LU85688A1 - COSMETIC ACCELERATING TANNING BASED ON FUROCHROMONES - Google Patents

Description

L'OREAL, U3 2.501 1

8u B ^ AXD-DUCHY OF LUXEMBOURG

U ^ .V W

December 1, 19 ^ ^ 4 Minister ’iSX-Pllî ^ Economy and the Middle Classes

Title issued: ...................................... Intellectual Property Service

--V’Igy LUXEMBOURG

Patent Application: I. Request

The company ..... anonymous ..... said; ....... L'OREAL. $. * A., 14, rue ... Roya I ç., ...... 7.50 .QS ...... (1)

Paris, France, represented by Maïtre A la in RU K AV J. NA. ,, lawyer.-lawyer in Luxembourg, lia, boulevard Joseph II / acting in his capacity as agent (2) .... .................................................. .................................................. .................................................. ...........................................

deposits (nt) this eighteenth. dec. ejnhre ... l90Q quatre — vi ngt — quatre .......... (3) at ...... 15. "Q.O. hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg:.

• 1. the present request for obtaining a patent of invention concerning: ............................... .................................................. .................................................. .................................................. .................................................. ..................................... m "Cosmetic composition that is accessible ... .. | ..e tanning based on ......................... 'fur oc h rom on es "....... .................................................. .................................................. .................................................. .................................................. ..

2. the delegation of power, dated ......................................... ............................... the .................. ..............................................

3. description in language .......... françai s0 .......................... of the invention in two copies; v 4 ........ DD ................. drawing boards, in two copies; 5. the receipt of the taxes paid to the Luxembourg Registration Office, v ... 1.8 ..... December ..... 19.8.4 .............. .................................................. .................................................. .................................................. .......................................

declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): ....................... .................................................. .................................................. .................................................. .................................................. .................................................. (5) claims (s) for the above patent application the priority of one (or more) request (s) from (6) DD .................... .................................................. .... filed in (7) .............. J J ...................... .................................................. ...........

on .................................. DD .............. .......... ........... .....-....................... .................................................. .................................................. ... (8) in the name of ................................ J .. J ..... .................................................. .................................................. .................................................. .......................................... (9)% elect (elect) for him / her and, if appointed, for his / her representative, in Luxembourg .................................. .

lia., ..... b..or.l evand ..... Joseph ...... U ...................... .................................................. .................................................. ....................................... (10) * request) the issue of a invention patent for the subject described and represented in the abovementioned appendices, - with postponement of this issue to eighteen ............: ....... months. (11)

Le .mâ.ndat.a’.i.r * e ..., ... / ... // - if________ ·. . , '

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v- 'Π. Procès-verbal de Dépôt _ The above application for a patent for invention has been filed with the Ministry of the Economy and

Middle Classes, Intellectual Property Service in Luxembourg, dated: D * 1 *

f. S

,; L- ’,’ Pr. The Minister at ... 1.5 .. * 00 ..... hours' 5. of Economy and the Middle Classes, jf P-d.

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2032/84 - FB / LF SERIE 343

So-called Anonymous Company; L'OREAL

Cosmetic composition accelerating grinding based on furochranones. - Invention of $ 5 t * *

Cosmetic composition accelerating tanning based on furochrcmones.

The invention relates to a solar cosmetic composition which, when applied to the human epidermis, accelerates the tanning thereof after exposure to the sun or to UV rays.

We know that natural "tanning" results from the action of ultraviolet rays on the human epidermis, the melanocytes being the specific cells of the periphery of the dermis which are responsible for melanchenesis.

It will be recalled that, from a biological point of view, melanogenesis is a sequence of enzymatic chain reactions leading from a simple amino acid, which is tyrosine, to more or less oxidized melanin pigments. On a cellular level, these pigments accumulate in cells called melanocytes. These cells, located at the periphery of the dermis, when they mature, release pigments (melanosomes) in the epidermis. These pigments are then picked up by cells called keratinocytes, the transfer taking place by cellular extensions called dendrites.

Proper functioning of this reaction has the direct consequence of producing a natural sunscreen, the tanning providing permanent protection.

20 The quality of the tan therefore depends on: - the chemical nature of the melanin, - the mode of aggregation and dispersion of the melanosomes in the kerati-. nocytes, and - the amount of melanin transferred and stored in the keratinocytes.

