Process for decolorizing pre-dyed keratinous hair fibers

Abstract

The present invention relates to a process for decolorizing keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers, comprising at least one (poly)carbodiimide compound and at least one colorant selected from pigments, direct dyes and mixtures thereof. The process comprises: i) applying to the keratinous hair fibers pre-dyed with the dyeing composition at least one decolorizing composition comprising at least one alkyl or alkylene carbonate; and ii) applying to the keratinous hair fibers a tong (1) having two arms A and B through which the keratinous hair fibers pass.

Description

Technical Field

[0001] The present invention relates to a process for decolorizing keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers, comprising at least one (poly)carbodiimide compound and at least one colorant selected from pigments, direct dyes and mixtures thereof. The process comprises, as described below, i) applying to the keratinous hair fibers pre-dyed with the dyeing composition at least one decolorizing composition comprising at least one alkyl or alkylene carbonate, and ii) applying to the keratinous hair fibers a tong having two arms A and B through which the keratinous hair fibers pass.

Background Art

[0002] In the field of dyeing keratinous hair fibers, especially human keratinous hair fibers, it is already known to color keratinous hair fibers via various techniques using direct dyes or pigments for non-permanent coloring, or dye precursors for permanent coloring.

[0003] There are basically three types of hair dyeing processes: a) "Permanent" dyeing: Its action can significantly modify the original color, penetrate into the hair fibers, and uses oxidation dyes that generate pigments via an oxidative condensation process. b) Non-permanent, semi-permanent or direct dyeing: Does not use an oxidative condensation process and withstands 4 to 5 shampooing operations. This involves dyeing keratinous fibers with a dye composition containing direct dyes. c) Temporary dyeing: Modifies the original color of the hair, remains from the first shampoo wash to the next shampoo operation, and serves to enhance or correct the already obtained color shade. This may be associated with a "makeup" process.

[0004] Regarding the last-mentioned type of dyeing, a technique is known which uses a colored polymer produced by grafting one or more dyes having the properties of azo, triphenylmethane, azine, indamine or anthraquinone onto a polymer chain. Such colored polymers are not entirely satisfactory, particularly with regard to the uniformity of the colored shade and its resistance, and it goes without saying that there are problems associated with their production, particularly reproducibility.

[0005] Other dyeing methods consist of using pigments. Specifically, when pigments are used on the surface of keratinous hair fibers, since the surface pigments hide the original color of the fibers, it is generally possible to achieve a coloring that can be recognized even on dark-colored hair. This dyeing method also has the advantage of producing a uniform-colored coating on keratinous hair fibers, especially on the hair, and at the same time can provide a dye composition that forms a coat resistant to shampooing operations and various attacking factors to which the hair may be subjected, such as brushing and / or friction without deteriorating the hair.

[0006] However, there is no process for decolorizing pre-dyed keratinous hair fibers using pigments that can efficiently implement decolorizing compositions and tools using this type of temporary dye composition that is resistant to shampooing operations.

[0007] Therefore, there is still a need for a process for efficiently decolorizing keratinous hair fibers such as hair pre-dyed with the said dye composition that is resistant to shampooing operations.

[0008] Therefore, an object of the present invention is to develop a process for efficiently decolorizing keratinous hair fibers such as hair.

Summary of the Invention

Means for Solving the Problems

[0009] Accordingly, the subject of the present invention is a process for decolorizing keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers, - at least one (poly)carbodiimide compound, and - at least one colorant selected from pigments, direct dyes and mixtures thereof, comprising, wherein the process i) applying to the keratinous hair fibers pre-dyed with the dyeing composition - at least one decolorizing composition comprising at least one alkyl or alkylene carbonate ; ii) applying to the keratinous hair fibers a tong having two arms A and B, the keratinous hair fibers passing between the two arms, each arm A and arm B comprising a support part and an active part, the arms A and B being movable between a spaced position in which the active parts are spaced apart from each other and a cooperating position in which the active parts are close to each other, the active part comprising an active surface and a facing surface, the active surface having bristles, wherein, in the cooperating position of the active parts, the bristles of the arms A and B are intermingled so as to grip the keratinous hair fibers without blocking them.

[0010] As described above, the combination of the composition for decolorizing comprising at least one alkyl or alkylene carbonate and the tong makes it possible to efficiently decolorize keratinous hair fibers pre-dyed with a dyeing composition, as described above.

[0011] "Keratinous hair fibers" means hair. In other words, the expressions "keratinous hair fibers" and "hair" are equivalent in the remainder of the description.

[0012] For the purposes of the present invention, "hair" means head hair. This term does not correspond to body hair, eyebrows or eyelashes.

[0013] The expression "at least one" means one or more.

[0014] Unless otherwise specified, the boundary values of a range of values are included in that range, in particular in expressions such as "between" and "in the range from... to...".

[0015] The present invention is not limited to the exemplary embodiments shown. The features of the various embodiments may in particular be combined within variants not shown.

[0016] For the purposes of the present invention and unless otherwise indicated, - an "alkyl" radical refers to a straight-chain or branched-chain saturated radical containing, for example, from 1 to 20 carbon atoms, - an "aminoalkyl" radical refers to an alkyl radical as defined above, in which the alkyl radical contains an NH2 radical, - a "hydroxyalkyl" radical refers to an alkyl radical as defined above, in which the alkyl radical contains an OH group, - an "alkylene" radical denotes a straight-chain or branched-chain divalent saturated C2-C4 hydrocarbon-based group such as methylene, ethylene or propylene, - a "cycloalkyl" or "alicycloalkyl" radical refers to a cyclic saturated monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group containing from 1 to 3 rings, preferably 2 rings, containing from 3 to 24 carbon atoms, in particular from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably from 5 to 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, and the cycloalkyl radical may be substituted by one or more (C1-C4) alkyl groups such as methyl, in which case, preferably, the cycloalkyl radical is understood to be an isobornyl group, - The "cycloalkylene" radical has the "cycloalkyl" defined above, preferably a divalent C3-C 12 refers to a cycloalkyl group, - The "aryl" radical is a monocyclic, bicyclic or tricyclic fused or non-fused unsaturated aromatic hydrocarbon-based cyclic radical containing 6 to 14 carbon atoms, preferably 6 to 12 carbon atoms. Preferably, the aryl group contains one ring having 6 carbon atoms, such as phenyl, naphthyl, phenanthryl. It is understood that phenyl can be a (C1-C4) alkyl group such as one or more methyl groups substituting the aryl radical, preferably tolyl, xylyl or methylnaphthyl. Preferably, the aryl group represents phenyl, - The "arylene" radical is a divalent aryl radical having the "aryl" defined above. Preferably, arylene represents phenylene, - The "heterocyclic" radical is a saturated or unsaturated non-aromatic or aromatic monocyclic or polycyclic hydrocarbon-based radical containing one or more heteroatoms, preferably 1 to 5 atoms selected from O, S or N, and containing 3 to 20 ring members, preferably 5 to 10 ring members, such as imidazolyl, pyrrolyl and furanyl, etc. - The "heterocycloalkylene" radical is a divalent heterocyclic group having the "heterocyclic" defined above, - The "aryloxy" radical refers to an aryloxy radical having the "aryl" defined above; - The "alkoxy" radical refers to an alkyl-oxy radical having the "alkyl" defined above, - The "acyloxy" radical refers to the ester radical R-C(O)-O- where R is the alkyl group defined above, - A "reactive" group is a group that can form a covalent bond with another identical or different group by a chemical reaction.

[0017] Unless otherwise specified, when referring to a compound in this application, this includes its optical isomers, its geometric isomers, its tautomers, or its salts, either alone or as a mixture.

[0018] "Keratinous hair fibers" means hair. In other words, the expressions "keratinous hair fibers" and "hair" are equivalent in the remainder of the description.

[0019] For the purposes of the present invention, "hair" means head hair. This term does not correspond to body hair, eyebrows or eyelashes.

[0020] Detailed description of the invention Dyeing composition: Polycarbodiimide compound As described above, the composition for dyeing keratinous hair fibers, which is used in connection with the process according to the invention, comprises at least one (poly)carbodiimide compound.

[0021] This composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0022] The term "(poly)carbodiimide compound" means a compound containing one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups, and in particular the number of carbodiimide groups does not exceed 200, preferably does not exceed 150, more preferably does not exceed 100.

[0023] "Carbodiimide group" means a divalent linear three-atom moiety represented by the general formula -(N=C=N)-.

[0024] The (poly)carbodiimide compound according to the present invention may optionally contain one or more reactive groups other than the carbodiimide group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane groups in its structure.

[0025] The reactive groups other than the carbodiimide group may be pendant groups or terminal groups. Preferably, the (poly)carbodiimide compound contains one or more terminal groups, preferably one or more terminal groups, selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide, and azacyclopropane groups.

[0026] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I):

Chemical formula

Chemical formula

[0027] According to another embodiment, the (poly)carbodiimide compound has the following formula (I')

Chemical formula

[0028] Preferably, Z1 and Z2 independently represent reactive end groups, and more preferably, Z1 and Z2 independently represent alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane groups.

[0029] Such (poly)carbodiimide compounds are sold, for example, under the name Permutex XR or RelcaLink 10 from Stahl B.V., or under the name Picassian XL, and under the name Carbodilite together with Series V-02, V-02-L2, SV-02, E-02, V-10, SW-12G, E-03A, E-04DG-T, E-05, V-04, V-02B, V-04PF, V-05 from Nisshinbo compounds.

[0030] Preferably, the (poly)carbodiimide compound is represented by the following formula (II): [Chemical formula] (wherein -X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group, -R1 and R2 independently represent a hydrocarbon radical in which one or more heteroatoms are optionally interposed, -n and z represent integers in the range of 1 to 20, n + z ≧ 2, w represents an integer in the range of 1 to 3, -L1 independently represents a divalent C1-C 18 aliphatic hydrocarbon radical, C3-C 15 cycloalkylene radical, C3-C 12 heterocycloalkylene radical or C6-C 14 arylene group and mixtures thereof, -E independently represents --O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 independently represent a divalent hydrocarbon radical in which one or more heteroatoms are optionally interposed, -R5 independently represents a covalent bond or a divalent saturated hydrocarbon radical in which one or more heteroatoms are optionally interposed, -R6 independently represents a hydrogen atom or a hydrocarbon radical in which one or more heteroatoms are optionally interposed) and is selected from the groups represented by the compound).

[0031] The term "hydrocarbon radical" means a saturated or unsaturated linear or branched radical having 1 to 300 carbon atoms, preferably 1 to 250 carbon atoms, more preferably 1 to 200 carbon atoms. Preferably, the hydrocarbon radical is a saturated linear radical.

[0032] The hydrocarbon radical may contain one or more cyclic groups.

[0033] Hydrocarbon radicals may in particular contain one or more heteroatoms selected from O, S or N, and / or may be substituted with one or more cations, anions, or zwitterions, or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or may contain metal ions that can be incorporated in the form of salts.

[0034] The term "heteroatom" also means halogen atoms such as Cl, F, Br and I in addition to oxygen O, sulfur S or nitrogen N atoms. When a heteroatom is contained in the chain of a hydrocarbon radical, this heteroatom is preferably selected from oxygen O, sulfur S or nitrogen N atoms.

[0035] Preferably, X1 and X2 each independently represent an oxygen atom.

[0036] Preferably, R1 and R2 are each independently selected from dialkylamino alcohols excluding hydroxyl groups, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols and mixtures thereof.

[0037] In a preferred embodiment, R1 and R2 are independently selected from the following groups (i) to (iv): (i) The following formula (III): R7-O-C(O)-C(R8)(H)- (III) (wherein R7 represents a C1-C3 alkyl group, R8 represents a hydrogen atom or a C1-C3 alkyl group, preferably R7 is methyl, and R8 is a hydrogen atom or methyl) compound. (ii) The following formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group, p represents an integer in the range of 1 to 3, preferably R9 is methyl, ethyl or butyl, and R10 is a hydrogen atom or a methyl group, and p is equal to 1) of the compound. (iii) The following formula (V): (R 11 )2N-CH2-C(H)(R 12 )- (V) (In the formula, R 11 represents a C1-C4 alkyl group, R 12 represents a hydrogen atom or a C1-C4 alkyl group, preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or a methyl group) of the compound. (iv) The following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (In the formula, R 13 represents a C1-C4 alkyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, q represents an integer in the range of 4 to 30, preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or a methyl group) of the compound.

[0038] Preferably, R1 and R2 independently represent a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30.

[0039] According to an alternative embodiment, R1 and R2 are different, one of the R1 or R2 radicals represents a compound of formula (IV) described above, and the other of the R1 or R2 radicals represents a compound of formula (VI) described above.

[0040] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, R 10 is a hydrogen atom or methyl, and p is equal to 1.

[0041] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, R 14 is a hydrogen atom or methyl, and q represents an integer in the range of 4 to 30.

[0042] According to another alternative embodiment, R1 and R2 are the same, representing a compound of formula (VI), R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30.

[0043] Preferably, n represents an integer in the range of 1 to 20, more preferably 2 to 20.

[0044] Preferably, z represents an integer in the range of 1 to 20, more preferably 2 to 20.

[0045] Preferably, w is equal to 1.

[0046] Preferably, w is equal to 1, and n + z represents an integer in the range of 4 to 10.

[0047] Preferably, L1 is selected from divalent C1-C 18 aliphatic hydrocarbon radicals such as methylene, ethylene and propylene, C3-C 15 cycloalkylene radicals such as cyclopentylene, cycloheptylene and cyclohexylene, C3-C 12 heterocycloalkylene groups such as imidazolene, pyrrolene and furanylene, or C6-C 14 arylene groups such as phenylene, and mixtures thereof.

[0048] For example, L1 can be selected from radicals derived from tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, phenylene diisocyanate, and mixtures thereof.

[0049] Preferably, L1 is a C3 - C 15 cycloalkylene radical or a C6 - C 14 arylene group and mixtures thereof, such as the following formula (VII):

Chemical formula

[0050] Preferably, L1 is 4,4-dicyclohexylene methane corresponding to the following formula (VIII).

Chemical formula

[0051] According to another embodiment, when L1 is a C6 - C 14 arylene group, L1 is not the m-tetramethylxylylene radical represented by the following formula (IX).

Chemical formula

[0052] As described above, E is independently --O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- (In the formula, R3 and R4 each independently represent a divalent hydrocarbon radical in which one or more heteroatoms are optionally interposed, -R5 each independently represents a covalent bond or a divalent saturated hydrocarbon radical in which one or more heteroatoms are optionally interposed, -R6 each independently represents a hydrogen atom or a hydrocarbon radical in which one or more heteroatoms are optionally interposed). It represents a group selected from.

