Patent Application
20230240954
The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, using a) one or more particular anthraquinone dyes and b) one or more fluorescent direct dyes; to a composition comprising a) and b). The present invention also relates to a multi-compartment device containing the compounds defined above.
Many people have sought for a long time to modify the colour of their hair and in particular to mask their grey hair.
It is especially known practice to dye keratin fibres, in particular human keratin fibres, with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
The shades obtained with these oxidation bases may be modified by combining them with couplers or colour modifiers. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
Another well-known method consists in obtaining semi-permanent dyeing by applying to the keratin fibres direct dyes, which are coloured and colouring molecules that have affinity for said fibres.
The direct dyes conventionally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes. The chemical species may be nonionic, anionic (acidic dyes) or cationic (basic dyes). The direct dyes may also be natural dyes.
Conventional direct dyeing processes consist in applying to keratin fibres dye compositions comprising direct dyes. After application, a leave-on time is observed so as to allow the dye molecules to penetrate by diffusion into the fibres. On conclusion of the process, the fibres are rinsed.
In contrast with oxidation dyeing, these direct dyeing processes have a tendency to better protect the integrity of the fibres. The resulting colourings are generally chromatic, but, however, are only semi-temporary. The nature of the interactions that bind the direct dyes to the keratin fibres and their desorption from the surface and/or the core of the fibre are responsible for their weak dyeing power.
Although a wide range of colours is currently accessible, it generally proves necessary to combine three dyes of complementary colours—trichromatic principle—in order to obtain a natural shade (see, for example, WO 95/15144 and WO 95/01772). This tripartite combination does not, however, show good persistence with respect to repeated shampooing. It generally, or even systematically, induces an unaesthetic changing of the colour, which the consumer finds dissuasive.
Another aim of the invention is thus to be able to dye light keratin fibres efficiently in chestnut-brown, dark chestnut-brown with a glint or even black, by mixing direct dyes, and preferably only two types of direct dye.
These colourings are furthermore not sufficiently fast in the face of external agents such as light or perspiration.
Thus, there is a real need to implement processes for the direct dyeing of keratin fibres, in particular of human keratin fibres such as the hair, which do not have the drawbacks mentioned above, i.e. which make it possible especially to lead to natural colourings that have good properties, especially in terms of chromaticity, power, intensity, sheen and selectivity, and which are persistent with respect to shampooing.
The Applicant has found, surprisingly, that a process for dyeing keratin fibres using a) one or more anthraquinone dyes chosen from those of formulae (I) and (II) and b) one or more fluorescent direct dyes makes it possible to achieve the objectives mentioned above; especially to lead to natural chestnut-brown, dark chestnut-brown with a glint or even black colourings, which are not only powerful and shiny, but also shampoo-resistant.
One subject of the present invention is especially a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising the application to said keratin fibres of ingredients a) and b) below:
in which formula (I) or (II):
—N(R7)—X1—W1 (a)
Another subject of the invention is a cosmetic composition comprising:
The combination of anthraquinone dye(s) of formula (I) or (II) and of fluorescent dye(s) makes it possible especially to obtain natural colourings that have good dyeing properties, especially in terms of chromaticity, power, intensity, sheen and selectivity.
Furthermore, the process and the composition according to the invention make it possible to dye light keratin materials efficiently in chestnut-brown, dark chestnut-brown with a glint or even black, by mixing direct dyes, and in particular only the ingredients a) and b) as defined previously as dyes, without the need to use additional (or complementary) dye(s) other than a) and b).
Moreover, the colourings obtained by means of the process and the composition according to the invention show good resistance to the various attacking factors to which the hair may be subjected, such as light, bad weather, washing and perspiration. They are in particular persistent with respect to shampooing, especially after at least three shampoo washes.
A subject of the present invention is also a multi-compartment device comprising a first compartment containing a composition comprising (a) one or more dyes of formula (I) or (II) as defined previously, and a second compartment containing a composition comprising (b) one or more fluorescent dyes as defined previously.
Another subject of the invention is the use of a) fluorescent dye(s) as defined previously, combined with b) one or more dyes of formula (I) or (II) as defined previously, for dyeing light keratin fibres, especially human keratin fibres such as the hair, in chestnut-brown, dark chestnut-brown or even black, without the need to use additional dye(s) other than a) or b).
Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.