25 These reactions are dependent on ultra violet solar radiation and often show a deficit in white skin having lost the habit of being regularly exposed to the sun.

; It is known that when a composition containing the essence of natural bergamot is spread over the skin, the action of solar radiation is combined, in a way, with that of the essential oil of natural bergamot and the there is a trigger and an increase in the speed and intensity of melanogenesis.

It is at this level that the 5-methoxy-psoralen, furocoumarin contained in the essence of bergamot, which appears to have the following triple action comes into play: 2 * - increase in the size of the melanocytes, - increase in the number of pigments and number of active melanocytes and - increase in the speed of the melanogenesis reaction.

Under the influence of ultraviolet radiation and from a certain threshold, which is approximately 10 ppm, the use of 5-methoxy-psoralen causes a phototoxic type reaction, the severity of which is proportional to its concentration. .

Thus, when using, to accelerate the tanning of human skin, a solar composition containing bergamot essence or '10 simply 5-methoxy-psoralen, one can see the appearance of erythemas, the intensity increases according to the dose of 5-methoxy-psoralen used, with "often various complications depending on the susceptibility of the individual, such as pruritus, edemas, blisters or eczematiform lesions, these skin accidents being followed by persistent pigmentations irregular.

15 These skin reactions caused by exposure to ultraviolet light are called "phototoxic reactions" and cause accelerated aging of the skin.

In addition, it has recently been shown that 5-methoxy-psoralen exerts a carcinogenic action on experimental animals following skin applications and repeated irradiation with long ultraviolet light (UV-A). and in particular at wavelengths close to 360 nm.

The Applicant has therefore sought a substance which, applied to the skin, would make it possible to obtain the same accelerating effect on natural pigmentation as 5-methoxy-psoralen, without causing phototoxic epidermal reactions or undesirable side effects.

It is as a result of this research that the applicant discovered that the compound of general formula: „f Ρ ° η3 ΛΛ-1 ω

30 J

ch3 ^ u J R

in which R denotes a hydrogen atom or the methoxy radical, when it is introduced into a suitable cosmetic support allowing both easy application to the skin and good penetration into the surface layers 3 of the epidermis, allows get a quick, even tan without causing phototoxic epidermal reactions or unwanted side effects.

The compound of formula (I) in which R denotes a hydrogen atom 5 is visnagine and the compound of formula (I) in which R denotes a: methoxy radical is fchelline, which are both natural furochrcmones isolated from Ammi Visnaga L.

The present invention therefore relates to a cosmetic composition having a pigmentogenic activity, intended to be applied to the human epidermis, which contains a compound of formula (I) above in a cosmetic support suitable for being easily applied to the skin and allow good * penetration of the compound of formula (I) into the surface layers of the epidermis.

Since the compound of formula (I) does not cause phototoxic reactions under the influence of ultraviolet radiation, its concentration in the cosmetic composition according to the invention can reach 0.001 to 5%, and preferably 0.01 to 2 % of the total weight of the composition.

The maximum activity of the compounds of formula (I) results from exposure to ultraviolet radiation of wavelength between 330 and 380 nm. According to a first embodiment of the invention, the cosmetic composition can constitute a tanning preparation composition containing only the compound of formula (I), which is applied daily to the skin for the days - generally 1 to 15 days - which precede the person's exposure to the sun, for example before going on vacation.

25 In this way, the skin is impregnated with active ingredient (I) and when the person arrives on vacation and exposes himself to the sun, he only has to protect himself from UV-B rays to avoid the formation of erythemas.

The cosmetic composition according to the invention can also constitute * a tanning composition containing only the compound of formula (I) 30 in a cosmetically acceptable carrier, which is intended to be applied to the skin immediately before exposure to UV-A rays to obtain an artificial tan.

According to another embodiment of the invention, the cosmetic composition with pigmentogenic activity can be a solar filtering composition 35 containing the compound of formula (I) and at least one ÜV-B filter, which is 4 ♦, applied to the skin immediately before sun exposure. The presence of the UV-B filter with maximum absorption in the wavelength region which extends from 280 to 320 nm is necessary to avoid the formation of erythemas.

