FR3076998A1 - CAPILLARY COLORING PROCESS USING TITANIUM SALT, OXIDATION COLOR, AND INTERMEDIATE RINSE - Google Patents

Abstract

The present invention relates to a multi-step process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated with i) a step containing at least one cosmetic composition Ci) comprising a) one or several salt (s) of titanium and b) optionally one or more particular carboxylic acids; and with ii) a step of staining with an aqueous coloring cosmetic composition Cii) whose pH is less than 7, comprising c) one or more oxidation dye (s), d) one or more oxidizing agent (s) ) chemical (s) such as hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, and e) one or more agent (s) alkaline (s) iii) possibly an intermediate rinsing step of said keratinous fibers preferably with water, between step i) and ii) or ii) and i).

Description

Hair coloring process using a titanium salt, an oxidation dye and an intermediate rinse

The present invention relates to a multi-step process for coloring keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated with i) a cosmetic composition Ci) comprising a) one or more salt (s) titanium and b) optionally one or more specific carboxylic acids; and with ii) an aqueous coloring cosmetic composition Cii) whose pH is less than 7, and comprising c) one or more oxidation dye (s), d) one or more chemical oxidizing agent (s) ) such as hydrogen peroxide or one or more system (s) generating hydrogen peroxide, and e) one or more basifying agents, it being understood that preferably between step i) and ii) or ii) and i) the keratin fibers are rinsed.

It is known to obtain so-called “permanent” colors with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or paraaminophenols and compounds. heterocyclic. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. This oxidation dyeing process consists of applying bases or a mixture of bases and couplers to the keratin fibers with hydrogen peroxide (H2O2 or hydrogen peroxide) as an oxidizing agent, to let it diffuse, then to rinse the fibers.

We seek to increase the efficiency of the reaction of the oxidation dyes used during this process, in particular in terms of power, color rise, color fastness on keratin fibers, in particular with respect to light, successive washings, sweat and / or color selectivity between the root and the tip of said fibers. Indeed, such (s) improvement (s) will allow (in) t in particular to reduce the contents of the oxidation dyes present in the dye compositions, reduce the exposure time on the keratin fibers and / or use other families dyes with a low tinctorial power and which may have a good toxicological profile. In addition, this would bring new nuances or lead to more tenacious coloring vis-à-vis external agents such as light or shampoos, or finally lead to better qualities of use such as less staining of the scalp, clothing, or even less coloring of the dye mixture (cleaner) during application or break time.

This object (s) is (are) achieved by the present invention which relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated, in several stages, with:

i) at least one step of treating said fibers with a cosmetic composition Ci) containing:

a) one or more titanium salt (s); in particular the titanium atom of said salt (s) is (are) with an oxidation state of 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ;

b) optionally one or more carboxylic acid (s) of formula (I) below or one of its salts;

(I)

Formula (I) in which:

-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 non-aromatic, optionally interrupted by one or several heteroatoms and / or optionally substituted in particular by one or more hydroxy and / or amino groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxy and / or amino groups;

- N represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; and ii) at least one step of coloring with an aqueous coloring cosmetic composition Cii) whose pH is less than 7, preferably less than or equal to 6.9; and containing:

c) one or more oxidation dye (s); one or more chemical oxidizing agent (s) chosen in particular from hydrogen peroxide or one or more system (s) generating hydrogen peroxide; and

e) one or more alkaline agent (s);

iii) preferably at least one intermediate rinsing step for said fibers, preferably with water, it being understood that:

- First composition Ci) is applied to said fibers, followed by one or more rinsing (s) of said fibers, preferably with water, then composition Cii) is applied to said fibers; or

- First the composition Cii) is applied to said fibers, followed by one or more rinsing (s) of said fibers, preferably with water, then composition Ci) is applied to said fibers.

Particularly preferably, the coloring process according to the invention implements an intermediate rinsing step iii).

Preferably, the composition Cii) is applied first to the said fibers, followed by one or more rinsing (s) of the said fibers, preferably with water, then the composition Ci) is applied to the said fibers.

The process according to the invention has the advantage of coloring human keratin fibers, with stubborn coloring results. In particular, the dyeing process according to the invention makes it possible to produce dyes which are resistant to washing, perspiration, sebum and light without damaging the fibers. The color consistency between the roots and the tips of the fibers is particularly good (low selectivity). In addition, the coloring process used makes it possible to induce a “rise” and / or very satisfactory coloring power.

Other objects, characteristics, aspects and advantages of the present invention will appear even more clearly on reading the description and the examples which follow.

a) the titanium salt (s):

The cosmetic composition Ci) implemented according to step i) of the process according to the invention comprise one or more organic (in) or inorganic salt (s) of titanium.

The titanium salt (s) of the invention can be one or more organic or inorganic salt (s) of titanium.

By “organic titanium salt” is understood within the meaning of the present invention the salts proper, resulting from the action of at least one organic acid on the Ti which may be of oxidation state 1,2, 3 or 4 , preferably of oxidation state 4 denoted Ti (IV).

The term “organic acid” means an acid, ie a compound capable of releasing an H + or H3O + cation or proton in aqueous media, which comprises at least one C1-C20 hydrocarbon chain, optionally unsaturated, linear or branched, a group (hetero ) cycloalkyl, or (hetero) aryl and at least one acidic chemical function being in particular chosen from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO3H2, PO4H2. Particularly the organic acid (s) is (are) to form the organic titanium salt (s) of the invention is (are) chosen (s) from the carboxylic acids (s) 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 acid (s) as defined above, preferably carboxylic acid (s) of formula (I) as defined above, is an optionally charged complex (in particular negatively charged) which is complexed by one or more carboxylate group (s) of carboxylic acid (s).

Preferably the organic salt (s) of titanium a) of the invention is (are) chosen from those of formula (I-A) below:

Γ ° x 1 P ^M 2 v lyijO n 0

(the)

Formula (l-A) in which:

• A is identical to that of formula (I) • n, n ’and n” identical or different are 1, 2, 3 or 4 with n ’+ n” being 6;

• M1 and M2, identical or different, represent a cationic counter ion in particular chosen from alkali metal cations such as Na, or K, alkaline earth metal such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom ;

• TiYn ”denoting Ti (OH) n”, or Ti (O) n ”/ 2, or Ti (OH) m1 (O) m2 with m1 + m2 = n”.

