WO2021190735A1

WO2021190735A1 - Cosmetic composition for making up or caring for keratin materials comprising a fluorescent compound from the family of 4-bora-3a,4a-diaza-s-indacenes, and/or from the family of difluoroborane beta-diketonates

Info

Publication number: WO2021190735A1
Application number: PCT/EP2020/058220
Authority: WO
Inventors: Cosimo PRETE; Alexis DEPAUW; Jérémy MALINGE
Original assignee: Crime Science Technology
Priority date: 2020-03-24
Filing date: 2020-03-24
Publication date: 2021-09-30

Abstract

The present invention pertains to the cosmetics field and more particularly relates to fluorescent compounds from the family of 4-bora-3a,4a-diaza-s-indacenes, and/or from the family of difluoroborane β-diketonates, and also to the use thereof in a method for making up or caring for human keratin materials and as an agent intended to give the keratin materials at least one property chosen from light reflection, sheen and unification, as a colouring agent, as an agent for intensifying radiance and brightening colours, as a bleaching agent, as an agent intended to give the complexion at least one quality chosen from: uniformity, homogeneity, transparency and porcelain appearance. It also relates to a composition for caring for keratin materials for the use thereof for protecting the skin from ultraviolet radiation.

Description

Title: Cosmetic composition for making up or caring for keratin materials comprising a fluorescent compound of the 4-bora-3a, 4a-diaza-s-indacenes family, and / or of the difluoroborane beta-diketonate family

Technical area

The present invention relates to the field of cosmetics and relates more particularly to fluorescent compounds of the family of 4-bora-3a, 4a-diaza-s-indacènes, and / or of the family of difluoroborane b-diketonate , as well as their use in a process for making up or caring for keratin materials in human beings and as an agent intended to confer on keratin materials at least one property chosen from light reflection, shine, G unification, as a coloring agent, as an agent for intensifying the radiance and brightening up the colors, as a bleaching agent, as an agent intended to give the complexion at least one quality chosen from: uniformity, homogeneity, transparency, porcelain appearance. It also relates to a composition for caring for keratin materials for its use for protecting the skin against ultraviolet radiation.

Prior art

[0002] The complexion, sometimes called complexion, is the color of the skin. It can be more or less dark, more or less homogeneous according to the genetic profile, the habits of life. The complexion begins to dull and blur with age. This natural aging process can be accelerated by external elements such as pollution, fatigue, stress, tobacco. It is thus desirable to obtain cosmetic compositions which make it possible to improve the appearance of keratin materials and in particular the appearance of its surface, and in particular the appearance of the complexion of the skin, an external sign of health. Cosmetic compositions comprising optical brighteners with certain cosmetic compounds such as skin whitening agents, filters, anti-wrinkles, and moisturizers have been described for their properties of giving the complexion greater uniformity, greater homogeneity. , greater transparency. For example, patent FR2778561 will be cited. [0003] Furthermore, damaged hair is perceived by the consumer as causing an unfavorable appearance and less manageability of the hair. This unfavorable appearance includes the alteration of the coloring of the original color, less shine, less reflections. The use of optical brighteners or fluorescent compounds in the field of hair care is known.

[0004] In addition, sun exposure is known to have harmful effects on the skin and hair. When ultraviolet (UV) rays penetrate the hair cuticle, highly reactive molecules called "free radicals" can be produced. The effects on the hair are therefore multiple. These molecules cause damage of several kinds such as the change of color caused by too much exposure to the sun, the hair fades and takes on a copper appearance as well as structural damage. The sun also causes premature aging of the skin and can cause and / or worsen the appearance of spots or irregular pigmentation on the skin. It is therefore necessary to provide protection against visible light.

Finally, pigments or fluorescent dyes are of great interest in cosmetics. They provide very bright and vivid colors that cannot be achieved with conventional dyes. When they do not absorb in the visible range, they also help to lighten and significantly increase the reflectance of the substrates on which they are deposited, such as skin or hair. These compounds, however, are difficult to formulate and the intensity of fluorescence can greatly decrease when included in formulations.

[0006] It is therefore desirable to have available cosmetic compositions which make it possible both to filter and / or protect keratin materials from UVA and UVB radiation and which, after application, have an aesthetic appearance, whether it be a healthy glow or skin effect. uniformity of skin tone when these compositions are applied to the skin, or shine and light reflection when applied to the hair. It is also desirable to have cosmetic compositions which make it possible to intensify the radiance and brighten up the shades of the cosmetic compositions during application to the skin, the hair or the nails.

Summary of the invention [0007] The aim of the invention is therefore to provide a cosmetic composition for making up or caring for keratin materials comprising fluorescent compounds exhibiting excellent stability and which retain their optical properties after inclusion in a cosmetic composition. Furthermore, the cosmetic compositions according to the present invention separately or jointly exhibit properties of filtering solar radiation while modifying the appearance and the color of the part treated and make it possible to offer cosmetic compositions combining protection and aesthetic appearance.