Any type of BV-B filter may be suitable in these compositions, and there may be mentioned, without this being limiting in nature, benzylidene camphor and its derivatives, esters and derivatives of p-aminobenzoic acid, cinnamates, salicy lates or · phenyl-2-benzimidazole-5 tallow θ'-nique (sold under the brand EUSOLEX 232) and its salts.

Among the benzylidene camphor derivatives, mention may be made of: (a) p-methyl benzylidene camphor; . (b) the compounds of formula (II) below:

'VT

15 0 \ Ζ ^ Η (II) M) —r

V

in which: (i) Y denotes a hydrogen atom, Z represents a group - ^ (CHg ^ R where R denotes a hydrogen atom or a C 1 -C 4 alkyl radical ^ Y 'denotes a d atom hydrogen or halogen or a methyl radical; these compounds are described in French patent 2,199,971;

(ii) Y and Y ’represent a hydrogen atom or an SO ^ H radical

Optionally salified, provided that at least one of the 2 groups is different from a hydrogen atom, Z represents a hydrogen or halogen atom, a radical: C 1 -C 4 alkyl; these compounds are described in French patent 2,236,515; 35 (üi) Y denotes a hydrogen atom or an optionally salified SO ^ H radical, Z denotes optionally salified SO ^ H, 5.

T ’denotes a hydrogen atom; these compounds are described in French patent 2,282,426; (iV) Y and Y ’represent a hydrogen atom or an SO H radical,

• J

optionally salified, provided that at least one has the value H, Z represents: -CH2I, -CH2R, -CHR'R ', -CHO, -COOR ", with R = -OR ^, -OCOR5, - SR6, -CK or -COOR ", R ^ denotes a hydrogen atom, an alkyl, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkylaminoalkyl, 10 R, radical. denotes an alkyl, alkenyl or aryl radical, an aromatic heterocycle or not with 5 or 6 members,

Rg denotes a hydrogen atom, an alkyl, carboxy-alkyl, aminoalkyl, hydroxyalkyl, aryl, alanyl-3 radical, R '= OR' ^ or SR'g, R '^ and R' ^ having the same values respectively that R ^ and R ^, except for the meanings hydrogen, polyoxyethylene, hydroxyalkyl, alanyl-3 and aryl, R "denotes a hydrogen atom or an alkyl radical; these compounds are described in French patents 2,383,904; 2,402,647 and 2,421,878; (V) Y denotes a hydrogen atom, Y 'and Z denote a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical or the radical A = ^ or R1 = H, C 1 -C 4 alkyl or hydroxyalkyl, R2 = H, alkyl, alkenyl, cycloalkyl, aryl or aralkyl, these various C 1 -C 4 radicals being able to be substituted by one or more hydroxy, alkoxy or dialkylamino groups ; R ^ and R2 cannot simultaneously denote a hydrogen atom; Y 'and Z are different from each other and one of the two must necessarily have the value A = -SO2-N— j; \ these compounds are described in Belgian patent 897,241; (Vi) Y denotes the group A = -SO ^, R ^ and R2 having the.

35 meanings given under (V), 6 * · Y ’and Z denote a hydrogen or halqgene atom, a C 1 -C 4 alkyl or alkoxy radical; these compounds are described in Belgian patent 897,241.

Among the esters and derivatives of p-aminobenzoic acid, there may be mentioned:

- ethyl p-aminobenzoate, sold under the brand name BENZOCAINE

- isopropyl p-aminobenzoate

- isobutyl p-aminobenzoate, sold under the brand CYCLQFORM

- glyceryl p-aminobenzoate, sold under the brand ESCÄLOL 106

-10 - allantoin p-aminobenzoate, sold under the brand ALPABA

- ethyl N-ethoxy p-aminobenzoate, sold under the name SC 9155

- ethyl N- (2-hydroxyprqpyl) p-aminobenzoate and ethyl N, N-bis (2-hydroxy-propyl) p-aminobenzoate, sold under the brand AMERSCREEN P

15 - ethyl 4- (dimethylamino) -benzoate - amyl 4- (dimethylamino) -benzoate or "Padimate" according to the international common name, sold under the brand ESCÂLOL 506 - 4- (dimethylamino) -benzoate of 2-ethylhexyl, sold under the brand ESCALOL 507 20 - 3,3,5-trimethylcyclohexyl 2-acetamido benzoate.

