A CAPILLARY COLORING PROCESS USING AT LEAST ONE DIRECT AND / OR NATURAL COLOR, TITANIUM SALT, CELLUL

专利摘要:
The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated from one or more cosmetic compositions comprising a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, b) one or more titanium salts and b1) optionally one or more particular carboxylic acids, c) one or more cellulosic polysaccharide (s), d) optionally one or more organic compound (s) liquid (s) at 25 ° C having a solubility parameter value δH of Hansen δH <16 (MPa) 1/2 at 25 ° C, e) optionally one or more chemical oxidizing agent (s) such as hydrogen peroxide or one or more hydrogen peroxide generator system (s).
公开号:FR3029407A1
申请号:FR1462061
申请日:2014-12-08
公开日:2016-06-10
发明作者:Boris Lalleman；Alain Lagrange；Francoise Albouy；Frederic Simonet
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The present invention relates to a process for the dyeing of keratinous fibers, in particular human keratinous fibers. such as the hair, wherein said fibers are processed from one or more cosmetic compositions comprising a) one or more synthetic direct dye (s) and / or dyes of natural origin, b) one or more titanium salts and b1) optionally one or more particular carboxylic acids, c) one or more cellulosic polysaccharide (s), d) optionally one or more liquid organic compound (s) ( s) at 25 ° C having a solubility parameter value 6H of Hansen 6H <16 (MPa)% at 25 ° C, e) optionally one or more chemical oxidizing agent (s) such (s) only hydrogen peroxide e or one or more system (s) generator (s) of hydrogen peroxide. It is known to dye keratin fibers, and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes that are used are in particular nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane or natural dyes. These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are colored molecules or dyes having an affinity for keratinous fibers. These compositions containing one or more direct dyes are applied to the keratinous fibers for a time necessary to obtain the desired coloration, and then rinsed. The resulting dyes are particularly chromatic colorations which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to light, washing, or perspiration. There is therefore still progress to be made in this field to provide powerful dyes, resistant and respecting the nature of the hair from compositions containing dyes including natural.
[0002] In the field of coloration from natural extract such as orthodiphenols (ODPs), it is also known to dye keratin materials such as hair or skin from ODPs in the presence of a metal salt, in particular of manganese (Mn) and / or zinc (Zn). In particular, the patent applications FR 2814943, FR 2814945, FR 2814946 and FR 2814947 provide compositions for coloring the skin or keratin fibers, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides. of Mn and / or Zn, alkalines of the hydrogencarbonate type in a particular ratio Mn, Zn / hydrogen carbonate and optionally an enzyme. According to these documents, it is possible to obtain dyes of the keratin materials with the oxygen of the air or any system generating oxygen. However, the colorations obtained from ODPs are insufficiently powerful, intense and / or are not very stubborn, especially in the case of hair fibers. It is known to use acid-level metals for dyeing keratinous fibers in amounts similar to those used for dyes using an etching process, which involves preparing the fibers prior to dyeing to obtain stubborn hues (Ullmann's Encyclopedia "Metal and Dyes", 2005 § 5.1, p 8). However, this process generally has the disadvantage of not always respecting the cosmetics of the keratin fiber. Other documents describe the use of ODPs associated with salts of Mn, Zn and other metal salts including titanium salts and a chemical oxidizing agent (FR297673, WO2011 / 086284, WO2011 / 086282, and FR2951374) . Nevertheless, improvements still need to be made, especially in terms of color tenacity with regard to shampoos and sweat. There is therefore a real need to develop staining methods which make it possible to obtain more powerful and / or stubborn stains from synthetic direct dyes and / or dyes of natural origin, in particular ODPs, preferably from natural extracts rich in ODPs, less aggressive for keratinous fibers, or requiring smaller quantities of dyes. More particularly, there is a need to obtain colorings which are satisfactorily resistant to external agents (light, weather, shampoos, sweat) which are stubborn and homogeneous, ie having low color selectivity between root and tip. , while remaining powerful and / or chromatic. In addition, it is necessary to obtain the satisfactory coloring performance, that the product is stable and has suitable use qualities that is to say a sufficient rheology not to flow during the pause time. For this reason, it is preferable that the staining medium does not interact with the staining process. This object (s) is (are) achieved by the present invention which relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated. , in one or more steps, by one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from ODPs; B) one or more salt (s) of titanium (Ti); in particular the Ti atom of the salt is of oxidation degree 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV); b1) optionally one or more carboxylic acid (s) of formula (I) below; OH A (I) 0 n Formula (I) or a salt thereof in which: 5-A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, hydrocarbon comprising from 1 to 50 carbon atoms saturated or unsaturated, cyclic or non-cyclic, aromatic or nonaromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted in particular with one or more hydroxyl groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxy groups; n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; c) one or more cellulosic polysaccharide (s); D) optionally one or more organic compound (s) liquid (s) at 25 ° C having a solubility parameter value 6H Hansen 6H lower 16 (MPa)% at 25 ° C; and e) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s). Preferably, the composition (s) used in the process of the invention is (are) aqueous (s). Another object of the invention is a cosmetic composition comprising ingredients a), b), c), optionally d); and optionally e) as defined above. Another object of the present invention is a multi-compartment device comprising ingredients a), b), c), optionally d); and possibly e) distributed in several compartments.
[0003] The multi-compartment device or "kit" is suitable for carrying out the coloring process according to the invention. The process according to the invention has the advantage of coloring human keratin fibers, with stubborn coloring results. In particular, the dyeing method according to the invention makes it possible to lead to colorings that are resistant to washes, perspiration, sebum and light without altering the fibers. The resistance to perspiration is particularly good. In addition, the coloring process used makes it possible to induce a "rise" and / or power of the satisfactory coloration.
[0004] Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the following description and examples. A) the dye (s) According to the present invention, the dyeing process uses a) one or more synthetic direct dye (s) and / or dyes of natural origin.
[0005] The dye (s) of the invention may be present in one or more cosmetic composition (s) used during the dyeing process. According to a particular embodiment of the invention, the dye (s) is (are) chosen from synthetic direct dyes. The synthetic direct dye (s) which may be used in the context of the invention may be chosen from anionic, cationic or neutral direct dyes, fluorescent or non-fluorescent dyes. . These synthetic direct dyes are in particular chosen from those conventionally used in direct dyeing all commonly used aromatic and / or nonaromatic dyes such as neutral neutral, acidic or cationic nitro benzene direct dyes, neutral azo direct dyes, acidic dyes, or neutral dyes. cationic, natural direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine, polyarylmethane direct dyes such as triarylmethanics, indoamines, polymethines such as styryls, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines. According to a particular embodiment of the invention, the dye (s) is (are) chosen from anionic direct dyes. These are dyes commonly referred to as "acid" or "acid dyes" direct dyes for their affinity for alkaline substances. By anionic direct dyes is meant any direct dye comprising in its structure at least one CO2R or 503R substituent with R denoting a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. The anionic dyes may be selected from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes. According to another particular embodiment of the invention, the dye (s) are chosen from cationic direct dyes or dyes commonly referred to as "basic" or "basic dyes" direct dyes for their affinity with the acidic substances. The cationic dyes are preferably chosen from hydrazono, (poly) azo dyes, polymethine such as styryl and (poly) arylmethane dyes. More preferentially, the cationic dye (s) of the invention are chosen from the hydrazono dyes of formula (Va) and (V'a), the azo (Via) and (VI'a) and the following diazo (Vila): Het + -C (Ra) = NN (Rb) -Ar, Q-Het + -N (Ra) -N = C (Rb) -Ar, Q-Het + -N = N-Ar, Q- (Va) (V'a) ) (Via) Ar + -N = N-Ar ", Q- and Het + -N = N-Ar'-N = N-Ar, Q- (VI'a) (Vila) formulas (Va), (V'a) ), (Via), (VI'a) and (Vila) with: - Het + representing a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially with one or more groups (C- C8) alkyl such as methyl; - Ar + representing an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferably ammonium particularly tri (C 1 -C 8) alkylammonium such as trimethylammonium; - Ar represents an aryl group, in particular phenyl, optionally substituted, preferentially p one or more electron donor groups such as i) (C1-C8) alkyl optionally substituted, ii) (C1-C8) optionally substituted alkoxy, iii) (di) (C1-C8) (alkyl) amino optionally substituted on the alkyl groups by a hydroxyl group, iv) optionally substituted aryl (C1-C8) alkylamino, v) N- (C1-C8) alkylN-aryl (C1-C8) alkylamino or Ar represents a julolidine group; Ar 'is an optionally substituted divalent (hetero) arylene group such as phenylene, especially para-phenylene, or naphthalene, optionally substituted, preferably with one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups; Ar - is an optionally substituted (hetero) aryl group such as optionally substituted phenyl or pyrazolyl, preferentially with one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) amino groups, ( C1-C8) alkoxy or phenyl; - Ra and Rb, identical or different, representing a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferably with a hydroxyl group, or the substituent Ra with a substituent of Hee and / or Rb with a substituent of Ar and / or Ra with Rb together with the atoms carrying them a (hetero) cycloalkyl, particularly Ra and Rb, representing a hydrogen atom or a group (C1-C4 ) alkyl optionally substituted by a hydroxyl group; C2- represents an anionic counterion as defined above. According to a preferred variant of the invention, the cationic dyes are chosen from polymethine dyes of formulas e (Villa) and (Vlll'a) VV + 4C (Rc) = C (Rd) 1, ', - Ar', Q Ar- [C (Rd) = C (Rc)] ,,, - W (Villa) (VIIa) formulas (VIIa) or (VIIIa) with: - W + representing a heterocyclic or cationic heteroaryl group, especially comprising a quaternary ammonium optionally substituted with one or more groups (C1-C8) ) alkyl optionally substituted in particular with one or more hydroxyl groups; - representing a heterocyclic or heteroaryl as defined for VV +; Ar represents a (hetero) aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C1-C8) alkyl, preferably C1-C4, groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8) alkoxy groups such as methoxy; v) one or more hydroxy (C1-C8) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (C1-C8) alkylamino groups, preferably with the C1-C4 alkyl part optionally substituted with a or more hydroxyl such as (di) hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as 5- or 6-membered piperazinyl, piperidinyl or heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl; Ar 'is a (hetero) aryl radical as defined for Ar; - m 'represents an integer inclusive between 1 and 4, particularly m is 1 or 2; more preferably 1; Rc, Rd, identical or different, represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferably C1-C4, or else Rc contiguous with VV + or Ve and / or Rd contiguous with Ar or Ar 'and / or Rc and Rd contiguous form with the atoms form with the atoms which carry them a (hetero) cycloalkyl, particularly Rc is contiguous with VV + or Ve and forms a (hetero) cycloalkyl such as cyclohexyl; As defined above, preferably represents a halide or a mesylate. Mention may more particularly be made of azo and hydrazono endocyclic cationic charge dyes of formula (Va), (V'a), (Via) and (VI'a) as defined above. More particularly those of formula (Va), (V'a) and (Via) from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably, the cationic dyes comprise a cationic charge endocyclic and of the following formula: ## STR3 ## wherein R 1 represents a (C 1 -C 4) alkyl group such that R 1 represents a (C 1 -C 4) alkyl group; than methyl; - R2 and R3, identical or different, represent a hydrogen atom or a group (C1-C4) alkyl such as methyl; and R4 represents a hydrogen atom or an electron-donor group such as (C1-C8) alkyl optionally substituted, (C1-C8) alkoxy optionally substituted, (di) (C1C8) (alkyl) amino optionally substituted on the alkyl group or groups; by a hydroxyl group; particularly R 4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferentially CH, 10-C2- as defined above, preferably represents a halide or a mesylate. In particular, the dyes of the invention are chosen from those of formula (IIIa-1) and (IVa-1) is chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: C1-13 N, C ^ H3 H3C / H3C'N NN NH2 N-CH3 H3C Q-Q- Basic Red 51 Basic Orange 31 Basic Yellow 87 With C2- as defined above, preferably represents a halide or mesylate. According to another particularly advantageous embodiment of the invention, the dye (s) is (are) chosen from dyes of natural origin or so-called natural dyes. Among the natural dyes, lawsone, juglone, indigo, isatin, curcumin, chlorophylline, laccaic acid, kermesic acid, carminic acid, sorghum, spinulosin, apigenidine, orceins, polyphenols or orthodiphenols (ODPs) and all extracts rich in ODPs. It is also possible to use the extracts or 3029407 8 decoctions containing these natural dyes and in particular poultices or extracts based on henna and / or indigo. According to a particularly preferred embodiment of the invention, the dye (s) are chosen from orthodiphenol (s) or ODP (s). The invention relates to one or more ODP (s) or mixtures of compounds comprising one or more aromatic rings of which at least one is a benzene ring substituted by at least two hydroxy groups (OH) carried by two adjacent carbon atoms of said benzene group being present in the structure of the orthodiphenol (s).