[0008] The subject of the invention is therefore, according to a first aspect, new fluorescent compounds of the family of 4-bora-3a, 4a-diaza-s-indacenes.

[0009] A subject of the invention is also a cosmetic composition for making up or caring for keratin materials comprising, in a physiologically acceptable medium, at least one fluorescent compound of the 4-bora-3a, 4a-diaza-s- family. indacenes and / or a compound of the difluoroborane b-diketonate family (BF2bdks).

[0010] A subject of the invention is also, according to a third aspect, a process for making up or caring for keratin materials comprising, on said keratin materials, the application of such a composition.

[0011] A subject of the invention, according to a fourth aspect, is the use of the new compounds or of a cosmetic composition according to the invention as an agent intended to confer on keratin materials at least one property chosen from the reflection of light. , shine, unification, as a coloring agent, as an agent for intensifying radiance and brightening colors.

[0012] A subject of the invention, according to a fifth aspect, is the use of the new compounds or of a cosmetic composition according to the invention as a bleaching agent, as an agent intended to give the complexion at least one quality chosen from: uniformity, homogeneity, transparency, porcelain appearance.

Finally, the subject of the invention is a composition for caring for keratin materials or a dermatological composition for its use for protecting the skin against ultraviolet radiation.

It is indeed to the merit of the Applicant to have observed that it was possible to formulate compositions exhibiting excellent stability and optical properties. remarkable and exhibiting fluorescence absorption and emission properties making it possible to protect and modify the appearance of the treated part.

Disclosure of the invention

[0015] The Applicant also deserves credit for having developed novel compounds which are particularly advantageous, in particular in cosmetic applications.

These compounds are compounds of the family of 4-bora-3a, 4a-diaza-s-indacene (s) of formula (I) below:

in which,

R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO ; acetyl, methacrylate and halogen.

R ² and R ² 'are independently selected from hydrogen and C 1 to C2 alkyl;

R ³ and R ³ 'are independently chosen from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, alkyl in C1 to C2, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;

R ⁴ and R ⁴ are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted with one or more groups chosen from C1 to C3 alkyl, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group

R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl

R ⁶ and R ⁶ 'are independently selected from C1 to C4 alkyl, C2 to C4 alkenyl, or aryl, said aryl being optionally substituted with one or more groups selected from C1 to C2 alkyl, hydroxy, R ⁵ COO- and halogen.

Preferred compounds of formula (I) of this embodiment are those in which one or more of RI, R2, R2 ', R3, R3', R4, R4 ', R5, R6, R6' are defined as follows:

R ¹ is a phenyl substituted with one or more groups chosen from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and is preferably methyl or G hydroxy;

R ² and R ² 'are independently selected from hydrogen and methyl;

R ³ and R ³ 'are independently chosen from hydrogen, C1 to C3 alkyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl , said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably hydrogen, methyl, ethyl, n-propyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, more preferably, R3 and R3 'are independently chosen from ethyl, n-propyl, methyl, vinyl, phenyl, phenanthryl, naphthyl, pyrenyl, thiophenyl, benzofuranyl, said vinyl, aryl and naphthyl being optionally substituted by one or more methyl, hydroxy, bromo, nitro and dimethylamino;

R ⁴ and R ⁴ 'are independently chosen from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R ⁴ and R ⁴ 'are independently chosen from methyl, vinyl, phenyl, phenanthracenyl, naphthalenyl, pyrenyl, thiphenyl, benzofuranyl, said vinyl, aryl and naphthalenyl being optionally substituted by one or more methyl, hydroxy, bromo, nitro and dimethylamino;

R ⁵ is C1 to C2 alkyl and preferably methyl or ethenyl.

R ⁶ and R ⁶ 'are independently selected from C1 to C4 alkyl, C2 to C4 alkenyl or aryl, said aryl being optionally substituted with one or more group (s) chosen from C1 to C2 alkyl, hydroxy, hydroxy, R ⁵ COO- and halogen, and preferably R ⁶ and R ⁶ are methyl or ethenyl

A particularly preferred compound is the compound of formula (II) set out below: The present invention also relates to a cosmetic composition for making up or caring for keratin materials, or a dermatological composition, comprising, in a physiologically acceptable medium, a compound of the 4-bora-3a, 4a-diaza-s- family. indacene (s) of formula (I).

The substitution of R ⁶ and R ⁶ 'by C1 to C4 alkyl, and in particular methyl, or C2 to C4 alkenyl is particularly advantageous for cosmetic applications, and does not induce loss of fluorescence properties compounds. The present invention also relates to a cosmetic composition for making up or caring for keratin materials, or a dermatological composition, comprising, in a physiologically acceptable medium, a compound of formula (II):

[0022] According to another embodiment, the cosmetic composition for making up or caring for keratin materials, or the dermatological composition, comprising, in a physiologically acceptable medium, a compound of the 4-bora-3a, 4a-diaza- family. s- indacene (s) of formula (I) or (II), may further comprise a compound of the difluoroborane b-diketonate family.