Among the cinnamates, mention may be made of: - benzyl cinnamate - menthyl or homomenthyl cinnamate - octyl cinnamate, sold under the brand PROSOLAL S 8 25 - CT ^ r-cyano- / 2> - ethyl phenylcinnamate, sold under the brand name IVINUL N 35 - l'c ^ -cyano - ^> - 2-ethylhexyl phenylcinnamate, sold under the brand UVINUL N 539 - 1 'ç / ~ cyano-y (3- 3Q hexyl p-methoxycinnamate - 2-ethylhexyl p-methoxycinnamate, sold under the brands

PARSOL MCX and NEO HELIOPAN AV

- amyl and isoamyl p-methoxycinnamate, sold under the brand NEO HELIOPAN E 1000 - propyl p-methoxycinnamate 35 - cyclohexyl p-methoxycinnamate - 2-ethoxyethyl p-methoxycinnamate or "CINOXATE" according to the international nonproprietary name, sold under the brand GIV-TAN F.

i 7

Among the salicylates, there may be mentioned; - 2-ethylhexyl salicylate - 4-isoprqpylbenzyle salicylate - benzyl salicylate 5 - menthyl and homomenthyl salicylates, sold respectively under the brands CONTRASOL and FILTRASOL A.

Certain benzoxazole derivatives such as 2- (p-toluene) benzoxazole and 5-methyl-2-phenylbenzoxazole, sold under the brand name WITISOL or other compounds such as 5- (3,3-dimethyl-2-norbomylidene) -3-penten-2-one, sold ÎO under the brand PROSOLAL S 9, ethyl urocanate or acid trioleate 3,4-dihydroxy-5- £ (3,4,5-trihydroxybenzoyl) ' xyxy3 benzoic acid, sold under the brand name SOLPROTEX 1, can also be used as UV-B filters in the compositions in accordance with the invention.

In order to control the photobiological activity of the compounds of formula 15 (I), it is also possible to add to the compositions according to the invention UV-A filters having a maximum absorption in the wavelength region which s extends from 320 to 400 nm, for example 4-tert.-butyl 4'-methoxy-dibenzoylmethane, sold under the brand "Parsol 1789", 4-isopropyl-diben-zoylmëthane, sold under the brand "Eusolex 8020" , the 2-hydroxydibenzoyl-20 methanes described in French patent application 2,513,992, the derivatives of 2-hydroxy-benzophenone or of 2-hydroxy-5-sulfobenzophenone, as well as the UV-A filters derived from benzylidene- camphor chosen from: - the 3-p-oxybenzylidene 2-bornanones of French patent n ° 2 430 938, of formula: “25 xx-d ^ -—.

30 N -! _ / R2 L -J q in which Z ^ and Z 'denote respectively a hydrogen atom or a radical SO ^ H, or a salt of this sulfonic acid with an inorganic or organic base, one at least of the two radicals Z ^ or Z '^ -representing an atom * I 8.

hydrogen; R ^ denotes a hydrogen atom, an optionally branched alkyl radical containing 2 to 18 carbon atoms, an alkenyl radical containing 3 to 18 carbon atoms, a radical / R3 - (CH2CH20) nH, (CH2-CHO ^ - H, -CI ^ -CHOH-CH ^ CÏ ^ -CI ^ N ^ ch2oh ^ r4 ^ R3 -CH2-CH0H-CH2 “N, - (CH2) mC02R in which R denotes B, an Λ alkyl radical containing 1 to 8 carbon atoms, - (CH _) _- SO „H or a salt of this acid 10 3 2'3 3. with an organic or mineral base, or a divalent radical - (CH2) m or -CH2-CH0H-CH2 ; m having the values 1 to 10, n the values 1 to 6; R ^ and R ^ each representing a hydrogen atom or an optionally branched or hydroxylated alkyl radical or else forming together an aminoalky heterocycle

phatic with the nitrogen atom, R0 denotes a hydrogen atom, a 15 L radical

alkoxy containing 1 to 4 carbon atoms, or a divalent radical -0-linked to the radical R ^ when the latter is also divalent, ^ denotes 1 or 2, it being understood that when q has the value 2, R ^ is a radical divalent and that when R ^ denotes hydrogen, R2 also denotes hydrogen; and further when R2 denotes alkoxy, R 1 can also denote methyl; - the benzylidene-camphor derivatives described in Belgian patent n ° 897,051, of formula: - “- <* 2 / \ - 0 25 __ z ch — czy in which R ^ denotes a hydrogen atom or a radical - SO ^ k ^ where M denotes a hydrogen atom, an alkali metal or a group ^ (R ^) ^, Rg denotes a hydrogen atom or a C1 to C4 alkyl or hydroxyalkyl radical Z represents a group "9 i '* £ ** n-1 / \ 5 in which R ^ has the same meanings as R ^ and can be equal to Rj or different from R ^ or a group