[0006] The aromatic ring is more particularly a condensed aryl or fused heteroaromatic ring, optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, and the like. indole, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chroman, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring having at least minus two hydroxy groups carried by two adjacent carbon atoms of the aromatic ring. Preferably, the aromatic ring of the ODPs according to the invention is a benzene ring. By "condensed ring" is meant that at least two saturated or unsaturated, heterocyclic or non-heterocyclic rings have a common bond, i.e. at least one ring is attached to another ring. The ODP (s) according to the invention may be salified or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.
[0007] More particularly, the ODP (s) a) represents (a) a compound of formula (II), or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or solvates such as hydrates: OH formula (II) in which: R 1 to R 4, which may be identical or different, represent: i) a hydrogen atom, ii) halogen, or a group chosen from iii) hydroxy, iv) carboxy, v) (C 1 -C 20) alkyl or (C 1 -C 20) alkoxycarbonyl carboxylate, vi) optionally substituted amino, vii) C 20) optionally substituted linear or branched alkyl, viii) (C 2 -C 20) optionally substituted linear or branched alkenyl, ix) cycloalkyl optionally substituted, x) (Cl-C20) alkoxy, x1) (C1-C20) alkoxy (C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii) aryl optionally substituted, xiv) aryl (xv) substituted aryl, xvi) heterocyclic, saturated or unsaturated, whether or not carrying a cationic or anionic charge, optionally ituated and / or optionally fused with a benzene aromatic ring, said aromatic ring being optionally substituted especially by one or more hydroxy or glycosyloxy groups, xvii) a radical containing one or more silicon atoms; or two of the substituents carried by two adjacent carbon atoms R1 - R2, R2 - R3 or R3 - R4 together with the carbon atoms carrying them a saturated or unsaturated ring, aromatic or otherwise, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. In particular, the compound of formula (II) comprises from one to four rings. A particular embodiment of the invention relates to one or more ODP (s) of formula (II) in which two adjacent substituents R1-R2, R2-R3 or R3-R4 can not form with the carbon atoms that carry them pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls. For the purposes of the present invention, and unless a different indication is given: the saturated or unsaturated rings, optionally condensed, may also be optionally substituted; the "alkyl" radicals are saturated, linear or branched, generally C 1 -C 20, especially C 1 -C 10, hydrocarbon radicals, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl, butyl or pentyl radicals; and hexyl; The "alkenyl" radicals are hydrocarbon radicals, linear or branched, unsaturated C 2 -C 20; preferably comprising at least one double bond such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene; the "aryl" radicals are mono- or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferentially chosen from the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl; the radicals "alkoxy" are alkyl-oxy radicals with alkyl as defined above, preferably C 1 -C 10, such as methoxy, ethoxy, propoxy and butoxy; The "alkoxyalkyl" radicals are (C1-C20) alkoxy (C1-C20) alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc .; the "cycloalkyl" radicals are C 4 -C 8 cycloalkyl radicals, preferably the cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups; The "alkyl" or "alkenyl" radicals, when they are "optionally substituted", may be substituted by at least one atom or group borne by at least one carbon atom, chosen from: i) halogen; ii) hydroxy; iii) (C1-C2) alkoxy; iv) (ClC10) alkoxycarbonyl; v) (poly) hydroxy (C2-C4) alkoxy; vi) amino; vii) 5- or 5- membered 5-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted with a (ClC4) alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxyl group, b) an amino group optionally substituted with one or two (C 1 -C 3) radicals optionally substituted alkyl, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, c) a quaternary ammonium group -N + R'R "R" ', M- for which R', R ", which may be identical or different, represent a hydrogen atom, or a C 1 -C 4 alkyl group, and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, d) or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferentially mét hyl; x) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a (C1-C4) alkyl radical optionally carrying at least one hydroxyl group; and the radical R 'is a C1-C2 alkyl radical; a carbamoyl radical ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a (C 1 -C 4) alkyl radical optionally bearing at least one hydroxyl group; xi) alkylsulfonylamino (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a (C1-C4) alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a (C1-C4) alkyl radical, a phenyl radical; xii) aminosulphonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally carrying at least one chosen group among a) hydroxy, b) carboxy-O (O) -OH in acidic or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); xiii) cyano; xiv) nitro; xv) carboxy or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted with one or more hydroxy groups; xvii) glycosyloxy; and phenyl optionally substituted with one or more hydroxy groups; The "aryl" or "heterocyclic" radicals or the aryl or heterocyclic radical radicals when they are "optionally substituted" may be substituted by at least one atom or group borne by at least one carbon atom chosen from: i ) (C1-C10) alkyl, preferably C1-C8, optionally substituted with one or more radicals selected from hydroxy, (C1-C2) alkoxy, (poly) hydroxyoxy C2-04, acylamino, substituted amino; by two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated ring optionally comprising another heteroatom identical to or different from nitrogen; ii) halogen; iii) hydroxy; iv) C 1 -C 2 alkoxy; v) C1-C10 alkoxycarbonyl; vi) (poly) hydroxyalkoxy C2-04; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferentially methyl; x) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxy, b) amino group optionally substituted by one or two optionally substituted C 1 -C 3 alkyl radicals , said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, c) a quaternary ammonium group - N + R'R "R" ', M- for which R', R ", which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group, and M- represents the counter-group; -ion of the organic acid, mineral or the corresponding halide, d) a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; xi) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl radical; xii) carbamoyl ((R) 2 N-C (O) -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; xiii) alkylsulphonylamino (R'S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical; xiv) aminosulphonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; (xv) carboxy in acidic or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); (xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferentially trifluoromethyl; xix) glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted with one or more hydroxy groups; xxi) a glycosyloxy group; and xxii) phenyl optionally substituted with one or more hydroxy groups; - By "glycosyl" radical is meant in the sense of the present invention a radical derived from a mono or polysaccharide; radicals "containing one or more silicon atoms" are preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane, stearoxydimethicone radicals; the "heterocyclic" radicals are radicals comprising, in at least one ring, one or more heteroatoms chosen in particular from O, N and S, preferably O or N, optionally substituted with in particular one or more alkyl, alkoxy, carboxy or hydroxy groups; , amine or ketone. These rings may contain one or more oxo groups on the carbon atoms of the heterocycle; among the heterocyclic radicals which may be used, mention may be made especially of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl and thienyl groups; more preferably, the heterocyclic groups are fused groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromannyl, isochromannyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl, these groups may be substituted, in particular by one or more OH groups. The ODP (s) useful in the process of the invention can be natural or synthetic. Natural ODPs include compounds that may be present in nature and are reproduced by (hemi) chemical synthesis. The salts of the ODPs of the invention may be salts of acids or bases. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid which leads to chlorides.
[0008] By "basifying agents" is meant the bases as defined for e) may be mineral or organic. Especially the bases are alkali hydroxides such as sodium hydroxide which leads to sodium salts. According to a particular embodiment of the invention, the composition comprises as ingredient a) one or more synthetic ODP (s) which do not exist in nature. According to another preferred embodiment of the invention, the composition that is useful in the process for staining keratinous fibers comprises as ingredient a) one or more natural ODP (s). More particularly, the ODP (s) usable in the process of the invention according to a) (is) are in particular: flavanols such as catechin and epichatechin gallate, flavonols such as quercetin, anthocyanidins such as cyanidine, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtilline, orthohydroxybenzoates, for example gallic acid salts, flavones such as luteolin, hydroxystilbenes, for example tetrahydroxy-3,3 ', 4,5'-stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 40-2,3-dihydroxyphenylalanine and its derivatives, 3029407 13 - 4,5-dihydroxyphenylalanine and its derivatives, - dihydroxycinnamates such as caffeic acid and chlorogenic acid, - orthopolyhydroxycoumarines, - orthopolyhydroxyisocoumarines, 5 - orthopolyhydroxycoumarones, - orthopolyhydroxyisocoumarones, - o orthopolyhydroxychalcones, - orthopolyhydroxychromones, - quinones, - hydroxyxanthones, - 1,2 dihydroxybenzene and its derivatives, - 1,2,4 trihydroxybenzene and its derivatives, - 1,2,3 trihydroxybenzene and its derivatives, - 2,4,5-trihydroxytoluene and its derivatives, proanthocyanidins and in particular proanthocyanidins Al, A2, B1, B2, B3 and C1, chromium and chromenic compounds proathocyanins, tannic acid, 20-1 ellagic acid; and mixtures of the foregoing compounds. According to the invention, "chromenic or chromanic" ODP compounds are understood to mean ODPs which comprise in their structure at least one bicycle of the following formula (A): (A) the intracyclic bond representing a single carbon-carbon bond or else a carbon-carbon double bond, as illustrated by the formula (A1) denoting the family of chromenes and the formula (A2) denoting the chroma family below: ## STR2 ## the ODPs of the invention are of formula (A) and preferably chosen from the dyes of the following formulas: - formula (III), comprising in its structure the bicycle of formula (A2), R4 OH R2 HO X 'and its forms tautomers and / or mesomers, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its hydrates; Formula (III) in which: - - represents a single carbon-carbon bond or a carbon-carbon double bond, the linking of these bonds denotes two single carbon-carbon bonds and two carbon-carbon double bonds, said bonds being conjugated X represents a group: HO-C or O = C 15 -R1, R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxyl group or an optionally substituted alkyl group; optionally substituted alkoxy, or an optionally substituted acyloxy group; and - formula (IV), comprising in its structure the bicycle of formula (A1): OR12 OR13 R14 OR16 R15 (IV) 20 as well as its tautomeric and / or mesomeric forms, its stereoisomers, its addition salts with an acid or a cosmetically acceptable base, and its hydrates; Formula (IV) in which: R29, R12, R13, R16, R19 and R20, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, and - R14, R15, R17 and R18 , identical or different, represent a hydrogen atom, a hydroxyl radical or a C1-C4 alkoxy radical.
[0009] With regard to the orthodiphenols of formula (III) as defined above, these may be in two tautomeric forms noted (IIIa) and (IIIb): ## STR2 ## The alkyl radicals mentioned in the previous definitions substituents are saturated, linear or branched, generally C 1 -C 20, especially C 1 -C 10, preferably C 1 -C 6, hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above, and preferably the alkoxy radicals are C1-C10, such as methoxy, ethoxy, propoxy and butoxy.
[0010] The alkyl or alkoxy radicals, when substituted, may be substituted by at least one substituent carried by at least one carbon atom selected from i) a halogen atom; or a group ii) hydroxy, iii) (C 1 -C 2) alkoxy, (iv) C 10 -C 20 alkoxycarbonyl, C 2-4 (poly) hydroxyalkoxy, vi) amino, vii) 5 or 6 membered heterocycloalkyl, viii) 5-membered heteroaryl, or 6-membered optionally cationic, preferably imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; ix) an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxyl group; b) an amino group optionally substituted with one or two C 1 -C 6 alkyl radicals; C3 optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom which may or may not be different from nitrogen; (c) a quaternary ammonium group - N + R'R "R" ', M- for which R', R ", which may be identical or different, represent a hydrogen atom, or a C 1 -C 4 alkyl group; represents the counter-ion of the corresponding organic, mineral or halide acid, d) or a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted by a (C 1 -C 4) alk radical; yl, HO (IIIa) 16 preferably methyl; x) an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is an alkyl radical; Cl-C2; xi) a carbamoyl radical ((R) 2 N-CO-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xii) an alkylsulphonylamino radical (R'SO2-NR-) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical; C1-C4 a phenyl radical; xiii) an aminosulphonyl radical ((R) 2 N -SO 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; (xiv) a carboxylic radical in acid or salt form (preferably with an alkali metal or ammonium, substituted or unsubstituted); xv) a cyano group; (xvi) a nitro group; xvi) a carboxy or glycosylcarbonyl group; xvii) a phenylcarbonyloxy group optionally substituted by one or more hydroxyl groups; xviii) a glycosyloxy group; and xix) a phenyl group optionally substituted with one or more hydroxy groups. By glycosyl radical is meant a radical derived from a mono or polysaccharide.