[0053] Preferably, R3 and R4 are C6-C such as phenylene, etc. in which one or more heteroatoms are optionally interposed 14 An arylene radical, a C3-C such as cyclopropylene and cyclobutylene 12 A cycloalkylene radical, a linear or branched C1-C such as methylene and ethylene 18 An alkylene radical and are independently selected from mixtures thereof.

[0054] More preferably, R3 and R4 are linear or branched C1-C such as methylene, butylene, propylene, ethylene, etc. in which one or more heteroatoms are optionally interposed 18 An alkylene radical and are independently selected from.

[0055] Preferably, when R5 is not a covalent bond, R5 is optionally a C6-C such as phenylene, etc. in which one or more heteroatoms are optionally interposed 14 An arylene radical, a C3-C such as cyclopropylene and cyclobutylene 12 A cycloalkylene radical, a linear or branched C1-C such as methylene and ethylene 18 An alkylene radical and are selected from mixtures thereof. Preferably, R6 is a C6-C such as phenylene, etc. in which one or more heteroatoms are optionally interposed 14 An arylene radical, a C3-C such as cyclopropylene and cyclobutylene 12 A cycloalkylene radical, a linear or branched C1-C such as methylene and ethylene 18 An alkylene radical and are selected from mixtures thereof.

[0056] Preferably, E represents an -O-R3-O- group, wherein R3 is a C6-C with one or more heteroatoms intervening optionally 14 arylene radical, C3-C 12 cycloalkylene radical, linear or branched C1-C 18 alkylene radical and mixtures thereof.

[0057] More preferably, E represents an -O-R3-O- group, and R3 is a linear or branched C1-C such as methylene, butylene, propylene, ethylene, etc. with one or more heteroatoms intervening optionally 18 represents an alkylene radical.

[0058] According to a specific embodiment, the (poly)carbodiimide compound has the following formula (X):

Chemical formula

[0059] In this embodiment, the term "alkyl group" is as defined above.

[0060] In this embodiment, the term "cycloalkyl group" is as defined above.

[0061] In this embodiment, n can represent an integer in the range of 2 to 50, preferably 3 to 30, and even more preferably 5 to 10.

[0062] According to another specific embodiment, the (poly)carbodiimide compound has the following formula (XI):

Chemical formula

[0063] The “alkyl group”, “cycloalkyl group” and “aryl group” are as defined above.

[0064] According to a preferred embodiment, the (poly)carbodiimide compound is selected from compounds of formula (I) or formula (II), wherein -X1 and X2 independently represent an oxygen atom, -R1 and R2 are independently selected from dialkylaminoalcohols excluding hydroxyl groups, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols excluding hydroxyl groups, more preferably R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30, which is the compound of formula (VI) described above, -When n and z are present, they represent integers in the range of 1 to 20, n + z ≧ 2, and w is equal to 1; -When L1 is present, this is a divalent C1-C 18 aliphatic hydrocarbon radical, C3-C 15 cycloalkylene radical, C3-C 12 heterocycloalkylene group or C6-C 14 arylene group and mixtures thereof, preferably C3-C 15 selected from cycloalkylene radicals, -When A is present, this is a divalent C1-C 18 aliphatic hydrocarbon radical, C3-C 15 cycloalkylene radical, C3-C12 A heterocycloalkylene group or a C6-C 14 arylene group and mixtures thereof, preferably a C3-C 15 selected from cycloalkylene radicals, - When -E is present, it is independently --O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 are independently a C6-C with one or more heteroatoms optionally intervening 14 arylene radical, C3-C 12 cycloalkylene radical, linear or branched C1-C 18 alkylene radical and mixtures thereof, - When -R5 is not a covalent bond and -R5 is present, it is a C6-C with one or more heteroatoms optionally intervening 14 arylene radical, C3-C 12 cycloalkylene radical, linear or branched C1-C 18 alkylene radical and mixtures thereof, and - When -R6 is present, it is a C6-C with one or more heteroatoms optionally intervening 14 arylene radical, C3-C 12 cycloalkylene radical, linear or branched C1-C 18 alkylene radical and mixtures thereof) represents a group selected from.

[0065] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein - X1 and X2 independently represent an oxygen atom, - R1 and R2 are independently selected from dialkylamino alcohols excluding hydroxyl groups, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols and mixtures thereof, - n and z represent integers in the range of 1 to 20, n + z ≧ 2, w is equal to 1, - L1 is a divalent C1-C18 An aliphatic hydrocarbon radical, C3-C 15 A cycloalkylene radical, C3-C 12 A heterocycloalkylene group or C6-C 14 Selected from an arylene radical and mixtures thereof, -E is, independently, --O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 are, independently, a C6-C arylene radical in which one or more heteroatoms are optionally interposed, 14 An arylene radical, C3-C 12 A cycloalkylene radical, a linear or branched C1-C 18 An alkylene radical and mixtures thereof, -When R5 is not a covalent bond, R5 is a C6-C arylene radical in which one or more heteroatoms are optionally interposed, 14 An arylene radical, C3-C 12 A cycloalkylene radical, a linear or branched C1-C 18 An alkylene radical and mixtures thereof, -R6 is a C6-C arylene radical in which one or more heteroatoms are optionally interposed, 14 An arylene radical, C3-C 12 A cycloalkylene radical, a linear or branched C1-C 18 An alkylene radical and mixtures thereof) Represents a group selected from.

[0066] More preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein -X1 and X2 independently represent an oxygen atom, -R1 and R2 are, independently, monoalkyl ethers of (poly)alkylene glycols from which a hydroxyl group has been removed, -n and z represent integers in the range of 1 to 20, n + z ≧ 2, w is equal to 1, -L1 is a C3-C 15 A cycloalkylene radical, -E is, independently, --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 are independently selected from C6-C 14 arylene radicals, C3-C 12 cycloalkylene radicals, linear or branched C1-C 18 alkylene radicals and mixtures thereof, -when R5 is not a covalent bond, R5 is selected from C6-C 14 arylene radicals, C3-C 12 cycloalkylene radicals, linear or branched C1-C 18 alkylene radicals and mixtures thereof, -R6 is selected from C6-C 14 arylene radicals, C3-C 12 cycloalkylene radicals, linear or branched C1-C 18 alkylene radicals and mixtures thereof) represents a group selected from.

[0067] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein -X1 and X2 independently represent an oxygen atom, -R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30) represents a compound of -n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, and w is equal to 1; -L1 is a C3-C cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, 15 and is a cycloalkylene radical, -E represents a -O-R3-O- group (wherein R3 is a C6-C arylene radical, a C3-C 14 cycloalkylene radical, a linear or branched C1-C 12 alkylene radical, or a mixture thereof, in which one or more heteroatoms are optionally interposed). 18

[0068] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein -X1 and X2 independently represent an oxygen atom, -R1 and R2 independently represent the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q - (VI) (wherein R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, more preferably methyl, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30) represents a compound of -n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, w is equal to 1, -L1 is a C3-C cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylene methane, 15 preferably 4,4-dicyclohexylene methane, -E represents a -O-R3-O- group (wherein R3 represents a linear or branched C1-C alkylene radical such as methylene, propylene, butylene, ethylene, etc., in which one or more heteroatoms are optionally interposed). 18

[0069] According to a preferred embodiment, the (poly)carbodiimide compound is of the following formula (XII): [Chemical formula] (wherein L1 is 4,4-dicyclohexylenemethane, n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, E is a -O-R3-O- group (wherein R3 is a linear or branched C1-C alkylene radical such as methylene, propylene, butylene or ethylene with one or more heteroatoms optionally intervening), and r and s represent integers in the range of 4 to 30) 18 and is a compound of) .

[0070] The total amount of the (poly)carbodiimide compound present in the dyeing composition is preferably in the range of 0.01% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 0.2% to 10% by mass, even more preferably 0.5% to 8% by mass, and even better 1% to 6% by mass, based on the total mass of the dyeing composition.

[0071] Colorant As described above, the composition for dyeing keratinous hair fibers used in connection with the process according to the invention comprises one or more colorants selected from pigments, direct dyes and mixtures thereof.

[0072] Preferably, the composition for dyeing keratinous hair fibers comprises one or more pigments.

[0073] The term "pigment" means any pigment that imparts color to keratinous materials. Their solubility in water at atmospheric pressure (760 mmHg) at 25 °C is less than 0.05% by mass, preferably less than 0.01% by mass.

[0074] The pigments that can be used are selected, inter alia, from organic and / or inorganic pigments known in the art, in particular from those described in Kirk - Othmer’s Encyclopedia of Chemical Technology and Ullmann’s Encyclopedia of Industrial Chemistry. These can be natural or non - natural products of natural origin.

[0075] These pigments can be in the form of pigment powder or paste. They may or may not be coated.

[0076] The pigment can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as pearlescent agents or glitter flakes and mixtures thereof. The pigment can be a mineral pigment. "Inorganic pigment" means any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopedia. Among the mineral pigments useful in the present invention are iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrates, ferric blue and titanium oxides.

[0077] The pigment can be an organic pigment. "Organic pigment" means any pigment that meets the definition in the chapter on organic pigments in Ullmann’s encyclopedia. Organic pigments can be selected, in particular, from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluoran, phthalocyanine, metal complexes, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0078] In particular, the white or colored organic pigments can be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments classified under the reference numbers CI 42090, 69800, 69825, 74100, 74160 in the Color Index, yellow pigments classified under the reference numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005 in the Color Index, green pigments classified under the reference numbers CI 61565, 61570, 74260 in the Color Index, orange pigments classified under the reference numbers CI 11725, 45370, 71105 in the Color Index, red pigments classified under the reference numbers CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470 in the Color Index, and pigments obtained by oxidative polymerization of indole or phenolic derivatives described in French Patent No. 2679771.

[0079] Examples of the pigment pastes of organic pigments also include products sold under the following names by Hoechst: - Cosmenyl Yellow 10G: Yellow 3 pigment (CI11710); - Cosmenyl Yellow G: Yellow 1 pigment (CI 11680); - Cosmenyl Orange GR: Orange 43 pigment (CI 71105); - Cosmenyl Red R: Red 4 pigment (CI 12085); - Cosmenyl Carmine FB: Red 5 pigment (CI 12490); - Cosmenyl Violet RL: Violet 23 pigment (CI 51319); - Cosmenyl Blue A2R; Blue 15.1 pigment (CI 74160); -Cosmenyl Green GG: Pigment Green 7 (CI 74260); -Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0080] The pigments according to the invention can also be in the form of composite pigments as described in European Patent No. 1184426. These composite pigments can in particular be composed of particles containing a core substance of an inorganic material, at least one binder for binding an organic pigment to the core substance, and at least one organic pigment covering at least a part of the core substance.

[0081] The organic pigment can be a lake. "Lake" means a dye adsorbed on insoluble particles and the aggregate thus obtained remains insoluble during use.

[0082] The inorganic substrate on which the dye is adsorbed is, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0083] Among the dyes, carminic acid can be mentioned. Also mentioned are dyes known by the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

[0084] Examples of lakes include products known by the following names: D&C Red 7 (CI 15 850:1).

[0085] The pigment may be a pigment having a special effect. "Pigment having a special effect" means a pigment that generally gives a non-uniform and changing colored appearance (characterized by a specific hue, a specific brilliance and a specific level of luminance) based on the conditions of observation (light, temperature, angle of observation, etc.). Thereby, they differ from colored pigments presenting standard uniform opaque, translucent or transparent hues.

[0086] There are several types of pigments having a special effect: those having a low refractive index such as fluorescent or photochromic pigments and those having a high refractive index such as pearlescent agents, interference pigments or glitter flakes.

[0087] Examples of pigments having a special effect that may be mentioned include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium, especially mica coated with Prussian blue or chromium oxide, mica coated with titanium and coated with the organic pigments defined above, and pearlescent pigments based on bismuth oxychloride. Examples of pearlescent agents include Cellini (mica - TiO2 - lake) sold by BASF, Prestige (mica - TiO2) sold by Eckart, Prestige Bronze (mica - Fe2O3) sold by Eckart or Colorona (mica - TiO2 - Fe2O3) sold by Merck.

[0088] Golden pearlescent pigments, especially those sold under the names Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) by BASF; bronze pearlescent pigments, especially those sold under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) by Merck and under the name Super bronze (Cloisonne) by BASF; orange pearlescent pigments, especially those sold under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) by BASF and under the names Passion orange (Colorona) and Matte orange (17449) (Microna) by Merck; brown pearlescent pigments, especially those sold under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite) by BASF; copper-colored pearlescent pigments, especially those sold under the name Copper 340A (Timica) by BASF; red-colored pearlescent pigments, especially those sold under the name Sienna fine (17386) (Colorona) by Merck; yellow-colored pearlescent pigments, especially those sold under the name Yellow (4502) (Chromalite) by BASF; red pearlescent pigments with a golden hue, especially those sold under the name Sunstone G012 (Gemtone) by BASF; peach pearlescent pigments, especially those sold under the name Tan opale G005 (Gemtone) by BASF; black pearlescent pigments with a golden hue, especially those sold under the name Nu antique bronze 240 AB (Timica) by BASF; blue pearlescent pigments, especially those sold under the name Matte blue (17433) (Microna) by Merck; white pearlescent pigments with a silver hue, especially those sold under the name Xirona Silver by Merck;And nacreous pearlescent agents that change to greenish-gold to pink to orange, in particular those sold by Merck under the name Indian summer (Xirona); and mixtures thereof are also included.;

[0089] As a further example of nacreous pearlescent agents, particles comprising a borosilicate substrate coated with titanium oxide are also included.

[0090] Particles comprising a glass substrate coated with titanium oxide are sold, in particular, by Toyal under the name Metashine MC1080RY.

[0091] Finally, as an example of nacreous pearlescent agents, polyethylene terephthalate glitter flakes, in particular those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver glitter flakes) are also included. Synthetic substrates, for example, multilayer pigments based on alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum etc. can also be envisaged.

[0092] Pigments with special effects can be selected from reflective particles, i.e., particles capable of reflecting incident light due to their size, structure, in particular the thickness of the layers that make it up, as well as their physical and chemical properties and surface state. This reflection, if appropriate, when applied to the support to be made up, can have a sufficient intensity to produce bright spots visible to the naked eye on the surface of the composition or mixture, i.e., points that are brighter and more prominent than the surroundings and appear shiny.

[0093] The reflective particles can be selected so as not to significantly change the color rendering effect brought about by the colorant combined with it, and more particularly to optimize this effect from the perspective of color rendering. These can have, more particularly, colors or shades of yellow, pink, red, bronze, orange, brown, gold and / or copper. These particles can have various forms and can in particular be in platelet or small spherical form, in particular spherical form.