For the purposes of the present invention and unless otherwise indicated:
In particular, the anionic counterions are chosen from halides such as chloride, bromide, fluoride or iodide; a hydroxide; a sulfate; a hydrogen sulfate; a linear or branched C1-C6 alkyl sulfate, such as the methylsulfate or ethylsulfate ion; carbonates and hydrogen carbonates; carboxylic acid salts such as formate, acetate, citrate, tartrate and oxalate; linear or branched C1-C6 alkylsulfonates, such as the methylsulfonate ion; arylsulfonates for which the aryl part, preferably phenyl, is optionally substituted with one or more C1-C4 alkyl radicals, for instance 4-tolylsulfonate; alkylsulfonates such as mesylate;
(a) Anthraquinone Dyes
The process for dyeing keratin fibres according to the present invention comprises the application to said keratin fibres of (a) one or more anthraquinone dyes chosen from the compounds of formulae (I) and (II) as defined previously, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the solvates thereof, and mixtures thereof.
In particular, the dyes of formulae (I) and (II) are violet, blue or green.
According to a particular embodiment of the invention, a) the anthraquinone dye(s) of the invention are chosen from the dyes of formula (I) as defined previously.
According to a particular embodiment of the invention, a) the anthraquinone dye(s) of the invention are chosen from one or more dyes of formula (I) and n is equal to 0. According to another embodiment, n is equal to 1. Preferably, the substituents R1, R2, R3 and R4 are in positions 1, 4, 5 and 8.
According to a particular embodiment of the invention, the dyes are of formula (I), with R1 and R3 representing an atom or group chosen from i) hydroxyl, ii) arylamino or aryl(C1-C6)alkylamino with the aryl group representing an optionally substituted aryl group, in particular a phenyl group optionally substituted with one or more groups chosen from hydroxyl, (C1-C4)alkyl, carboxyl, (C1-C4)alkoxycarbonyl, (di)(hydroxy)(C1-C4)(alkyl)amino, tri(C1-C4)alkylammonium, (C1-C4)alkoxy, (di)hydroxysulfonyloxy(C1-C4)alkylamino, hydroxysulfonyl, iii) (di)(hydroxy)(C1-C6)(alkyl)amino, iv) (di)(C1-C4)(alkyl)amino(C1-C6)alkylamino, v) (C1-C4)alkylcarbonylamino(C1-C6)alkylamino, vi) arylsulfonylamino with the aryl group possibly being optionally substituted, aryl preferably representing a phenyl group, vii) (di)halo(C1-C4)alkylamino, viii) (di)(hydroxy)(C1-C4)alkoxy(C1-C4)alkylamino, ix) (di)tri(C1-C4)alkylammonium(C1-C6)alkylamino, x) heterocycloalkyl(C1-C6)alkylamino, heterocycloalkyl(C1-C4)alkylcarbonylamino, heterocycloalkyl(C1-C4)alkylamino(C1-C4)alkylcarbonylamino or heterocycloalkyl(C1-C4)alkylcarbonylamino(C1-C6)alkylamino, said heterocycloalkyl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl or benzyl groups, xi) halo(C1-C4)alkylcarbonylamino(C1-C6)alkylamino, xii) hydroxysulfonyl, xiii) halo such as chlorine, xiv) heteroaryl(C1-C6)alkylamino, said heteroaryl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl groups, xv) heteroaryl(C1-C4)alkylcarbonylamino(C1-C6)alkylamino, said heteroaryl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl groups, xvi) R′R″N— with R′ and R″, which may be identical or different, representing a hydrogen, a (halo)(C1-C4)alkylcarbonylamino(C1-C6)alkyl group, a (halo)(C1-C4)alkylaminocarbonyl (C1-C6)alkyl group, (halo)(C1-C4)alkylcarbonyl group, a carboxy(C1-C6)alkyl group, the alkyl group possibly being substituted with one or more amino or hydroxyl groups, a (poly)hydroxy(C1-C6)alkyl group, xvii) (C1-C16)alkylaminocarbonylamino(C1-C6)alkylamino, xviii) formylamino(C1-C6)alkylamino, xix) (hydroxy)(C1-C6)alkylamino(C1-C6)alkylamino, xix) (poly)hydroxysulfonyl(C1-C6)alkylamino(C1-C6)alkylamino, xx) sulfonato(C1-C6)alkyl(di(C1-C4)alkyl)ammonium(C1-C6)alkylamino, xxi) hydroxysulfonyl(C1-C6)alkoxy(C1-C6)alkylamino, xxi) heteroaryl(C1-C4)alkylcarbonylamino, said