[0011] Preferably, the alkyl or alkoxy radicals of formula (III) are unsubstituted. According to one particular embodiment of the invention, the dyes of formula (III) comprise an R 6 radical representing a hydroxyl group. Another particular embodiment of the invention relates to the ODPs of formula (III), for which the radical R1 represents a hydrogen atom or a hydroxyl group.
[0012] More particularly, the composition according to the invention may comprise one or more ODP (s) of formula (III) chosen from hematoxylin, haematein, brazilin and braziline. HO HO Hemeinine Braziline 3029407 Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) CAS 474-07-7) BRAZILINE is a conjugated form of a chroman compound of formula (A2). The diagram below shows the tautomeric structures (111a) and (111b) illustrated above.
[0013] Among the ODPs of the hematoxylin / haematin and brazilin / braziline type, there may be mentioned, by way of example, hematoxylin (Natural Black 1 according to the INCI name) and brazilin (Natural Red 24 according to the INCI name), dyes of the family of 10 indochromanes, which are commercially available. These may exist in an oxidized form and be obtained by synthesis or by extraction of plants or plants known to be rich in these dyes. The ODPs of formula (III) can be used in the form of extracts. The following plant extracts (genus and species) may be used: Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extraction of various parts of plants, such as, for example, the root, the wood, the bark or the leaf. According to a particular embodiment of the invention, the ODP or ODPs are of formula (I) natural and are derived from logwood, pernambuco wood, sappan wood and brazil wood. According to a particular embodiment of the invention the ODPs are of formula (IV), preferably those for which R11 and R13 represent an alkyl radical, preferably methyl.
[0014] Preferably, R12, R16, R19 and R20 denote, independently of one another, a hydrogen atom or an alkyl radical, preferably methyl. Preferably, R 14 and R 17 denote, independently of one another, a hydrogen atom or an alkoxy radical, preferably methoxy. Preferably, R 18 and R 15 denote, independently of one another, a hydrogen atom, a hydroxyl radical or an alkoxy radical, preferably methoxy. A particularly preferred first family of ODPs suitable for the present invention are those dyes of formula (II) above wherein R12, R15, R16, R17, R19 and R20 each represent a hydrogen atom. R11 and R13 each represent a methyl radical and R14 represents a methoxy radical. Among the preferred ODPs of this first family include those, for which R18 represents a methoxy (santaline B) or hydroxy (santaline A) radical.
[0015] A second particularly preferred family of ODPs suitable for the present invention is that of the dyes of formula (IV) above for which: R 11 and R 13 each represent a methyl radical, R 17 represents the methoxy radical. A preferred dye of this second family is that for which, in addition, R19 represents a methyl radical, R20, R12, R14, R18 and R16 each represent a hydrogen atom, and R15 represents the hydroxyl radical (santarubin A). A second preferred dye of this second family is that for which R18, R20, R12, R14 and R16 represent a hydrogen atom, R15 represents a methoxy radical and R19 represents a methyl radical (Santarubine B).
[0016] A third family of preferred ODPs of this second family is that for which R 20, R 12, R 14, R 15, R 16 and R 19 represent hydrogen and R 18 represents the hydroxyl radical (santarubine C). The preferred ODP or ODPs of this second family is that for which R15 represents a methoxy radical, and R18 and R14 represent a hydrogen atom and R20, R12, R16 and R19 represent a methyl radical (tetra-O-methylcantarubine). The ODP or ODPs of formula (IV) may be used in the form of extracts. Redwood plant extracts can be used, generally including Asian and West African redwood species of the genus Pterocarpus and the genus Baphia. These woods are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida. These woods can still be called padauk, sandalwood (sandalwood), narrawood, camwood or barwood. Thus, usable extracts containing ODPs of formula (II) in the present invention may for example be obtained from Red Sandalwood (Pterocarpus santalinus), by aqueous basic extraction, such as the product sold under the trade name Sandalwood. SL 709C concentrate by the company COPIAA or else by means of a solvent extraction of sandalwood powder such as the product sold under the trade name Sandalwood Powder SL PP by the same company COPIAA. We can also mention the hydroalcoholic extract of Sandalwood red powder from the company ALBAN MULLER.
[0017] Extracts also suitable for the present invention can be obtained from woods such as Camwood (Baphia nitida) or Barwood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus fractionated and then ground: a conventional alcoholic extraction or by percolation is then carried out on this ground 5 in order to collect a pulverulent extract particularly suitable for the implementation of the present invention. The ODP salts of formula (III) and (IV) of the invention may be cosmetically acceptable acid or base salts. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid leading to the chlorides. The bases can be mineral or organic. Especially the bases are alkali hydroxides, such as sodium hydroxide leading to sodium salts. Preferably, the ODP or ODPs of formula (III) and (IV) included in the composition according to the invention are derived from plant extracts. Mixtures of plant extracts can also be used. The natural extracts of ODPs according to the invention can be in the form of powders or liquids. Preferably, the extracts are in powder form. Particularly the ODPs of the invention are comprised of catechin, quercetin, brazilin, haematein, hematoxylin, chlorogenic, caffeic, gallic acids, catechol, gallic acid, L DOPA, pelargonidine, cyanidine, (- ) -Epicatechin, (-) - Epigallocatechin, (-) - Epigallocatechin 3-gallate (EGCG), (+) - Catechin, Isoquercetin, Pomiferin, esculetin, 6,7-Dihydroxy-3- (3-hydroxy-2,4-hydroxy) - dimethoxyphenyl) coumarin. Santalin AC, Mangiferine, Butein, Maritimetine, Sulfuretine, Robtein, Betanidine, Pericampylinone A, Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, ProanthocyanidinCl, Procyanidins DP 4-8, Tannic Acid, Purpurogalline, 5,6-Dihydroxy-2-methyl -1,4-naphthoquinone, Alizarin, Wedelolactone, Variegatic acid, Gomphidic acid, Xerocomic acid, Carnosol, and natural extracts containing them. Preferably, the ODPs of the invention are chromenic or chromanic and are selected from haematein, hematoxylin, brasiline, brasiline, santaline A. By "carboxylate" is meant carboxylic acid salt. When the dye precursors have D and L forms, both forms can be used in the compositions according to the invention, as well as the racemates. According to one embodiment, the natural ODPs are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in whole or in part. In particular concerning the plants the extracts are from fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in ODPs as defined above. Preferably, the natural ODP or ODPs of the invention are derived from plant extracts 40 or parts of plants.
[0018] Within the meaning of the invention, these extracts will be assimilated as compounds a). The extracts are obtained by extraction of various parts of plants such as for example root, wood, bark, leaf, flower, fruit, seed, pod, peel.
[0019] Herbal extracts include tea leaf extract, rose extract. Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or pods of cocoa. Among the vegetable extracts, there may be mentioned potato extracts, onion peels.
[0020] Among the extracts of tree wood, mention may be made of pine bark extracts, extracts of logwood. It is also possible to use mixtures of plant extracts. According to a particular embodiment of the invention, the orthodiphenol derivative (s) are natural extracts rich in ODPs.
[0021] According to a preferred embodiment, the dye (s) of the invention are only natural extracts. Preferably, the dye (s) according to the invention is (are) chosen from catechin, quercetin, haematein, hematoxylin, brasiline, brasiline, gallic acid, tannic acid and natural extracts containing them selected from grape pomace, pine bark, green tea, onion, cocoa bean, logwood, red wood and gall-nut. More preferably, the ODP (s) of the invention is (are) chosen from: - haematein, brazile, gallic acid, tannic acid, when the dyeing process does not no use of chemical oxidizing agent; Or else - hematoxylin, brasiline, gallic acid, tannic acid, when the dyeing process uses a chemical oxidizing agent The natural extracts according to the invention can be in the form of powders or liquids. Preferably, the extracts of the invention are in the form of powders. According to the invention, the synthetic dye (s), natural (s), and / or the natural extract (s) used as ingredient (a) in one or more compositions ( s) cosmetic (s) useful (s) in the process according to the invention is (are) preferably from 0.001% to 20% by weight of the total weight of the composition or compositions containing them .. As for the pure dyes, especially pure ODPs, the content in the composition or compositions containing them is preferably between 0.001 and 5% by weight of each of compositions containing them. With regard to the extracts, the content in the composition or compositions containing the extracts as such is preferably between 0.1 and 20% by weight of each of these compositions, and better still between 0.5 and 10% by weight. b) the titanium salt (s): The titanium salt (s) of the invention may be one or more organic or inorganic salt (s) (s). s) titanium. For the purposes of the present invention, the term "organic titanium salt" is intended to mean the salts themselves resulting from the action of at least one organic acid on Ti. By "organic acid" is meant an acid ie a compound capable of releasing a cation or proton H +, or H30 + in aqueous media, which comprises at least one hydrocarbon chain C1-C20, optionally unsaturated, linear or branched, a group ( hetero) cycloalkyl, or (hetero) aryl and at least one acidic chemical function being in particular selected from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO31-12, PO4H2. In particular, the organic acid (s) is (are) to form the organic titanium salt (s) of the invention is (are) chosen from carboxylic acids of Formula (I) as defined above and preferably is or are an alpha hydroxy acid such as lactic, glycolic, tartaric or citric acids. Preferably, the organic titanium salt resulting from the action of one or more organic acids as defined above, preferably carboxylic acid (s) of formula (I) ) as defined above, is an optionally charged complex (in particular negatively) which is complexed with one or more carboxylate group (s) of carboxylic acid (s). Preferably, the titanium organic salt (s) of the invention is (are) chosen from those of the following formula (IA): ## STR2 ## Formula (IA) in which: - A is identical to that of the formula (I) - n, n 'and n "identical or different are 1,2,3 or 4 with n' + n" val6; M1 and M2, which may be identical or different, represent a cationic counterion, chosen in particular from alkali metal cations such as Na, or K, alkaline earth metal such as Ca or organic such as ammonium, preferably ammonium or an atom hydrogen; - designating Ti (01-1), r, or Ti (0), r / 2, or Ti (01-1) ,, 1 (0) ,, 2with m1 + m2 = n ".
[0022] Preferably, the radical A of the compound (IA) as defined above represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxyl groups, and n representing an integer inclusive between 0 and 5, such as between 0 and 2, particularly the one or more carboxylic acids used to form the organic titanium salt or salts of the invention are chosen from α-hydroxy acids; preferably the acid is selected from citric acid, lactic acid, tartaric acid, and glycolic acid, more preferably from lactic and glycolic acid. Preferably, the titanium organic salt (s) of the invention is (are) chosen from those of the following formula (IB): Formula (IB) in which: L 'and L ", identical or different, represent a divalent group (hetero) arylene, C6) alkylene, (C2-C6) alkenylene, said alkylene and arylene groups being optionally substituted by one or more atoms or groups selected from halo, (C1-C4) alkyl , hydroxy, thiol, and (di) (C 1 -C 4) (alkyl) amino, carboxy, and / or optionally interrupted by one or more heteroatoms such as oxygen, preferably L 'and L "are identical and represent a methylene group or ethylene optionally substituted with a (C1-C4) alkyl group; 20 - X 'and X ", which are identical or different, represent a heteroatom such as oxygen, sulfur or Rc-N amino with Rc representing a hydrogen atom or a (CiC4) alkyl group, preferably X' and X" are identical; and represent an oxygen atom; Y and Y ', which are identical or different, are as defined for X' and X ", preferably Y and Y 'are identical and represent an oxygen atom, Ra and Rb, which may be identical or different, represent an atom hydrogen, or a (C1-C6) alkyl, (C2-C6) alkenyl, or (hetero) aryl group, particularly Ra and Rb, identical represent a hydrogen atom or a (C1-C4) alkyl group, preferably hydrogen, M +, identical or different, represents a cationic counterion such as alkali (Na, K), alkaline earth (Ca) or organic metal cation such as ammonium, preferably ammonium. The titanium organic (s) of the dyeing process are the dihydroxybis (lactate) titaniumlV salts such as those of the following formula: ## STR1 ## 2NH4 + O OH Cf 2- H3C r0 O. / TiN ° 0 TIN OH 0 The staining process may use one or more organic acids b1) of formula (I) such than previously defined.
[0023] According to an advantageous variant, the dyeing method also uses b1) one or more carboxylic acid (s) of formula (I) as defined above. More preferentially, the carboxylic acid or acids b1) are different from the carboxylic acids complexed with the Ti salts.
[0024] For example, if the carboxylic acid complexed with the titanium salt b) is lactic acid or its carboxylate salt (lactate), the second acid b1) other than lactic acid or lactate, and may be for example the acid glycolic. For the purposes of the present invention, the term "inorganic titanium salt" means the salts themselves, derived from the action of an inorganic acid on Ti.
[0025] By "inorganic acid" is meant an acid which does not have carbon atoms other than carbonic acid. Inorganic salts of titanium are preferably selected from titanium halides, titanium sulfates and titanium phosphates. The titanium salts are preferably inorganic salts of Ti (II), Ti (III) or Ti (IV), more particularly Ti (III) or Ti (IV).
[0026] Preferably, the titanium salt (s) is (are) organic titanium salts, and more preferably organic Ti (IV) salts. According to an advantageous embodiment of the invention, the organic salt of Ti consists of a Ti (IV) atom and from 2 to 3 molar equivalents of at least one carboxylic acid of formula (I).