[0094] Regardless of their form, the reflective particles may or may not have a multilayer structure. In the case of a multilayer structure, they may have, for example, a uniform thickness and, in particular, may have at least one layer of a reflective material. When the reflective particles do not have a multilayer structure, they may be composed of metal oxides, in particular titanium oxide or iron oxide obtained synthetically.

[0095] When the reflective particles have a multilayer structure, they may include, for example, a natural or synthetic substrate, in particular a synthetic substrate, at least partially coated with a reflective material, in particular at least one layer of at least one metal or metallic material. The substrate can be made from one or more organic materials and / or inorganic materials.

[0096] More specifically, this may be selected from, but is not limited to this list, glass, ceramics, graphite, metal oxides, alumina, silica, silicates, in particular aluminosilicates and borosilicates and synthetic mica and mixtures thereof.

[0097] The reflective material may include a layer of a metal or metallic material.

[0098] The reflective particles are described, in particular, in JP-A-09-188830, JP-A-10-158450, JP-A-10-158541, JP-A-07-258460 and JP-A-05-017710.

[0099] As a further example of reflective particles including an inorganic substrate coated with a metal layer, particles including a borosilicate substrate coated with silver are also mentioned.

[0100] Particles of a silver-coated glass substrate in platelet form are sold by Toyal under the name Microglass Metashine REFSX 2025 PS. Particles of a glass substrate coated with a nickel / chromium / molybdenum alloy are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0101] Particles containing a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, or titanium can also be used, and the substrate is coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0102] Examples include aluminum powder, bronze powder, or copper powder coated with SiO2, sold under the name Visionaire by Eckart.

[0103] Interference pigments such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments from Spectratek or Spectra f / x) that are not bonded to the substrate can also be mentioned. Special effect pigments include fluorescent pigments (either substances that fluoresce in daylight or substances that produce ultraviolet fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments, and quantum dots sold, for example, by Quantum Dots Corporation.

[0104] The diversity of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also to obtain specific optical effects such as metallic effects or interference effects.

[0105] The size of the pigments used in the composition according to the present invention is generally from 10 nm to 200 μm, preferably from 20 nm to 80 μm, and more preferably from 30 nm to 50 μm.

[0106] The pigments may be dispersed in the composition by a dispersant.

[0107] Dispersants have the effect of protecting the dispersed particles from flocculation or aggregation. The dispersant can be a surfactant, oligomer, polymer, or a mixture of some of these having one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, these can become physically or chemically bonded to the pigment surface. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid, especially C8-C20 fatty acids and polyols such as glycerol or diglycerol, for example, poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, for example, a product sold under the name Solsperse 21000 from Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the trade symbol Dehymyls PGPH from Henkel, or other polyhydroxystearic acids, for example, a product sold under the trade symbol Arlacel P100 from Uniqema and mixtures thereof are used.

[0108] Other dispersants that can be used in the composition of the present invention include quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17000 sold by Avecia, and polydimethylsiloxane / oxypropylene mixtures, such as those sold under the reference numbers DC2-5185 and DC2-5225 C by Dow Corning.

[0109] The pigments used in the composition may be surface-treated with an organic agent.

[0110] Therefore, the pre-surface-treated pigments useful in connection with the present invention are pigments that have been surface-treated, either fully or partially, with organic agents to impart chemical, electronic, electrochemical, mechanochemical, or mechanical properties, such as those particularly described in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53 - 64, and are then dispersed in the compositions according to the present invention. These organic agents include, for example, waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols, and their derivatives such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid, and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc, or aluminum salts of fatty acids such as aluminum stearate or aluminum laurate; metal alkoxides; polyethylene; (meth)acrylic acid polymers such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds such as silicones, particularly polydimethylsiloxane; organic fluorine compounds such as perfluoroalkyl ethers; and fluorosilicone compounds, which may be selected.

[0111] The surface-treated pigments useful in the present compositions can be those treated with mixtures of these compounds and / or can be those that have been surface-treated several times.

[0112] The surface-treated pigments useful in connection with the present invention can be prepared according to surface treatment techniques well-known to those skilled in the art or can be commercially available as such.

[0113] Preferably, the surface-treated pigments are coated with an organic layer.

[0114] The organic agents for treating the pigments can be deposited on the pigments by evaporating the solvent, causing a chemical reaction between the molecules of the surface treatment agent, or forming a covalent bond between the surface treatment agent and the pigment.

[0115] Accordingly, the surface treatment can be carried out, for example, by causing a chemical reaction between a surface treatment agent and the pigment surface to generate a covalent bond between the surface treatment agent and the pigment or filler. This method is described in particular in U.S. Patent No. 4,578,266.

[0116] Organic agents that covalently bond with the pigment are preferably used.

[0117] The surface treatment agent can account for 0.1% to 50% by mass, preferably 0.5% to 30% by mass, and even more preferably 1% to 20% by mass of the total mass of the pigment to be surface-treated.

[0118] Preferably, the surface treatment agent for the pigment is selected from the following treatment agents: - PEG-silicone treatment agents, such as the AQ surface treatment agent sold by LCW; - Methicone treatment agents, such as the SI surface treatment agent sold by LCW; - Dimethicone treatment agents, such as the Covasil 3.05 surface treatment agent sold by LCW; - Dimethicone / trimethylsiloxysilicate treatment agents, such as the Covasil 4.05 surface treatment agent sold by LCW; - Magnesium myristate treatment agents, such as the MM surface treatment agent sold by LCW; - Aluminum dimyristate treatment agents, such as the MI surface treatment agent sold by Miyoshi, - Perfluoropolyisopropyl methyl ether treatment agents, such as the FHC surface treatment agent sold by LCW; - Isostearyl sebacate treatment agents, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - Perfluoroalkyl phosphate treatment agents, such as the PF surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment agents, such as the FSA surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment agent, such as FS01 surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate / dimethicone copolymers treatment agent, such as ASC surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Isopropyl titanate triisostearate treatment agent, such as ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate copolymer treatment agent, such as APD surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Perfluoroalkyl phosphate / isopropyl titanate triisostearate treatment agent, such as PF + ITT surface treatment agent sold by Daito Kasei Kogyo Co., Ltd. is selected from.

[0119] According to a specific embodiment of the present invention, the dispersant is present in Composition B together with an organic or inorganic pigment in the form of submicron-sized particles.

[0120] "Submicron" or "submicron-sized" means a pigment having a particle diameter micronized by a micronization method and an average particle diameter of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, preferably 0.2 to 0.6 μm.

[0121] According to one embodiment, the dispersant and the pigment are present in an amount of 1:4 to 4:1, particularly 1.5:3.5 to 3.5:1, or even better 1.75:3 to 3:1 (dispersant:pigment) according to the mass ratio.

[0122] Therefore, the dispersant may have a silicone backbone such as silicone polyether and a dispersant of an amino silicone type other than the amino silicone described later. Suitable dispersants include the following: -Aminosilicones, i.e., silicones containing one or more amino groups, such as those sold by BYK under the name and reference number: BYK LPX 21879, those sold by Genesee Polymers, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967, and GP-988-1, -Acrylic acid silicones, such as those sold by Evonik, Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043, -Polydimethylsiloxane (PDMS) silicones having carboxylic groups, such as X-22162 and X-22370 by Shin-Etsu Chemical Co., Ltd., epoxy silicones, such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers or Tego® RC 1401, Tego® RC 1403, Tego® RC 1412 by Evonik.

[0123] According to a particular embodiment, the dispersant is of the aminosilicone type other than the aminosilicones described below and is cationic.

[0124] Preferably, the pigment is selected from inorganic pigments, inorganic-organic mixed pigments, or organic pigments.

[0125] In a variant of the present invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic agent selected from silicone compounds. In another variant of the present invention, the pigment is a mineral pigment.

[0126] Preferably, the pigment is selected from iron oxides, especially red, brown, or black iron oxides, nacreous pearlescent agents, especially mica coated with titanium or bismuth oxychloride, mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium, and mixtures thereof.

[0127] As an example of iron oxide, there is iron oxide sold under the trade name SunPuro® Red Iron Oxide by Sun Chemical.

[0128] As an example of a pearlescent agent, mica and iron oxide sold by Sudarshan Chemical under the trade name Pearlescent Pigment Prestige soft bronze are mentioned.

[0129] According to a preferred embodiment, the dyeing composition according to the invention comprises a mixture of pigments, in particular iron oxide, and pearlescent agents, in particular mica coated with titanium or bismuth oxychloride, mica coated with titanium and iron oxide, mica coated with iron oxide, mica coated with titanium.

[0130] Direct dyes The composition for dyeing keratinous hair fibers used in connection with the process according to the invention may comprise one or more direct dyes.

[0131] "Direct dyes" means natural and / or synthetic dyes other than oxidative dyes. These are dyes that diffuse superficially on the fiber.

[0132] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0133] Examples of suitable direct dyes include azo direct dyes, alone or in mixture form; (poly)methine dyes, such as cyanine, hemicyanine and styryl; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes; and natural direct dyes.

[0134] The direct dye is preferably a cationic direct dye. Examples include hydrazonocationic dyes of the following formulas (XIII) and (XIV) and azocationic dyes of the formulas (XV) and (XVI). Het + -N(Ra)-N=C(Rb)-Ar,Q-(XIII), Het + -C(Ra)=N-N(Rb)-Ar,Q(XIV), Het + -N=N-Ar,Q-(XV), Ar + -N=N-Ar’’,Q-(XVI), In the formulas (XIII) to (XVI), -Het+ represents a cationic heteroaryl radical which is preferably optionally substituted with at least one (C1-C8) alkyl group such as methyl, and preferably has an in-ring cationic charge, for example, imidazolium, indolium or pyridinium, etc. -Ar+ represents an aryl radical such as phenyl or naphthyl which has an out-of-ring cationic charge, preferably ammonium, especially tri(C1-C8) alkylammonium such as trimethylammonium. -Ar is an aryl group which preferably represents an aryl group optionally substituted with one or more electron-donating groups, for example, i) optionally substituted (C1-C8) alkyl, ii) optionally substituted (C1-C8) alkoxy, iii) (di)(C1-C8)(alkyl)amino in which the alkyl group is optionally substituted with a hydroxyl group, iv) aryl(C1-C8)alkylamino, v) optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino, especially phenyl, or alternatively, Ar represents a djuridin group. -Ar’’ represents an optionally substituted (hetero)aryl group, for example, preferably phenyl or pyrazolyl optionally substituted with one or more (C1-C8) alkyl, hydroxyl, (di)(C1-C8)(alkyl)amino, (C1-C8) alkoxy or phenyl groups. -Ra and Rb are the same or different and each represents a hydrogen atom or, preferably, an optionally hydroxysubstituted (C1-C8) alkyl group; or The substituents of Ra and Het+ and / or the substituents of Rb and Ar together with the atoms bearing them form a (hetero)cycloalkyl, and in particular, Ra and Rb each represents a hydrogen atom or an optionally hydroxysubstituted (C1-C4) alkyl group, -Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

[0135] In particular, azo and hydrazono direct dyes having an intracyclic cationic charge of the formulas (XIII) to (XVI) defined above, and more particularly, cationic direct dyes having an intracyclic cationic charge as described in International Publication Pamphlet No. WO 95 / 15144, International Publication Pamphlet No. WO 95 / 01772, and European Patent No. EP 714954, preferably include the following direct dyes:

Chemical formula

[0136] In particular, the dyes of formulas (XVII) and (XVIII) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof, and Q' is an anionic counterion as defined above, in particular a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesityl sulfate.

[0137] The direct dye may be selected from anionic direct dyes. The anionic direct dyes of the present invention are generally referred to as "acid" direct dyes due to their affinity for alkaline substances. "Anionic direct dyes" mean direct dyes containing at least one CO2R or SO3R substituent (wherein R represents a hydrogen atom or a cation or ammonium ion derived from a metal or an amine) in their structure. The anionic dyes can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigoid dyes and natural acid dyes.

[0138] Examples of acid dyes useful in the present invention include dyes of the following formulas (XIX), (XIX'), (XX), (XX'), (XXI), (XXI'), (XXII), (XXII'), (XXIII), (XXIV), (XXV) and (XXVI). a) Diaryl anionic azo dyes of formula (XIX) or (XIX'): [Chemical formula] (In formulas (XIX) and (XIX'), - R7, R8, R9, R 10 , R'7, R'8, R'9 and R' 10 are the same or different and represent a hydrogen atom, or - alkyl; - alkoxy, alkylthio; - hydroxyl, mercapto; - nitro, nitroso; -R°-C(X)-X’-、R°-X’-C(X)-、R°-X’-C(X)-X’’- (wherein R° represents a hydrogen atom, an alkyl or aryl group, and X, X’ and X’’ are the same or different and represent an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group); -(O)2S(O-)-,M+ (wherein M+ represents a hydrogen atom or a cationic counterion); -(O)CO--,M+ (wherein M+ is as defined above); -R’’-S(O)2- (wherein R’’ represents a hydrogen atom, an alkyl group, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferably represents a phenylamino or phenyl group); -R’’’-S(O)2-X’- (wherein R’’’ represents an optionally substituted alkyl or aryl group, and X’ is as defined above); -(di)(alkyl)amino; -i) nitro; ii) nitroso; iii) (O)2S(O-)-, M+ and iv) aryl(alkyl)amino optionally substituted with one or more groups selected from alkoxy, wherein M+ is as defined above; -optionally substituted heteroaryl; preferably a benzothiazolyl group; -cycloalkyl, especially cyclohexyl represents a group selected from -Ar-N=N- (wherein Ar represents an optionally substituted aryl group, preferably phenyl optionally substituted by one or more alkyl, (O)2S(O-)-, M+ or phenylamino groups) represents a group selected from -or alternatively, two adjacent groups R7 and R8 or R8 and R9 or R9 and R 10 together form a fused benzo group A’, and R’7 and R’8 or R’8 and R’9 or R’9 and R’ 10 together form a fused benzo group B’, and A’ and B’ are i) nitro; ii) nitroso; iii) (O)2S(O - )-,M +; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)-; ix) R°-X’-C(X)-X’’-; x) Ar-N=N-, and xi) optionally substituted aryl(alkyl)amino; optionally substituted with one or more groups selected from, M + , R°, X, X’, X’’ and Ar are as defined above, -W represents a sigma bond σ, an oxygen or sulfur atom or a divalent radical, i) -NR- where R is as defined above, or ii) methylene -C(Ra)(Rb)-, where Ra and Rb are the same or different and represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom bearing them form a spirocycloalkyl, preferably, W represents a sulfur atom or Ra and Rb together form cyclohexyl; It is understood that Formulas (XIX) and (XIX’) contain at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical (O)CO--, M+ on one of Rings A, A’, B, B’ or C, preferably sodium sulfonate.