-CH = C

10 0 R ^ denoting a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical optionally substituted by halogen atoms or by C 1 -C 4 alkyl or alkoxy groups, ^ R9

15 a -CN, -COOR ^ or -CON group

R10 and R, denotes a group -C00Ro or -CON ,.

* 10 20 R ^ and Rg, which are identical or different, being alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most 20 carbon atoms optionally substituted by hydroxy, alkoxy, amine or quaternary ammonium groups,

Rg and R10, identical or different, denoting a hydrogen atom or alkyl, alkenyl, cycloalkyl or aralkyl radicals containing at most * 20 carbon atoms, optionally substituted by hydroxy, alkoxy, amine or quaternary ammonium groups.

or when R ^ denotes a hydrogen atom, an optionally substituted alkyl or aryl radical, R ^ can also represent a radical -C0 (BF, 30 M being defined as above, the two methylidene camphor radicals on the one hand and Z, on the other hand, being fixed on the aromatic ring A in the para position relative to one another; - the sulfonamides derived from 3-benzylidene-camphor described in Belgian patent 4 10 ηβ 897 241, of formula: ch2 - x1

K

”'X

in which X ^ denotes the radical Y; X ^ denotes a radical Z; Χ ^ denotes a hydrogen atom; 15 - ^ Y denotes the group -SO ^ NT ^ in which ^ R2 R ^ denotes a hydrogen atom or a C 1 -C 4 alkyl or hydroxyalkyl radical; R 2 denotes a hydrcgene atom or a linear alkyl or alkenyl radical area or branched, cycloalkyl, aryl or aralkyl, these different radicals in Cj-C2q can be substituted by one or more hydroxy, alkoxy or dialkylamino groups: R ^ and R2 cannot simultaneously denote a hydrogen atom; Z denotes the one of the following groupings: ch2y Z, = 30 -CH ===== s ^ y * 11 t "or Y has the meaning mentioned above or Z2 = CH3 5 ~ CE == x /

The total concentration of UV-B and UV-A sunscreens depends on the type of skin on which the composition is to be applied. In general, it is between 0.5 and 20%, and preferably between 2 and 10% relative to the total weight of the composition.

The cosmetic composition according to the invention may also contain other ingredients such as carotenoids (^ -carotene or canthaxantine) whose beneficial effect for skin sensitive to solar radiation is well known.

15

The cosmetic composition according to the invention may be in emulsion in the form of milk or cream or in solution in the form of an oleoalcoholic lotion or oil or also in the form of an olioalcoholic gel or be packaged as an aerosol.

Among the main adjuvants which may be present in such a composition, mention may be made of solubilizing agents such as lower monoalcohols containing 1 to 6 carbon atoms, glycols, triglycerides of fatty acids Cg-C ^ g. Particularly preferred monoalcohols or glycols are ethanol, isopropanol and propylene glycol.

25. The cosmetic composition according to the invention may also contain emulsifiers.

It may be useful to use thickeners as well as other adjuvants commonly used in cosmetics and in particular softeners, humectants, emollients, wetting agents, preservatives, defoamers, perfumes, dyes.

One embodiment of the invention is an emulsion in the form of a cream or milk comprising, in addition to the compound of formula (I), fatty alcohols, ethoxylated fatty alcohols, fatty acid esters or triglycerides. fatty acids, lanolin, synthetic oils, animal and vegetable, in the presence of water.

Another embodiment consists of lotions such as oleoalcoholic lotions based on lower alcohols such as ethanol or glycols such as propylene glycol, and fatty acid esters or fatty acid triglycerides.

The cosmetic composition of the invention can also be an oleoalcoholic gel, comprising one or more lower alcohols such as ethanol and propylene glycol and a thickener, in the presence of oil.

