treatments, for the skin, the lips and the hair, including the scalp, in particular for protecting and/or caring for the skin, the lips and/or the hair, and/or for making up the skin and/or the lips.
Another subject of the present invention is constituted 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, the lips, the nails, the hair, the eyelashes, the eyebrows and/or the scalp, in particular care products, antisun products and makeup products.
The cosmetic compositions according to the invention may be used, for example, as a makeup product.
Another subject of the present invention is constituted of a non- therapeutic cosmetic process for caring for and/or making up a keratin material, which consists in applying, to the surface of said keratin material, at least one composition according to the invention as defined above.
The cosmetic compositions according to the invention may be used, for example, as a care product and/or antisun product for the face and/or body, with a liquid to semi-liquid consistency, such as milks, more or less smooth creams, cream gels or pastes. They may optionally be packaged in aerosol form and may be in the form of a mousse 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 hair in the form of fine particles by means of pressurizing devices. The devices in accordance with the invention are well known to those skilled in the art and comprise non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. These devices are described in patents US 4 077 441 and US 4 850 517.
The compositions packaged in aerosol form in accordance with the invention generally contain conventional propellants, for instance hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in amounts ranging from 15% to 50% by weight relative to the total weight of the composition.
ASSEMBLY
According to another aspect, the invention also relates to a cosmetic assembly comprising: i) a container delimiting one or more compartments, said container being closed by a closing member and optionally being unsealed; and ii) a makeup and/or care composition in accordance with the invention placed inside said compartment(s).
The container may be, for example, in the form of a jar or a box.
The closing member may be in the form of a lid comprising a cap mounted so as to be able to move by translation or by pivoting relative to the container housing said makeup and/or care composition(s).
EXAMPLES
The examples that follow serve to illustrate the invention without, however, being limiting in nature. In these examples, the amounts of the composition ingredients are given as % by weight of starting materials, relative to the total weight of the composition.
Example A1: Preparation of compound (14)
[formula 14]
122.23 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 75.45 grams of ethyl cyanoacetate in approximately equimolar proportions in the presence of a base and optionally of a solvent.
The base/solvent combinations indicated in the following table are used.
[Table 3]
The completion of the alkylation reaction can be monitored for example by methods such as TLC, GC or HPLC.
162.30 grams of compound (14) are obtained in the form of a brown oil.
After crystallization, the product is obtained in the form of yellowish crystals. Melting point: 92.7°C.
Example A2: Preparation of compound (15)
[formula 15] 101.00 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 86.00 grams of 2-cyano-N-(3-methoxypropyl)acetamide in approximately equimolar proportions in the presence of a base and optionally of a solvent.
The base/solvent combinations indicated in the following table are used. [Table 4]
The crude product (15) is obtained in the form of a dark brown oil.
After silica gel column chromatography (eluent: 99/1 toluene/methanol), 81 .8 grams of product are obtained in the form of yellowish crystals.
Melting point: 84.7-85.3°C.
Example A3: Preparation of compound (27)
[formula 27]
13.09 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 10.12 grams of isobutyl cyanoacetate in the presence of a base and optionally of a solvent. The base/solvent combinations indicated in the following table are used.
[Table 5]
15.97 grams of crude product (27) are obtained in the form of a dark brown oil.
After silica gel column chromatography (eluent: toluene/acetone), 13.46 grams of product are obtained in the form of yellowish crystals.
Melting point: 96.3°C.
Example A4: Preparation of compound (25)
[formula 25]
148.4 grams of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1 -one are alkylated with dimethyl sulfate or alternatively with diethyl sulfate and treated with 130.00 grams of 2-ethoxyethyl cyanoacetate in the presence of an organic base and of a solvent. The base/solvent combinations indicated in the table below are used.
[Table 6] Example of preparation of acrylic polymers:
Determination of the molecular weight by gel permeation chromatography (GPC):
The sample is prepared by preparing a solution of the polymer at 10 mg/ml in tetrahydrofuran. The sample is placed in an oven at 54°C for 10 minutes and then in an oscillating shaker for 60 minutes to aid dissolution. After visual inspection, the sample appears to be totally dissolved in the solvent.