[0139] Examples of the dyes of formula (XIX) include Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow, Examples of the dyes of formula (XIX’) include Acid Red 111, Acid Red 134, Acid Yellow 38.

[0140] b) Pyrazolone anionic azo dyes of formula (XX) and (XX’): [Chemical formula] (In formula (XX) and (XX’), -R 11 , R 12 and R 13 are the same or different and represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O-),M+ (where M+ is as defined above), -R 14 represents a hydrogen atom, an alkyl group or -C(O)O - ,M + group (wherein M + is as defined above), and -R 15 represents a hydrogen atom, -R 16 represents an oxo group, in which case R’ 16 is absent or, alternatively, R 15 is R 16 together with forms a double bond, -R 17 and R 18 are the same or different and represent a hydrogen atom or -(O)2S(O-)-,M+ (wherein M+ is as defined above); -Ar-O-S(O)2- (wherein Ar represents an optionally substituted aryl group, preferably phenyl optionally substituted with one or more alkyl groups) represents a group selected from -R 19 and R 20 together form either a double bond or an optionally substituted benzo group D’, -R’ 16 , R’ 19 and R’ 20 are the same or different and represent a hydrogen atom or an alkyl group or a hydroxyl group, -R 21 represents a hydrogen atom or an alkyl group or an alkoxy group, -Ra and Rb are the same or different and are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group, -Y represents either a hydroxyl group or an oxo group, -

Chemical Structure

[0141] Examples of dyes of formula (XX) include Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and an example of a dye of formula (XX') is Acid Yellow 17.

[0142] c) Anthraquinone dyes of formulas (XXI) and (XXI'):

Chemical formula

[0143] Examples of the dyes of formula (XXI) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No. 2, and an example of the dye of formula (XXI') is Acid Black 48.

[0144] d) Nitro dyes of formula (XXII) and (XXII'): [Chemical formula] (In formula (XXII) and (XXII'), -R 30 , R 31 , and R 32 are the same or different and represent a hydrogen or halogen atom, or -alkyl; -alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups; -hydroxyl, mercapto; -nitro, nitroso; -polyhaloalkyl; -R°-C(X)-X'-、R°-X'-C(X)-、R°-X'-C(X)-X''-(wherein R°, X, X' and X'' are as defined above); -(O)2S(O-)-, M+ (wherein M+ is as defined above); -(O)CO--, M+ (wherein M+ is as defined above); -(di)(alkyl)amino; -(di)(hydroxyalkyl)amino; -heterocycloalkyl such as piperidino, piperazino or morpholino represents a group selected from, and in particular, R 30 , R 31 and R32 represents a hydrogen atom, -Rc and Rd, which may be the same or different, each represent a hydrogen atom or an alkyl group, -W is as defined above, and W particularly represents an -NH- group, -ALK represents a straight-chain or branched divalent C1-C6 alkylene group, and particularly, ALK represents a -CH2-CH2- group, -n is 1 or 2, -p represents an integer from 1 to 5 (inclusive of both end values), -q represents an integer from 1 to 4 (inclusive of both end values), -u is 0 or 1, When -n is 1, J represents a nitro or nitroso group, particularly nitro, When -n is 2, J represents an oxygen or sulfur atom or a divalent -S(O) m - radical (wherein m represents an integer of 1 or 2), and preferably, J represents a -SO2- radical, -M’ represents a hydrogen atom or a cationic counterion, -

Chemical formula

[0145] Examples of the dyes of formula (XXII) include Acid Brown 13 and Acid Orange 3, and examples of the dyes of formula (XXII’) include Acid Yellow 1, the sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4’-N,N-2’’-hydroxyethyl)amino-2’-nitro)aniline ethanesulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; EXT D&C Yellow 7.

[0146] e) Triarylmethane dyes represented by formula (XXIII):

Chemical formula

[0147] Examples of the dyes of formula (XXIII) include AcidBlue1; AcidBlue3; AcidBlue7, AcidBlue9; AcidViolet49; AcidGreen3; AcidGreen5 and AcidGreen50.

[0148] f) Xanthene dyes of formula (XXIV): [Chemical formula] (In formula (XXIV), -R 45 , R 46 , R 47 and R 48 represent, independently of each other, a hydrogen or halogen atom, -R 49 , R 50 , R 51 and R 52 represent, independently of each other, a hydrogen or halogen atom, or -alkyl; -alkoxy, alkylthio; -hydroxyl, mercapto; -nitro, nitroso; -(O)2S(O-)-, M+ (where M+ represents a hydrogen atom or a cationic counterion); -(O)CO--, M+ (where M+ is as defined above) represents a group selected from, In particular, R 49 , R 50 , R 51 and R 52 represent a hydrogen or halogen atom, -G represents an oxygen or sulfur atom or an NRe group (where Re is as defined above), in particular, G represents an oxygen atom, -L represents an alkoxide O - , M + , a thioalkoxide S - , M + or an NRf group (where Rf represents a hydrogen atom or an alkyl group, M + is as defined above, and M + is in particular sodium or potassium), - L’ represents an oxygen or sulfur atom or an ammonium group: N+RfRg (wherein Rf and Rg are the same or different and represent a hydrogen atom or an optionally substituted alkyl or aryl group), and L’ particularly represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl or (O)mS(O-)-, M+ groups (wherein m and M+ are as defined above). - Q and Q’ are the same or different and represent an oxygen or sulfur atom, and particularly, Q and Q’ represent an oxygen atom. - M + is as defined above).

[0149] Examples of the dyes of formula (XXIV) include Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9.

[0150] g) Indole dyes of formula (XXV):

Chemical formula

[0151] An example of the dye of formula (XXV) is Acid Blue 74.

[0152] h) Quinoline-based dyes of formula (XXVI):

Chemical formula

[0153] Examples of the dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

[0154] Among the natural direct dyes that can be used according to the present invention, there are Lawson, Juglone, Alizarin, Purpurin, Carmic acid, Kermesic acid, Purpurogallin, Protocatechuic aldehyde, Indigo, Isatin, Curcumin, Spinulosin, Apigenidin, and Orcein. Extracts or decoctions containing these natural dyes, particularly pastes or extracts based on henna dyes, may also be used.

[0155] Preferably, the direct dye is selected from anionic direct dyes.

[0156] The colorant may be present in a total amount in the range of 0.001% to 20% by mass, preferably 0.005% to 15% by mass, based on the total mass of the dyeing composition. Preferably, the colorant is selected from pigments.

[0157] The pigment may be present in a total amount in the range of 0.05% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 0.5% to 10% by mass, based on the total mass of the dyeing composition.

[0158] The direct dye may be present in a total amount in the range of 0.001% to 10% by mass, preferably 0.005% to 5% by mass, based on the total mass of the composition.

[0159] Non-carboxylic acid anionic thickener The composition for dyeing keratinous hair fibers may also contain a non-carboxylic acid anionic thickener.

[0160] For the purposes of the present invention, a "non-carboxylic acid agent" means an agent that does not contain a carboxylic acid functional group (-COOH) or a carboxylate functional group (-COO - )

[0161] For the purposes of the present invention, the "thickener" refers to a compound which, when introduced at a concentration of 0.05% by mass relative to the total mass of the composition, increases the viscosity of the composition into which it is introduced at room temperature (25 °C) and atmospheric pressure at a shear rate of 1 s -1 to at least 20 cps, preferably at least 50 cps (the viscosity can be measured using a cone / plate viscometer such as a Haake R600 rheometer).

[0162] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, more preferably anionic polymers having sulfone groups.

[0163] For the purposes of the present invention, an "anionic polymer" means a polymer containing one or more anionic groups or anionic groups and no cationic groups or cationized groups.

[0164] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers containing at least one ethylenically unsaturated monomer having a sulfone group in free form or in partially or fully neutralized form.

[0165] This polymer may or may not be crosslinked. They are preferably crosslinked. These polymers can be associative or non-associative, preferably non-associative.

[0166] It should be recalled that an "associative polymer" is a polymer that can reversibly associate with each other or with other molecules in an aqueous medium.

[0167] Their chemical structure more particularly includes at least one hydrophilic zone and at least one hydrophobic zone.

[0168] The "hydrophobic group" means a radical or polymer having a saturated or unsaturated, linear or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0169] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group can be derived from a fatty alcohol, for example, stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also represent a hydrocarbon-based polymer (for example, polybutadiene).

[0170] The ethylenically unsaturated monomer carrying a sulfonic acid group is particularly selected from vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylamide (C1-C 22 )alkyl sulfonic acid, N-(C1-C 22 )alkyl(meth)acrylamide (C1-C 22 )alkyl sulfonic acid, for example undecylacrylamide methanesulfonic acid and also its partially or fully neutralized forms.

[0171] More preferably, (meth)acrylamide (C1-C 22 )alkyl sulfonic acid, for example, acrylamide methanesulfonic acid, acrylamide ethanesulfonic acid, acrylamide propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamide-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, in addition to their partially or fully neutralized forms will be used.

[0172] More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0173] Among the 2-acrylamido-2-methylpropanesulfonic acid copolymers, partially or fully neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide can be mentioned, and the products described in Example 1 of European Patent No. 503853 can be particularly mentioned, and reference can be made to this document regarding these polymers.

[0174] Copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT10 by SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer), can also be mentioned.

[0175] Associative AMPS polymers are, in particular, C6-C 22 Random associative AMPS polymers modified by reaction with n-monoalkylamine or di-n-alkylamine and those described in International Patent Application Publication No. 00 / 31154 pamphlet (forming an essential part of the contents of the specification) can be selected. These polymers may also include those selected from other ethylenically unsaturated hydrophilic monomers, such as (meth)acrylic acid derivatives, such as esters with its monohydric alcohol or mono- or polyalkylene glycol, (meth)acrylamide, vinyl pyrrolidone, or mixtures of these compounds.

[0176] Preferred polymers of this line are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0177] These same copolymers may also contain one or more ethylenically unsaturated monomers without an aliphatic chain, such as (meth)acrylic acid derivatives, especially esters obtained with monohydric alcohol or mono- or polyalkylene glycol, (meth)acrylamide, vinyl pyrrolidone, maleic anhydride, itaconic acid, or maleic acid, or mixtures of these compounds.

[0178] These copolymers are described, in particular, in European Patent Application Publication No. A750899, U.S. Patent No. 5089578, and the following publications by Yotaro Morishima: -Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol.18, No.40, (2000), 323-336; -Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, Vol.33, No.10, (2000), 3694-3704; -Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte::salt effects on rheological behavior-Langmuir, Vol.16, No.12, (2000)5324-5332; -Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers-Polym.Preprint, Div.Polym.Chem., 40(2), (1999), 220-221。

[0179] Among these polymers, the following are mentioned: - From 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8 - C 16 ) alkyl (meth) acrylamide or (C8 - C 16 ) alkyl (meth) acrylate units, of a crosslinked or non - crosslinked, neutralized or non - neutralized copolymer, such as those described in European Patent Application Publication No. A750899; - From 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units, and from 5 mol% to 80 mol% of n - (C6 - C 18 ) alkylacrylamide units, of a terpolymer, such as those described in U.S. Patent No. 5089578.

[0180] Also included are fully neutralized copolymers of AMPS and dodecyl methacrylate and also crosslinked and non - crosslinked copolymers of AMPS and n - dodecyl methacrylamide, such as those described in the above - mentioned Morishima paper.

[0181] Preferably, the non - carboxylic acid anionic thickener is selected from the sodium 2 - acrylamido - 2 - methylpropanesulfonate / hydroxyethyl acrylate copolymer (INCI name hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer) sold by SEPPIC.

[0182] Advantageously, the total amount of the non - carboxylic acid anionic thickener can be in the range of from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, even more preferably from 0.1% to 3% by weight, based on the total weight of the dyeing composition.

[0183] Silicone The composition for dyeing keratinous hair fibers may also contain at least one silicone.

[0184] The silicone is other than a compound having at least one carboxylic acid group as defined below.

[0185] Preferably, the dyeing composition contains at least one silicone selected from non - amino silicone, amino silicone and mixtures thereof.

[0186] The silicone can be solid or liquid under atmospheric pressure (1.013×10 5 Pa) at 25 °C and can be volatile or non - volatile.

[0187] The silicone that can be used can be soluble or insoluble in the composition according to the present invention, and these can be in the form of oils, waxes, resins or gums, and silicone oils are preferred.

[0188] Silicones are described in detail, in particular, in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0189] Preferably, the dyeing composition contains one or more silicones that are liquid under atmospheric pressure (1.013×10 5 Pa) at 25 °C.

[0190] Volatile silicones can have a boiling point of 60 °C to 260 °C (under atmospheric pressure) and can be more particularly selected from the following: i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5 silicon atoms, such as the following, - octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0191] Products sold under the name Volatile Silicone 7207 from Union Carbide or Silbione 70045 V 2 from Rhodia, and under the name Volatile Silicone 7158 from Union Carbide or Silbione 70045 V 5 from Rhodia can be mentioned; - Dimethylsiloxane / methylalkylsiloxane type cyclic copolymer having the following chemical structure: [Chemical formula] Preferably, it is cyclomethylsiloxane.

[0192] Examples include Volatile Silicone FZ 3109 sold by Union Carbide. - Mixtures of cyclic silicones and silicon-based organic compounds, such as mixtures of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and mixtures of octamethylcyclotetrasiloxane and 1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane; ii) Generally, linear polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity at 25°C of 5×10 -6 m 2 / s or less, such as decamethyltetrasiloxane.

[0193] Other silicones belonging to this classification are described in the article published in Cosmetics and Toiletries, Vol.91, Jan.76, pp.27~32, Todd & Byers Volatile silicone fluids for cosmetics, and examples include products sold under the name SH 200 by Toray Silicone Co., Ltd.