The present invention also relates to a process intended to accelerate the tanning of the human epidermis, consisting in applying to the skin a cosmetic composition containing a compound of formula (1) in a cosmetic support suitable for being easily applied to the skin. skin and allow good penetration of the active component into the surface layers of the epidermis, then exposing the skin to UV-A radiation.

The present invention will be better illustrated with the aid of the following nonlimiting examples.

EXAMPLE 1

Preparing lotion for tanning.

20 Khelline 1 g

Miglyol 812 (C_-C_ fatty acid triglycerides) 10 g

Ethanol at 96 ° qs 100 g

This lotion is applied daily to the body for 1 to 2 weeks before sun exposure.

25 EXAMPLE 2 »

Sunscreen cream promoting tanning, Khelline 0.5 g Methyl sulfate 4 £ Î2-oxo-3-bornylidene) methyl] ~] 20 phenyl trimethylammonium 3 g Mixture of cetylstearyl alcohol and oxyethylenated cetylstearyl alcohol with 33 moles of oxide ethylene 7 g

Glycerol monostearate 2 g 13.

Miglyol 812 30 g

Silicone oil (dimethyl polysiloxane) 1.5 g

Cetyl alcohol 1.5 g

Distilled water qs 100 g 5 This cream, which is an O / W emulsion, is applied to the skin just before the person is exposed to the sun.

EXAMPLE 3

Sunscreen milk promoting tanning Khelline O »3 g 10 Benzyl camene camene 2 g 4'-butoxy 3'-methoxy 3-benzylidene bornanone 1 g Mixture of cetylstearyl alcohol and cetylstearyl alcohol oxyethylenes with 33 moles of oxides ethylene 5 g

Glycerol monostearate 1.5 g 15 Isoprqpyle myristate 3 g

Miglyol 812 21 g

Silicone oil 1 g

Cetyl alcohol 1 g

Distilled water qs 100 g 20 This milk, which is an O / W emulsion, is applied to the body just before exposure to the sun.

EXAMPLE 4

Cream promoting tanning

Khelline. 0.2 g 25 Miglyol 812 15 g, Polyoxyethylene hydrogenated palm oil 5 g

Oxyethylenated cetylstearyl alcohol containing 15 moles of ethylene oxide 5 g

Lanolin 3 g 30 Prqpylèneglycol 5 g

Water qs 100 g

This cream, which is an O / W emulsion, is applied to the body just before the person is exposed to a UV-A lamp.

Claims (13)