heteroaryl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl groups, xxii) heterocycloalkyl(C1-C4)alkylcarbonylamino, said heterocycloalkyl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl or benzyl groups, xxiii) (di)(C1-C4)(alkyl)amino(C1-C6)alkylamino, the (C1-C6)alkyl group possibly being substituted with one or more hydroxyl groups, xxiv) heterocycloalkylamino(C1-C6)alkylamino or heterocycloalkylamino, said heterocycloalkyl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl or benzyl groups, xxv) heteroarylalkylamino(C1-C6)alkylamino or heteroarylalkylamino, said heteroaryl possibly being optionally cationic and/or substituted especially with one or more (C1-C4)alkyl groups, xxvi) tri(C1-C6)alkylammonium(C1-C6)alkylamino, xxvii) (C1-C4)alkoxycarbonyl(C1-C6)alkyl(di(C1-C4)alkyl)ammonium(C1-C6)alkylamino, xxviii) carboxylato(C1-C6)alkyl(di(C1-C4)alkyl)ammonium(C1-C6)alkylamino, xxix) carboxy(C1-C6)alkylamino(C1-C6)alkylamino, xxx) aryl(C1-C4)alkyl(di(C1-C4)alkyl)ammonium(C1-C6)alkylamino, xxxi) sulfonic SO3H or sulfonate SO3—, M+ with M+ representing a cationic counterion, xxxii) (C1-C6)alkyl, xxxiii) hydroxysulfonyl(C1-C4)amino, xxxiv) phenylsulfonylamino.
Preferably, the dyes of formula (I) are such that n is equal to 1 and the groups R2 and R4 are in positions 1 and 4.
According to a particular embodiment of the invention, the dyes are of formula (I) with R2 and R4 representing a hydrogen atom.
According to a particular embodiment of the invention, the dyes are of formula (I) with R2 and R4, which may be identical or different, representing a hydrogen atom or a group as defined previously for R1 and R3 i) to xxxii), preferably chosen from:
According to another particular embodiment of the invention, the dyes are of formula (I), with R2 and R3 representing a hydrogen atom, and R1 and R4 are preferably in positions 8 and 4, respectively, and R1 and R4 are as defined previously, in particular represent an atom or group as defined previously for R1 and R3 i) to xxxii), preferably R1 and R4 are chosen from:
According to another particular embodiment of the invention, the dyes are of formula (I), with R3 and R4 representing a hydrogen atom, and R1 and R2 are preferably in positions 8 and 1, respectively, and R1 and R2, are as defined previously, in particular represent an atom or group as defined previously for R1 and R3 i) to xxxii), preferably R1 and R2 are chosen from:
According to another particular embodiment of the invention, the dyes are of formula (I), with R1 and R3 representing a hydrogen atom, and n is equal to 2, R2 and R4 are preferably in positions 1, 2 and 4, respectively, and R2 and R4, are as defined previously, in particular represent an atom or group as defined previously for R1 and R3 i) to xxxii), preferably R2 and R4 are chosen from:
According to another particular embodiment of the invention, the dyes are of formula (I), n is equal to 0, R1, R3 and R4 are preferably in positions 8, 5 and 4, respectively, and are as defined previously, in particular represent an atom or group as defined previously for R1 and R3 i) to xxxii), R1 and R3 preferably representing a hydrogen atom.
According to one embodiment, n is equal to 0, R3 and R4 represent a hydrogen atom, and R1 is as defined previously and is in position 7 or 8.
According to another particular embodiment of the invention, a) the anthraquinone dye(s) are chosen from the symmetrical dyes bearing a disulfide group of formula (II′):
with R′1, R′2, R′3 and R′4, T1 and Xa as defined previously, Xa, preferably represents a N(Ra) and particularly NH. More particularly, R′2 and R′4 represent a hydrogen atom and R′1 and R′3 are in particular as defined previously for R1 and R3 i) to xxxii); preferably, R′3 and R′4, which may be identical or different, represent a group chosen from (C1-C6)alkyl and (di)(hydroxy)(C1-C4)(alkyl)amino.