[0194] Among non-volatile silicones, organopolysiloxanes (or organically modified polysiloxanes or alternatively organically modified silicones) that are, alone or as a mixture, polydialkylsiloxanes, in particular polydimethylsiloxane (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and that contain, within their structure, one or more organic functional groups generally bonded via a hydrocarbon group and preferably selected from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups, are mentioned. Preferably, the non-volatile silicone is optionally selected from oxyethylenated and oxypropylenated polydimethyl / methylsiloxanes. The organically modified silicone may be a polydiarylsiloxane, in particular polydiphenylsiloxane, and a polyalkylarylsiloxane that are modified with the organic functional groups described above. The polyalkylarylsiloxane is in particular selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0195] Among organically modified silicones, organopolysiloxanes containing the following are mentioned: - Polyoxyethylene and / or polyoxypropylene groups optionally containing a C6 - C 24 alkyl group, for example dimethicone copolyol, in particular that sold under the name DC 1248 by Dow Corning or the oils Silwet® L 722, L7500, L77 and L711 from Union Carbide, or (C12) alkylmethicone copolyol, in particular that sold under the name Q2 5200 by Dow Corning; - Substituted or unsubstituted amine groups, in particular C1 - C4 aminoalkyl groups, products sold under the names GP4 Silicone Fluid and GP7100 by Genesee, or products sold under the names Q2-8220 and DC929 or DC939 by Dow Corning; - Thiol groups, for example, products sold under the names GP72A and GP71 by Genesee; - Products commercially available under the name Silicone Copolymer F-755 from SWS Silicones, and products commercially available under the names Abil Wax® 2428, 2434, and 2440 from Goldschmidt; - Hydroxylated groups; for example, polyorganosiloxanes having hydroxyalkyl groups; - Acryloyloxyalkyl groups; for example, polyorganosiloxanes described in U.S. Patent No. A-4957732; - Carboxylic acid-type anionic groups, for example, those described in European Patent No. 186507 or anionic groups of the alkylcarboxylic acid type, for example, product X-22-3701E from Shin-Etsu Chemical Co., Ltd. or 2-hydroxyalkylsulfonate-type or 2-hydroxyalkylthiosulfate-type anionic groups, for example, products sold under the names Abil® S201 and Abil® S255 from Goldschmidt; - Hydroxyacylamino groups, for example, polyorganosiloxanes described in European Patent Application Publication No. 342834, for example, product Q2-8413 from Dow Corning.

[0196] The silicone can be selected from polydialkylsiloxanes, among which, mainly, polydimethylsiloxanes having trimethylsilyl end groups can be mentioned. Among these polydialkylsiloxanes, the following commercially available products can be mentioned: - Silbione® oils of series 47 and 70 047 sold by Rhodia or Mirasil®, for example, oil 70 047 V 500 000; - Oils of the Mirasil® series sold by Rhodia; - Oils of the 200 series from Dow Corning, for example, with a viscosity of 60000 mm 2DC200, with a viscosity of / s; - Viscasil® oil from General Electric and certain oils from the SF series from General Electric (SF 96, SF 18).

[0197] Also included are polydimethylsiloxanes with dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia.

[0198] Also included in this classification of polydialkylsiloxanes are products sold under the names Abil Wax® 9800 and 9801 from Goldschmidt, which are poly(C1 - C20) dialkylsiloxanes.

[0199] More specifically, the products that can be used according to the present invention are mixtures such as the following: - A mixture produced from polydimethylsiloxane with a hydroxy group at the chain end, i.e., dimethiconol (CTFA) and cyclic polydimethylsiloxane also known as cyclomethicone (CTFA), such as the product Q2 - 1401 sold by Dow Corning. - A mixture produced from polydimethylsiloxane with a hydroxy group at the chain end, i.e., dimethiconol (CTFA) and polydimethylsiloxane also known as dimethicone (CTFA), such as the product Xiameter® PMX - 1503 sold by Dow Corning.

[0200] The polyalkylaryl siloxanes are selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes, especially those having a viscosity in the range of 1×10 -5 ~5×10 -2 m 2 / s at 25°C.

[0201] Among these polyalkylaryl siloxanes, products sold under the following names can be mentioned: - Silbione® oil of the 70 641 series from Rhodia; - Rhodorsil® oil of the 70 633 and 763 series from Rhodia; - Dow Corning 556 Cosmetic Grade Fluid, an oil from Dow Corning; - PK series silicones from Bayer, such as product PK20; - PN and PH series silicones from Bayer, such as products PN1000 and PH1000; - Certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

[0202] Preferably, the dyeing composition contains at least one amino silicone. "Amino silicone" means any silicone containing at least one primary, secondary, tertiary amine or quaternary ammonium group.

[0203] The mass average molecular weight of these amino silicones can be measured by gel permeation chromatography (GPC) at room temperature (25 °C) as polystyrene equivalent. The columns used are μ-styragel columns. The eluent is THF and the flow rate is 1 ml / min. 200 μl of a solution containing 0.5% by mass of silicone in THF is injected. Detection is carried out by refractive index measurement and UV measurement.

[0204] Preferably, the amino silicones that can be used in connection with the present invention are selected from the following: a) Formula (A):

Chemical formula

[0205] Preferably, the amino silicone is selected from the amino silicones of formula (B). Preferably, the amino silicone of formula (B) is selected from the amino silicones corresponding to the following formulas (C), (D), (E), (F) and / or (G).

[0206] According to the first embodiment, the amino silicone corresponding to formula (B) is of formula (C):

Chemical formula

[0207] According to the second embodiment, the amino silicone corresponding to formula (B) is the following formula (D):

Chemical formula

[0208] Preferably, the alkoxy radical is a methoxy radical.

[0209] The molar ratio of hydroxy / alkoxy is preferably in the range of 0.2:1 to 0.4:1, preferably 0.25:1 to 0.35:1, and more specifically 0.3:1.

[0210] The mass average molecular weight (Mw) of these silicones is preferably in the range of 2,000 to 1,000,000, and more specifically in the range of 3,500 to 200,000.

[0211] According to the third embodiment, the aminosilicone corresponding to formula (B) is the following formula (E):

Chemical formula

[0212] Preferably, the alkoxy radical is a methoxy radical.

[0213] The molar ratio of hydroxy / alkoxy is generally in the range of 1:0.8 to 1:1.1, preferably in the range of 1:0.9 to 1:1, and more specifically 1:0.95.

[0214] The mass average molecular weight (Mw) of the silicone is preferably in the range of 2,000 to 200,000, even more specifically in the range of 5,000 to 100,000, and more specifically in the range of 10,000 to 50,000.

[0215] Commercially available products containing the silicone of structure (D) or (E) may contain one or more other aminosilicones having structures other than formula (D) or (E) in their composition.

[0216] Products containing the amino silicone of structure (D) are sold by the company Wacker under the name Belsil® ADM652.

[0217] Products containing the amino silicone of structure (E) are sold by Wacker under the name Fluid WR 1300® or the name Belsil® ADM LOG 1.

[0218] When these amino silicones are used, one particularly advantageous embodiment involves using them in the form of a water-in-oil emulsion. The water-in-oil emulsion may contain one or more surfactants. The surfactant can be of any nature, but is preferably cationic and / or nonionic. The number average particle diameter of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, especially for the amino silicone of formula (E), a microemulsion with an average particle diameter in the range of 5 nm to 60 nm (including both end values), more particularly in the range of 10 nm to 50 nm (including both end values), is utilized. Thus, according to the present invention, the amino silicone microemulsion of formula (E) sold by the company Wacker under the name Finish CT 96 E® or SLM 28020® can be used.

[0219] According to a fourth embodiment, the amino silicone corresponding to formula (B) has the following formula (F): [Chemical formula] (wherein, -m and n are numbers such that the sum (n + m) ranges from 1 to 2000, particularly from 50 to 150, and n can represent a number from 0 to 1999, particularly from 49 to 149, and m can represent a number from 1 to 2000, particularly from 1 to 10, -A represents a linear or branched alkylene radical having 4 to 8 carbon atoms, preferably 4 carbon atoms) is selected from silicone. This radical is preferably linear.

[0220] The mass average molecular weight (Mw) of these amino silicones is preferably in the range of 2,000 to 1,000,000, more particularly in the range of 3,500 to 200,000.

[0221] Another silicone corresponding to formula (B) is, for example, Xiameter MEM 8299 Emulsion from Dow Corning (INCI name: amodimethicone and trideceth-6 and cetrimonium chloride).

[0222] According to the fifth embodiment, the amino silicone corresponding to formula (B) is the following formula (G):

Chemical formula

[0223] The mass average molecular weight (Mw) of these amino silicones is preferably in the range of 500 to 1,000,000, even more particularly in the range of 1,000 to 200,000.

[0224] The silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.

[0225] c) Formula (H):

Chemical formula

[0226] Such amino silicones are particularly described in US Patent No. 4,185,087.

[0227] d) Formula (I):

Chemical formula

[0228] These silicones are described, for example, in European Patent Application Publication No. A0530974.

[0229] e) Formula (J):

Chemical formula

[0230] f) (AB)n type multi-block polyoxyalkylene amino silicone (A is a polysiloxane block and B is a polyoxyalkylene block containing at least one amine group).

[0231] The silicone preferably has the following general formula: [-(SiMe2O)xSiMe2-R-N(R’’)-R’-O(C2H4O) a (C3H6O) b -R’-N(H)-R-] or alternatively, [-(SiMe2O)xSiMe2-R-N(R’’)-R’-O(C2H4O)a(C3H6O)b-] (wherein, -a is an integer in the range of 1 or more, preferably 5 to 200, more specifically 10 to 100, -b is an integer in the range of 0 to 200, preferably 4 to 100, more specifically 5 to 30, -x is an integer in the range of 1 to 10000, more specifically 10 to 5000, -R’’ is a hydrogen atom or methyl, -R is the same or different and represents a linear or branched divalent C2-C hydrocarbon radical optionally containing one or more heteroatoms such as oxygen, 12 preferably, R represents an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical, and preferentially, R represents a -CH2CH2CH2OCH2CH(OH)CH2- radical, -R’ is the same or different and represents a linear or branched divalent C2-C hydrocarbon radical optionally containing one or more heteroatoms such as oxygen, 12 preferably, R’ represents an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a -CH2CH2CH2OCH2CH(OH)CH2- radical, and preferentially, R’ represents a -CH(CH3)-CH2-) and is formed from repeating units having

[0232] The siloxane block preferably represents 50 mol% to 95 mol%, more specifically 70 mol% to 85 mol% based on the total mass of the silicone.

[0233] The amine content is preferably 0.02 to 0.5 meq / g, more specifically 0.05 to 0.2 in a solution containing 30% of the copolymer in dipropylene glycol.

[0234] The mass average molecular weight (Mw) of the silicone is preferably 5000 to 1000000, more specifically 10000 to 200000.

[0235] In particular, silicones sold under the name Silsoft A-843 or Silsoft A+ from Momentive can be mentioned.

[0236] g) and their mixtures.

[0237] Preferably, the amino silicone of formula (B) is selected from the amino silicones corresponding to formula (E).

[0238] Preferably, the dyeing composition comprises at least one amino silicone having the INCI name amodimethicone, preferably introduced in the form of an emulsion or microemulsion together with a surfactant.

[0239] Preferably, the dyeing composition comprises at least one amino silicone having the INCI name amodimethicone as an emulsion or microemulsion together with a surfactant having the INCI names trideceth-5 and trideceth-10.

[0240] The silicone can be present in a total amount in the range of 0.01% to 20% by mass, preferably 0.05% to 15% by mass, more preferably 0.1% to 10% by mass, and even more preferably 0.5% to 5% by mass based on the total mass of the dyeing composition.

[0241] The amino silicone can be present in a total amount in the range of 0.01% to 20%, preferably 0.05% to 15%, more preferably 0.1% to 10%, and even more preferably 0.5% to 5% by mass based on the total mass of the dyeing composition.

[0242] Associative polymer The composition for dyeing keratinous hair fibers, used in connection with the color removal process according to the invention, can also comprise at least one associative polymer other than the aforementioned non-carboxylic acid anionic thickener.

[0243] It should be recalled that an "associative polymer" is a polymer that can reversibly associate with itself or with other molecules in an aqueous medium.

[0244] More specifically, their chemical structures include at least one hydrophilic zone and at least one hydrophobic zone.

[0245] A "hydrophobic group" means a radical or polymer having a saturated or unsaturated, linear or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably 10 - 30 carbon atoms, particularly 12 - 30 carbon atoms, and more preferably 18 - 30 carbon atoms.

[0246] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, the hydrophobic group can be derived from a fatty alcohol, for example, stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also represent a hydrocarbon-based polymer (e.g., polybutadiene).

[0247] The associative polymer can be nonionic, anionic, cationic or amphoteric.

[0248] Preferably, the associative polymer is selected from anionic associative polymers.

[0249] Among the anionic associative polymers that can be cited are the following: -(a) Those containing at least one hydrophilic unit and at least one fatty chain allyl ether unit, more specifically, those in which the hydrophilic unit is formed from an anionic ethylenically unsaturated monomer, more specifically, those formed from a vinyl carboxylic acid, and most specifically, those formed from acrylic acid or methacrylic acid or a mixture thereof.

[0250] Among these anionic associative polymers, those particularly preferred according to the present invention are polymers formed from 20% to 60% by mass of acrylic acid and / or methacrylic acid, 5% to 60% by mass of lower (meth)acrylic acid alkyl esters, 2% to 50% by mass of fatty chain allyl ethers, and 0% to 1% by mass of a crosslinking agent (a well-known copolymerizable unsaturated polyethylene monomer such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylbisacrylamide).

[0251] Among the latter polymers, particularly preferred is an aqueous 30% emulsion of a crosslinked terpolymer of methacrylic acid, ethyl acrylate, and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), especially a crosslinked terpolymer (40 / 50 / 10) of methacrylic acid, ethyl acrylate, and Steareth-10 allyl ether, which is sold under the names Salcare SC 80 (registered trademark) and Salcare SC 90 (registered trademark) by Ciba.

[0252] -(b) i) at least one hydrophilic unit of an unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit such as an (C 10 ~C 30 ) alkyl ester of an unsaturated carboxylic acid.

[0253] The (C 10 ~C 30 ) alkyl esters of unsaturated carboxylic acids useful in the present invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylic acid esters, namely lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0254] This type of anionic polymer is described and prepared, for example, by U.S. Patent No. 3,915,921 and U.S. Patent No. 4,509,949.

[0255] Among this type of anionic associative polymers, more specifically, those such as the above-mentioned ones, 95% to 60% by mass of acrylic acid (hydrophilic unit), 4% to 40% by mass of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0% to 6% by mass of a crosslinkable monomer, or alternatively 98% to 96% by mass of acrylic acid (hydrophilic unit), 1% to 4% by mass of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by mass of a crosslinkable monomer are used.

[0256] Among the above-mentioned polymers, according to the present invention, the most particularly preferred ones are Pemulen TR1 (registered trademark), Pemulen TR2 (registered trademark), Carbopol 1382 (registered trademark), and more preferably, products sold by Goodrich under the trade name of Pemulen TR1 (registered trademark) and products sold by SEPPIC under the name of Coatex SX (registered trademark).