Preferably, the radical A of the compound (1A) as defined above represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxy groups or one or more amino groups, preferably by a or more hydroxy groups, and n representing an integer inclusive between 0 and 5, such as between 0 and 2, particularly the carboxylic acid (s) used to form the organic titanium salt (s) of the invention are chosen from α- hydroxy acids and α-amino acids; preferably the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and serine, more preferably chosen from lactic and glycolic acid.

Preferably, the organic salt (s) of titanium a) of the invention is (are) chosen from those of formula (I-B) below:

2M ⁺ M ⁺

Formula (l-B) in which:

• L 'and L ”, identical or different, represent a divalent (hetero) arylene, (C1C6) alkylene, (C2-C6) alkenylene group, said alkylene and arylene groups being optionally substituted by one or more atoms or groups chosen from halo , (C1-C4) alkyl, hydroxy, thiol, and (di) (C1-C4) (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 or ethylene group optionally substituted by a (C1-C4) alkyl group;

• X 'and X ”, identical or different, represent a heteroatom such as oxygen, sulfur or amino Rc-N with Rc representing a hydrogen atom or a (C1-C4) alkyl group, preferably X' and X” are identical and represent an oxygen atom;

• Y and Y ’, identical or different, are as defined for X’ and X ”, preferably Y and Y’ are identical and represent an oxygen atom;

• Ra and Rb, identical or different, represent a hydrogen atom, 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 counter ion such as an alkali (Na, K), alkaline earth (Ca) or organic metal cation such as ammonium, preferably ammonium.

Preferably, the organic salt (s) of Titanium (a) of the coloring process is the dihydroxybis (lactato) titaniumlV salt such as those of the following formula:

+ % ( ) H ../θ ' Z 2NH ₄ 1 The h ₃ c o ch ₃ OH

By "inorganic titanium salt" is meant within the meaning of the present invention the actual salts derived from the action of an inorganic acid on Ti.

By "inorganic acid" is meant an acid that has no carbon atoms except carbonic acid.

According to a particular embodiment of the invention the titanium salt (s) a) is (are) inorganic (s). It (s) is (are) particularly chosen (s) from titanium halides, titanium sulfates and titanium phosphates. Preferably the inorganic titanium salts are salts of Ti (II), Ti (III) or Ti (IV), more particularly Ti (III) or Ti (IV), even more preferably Ti (IV).

According to a preferred embodiment of the invention, the titanium salt or salts a) is (are) organic salts of titanium, and better still organic salts of Ti (IV). According to an advantageous embodiment of the invention, the organic Ti salt consists of a Ti atom (IV) and from 2 to 3 molar equivalents of at least one carboxylic acid of formula (I).

The titanium salt (s) a) is (are) present in the cosmetic composition i) of the coloring process according to the invention in a content ranging from 0.001% to 20% by weight relative to the weight total of said composition i) as defined above.

In particular, the organic titanium salt or salts as well as 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.

b) one or more carboxylic acid (s)

The cosmetic composition Ci) implemented according to step i) of the method according to the invention may also preferably comprise one or more carboxylic acid (s).

By “carboxylic acid” is meant a compound comprising at least one carboxylic acid group -C (O) -OH, preferably of formula (I) as defined above, preferably comprising between 1 and 4 carboxylic acid groups such as 1 or 2; or chosen from: i) (C1-C10) alkyl- [C (O) -OH] n and ii) heter- [C (O) -OH] n, with n an integer inclusive between 1 and 4, preferably between 1 and 2, heter representing a heterocyclic group such as pyrrolidone, the alkyl or heter group possibly being optionally substituted by one or more groups, in particular chosen from OH, and (di) (C1C6) (alkyl) amino.

According to an advantageous variant, the coloring process also implements b) one or more carboxylic acid (s) of formula (I) as defined above. More preferably, the carboxylic acid (s) b) are different from the carboxylic acids complexed with Ti salts, preferably glycolic acid, citric acid, lactic acid or one of their salts.

For example if the carboxylic acid complexed with the titanium salt a) is lactic acid or its carboxylate salt (lactate), the second acid b) different from lactic acid or lactate, and may for example be glycolic acid .

The salts of the acids of formula (I) may be salts of organic or inorganic bases or of basifying agents e) as defined below. Preferably the salts are soda, ammonia, or potassium salts or salts of organic amines such as alkanolamines.

The acids of formula (I) or their salts are present in composition i) in a content ranging from 0.1 to 20% by weight, relative to the total weight of said composition i).

c) the oxidation dye (s)

According to the present invention, the coloring composition Cii) implemented according to step ii) of the method according to the invention comprises one or more oxidation dye (s).

The oxidation dye precursors which can be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers.

The oxidation bases can be chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Preferably, the oxidation base or bases of the invention are chosen from para-phenylenediamines and heterocyclic bases. Among the para-phenylenediamines, mention may be made, for example, of para-phenylenediamine, paratoluylenediamine, 2chloro-paraphenylenediamine, 2,3 -dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, Ν, Ν-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, Ν, Ν-diprop paraphenylenediamine, 4-amino-N, N-diethyl-3methylaniline, N, N-bis- (p-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (phydroxyethyl) amino 2-methyl aniline N, N-bis- (p-hydroxyethyl) amino-2-chloroaniline, 2-p-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2isopropyl paraphenylenediamine, N- (p-hydroxypropyl) paraphenylenediamine, 2 hydroxymethyl paraphenylenediamine ne, 2-methoxymethyl paraphenylenediamine, N, N-dimethyl-3-methyl paraphenylenediamine, N, N- (ethyl, -p-hydroxyethyl) paraphenylenediamine, N- (p, y-dihydroxypropyl) paraphenylenediamine, N- (4 'aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-βhydroxyethyloxy para-phenylenediamine, 2-p-acetylaminoethyloxy para-phenylenediamine, N- (p-methoxyethyl) para-phenylenediamine-2-phenylenediamine -β hydroxyethylamino 5amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2 ^ -hydroxyethyl paraphenylenediamine, 2 ^ -hydroxyethyloxy paraphenylene diamine, 2,6-dimethyl paraphenylenediamine paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis - ^ - hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2 ^ -acetylaminoethyloxy paraphenylenediamine, 2methoxymethyl paraphenylenediamine and their addition salts and their acid salts and their addition salts preferred.

Among the bis-phenylalkylenediamines, there may be mentioned by way of example, N, N'-bis- ^ hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N '-bis- ^ hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis - ^ - hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine,

N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3 'methylphenyl) ethylenediamine, 1,8-bis- (2,5diaminophenoxy) -3,6-dioxaoctane, and their addition salts.