14 1. Cosmetic composition having a pigmentogenic activity, intended to be applied to the human epidermis, characterized in that it contains a compound of formula: 5 d? 9Œ3 ^ in which R denotes a hydrogen atom or the methoxy radical, in a cosmetic support suitable for being easily applied to the skin and allowing good penetration of the compound of formula (I) into the surface layers of the epidermis. 2. Composition according to claim 1, characterized in that it contains Khellin. 3. Composition according to claim 1 or 2, characterized in that it contains 0.001 to 5%, preferably 0.01 to 2% by weight of compound of formula (I). 4. Composition according to any one of claims 1 to 3, characterized in that it constitutes a tanning preparation composition, intended to be applied to the skin during the days before exposure to the sun. 5. Composition according to any one of claims 1 to 3, characterized in that it constitutes a tanning composition, intended to be applied to the skin immediately before exposure to 25 * IJV-A rays to obtain an artificial tan. 6. Composition according to any one of claims 1 to 3, characterized in that it constitutes a filtering solar composition intended to be applied to the skin immediately before exposure to the sun to obtain a natural tan, further containing at least one UV-B filter chosen from: - benzylidene camphor; - p-methylbenzylidene camphor; 15 - the benzylidene camphor derivatives of formula (II) below: 5 - k J = Cà (II) _f_r V 10. in which: (!) Y denotes a hydrogen atom Z represents a group - ^ ( CHg ^ R where R denotes a hydrogen atom or a C 1 -C 19 alkyl radical Y 'denotes a hydrogen or halogen atom or a methyl radical; (ii) Y and Y' denote a d atom hydrogen or an optionally salified SO 2 H radical, provided that at least one of the two groups is different from a hydrogen atom 20. represents a hydrogen or halogen atom, a C 1 alkyl radical ^ -C ^; (iii) Y denotes a hydrogen atom or an SO ^ H radical optionally salified Z denotes SO ^ B optionally salified Y 'denotes a hydrogen atom;, (iV) Y and Y' represent a hydrogen atom or an S03H radical, optionally salified, provided that at least one has the value H • Z represents î -CH2I, -CH2R, -CHR'R ', -CHO, -COOR "with 30 R = -OR ^, -OCOR5, -SRg, -CN or -COOR "; R ^ denotes a hydrcgene atom, an alkyl, polyoxyethylene, substituted or unsubstituted aryl, menthyl, dialkylaminoalkyl radical R ^ denotes an alkyl, alkenyl, aryl radical, an aromatic heterocycle or not with 5 or 6 members "16 Rg denotes an atom of" hydrogen, an alkyl, carboxyalkyl, aminoalkyl, hydroxyalkyl, axyl, alanyl-3 radical R '= OR' ^ or SR'g, R '^ and R * g having the same values as R ^ and Rg respectively, except for the hydrogen, polyoxyethylene, hydroxyalkyl, alanyl-3 and aryl meanings R "denotes a hydrogen atom or an alkyl radical; (V) Y denotes a hydrogen atom Y ’and Z denotes a hydrogen or halogen atom, a C 1 -C 6 alkyl or alkoxy radical. or the radical A · =. 14. v. 1 10 ^ r2 where R ^ = H, C ^ -C ^ alkyl or hydroxyalkyl R2 * = H, alkyl, alkenyl, cycloalkyl, aryl or aralkyl, these different radicals in Cj-C2Q can be substituted by one or more hydroxy groups , alkoxy or dialkylamino 15 R 1 and R 2 which cannot simultaneously designate a hydrogen atom Y ′ and Z are different from each other and one of the two necessarily has the value A = -------; (Vi) Y denotes the group A = -SC ^ -N "· * ^, R and R2 having XvR2 the meanings given under (V) Y ’and Z denote a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical; esters and derivatives of p-aminobenzoic acid, cinnamates, salicylates, 2-phenyl-5-benzimidazole sulfonic acid and its salts, certain benzoxazole derivatives such as 2- ( p-toluene) benzoxazole and 5-methyl-2-phenylbenzoxazole, 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one, ethyl urocanate or trioleate 3,4-dihydroxy-5- £ acid (3,4,5-30 trihydroxybenzoyiyôxy ^ J benzoic. 7. Composition according to Claim 6, characterized in that it also contains at least one UV-A filter chosen from: 4-tert.-butyl 4'-methoxy dibenzoylmethane, 4-isopropyl dibenzqyl methane, derivatives 2-hydroxybenzophenone or 2-hydroxy sulfobenzophenone, UV-A filters derived from benzylidene camphor or 2-hydroxydibenzoyl-methanes. 17 8. Composition according to claim 6 or 7, characterized in that the total concentration of UV-A and UV-B sun filters is between 0.5 and 20% by weight, and preferably between 2 and 10% by weight , relative to the total weight of the composition. 9. Composition according to any one of claims 6 to 8, characterized in that it also contains carotenoids such as f £ y-carotene or canthaxantine. 10. Composition according to any one of claims 1 to 9, characterized in that it additionally contains at least one solubilizing agent 4 chosen from lower monoalcohols containing 1 to 6 carbon atoms, glycols and triglycerides of fatty acids in C8 “C18 * 11. Composition according to any one of claims 1 to 10, characterized in that it also contains cosmetic adjuvants chosen from emulsifiers, thickeners, softeners, humectants, emollients, wetting agents, preservatives, defoamers, perfumes and dyes. 12. Composition according to any one of claims 1 to 11, characterized in that it is in emulsion in the form of milk or cream, in solution in the form of oleoalcoholic lotion or oil, or in the form of oleoalcoholic gel or is packaged as an aerosol. 13. A method for accelerating the tanning of the human epidermis, characterized in that a composition as defined in claim 1 is applied to the skin, and the skin is exposed to UV-A radiation . * ‘EssiriE: ........ XL boards / fß. cscoc ccr-t A ... rare d = Ah;? ·:: · .. ï - ”6. · = ':: r λ · -r-. • JxerribcLTfc, \ î HL £ 1 * ffiSP.ii * ~ Λ U - r * i