[0257] Also included is an acrylic acid / lauryl methacrylate / vinyl pyrrolidone terpolymer sold by ISP under the name of Acrylidone LM.

[0258] -(c) maleic anhydride / C30 - C38 α-olefin / alkyl maleate terpolymer, for example, a product sold by Newphase Technologies under the trade name of Performa V 1608 (registered trademark) (maleic anhydride / C30 - C38 α-olefin / isopropyl maleate copolymer).

[0259] -(d) acrylic terpolymers containing the following: i) approximately 20% to 70% by mass of α,β-monoethylenically unsaturated carboxylic acid [A], ii) Approximately 20% to 80% by mass of an α,β-monoethylenically unsaturated non-surfactant monomer other than [A], iii) A nonionic monourethane that is a reaction product of a surfactant having one hydroxyl group and a monoethylenically unsaturated monoisocyanate, in an amount of approximately 0.5% to 60% by mass, For example, the terpolymer described in European Patent Application Publication No. A0173109, more specifically, the terpolymer described in Example 3, namely, an aqueous 25% dispersion of a terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meth-isopropenylbenzyl isocyanate ethoxylate (40 EO).

[0260] -(e) Among these monomers, copolymers containing esters of α,β-monoethylenically unsaturated carboxylic acids and esters of esters of α,β-monoethylenically unsaturated carboxylic acids and oxyalkylated fatty alcohols can be mentioned.

[0261] Preferably, these compounds further contain, as monomers, esters of α,β-monoethylenically unsaturated carboxylic acids and C1-C4 alcohols.

[0262] Examples of this type of compound include Aculyn 22 (registered trademark) sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / oxyalkylated stearyl methacrylate, and also Aculyn 88 sold by Roehm & Haas.

[0263] Advantageously, the associative polymers other than non-carboxylic acid anionic thickeners are selected from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0264] Particularly preferably, the associative polymers are selected from copolymers containing α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids and oxyalkylated fatty alcohols among their monomers.

[0265] Advantageously, the total amount of the associative polymer ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 1% by weight, based on the total weight of the dyeing composition.

[0266] Compound having at least one carboxylic acid group The composition for dyeing keratinous hair fibers used in connection with the decolorization process according to the invention may also contain at least one compound other than the aforementioned associative polymer, having at least one carboxylic acid group.

[0267] "Carboxylic group" means a COOH or COO- functional group, and the counterion of the COO- group can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0268] Preferably, the compound other than the associative polymer having at least one carboxylic acid group is selected from polyurethanes, non-silicone acrylic polymers, silicone acrylic copolymers and mixtures thereof.

[0269] Polyurethanes and acrylic polymers According to a preferred embodiment, the composition for dyeing keratinous hair fibers contains one or more compounds other than the associative polymer having at least one carboxylic acid group, selected from polyurethanes, non-silicone acrylic polymers and mixtures thereof.

[0270] Preferably, the compound other than the associative polymer having at least one carboxylic acid group is in the form of an aqueous dispersion of polymer particles selected from polyurethanes, non-silicone acrylic polymers and mixtures thereof.

[0271] Preferably, the composition for dyeing keratinous hair fibers comprises one or more compounds other than an associative polymer having at least one carboxylic acid group in the form of an aqueous dispersion of polymer particles selected from polyurethanes, non-silicone acrylic polymers, and mixtures thereof.

[0272] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is other than an associative polymer.

[0273] This dispersion can be a simple dispersion in which the cosmetic composition is dispersed in an aqueous medium. Specific examples of the dispersion include latex. The aqueous dispersion of polymer particles can be selected from aqueous dispersions of polyurethane particles.

[0274] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - the following formula (A):

Chemical formula

[0275] Among the dihydroxylated compounds that can be used according to the present invention, in particular, compounds having two hydroxyl groups and a number average molecular weight of approximately 700 to approximately 16,000, preferably approximately 750 to approximately 5,000, can be mentioned. Examples of the dihydroxylated compounds having a high molecular weight include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof.

[0276] Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0277] The polyisocyanate that can be used according to the present invention is particularly selected from organic diisocyanates having a molecular weight of approximately 112 to 1000, preferably approximately 140 to 400.

[0278] Preferably, the polyisocyanate is selected from diisocyanates, and more specifically, those represented by the general formula R2(NCO)2 (wherein, R2 represents a divalent aliphatic hydrocarbon-based group having 4 to 18 carbon atoms, a divalent alicyclic hydrocarbon-based group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group having 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon-based group having 6 to 15 carbon atoms).

[0279] Preferably, R2 represents an organic diisocyanate. As examples of the organic diisocyanate, the following can be particularly selected: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI), such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4'-diisocyanate and its diphenylmethane 2,4-diisocyanate isomer, and optionally a mixture with diphenylmethane 2,2'-diisocyanate, naphthalene 1,5-diisocyanate isomers and mixtures thereof.

[0280] Preferably, the diisocyanate is an aliphatic and alicyclic diisocyanate, more preferably selected from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate and mixtures thereof.

[0281] According to the present invention, "low molecular weight diol" means a diol having a molecular weight of approximately 62 to 700, preferably 62 to 200. These diols may contain an aliphatic group, an alicyclic group or an aromatic group. Preferably, these contain only aliphatic groups.

[0282] Preferably, R3 represents a low molecular weight diol having more than 20 carbon atoms, more preferably ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0283] The low molecular weight diol may optionally contain an ionic or potentially ionic group. Examples of low molecular weight diols containing an ionic or potentially ionic group are described, in particular, in the patent U.S. Patent No. 3,412,054. Compounds of this type are preferably selected from dimethylolbutanoic acid, dimethylolpropionic acid, polycaprolactone diols containing a carboxyl group, and mixtures thereof.

[0284] When low molecular weight diols containing an ionic or potentially ionic group are used, these are preferably used in an amount such that there is less than 0.30 meq of COOH per gram of polyurethane in the polyurethane dispersion.

[0285] The prepolymer is extended by two families of chain extenders. The first group of chain extenders corresponds to compounds of the general formula (B).

[0286] The chain extender of formula (B) is preferably an alkylene diamine such as hydrazine, ethylene diamine, propylene diamine, 1,4-butylene diamine, piperazine; an alkylene oxide diamine such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wis.), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexamethylenediamine, isophorone diamine, 4,4-methylenedi(cyclohexylamine), ether-amines of the DPA series available from Tomah Products, Milton, Wis. such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propanediol, dipropylamine 2-methyl-1,3-propanediol, dipropylamine 1,4-butanediol, dipropylamine 1,3-butanediol, dipropylamine 1,6-hexanediol and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0287] A second group of chain extenders corresponds to compounds of general formula (C). Compounds of this type preferably have an ionic or potentially ionic group and two groups capable of reacting with isocyanate groups. Compounds of this type may optionally contain two groups reacting with isocyanate groups and one group which is ionic or capable of forming an ionic group.

[0288] Ionic or potentially ionic groups can preferably be selected from tertiary or quaternary ammonium groups or groups convertible thereto, carboxyl groups, carboxylate groups, sulfonic acid groups and sulfonate groups. At least partial conversion of groups convertible to salts of tertiary or quaternary ammonium groups may be carried out before or during mixing with water.

[0289] The chain extender of formula (C) is preferably selected from diaminosulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid and mixtures thereof.

[0290] The polyurethane that can be used according to the present invention may optionally also contain a compound (chain terminator) located at each chain end and terminating the chain. This kind of compound is described in particular in US Patent No. 7,445,770 and / or US Patent No. 7,452,770.

[0291] Preferably, the viscosity of the aqueous dispersion of polyurethane particles is less than 2000 mPa·s at 23 °C, more preferably less than 1500, even better less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0 °C.

[0292] Also preferably, the polyurethane (or active substance or dry matter) content of the aqueous polyurethane dispersion is 20% to 60% by mass, more preferably 25% to 55% by mass, even better 30% to 50% by mass based on the mass of the dispersion. This means that the polyurethane content (dry matter) of the aqueous dispersion is preferably 20% to 60% by mass, more preferably 25% to 55% by mass, even better 30% to 50% by mass based on the total mass of the dispersion.

[0293] Also preferably, the glass transition temperature (Tg) of the aqueous dispersion of polyurethane particles is -25 °C or lower, preferably less than -35 °C, more preferably less than -40 °C.

[0294] The polyurethane particles can have an average diameter in the range of up to approximately 1000 nm, for example, approximately 50 nm to approximately 800 nm, and more preferably approximately 100 nm to approximately 500 nm. These particle diameters can be measured using a laser particle size distribution measuring device (for example, Brookhaven BI90).

[0295] Non-limiting examples of the aqueous polyurethane dispersions include those sold under the name Baycusan® by Bayer, for example, Baycusan® C1000 (INCI name: Polyurethane-34), Baycusan® C1001 (INCI name: Polyurethane-34), Baycusan® C1003 (INCI name: Polyurethane-32), Baycusan® C1004 (INCI name: Polyurethane-35), and Baycusan® C1008 (INCI name: Polyurethane-48).

[0296] Aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, for example, Luviset® PUR from BASF), polyurethane of polycarbonate, polyurethane of aliphatic polyester, and aliphatic polyurethane (for example, the Neorez® series from DSM, for example, Neorez® R989, Neorez® and R-2202) are also included.

[0297] According to a particular embodiment, the aqueous dispersion of the polyurethane particles can be selected from the aqueous dispersions of particles of a compound having the INCI name Polyurethane-35 or a compound having the INCI name Polyurethane-34.

[0298] According to a preferred embodiment, the compound other than the associative polymer having at least one carboxylic acid group is in the form of an aqueous dispersion of particles of a non-silicone acrylic polymer, more preferably in the form of an aqueous dispersion of film-forming non-silicone acrylic polymer particles.

[0299] For the purposes of the present invention, "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds known as monomers). This or these units are repeated at least twice, preferably at least three times.

[0300] "Film-forming polymer" means a polymer that can form a macroscopically continuous film, preferably an adhesive film, on a support, particularly on a keratinous material, either alone or in the presence of an auxiliary film-forming agent.

[0301] For the purposes of the present invention, "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylic acid esters and / or (meth)acrylic acid amides.

[0302] Units derived from (meth)acrylic acid monomers of the polymer can optionally be in the form of salts, particularly alkali metal salts, alkaline earth metal salts or ammonium salts or organic base salts.

[0303] (Meth)acrylic acid esters (also known as (meth)acrylates) are preferably alkyl (meth)acrylates, particularly C1-C 30 , preferably C1-C 20 , more preferably C1-C 10 alkyl (meth)acrylates, aryl (meth)acrylates, particularly C6-C 10 aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, particularly C2-C6 hydroxyalkyl (meth)acrylates.

[0304] Among alkyl (meth)acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and cyclohexyl (meth)acrylate may be mentioned.

[0305] Among hydroxyalkyl (meth)acrylates, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate may be mentioned.

[0306] Among aryl (meth)acrylates, benzyl acrylate and phenyl acrylate may be mentioned.

[0307] Particularly preferred (meth)acrylic acid esters are alkyl, preferably C1-C 30 , more preferably C1-C 20 , even more preferably C1-C 10 , even more particularly C1-C4 alkyl (meth)acrylates.

[0308] According to the present invention, the alkyl group of the ester can be fluorinated or further perfluorinated, i.e., some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0309] Examples of (meth)acrylamides include, in addition to (meth)acrylamide, N-alkyl (meth)acrylamides, particularly N-(C2-C12 alkyl) (meth)acrylamides. Among N-alkyl (meth)acrylamides, N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide, and N-undecylacrylamide may be mentioned.

[0310] The acrylic polymer according to the present invention can be a homopolymer or a copolymer, preferably a copolymer, more preferably a copolymer of (meth)acrylic acid and (meth)acrylic acid ester.

[0311] Preferably, the acrylic polymer according to the present invention comprises the following monomers: a) (Meth)acrylic acid, and b) C1-C 30 , more preferably C1-C 20 , even better C1-C 10 , and more particularly one or more units derived from C1-C4 alkyl (meth)acrylate.

[0312] Preferably, the aqueous dispersion of non-silicone acrylic polymer particles does not contain a surfactant.

[0313] "Surfactant" means any agent capable of altering the surface tension between two surfaces.

[0314] Among the acrylic polymers according to the present invention, there may be mentioned copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, in particular copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the polyacrylate-2 cross-polymer sold by Lubrizol under the trade name Fixate Superhold Polymer, or the acrylate copolymer sold by Toagosei Co., Ltd. under the trade name Daitosol 3000VP3, or the acrylate polymer sold by Toagosei Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1.

[0315] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylate ester and / or (meth)acrylamide monomer.

[0316] Examples of additional monomers may include, for example, styrene monomers, especially styrene and α-methylstyrene, preferably styrene.

[0317] In particular, the acrylic polymer is a polymer selected from styrene / (meth)acrylate copolymers, especially copolymers obtained by polymerizing at least one styrene monomer and at least one C1-C 20 , preferably C1-C 10 alkyl (meth)acrylate monomer.

[0318] C1-C 10 The alkyl (meth)acrylate monomer can be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate.

[0319] Examples of non-silicone acrylic polymers include styrene / (meth)acrylate copolymers sold by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F and by Interpolymer under the name Syntran 5760 CG.

[0320] Silicone acrylic copolymer According to a preferred embodiment, the compound other than the associative polymer having at least one carboxylic acid group is selected from silicone acrylic copolymers.

[0321] Preferably, the silicone acrylic copolymer - contains at least one acrylic, methacrylic or croton unit; and - contains at least one polydimethylsiloxane (PDMS) unit.

[0322] For the purposes of the present invention, "polydimethylsiloxane" (also known as PDMS for short) means, according to what is generally recognized, any organosilicon polymer or oligomer having a linear structure with a variable molecular weight, which is obtained by appropriately polymerizing and / or polycondensing functional silanes and is essentially composed of repeating main units (wherein silicon atoms are linked together by oxygen atoms (siloxane -Si -O -Si- bonds)) and contains methyl radicals directly bonded to said silicon atoms via carbon atoms.

[0323] The PDMS chains that can be used to obtain the copolymers used according to the present invention preferably contain at least one polymerizable radical group located at at least one of the ends of the chain, that is, the PDMS can, for example, have polymerizable radical groups at each of the two ends of the chain, or can have one polymerizable radical group at one end of the chain and one trimethylsilyl end group at the other end of the chain.

[0324] "Polymerizable radical group" means a radical that can polymerize with other polymerizable radical groups or monomers. Preferably, the polydimethylsiloxane units contain at least one polymerizable radical group.