According to another embodiment, there is also provided a cosmetic composition for making up or caring for keratin materials, or a dermatological composition, comprising, in a physiologically acceptable medium, a fluorescent compound of the 4-bora-3a family. , 4a-diaza-s-indacenes of formula (III):

in which,

R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO and halogen;

R ² and R ² 'are independently selected from hydrogen and C1 to C2 alkyl; R ³ and R ³ 'are independently chosen from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, alkyl in

C1 to C2, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;

R ⁴ and R ⁴ 'are independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted with one or more groups chosen from C1 to C3 alkyl, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen , hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;

R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl;

R ⁶ and R ⁶ 'are independently chosen from C1 to C4 alkyl, C2 to C4 alkenyl or aryl, said aryl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy,

R5COO- and halogen; and / or a fluorescent compound of the difluoroborane b-diketonate family of formula (BF2bdks) (IV)

in which,

L ¹ is an unsaturated or nonexistent aliphatic chain,

L ² is an unsaturated or non-existent aliphatic chain,

R ¹ is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group,

R ² is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group, and

R ³ is chosen from hydrogen, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.

The compounds 4-bora-3a, 4a-diaza-s-indacenes are fluorescent dyes, the first synthesis of which was published in 1968 (A. Treibs et al, Justus Liebigs Ann. Chem. 1968, 718, 208). Since then, several other syntheses have been published (for example: Chem. Eur. J., 2009, 15, 5823; J. Phys. Chem. C, 2009, 113, 11844; Chem. Eur. J., 2011, 17, 3069; J. Phys. Chem. C, 2013, 117, 5373) and many 4-bora-3a, 4a-diaza-s-indacene compounds are commercially available, for example from ThermoFisher Scientific (Waltham, MA USA). The fluorescence of these compounds is in particular due to the presence of the 4-bora-3a, 4a-diaza-s-indacenes nucleus which exhibits a conjugation of the bonds of the heterocycles.

They have remarkable absorption and emission properties and in particular have relatively narrow fluorescent excitation and emission bands with high quantum yields f of between 0.5 and 1, which makes them very fluorescent . These molecules are initially known for uses as biological fluorescent probes or more recently for securing products.

[0026] In addition, these compounds exhibit good photostability as well as significant thermal stability. Indeed, the fluorescent dyes according to the invention are generally stable up to 300 ° C.

[0027] Compounds of the 4-bora-3a, 4a-diaza-s-indacenes family can be synthesized according to methods known to those skilled in the art. He may in particular refer to the publication of A. Loudet et al. (Chem. Rev. 2007, 107, 4891-4932).

A first compound of the difluoroborane b-diketonate family was described by GT Morgan and RB Tundstall in 1924 (J. Chem Soc. 125 (1924) 1963-1964) and since then, a multitude of compounds have been described and studied. For example, the document by P. -Z. Chen et al. Difluoroboron b-diketonate dyes: spectroscopic properties and applications, Coord. Chem. Rev. (2017) is a review describing synthesis methods, photophysical properties as well as applications of certain compounds of the difluoroborane b-diketonate family. This review mentions that these compounds exhibit exploitable fluorescence properties both in solution and in the solid state, and find applications as luminescent probe or optoelectronic device.

Likewise, the compounds of this family have remarkable absorption and emission properties. They have in particular relatively narrow fluorescent excitation and emission bands with high quantum yields f between 0.5 and 1, which also makes them very fluorescent. In addition, these compounds also exhibit good photostability as well as significant thermal stability.

For the description of the compounds used in the present invention, the terms and expressions used should, unless otherwise indicated, be interpreted according to the definitions below.

The term "halogen" denotes fluoro, chloro, bromo or iodo. Preferred halogen groups are fluoro and bromo, fluoro being particularly preferred.

The term "alkyl" denotes a hydrocarbon radical of formula CnH2n + 1, linear or branched, in which n is an integer greater than or equal to 1. Preferred alkyl groups are alkyl groups C1 to C6, linear or branched.

The term "alkenyl" denotes an unsaturated, linear or branched alkyl group comprising one or more carbon-carbon double bonds. Suitable alkenyl groups comprise from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms and more preferably still 2 or 3 carbon atoms. Non-limiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, with ethenyl and 2-propenyl being preferred.

The term "cycloalkyl (e)", alone or as part of another group, denotes a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, in particular 5 to 10 carbon atoms, more particularly 6 to 10 carbon atoms. Suitable cycloalkyl radicals include, but are not limited to, cyclopentyl, cyclohexyl, norbornyl, adamantyl, especially cyclohexyl and adamantyl. Preferred cycloalkyl groups include cyclohexyl, adamant-1-yl, and adamant-2-yl.