Preferably, T1 represents a saturated linear divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, preferably between 2 and 10 carbon atoms, optionally interrupted with one or more groups chosen from N(Rb), C(O), —N+(R8)(R9)-An, cationic heteroaryl such as imidazolium, An or combinations thereof, with Ra and R9, which may be identical or different, represent a C1-C6 alkyl radical; Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably said hydrocarbon-based chain is interrupted with one or more groups chosen from —N+(R8)(R9)-An, N(Rb), C(O), and combinations thereof such as —C(O)—N(Rb)— or —N(Rb)—C(O)—, N+(R8)(R9)-An.
Preferably, T1 represents a divalent group —(CH2)n-Ta-(CH2)m-Tb-(CH2)p— with Ta, and Tb, which may be identical or different, represent a bond or a group chosen from N(Rb), C(O), —N+(R8)(R9)-An, cationic heteroaryl such as imidazolium, An or combinations thereof, with R8 and R9, which may be identical or different, represent a C1-C6 alkyl radical; Rb representing a hydrogen atom or a (C1-C4)alkyl group, preferably —N+(R8)(R9)-An, —C(O)—N(Rb)— or —N(Rb)—C(O)—, n, m and p, which may be identical or different, represent an integer between 1 and 10 inclusive, with the sum n+m+p inclusively between 1 and 20, preferably between 2 and 10.
Preferentially, the groups R′1 and R′3 are in positions 2′ and 4′, and R′2 and R′4 are in positions 5′ and 8′.
More particularly, a) the anthraquinone dye(s) of the invention are chosen from the symmetrical dyes bearing a disulfide group of formula (II″):
in which formula (II″) R′1, R′2, R′3 and R′4, T1 and Xa are as defined previously for (II′).
According to a particular embodiment of the invention, a) the anthraquinone dye(s) of the invention are chosen from the dyes of formula (II) as defined previously in which Y represents a hydrogen atom or a thiol-function protecting group.
The anthraquinone dyes of the invention which contain a function SY of formula (II) may be in the covalent form —S—Y or the ionic form —S−Y+ depending on the nature of Y and the pH of the medium.
One particular embodiment concerns the anthraquinone thiol dyes of formula (II) bearing a function SY in which Y represents a hydrogen atom or an alkali metal. Advantageously, Y represents a hydrogen atom.
In accordance with another particular embodiment of the invention, in the abovementioned formula (II), Y is a protecting group known to those skilled in the art, for instance those described in the publications “Protective Groups in Organic Synthesis”, T. W. Greene, published by John Wiley & Sons, N Y, 1981, pages 193-217; “Protecting Groups”, P. Kocienski, Thieme, 3rd edition, 2005, chapter 5.
In particular, when Y represents a thiol-function protecting group, Y is chosen from the following radicals:
According to a particular embodiment, the thiol-protected anthraquinone dyes of formula (II) comprise a group Y chosen from i) aromatic cationic 5- or 6-membered monocyclic heteroaryl comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8- to 11-membered bicyclic heteroaryl such as indolinium, benzimidazolium, benzoxazolium, benzothiazolium, these monocyclic or bicyclic heteroaryl groups optionally being substituted with one or more groups such as alkyl, for instance methyl, or polyhalo(C1-C4)alkyl such as trifluoromethyl; iii) or the following heterocyclic:
in which R′c and R′d, which may be identical or different, represent a hydrogen atom or a group (C1-C4)alkyl; preferentially, R′c to R′d represent a group (C1-C4)alkyl such as methyl; and An represents a counterion.
In particular, Y represents an alkali metal or a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted with one or more (C1-C4)alkyl groups, especially methyl.
In particular, Y represents an alkali metal or a protecting group such as:
Preferably, the anthraquinone dye(s) are chosen from the following compounds, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the solvates thereof, and mixtures thereof:
with An, which may be identical or different, representing an anionic counterion as defined previously, preferably chosen from mesylate, tosylate and halide such as Cl− and I−.
The dyes of formulae (I) and (II) of the invention are known commercial products, or are accessible via standard synthetic routes known to those skilled in the art. Examples that may be mentioned include: Chemical Reviews, “The chemistry of anthraquinones”, 6, pages 157-174 (1926); and Colourage “Blue disperse dyes—structural diversities”, 55 (11), pages 36, 38 and 42 (2008).