[0325] Preferably, the polymerizable radical group contains at least one vinyl group.

[0326] Preferably, the polydimethylsiloxane (PDMS) units contain at least one polymerizable radical group containing at least one vinyl group, preferably at least two polymerizable radical groups containing at least one vinyl group, preferably located at at least one of the ends of the chain.

[0327] As described above, the silicone acrylic copolymer contains at least one acrylic, methacrylic or croton unit, that is, at least one unit containing a carboxylic acid group.

[0328] Preferably, the silicone acrylic copolymer - At least one acrylic, methacrylic or croton unit, and at least one acrylate, methacrylate or vinyl ester unit; and - At least one polydimethylsiloxane (PDMS) unit.

[0329] More preferably, the dyeing composition comprises one or more silicone acrylic copolymers comprising: - At least one unit selected from at least one croton unit and an alkyl crotonate unit, wherein the alkyl radical is a linear or branched saturated radical containing 1 to 20 carbon atoms; a vinyl acetate unit; a vinyl alkyl ester unit wherein the alkyl group is a linear or branched saturated group containing 2 to 20 carbon atoms; and mixtures thereof; and - At least one polydimethylsiloxane (PDMS).

[0330] The "croton unit" means a unit derived from a crotonic acid monomer or a salt thereof.

[0331] The "alkyl crotonate unit" means a unit derived from a crotonic acid ester monomer unit having a linear or branched saturated alkyl radical containing 1 to 20 carbon atoms.

[0332] The "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer unit and having a linear or branched saturated alkyl radical containing 2 to 20 carbon atoms. The "vinyl acetate unit" means a unit derived from a vinyl acetate monomer.

[0333] According to a preferred embodiment, the silicone acrylic copolymer is - At least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a linear or branched saturated radical containing 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, and at least one polydimethylsiloxane (PDMS) unit.

[0334] According to a particularly preferred embodiment, the silicone acrylate copolymer is - At least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a linear or branched saturated radical containing 6 to 16 carbon atoms, at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, and - At least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical containing at least one vinyl group.

[0335] More preferably, the dyeing composition comprises one or more silicone acrylate copolymers comprising: - At least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a linear or branched saturated radical containing 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, and - At least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical containing at least one vinyl group.

[0336] Even more preferably, the dyeing composition comprises one or more silicone acrylate copolymers comprising: - At least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, wherein the alkyl radical is a linear or branched saturated radical containing 6 to 16 carbon atoms, at least one croton unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit, and - At least one polydimethylsiloxane (PDMS) unit containing at least one polymerizable radical group containing at least one vinyl group.

[0337] Among the silicone acrylate copolymers that can be used in connection with the present invention, there is mentioned a compound sold by Wacker Chemie AG under the trade name Belsil® P1101, having the INCI name crotonic acid / vinyl C8-12 isoalkyl ester / VA / bis-vinyl dimethicone crosspolymer.

[0338] Preferably, the dyeing composition comprises at least one aqueous dispersion of non-silicone acrylic polymer particles.

[0339] More preferentially, the dyeing composition comprises at least one aqueous dispersion of non-silicone acrylic polymer particles containing one or more units derived from the following monomers: a) (Meth)acrylic acid, and b) C1-C 30 , more preferentially C1-C 20 , even better C1-C 10 , more specifically C1-C4 alkyl (meth)acrylate.

[0340] Preferably, the acrylic polymer (or active substance or dry matter) content of the aqueous dispersion of non-silicone acrylic polymer particles is 20% to 60% by mass, more preferentially 22% to 55% by mass, even better 25% to 50% by mass based on the mass of the dispersion.

[0341] The total amount of compounds other than the associative polymer having at least one carboxylic acid group is preferably in the range of 0.1% to 35% by mass, more preferably 0.5% to 30% by mass, still better 1% to 25% by mass, and even more preferably 3% to 15% by mass based on the total mass of the dyeing composition.

[0342] The total amount of the aqueous dispersion of particles of a polymer other than the aforementioned associative polymer, selected from polyurethane, non-silicone acrylic polymers, and mixtures thereof, is preferably in the range of 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, still better 1% to 30% by mass, and even more preferably 3% to 20% by mass based on the total mass of the dyeing composition.

[0343] According to a preferred embodiment, the total amount of the aqueous dispersion of particles of a non-silicone acrylic polymer other than the aforementioned associative polymer is preferably in the range of 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, still better 1% to 30% by mass, and even more preferably 3% to 20% by mass based on the total mass of the dyeing composition.

[0344] organic solvent The dyeing composition used in connection with the process according to the present invention may contain one or more organic solvents.

[0345] Examples of organic solvents include lower C1 - C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and monomethyl ether, and in addition aromatic alcohols such as benzyl alcohol or phenoxyethanol and mixtures thereof.

[0346] Preferably, the dyeing composition contains one or more organic solvents selected from C1 - C4 lower alkanols, more preferably ethanol.

[0347] The organic solvent may be present in a total amount of approximately 0.01% to 60% by mass (including the boundary values), preferably 0.05% to 50% by mass, more preferably 0.1% to 40% by mass (including the boundary values) based on the total mass of the dyeing composition. The dyeing composition used in connection with the process according to the present invention is preferably aqueous. The water content may be in the range of 20% to 99% by mass, preferably 30% to 98% by mass, more preferably 40% to 95% by mass based on the total mass of the dyeing composition.

[0348] Additive The composition for dyeing keratinous hair fibers used in connection with the process according to the present invention may contain any conventional adjuvant or additive.

[0349] Among the additives that may be included in the composition, reducing agents, softening agents, antifoaming agents, moisturizing agents, UV screening agents, peptidizing agents, solubilizing agents, fragrances, proteins, vitamins, polymers other than the aforementioned polymers, anionic, cationic, nonionic or amphoteric surfactants, preservatives, oils, waxes and mixtures thereof may be mentioned.

[0350] The composition for dyeing keratinous hair fibers may in particular be in the form of a suspension, dispersion, gel, emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion or a multiple emulsion (W / O / W type or polyol / O / W type or O / W / O type), cream, mousse, stick, vesicle, in particular a dispersion of ionic or nonionic lipids or a two-phase or multiple-phase lotion.

[0351] Based on general knowledge, those skilled in the art can select, in addition to the appropriate delivery form, a method for preparing it, first considering the nature of the components used, in particular their solubility in the carrier, and then considering the intended use of the composition.

[0352] Application of Composition D The process for decolorizing keratinous hair fibers such as hair according to the present invention may also include the step of applying a composition D containing at least one silicone compound containing at least one carboxyl group to the keratinous hair fibers, and the application of the composition D is carried out before the application of the decolorizing composition.

[0353] Preferably, the silicone compound containing at least one carboxylic acid group is a silicone compound other than a silicone acrylate copolymer containing at least one carboxylic acid group and a silicone compound other than the aforementioned aminosilicone.

[0354] "Carboxylic acid group" means COOH or COO - functional group, and the counter ion of the COO - group can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0355] The silicone that can be used can be soluble or insoluble in the composition D, and these can be in the form of oils, waxes, resins or rubbers, and silicone oils and rubbers are preferred.

[0356] Silicones are described in detail, in particular, in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0357] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXVII):

Chemical formula

[0358] In particular, silicone compounds containing at least one carboxylic acid group may be selected from organosiloxanes of the following formula (XXVIII).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0359] Among the organosiloxanes of formula (XXVIII), polydimethylsiloxane (PDMS) having carboxyl end groups, for example, the compound sold under the trade name Silform INX by Momentive (INCI name: bis-carboxydecyl dimethicone), can be mentioned.

[0360] Among the organosiloxanes of formula (XXIX), polydimethylsiloxane (PDMS) having pendant carboxyl groups, for example, the compound sold under the trade name X-22-3701E by Shin-Etsu Chemical Co., Ltd., can be mentioned.

[0361] Among the organosiloxanes of formula (XXX), polydimethylsiloxane (PDMS) having carboxyl end groups, for example, the compound sold under the trade name X-22-3710 by Shin-Etsu Chemical Co., Ltd., can be mentioned.

[0362] Among the organosiloxanes of formula (XXXI), mention may be made of the compound sold under the trade name Grandsil SiW-PCA-10 by Grant Industries (INCI name: Dimethicone (and) PCA Dimethicone (and) Butylene Glycol (and) Decyl Glucoside).

[0363] Silicone compounds containing a carboxyl group may correspond, for example, to the compounds described in European Patent No. 186507 in the name of Chisso Corporation, which is hereby incorporated by reference into the present specification.

[0364] Preferably, the silicone compound containing at least one carboxyl group is selected from organopolysiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX), and mixtures thereof.

[0365] More preferably, the silicone compound containing at least one carboxyl group is the following formula (XXVIII):

Chemical formula

[0366] Advantageously, the total amount of the silicone compound containing at least one carboxylic acid group is in the range of 0.01% to 20% by mass, preferably 0.1% to 15% by mass, more preferably 0.5% to 10% by mass, and even better 1% to 5% by mass, based on the total mass of Composition D.

[0367] Oil Composition D may contain one or more oils other than the silicone compound containing the aforementioned carboxylic acid group.

[0368] Preferably, Composition D contains one or more oils. More preferably, Composition D contains one or more oils selected from alkanes.

[0369] "Oil" means a fatty substance that is liquid at room temperature (25 °C) and atmospheric pressure (760 mmHg, i.e., 1.013×10 5 Pa).

[0370] The oil can be volatile or non-volatile.

[0371] "Volatile oil" means an oil that can evaporate in less than 1 hour at room temperature and atmospheric pressure when in contact with the skin. The volatile oil is a cosmetic volatile oil that is liquid at room temperature. More specifically, the evaporation rate of the volatile oil is 0.01 to 200 mg / cm 2 / min (including both end values) (see the measurement procedure for the evaporation rate described later in the text).

[0372] "Non-volatile oil" means an oil that remains on the skin or keratinous hair fibers at room temperature and atmospheric pressure. More specifically, the evaporation rate of the non-volatile oil is strictly less than 0.01 mg / cm2 / min (see the evaporation rate measurement procedure described later in the text).

[0373] Preferably, the composition contains one or more oils selected from C6-C 16 alkanes and / or mixtures thereof.

[0374] C6-C 16 Regarding C6-C alkanes, these can be straight-chain or branched and optionally cyclic.

[0375] In particular, branched C8-C 16 alkanes, such as C8-C 16 isoalkanes (also known as isoparaffins), isododecane, isodecane or isohexadecane, for example oils sold under the trade names Isopar or Permethyl and mixtures thereof.

[0376] Also included are linear alkanes containing 7 to 15 carbon atoms, particularly 9 to 14 carbon atoms, and more particularly 11 to 13 carbon atoms, preferably of plant origin.

[0377] Examples of linear alkanes suitable for the present invention include n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14) and n-pentadecane (C15) and mixtures thereof, particularly the mixture of n-undecane (C11) and n-tridecane (C13) described in Example 1 of WO 2008 / 155059 pamphlet, which is a patent application by Cognis. In addition to n-dodecane (C12) and n-tetradecane (C14) sold under the product symbols Parafol 12-97 and Parafol 14-97 respectively from Sasol, mixtures thereof are also included.

[0378] Examples of alkanes suitable for the present invention include those described in the patent applications WO 2007 / 068371 pamphlet and WO 2008 / 155059 pamphlet. These alkanes are obtained from fatty alcohols, which in turn are obtained from coconut oil or palm oil.

[0379] According to a particular embodiment, the composition contains isododecane. This type of compound is, for example, the isododecane sold by Ineos under the trade symbol Isododecane.

[0380] Preferably, composition D contains one or more oils selected from C8 - C 16 alkanes, more preferably isododecane, isohexadecane, tetradecane and / or mixtures thereof. More preferably, composition D contains isododecane.

[0381] Composition D may contain one or more oils other than silicone compounds containing carboxylic acid groups, present in a total amount of 30% to 99% by weight, preferably 50% to 99% by weight, more preferably 70% to 99% by weight, based on the total weight of composition D.

[0382] Composition D may contain at least one colorant selected from the pigments, direct dyes and mixtures thereof described above.

[0383] The bleaching composition As described above, the process of bleaching keratinous hair fibers, especially hair, involves applying to the keratinous hair fibers pre - dyed using at least one composition for dyeing keratinous hair fibers as defined above, at least one bleaching composition containing at least one alkyl or alkylene carbonate.

[0384] This depigmenting composition is intended to create a chemical action that alters the integrity of the colored coating formed around the keratinous hair fibers in order to effect the removal of this colored coating from the keratinous hair fibers.

[0385] Alkyl or alkylene carbonate "Alkyl carbonate" means an alkyl or dialkyl carbonate.

[0386] Preferably, the alkyl or alkylene carbonate is C1 - C 30 , preferably a C1 - C6 alkyl carbonate, or C1 - C 30 , preferably a C1 - C6 alkylene carbonate.

[0387] More preferably, the alkyl or alkylene carbonate is selected from alkylene carbonates, even more preferably selected from propylene carbonate, butylene carbonate, pentylene carbonate and mixtures thereof.

[0388] Particularly preferably, the alkyl carbonate or alkylene carbonate is selected from propylene carbonate.

[0389] Advantageously, the total content of the alkyl or alkyl carbonate is in the range of 10% to 60% by weight, preferably 15% to 50% by weight, based on the total mass of the depigmenting composition.

[0390] Glycol ether The depigmenting composition used in connection with the process according to the invention may also contain at least one glycol ether.

[0391] "Glycol ether" means one or more glycol ethers which may or may not contain a hydroxyl group.

[0392] Preferably, the glycol ether has the formula R 11 (-O-CH(CH3)-CH2)n OH (wherein R 11 represents a C1-C 30 , preferably C1-C6, more preferably C1-C4 alkyl radical, and n is 1-50, preferably 2-50, even more preferably 2-10, and preferably 2-5).

[0393] Advantageously, the glycol ether is of the formula CH3(-O-CH(CH3)-CH2) n OH (wherein n is 2-50, preferably 2-10, and more preferably 2-5).

[0394] Particularly preferably, the glycol ether is selected from tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol butyl ether and mixtures thereof, preferably tripropylene glycol methyl ether.

[0395] The total content of the glycol ether can range from 0.1% to 40% by weight, preferably 1% to 30% by weight, and more preferably 5% to 20% by weight, based on the total weight of the decolorizing composition.

[0396] Polyol The decolorizing composition used in connection with the process according to the invention may contain at least one polyol other than the aforementioned glycol ethers.

[0397] For the purposes of the present invention, "polyol" means an organic compound composed of a hydrocarbon chain having at least two free hydroxyl groups (-OH) possessed by different carbon atoms, with one or more oxygen atoms optionally intervening, and this compound can be cyclic or acyclic, straight-chain or branched, and saturated or unsaturated.