[0027] The salt (s) of titanium (b) is (are) present in the cosmetic composition (s) used in the process according to the invention in a content ranging from 0.001 % to 20% by weight relative to the total weight of the composition or compositions containing them.
[0028] In particular, the titanium organic salt (s) and the inorganic titanium salts according to the invention are soluble in water in a proportion of at least 0.0001 g / l, better still at least 1 g / l. . c) The cellulosic polysaccharide (s) According to the present invention, the dyeing process involves c) one or more cellulosic polysaccharide (s) ie one or more polymer (s) cellulosic polysaccharide (s), which preferably is (are) thickener (s). The cellulosic polymers may be anionic, cationic, amphoteric or nonionic, associative or non-associative polymers.
[0029] By "cellulosic polysaccharide" is meant according to the invention any polymer having in its structure chains of glucose residues united by R-1,4 bonds; in addition to unsubstituted celluloses, the cellulose derivatives may be anionic, cationic, amphoteric or nonionic. Thus, the cellulosic polysaccharides of the invention may be selected from unsubstituted celluloses including microcrystalline form and cellulose ethers. Among these cellulosic polysaccharides, there are cellulose ethers, cellulose esters and cellulose ether esters. Among the cellulose esters, there are the inorganic esters of cellulose (cellulose nitrates, sulphates or phosphates, etc.), the cellulose organic esters (cellulose monoacetates, triacetates, aminopropionates, acetate butyrates, acetate propionates or acetatetrimellitates). .) and mixed organic / inorganic cellulose esters such as cellulose acetate-butyrate sulphates and cellulose acetate propionates. Among the cellulose ether esters, mention may be made of hydroxypropyl methylcellulose phthalates and ethylcellulose sulphates. By "associative polymers" is meant polymers capable, in an aqueous medium, to associate reversibly with one another or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone, preferably one or more hydrophobic lateral hydrocarbon chains. By "hydrophobic group" is meant a linear or branched, saturated or unsaturated, hydrocarbon-based radical or polymer comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 atoms. carbon and more preferably from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. According to one particular embodiment of the invention, the cellulosic polysaccharide or polysaccharides are non-associative. The "non-associative" cellulosic polysaccharides of the invention are cellulosic polysaccharides having no fatty chain i.e. preferably not having a C 10 -C 30 chain in their structure. According to a first variant, the non-associative cellulosic polysaccharide (s) are nonionic. Mention may be made of non-ionic cellulose ethers without a fatty chain in C 10 -C 30, ie "non-associative", mention may be made of (C 1 -C 4) alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Ethocel standard 100 Premium of 40 DOW CHEM ICAL); (poly) hydroxy (C1-C4) alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR proposed by AQUALON) and hydroxypropylcelluloses (for example Klucel EF from AQUALON); mixed (poly) hydroxy (C 1 -C 4) alkyl- (C 1 -C 4) alkylcellulose celluloses such as hydroxypropyl methylcelluloses (for example Methocel E4M from DOW CHEMICAL), hydroxyethyl methylcelluloses, hydroxyethyl ethylcelluloses (for example Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutyl methylcelluloses. According to a second variant, the non-associative cellulosic polysaccharide (s) are anionic. Among the anionic cellulose ethers without fatty chain, mention may be made of (poly) carboxy (C1-C4) alkylcelluloses and their salts. By way of example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts. According to a third variant, the non-associative cellulosic polysaccharide (s) are cationic. Among the non-fatty chain cationic cellulose ethers, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as (poly) hydroxy (C1-C4) alkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyltrimethylammonium, methacrylmidopropyl trimethylammonium, dimethyl-diallylammonium. The commercial products corresponding to this definition are more particularly the products sold under the name "Celquat® L 200" and "Celquat® H 100" by the company National Starch. According to another particular embodiment of the invention, the cellulosic polysaccharide (s) 25 are associative. Quaternized (poly) hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof, may especially be mentioned. The alkyl radicals carried by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses, such as QUATRISOFT LM 200e, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18-B® (alkyl) are exemplified. C12) and QUATRISOFT LM-X 529-8® (O-alkyl) sold by AQUALON, the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (O18 alkyl) sold by the company CRODA company and the SOFTCAT SL 100® product sold by AQUALON. Mention may also be made of celluloses or their derivatives, modified with groups comprising at least one fatty chain such as alkyl groups, arylalkyls, alkylaryls or mixtures thereof, in which the alkyl groups are in the form of C 8 - and in particular: alkylhydroxyethylcelluloses nonionics such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (C16 alkyl) sold by the company AQUALON; nonionic nonoxynylhydroxyethylcelluloses such as the AMERCELL HM-1500 product sold by the company Amerchol; nonionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL.
[0030] Among the cellulosic polysaccharides according to the invention, mention may be made of the thickeners for the fatty phase, in particular the polymers carrying in the backbone at least one crystallizable block. As polysaccharides, especially polysaccharides, of the fatty phase, it is thus possible to use polysaccharides. semi-crystalline cellulosics. The semi-crystalline cellulosic polysaccharides which may be used in the context of the invention may be uncrosslinked or partially crosslinked, provided that the degree of crosslinking does not hinder their dissolution or dispersion in the liquid oily phase by heating above their melting temperature. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen or dipolar type bonds between groups carried by the polysaccharide, such as for example the dipolar interactions between ionomers carboxylates, these interactions being in effect. low amount and carried by the polymer backbone; or at a phase separation between the crystallizable blocks and the amorphous blocks carried by the polysaccharide.
[0031] Preferably, the semi-crystalline cellulosic polysaccharides suitable for the invention are uncrosslinked. According to one particular embodiment of the invention, the cellulosic polysaccharide or polysaccharides are especially mono or polyalkyl esters of cellulose and of fatty acid (s) and in particular of the following formula (Cl): ## STR2 ## ) Formula (C1) in which: n is an integer ranging from 3 to 200, in particular ranging from 20 to 150, and in particular from 25 to 50, R1, R2 and R3, which are identical or different, are chosen; from hydrogen or an acyl group (RC (O) -) in which the radical R is a hydrocarbon group, linear or branched, saturated or unsaturated, having from 7 to 29, in particular from 7 to 21, in particular from 11 to at 19, more particularly 13 to 17, or even 15, carbon atoms, provided that at least one of said radicals R1, R2 or R3 is different from hydrogen. In particular, R 1, R 2 and R 3 may represent hydrogen or an acyl group (RC (O) -) in which R is a hydrocarbon radical as defined above, with the proviso that at least two of said radicals R 1, R 2 or R3 are identical and different from hydrogen. The set of radicals R1, R2 and R3 can be an acyl group (R-C (O)) identical or different, and in particular identical. In particular, n previously discussed advantageously ranges from 25 to 50, especially 38 in the general formula of the saccharide ester usable in the present invention. In particular, when the radicals R 1, R 2 and / or R 3, identical or different, are an acyl group (RC (O)), these may be chosen from caprylic, capric, (auric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic , elaidic, asclepine, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearic, and mixtures thereof Cellulosic polysaccharides, in particular thickening agents, may be used alone or in mixtures in all proportions. thickeners of aqueous phase. reference, the cellulosic polysaccharides according to the present invention are advantageously in solution or in dispersion, at 1% of active substance in water, a viscosity measured by means of a rheometer, at 25 ° C., greater than 0, 1 ps, and more preferably still greater than 0.2 cp, at a shear rate of 200 s-1. Preferably, the cellulosic polysaccharide or polysaccharides of the invention c) are chosen from cellulose ethers, in particular hydroxyalkylcelluloses, in particular hydroxyalkyl (Ci-C4) celluloses, and especially chosen from hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses. . The hydroxyalkylcelluloses may be nonionic, cationic and anionic. They are preferably nonionic. The hydroxyalkylcelluloses of the invention are preferably hydroxyethyl celluloses and more preferably hydroxyethyl nonionic celluloses. Still more preferably nonionic hydroxyethylcelluloses without fatty chains or cetylhydroxyethylcelluloses, for example the compounds sold under the names Polysurf 67CS®, Natrosol 250MR®, Natrosol 250HHR® and Natrosol Plus 330® by the company Ashland, and mixtures thereof. The cellulosic polysaccharide (s) of the invention may be present in the dyeing composition (s) of the invention in contents ranging from 0.01% to 30% by weight, in particular from 0.05% to 20% by weight. and more preferably from 0.1% to 10% by weight, based on the total weight of the composition (s) containing them. D) the liquid organic compound (s) having a value of 5H <16 (MPa) According to one particular embodiment of the invention, the dyeing process also uses d) a or more organic liquid compound (s) which have a Hansen solubility parameter value of 6H less than 16 (MPa) 112 at 25 ° C, preferably less than or equal to 15 (MPa) ) 112. It is understood that the liquid organic compound (s) having a Hansen solubility parameter value 6H of less than 16 (MPa) 112 at 25 ° C d) is (are) different (s) the carboxylic acid (s) b1) of formula (I) as defined above. It is also understood that the organic compound (s) having a solubility parameter value 6H <16 (MPa) 112 at 25 ° C d) is (are) soluble in water with solubility greater than 10 g / l of water at 25 ° C. For the purposes of the present invention, the term "organic liquid compound" is intended to mean an organic compound which is liquid at ambient temperature at 25.degree.
[0032] The liquid organic compound (s) having a Hansen solubility parameter value 6H of less than 16 (MPa) 112 at 25 ° C are, for example, described in the reference book "Hansen solubility parameters A user's handbook", Charles M. Hansen, CRC Press, 2000, pages 167 to 185 and in the book "Handbook of solubility parameters and other cohesion parameters" CRC, Press, pages 95 to 121 and pages 177 to 185, "The 3 dimensional solubility parameter & solvent diffusion coefficient, their importance in surface coating formulation ", Charles M. HANSEN, Copenhagen danish technical press, 1967, p. 13-29. As a reminder, the organic compounds have a global solubility parameter 6 according to Hansen, which is defined in the article "Solubility parameters values" by Eric A. Grulke of "Polymer Handbook", 3rd edition, Chapter VII, pages 519-559 by the relation: = (6d2 8p2 + 8h2) 1/2 Relation in which: - 6d characterizes the dispersion forces of LONDON resulting from the formation of dipoles 3029407 induced during molecular shocks, this is ie non-polar interactions, - 8p characterizes the DEBYE interaction forces between permanent dipoles, - 8h characterizes the interaction forces of the hydrogen bonding type Thus the Hansen solubility parameter .3H accounts for the solubility In one embodiment, the liquid organic compound (s) has a value of the Hansen solubility parameter .3H ranging from 6 (MPa) 14 (MPa) 112 at 25 ° C, and preferably ranging from 4 (MPa) 112 to 10 (MPa) 112 at 25 ° C. Preferably, the liquid organic compound (s) comprise a molecular weight of less than 500 g / mol and even more preferentially less than 250 g / mol. Among the liquid organic compounds having a Hansen solubility parameter value of less than 3 and particularly preferably less than or equal to 15 (MPa) 112 at 25 ° C., mention may be made of propylene glycol derivatives, phenyl alcohols such as benzyl alcohol, alkylenecarbonates, lactones, especially lactones of formula (D1): 1: Z (C12) n (D1) Formula (D1) wherein: n is 1, 2 or 3; R 'represents a hydrogen atom; a linear or branched C1-C8 alkyl radical; a hydroxyalkyl radical, linear or branched C1-C4. According to an advantageous embodiment, the liquid organic compound (s) having a Hansen solubility parameter value of less than 16 (MPa) 112 at 25 ° C are selected from the following compounds: Denomination SH Benzyl alcohol 13, 7 Dipropylene glycol methyl ether 11.2 Tripropylene glycol methyl ether 10.4 propylene glycol n-butyl ether (PnB) 9.2 propylene glycol n-propyl ether (PnP) 9.2 Dipropylene glycol monomethyl ether acetate 8 3-phenyl-1-propanol 12 1,2-phenyl-1-propanol 12.9 Ethylene glycol 2-ethyl hexyl ether 5.1 3029407 1-octanol 11.9 1-decanol Tridecyl alcohol 9-Butyrolactone 7.4 Propylene Carbonate 4.1 Preferably the liquid organic compound (s) having a Hansen solubility parameter value of less than 16 (MPa) 112 at 25 ° C are selected from alcohols, ethers, acids and / or a mixture of these compounds.
[0033] According to one embodiment, the liquid organic compound (s) having a Hansen solubility parameter value of less than 16 (MPa) 112 at 25 ° C are selected from alcohols. In particular, the one or more alcohols which can be used as liquid organic compounds having a Hansen solubility parameter 8h as described above can be chosen from aromatic alcohols, in particular from benzyl alcohol, 3-phenylphenol, and the like. 1-propanol, 2-phenyl-1-ethanol, and / or a mixture of these compounds. According to one embodiment, the liquid organic compound (s) having a Hansen solubility parameter value 8h of less than 16 (MPa) 112 at 25 ° C are chosen from ethers.