(b) Fluorescent Dyes
The process for dyeing keratin fibres according to the present invention and the composition of the invention also use, or comprise, (b) one or more fluorescent dyes. Preferably, the fluorescent dye(s) of the invention are direct dyes. More particularly, the fluorescent dyes of the invention are other than fluorescent dyes comprising a disulfide bond; preferably, the fluorescent dyes of the invention are direct and do not comprise a bond with identical contiguous heteroatoms.
As fluorescent dyes that may be used in the present invention, mention may be made of the following dyes: acridines, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}borons (BODIPY®), dipyrinones, diketopyrrolopyrroles, fluorindines, (poly)methines (especially cyanins and styryls/hemicyanins), naphthalimides, naphthanilides, naphthylamine (such as dansyls), naphtholactams, oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes, xanthenes, thioxanthenes and thiazines. Mention may also be made of the fluorescent dyes described in EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144, EP 714 954 and those listed in the encyclopaedia The chemistry of synthetic dyes by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in Kirk Othmer's encyclopaedia Chemical Technology, in the chapter “Dyes and Dye Intermediates”, 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry 7th edition, Wiley and Sons, especially in Ullmann's Encyclopedia of Industrial Chemistry in the chapter “Fluorescent Dyes”, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/143560007.a 1_279; in The Handbook—A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/Invitrogen—Oregon 2005 circulated by Internet or in the preceding printed editions.
Preferably, the fluorescent dyes (b) of the invention are chosen from coumarin dyes, (poly)methine dyes, in particular cyanin and styryl/hemicyanin dyes, and naphthalimide dyes. More particularly, the fluorescent dyes of the invention are cationic.
In particular, the fluorescent dye(s) of the invention are direct dyes chosen from (poly)methyl dyes, in particular cyanin dyes and styryl/hemicyanin dyes, and naphthalimide dyes, and mixtures thereof; more particularly, the fluorescent dyes are cationic; preferably, the fluorescent dye(s) (b) are chosen from styryl or hemicyanin cationic dyes.
Better still, the fluorescent dyes of the invention absorb light in the yellow, orange and red range, preferably in the absorption wavelength λabs between 400 nm and 500 nm inclusive.
According to one variant, the fluorescent dyes of the invention contain at least one cationic radical borne by, or included in, at least one of the fluorescent chromophores.
Preferably, the cationic radical is a quaternary ammonium; better still, the cationic charge is endocyclic.
These cationic radicals are, for example, a cationic radical:
According to a preferred variant of the invention, the fluorescent dyes of the invention bear at least one cationic chromophore and comprise at least one quaternary ammonium radical such as polymethine chromophores chosen from formulae (III) and (IV) below:
W+—[C(Rc)═C(Rd)]m′—Ar′-(*)Q− (III)
Ar—[C(Rd)═C(Rc)]m′—W′+-(*)Q− (IV),
in which formulae (III) and (IV):
Preferably, W+ or W′+ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium radical optionally substituted with one or more identical or different C1-C4 alkyl radicals.
According to a particularly preferred embodiment of the invention, the fluorescent chromophore(s) of the dye (III) or (IV) are those defined previously with m′=1, Ar representing a phenyl group substituted para to the styryl group —C(Rd)═C(Rc)— with a (di)(hydroxy)(C1-C6)(alkyl)amino group such as dihydroxy(C1-C4)alkylamino, and W′+ representing an imidazolium or pyridinium group, preferentially ortho- or para-pyridinium.
According to another preferred variant of the invention, the fluorescent chromophore(s) of the dyes are cationic and comprise at least one quaternary ammonium radical such as a naphthimidyl bearing a cationic exocyclic charge of formula (IIIa) or (IVa):
in which formulae (IIIa) and (IVa) Re, Rf, Rg and Rh, which may be identical or different, represent a hydrogen atom or a (C1-C6)alkyl group which is optionally substituted, preferably with a di(C1-C6)alkylamino or tri(C1-C6)alkylammonium group such as trimethylammonium. According to a particular embodiment, the fluorescent dye(s) (b) of the invention are chosen from those of formula (V), (VI) or (VII) below:
and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formulae (V), (VI) and (VII):
According to a preferred embodiment, the fluorescent dyes of the invention are chosen from the styryl dyes of formula (VIII) below:
and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates;
in which formula (VIII) G, G1, Ra, R′a, R″a, Rb, R′b, R″b, Ri, R′i, R1, R2 and m are as defined previously for (V).