Among the para-aminophenols, mention may be made, for example, of para-amino phenol, 4-amino-3-methyl phenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4 amino-3- hydroxymethyl phenol, 4-amino-2-methyl phenol, 4-amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl phenol, 4amino 2- (p-hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2 amino-5- methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and their addition salts.

Among the heterocyclic bases, there may in particular be pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5 diamino pyridine, 2- (4methoxyphenyl) amino 3 amino pyridine, 3,4- diamino pyridine, and their addition salts.

Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1,5 a] -pyridine oxidation bases or their addition salts described for example in patent application FR 2801308.

By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-

a] pyridine-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridine-7-yl) -methanol; 2- (3-aminopyrazolo [1,5-a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) -ethanol; (3-amino-pyrazolo [1,5-a] pyridine-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) -amino] -ethanol; 2 - [(3-amino-pyrazolo [1,5a] pyridin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [1,5-a] pyridine-6-ol; 3 amino- pyrazolo [1,5-a] pyridine-7-ol; 2-p-hydroxyethoxy-3-amino-pyrazolo [1,5a] pyridine; 2- (4-dimethylpyperazinium-1-yl) -3-amino-pyrazolo [1,5-a] pyridine; as well as their addition salts.

More particularly, the oxidation bases according to the invention are chosen from 3-aminopyrazolo- [1,5 a] -pyridines preferably substituted in position 2 by:

a) a (di) (C1-C6) (alkyl) amino group, the alkyl groups being able to be substituted by one or more hydroxy, amino or imidazolium groups;

b) a heterocycloalkyl group comprising from 5 to 7 members, and from 1 to 3 heteroatoms, cationic or not, optionally substituted by one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium;

c) an (C1-C6) alkoxy group optionally substituted by one or more hydroxy groups such as β-hydroxyalkoxy as well as their addition salts.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in patents DE 2359399; JP 88 169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4 hydroxy 2,5,6triaminopyrimidine, 2 hydroxy 4,5,6-triaminopyrimidine, 2,4 dihydroxy 5 , 6diaminopyrimidine, 2,5,6 triaminopyrimidine and their addition salts and their tautomeric forms, when there is a tautomeric equilibrium.

Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4.5 diamino 1-methyl pyrazole, 4,5-diamino 1- (βhydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino -1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1,3-dimethyl -5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert -butyl 3-methyl pyrazole, 4,5-diamino-1 - $ - hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1- ethyl-3- (4'methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl 3-hydroxymethyl pyrazole, 4,5diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl -1-isopropyl pyrazole, 4,5-diamino-3-methyl-1- isopropyl pyrazole, 4-amino-5- (2'aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4,5triamino pyrazole, 3,5 -diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- $ hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1 - ^ - hydroxyethyl) pyrazole. It is also possible to use 4-5-diamino1 - ^ - methoxyethyl) pyrazole.

Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1 - $ - hydroxyethyl) -pyrazole and / or one of its salts will be used.

As pyrazole derivatives, mention may also be made of diamino N, Ndihydropyrazolopyrazolone and in particular those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6,7 -dihydro1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-1-one, 2 -amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H , 5H-pyrazolo [1,2-a] pyrazol-1one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-diethyl -1,2dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one, 2 amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2 amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-510 ( pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5- (3-dimethylamino-pyrrolidin- 1-yl) 1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1 H, 5Hpyrazolo [1,2-a] pyrazol -1-one.

It is preferable to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or one of its salts.

As heterocyclic bases, use will preferably be made of 4,5-diamino-1- (phydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1one and / or a salt thereof.

The oxidation base (s) used in the context of the invention are generally present in an amount ranging from 0.001 to 10% by weight approximately of the total weight of the coloring composition, preferably ranging from 0.005 to 5%.

The additional couplers conventionally used for dyeing keratin fibers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and also their addition salts.

By way of example, there may be mentioned 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 1-hydroxy-3-aminobenzene, 2-methyl5-aminophenol, 3-amino-2-chloro-6-methyl phenol, 2-methyl-5hydroxyethylaminophenol, 2,4-diamino-1- (B-hydroxyethyloxy) benzene, 2-amino-4 ( β-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis- (2,4diaminophenoxy) propane, 3-ureido aniline, 3-uréido 1-dimethylamino benzene, sesamol, thymol , 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, Γα-naphthol, 2 methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2- amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6dimethoxypyridine, 1-N- (B-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis (B -hydroxyethylamino) toluene, 6-hydroxy indoline, 2,6-dihydroxy 4-methyl pyridine, 1-H-3-methyl pyrazole-5-one, 1-pheny l-3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo- [1,5-b] -1,2,4-triazole, 2,6-dimethyl- [3,2-c] -1 , 2,4-triazole, 6-methyl pyrazolo [1,5-a] -benzimidazole, their acid addition salts, and mixtures thereof.

In general, the addition salts of the oxidation bases and of the couplers which can be used in the context of the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

In the context of the present invention, the coupler (s) are generally present in a total amount ranging from 0.001 to 10% by weight approximately of the total weight of the coloring composition, preferably ranging from 0.005 to 5% by weight relative to the total weight of the coloring composition.

d) chemical oxidizing agent (s)

The composition Cii) used in the coloring process according to the invention comprises one or more oxidizing agent (s) chemical (s) d). By chemical oxidizing agent is meant an oxidizing agent different from oxygen in the air. More particularly, the coloring process uses one or more chemical oxidizing agent (s)

d) selected from i) hydrogen peroxide ii) urea peroxide; iii) polymer complexes capable of releasing hydrogen peroxide such as polyvinylpyrrolidone / H2O2 in particular in the form of powders and the 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); v) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; vi) perborates; and / or vii) percarborates.

The chemical oxidizing agent can, preferably, be implemented by adding extemporaneously in the composition Cii) preferably just before the application of the said composition to the keratin fibers.

According to a preferred embodiment of the invention, the composition Cii) contains one or more chemical oxidizing agent (s) chosen from i) hydrogen peroxide ii) urea peroxide , iii) polymer complexes capable of releasing hydrogen peroxide chosen from polyvinylpyrrolidone / H2O2; vi) perborates and vii) percarborates.

Preferably, the coloring process uses hydrogen peroxide.

Furthermore, the composition or compositions comprising hydrogen peroxide or hydrogen peroxide generating system may or may also contain various adjuvants conventionally used in compositions for dyeing keratin fibers as defined below.