The term "aryl" denotes a polyunsaturated, aromatic, monocyclic (for example phenyl) or polycyclic (for example naphthyl, anthracene, phenanthryl, pyrenyl) radical. Preferred aryl groups include phenyl, naphthyl, anthracene, phenanthryl, pyrenyl.

The term "heteroaryl" denotes an aromatic ring having 5 to 12 carbon atoms in which at least one carbon atom is replaced by an oxygen, nitrogen or sulfur atom or by -NH, which atoms nitrogen and sulfur may optionally be oxidized and which nitrogen atom may optionally be quaternized, or a cyclic system containing 2 to 3 fused rings each typically containing 5 or 6 atoms and of which at least one ring is aromatic, at least one carbon atom of the at least one aromatic ring being replaced by an oxygen atom, of nitrogen or sulfur or by -NH, which nitrogen and sulfur atoms can optionally be oxidized and which nitrogen atom can optionally be quaternized. Examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyridinyl, and benzofuranyl.

Preferred compounds of formula III are those in which one or more of RI, R2, R2 ’, R3, R3’, R4, R4 ’, R5, R6 and R6’ are defined as follows:

RI is a phenyl substituted with one or more groups chosen from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and more preferably from methyl or fluoro;

R2 and R2 'are independently selected from hydrogen and methyl;

R3 and R3 'are independently selected from hydrogen, C1 to C3 alkyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably hydrogen, methyl, ethyl, n-propyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, more preferably R3 and R3 'are independently selected from ethyl, n-propyl, methyl, vinyl, phenyl, phenanthryl, naphthyl, pyrenyl, thiophenyl, benzofuranyl, said vinyl, aryl and naphthyl being optionally sub stituated by one or more methyl, hydroxy, bromo, nitro and dimethylamino; R4 and R4 'are independently chosen from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with a or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R4 and R4 'are independently chosen from methyl, vinyl, phenyl, phenanthryl, naphthyl, pyrenyl, thiophenyl, benzofuranyl, said vinyl , aryl and naphthyl being optionally substituted by one or more methyl, hydroxy, bromo, nitro and dimethylamino;

R5 is methyl or ethenyl.

R6 and R6 'are independently selected from fluoro, C1 to alkyl

C4, C2 to C4 alkenyl or aryl, said aryl being optionally substituted by one or more groups selected from C1 to C2 alkyl, hydroxy, R5COO- and halogen, preferably R6 and R6 'are fluoro.

According to a particular embodiment, the compound (s) 4-bora-3a, 4a-diaza-s-indacene (s) used in the present invention can be chosen from those of formula (V ) below :

in which,

R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted by a or more groups selected from C1 to C2 alkyl, hydroxy, R ⁵ COO and halogen;

R ² and R ² 'are independently selected from hydrogen and C 1 to C2 alkyl;

R ³ and R ³ 'are independently selected from hydrogen and C 1 to C3 alkyl;

R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ;

R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl.

Preferred compounds of formula (V) of this embodiment are those in which one or more of R1, R2, R2 ’, R3, R3’, R4, R4 ’and R5 are defined as follows:

R ¹ is a phenyl substituted with one or more groups chosen from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and more preferably from methyl or fluoro; R ² and R ² 'are independently selected from hydrogen and methyl;

R ³ and R ³ 'are independently selected from hydrogen, methyl, ethyl, n-propyl and preferably ethyl;

R ⁴ and R ⁴ 'are independently chosen from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R ⁴ and R ⁴ 'are independently chosen from methyl, vinyl, phenyl, phenanthracenyl, naphthalenyl, pyrenyl, thiphenyl, benzofuranyl, said vinyl, aryl and naphthalenyl being optionally substituted by one or more methyl, hydroxy, bromo, nitro and dimethylamino; R ⁵ is methyl or ethenyl.

Particularly preferred compounds of formula V are those of Table 1 below:

Table 1

As mentioned above, all of the compounds according to the invention are fluorescent due to the presence of the 4-bora-3a, 4a-diaza-s-indacenes nucleus.

Preferred compounds of the difluoroborane b-diketonate family of formula IV are those in which one or more of L1, L2, RI, R2, and R3 are defined as follows:

L ¹ is an unsaturated aliphatic chain, preferably C2 to C8 or nonexistent,

L ² is an unsaturated aliphatic chain, preferably C2 to C8 or nonexistent,

R 1 is an unsubstituted or substituted aryl group, preferably an aryl group which is unsubstituted or substituted by at least one electron-donor or electron-withdrawing group,

R2 is an unsubstituted or substituted aryl group, preferably an aryl group which is unsubstituted or substituted by at least one electron-donor or electron-withdrawing group, and R3 is chosen from hydrogen and a substituted or unsubstituted aryl group.