In particular, the dye(s) of the invention are chosen from those of formula (VIII) for which:
and also the organic or mineral acid salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates;
in which formula (IX) G, G1, Ra, R′a, Rb, R′b and m are as defined previously.
According to a particular embodiment, the group G is in the para position relative to the —CH═CH— group, i.e. in position 4′ of the phenyl group. According to another particular embodiment of the invention, the group G is in the ortho position relative to the —CH═CH— group, i.e. in position 2′ of the phenyl group. According to one embodiment, the —CH═CH— group is in the para position of the pyridinium group, i.e. in position 4.
According to another advantageous variant, the —CH═CH— group is in the ortho position of the pyridinium group, i.e. in position 2.
According to a preferred embodiment of the invention, the fluorescent dyes of the invention (b) are chosen from the compounds of formulae (X) and (XI) below:
and also the organic or mineral acid salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates; in which formulae (X) and (XI):
and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
According to one embodiment, the fluorescent dye(s) (b) are of formula (XI) with:
and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
Another subject of the invention is novel dyes chosen from those of formulae (X′) and (XI′) below:
in which formulae (X′) and (XI′) R5, R7, R8 and m are as defined previously for (X) and (XI), in particular:
and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
According to a preferred embodiment of the invention, the fluorescent dyes (b) of the invention are chosen from the compounds of formulae (XII) and (XIII) below:
and also the organic or mineral acid salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates;
in which formulae (XII) and (XIII):
and also the organic or mineral acid or base salts thereof, the optical isomers, geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
According to one embodiment, the dye(s) are of formula (XIII) with:
and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
More particularly, the fluorescent dye (b) of the invention are chosen from those of formulae (XII′) and (XIII′) below:
in which formulae (XII) and (XIII) R5, R7, R8 and m are as defined previously for (X) and (XI), in particular:
and also the organic or mineral acid or base salts thereof, the geometrical isomers and tautomers thereof, and the solvates thereof such as hydrates.
More particularly, the fluorescent dyes (b) of the invention are chosen from those of formula (V), (VIII) or (IX) as defined previously in which G represents a hydrogen atom.
More particularly, the fluorescent dyes (b) of the invention are chosen from those of formulae (XIV) and (XV) below:
in which formulae (XIV) and (XV) R5, R7, R8 and m are as defined previously for (X) and (XI), in particular:
According to one embodiment, the fluorescent dye(s) (b) of the invention are chosen from the following compounds, the geometrical isomers thereof, the tautomers thereof, the solvates thereof, and mixtures thereof:
with Y— representing an anionic counterion and Q+ representing a cationic counterion as defined previously.
The process for dyeing keratin fibres according to the present invention may optionally also comprise the application to said keratin fibres of one or more oxidizing agents.
Preferably, the oxidizing agent(s) are chosen from chemical oxidizing agents.
The term “chemical oxidizing agent” means an oxidizing agent other than atmospheric oxygen.
More particularly, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, hydrogen peroxide-generating systems, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof and percarbonates of alkali metals or alkaline-earth metals, and mixtures thereof.
Preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide and hydrogen peroxide-generating systems.
According to a preferred embodiment, the hydrogen peroxide-generating system(s) are chosen from urea peroxide, polymeric complexes that can release hydrogen peroxide, chosen from polyvinylpyrrolidone/H2O2; oxidases; perborates; and percarbonates.
Preferably, the chemical oxidizing agent is hydrogen peroxide, and more preferentially aqueous hydrogen peroxide solution.
The chemical oxidizing agent(s) are advantageously applied in the form of an aqueous solution of which the content of chemical oxidizing agents is preferably between 0.05% and 5% by weight and more preferentially between 0.1% and 2% by weight, relative to the total weight of the aqueous solution.
According to a preferred embodiment of the invention, the dyeing process does not use any oxidizing agent. According to a preferred embodiment of the invention, the cosmetic composition comprising ingredients (a) and (b) does not comprise any oxidizing agent.