According to a particular embodiment of the invention, the chemical oxidizing agent (s) used preferably represent from 0.01% to 12% by weight of chemical oxidizing agents (preferably hydrogen peroxide), preferably 0.2 to 6% relative to the total weight of the composition or compositions containing it or them and even more preferably from 0.2% to 3% by weight.

e) the basifying agent (s)

The composition Cii) used in the coloring process according to the invention comprises one or more basifying agent (s). These basifying agents are bases which make it possible to increase the pH of the composition or compositions in which it is found. However, the pH of the composition Cii) of the process according to the invention is less than 7, preferably less than or equal to 6.9.

The basifying agent is a base of Bronsted, Lowry or Lewis. It can be mineral or organic.

In particular, said agent is chosen from i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines as well as their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v ) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids of basic preferences such as arginine, lysine, ornithine, citrulin and histidine, and viii ) the compounds of formula (II) below:

^R a \ Λ

NWN ^R c ^R d (JJ)

Formula (II) in which W is a divalent (C1-C8) alkylene radical optionally substituted by at least one hydroxy 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 mineral or organic hydroxides are preferably chosen from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, c) the hydroxides of a metal transition, such as hydroxides of metals of groups III, IV, V and VI, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide.

The hydroxide can be formed in situ, such as, for example, guanidine hydroxide by the reaction of calcium hydroxide and guanidine carbonate.

By (bi) carbonates i) is understood:

a) alkali metal carbonates (Met2 +, CO32-), alkaline earth metal (Met'2 +, CO32-) of ammonium ((R ”4N +) 2, CO32-) or phosphonium ((R” 4P + ) 2, CO32with Met 'representing an alkaline earth metal and Met representing an alkali metal, and R ”, identical or different, represent a hydrogen atom, an optionally substituted (C1-C6) alkyl group such as hydroxyethyl), and

b) bicarbonates, also called hydrogen carbonates, of the following formulas:

> R '+, HCO3- with R' representing a hydrogen atom, an alkali metal, an ammonium group R ”4N + - or phosphonium R” 4P + - where R ”, identical or different, represent a hydrogen atom, a optionally substituted (C1-C6) alkyl group such as hydroxyethyl and when R 'represents a hydrogen atom the hydrogen carbonate is then called dihydrogen carbonate (CO2, H2O); and> Met’2 + (HCO3-) 2 with Met ’representing an alkaline earth metal.

Preferably, the basifying agent is chosen from alkali or alkaline earth metal (bi) carbonates, ammonia, alkanolamines such as mono-, di- and triethanolamines and amino acids such as arginine, and their mixtures;

preferably alkali metal (bi) carbonates, alkanolamines and amino acids, and mixtures thereof.

Mention may be made of the carbonates or hydrogen carbonates of Na, K, Mg, Ca and their mixtures, and in particular of sodium hydrogen carbonate. These hydrogencarbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, water from Badoit (cf. patent for example the document FR 2 814 943). Particular mention may be made of sodium carbonate [497-19-8] = Na2CO3, sodium hydrogen carbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2.

According to a particularly advantageous embodiment, the basifying agent (s) is (are) chosen from alkanolamines, preferably such as monoethanolamine.

According to an advantageous embodiment of the invention, the composition Cii) does not contain ammonia.

The basifying agent (s) as defined above preferably represent from 0.001% to 10% by weight of the weight of the composition or compositions containing them. More particularly from 0.005% to 8% by weight of the composition.

f) the additional dye (s)

According to a particular embodiment of the invention, the coloring method uses one or more additional dye (s) different from c).

Particularly the coloring process uses in one of the compositions or in an additional composition f) one or more synthetic or natural direct dyes, chosen from anionic, cationic and nonionic species, preferably cationic or nonionic species, either as unique dyes either in addition to the oxidation dye (s). Preferably the additional dye (s) are found with c).

More particularly, the additional direct dyes are chosen from azo direct dyes; nitro dyes; (poly) methine dyes such as cyanines, hemicyanins and styryles; carbonyl dyes; azine dyes; nitro (hetero) aryl dyes; tri (hetero) arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of the formulas (Ilia) and (Ill’a), the cationic dyes azo (IVa) and (IV’a) and the cationic dyes diazo (Va) below:

Het + -C (Ra) = N-N (Rb) -Ar, An (Hla) Het + -N (Ra) -N = C (Rb) -Ar, An- (lll’a) Het + -N = N-Ar, An (IVa) Ar + -N = N-Ar ”, An- and Het + -N = N-Ar’-N = N-Ar, An-

(IV’a) (Va) in which formulas (Ilia), (lll’a), (IVa), (IV’a) and (Va):

> Het + represents a heteroaryl cationic radical, preferably carrying an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferably, by one or more (C1-C8) alkyl groups, such as methyl;

> Ar + represents an aryl radical, such as phenyl or naphthyl, carrying an exocyclic cationic charge, preferably ammonium, in particular tri (C1C8) alkylammonium such as trimethylammonium;

> Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably by one or more electron donor groups, such as i) (C1-C8) optionally substituted alkyl, ii) (C1-C8) optionally alkoxy substituted, iii) (di) (C1-C8) (alkyl) amino optionally substituted on the alkyl group (s) by a hydroxyl group, iv) aryl (C1-C8) alkylamino, v) N- (C1-C8 ) optionally substituted alkyl-Naryl (C1-C8) alkylamino or, alternatively, Ar represents a julolidine group;

> Ar 'represents an optionally substituted divalent (hetero) arylene group, such as phenylene, in particular para-phenylene, or naphthalene, which are optionally substituted, preferably by one or more (C1-C8) alkyl, hydroxyl or (C1 -C8) alkoxy;

> Ar ”represents an optionally substituted (hetero) aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferably by one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) groups ) amino, (C1C8) alkoxy or phenyl;

> Ra and Rb, which may be the same or different, represent a hydrogen atom or a (C1-C8) alkyl group, which is optionally substituted, preferably by a hydroxyl group;

or, alternatively, the substituent Ra with a substituent of Het + and / or Rb with a substituent of Ar and / or Ra with Rb form, together with the atoms which carry them, a (hetero) cycloalkyl;

in particular, Ra and Rb represent a hydrogen atom or a (C1-C4) alkyl group, which is optionally substituted by a hydroxyl group;

> An- represents an anionic counterion, such as mesylate or halide.