The sample prepared was analysed using two polypore 300x7.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, a tetrahydrofuran mobile phase and detection by refractive index. The sample was filtered through a 0.45 pm nylon filter, before being injected into the liguid chromatograph. The standards used for the calibration are the Easi Vial narrow polystyrene (PS) standards from Agilent Technologies.
Polystyrene standards ranging from 2 520 000 to 162 daltons were used for the calibration.
The system is eguipped with a PSS SECcurity 1260 Rl detector. The polystyrene calibration curve was used to determine the average molecular weight. The recording of the diagrams and the determination of the various molecular weights were performed by the Win GPC Unichrom 81 program.
Determination of the melting point by differential scanning calorimetry (or DSC):
This method describes the general procedure for determining the melting point of polymers by differential scanning calorimetry. This method is based on the standards ASTM E791 and ASTM D 34182 and the DSC calibration is performed according to standard ASTM E 9672. Behenyl acrylate/2-hvdroxyethyl acrylate copolymer (Polymer 1):
In a 4-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and an extension for two other necks, 175 g of behenyl acrylate, 25 g of 2-hydroxyethyl acrylate and 0.4 g of 2,2'-azobis(2-methylbutyronitrile) (Akzo Nobel) were added, over the course of 60 minutes at 80°C, to 40 g of isopropanol, with stirring, after having removed the oxygen from the system by means of a nitrogen flush for 20 minutes. The mixture was stirred at 80°C for 3 hours. The solvent was then removed by vacuum distillation, 1 g of dilauryl peroxide was then added and the reaction was continued for 60 minutes at 110°C. The step was repeated. The mixture was then cooled to 90°C, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.
Molecular weight: Mn = 7300 g/mol, Mw = 21 000, Mw/Mn = 2.8
Melting point: 65°C
Stearyl acrylate/2-hvdroxyethyl acrylate copolymer (Polymer 2):
In a 4-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and an extension for two other necks, 155 g of stearyl acrylate, 45 g of 2-hydroxyethyl acrylate and 0.4 g of 2,2'-azobis(2-methylbutyronitrile) (Akzo Nobel) were added, over the course of 90 minutes at 80°C, to 50 g of isopropanol, with stirring, after having removed the oxygen from the system by means of a nitrogen flush for 20 minutes. The mixture was stirred at 80°C for 3 hours. The solvent was then removed by vacuum distillation, 1 g of dilauryl peroxide was then added and the reaction was continued for 60 minutes at 125°C. The step was repeated. The mixture was then cooled to 90°C, a stream of demineralized water was added and the mixture was then stirred. The water was removed by vacuum distillation.
Molecular weight: Mn = 7500 g/mol, Mw = 19 000, Mw/Mn = 2.6
Melting point: 49°C Formulation examples
Protocol for evaluating solubility
The solubility of merocyanine in the oily solutions can be evaluated macroscopically and/or microscopically. It is considered that the merocyanine is soluble if, at ambient temperature, the solution appears to the eye to be clear and translucent, and it does not have any visible crystals under a whitelight or polarized-light microscope (objective *20 to *40).
In the examples that follow, the solubility is evaluated macroscopically. It is evaluated at ambient temperature, on the day the solution is prepared and then over time. During this time period, the solutions are stored at ambient temperature or at 4°C.
Examples 1 to 4: oily solutions The following solutions were prepared according to the process below:
[Table 7]
Examples 5 to 9:
[Table 8]
[Table 9]
Oil preparation method:
The compositions described in Examples 1 and 9 are prepared in the following way: the screening agents and the oils are introduced successively into a container, before being stirred by means of a magnetic stirrer and being heated at from 80 to 90°C for between 10 min and 1 hour, until the merocyanine has dissolved.
The results obtained show that the tricarboxylic acid ester according to the invention makes it possible to maintain the solubility of the merocyanine even in the presence of additional UV-screening agents.