[0034] In particular, the ethers which can be used as liquid organic compounds having a Hansen solubility parameter 8h as described above can be propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, and the like. . Preferably, the liquid organic compound (s) having a Hansen solubility parameter value of less than 16 (MPa) 112 at 25 ° C are selected from benzyl alcohol. The liquid organic compound (s) having a Hansen solubility parameter of less than 16 (MPa) 112 at 25 ° C. can be present in the composition containing them in a content of greater than or equal to 0.5% by weight, of preferably in a content greater than or equal to 1%, by weight, and more preferably in a content ranging from 1% to 40% by weight, better still from 5% to 30% by weight relative to the total weight of the composition on or containing them. e) the chemical oxidizing agent (s) According to one particular embodiment of the invention, the dyeing method also uses one or more chemical oxidizing agents (s) ). By chemical oxidizing agent is meant an oxidizing agent different from the oxygen of the air. More particularly, the dyeing process uses i) hydrogen peroxide ii) urea peroxide; iii) polymeric complexes capable of releasing hydrogen peroxide such as polyvinylpyrrolidone / H 2 O 2 in particular being in the form of powders and other polymer complexes described in US 5,008,093; US 3,376,110; US 5,183,901; iv) oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); y) the peroxides of metals generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; vi) perborates; and / or vii) percarborates. According to a preferred embodiment of the invention, the composition contains one or more chemical oxidizing agent (s) chosen from i) urea peroxide, ii) polymeric complexes which can release hydrogen peroxide selected from polyvinylpyrrolidone / H2O2; iii) oxidases; iv) perborates and y) percarborates. In particular, the dyeing process uses hydrogen peroxide. Furthermore, the composition or compositions comprising hydrogen peroxide or hydrogen peroxide generating system may also contain various adjuvants conventionally used in compositions for dyeing keratinous fibers as defined below. According to one particular embodiment of the invention, the chemical oxidizing agent or agents used preferably represent from 0.001% to 12% by weight of chemical oxidizing agents (of hydrogen peroxide) with respect to the total weight of the composition or the compositions containing them or, more preferably, from 0.2% to 2.7% by weight. T) the alkalinizing agent (s) According to one particular embodiment of the invention, the dyeing method uses one or more alkalinizing agent (s) f). This is a base (s) for increasing the pH of the composition (s) in which it is found. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. Particularly the said agent is chosen from i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, y ) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) basic preference amino acids such as arginine, lysine, ornithine, citruline and histidine, and viii) the compounds of formula (XIII) below: ## STR2 ## in which W is a divalent (C1-C8) alkylene radical optionally substituted with at least one hydroxyl group or at least one (C1-C4) alkyl radical and / or optionally interrupted by at least one heterotatome such as oxygen, sulfur or by a group -N (Re) -; Ra, Rb, Rc, Rd and Re, identical or different, represent a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl radical, preferably W represents a propylene radical. The inorganic or organic hydroxides are preferably chosen from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or of potassium, c) the hydroxides of a transition metal, such as Group III, IV, V and VI metal hydroxides, d) Lanthanide or actinide hydroxides, Quaternary ammonium hydroxides and Guanidinium hydroxide. The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate.
[0035] By (bi) carbonates i) is understood to mean: a) alkali metal (Met2 +, CO2), 3- alkaline earth metal (Met2 +, CO2) 3 ammonium carbonates ((R "4N +) 2 , CO32-) or phosphonium ((R "4P +) 2, CO32- with Met 'representing an alkaline earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom, a grouping (C-C6) optionally substituted alkyl such as hydroxyethyl), and b) bicarbonates, also known as hydrogenocarbonates, of the following formulas: - R '+, HCO3 with R' representing a hydrogen atom, an alkali metal, a group ammonium R "4N + - or phosphonium R" 4P + - where R ", identical or different, represent a hydrogen atom, an optionally substituted (C1-C6) alkyl group such as hydroxyethyl and when R 'represents an atom of hydrogen hydrogen carbonate is then called dihydrogen carbonate (002, H2O); and - Met2 + (1-1CO3) 2 with Met 'representing an alkaline earth metal. More particularly, the basifying agent is chosen from alkali metal or alkaline earth metal (bi) carbonates and amino acids such as arginine; preferentially alkali metal (bi) carbonates and amino acids. There may be mentioned carbonates or hydrogenocarbonates of Na, K, Mg, Ca and mixtures thereof, and in particular Na hydrogen carbonate. These hydrogencarbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, Badoit water (see patent for example FR 2 814 943). Particularly mention may be made of sodium carbonate [497-19-8] = Na2CO3, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2. According to a particularly advantageous embodiment, the alkalinizing agent (s) f) is (are) chosen from amino acids such as arginine and (bi) carbonates which are particularly alkaline or alkaline earthy. , alone or in mixtures. They are preferably together during the coloring process. The alkalinizing agent (s) as defined above preferably represent from 0.001% to 10% by weight relative to the weight of the composition (s) containing them. More particularly from 0.005% to 8% by weight of the composition.
[0036] Water: According to one embodiment of the invention, water is preferably included in the process of the invention. It may come from the wetting of the keratinous fibers and / or the composition or compositions comprising the compounds a) to e) as defined above or from one or more other compositions. Preferably, the water comes from at least one composition comprising at least one compound chosen from a) to f) as defined above.
[0037] Compositions: The compositions according to the invention generally comprise water or a mixture of water and one or more organic solvents or a mixture of organic solvents.
[0038] By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it. The compositions according to the invention may optionally comprise an organic solvent which is different from the liquid organic compound or compounds which have a Hansen solubility parameter value of less than 16 (MPa) 112 at 25 ° C. d) as defined above. Adjuvants: The composition (s) of the dyeing method according to the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic surfactants, amphoteric, zwitterionic or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or their mixtures other than cellulosic polysaccharides c) as defined above, inorganic or organic thickening agents other than cellulosic polysaccharides c) as defined previously, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example volatile or non-volatile silicones modified or unmodified islands, film-forming agents, ceramides, preservatives, opacifying agents. The dyeing process of the invention may also use in addition to the compounds a), b), optionally c) and optionally d) at least one other particular carboxylic acid of formula (I) as defined above. More particularly, the carboxylic acid (s) of formula (I) are such that A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxyl groups, and n represents an integer inclusive. inclusively between 0 and 5, such as between 0 and 2. More particularly the carboxylic acid (s) of the invention are chosen from the acids of formula (I) having a solubility in water greater than or equal to 1% by weight. at 25 ° C and at atmospheric pressure. Preferably the acids of formula (I) comprise at least one hydroxy group in their structure. Even more preferentially, the acid is chosen from α-hydroxy acids. The preferred acids of the invention are selected from glycolic acid, lactic acid, tartaric acid and citric acid. The salts of the acids of formula (I) can be organic or inorganic base salts such as sodium hydroxide, ammonia, or potassium hydroxide or organic amine salts such as alkanolamines. The acids of formula (I) or their salts are present in the composition or compositions containing them in a content ranging from 0.1 to 20% by weight. Said adjuvants are preferably selected from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the dyeing process according to the invention do not not, or not substantially, impaired by the addition or additions envisaged.
[0039] The cosmetic composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form suitable for carrying out a dyeing of keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. PH of the composition (s): According to a preferred embodiment of the invention the pH of at least one of the cosmetic compositions comprising at least one of the ingredients a), b), c), d) and e) 40 is acidic, ie less than 7.0, preferably less than 5.0, particularly at a pH of between 0 and 4, more preferably between 0.5 and 3.5. According to one embodiment, the pH of the cosmetic composition (s) containing one or more alkaline agents preferably chosen from (bi) carbonates is alkaline, being greater than 7, preferably between 8 and 12 and, more particularly, inclusive between 8 and 10.5. When the process according to the invention uses one or more ODP dyes, the composition containing the ODP (s) a) preferably has an acidic pH of less than 7, preferably less than 5, especially at a pH between 0 and 0 inclusive. 4, better between 1 and 3.
[0040] According to one particular embodiment of the invention, the composition containing the titanium salt (s) b), and not containing (bi) carbonates, has a pH of less than 7, and preferably less than 5, especially at least one pH between 0 and 4, more preferably between 0.5 and 3.5. The pH of these compositions can be adjusted to the desired value by means of basifying agents as defined previously in f) or from acidifying agents usually used in dyeing keratinous fibers or else using conventional buffer systems. Among the acidifying agents of the compositions used in the invention, mention may be made, for example, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. By "carboxylic acid" is meant a compound comprising at least one carboxylic acid group -O (O) -OH, preferably of formula (I) as defined above, preferably comprising between 1 and 4 carboxylic acid groups such as 1 or 2; or selected from: i) (C1-C10) alkyl- [C (O) -OH] n and ii) h- [C (O) -OH] n, where n is an integer inclusive of 1 to 4, preferably between 1 and 2, hetero-cyclic group such as pyrrolidone, the alkyl or hetero group may be optionally substituted with one or more groups, especially selected from OH, and (di) (CiC6) (alkyl) amino.
[0041] Staining process in one or more steps The method for staining keratinous fibers consists in treating, in one or more steps, one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin as defined previously, preferably chosen from ODPs as defined previously; b) one or more titanium salt (s); optionally b1) one or more carboxylic acid (s) of formula (I) as defined above; (C) one or more cellulosic polysaccharide (s) as defined previously; d) optionally one or more liquid organic compounds which have a Hansen solubility parameter value 6H of less than 16 (MPa) 112 at 25 ° C, preferably less than or equal to 15 (MPa) 112; e) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s); preferably, the composition or at least one of the compositions used in the dyeing process is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH between 0 and 4 inclusive. In particular embodiment of the invention, the dyeing process is carried out in at least two steps which comprises a first step in which the keratin fibers are treated with a cosmetic composition comprising a) one or more dyes selected from synthetic direct dyes and dyes of natural origin, preferably one or more ODP (s) as defined previously, b) one or more salt (s) of titanium and optionally b1) one or more carboxylic acid (s) as defined previously, c) one or more cellulosic polysaccharide (s) as defined previously, and d) optionally one or more several organic compounds uids which have a solubility parameter value of 6H Hansen <16 (MPa) 112 at 25 ° C, preferably less than or equal to 15 (MPa) 112; followed by a second step in which is applied an alkaline cosmetic composition ie whose pH is greater than 7, and preferably between 8 and 12, especially between 8 and 10.5, which comprises e) one or more agent (s) alkalinizing (s) and optionally e) one or more chemical oxidizing agent (s). Preferably the composition comprising a) + b) + c) + optionally d) and optionally b1) and optionally e) is acidic pH, ie less than 7, preferably less than 5, particularly at a pH inclusive between 1 and 3 .
[0042] Preferably, the cosmetic composition applied to the keratinous fibers during the second step further comprises e) one or more chemical oxidizing agent (s), chosen in particular from hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, preferably hydrogen peroxide. The pause time after application of the composition comprising the dye (s) ODP (s) such (s) as defined above is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes.
[0043] According to a particular embodiment of the invention, the method for dyeing keratinous fibers is carried out in two stages by the application to the keratin fibers of a dye composition comprising the ingredients a), b) and b1). , c) and optionally d), as defined above, then, in a second step, a composition comprising the ingredient e) and optionally the ingredient f) as defined above is applied to said keratinous fibers, it being understood that at least one of the two compositions is aqueous. Preferably, the composition comprising the dye (s) in particular ODP (s) a) is aqueous. Even more preferentially, the two compositions used in this embodiment are aqueous. According to a particular embodiment of the invention, the dyeing process is carried out in several steps by application to the keratinous fibers in a first step of a cosmetic composition comprising: a) one or more ODP (s), such ( s) as defined above, in particular chosen from: - haemaine, brazile, gallic acid, tannic acid, when the dyeing process does not use a chemical oxidizing agent e); or else - hematoxylin brasiline, when the staining process uses a chemical oxidizing agent e); b) one or more organic titanium salt (s) as defined previously; Advantageously, ingredient b) is selected from the salts or complexes of Ti (IV); b1) optionally one or more carboxylic acid (s) of formula (I) as defined above; and c) one or more cellulosic polysaccharide (s) as defined previously; d) optionally one or more organic compound (s) liquid (s) at 25 ° C having a solubility parameter value SH lower than 16 (MPa) at 25 ° C as defined previously; then in a second step the application on said fibers of a cosmetic composition comprising: e) optionally one or more chemical oxidizing agent (s) chosen from hydrogen peroxide or one or several system (s) generator (s) of hydrogen peroxide as defined above; f) one or more basifying agent (s) chosen (s) from amino acids and (bi) carbonates particularly alkaline or alkaline earth alone or in mixture; it being understood that: preferably the composition comprising a) + b) + c) + optionally d) and optionally b1) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH inclusive between 1 and 3; and the composition comprising the basifying agent (s) is at alkaline pH, preferably between 8 and 12, and more particularly between 8 and 10.