Preferred compounds of the difluoroborane b-diketonate family of formula IV are those in which one or more of L ¹ , L ² , R ¹ , R ² , and R ³ are defined as follows:

L ¹ is an unsaturated C2 to C4 aliphatic chain or nonexistent,

L ² is an unsaturated C2 to C4 aliphatic chain or nonexistent, Ri is an aryl group unsubstituted or substituted by at least one group chosen from hydroxy, alkoxy, alkyl, aryl, dialkylamino, thioalkoxy, halogen,

R2 is an aryl group unsubstituted or substituted by at least one group selected from hydroxy, alkoxy, alkyl, aryl, dialkylamino, thioalkoxy, halogen, and R3 is selected from hydrogen and an unsubstituted aryl group.

L ¹ is an unsaturated C2 to C4 aliphatic chain or nonexistent,

L ² is an unsaturated C2 to C4 aliphatic chain or nonexistent,

R 1 is an aryl group which is unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, C1 to C8 alkyl, aryl, C1 to C4 dialkylamino, C1 to C4 thioalkoxy, halogen, preferably fluorine,

R2 is an aryl group which is unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, C1 to C8 alkyl, aryl, C1 to C4 dialkylamino, C1 to C4 thioalkoxy, halogen, preferably fluorine, and

R3 is a hydrogen atom.

L ¹ is an unsaturated C2 or non-existent aliphatic chain,

L ² is an unsaturated C2 or non-existent aliphatic chain,

R 1 is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, preferably methoxy, C1 to C8 alkyl, preferably tert-butyl, aryl , C1 to C4 alkylamino, preferably dimethylamino,

R2 is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, preferably methoxy, C1 to C8 alkyl, preferably tert-butyl, aryl , C1 to C4 alkylamino, preferably dimethylamino, and

R3 is a hydrogen atom.

Preferred compounds of the difluoroborane b-diketonate family are those of formula IV2 below: wherein R ¹ , R ² and R ³ are as defined in formula IV.

Preferred compounds of the difluoroborane b-diketonate family are those of formula IV3 below:

wherein L ¹ , R ¹ , R ² and R ³ are as defined in formula IV.

Preferred compounds of the difluoroborane b-diketonate family are those of formula IV4 below:

Wherein L ² , R ¹ , R ² and R ³ are as defined in formula P.

Particularly preferred compounds of the difluoroborane b-diketonate family of formula IV are those below:

Compound 1 Compound 2

Compound 3 Compound 4

Compound 13 Compound 14 For the purposes of the present invention, the expressions “fluorescent compound of the family of 4-bora-3a, 4a-diaza-s-indacenes”, “fluorescent compounds of the family of difluoroborane b-diketonate” and “compound fluorescent ”are considered synonymous except where the context will clearly identify that this is not the case.

The composition according to the invention comprises a physiologically acceptable medium, and preferably cosmetically or dermatologically acceptable. The expression “physiologically acceptable medium” or “cosmetically acceptable” or “dermatologically acceptable” within the meaning of the present invention means any medium which does not exhibit deleterious side effects and in particular which does not produce redness or overheating, unacceptable tightness or stinging for a user of cosmetic products. The medium is thus compatible with the keratin materials of human beings such as the skin, the mucous membranes, the scalp or the hair, the hair system, the nails.

The composition according to the invention can be in all the galenic forms used in the cosmetics field, normally used for topical application such as emulsions (in particular cream or milk), gels, creams, solutions, dispersions of the lotion or serum type, emulsions of liquid or semi-liquid consistency obtained by dispersing a fatty phase in an aqueous phase (oil-in-water emulsion, O / W) or vice versa (water-in-oil emulsion , W / O), suspensions, lotions, loose, compact powders, sticks, microemulsions, microcapsules, microparticles or vesicular dispersions of ionic and / or nonionic type, varnishes, body oils, masks, ointments, ointments, concentrated solutions. These dosage forms are obtained according to the usual methods known to those skilled in the art. These dosage forms additionally contain usual and cosmetologically acceptable excipients and carriers.

These excipients suitable for the formulation are well known to those skilled in the art and in particular comprise penetrating agents such as phytantriol, octyl dodecanol and escin; thickeners such as natural gums and synthetic polymers; surfactants; emollients such as cetearyl octanoate, isopropyl myristate, cetearyl isononanoate, dimethicone, cyclomethicone, polyglyceryl 3-diisostearate, hydrogenated polyisobutene, cetyl alcohol, cetyl palmitate, phosphate cetyl; emulsifiers such as polyglycerol derivatives; preservatives such as phenoxyethanol and dehydroacetic acid; dyes; the perfumes ; etc ...

As other ingredients which can be used in the compositions of the invention, mention may be made of moisturizing agents such as glycerin, butylene glycol, the sodium salt of pyrrolidone carboxylic acid (sodium PCA), as well as combinations of glucosic derivatives with a hydrating and restructuring effect, as well as antioxidant vitamins.