The process for dyeing keratin fibres according to the present invention may optionally also comprise the application to said keratin fibres of one or more reducing agents. The reducing agent(s) that are useful in the present invention are advantageously chosen from the compounds of formula (XVI) below, and also the addition salts thereof, and mixtures thereof:
H(X)q(R10)t (XVI)
in which compound of formula (XVI):
According to a preferred embodiment of the invention, the dyeing process does not use any reducing agent. According to a preferred embodiment of the invention, the cosmetic composition comprising ingredients (a) and (b) does not comprise any reducing agent.
The anthraquinone compound(s) of formula (I) or (II) as defined previously, and (b) the fluorescent dye(s) as defined previously, and also, when they are present, the oxidizing agent(s) and/or the reducing agent(s), may be dissolved beforehand before being applied to the keratin fibres.
In other words, the ingredients used in the dyeing process of the present invention may be present in one or more compositions.
The composition(s) comprising the ingredients according to the present invention are cosmetic compositions, i.e. they are preferably aqueous. Besides water, they may comprise one or more organic solvents, or mixtures thereof.
Examples of organic solvents that may be mentioned include linear or branched C2 to C4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, for instance benzyl alcohol or phenoxyethanol, and mixtures thereof.
The pH of the composition(s) used in the dyeing process of the invention and of the composition of the invention comprising ingredients (a) and (b) is particularly between 2 and 12 approximately and preferably between 3 and 11 approximately. It may be adjusted to the desired value by means of acidifying or alkaline agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
The pH of the composition which comprises (a) and (b) and that of the composition(s) used in the dyeing process of the invention is preferentially between 6 and 11 inclusive, particularly between 7 and 10 and more particularly between 7.5 and 9.5, such as between 9 and 9.5.
Among the acidifying agents, mineral and organic acids as defined previously, mention may be made, by way of example, of mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Among the alkaline agents that may be mentioned, for example, are aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamines, diethanolamines and triethanolamines, and other alkaline agents as defined previously.
The composition(s) comprising the dye(s) of formula (I) as defined previously, and the fluorescent dye(s) as defined previously, may be in various presentation forms, such as in the form of liquids, lotions, creams or gels or in any other form that is suitable for dyeing keratin fibres. It may also be packaged under pressure in an aerosol container in the presence of a propellant or in a non-aerosol container and may form a foam.
When the ingredients used in the dyeing process according to the present invention are present in one or more composition(s), said composition(s) may also optionally comprise one or more additives, different from the ingredients of the invention and among which mention may be made of fatty substances, cationic, anionic, nonionic, amphoteric or zwitterionic surfactants, cationic, anionic, nonionic or amphoteric polymers or mixtures thereof, antidandruff agents, anti-seborrhoea agents, agents for preventing hair loss and/or for promoting hair regrowth, vitamins and provitamins including panthenol, sunscreens, mineral or organic pigments, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids, fragrances, preserving agents, pigments and ceramides.
Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the composition(s) in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition comprising them.
The process for dyeing keratin fibres according to the present invention comprises the application to said keratin fibres of the following ingredients:
In other words, the dyeing process according to the present invention may be performed in one or more steps.
According to a particularly preferred embodiment, the anthraquinone dye(s) of formulae (I) and/or (II) and the fluorescent dye(s) (b), as defined previously, are applied together (or jointly), i.e. simultaneously, to the keratin fibres. According to this embodiment, the dyeing process is performed in one step. One variant of the dyeing process of the invention involves applying a cosmetic composition according to the invention which comprises (a) the anthraquinone compound(s) of formulae (I) and/or (II) and (b) the fluorescent dye(s) as defined previously to the keratin fibres.
According to another particularly preferred embodiment, the anthraquinone dye(s) of formulae (I) and/or (II) as defined previously and the fluorescent dye(s) as defined previously are applied sequentially, i.e. successively. According to this other embodiment, the dyeing process is performed in at least two steps.
According to a first embodiment in at least two steps, the fluorescent dye(s) as defined previously are applied to the keratin fibres subsequently to the anthraquinone dye(s) of formulae (I) and/or (II) as defined previously. In other words, the fluorescent dye(s) as defined previously are applied after the anthraquinone dye(s) of formulae (I) and/or (II) as defined previously.
According to this first embodiment, the process for dyeing keratin fibres comprises the following steps:
According to a preferred embodiment in at least two steps, the anthraquinone dye(s) of formulae (I) and/or (II) as defined previously are applied to the keratin fibres subsequently to the fluorescent dye(s). In other words, the anthraquinone dye(s) of formulae (I) and/or (II) are applied after the fluorescent direct dye(s).