[0044] For this coloring process, the pause time after application for the first step is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes. The application time of the composition comprising the ingredient e) during the second step is generally set between 3 and 120 minutes and preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes. According to another embodiment, the method for dyeing keratin fibers is in two or three steps. According to this embodiment, the method for dyeing keratinous fibers is carried out in several steps by application to the keratinous fibers in a first step of a cosmetic composition comprising: a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, in particular one or more ODP (s), in particular chosen from: 15 - haematein, brasiline, gallic acid, tannic acid, when the dyeing process does not cause use of chemical oxidizing agent e); or else - hematoxylin brasiline, when the staining process uses a chemical oxidizing agent e); B) one or more titanium salt (s) as defined above and b1) optionally one or more carboxylic acid (s) of formula (I) as defined (s) ) previously with A representing a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxyl groups, and n representing an integer between 0 and 5, such as between 0 and 25; more particularly, the carboxylic acid or acids of the invention are chosen from citric acid, lactic acid, glycolic acid and tartaric acid; then in a second step the application on said fibers of a cosmetic composition comprising: c) one or more cellulosic polysaccharide (s) as defined previously and particularly nonionic (s) and non-associative (s), preferably selected from hydroxy (C1-C4) alkylcelluloses such as hydroxyethylcelluloses (HEC); d) optionally one or more liquid organic compounds which have a solubility parameter value of Hansen <16 (Ripe / 2 at 25 ° C, preferably selected from aromatic alcohols such as benzyl alcohol; e) optionally one or a plurality of chemical oxidizing agent (s) selected from hydrogen peroxide or one or more hydrogen peroxide generator system (s); f) one or more basifying agent (s) chosen (s) from amino acids such as arginine and (bi) carbonates particularly alkaline or alkaline earth, alone or in mixtures; It being understood that: - preferably the composition comprising a) + b) and optionally b1) is at acidic pH, i.e. less than 7, preferably less than 5, particularly at a pH inclusive of between 1 and 3; and the composition comprising the basifying agent (s) is at alkaline pH, preferably between 8 and 12, and more particularly between 8 and 10. In particular, the dyeing process of the invention is carried out in at least two stages, in the first step the ingredients a), b), c) and optionally d) are applied together on the keratinous fibers, in particular the hair, then in the second step the ingredients e) and f) are applied together on said fibers. Whatever the mode of application, the application temperature is generally between room temperature (15 to 25 ° C) and 220 ° C and more particularly between 15 and 45 ° C. Thus, it is advantageous, after application of the composition according to the invention, to subject the hair to heat treatment by heating at a temperature of between 30 and 60.degree. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. Both heating and smoothing of the hair can be used to heat a heating iron at a temperature between 60 and 220 ° C and preferably between 120 and 200 ° C. Whatever the mode of application, it is possible to perform a mechanical rinsing or wiping and / or drying of the keratinous fibers between each step, in particular before carrying out the last step comprising the application of a composition containing the ingredient ). The mechanical wiping and intermediate drying steps are also referred to as "non-rinsed mastered" to differentiate from "conventional wet rinse" and "non-rinsed". By "mechanical wiping" of the fibers is meant the rubbing of an absorbent object on the fibers and the physical removal by the absorbent object of the excess ingredient (s) that has not penetrated the fibers. The absorbent object may be a piece of cloth such as a particularly sponge towel, a cloth, absorbent paper such as paper towels. According to a particularly advantageous method of the invention, the mechanical wiping is carried out without total drying of the fiber, leaving the fiber wet.
[0045] Drying means the action of evaporating organic solvents and / or water in one or more compositions used in the process of the invention, comprising or not one or more ingredients a) to e) such than previously defined. The drying can be done by thermal source (convection, conduction or radiation) by sending for example a hot gas stream such as the air necessary for the evaporation 40 of the solvent or solvents. As a heat source there may be mentioned a hair dryer, 3029407 40 hair helmets, a hair straightener, an infrared ray dispenser and other conventional heating devices. A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C). In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which may result from the extemporaneous mixing of two or more compositions, and in particular of compositions present in dyeing kits. Dyeing device or "kit" Another object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed the ingredients a) to e) as defined previously can be aqueous or powder, with particularly at least one of said compositions being aqueous. According to a first variant, the kit comprises 5 compartments, the first 4 compartments comprising respectively ingredients a), b), c) and f) as defined above and in the 5th compartment containing an aqueous oxidizing composition such as water comprising e) as defined above. Optionally d) and / or b1) are preferably contained with a). In this other embodiment, at least one of the four compositions is aqueous and the dye (s), in particular the ODP (s) can be in powder form.
[0046] In another variant of the kit, the latter comprises two compartments, in which the first composition contained in the first compartment comprises a), b) and c) the second compartment comprises e) in the form of a powder or in an aqueous medium, preferably second composition is aqueous. In another kit variant, the latter comprises four compartments, in which the first composition contained in the first compartment comprises a) the second compartment comprises b) the third compartment comprises e) and the fourth compartment comprises f). c) can be in any compartment but preferably with a), compound d) preferably with a), compound b1) preferably with b).
[0047] In another variant of the kit, the latter comprises three compartments, in which the first composition contained in the first compartment comprises a) the second compartment comprises e) in the form of a powder or in an aqueous medium, preferably the second composition is aqueous and the 3rd compartment includes f).
[0048] Compound b) can be in any compartment but preferably 3029407 with a). Compound b) being with a) or e) and preferably with a). Compound d) preferably with a) According to a particular embodiment of the invention the kit comprises 5 separate compartments in which the Zef compartment contains a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from ODPs as defined previously, the 2nd compartment contains b) the salt (s) of Ti as defined (s) previously, and optionally b1) one or more carboxylic acid (s) as defined previously, the third compartment contains c) one or more cellulosic polysaccharide (s) such (s) as defined previously, the fourth compartment contains e) one or more chemical oxidizing agent (s) as defined previously including hydrogen peroxide and a 5th compartment which comprises f) one or more alkaline agent (s), it being understood that the solvent d) as defined above, It may possibly be in at least one of the compartments. According to one particular embodiment of the invention, the kit comprises 4 separate compartments in which the first compartment contains a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from among the ODPs, as defined previously, the 2 compartment contains b) the salt (s) of Ti as defined previously, and optionally b) one or more carboxylic acid (s) as defined previously, the third compartment contains e) one or more chemical oxidizing agent (s) such (s) that defined previously including hydrogen peroxide and a fourth compartment which comprises f) one or more alkaline agent (s), it being understood that: c) one or more cellulosic polysaccharide (s) as previously defined (s) is (are) in at least one of the 4 compartments, and - the solvent d) as defined above can vent be in at least one of the four compartments. According to a particular embodiment of the invention, the kit comprises 3 separate compartments in which the compartment contains a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from ODPs as defined previously, the 2nd compartment contains e) one or more chemical oxidizing agent (s) such as defined (s) ) previously especially hydrogen peroxide and a third compartment which comprises f) one or more alkaline agent (s), it being understood that: b) the salt (s) of Ti such as defined (s) previously, and optionally b1) one or more carboxylic acid (s) as defined previously, are found with the 3029407 42 or the dye (s) or with the agent (s) (s) chemical oxidizing agent (s), in particular H 2 O 2, preferably the salt (s) of Ti is (are) with the dye (s), c) one or more polysa The cellulosic acid (s) as defined above is (are) present in at least one of the 3 compartments, preferably with the dye (s), and the solvent d) such that previously defined can possibly be in at least one of the 4 compartments. According to a variant, the device according to the invention further comprises an additional composition comprising one or more treating agents. The compositions of the device according to the invention are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges. The device mentioned above can also be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2586913. The invention also relates to the use of said dye cosmetic composition for dyeing keratinous fibers. The invention also relates to a cosmetic composition for the staining of keratin fibers containing compounds a), b), b1), c), d) and e) as defined above. For the purposes of the present invention, the term "rise" of the color of the keratinous fibers is understood to mean the variation in color between strands of unstained white hair and strands of colored hair. The following example serves to illustrate the invention without being limiting in nature.
[0049] Examples of staining Example 1 The following compositions are prepared from the following ingredients in the following proportions indicated in grams per 100 grams of composition: Colorant: Ingredients Composition 1 Composition 2 Composition 3 Hematoxylin, a) 4 g 4 g 4 g marketed by sigma Cas = 517-28-2 Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight b) 12.1 g 12.1 g 12.1 g 19495-50-8 Lactic acid b1) 10.1 9 10.1 g 10.1 g Hydroxyethylcellulose (HEC) c) marketed under the name NATROSOL 250 Mr by Ashland 1.6 g HEC c) marketed under the name NATROSOL 250 HHR CS by Ashland 1.4 g 1, 2 g Ethanol 15 g 15 g 15 9 XANTHAN GUM sold under the name RHODICARE XC by Rhodia - 0.4 g Water qs 100 g qs 100 g qs 100 g pH agent qs pH = 2 ± 0.2 revealing omposition: Composition B quantity 2.4 g Hydrogen peroxide (50%): e) L-arginine: f) 7 g sodium bicarbonate: f) 5 g Hydroxypropyl s tarch phosphate marketed under the name STRUCTURE ZEA by AKZO NOBEL 5 g 3029407 44 Water qs 100 g. PH agent pH 10 ± 0.3 The coloring compositions 1 to 3 and then the composition B are applied with a brush to Caucasian hair with 90% of permed white hair, then a setting time of 45 minutes is observed at 40 ° C. for the compositions 1 to 3 and 5 of 15 minutes at 40 ° C for the composition B. A rinsing is carried out before the application of the composition B. At the end of these exposure times, the locks are washed with the shampoo Elseve mufti-vitamins, rinsed, then dried with the helmet.
[0050] Results of colorations It is found that black locks are very intensely colored, which is corroborated with the colorimetric measurements below. In addition, it appears that the coloration is visually homogeneous and tenacious with respect to successive shampoos.
[0051] The color of the locks was evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM3600D colorimeter. In this system L * a * b *, the three parameters denote respectively the intensity of the color (L *), a * indicates the green / red color axis and b * the blue / yellow color axis.
[0052] Rise of color: The color variation between the strands of causasian hair at 90% white permed before and after treatment or staining are defined by (AE *) according to the following equation: AE * = V (L * -1) In this equation, L *, a * and b * represent the values measured on locks of hair after staining and Lo * * *) 2 + (a * -ao *) 2 + (b * -130 *) 2 , ao * and bo * represent the values measured on locks of unstained virgin hair. The higher the value of AE *, the better the rise of the color. The results L, a, b of rise in color are listed in the table below: 30 Types of hair and color treatment L * a * AE * rise Composition 1 then B Natural Caucasian 90% white Black 22,16 1, 97 2.39 42.9 permed Composition 2 then B Natural Caucasian 90% white Black 21.99 2.32 2.51 I 43.04 3029407 After the keratinous fibers have been treated with compositions 1 to 3, the locks obtained are a black very powerful, and intense. EXAMPLE 2 The following coloring compositions are prepared according to the same protocol as in Example 1: Coloring composition Ingredients composition 4 composition Disperse red 13, a) 3180-81-2 0.5 g HC VIOLET 2: 2-N- hydroxypropylamino-5-N, N-bis (b-hydroxyethyl) amino nitrobenzene a) 0.5 g Glycolic acid b1) 15 g 15 g 10.3 g 10.3 g dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight b) HEC marketed under the name NATROSOL 250 HHR CS by Ashland, c) 1.2 g HEC marketed under the name Natrosol 250 Mr by Ashland, c) 1 g Ethanol 15 g 15 9 Benzyl alcohol d) 5 g 5 g Water qs 100g qs 1009_ ± 0.2 _ _ pH agent Qsp pH = 2 Red locks (composition 4) and violets (composition 5) are obtained very intensely colored. Composition 3 and then B Natural Caucasian 90% White Black permed 21,16 1,88 1,86 44,01 10 15