Examples 10, 11 and 12: Emulsions
[Table 10]
Method for preparing emulsion 10
The aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained. Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained. Phase B2 is then introduced at 75°C, and then phase B3 at 65°C. The emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 min at 65°C. Phase C is then introduced at 55°C and the mixture is left to homogenize for 5 minutes. Phase D is then introduced at 25°C.
[Table 11 ]
Method for emulsion 11 The aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained. Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained. Phase B2 is then introduced at 65°C. The emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes at 65°C. The emulsion is then cooled to 35°C, while maintaining stirring, and then phase C is introduced (stirring for 10 minutes). Phase D is then added, then phase E, with stirring. Finally, phase F is introduced at 25°C. The final emulsion is characterized by drops of 1 pm to 20 pm.
[Table 12] Method for preparing emulsion 12
The aqueous phase A is prepared by mixing all the starting materials at 65°C until a homogeneous phase is obtained. Phase B is mixed in several stages: phase B1 is mixed at 80°C until a homogeneous phase is obtained.
Next, phase B2 is added and then phase B3 at65°C. The emulsion is prepared by introducing phase B into phase A with vigorous stirring for 10 minutes at 65°C. The emulsion is then cooled to 25°C, while maintaining stirring, and then phase C is introduced. The final emulsion is characterized by drops of 1 pm to 20 pm.

Claims

64 Claims [Claim 1 ] Cosmetic or dermatological composition comprising: a) at least one merocyanine corresponding to either of formulae (1 ) and (2) below or one of the geometric isomer forms, in particular E/E or E/Z geometric isomer forms, thereof:
[Formula 1 ] and
[Formula 2]
(2) in which:
Ri and R2, independently of each other, are hydrogen; a C1-C22 alkyl group, a C2-C22 alkenyl group, or a C2-C22 alkynyl group, these groups possibly being substituted with at least one hydroxyl group or else interrupted with at least one -O-; or else R1 and R2 form, together with the nitrogen atom which links them, a -(CH2)n- ring which may be optionally interrupted with -0- or -NH-;
R3 is a -(C=O)ORe group; or a -(CO)NHRe group;
Re is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being substituted with one or more OH;
R4 and R5 are hydrogens; or R4 and R5 form a -(CH2)n- ring which may be substituted with a C1-C4 alkyl group and/or interrupted with one or more -0- or with -NH-; 65 n is a number between 2 and 7;
R? and Rs, independently of each other, are hydrogen; a C1-C22 alkyl group, a C2- C22 alkenyl group, a C2-C22 alkynyl group, said groups possibly being interrupted with one or more 0 and/or substituted with one or more OH; a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more -O-; or else R7 and Rs form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with one or more -O-;
R9 and R10 are hydrogen; or R9 and R10 form a -(CH2)n- ring potentially substituted with a C1-C4 alkyl and/or interrupted with an -0- or -NH-;
A is -O-; or -NH;
R11 is a C1-C22 alkyl group; a C2-C22 alkenyl group; a C2-C22 alkynyl group; a C3- C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0; or a C1-C22 alkyl group or a C2-C22 alkenyl group which is substituted with a C3-C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said C3-C22 cycloalkyl group or C3-C22 cycloalkenyl group possibly being interrupted with one or more -O-; and b) at least one oily phase comprising at least one ester of C3-C22 di- or tricarboxylic acid and of C1-C24 alcohols.
[Claim 2] Composition according to Claim 1 , wherein the compounds of formula (1 ) are chosen from those for which:
Re is a C1-C12 alkyl group, which may be substituted with one or more hydroxyls; one of the radicals R1 or R2 is a C4-C22 alkyl group; or else R1 and R2 form, together with the nitrogen which links them, a -(CH2)n- ring which may be interrupted with -0- and/or -NH-; and
R4 and R5 and n have the same meanings as in Claim 1 .
[Claim 3] Composition according to either one of Claims 1 and 2, wherein the compounds of formula (2) are chosen from those for which:
R11 is a -(CH2)m-O-R-i2 radical, in which
R12 is a C1-C12 alkyl group; or a C-i-Ce alkoxy-C-i-Ce alkyl group; m is a number from 1 to 5; and
R7, Rs, R9, R10 and A have the same meanings as in Claim 1 . 66
[Claim 4] Composition according to any one of Claims 1 to 3, wherein the compounds of formula (1 ) or (2) are chosen from those for which:
Ri and R2, on the one hand, and R7 and Rs, on the other hand, respectively form, together with the nitrogen atom to which they are respectively bonded, a piperidyl radical or a morpholinyl radical.