The composition according to the present invention may comprise at least one additional coloring material. The term "coloring matter" denotes any organic or inorganic substance capable of providing a colored effect. Typically, fat-soluble or water-soluble dyes could be used. For illustrative purposes only, ALLURA RED 123, AMARANTH E123, AZORUBIN, BRILLIANT BLUE FCFE133, SUN YELLOW El 10, b-carotene, soybean oil.

Usually used pigments and nacres can also be incorporated into the cosmetic composition according to the invention. The pigments can be white or colored, mineral and / or organic. The pigments can be chosen from titanium dioxide, zirconium or cerium oxides, iron or chromium oxides, manganese violet, ferric blue. The pearlescent pigments may be chosen from white pearlescent pigments such as mica covered with titanium or titanium mica with iron oxides, titanium mica with ferric blue.

According to a particular embodiment, the compound (s) according to the invention is / are incorporated (s) in a matrix formed by a polymer or in an emulsion or a particle is / are encapsulated. This incorporation can be done by any techniques known to those skilled in the art to encapsulate the compound (s) according to the invention.

Typically, the incorporation can be done by polymerization. The incorporation can be done in all types of polymer such as for example polyacrylates, polymethacrylates, polyvinyls, polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, polyesters, polyvinyl alcohols, polymers and copolymers of vinylpyrrolidone, latexes, celluloses and their derivatives, acrylates copolymer or Styrene / Acrylates / ammonium Methacrylate Copolymer, polysaccharides such as chitosan or acacia gum.

The encapsulation or incorporation of the compound (s) according to the invention can be carried out by spray drying, also called spray drying. The process allows the formation of particles. Typically, polysaccharide solutions can be used to implement spray drying.

The spray cooling technique, also called atomization cooling or prilling, also called prilling process, can be used to obtain microspheres containing the fluorescent compound (s) according to the invention.

Mention will also be made of the coating process in a fluidized bed, encapsulation by extrusion or the SAS (Supercritical Antisolvent Cystallization) method.

The compound (s) according to the invention may / may also be incorporated in the form of emulsions by simple emulsion techniques (Oil / Oil or Oil / Water) according to which the compound (s) according to the invention is / will be dissolved in a dispersed phase, consisting, by way of illustration of a polymer solution, such as polylactic (PLA) or poly (lactic-co-glycolic) acids and in an organic solvent such as dichloromethane or ethyl acetate. The organic solution thus obtained is added to the continuous phase which can be an oil (oil / oil emulsion), or an aqueous solution (oil / water emulsion). The fluorescent compounds can also be incorporated by double emulsion (water / oil / water or oil / water / oil).

Simple or complex coacervation techniques can also be used in order to encapsulate the fluorescent compounds according to the invention in order to obtain particles, generally microcapsules, incorporating the compounds according to the invention. Alternatively, the compound (s) according to the invention may be incorporated into vesicular systems such as liposomes or else in vesicles of multilamellar types.

Thus, and advantageously, the compounds of 4-bora-3a, 4a-diaza-s-indacene (s) and b-diketonate of difluoroborane are intimately integrated in a matrix so as to form a homogeneous mixture. Thanks to their high thermal stability, the compounds according to the invention can be easily incorporated into polymer matrices, in particles or in emulsions. Advantageously, and against all expectations, the performance in terms of absorption and emission of fluorescence is not impaired by this encapsulation.

According to a preferred embodiment, the cosmetic composition has an amount of compounds according to the invention, between 0.01% and 5% by weight relative to the total weight of the composition, preferably between 0.01 and 0.5%, and more preferably between 0.5 and 0. 1%.

A subject of the invention is also a process for making up or caring for keratin materials comprising the application to said keratin materials of at least one composition as defined above.

The application to "keratin materials" means the application of at least one composition as defined above, to the skin, scalp, hair, body hair, lips, nails, ...

A further subject of the invention, according to another aspect, is the non-therapeutic use of fluorescent compounds according to formulas (I) or (II) as well as of cosmetic compositions according to the present invention as an agent intended to impart to the materials. keratin at least one property chosen from light reflection, shine, unification, as a coloring agent, as an agent for intensifying shine and brightening colors, as a bleaching agent, as an agent intended to impart to the complexion at least one quality chosen from: uniformity, homogeneity, transparency, porcelain appearance, healthy glow effect.

According to one embodiment, the present invention relates to the non-therapeutic use of a cosmetic composition comprising fluorescent compounds according to the invention as a bleaching agent, as an agent intended to impart the complexion to the skin. less one quality chosen from: uniformity, homogeneity, transparency, porcelain appearance, healthy glow.