Mention may in particular be made of the cationic azo and hydrazono dyes carrying an endocyclic cationic charge of the formulas (Ilia), (IIIa) and (IVa) as defined above. More particularly, those of formulas (Ilia), (IIIa) and (IVa) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP714954.

Preferably, the cationic part is derived from the following derivatives:

^{R, _ Ν} Ο ^ η “ ^{ν_ r2} , An- R ¹ r - N ⁺ / ⁼⁼ \ _z ^r2 H ^R , An- (IIIa-1) (IVa-1)

formulas (111-1) and (IV-1) with:

- R1 representing a (C1-C4) -alkyl group such as methyl;

- R2 and R3, which are identical or different, represent a hydrogen atom or a (C1-C4) -alkyl group, such as methyl; and

- R4 represent a hydrogen atom or an electron donor group, such as an optionally substituted (C1-C8) alkyl group, (optionally substituted alkoxy (C1-C8) or (di) (C1-C8) (alkyl) amino optionally substituted on the alkyl group (s) by a hydroxyl group; in particular R4 represents a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferably CH;

- An- represents an anionic counterion, such as mesylate or halide.

In particular, the dye of the formulas (llla-1) and (IVa-1) is chosen from Basic Red

51, Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:

H, C \ ³ N H, C \ ³ N H, C ³ \ + N— \ 0 \\ Y NOT NOT H H NOT \ \ / NOT / \ \ \ H, C z — ά n-ch ₃ nh ₂ . ² Year- τΛ h ₃ c \ = / Year- Year- Basic Red 51 Basic Orange 31 Basic Yellow 87

Among the natural direct dyes which can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine and orcein. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna can also be used.

When they are present, the direct dye (s) represent more particularly 0.001% to 10% by weight and preferably 0.005% to 5% by weight of the total weight of the composition.

Intermediate rinse:

The method according to the invention may preferably comprise at least one step iii) of intermediate rinsing ie a rinsing step between the step of application to the keratin fibers of the composition Ci) as defined above and Cii) as defined previously.

According to an embodiment of the invention, water is preferably used during the intermediate rinsing step. In particular, the intermediate rinsing step is carried out with water without adding additives as defined below. Preferably the intermediate rinsing iii) is carried out by treating the keratin fibers with tap water. More preferably, the intermediate rinsing is carried out with tap water until the residual water is clear and visually transparent, in the case where said rinsing is carried out after the application of the coloring composition Cii, or in the case where the intermediate rinsing is carried out after the application of the composition Ci, said rinsing is carried out for 1s to 5 minutes, better still from 5 seconds to 1 minutes.

Preferably, the hair is wrung out at the end of the intermediate rinsing.

The essays:

The coloring composition Cii) comprises water or a mixture of water and one or more organic solvents

Composition Ci) generally comprises water or a mixture of water and one or more organic solvents or a mixture of organic solvents.

By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.

Organic solvents:

As additional organic solvent, mention may, for example, be made of lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol.

The organic solvents are present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The additives :

The compositions of the dyeing process in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric, zwitterionic polymers or mixtures thereof, mineral or organic thickeners and in particular associative thickeners anionic, cationic, nonionic and amphoteric polymers, antioxidants, penetration agents, sequestering agents , perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or their mixtures and mineral or organic thickening agents.

The above adjuvants are generally present in an amount for each of them of 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 coloring process according to the invention are not not, or not substantially, altered by the planned addition (s).

The cosmetic composition (s) of the invention may be in various dosage forms, such as a powder, a lotion, a foam, a cream, a gel or in any other form suitable for producing a dyeing of keratin 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 compositions:

Composition Cii)

The composition Cii) is an aqueous composition. The pH of the composition Cii) is acidic, ie has a pH of less than 7.0, preferably less than or equal to 6.9, particularly at a pH of between 2 and 6.9 inclusive, more particularly of between 3 and 6 , 8, better between 4 and 6.

The pH of the composition Cii) can be adjusted to the desired value by means of basifying agents as defined above in e) or from acidifying agents f) usually used in dyeing keratin fibers or even using of conventional buffer systems.

Thus, in a particularly preferred manner, the composition Cii) comprises one or more acidifying agents f) chosen from mineral or organic acids such as hydrochloric acid, phosphoric acid, orthophosphoric acid, sulfuric acid, carboxylic acids as defined above such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids. Preferably, the acidifying agent (s) f) is (are) chosen from mineral acids, in particular hydrochloric acid, phosphoric acid, orthophosphoric acid, sulfuric acid, preferably acid phosphoric.

Composition Ci)

Preferably, the composition Ci) is an aqueous composition. Preferably, the pH of the cosmetic composition Ci) is acid, ie has a pH of less than 7.0, preferably of less than 5.0, particularly at a pH between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferably between 1 and 3. Preferably the composition i) is acidic, preferably has a pH of less than 5.0, particularly at a pH between 0 and 4, more particularly between 0.5 and 3.5, preferably between 1 and 3.

The pH of the composition Ci) can be adjusted to the desired value by means of basifying agents as defined above or from acidifying agents as defined above.

Multi-step coloring process

The keratin fiber coloring process of the invention implements:

> either the application to said fibers of the composition Ci), then preferably at least one rinsing of the said fibers preferably with water in particular with tap water, then the application to the said fibers of the composition Cii) ;

> either the application to said fibers of the composition Cii), then preferably at least one rinsing of said fibers preferably with water in particular with tap water, then the application to said fibers of the composition Ci) ;

in which :

- The cosmetic composition Ci) comprises a) one or more titanium salt (s); in particular the titanium atom of said salt (s) is (are) with an oxidation state of 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ; and

the aqueous coloring composition Cii) whose pH is less than 7 comprises c) one or more oxidation dye (s), d) one or more chemical oxidizing agent (s), and e) a or more alkaline agent (s).

Preferably, the process for dyeing keratin fibers of the invention implements the application to said fibers of the composition Cii), then at least one rinsing of said fibers preferably with water, in particular with tap water. , then the application to said fibers of the composition Ci).

According to a particular embodiment, the composition Ci) of the coloring process of the invention further comprises b) one or more carboxylic acid (s) of formula (I) below or one of its salts;

(I)

Formula (I) in which:

-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 non-aromatic, optionally interrupted by one or several heteroatoms and / or optionally substituted in particular by one or more hydroxy groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1C6) 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.

Preferably the organic salt (s) of titanium of composition i) of the process of the invention is (are) chosen (s) from those of formula (1A), (1B), or the dihydroxybis salts (lactato) titaniumlV as defined above.