[Claim 5] 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:
R4 and R5 and R9 and R10 respectively form a carbon-based ring which contains 6 carbon atoms.
[Claim 6] Composition according to any one of Claims 1 to 5, wherein the compounds of formula (1 ) are chosen from those for which:
R1 and R2, independently of each other, are a hydrogen; or a C1-C22 alkyl group; or a C1-C22 hydroxyalkyl group; or R1 and R2 form, together with the nitrogen atom to which they are bonded, a piperidyl or morpholinyl radical;
R3 is a -(C=O)ORe group; or a -(CO)NHRe group;
Re is a C1-C22 alkyl group, which may be substituted with one or more -OH;
R4 and R5 are a hydrogen; or R4 and R5 are linked together to form a carbonbased ring which contains 6 carbon atoms.
[Claim 7] Composition according to any one of Claims 1 to 6, in which the compounds of formula (1 ) are chosen from those for which:
R1 and R2, independently of each other, are a hydrogen; or a C1-C22 hydroxyalkyl group; in which at least one of the radicals R1 and R2 is a C1-C22 hydroxyalkyl group;
R3 is a -(C=O)ORe group; or a -(C=O)NHRe group;
Re is a C1-C12 alkyl group;
R4 and R5 are hydrogens; or R4 and R5 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
[Claim 8] Composition according to any one of Claims 1 to 7, wherein the compounds of formula (2) are chosen from those for which:
R7 and Rs, independently of each other, are a hydrogen or a C-i-Ce alkyl group, which may be interrupted with one or more -O-;
A is -0- or -NH;
R11 is a C1-C22 alkyl; and 67
R9 and R10 are a hydrogen; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
[Claim 9] Composition according to any one of Claims 1 to 8, in which the compounds of formula (2) are chosen from those for which:
R7 and Rs form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
A is -O-; or -NH;
R11 is a C1-C22 alkyl group, which may be interrupted with one or more -O-; and R9 and R10 are hydrogens; or R9 and R10 are bonded together to form a carbonbased ring which contains 6 carbon atoms.
[Claim 10] Composition according to any one of Claims 1 to 9, in which the compounds of formula (2) are chosen from those for which:
R11 is a -(CH2)m-O-Ri2 radical, in which
R12 is a C1-C4 alkyl group; or a Ci-C4 alkoxy-Ci-C4 alkyl group; m is a number from 1 to 3;
R7 and Rs, independently of each other, are a hydrogen; a C1-C12 alkyl group, which may be interrupted with one or more 0; or R7 and Rs form, together with the nitrogen atom to which they are bonded, a morpholinyl or piperidyl radical;
R9 and R10 are hydrogens or together form a carbon-based ring which contains 6 carbon atoms; and
A is -0- or -NH.
[Claim 11 ] Composition according to any one of Claims 1 to 10, wherein the compounds of formula (1 ) or (2) are chosen from the following compounds and also the geometric isomer forms, in particular E/E or E/Z geometric isomer forms, thereof:
[Table 1 ] 68
[Claim 12] Composition according to any one of Claims 1 to 11 , wherein the compounds of formula (1 ) or (2) are chosen from those corresponding to formula (3) below and also the geometric isomer forms, in particular E/E or E/Z geometric isomer forms, thereof:
[Formula 3] in which:
A is -0- or -NH;
R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3- C22 cycloalkyl group or a C3-C22 cycloalkenyl group, said groups possibly being interrupted with one or more 0.
[Claim 13] Composition according to Claim 12, wherein the merocyanines of formula (3) are chosen from the following compounds and also the geometric isomer forms, in particular E/E or E/Z geometric isomer forms, thereof: 72
[Table 2] 73
[Claim 14] Composition according to either one of Claims 12 and 13, wherein 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 having the following structure: [Formula 6] and/or in its E/E geometric configuration having the following structure:
[Formula 7] 74
[Claim 15] Composition according to any one of Claims 1 to 14, comprising at least one ester of C3-C22 tricarboxylic acid, preferably citric acid, and of C1- Ce alcohols.