[0072] According to one embodiment, the subject of the present invention is a composition for caring for keratin materials or a dermatological composition comprising fluorescent compounds according to the invention for its use for protecting the skin against ultraviolet radiation.

According to one embodiment, the present invention relates to G non-therapeutic use of a cosmetic composition comprising fluorescent compounds according to the invention, as an agent intended to confer on keratin materials at least one property chosen from the reflection of light, shine, G unification as a coloring agent, as an agent for intensifying shine and brightening up colors.

The compounds 4-bora-3a, 4a-diaza-s-indacene (s) and b-diketonate of difluoroborane have an absorption band in the ultraviolet (below 400 nm) or in the visible (between 400 and 800 nm). In the case of an ultraviolet absorption band, the compound incorporated into any matrix will not be visible to the naked eye. In the case of a visible absorption band, the color perceived by the naked eye will correspond to the color complementary to the color absorbed. For example, a compound absorbing around 500-520 nm, which corresponds to a green / blue color, will appear to the naked eye in orange / red tones. Regarding fluorescence properties, these compounds all have intense and very narrow emission bands in the visible range.

The compounds according to the invention exhibit both good absorption and fluorescence emission properties. These combined absorption and fluorescence emission properties give these molecules optical properties allowing them to be stimulated in particular by sunlight or even artificial lighting with fluorescence visible to the eye. naked. This makes it possible to jointly obtain properties of filtering solar radiation while modifying the appearance and color of the treated part.

Thus, this property thus makes it possible to protect the treated keratin materials from UV rays while giving the complexion a uniform appearance and a good-looking appearance, when the cosmetic compositions according to the invention are applied to the skin. When these compositions are applied to the hair, the compositions according to the invention will make it possible to protect the hair fibers thanks to their filtering properties against solar radiation, while intensifying the shine and the color of the hair fibers and by increasing the shine and light reflection of hair.

These fluorescence absorption and emission properties allow the compounds according to the present invention to modify the color of the treated part, and thus to act as a coloring agent.

[0079] In addition, this property allows the compounds according to the present invention to intensify the radiance and to brighten the colors of the cosmetic compositions comprising them during application to the skin, the hair or the nails. Thus, the effect of the compounds according to the invention is observed on a colored support (the hair) or in a colored composition (makeup such as mascara, nail varnish, lipstick). Indeed, once incorporated into the cosmetic composition, the compounds according to the invention exhibit a given shade under indirect lighting corresponding to their intrinsic color and can instantly and reversibly change shade under direct lighting (fluorescence color). When the cosmetic composition incorporating the compounds is applied to a curved surface, for example on the nails, the lips, the eyelashes, the hair, the fluorescence color will appear more preferably on the curved areas thus coloring said areas while the intrinsic color will be present on the flatter surfaces of said areas. Thus, the compounds according to the invention will make it possible to color the curved keratin materials to which they are applied, while intensifying the color of the keratin material or that of the cosmetic composition containing the compound.

[0080] Furthermore, the optical properties of the compounds according to the present invention make it possible to give the cosmetic composition skin whitening properties and thus to give the complexion greater uniformity, homogeneity, transparency, porcelain appearance.

This whitening property can also be used in a composition or for the preparation of a composition as a concealer or for masking scars, skin redness or skin lesions such as brown spots, commonly called "spots. "age spots, hyperpigmentation spots, spots secondary to fungal infection, wine spots, or acne. Properties optics of the compounds according to the invention will make it possible to “blur” the aforementioned lesions.

The non-therapeutic use of the cosmetic composition in accordance with the invention comprises all body and skin care including sun products, protectors and tanners, products ensuring the improvement of the appearance of the skin. , including alleviation of acne, skin redness and skin lesions. The non-therapeutic use in accordance with the invention also includes make-up products such as varnishes, mascaras, lipsticks, or hair products such as shampoos, conditioners, treatments, masks, restorative hair oils and / or protective. Advantageously, the compounds according to the invention can be incorporated in all body and skin care products as well as in all the makeup products mentioned above.

Preferably, the compounds according to the invention will be incorporated into nail varnishes. The composition according to the invention can in particular be provided in the form of a care, makeup and / or sun protection composition.

Examples

Example 1: sun protection composition

For this example, the fluorescent compound of the 4-bora-3a, 4a-diaza-s-indacenes family used is the compound of formula below:

This compound has a maximum absorption wavelength (L _m ax) at 526 nm, a maximum emission wavelength (L _m ax) at 542 nm, a quantum efficiency f of 75%, and a molar absorption coefficient e = 58000 L. mol ¹ . cm ¹ . The fluorescence of the compound under excitation by natural light is yellow / green in color.

This compound is added in a sun protection composition so as to obtain a final amount of 0.2% of fluorescent compound relative to the total weight of the composition.

The composition is then applied to the hair or the skin.