权利要求:
Claims (19)
[0001]
REVENDICATIONS1. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in one or more steps, with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the the following ingredients: a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols (ODPs); b) one or more titanium salt (s); optionally b1) one or more carboxylic acid (s) of formula (I) below; (HO) OH (I) formula (I) and its salts, in which: A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, hydrocarbon comprising 1 to 50 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or nonaromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted, in particular not one or more hydroxyl groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (Cr C6) alkylene group optionally substituted with one or more hydroxyl groups; - n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as 0, 1 or 2; c) one or more cellulosic polysaccharide (s); d) optionally one or more organic compound (s) liquid (s) at 25 ° C having SH Hansen SH solubility parameter value lower than 16 (MPa)% at 25 ° C and e) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s).
[0002]
2. The method of dyeing according to claim 1, characterized in that at least one of the compositions used in the dyeing process is at acidic pH, ie less than 7.0, preferably less than 5, particularly at a pH value. included 3029407 47 inclusive between 0 and 4.
[0003]
3. Staining process according to any one of the preceding claims, characterized in that ingredient a) is an aromatic ring ODP, this aromatic ring being chosen from benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydro-benzofuran, chromane, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring having at least two hydroxy groups carried by two contiguous adjacent atoms of the aromatic ring.
[0004]
4. Staining process according to any one of the preceding claims, characterized in that ingredient a) is a ODP of formula (II) below or one of its oligomers, tautomers, optical isomers, geometric isomers, and its salts or its solvates such as the hydrates: OH formula (II) in which: R1 to R4, identical or different, represent: i) a hydrogen atom, ii) halogen, or a group selected from iii ) hydroxy, iv) carboxy, v) (C1-C20) alkyl carboxylate or (C1-C20) alkoxycarbonyl, vi) optionally substituted amino, vii) (C1-C20) optionally substituted linear or branched alkyl, viii) (C2) -C20) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) (C1-C20) alkoxy, x1) (C1-C20) alkoxy (C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii ) optionally substituted aryl, xiv) aryl, xv) substituted aryl, xvi) heterocyclic, saturated or unsaturated, with or without a cationic or anionic charge, optionally substituted and / or optionally fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more silicon atoms; Or two of the substituents carried by two adjacent carbon atoms a - R2, R2 - R3 or R3 - R4 form together with the carbon atoms bearing them a saturated or unsaturated ring, aromatic or otherwise, optionally containing one or more hetero atoms. and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms; particularly, R1 to R4 together form from one to four rings; more particularly, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring carrying both hydroxy; particularly the ODP (s) a) is (are) chosen from: - flavanols such as catechin and epichatechin gallate, - flavonols such as quercetin, anthocyanidins such as cyanidine, delphinidine, petunidine, - anthocyanins or anthocyanins such as myrtillin, - orthohydroxybenzoates, for example gallic acid salts, flavones such as luteolin, hydroxystilbenes, for example 3,3 'tetrahydroxy, 4,5'- stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid, orthopolyhydroxycoumarines, orthopolyhydroxyisocoumarines, orthopolyhydroxycoumarones, orthopolyhydroxyisocoumarones, orthopolyhydroxychalcones, orthopolyhydroxychromones, quinones, hydro xyxanthones, 1,2-dihydroxybenzene and its derivatives, 1,2,4-trihydroxybenzene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 2,4,5-trihydroxytoluene and its derivatives, proanthocyanidins and especially proanthocyanidins A1, A2, B1, B2, B3 and C1, - chromanics, and chromenics, proathocyanines, - tannic acid, - ellagic acid, and mixtures of the foregoing compounds; preferably the ortho-diphenol (s) are chosen from haematein, brasiline, gallic acid, tannic acid, hematoxylin and brasiline, and mixtures thereof. 3029407 49
[0005]
5. Staining process according to any one of claims 3 or 4, characterized in that the ODP (s) natural (s) a) is (are) chosen (s) from animal extracts, bacteria , mushrooms, seaweed, plants and fruits. 5
[0006]
6. Staining process according to any one of the preceding claims, characterized in that the acid (s) b1) is (are) present (s) and is (are) of formula (I) with A representing a group monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene optionally substituted with one or more hydroxyl groups, and n representing an integer inclusive of between 0 and 5, such as 0, 1 or 2, particularly the acid (s); carboxylic compounds of the invention are selected from α-hydroxy acids; preferentially, the acid (s) 1) 1) is (are) chosen from citric acid, lactic acid, tartaric acid and glycolic acid. 15
[0007]
7. Coloring method according to any one of the preceding claims, wherein the acid (s) b1) of formula (I) or their salts, is (are) present in the composition or compositions containing them in a content ranging from 0.1 to 20% by weight.
[0008]
8. Staining process according to any one of the preceding claims, characterized in that the salt (s) of titanium is (are) chosen from organic or inorganic salts of titanium, preferably from salts organic titanium, and in particular in which the titanium is of oxidation state 2, 3 or 4 preferably of oxidation degree 4. 25
[0009]
9. The method of dyeing according to the preceding claim, characterized in that the organic salt (s) titanium (s) b) is (are) from (s) the reaction of acid (s) organic (s) on titanium, wherein the organic acid (s) is (are) chosen from organic acids which comprise: a) at least one C 1 -C 20 hydrocarbon chain, optionally unsaturated, linear or branched, a (hetero) cycloalkyl, or (hetero) aryl group, and b) at least one acidic chemical function being in particular selected from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO3H2, PO41-12; preferably the organic acid (s) is (are) chosen from carboxylic acids (s) of formula (I) as defined in claim 1 or 7, more preferably from citric acids, lactic, tartaric and glycolic and more particularly lactic and glycolic acids.
[0010]
10. The method of dyeing according to any one of the preceding claims, characterized in that the acid (s) b1) is (are) of formula (I) as defined in the claim 3029407 50 1 or 6 and the latter is (are) different from the organic acid (s) of the titanium salt as defined in claim 8 or 9.
[0011]
11. Coloring process according to any one of the preceding claims, characterized in that the organic salt (s) of titanium (b) is (are) chosen from those of formula (IA) below: Formula ( IA) in which: - A is as defined in claim 1 or 6; N, n 'and n ", identical or different, are 1,2,3, or 4 with n' + n" = 6; - M1 and M2 identical or different, represent a cationic counter ion such as an alkali metal cation such as Na, or K, alkaline earth such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom; - TiYn., Represents Ti (OH) ,,., Ti (O) n.72, or Ti (OH) ,, i (O), 2 with m1 + rn2 = n "; Titanium organic (s) of the dyeing process is the dihydroxybis (lactato) titaniumlV salt such as those of the following formula: 2- 2NH4 + 20
[0012]
12. Staining process according to any one of the preceding claims, characterized in that said method uses c) one or more associative (s) or non-associative (s) nonionic cellulosic (s) polysaccharide (s) ); in particular the cellulosic polysaccharide (s) c) is (are) non-associative (s) and nonionic (s), preferably chosen from nonionic cellulose ethers: (C 1 -C 4) alkylcelluloses such as methylcelluloses and ethylcelluloses; (poly) hydroxy (Cr C4) alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses; mixed (poly) hydroxy (CrC4) alkyl- (C1-C4) alkylcellulose celluloses such as hydroxypropyl-methylcelluloses, hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses and hydroxybutyl-methylcelluloses; More preferably the cellulosic polysaccharide (s) c) is (are) chosen from hydroxyalkylcelluloses, in particular hydroxyalkyl (Ci-C4) celluloses, and 3029407 51 chosen in particular from hydroxymethylcelluloses, hydroxyethylcelluloses, and hydroxypropylcelluloses; , in particular nonionic hydroxyethylcelluloses.
[0013]
13. Staining process according to any one of the preceding claims, characterized in that said process uses d) one or more organic compound (s) liquid (s) at 25 ° C having a parameter value of solubility SH less than 16 (MPa)% at 25 ° C., preferably chosen from organic solvents, chosen in particular from aromatic alcohols such as benzyl alcohol 10
[0014]
14. The method of dyeing according to any one of the preceding claims, characterized in that said method uses e) one or more chemical oxidizing agent (s) chosen (s) from hydrogen peroxide. or one or more system (s) generator (s) of hydrogen peroxide, in particular selected from hydrogen peroxide or urea peroxide, preferably hydrogen peroxide. 15
[0015]
15. A dyeing method according to any one of the preceding claims, characterized in that the dyeing process uses f) one or more alkalinizing agent (s) particularly selected from: i) the (bi) ) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) silicates alkali metals such as sodium metasilicates, vii) basic amino acids such as arginine, lysine, ornithine, citruline and histidine, and viii) compounds of the following formula (XIII): Ra Embedded image Formula (XIII) wherein W is a divalent (C1-C8) alkylene radical optionally substituted with at least one hydroxy group or at least one (C1-C4) alkyl group and or optionally interrupted by at least one heterotome te l that oxygen, sulfur or a group -N (Re) -; Ra, Rb, Rb, Rd and Re, identical or different, represent a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl radical, preferably W represents a propylene radical, preferably the one or more Basifying agents are chosen from (bi) carbonates and amino acids, alone or in mixtures.
[0016]
16. A dyeing method according to any one of the preceding claims, characterized in that said process is carried out in at least two steps which comprises a first step in which the keratinous fibers are treated with a cosmetic composition comprising a) a or more dye (s) chosen from synthetic direct dyes and / or dyes of natural origin, in particular ODP (s) as defined in any one of Claims 1 to 5, (b) one or more titanium salt (s) chosen especially from organic titanium salts as defined in any one of claims 1, 8, 9 or 11; b1) one or more carboxylic acid (s) of formula (I) as defined in any one of claims 1, 6, or 10; c) one or more cellulosic polysaccharide (s) as defined in claim 1 or 12 and optionally d) one or more organic compound (s) liquid (s) at 25 ° C having a solubility parameter value of 8H less than 16 (MPa) Y 'at 25 ° C as defined in claim 1 or 13; followed by a second step in which is applied an alkaline cosmetic composition ie whose pH is greater than 7, and preferably between 8 and 12 inclusive, particularly between 8 and 10.5, which comprises f) one or more agent (s) alkalinizing (s) as defined (s) in claim 15, preferably the cosmetic composition applied to the keratin fibers in the second step further comprisese) one or more oxidizing agent (s) (s) ) chemical (s) as defined in claim 14, in particular selected from hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, of preferably hydrogen peroxide. 20
[0017]
17. The method of dyeing according to the preceding claim made in several steps by application to the keratin fibers in a first step of a cosmetic composition comprising: a) one or more ODP (s), as defined in (s) in any of claims 1 to 5, in particular chosen from: - haematein, brasiline, gallic acid, tannic acid, when the dyeing process does not use a chemical oxidizing agent; ); or else - hematoxylin or brasiline, when the staining process uses a chemical oxidizing agent e); b) one or more organic titanium salt (s) as defined in any one of claims 1, 8, 9 or 11; advantageously, ingredient b) is chosen from the salts or complexes of Ti (IV); b1) optionally one or more carboxylic acid (s) of formula (I) as defined in any one of claims 1, 6, or 10; and c) one or more cellulosic polysaccharide (s) as defined in any one of claims 1 or 12; d) optionally one or more organic compound (s) liquid (s) at 25 ° C having a solubility parameter value 8FI lower 16 (MPa) 'at 25 ° C as defined 3029407 53 ) in claim 1 or 13; then in a second step the application on said fibers of a cosmetic composition comprising: e) optionally one or more chemical oxidizing agent (s) chosen from hydrogen peroxide or one or a plurality of hydrogen peroxide generator systems as defined in claim 14; f) one or more basifying agent (s) chosen (s) from amino acids and (bi) carbonates particularly alkaline or alkaline earth alone or in mixture; it being understood that: 10 - preferentially the composition comprising a) + b) + c) + optionally d) and optionally b1) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH inclusive between 1 and 3; and the composition comprising the basifying agent (s) is at alkaline pH, preferably between 8 and 12, and more particularly between 8 and 10.
[0018]
18. Cosmetic composition for the dyeing of keratinous fibers containing compounds a), b), dl), c), d) and e) as defined according to any one of claims 1 to 17.
[0019]
19. Multi-compartment device comprising 2 to 5 compartments containing from 2 to 5 compositions, in which are distributed ingredients a), b), b1), c), d) and e), as defined according to one of the following: any of claims 1 to 17, said compositions being aqueous or powdery, with at least one of these compositions being aqueous. 25