According to this preferred embodiment, the process for dyeing keratin fibres comprises the following steps:
Preferably, ingredients (a) and (b) are applied to the keratin fibres in a bath ratio that may range from 0.1 to 10 and more particularly from 0.2 to 8. For the purposes of the present invention, the term “bath ratio” means the ratio between the total weight of ingredient (a) or (b) and the total weight of keratin fibres to be treated.
When the dyeing process is performed in one step, ingredients (a) and (b) are advantageously left to stand on the keratin fibres for a time ranging from 1 to 90 minutes and more preferentially for a time ranging from 5 to 60 minutes.
When the dyeing process is performed in at least two steps, each of the ingredients (a) and (b) may be advantageously left to stand on the keratin fibres for a time ranging from 1 to 60 minutes and more preferentially for a time ranging from 5 to 45 minutes.
On conclusion of the dyeing process according to the invention, in one or at least two steps, the keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.
When the dyeing process is performed in at least two steps, the keratin fibres are advantageously rinsed with water between each step. In other words, the dyeing process may comprise an intermediate rinsing step between the application of the first ingredient and the application of the second ingredient. During this intermediate rinsing step, the keratin fibres may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.
The dyeing process according to the present invention may be performed at room temperature (25° C.) or with heating.
When they are present, the reducing agent(s) may be applied separately or together with one of the ingredients (a) or (b). Preferably, when they are present, the reducing agent(s) are applied together with the ingredient (b).
When they are present, the oxidizing agent(s) may be applied separately or together with one of the ingredients (a) or (b). Preferably, when they are present, the oxidizing agent(s) are applied after application of ingredients (a) and (b).
According to a particular embodiment, the process for dyeing keratin fibres according to the present invention comprises the following successive steps:
According to a particular embodiment of the dyeing process of the invention, no step of said process involves an oxidizing agent.
According to an advantageous embodiment of the dyeing process of the invention, no step of said process involves a reducing agent.
The dyeing process according to the present invention may be applied to wet or dry, preferably dry, keratin fibres.
The present invention also relates to a multi-compartment device comprising a first compartment comprising one or more anthraquinone dyes of formula (I) and/or (II) as defined previously, and a second compartment comprising one or more fluorescent dyes as defined previously.
According to a particular embodiment, the “keratin fibres” are human keratin fibres and more particularly the hair.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
The tests were performed:
The fluorescent dyes of the styrylpyridinium series evaluated in the context of the invention are the following:
The combinations of dyeing compounds were prepared on a 0.5 g lock of natural hair containing 90% white hairs as a mixture (NW90) according to 3 application modes:
In Reducing Medium:
In Non-Reducing Medium:
The following hair dyeing results were obtained:
It is seen that the process of the invention makes it possible to obtain very aesthetic and powerful brown colours just by combining a blue dye and a fluorescent dye.
3 series of locks (90% natural with hair—90 NW) have been carried out with an equimolar association of a reductive or not medium vs. comparative prior art EP0852943A1.
The tests has been carried out at a molar concentration of 5×10-3 mol % for each dye. The compositions are adjusted to pH 9-9.5 with an ammonia solution. The compounds tested on locks of 0.5 g of natural white hair (90 NWV) are the following:
The blue disulfide anthraquinone dye, and the hemicyanin dyes have been evaluated in the context of the comparison as follows:
After treating keratin fibers with dyes and shampoo locks have been dried and color on the locks has been measured with spectrocolorimeter Minolta CM2600d (angle 10°, illuminant D65) in the CIEL*a*b* system.
In this system, L* represents intensity of the color, a* represents the green/red color axis and b* the blue/yellow color axis.
The lowest L* measured, the most intensive is the color.
These results of the table show that the method according to the invention, using only two direct fluorescent dyes b), anthraquinone dye of formula (I) and/or (II) of the invention associated with a cationic fluorescent dye, makes it possible to obtain natural brown colors. This is not the case of the combination of an anthraquinone dye of formula (I) and/or (II) of EP0852943A1 combined with a non-cationic fluorescent dye a) for which the color obtained is blue (non natural color).
| Number | Date | Country | Kind |
|---|---|---|---|
| 1663123 | Dec 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/084192 | 12/21/2017 | WO |