[Claim 16] Composition according to any one of Claims 1 to 15, comprising at least one ester of tricarboxylic acid and of C-i-Ce alcohols having the following formula:
(RIO-CO)CH2-C(R)(OC-OR2)-CH2(OC-OR3) in which:
R1, R2 and R3 represent, independently of each other, a hydrogen atom or a monovalent, saturated or unsaturated, aliphatic, cyclic or aromatic hydrocarbon- based group having from 1 to 6 carbon atoms;
R represents a hydrogen atom or a hydroxyl radical.
[Claim 17] Composition according to any one of Claims 1 to 16, wherein the ester of tricarboxylic acid and of C-i-Ce alcohols has the following formula: [Formula 10]
[Claim 18] Composition according to any one of Claims 1 to 17, comprising at least one polymer comprising monomer units of formulae (A) and (B):
[formula A] [formula B] 75 in which:
Ri , independently at each instance, is chosen from alkyl or alkylene radicals, and at least 60% by weight of the Ri groups are radicals chosen from stearyl and behenyl radicals, the percentage by weight relating to the sum of all the Ri groups present in the polymer, and the weight ratio of the sum of all the hydroxyethyl acrylate units to the sum of all the acrylate units bearing the Ri group ranges from 1 :30 to 1 :1 ; and the sum of the total of units A and B is at least 95% by weight relative to the total weight of the polymer, the polymer having a number-average molecular weight Mn ranging from 2000 to 9000 g/mol.
[Claim 19] Composition according to Claim 18, wherein, in the additional polymer, Ri is constituted of an alkyl radical, preferably of a C16-C22 alkyl radical, and more preferentially of a behenyl or stearyl radical.
[Claim 20] Composition according to either of Claims 18 and 19, wherein, in the additional polymer, at least 70% by weight of the Ri groups are behenyl or stearyl radicals, preferentially at least 80% by weight, more preferentially at least 90% by weight.
[Claim 21 ] Composition according to any one of Claims 18 to 20, wherein, in the additional polymer, all the Ri groups are stearyl or behenyl radicals.
[Claim 22] Composition according to any one of Claims 18 to 21 , wherein, in the additional polymer, said weight ratio ranges from 1 :15 to 1 :1 and preferentially ranges from 1 : 10 to 1 :4.
[Claim 23] Composition according to any one of Claims 18 to 22, wherein the additional polymer has a number-average molecular weight Mn ranging from 5000 to 9000 g/mol.
[Claim 24] Composition according to any one of Claims 18 to 23, wherein the additional polymer has a melting point ranging from 40°C to 70°C, and preferentially ranging from 45°C to 67°C.
[Claim 25] Composition according to any one of Claims 18 to 24, wherein, in the additional polymer, at least 60% by weight of the Ri groups are stearyl 76 radicals, and said additional polymer has a melting point ranging from 40 to 60°C, and preferentially ranging from 45 to 55°C.
[Claim 26] Composition according to any one of Claims 18 to 25, wherein, in the additional polymer, at least 60% by weight of the Ri groups are behenyl radicals, and said additional polymer has a melting point ranging from 60°C to 70°C, and preferentially ranging from 63°C to 67°C.
[Claim 27] Composition according to any one of Claims 1 to 26, also comprising one or more additional UV-screening agents.
[Claim 28] 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 as defined in any one of Claims 1 to 27.