Thanks to the emission and absorption properties of the compound according to the present invention, the composition makes it possible to filter solar radiation and protect the skin from accelerated aging. Furthermore, the sunlight will generate the stimulation of the compounds contained in the composition according to the invention and modify the appearance of the treated keratin part. Thus, the sun protection composition according to the invention and thanks to its fluorescence will make it possible to unify the complexion when said composition is applied to the skin and will intensify the shine of the hair and their light-reflecting properties when applied to the skin. hair.

Example 2: nail varnish

For this example, the fluorescent compound of the 4-bora-3a, 4a-diaza-s-indacenes family used is the compound as described in Example 1 and is incorporated into a nail varnish.

This compound is added to a nail varnish so as to obtain a final amount of 0.3% relative to the total weight of the composition.

[0087] Once applied, the fluorescence color will appear more preferably on the curved areas of the nail and will color these areas while the intrinsic color will be present on the flatter surfaces.

Thus, and in the case of a nail varnish typically, the compounds according to the invention will make it possible to color certain areas of the nail while intensifying the shine and by brightening the base color of the nail varnish, once applied to the nail, but also in the bottle, causing an edge effect.

Claims

[Claim 1] Fluorescent compound of formula (II):

[Claim 2] Cosmetic composition for making up or caring for keratin materials comprising, in a physiologically acceptable medium, a fluorescent compound of the 4-bora-3a, 4a-diaza-s-indacene family of formula (I)

in which,

R ¹ is C1-C6 alkyl, C5-C6 cycloalkyl, C5-C heteroalkyl

C6, phenyl, said phenyl group being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO; acetyl, methacrylate, and halogen. R ² and R ² 'are independently selected from hydrogen and C 1 to C2 alkyl;

R ³ and R ³ 'are independently chosen from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group; R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group

R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl

R ⁶ and R ⁶ 'are independently selected from C1 to C4 alkyl, C2 to C4 alkenyl, or aryl, said aryl being optionally substituted with one or more groups selected from C1 to C2 alkyl, hydroxy, R5COO- and halogen

[Claim 3] Cosmetic composition according to claim 2 characterized in that

R ¹ is a phenyl substituted with one or more groups chosen from methyl or G hydroxy.

R ² and R ² 'are independently selected from hydrogen and methyl;

R ³ and R ³ 'are independently selected from among hydrogen, C1 to C3 alkyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine,

R ⁴ and R ⁴ 'are independently chosen from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted with one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine,

R ⁵ is C1 to C2 alkyl;

R ⁶ and R ⁶ 'is C1 to C2 alkyl.

[Claim 4] Cosmetic composition according to claims 2 or 3, characterized in that the fluorescent compound is a compound of formula (II):

[Claim 5] Cosmetic composition for making up or caring for keratin materials comprising, in a physiologically acceptable medium, a fluorescent compound of the 4-bora-3a, 4a-diaza-s-indacenes family of formula (III): in which,

R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted with one or more groups chosen from C1 to C2 alkyl, hydroxy,

R ⁵ COO and halogen;

R ² and R ² 'are independently selected from hydrogen and C1 to C2 alkyl;

R ³ and R ³ 'are independently chosen from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;

R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ; R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl;

R ⁶ and R ⁶ 'are independently selected from C1 to C4 alkyl, or aryl, said aryl being optionally substituted by one or more groups selected from C1 to C2 alkyl, hydroxy, R5COO- and halogen; and / or a fluorescent compound of the difluoroborane b-diketonate (BF2bdks) family of formula (IV)

in which,

L ¹ is an unsaturated or nonexistent aliphatic chain,

L ² is an unsaturated or non-existent aliphatic chain,

[Claim 6] Composition according to any one of claims 2 to 5, characterized in that said compound or said compounds is / are incorporated (s) in a matrix formed by a polymer or in an emulsion or is / are encapsulated (s) ) in a particle.

[Claim 7] Composition according to any one of claims 2 to 6, characterized in that the amount of fluorescent compounds is between 0.01 and 5% by weight relative to the total weight of the composition.

[Claim 8] A process for making up or caring for keratin materials comprising the application to said keratin materials of at least one composition according to one of claims 2 to 7 or of a compound according to claim 1.

[Claim 9] Non-therapeutic use of a cosmetic composition according to any one of claims 2 to 7 or of a compound according to claim 1, as a bleaching agent, as an agent intended to impart to the complexion at least one quality chosen from among : uniformity, homogeneity, transparency, porcelain appearance.

[Claim 10] Non-therapeutic use of a cosmetic composition according to any one of Claims 2 to 7 or of a compound according to Claim 1, as an agent intended to confer on keratin materials at least one property chosen from the reflection of the skin. light, shine, unification, or as a coloring agent, as an agent for intensifying radiance and brightening colors.

[Claim 11] A composition for caring for keratin materials according to any one of claims 2 to 7 or a compound according to claim 1 for its use for protecting the skin against ultraviolet radiation.