According to a particular embodiment of the invention, the coloring process implements the application to said fibers of the composition Ci) as defined above, then a rinsing preferably with water of said fibers, then the application on said fibers of the composition Cii) as defined above.

According to another particular embodiment of the invention, the dyeing process implements the application to said fibers of the composition Cii) as defined above, then rinsing preferably with water of said fibers, then application to said fibers of the composition Ci) as defined above.

Particularly in the coloring process of the invention, the pause time on the keratin fibers of the composition Ci) as defined above is between 5 minutes and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 5 and 30 minutes. Preferably, the pause of the composition Ci) on the keratin fibers is carried out at a temperature between 20 ° C. and 50 ° C., more preferably between room temperature (27 ° C.) and 40 ° C.

Between the application of the compositions Ci) and Cii) or Cii) and Ci), at least one rinsing is carried out in the process of the invention. Preferably a rinse is carried out with tap water, preferably until the residual water for rinsing the keratin fibers is clear and visually transparent, identical to the water before treatment of the keratin fibers.

The composition Cii) of the coloring process of the invention further comprises one or more oxidizing agent (s) chemical (s) in particular chosen (s) from hydrogen peroxide or one or more generating system (s) (s) of hydrogen peroxide as defined above.

The composition Cii) which comprises at least one oxidation dye and at least one chemical oxidizing agent is also called "ready-to-use" oxidation dye composition. This ready-to-use coloring composition is preferably produced a few minutes before the application, in particular between 1 minute and 20 minutes, more particularly between 5 minutes and 10 minutes before the application. The ready-to-use composition is prepared by uniformly mixing the coloring composition comprising c) at least one oxidation base as defined above and optionally at least one coupler as defined above, with an oxidizing composition comprising d) minus a chemical oxidizing agent as defined above.

Once the coloring composition ready for use prepared, it is preferably applied immediately to the keratin fibers. The pause time of the composition Cii) and in particular of the ready-to-use coloring composition, on the keratin fibers is between 1 minutes and 2 hours, preferably between 5 minutes and 1 hour, more preferably the pause time is 15 to 30 minutes.

Preferably, the composition Ci) used in the process of the invention is also aqueous.

Preferably, the composition Ci) used in the coloring process is at an acidic pH, ie less than 7.0, preferably less than 5, particularly at a pH inclusive between 0 and 4, more particularly between 0.5 and 3.5 and more preferably between 1 and 3. In particular the composition Ci) according to the invention is at an acidic pH preferably less than 5, particularly at a pH inclusive between 0 and 4, more particularly between 0.5 and 3.5 and more preferably between 1 and 3.

The composition Cii) used in the process according to the invention is at acidic pH, i.e. less than 7.0. Preferably, the composition Cii) has a pH less than or equal to 6.9.

Preferably, the composition Cii) has a pH between 2 and 6.9, more particularly between 3 and 6.8, preferably between 4 and 6.8

The coloring composition Cii) used according to the invention, comprising the oxidation dye or dyes as defined above, further comprises one or more basifying agents e) as defined above, preferably ammonia or monoethanolamine. Despite the presence of these alkaline agents, the pH of the composition Cii) is acidic, as described above.

After the application of the compositions Ci), the optional rinsing of the keratin fibers and the application of the composition Cii), and vice versa in the case where the composition Cii) is used before the composition Ci), the coloring process of the invention may use one or more shampoos, followed by one or more rinses with water of the keratin fibers and optionally followed by drying by a heat treatment by heating at a temperature between 30 and 60 ° C. . In practice, this operation can be carried out using a hairdressing helmet, a hair dryer, an infrared ray dispenser and other conventional heating devices.

It is also possible to use, both as a means of heating and smoothing the hair, a heating iron at a temperature between 60 and 220 ° C. and preferably between 120 and 200 ° C.

By drying is meant the action of evaporating organic solvents and / or water present in one or more compositions used in the process of the invention, comprising or not comprising one or more ingredients a) to e) such as 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 of the solvent (s). Heat sources include a hair dryer, hair helmets, a hair straightener, an infrared ray dispenser and other conventional heaters.

A particular embodiment of the invention relates to a coloring 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 can result from the extemporaneous mixture of two or more of two compositions and in particular of compositions present in dye kits.

The following examples serve to illustrate the invention without, however, being limiting in nature.

COLORING EXAMPLES

Coloring step:

The following coloring and oxidizing compositions were prepared from the following ingredients in the following proportions per 100 grams of composition:

Coloring Composition

Coloring Composition LAURIC ALCOHOL OXYETHYLENE (12 EO) 3

OXYETHYLENE OLEOCETYL ALCOHOL (30 EO) 2 CETOSTEARYL SODIUM SULFATE (C16 / C18 50/50) 1.44 my LAURIC ALCOHOL OXYETHYLENE (2.5 EO) 8 OXYETHYLENE RASP ACID AMIDE (4 EO) 3.7 my ALKYL ACID MONOETHANOLAMIDE (C13 / C15 70/30 50% LINEAR) CARBOXYL ETHER (2 EO) 4 GLYCERIN 3 POLY DI-METHYL DI-ALLYL CHLORIDE AMMONIUM IN WATER AT 40% NOT STABILIZED 2 HYDROXY-ETHYL CELLULOSE ALKYLE (C14 / 16) 0.4 SODIUM SULPHITE 0.1 ETHYLENE DIAMINE TETRACETIC ACID 0.2 ERYTHORBIC ACID (OR DISOASCORBIC ACID) 0.4 1-METHYL-2,5-diaminobenzene 0.49 1-HYDROXY-4-AMINO-BENZENE 0,230 1,3-DIHYDROXYBENZENE (RESORCINOL) 0.406 1-HYDROXY-3-AMINO-BENZENE 0.287 1-beta-hydroxyethyloxy-2,4-diamino BENZENE DICHLORHYDRATE 0,022 6-hydroxyindole 0.04 2-AMINO-3-hydroxypyridine 0,008 1-METHYL-2-HYDROXY-4-BETA- Hydroxyethylamino-BENZENE 0,011 1-METHYL-2-HYDROXY-4-AMINO-BENZENE 0,029 PERFUME qs TITANIUM OXIDE (UNTREATED ANATASE) (Cl: 77891) 0.1 MONOETHANOLAMINE 0.3 WATER QSP 100