EP21836527.8A 2020-12-18 2021-12-14 Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester Pending EP4262719A1 (en)

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FR2013605A FR3117824A1 (en) 2020-12-18 2020-12-18 Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester
PCT/EP2021/085710 WO2022129059A1 (en) 2020-12-18 2021-12-14 Cosmetic or dermatological composition comprising a merocyanine and an oily phase comprising at least one citric acid ester

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Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
FR2315991A1 (en) 1975-06-30 1977-01-28 Oreal METHOD OF MANUFACTURING AQUEOUS DISPERSIONS OF LIPID SPHERULES AND CORRESPONDING NEW COMPOSITIONS
US4077441A (en) 1976-08-16 1978-03-07 National Instrument Company Convertible filling machine
JPS53128333A (en) 1977-04-15 1978-11-09 Fuji Photo Film Co Ltd Prevention of influences of ultraviolet ray upon photosensitive material of silver halogenide
FR2416008A1 (en) 1978-02-02 1979-08-31 Oreal LIPOSOME LYOPHILISATES
DE8322682U1 (en) 1983-08-05 1986-02-13 Siemens AG, 1000 Berlin und 8000 München Mechanical overload protection
DE3531383A1 (en) 1985-09-03 1987-03-05 Agfa Gevaert Ag PHOTOGRAPHIC RECORDING MATERIAL WITH A UV ABSORBER AND NEW UV ABSORBER
NL8502651A (en) 1985-09-27 1987-04-16 Airspray Int Bv Atomizer for a container for a liquid to be atomized.
US5624663A (en) 1987-08-28 1997-04-29 L'oreal Photostable cosmetic filter composition cotaining a UV-A filter and a substituted dialkylbenzalmalonate, the use of substituted dialkylbenzalmalonates in cosmetics as broad-band solar filters and novel substituted dialkyl malonates
FR2668080B1 (en) 1990-10-17 1993-08-13 Seppic Sa SELF-EMULSIONABLE COMPOSITIONS BASED ON FATTY ALCOHOLS, THEIR PREPARATION PROCESS AND THEIR USE FOR MAKING EMULSIONS.
US5237071A (en) 1991-01-22 1993-08-17 Fairmount Chemical Company, Inc. Process for preparing 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-hydrocarbyl phenols)
US5166355A (en) 1991-02-04 1992-11-24 Fairmount Chemical Co., Inc. Process for preparing substituted 2,2'-methylene-bis-[6-(2H-benzotriazol-2-yl)-4-hydrocarbyl-phenols]
FR2677544B1 (en) 1991-06-14 1993-09-24 Oreal COSMETIC COMPOSITION CONTAINING A MIXTURE OF NANOPIGMENTS OF METAL OXIDES AND MELANIC PIGMENTS.
FR2680683B1 (en) 1991-08-29 1993-11-12 Oreal COSMETIC FILTERING COMPOSITION CONTAINING A HYDROCARBON STRUCTURED FILTER POLYMER AND A FILTERED SILICONE.
DE59509233D1 (en) 1994-02-24 2001-06-13 Haarmann & Reimer Gmbh COSMETIC AND DERMATOLOGICAL PREPARATIONS CONTAINING PHENYLENE-1,4-BISBENZIMIDIAZOLESULFONIC ACIDS
GB9515048D0 (en) 1995-07-22 1995-09-20 Ciba Geigy Ag Sunscreen compositions
IT1284525B1 (en) 1996-09-13 1998-05-21 3V Sigma Spa DERIVATIVES OF BENZOSSAZOLE USED AS STABILIZERS AGAINST UV RADIATION
FR2755692B1 (en) 1996-11-08 1998-12-04 Oreal NOVEL SOLAR FILTERS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES
DE19726184A1 (en) 1997-06-20 1998-12-24 Beiersdorf Ag Oil-in-water or multiple emulsion with high concentration of suspended UVB filter
GB9715751D0 (en) 1997-07-26 1997-10-01 Ciba Geigy Ag Formulations
DE19755649A1 (en) 1997-12-15 1999-06-17 Basf Ag Use of 4,4-diarylbutadienes as photostable UV filters in cosmetics
DE19746654A1 (en) 1997-08-13 1999-02-18 Basf Ag Use of 4,4-di:aryl-butadiene derivatives as photostable UV filter compounds