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FR3037241A1|2016-12-16|A CAPILLARY COLORING PROCESS USING A TITANIUM SALT, A COLOR, AND A PARTICULAR SOLVENT

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FR3029408A1|2016-06-10|A CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, A TITANIUM SALT, AND A CATIONIC HYDROPHOBIC CELLULOSIC POLAR

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FR2949196A1|2011-02-25|CAPILLARY COLORING PROCESS USING CHROMENIC OR CHROMANIC COLOR

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FR3029406A1|2016-06-10|CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, ONE TITANIUM SALT, AND ANIONIC THICKENING POLYMER

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FR2976794A1|2012-12-28|Dyeing keratin fibers, preferably hair, comprises treating fibers with compositions containing ortho-diphenol derivatives, manganese or zinc salts, hydrogen peroxide, |carbonates, basifying agents and titanium salts to keratin fibers

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FR3037238A1|2016-12-16|CAPILLARY COLORING PROCESS, FREE OF CHEMICAL OXIDANT, USING TITANIUM SALT, AND PARTICULATE COLOR

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FR3075640A1|2019-06-28|CAPILLARY COLORING PROCESS COMPRISING A COLORING STEP WITH HENNE AND / OR INDIGO AND A TREATMENT STEP COMPRISING THE APPLICATION COMPRISING A BUFFER SYSTEM

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FR3019037A1|2015-10-02|PROCESS FOR COLORING KERATIN FIBERS FROM ORTHODIPHENOLS, METAL SALTS, OXIDIZING AGENT AND BASIC COMPOUND

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FR3075643A1|2019-06-28|PROCESS FOR COLORING MULTI-STAGE KERATIN FIBERS FROM INDIGOFERE | PLANT POWDER AND ACID PROCESSING COMPRISING A PARTICULATE COLOR

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FR3030230A1|2016-06-24|PROCESS FOR COLORING FROM ORTHODIPHENOL

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FR2996124A1|2014-04-04|A CAPILLARY COLORING PROCESS USING AT LEAST ONE ORTHOMETHOXYPHENOL DERIVATIVE, A MANGANESE OR ZINC SALT, HYDROGEN PEROXIDE AND | CARBONATE

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FR3037240A1|2016-12-16|MULTI-STAGE HAIR COLORING PROCESS USING AT LEAST ONE TITANIUM SALT AND SYNTHETIC DIRECT COLOR

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FR3075617A1|2019-06-28|PROCESS FOR COLORING KERATIN FIBERS IN ONE OR MORE STEPS FROM INDIGOFERE | PLANT POWDER AND TREATMENT COMPRISING THE MONASCUS EXTRACT

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FR3075614A1|2019-06-28|PROCESS FOR COLORING MULTI-STAGE KERATIN FIBERS FROM INDIGOFERE | PLANT POWDER AND ALKALINE COLORING TREATMENT

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FR3090332A1|2020-06-26|Hair coloring process, using a titanium salt, a fatty ether and a natural dye

同族专利:

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公开号 | 公开日

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FR3029407B1|2016-12-09|

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CN107205897A|2017-09-26|

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US10524992B2|2020-01-07|

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WO2016091814A1|2016-06-16|

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JP2017537161A|2017-12-14|

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BR112017011001A2|2018-02-14|

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ES2739537T3|2020-01-31|

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EP3229755B1|2019-06-12|

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EP3229755A1|2017-10-18|

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US20170333312A1|2017-11-23|

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FR2976793B1|2011-06-23|2013-07-26|Oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE ORTHODIPHENOL, MANGANESE OR ZINC SALT, HYDROGEN PEROXIDE, CARBONATE, ALKALINE AGENT AND TITANIUM SALT|

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FR3014682B1|2013-12-13|2015-12-18|Oreal|CAPILLARY COLORING PROCESS IMPLEMENTING AT LEAST ONE ORTHODIPHENOL, A TITANIUM DERIVATIVE, AND A CARBOXYLIC ACID|

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FR3029405B1|2014-12-08|2019-08-02|L'oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, TITANIUM SALT, AND INSOLUBLE SILICATE|

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FR3029406B1|2014-12-08|2016-12-09|Oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, ONE TITANIUM SALT, AND ANIONIC THICKENING POLYMER|

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FR3029409B1|2014-12-08|2016-12-09|Oreal|A CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, AN ORGANIC TITANIUM SALT, AND A NON-CELLULOSIC POLYSACCHARIDE|FR3029409B1|2014-12-08|2016-12-09|Oreal|A CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, AN ORGANIC TITANIUM SALT, AND A NON-CELLULOSIC POLYSACCHARIDE|

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FR3029406B1|2014-12-08|2016-12-09|Oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, ONE TITANIUM SALT, AND ANIONIC THICKENING POLYMER|

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FR3029405B1|2014-12-08|2019-08-02|L'oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, TITANIUM SALT, AND INSOLUBLE SILICATE|

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CN109022513A|2018-09-14|2018-12-18|中国热带农业科学院海口实验站|The method of ultrasonic wave auxiliary biological complex enzyme enzymolysis and extraction hill gooseberry's anthocyanidin|

法律状态:
2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |

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2016-06-10| PLSC| Search report ready|Effective date: 20160610 |

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2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |

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2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |

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2019-11-15| PLFP| Fee payment|Year of fee payment: 6 |

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2021-09-10| ST| Notification of lapse|Effective date: 20210806 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1462061A|FR3029407B1|2014-12-08|2014-12-08|A CAPILLARY COLORING PROCESS USING AT LEAST ONE DIRECT AND / OR NATURAL COLOR, TITANIUM SALT, CELLULOSIC POLYSACCHARIDE AND, WHERE POSSIBLE, A PARTICULAR ORGANIC SOLVENT|FR1462061A| FR3029407B1|2014-12-08|2014-12-08|A CAPILLARY COLORING PROCESS USING AT LEAST ONE DIRECT AND / OR NATURAL COLOR, TITANIUM SALT, CELLULOSIC POLYSACCHARIDE AND, WHERE POSSIBLE, A PARTICULAR ORGANIC SOLVENT|

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JP2017548332A| JP2017537161A|2014-12-08|2015-12-07|Hair dyeing method using at least one direct and / or natural dye, titanium salt, cellulosic polysaccharide and optionally a specific organic solvent|

---

EP15804850.4A| EP3229755B1|2014-12-08|2015-12-07|Hair dyeing process using at least one direct and/or natural dye, a titanium salt, a cellulose-based polysaccharide and optionally a particular organic solvent|

---

PCT/EP2015/078844| WO2016091814A1|2014-12-08|2015-12-07|Hair dyeing process using at least one direct and/or natural dye, a titanium salt, a cellulose-based polysaccharide and optionally a particular organic solvent|

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BR112017011001A| BR112017011001A2|2014-12-08|2015-12-07|keratin fiber dyeing process, cosmetic composition and multi-compartment device|

---

ES15804850T| ES2739537T3|2014-12-08|2015-12-07|Procedure for dyeing hair using at least one direct and / or natural dye, a titanium salt, a cellulose-based polysaccharide and optionally a particular organic solvent|

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CN201580075688.2A| CN107205897A|2014-12-08|2015-12-07|Use the hair colouring methods of at least one direct and/or natural dye, titanium salt, the polysaccharide based on cellulose and optional specific organic solvent|

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US15/534,283| US10524992B2|2014-12-08|2015-12-07|Hair dyeing process using at least one direct and/or natural dye, a titanium salt, a cellulose-based polysaccharide and optionally a particular organic solvent|