Oxidizing composition

Composition oxidising CETYLSTEARYLIC / ALCOHOL ALCOHOL MIXTURE CETYLSTEARYLIQUE OXYETHYLENE (30OE) 2.85 TETRA-SODIUM PYROPHOSPHATE, 10 H2O 0.02 ALKYL ACID MONOETHANOLAMIDE (C13 / C15 70/30 50% LINEAR) CARBOXYL ETHER (2 EO) 0.85 PENTACETIC DIETHYLENETRIAMINE ACID? PENTASODIC SALT IN AQUEOUS SOLUTION 40% 0.15 PHOSPHORIC ACID QS pH 2 HYDROGEN PEROXIDE 50% SOLUTION (OXYGENATED WATER 200 VOL.) 5.4 GLYCERIN 0.5 SODIUM STANNATE 0.04 DEIONIZED WATER QSP 100

The coloring composition is mixed with the above oxidizing composition in ratio 1 + 1.5 then the ready-to-use mixture (composition Ci) (pH = 6.4) was applied at the rate of 4 grams of product per gram of lock on Caucasian hair at 90% of 5 natural white hairs with a pause time of 20 minutes at room temperature then rinsed for 2 minutes.

Post-processing step:

The following post-treatment composition was prepared from the following ingredients in the following proportions indicated in grams:

Composition Ci Glycolic acid 7.5 Dihydroxybis (ammonium lactato) titanium (IV) at 40% by weight in an ISOPROPYL ALCOHOL / Water 40:20 mixture marketed by -MATSUMOTO FINE CHEMICAL- under the name ORGATIX TC-300 6 Water qs 100 PH agent (hydrochloric acid) Qsp pH = 2.2

This composition Ci) is applied to previously colored hair, at the rate of

2.5 g of composition 1 for 1 gram of hair, left to stand then rinsed for 30 15 seconds and shampooed with a Dop Chamomile Commercial Shampoo.

Results:

The colorimetric measurements were carried out using a Minolta CM3600D spectrocolorimeter (illuminant D65, angle 10 °, specular component included) in the CIELab system. (please check the device ref?)

In this system, L * represents clarity. The lower the value of L *, the darker and more powerful the coloration obtained.

The rise in color is represented by the difference in color ΔΕ between the non-colored lock and the colored lock: the higher the value of ΔΕ, the greater the rise in color. This value is calculated from the following equation (i):

ΔΕ = 7 (L * -L ₀ *) ² + (a * -a0 *) ² + (b * -b0 *) ² _(j)

In equation (i), L *, a * and b * represent the values measured on locks of non-colored permed hair, and LO *, aO * and bO * represent the values measured on locks of colored permed hair .

The results are given in the table below.

The colorimetric measurements show that the process of the invention makes it possible to obtain a more intense color (significantly higher ΔΕ) in the case of the titanium post-treatment.

hair L * at* b * ΔΕ * climb Color Reference undyed hair: Natural Caucasian 90% white BN 68.01 1.26 19.18 - - Hair dyed with Mixing Color + Oxidizing composition and without post treatment (comparative) BN 35.52 5.65 8.13 34.6 Brown Hair dyed with Mixture Colorant + Oxidant composition followed by post treatment (invention) BN 33,31 6.15 6.01 37.44 more intense brown

It appears that the implementation of the post-treatment step in the coloring process makes it possible to significantly improve the rise in color, since the 25 ΔΕ * is higher with the coloring process of the invention compared to the comparative method not using post-treatment comprising titanium.

In addition, the coloration obtained is more intense (lower L * value) with the method according to the invention compared to the comparative method.

Claims (21)

1. Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, in which said fibers are treated, in several stages, with: i) at least one step of treatment i) of said fibers with a cosmetic composition Ci) containing: a) one or more titanium salt (s); in particular the titanium atom of said salt (s) is (are) with an oxidation state of 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ; b) optionally one or more carboxylic acid (s) of formula (I) below or one of its salts; (I) Formula (I) in which: -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 non-aromatic, optionally interrupted by one or several heteroatoms and / or optionally substituted in particular by one or more hydroxy and / or amino groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxy and / or amino groups; - N represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; and ii) at least one step of coloring said fibers with an aqueous cosmetic composition Cii) whose pH is less than 7, preferably less than or equal to 6.9; containing: c) one or more oxidation dye (s); d) one or more chemical oxidizing agent (s) especially chosen from hydrogen peroxide or one or more system (s) generating hydrogen peroxide; and e) at least one alkaline agent; iii) preferably at least one intermediate rinsing step for said fibers, preferably with water, it being understood that: - First composition Ci) is applied to said fibers, optionally followed by one or more rinsing (s) of said fibers, preferably with water, then composition Cii) is applied to said fibers; or - First the composition Cii) is applied to said fibers, optionally followed by one or more rinsing (s) of said fibers, preferably with water, then composition Ci) is applied to said fibers. 2. A dyeing method according to the preceding claim, characterized in that a) the titanium salt (s) of the invention is (are) chosen from the organic salt (s) in particular among the organic salt (s) of Ti (IV); preferably chosen from those of formula (I-A) below: n (l-A) Formula (l-A) in which: • A is identical to that of formula (I) as defined in the preceding claim; • n, n ’and n” identical or different are worth 1,2, 3 or 4 with n ’+ n” being worth 6; • M1 and M2, identical or different, represent a cationic counter ion in particular chosen from alkali metal cations such as Na, or K, alkaline earth metal such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom ; • TiYn ”denoting Ti (OH) n”, or Ti (O) n ”/ 2, or Ti (OH) m1 (O) m2 with m1 + m2 = n”. 3. Dyeing method according to the preceding claims, characterized in that a) the titanium salt (s) is (are) chosen from those of formula (lA) in which the radical A represents a monovalent group (C1 -C6) alkyl or polyvalent (C1-C6) alkylene optionally substituted by one or more hydroxy groups or one or more amino groups, preferably by one or more hydroxy groups, and n representing an integer inclusive between 0 and 5, such that between 0 and 2, particularly the carboxylic acid (s) used to form the organic titanium salt (s) of the invention are chosen from α-hydroxy acids and α-amino acids; preferably the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and serine, more preferably chosen from lactic and glycolic acid. 4. A coloring method according to any one of the preceding claims, characterized in that a) the titanium salt (s) is (are) chosen from those of formula (I-B) below: 2M ⁺ M ⁺ Formula (l-B) in which: • L 'and L ”, identical or different, represent a divalent (hetero) arylene, (C1C6) alkylene, (C2-C6) alkenylene group, said alkylene and arylene groups being optionally substituted by one or more atoms or groups chosen from halo , (C1-C4) alkyl, hydroxy, thiol, and (di) (C1-C4) (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 or ethylene group optionally substituted by a (C1-C4) alkyl group; • X 'and X ”, identical or different, represent a heteroatom such as oxygen, sulfur or amino Rc-N with Rc representing a hydrogen atom or a (C1-C4) alkyl group, preferably X' and X” are identical and represent an oxygen atom; • Y and Y ’, identical or different, are as defined for X’ and X ”, preferably Y and Y’ are identical and represent an oxygen atom; • Ra and Rb, identical or different, represent a hydrogen atom, 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 counter ion such as an alkali (Na, K), alkaline earth (Ca) or organic metal cation such as ammonium, preferably ammonium. 5. A dyeing method according to any one of the preceding claims, characterized in that a) the titanium salt (s) is (are) chosen from dihydroxybis (lactato) titaniumlV salts, in particular those of the following formula : + % OH f ⁰ -Οχ / 0- 2NH ₄ ; h ₃ c V ch ₃ OH 6. A coloring method according to claim 1, characterized in that a) the titanium salt (s) of the invention is (are) chosen (s) from the inorganic salt (s) in particular inorganic salt (s) of Ti (II), Ti (III) and Ti (IV), more particularly of Ti (III) and Ti (IV) even more particularly of Ti (IV); preferably the titanium salt (s) a) is (are) chosen from titanium halides, titanium sulfates and titanium phosphates. 7. Dyeing method according to any one of the preceding claims, characterized in that a) the titanium salt (s) is (are) present in composition i) in a content ranging from 0.001% to 20% by weight relative to the total weight of the composition i). 8. A coloring method according to any one of the preceding claims, characterized in that the composition Ci) comprises b) one or more carboxylic acid (s) of formula (I) or one of their (s) salt (s) as defined in claim 1; particularly the carboxylic acid (s) b) is (are) different from the carboxylic acids complexed with the Ti salts as defined in any one of Claims 1 to 5, preferably glycolic acid, lactic acid, citric acid or a salt thereof. 9. A coloring method according to any one of the preceding claims, characterized in that the composition Ci) comprises b) one or more carboxylic acid (s) of formula (I) or one of their (s) salt (s) as defined in claim 1 in a content ranging from 0.1 to 20% by weight, relative to the total weight of composition i). 10. A coloring method according to any one of the preceding claims, characterized in that the composition Ci) is acidic, in particular has a pH of less than 5.0, more particularly at a pH between 0 and 4, preferably between 0, 5 and 3.5, more preferably between 1 and 3. 11. A coloring method according to any one of the preceding claims, characterized in that the composition Cii) comprises c) one or more oxidation dye (s) chosen from the oxidation bases, and optionally one or more couplers; the oxidation base (s) is (are) particularly chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts and the or the coupler (s) is (are) particularly chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and also their addition salts. 12. A coloring method according to any one of the preceding claims, characterized in that the composition Cii) comprises c) one or more oxidation base (s) present (s) in an amount ranging from 0.001 to 10% by weight of the total weight of the composition Cii), preferably ranging from 0.005 to 5% by weight of the composition Cii); and optionally one or more coupler (s) present in total amount ranging from 0.001 to 10% by weight of the total weight of the composition Cii), preferably ranging from 0.005 to 5% by weight relative to the total weight of the composition Cii). 13. A coloring method according to any one of the preceding claims, characterized in that the oxidizing agent (s) (s) chemical (s) is (are) chosen (s) from hydrogen peroxide, peroxide urea; polymer complexes which can release hydrogen peroxide such as polyvinylpyrrolidone / H2O2, oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase), peroxides metals generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide, perborates and percarborates; particularly the oxidizing agent (s) chemical (s) is (are) chosen (s) from hydrogen peroxide. 14. Coloring method according to any one of the preceding claims, characterized in that the basifying agent (s) is (are) chosen from (i) (bi) carbonates, (ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines as well as their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi) alkali metal silicates such as metasilicates sodium, vii) amino acids of basic preferences such as arginine, lysine, ornithine, citrulin and histidine, and viii) compounds of formula (II) below: ^R a \ Λ NWN ^R c ^R d _(n) Formula (II) in which W is a divalent (C1-C8) alkylene radical optionally substituted by at least one hydroxy 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; and their mixtures. ; more preferably the basifying agent (s) is (are) chosen from basic amino acids and / or alkanolamines, preferably from monoethanolamine. 15. A coloring method according to the preceding claim, characterized in that the basifying agent (s) is (are) chosen from basic amino acids and / or alkanolamines preferably from monoethanolamine 16. Staining method according to the preceding claim, characterized in that the composition Cii) has a pH less than or equal to 6.9, preferably between 2 and 6.9 inclusive, more particularly between 3 and 6.8, better between 4 and 6.8. 17. Dyeing method according to any one of the preceding claims, characterized in that the composition Ci) as defined in any one of the preceding claims, is applied first to the keratin fibers, optionally rinsing preferably with water is then produced on said fibers, then the composition Cii) as defined in any one of the preceding claims is applied to said fibers. 18. Dyeing method according to any one of claims 1 to 16, characterized in that the coloring composition Cii) as defined in any one of the preceding claims, is applied first to the keratin fibers, rinsing preferably with water is then produced on said fibers, then composition Ci) as defined in any one of the preceding claims, is applied to said fibers. 19. A coloring method according to any one of the preceding claims, characterized in that it implements an intermediate rinsing step iii). 20. Dyeing method according to any one of the preceding claims, characterized in that the pause time on the keratin fibers of the composition Ci) as defined according to any one of the preceding claims is between 5 minutes and 2 hours, particularly between 5 minutes and 1 hour, preferably between 5 minutes and 30 minutes and / or the pause of the composition Ci) on the keratin fibers is maintained at a temperature between 20 ° c and 50 ° C, preferably between room temperature (27 ° C) and 40 ° C. 5 21. Dyeing method according to any one of the preceding claims, characterized in that the pause time on the keratin fibers of the composition Cii) as defined in any one of the preceding claims is between 1 minutes and 2 hours, preferably between 5 minutes and 1 hour, more preferably the pause time is 15 to 30 minutes and / or the pause of the composition Cii) on the 10 keratin fibers is maintained at a temperature between 20 ° c and 50 ° C, preferably between room temperature (27 ° C) and 40 ° C.