DE19828463A1 (en) 1998-06-26 1999-12-30 Basf Ag 4,4-Diarylbutadienes as water-soluble, photostable UV filters for cosmetic and pharmaceutical preparations
DE19855649A1 (en) 1998-12-03 2000-06-08 Basf Ag Dimeric alpha-alkyl-styrene derivatives as photostable UV filters in cosmetic and pharmaceutical preparations
DE19857127A1 (en) 1998-12-11 2000-06-15 Basf Ag Oligomeric diarylbutadienes
IT1312374B1 (en) 1999-01-11 2002-04-15 3V Sigma Spa SOLAR FILTER ASSOCIATIONS AND COSMETIC COMPOSITIONS THAT CONTAIN IT
US6225467B1 (en) 2000-01-21 2001-05-01 Xerox Corporation Electroluminescent (EL) devices
DE10012408A1 (en) 2000-03-15 2001-09-20 Basf Ag Use of sunscreen combinations which contain as essential constituent amino-substituted hydroxybenzophenones as photostable UV filters in cosmetic and pharmaceutical preparations
FR2815961B1 (en) 2000-10-26 2008-11-28 Centre Nat Rech Scient NEW INTERMEDIATES USEFUL FOR RETINOID SYNTHESIS
ITMI20012037A1 (en) 2001-10-02 2003-04-02 3V Sigma Spa SOLAR FILTER ASSOCIATIONS
DE10162844A1 (en) 2001-12-20 2003-07-03 Beiersdorf Ag Cosmetic and dermatological light protection formulations containing bis-resorcinyltriazine derivatives and benzoxazole derivatives
JP3973941B2 (en) 2002-03-25 2007-09-12 富士フイルム株式会社 Method for producing δ-aminopentadienoic acid ester derivative
AU2003250866B2 (en) 2002-07-10 2008-10-02 Ciba Holding Inc. Merocyanine derivatives for cosmetic use
JP4764817B2 (en) 2003-03-24 2011-09-07 チバ ホールディング インコーポレーテッド Symmetric triazine derivatives
DE102004047285A1 (en) 2004-09-27 2006-04-20 Beiersdorf Ag Cosmetic sunscreen emulsion containing organic micropigments
DE102004047282A1 (en) 2004-09-27 2006-04-20 Beiersdorf Ag W / O emulsion with UV sunscreen filter pigments
DE102004047288B4 (en) 2004-09-27 2006-11-30 Beiersdorf Ag Sunscreen emulsion with a high proportion of sunscreen filter pigments
DE102004047281A1 (en) 2004-09-27 2006-04-20 Beiersdorf Ag Sunscreen concentrate with organic micropigments
DE102004047286B4 (en) 2004-09-27 2006-11-23 Beiersdorf Ag Cosmetic sunscreen preparation based on micropigments
DE102004047283A1 (en) 2004-09-27 2006-04-13 Beiersdorf Ag O / W emulsions with inorganic UV photoprotective pigments
EP1798213A1 (en) 2005-12-14 2007-06-20 Cognis IP Management GmbH Process for the production of hydrocarbons
GB2433499A (en) 2005-12-20 2007-06-27 Ciba Sc Holding Ag Merocyanine derivatives useful as UV absorbing agents
GB2433439A (en) 2005-12-21 2007-06-27 Ciba Sc Holding Ag Use of transmission dyes to protect human skin from UV radiation
CA2650819A1 (en) 2006-05-11 2007-11-22 Air Products And Chemicals, Inc. Personal care compositions containing functionalized polymers
WO2008155059A2 (en) 2007-06-19 2008-12-24 Cognis Ip Management Gmbh Hydrocarbon mixtures and use thereof
JP5270134B2 (en) 2007-11-12 2013-08-21 株式会社コーセー Ultraviolet absorber water dispersion composition
WO2013010590A1 (en) 2011-07-21 2013-01-24 L'oreal Cosmetic and/or dermatological composition containing a merocyanine derivative comprising specific polar groups consisting of hydroxyl- and ether-functionalities
FR3046929B1 (en) * 2016-01-26 2018-03-02 L'oreal COSMETIC OR DERMATOLOGICAL COMPOSITION COMPRISING A MEROCYANINE AND AN OILY PHASE COMPRISING AT LEAST ONE DI OR TRICARBOXYLIC ACID ESTER

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