[0398] More specifically, the polyol contains 2-30 hydroxyl groups, more preferably 2-10 hydroxyl groups, and even more preferably 2-3 hydroxyl groups.

[0399] The decoloring composition may preferably contain one or more polyols selected from diglycerol, glycerol, propylene glycol, propane-1,3-diol, 1,3-butylene glycol, pentane-1,2-diol, octane-1,2-diol, dipropylene glycol, hexylene glycol, ethylene glycol, polyethylene glycol, sorbitol, sugars such as glucose, and mixtures thereof.

[0400] Particularly preferably, the polyol is propylene glycol.

[0401] The content of the polyol is advantageously in the range of 1% to 70% by mass, preferably 5% to 60% by mass, more preferably 10% to 50% by mass, based on the total mass of the decoloring composition.

[0402] The decoloring composition used in connection with the process according to the present invention may contain water.

[0403] According to another specific embodiment, the decoloring composition does not contain water.

[0404] Furthermore, the above-mentioned additives may be included in the decoloring composition used in connection with the process according to the present invention.

[0405] The decoloring composition used in connection with the process according to the present invention may contain the aforementioned one or more non-carboxylic acid anionic thickeners in a total content in the range of preferably 0.01% to 10% by mass, more preferably 0.1% to 5% by mass, even more preferably 0.2% to 2% by mass, based on the total mass of the composition.

[0406] Tongs for keratinous hair fibers As shown previously, the process for bleaching keratinous hair fibers, especially hair, involves applying to the keratinous hair fibers pre-dyed using a dyeing composition as described previously and bleached with a bleaching composition, a tong having two arms A and B, through which the keratinous hair fiber passes between the arms.

[0407] The tong for keratinous hair fibers, especially hair, can have a joint axis (Z) about which the arms A and B articulate, as described above.

[0408] According to a preferred embodiment, the arms A and B can articulate about the joint axis (Z) and move at an angle towards each other.

[0409] Each of the arms A and B comprises a support part and an active part.

[0410] The support part corresponds to the part for the user to grip the tong. The active part corresponds to the part in contact with the keratinous hair fiber.

[0411] The arms A and B are movable between a separated position where the active parts are spaced apart from each other and a cooperating position where the active parts are close to each other.

[0412] According to a preferred embodiment, the active parts of the arms A and B are arranged opposite to each other.

[0413] According to a preferred embodiment, the arms A and B can articulate about the joint axis (Z) and move at an angle towards each other such that the active parts of the arms A and B contact each other.

[0414] When the active parts of the arms A and B are in contact, the keratinous hair fiber is gripped between the active parts of the arms A and B.

[0415] The active parts of arm A and arm B can be provided with an active surface and an opposing surface, and the active surface has bristles.

[0416] The bristles can be arranged in the form of a tuft of bristles.

[0417] There is free space between the tufts of each bristle.

[0418] Preferably, the active surfaces of arm A and arm B have tufts of bristles and free space.

[0419] The tufts of bristles are generally made of natural materials such as natural silk, or animal hair such as rabbit, wild boar or goat hair.

[0420] Using natural materials to manufacture this type of tongs significantly increases the manufacturing cost. Therefore, tongs have been developed in which the tufts of bristles are made of synthetic hair that substantially reproduces the mechanical properties of tongs with tufts of bristles made of natural hair.

[0421] Each of the active parts of arm A and arm B can include rows of tufts of bristles.

[0422] There is free space between each row of tufts of bristles.

[0423] Preferably, the active surfaces of arm A and arm B have rows of tufts of bristles separated by free space.

[0424] According to a preferred embodiment, the rows of tufts of bristles of the active part are arranged parallel to each other.

[0425] In this embodiment, each row of tufts of bristles is separated by free space.

[0426] Keratinous hair fibers can be arranged between the tufts of bristles so as to form waves. At the cooperating positions of the active parts, the bristles of arm A and arm B are intermingled so as to grip without blocking the keratinous hair fibers.

[0427] Preferably, at the cooperating positions of the active parts of the arms A and B, the rows of the bundles of the arm A are mixed with the rows of the bundles of the bristles of the arm B and grip the keratinous hair fibers without blocking them.

[0428] At the cooperating positions of the arms A and B, the tongs according to the invention can move along the keratinous hair fibers, i.e., from the root to the tip of the keratinous hair fibers, without blocking them.

[0429] By moving the tongs according to the invention along the keratinous hair fibers while maintaining the cooperating positions of the arms A and B, the said bundles of the bristles of the arms A and B are dyed and then decolored to apply a frictional force to the keratinous hair fibers that have been dyed and then decolored in order to remove the remaining colored coating present on the said keratinous hair fibers.

[0430] The frictional force applied to the keratinous hair fibers is 5 N to 20 N.

[0431] The present invention can be better understood by reading the following detailed description and referring to the accompanying drawings.

Brief Description of the Drawings

[0432]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0433] FIG. 1 shows the above-mentioned tong 1 for keratinous hair fibers, especially for hair. The tong 1 comprises two arms A and B, through which the keratinous hair fibers pass.

[0434] Arm A and arm B can perform articulating movements about the articulation axis (Z), and in particular can move angularly towards each other via one or more springs (not shown).

[0435] Considering that arm A and arm B are driven by an external force to move along the keratinous hair fiber, they can cover the keratinous hair fiber.

[0436] Each of arm A and arm B includes a support portion 2 and an active portion 3.

[0437] The active portions 3 of arm A and arm B can be arranged to face each other.

[0438] The two arms A and B can perform articulating movements about the articulation axis (Z), and can move angularly towards each other such that the active portions 3 of arm A and arm B come into contact with each other.

[0439] The said active portions 3 of arm A and arm B include an active surface 4 and an opposing surface 5.

[0440] The active surfaces 4 of arm A and arm B have bristles 6. Preferably, the opposing surfaces of arm A and arm B do not have bristles.

[0441] The bristles can be grouped together into tufts of bristles 6.

[0442] Figure 2 shows the active surfaces 4 of the active portions 3 of arm A and arm B arranged side by side.

[0443] The active surfaces of arm A and arm B have bristles 6, and the said bristles are configured in the form of tufts of bristles 6.

[0444] There may be a free space 8 between the tufts of each bristle 6.

[0445] The active surfaces of arm A and arm B can include rows 7 of tufts of bristles 6.

[0446] There may be a free space 8 between each row 7 of the tufts of the bristles 6.

[0447] The rows 7 of the tufts of the bristles 6 may be parallel to each other.

[0448] Thus, the keratinous hair fibers can be arranged between the tufts of the bristles so as to form waves.

[0449] The rows 7 of the tufts of the bristles 6 on the active surface 4 of the arm A are complementary to the rows 7 of the tufts of the bristles 6 on the active surface 4 of the arm B.

[0450] To use the tongs, the user can place a tuft of keratinous hair fibers between the arm A and the arm B with its active part when the tongs are in the separated position (i.e., the active parts are separated from each other).

[0451] Next, the user applies a pressing force to the tongs so as to bring the tongs to the cooperating position (i.e., bringing the active parts closer to each other).

[0452] At the cooperating position of the active parts, the bristles of the arm A and the arm B are intermingled so as to grip the keratinous hair fibers without blocking them.

[0453] The user can slide the tongs along the tuft of hair, i.e., from the root to the tip of the tuft of hair, while maintaining a specific pressing force.

[0454] The tongs can be repeatedly passed along the tuft of keratinous hair fibers.

[0455] Protocol The composition for dyeing keratinous hair fibers and any of the above composition D can be used on dry or wet keratinous hair fibers, and on any kind of fair or dark-colored, natural or colored, permanently waved, bleached or hair straightened keratinous hair fibers.

[0456] According to a preferred embodiment, the dyeing composition and Composition D are applied simultaneously to keratinous hair fibers.

[0457] According to another preferred embodiment, after the dyeing composition has been applied to the keratinous hair fibers, Composition D is applied to the keratinous hair fibers.

[0458] According to another preferred embodiment, Composition D is applied to the keratinous hair fibers before the composition for dyeing the keratinous hair fibers is applied.

[0459] According to a specific embodiment of the present invention, keratinous hair fibers, such as hair, are washed before applying the composition for dyeing the keratinous hair fibers and any Composition D.

[0460] Preferably, after the dyeing composition has been applied to the keratinous hair fibers and optionally before applying Composition D to the keratinous hair fibers, a washing, rinsing, draining or drying step is carried out.

[0461] The application of the composition for dyeing keratinous hair fibers and any Composition D to the keratinous hair fibers is generally carried out at room temperature (15 °C to 25 °C).

[0462] According to a preferred embodiment, the application of the composition for dyeing keratinous hair fibers and any Composition D to the keratinous hair fibers is carried out at a temperature of 15 °C to 50 °C, more preferably 20 °C to 40 °C.

[0463] After applying the dyeing composition to the keratinous hair fibers, for example before applying Composition D to the keratinous hair fibers, or for example before a washing, rinsing, draining or drying step, it is possible to wait for 1 minute to 6 hours, in particular 1 minute to 2 hours, more specifically 1 minute to 1 hour, more preferably 1 minute to 30 minutes.

[0464] Preferably, there is no leave-on time after applying the dyeing composition to the keratinous hair fibers and before applying Composition D to the keratinous hair fibers.

[0465] After applying the dyeing composition and any composition D, the fibers may be dried, or may be dried, for example, at a temperature of 30°C or higher.

[0466] Thus, the process according to the invention may include a step of applying heat to the keratinous hair fibers using a heating appliance.

[0467] The heat application step of the process of the present invention can be carried out using a hood, a hair dryer, a straightening iron or a curling iron, Climazon, etc.

[0468] Preferably, the step of applying heat in the process of the present invention is carried out using a hair dryer.

[0469] When the process of the present invention includes a step of applying heat to the keratinous hair fibers, the step of applying heat to the keratinous hair fibers is carried out after applying the composition for dyeing the keratinous hair fibers and any composition D to the keratinous hair fibers.

[0470] During the step of applying heat to the keratinous hair fibers, a mechanical action such as combing, brushing or using a hand comb can be applied to the hair bundle.

[0471] When the step of applying heat to the keratinous hair fibers is carried out using a hood-type dryer or a hair dryer, the temperature is preferably 30°C to 110°C, preferentially 50°C to 90°C.

[0472] When the step of applying heat to the keratinous hair fibers is carried out using a straightening iron, the temperature is preferably 110°C to 220°C, preferably 140°C to 200°C.

[0473] In certain variants, the process of the invention comprises a step (b1) of applying heat using a hood dryer, a hair dryer or a crimper, preferably a hair dryer, and a step (b2) of applying heat using a straightening iron or a curling iron, preferably a straightening iron.

[0474] Step (b1) may be carried out before step (b2).

[0475] During the implementation of step (b1), also referred to as the drying step, the keratinous hair fibers may be dried, for example, at a temperature of 30 °C or more. According to certain embodiments, this temperature exceeds 40 °C. According to certain embodiments, this temperature exceeds 45 °C and is less than 110 °C.

[0476] Preferably, when drying the keratinous hair fibers, in addition to the supply of heat, they are dried by using an air flow. By using an air flow during drying in this way, it is possible to improve the separation of the coating of the hair tresses.

[0477] During drying, a mechanical action such as combing, brushing or using a hairbrush may be applied to the hair tresses.

[0478] During the implementation of step (b2), the temperature when sliding the straightening iron or the curling iron may preferably be in the range of 110 °C to 220 °C, preferably 140 °C to 200 °C.

[0479] After the heating step, the shaping step may be carried out, for example, with a corrective iron, and the temperature of the shaping step is between 110 °C and 220 °C, preferably between 140 °C and 200 °C.

[0480] Preferably, the step of applying the dyeing composition to the keratinous hair fibers is repeated several times.

[0481] According to a preferred embodiment, the process of the present invention is a process for decolorizing pre-dyed keratinous hair fibers, and in particular, at the time of use, it includes the steps of immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, and applying the dyeing composition to the keratinous hair fibers. - Composition A contains at least one of the (poly)carbodiimide compounds described above. - Composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0482] According to a preferred embodiment, the process of the present invention is a process for decolorizing pre-dyed keratinous hair fibers, and in particular, at the time of use, it includes the steps of immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, and applying the dyeing composition to the keratinous hair fibers. - Composition A contains at least one of the (poly)carbodiimide compounds described above. - Composition B contains at least one compound having at least one carboxylic acid group other than the associative polymer described above. Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0483] According to another preferred embodiment, the process of the present invention is a process for decolorizing pre-dyed keratinous hair fibers, and in particular, at the time of use, it includes the steps of immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, and applying the dyeing composition to the keratinous hair fibers. - Composition A contains at least one of the (poly)carbodiimide compounds described above. - Composition B contains at least one compound having at least one carboxylic acid group other than the associative polymer described above. Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof. The aforementioned Composition D is preferably applied to keratinous hair fibers before and / or after applying the mixture of Compositions A and B to the keratinous hair fibers, preferably after.

[0484] Preferably, Compositions A and B are mixed preferably less than 15 minutes before application to keratinous hair fibers, more preferably less than 10 minutes before application, even better less than 5 minutes before application.

[0485] The mass ratio of Composition A to Composition B is preferably in the range of 0.1 to 10, more preferably 0.2 to 5, even better 0.5 to 2, and further 0.6 to 1.5.

[0486] In a specific embodiment, the mass ratio of Composition A to Composition B is equal to 1.

[0487] Preferably, Composition A contains at least one of the aforementioned amino silicones.

[0488] Preferably, Composition A contains at least one of the aforementioned non-carboxylic acid anionic thickeners.

[0489] Preferably, Composition B contains at least one of the aforementioned amino silicones.

[0490] Preferably, Composition B contains at least one associative polymer other than the aforementioned non-carboxylic acid anionic thickener as described above.

[0491] Preferably, Composition B contains at least one compound having at least one of the aforementioned carboxylic acid groups other than the associative polymer.

[0492] The total amount of the (poly)carbodiimide compound is preferably in the range of 0.01% to 40% by mass, more preferably 0.1% to 30% by mass, still more preferably 0.5% to 20% by mass, and even more preferably 1% to 12% by mass based on the total mass of Composition A.

[0493] The total amount of the compound having at least one carboxylic acid group is preferably in the range of 2% to 60% by mass, more preferably 5% to 40% by mass, and still more preferably 5% to 20% by mass based on the total mass of Composition B.

[0494] The amino silicone can be present in a total amount in the range of 0.01% to 20%, preferably 0.05% to 15%, more preferably 0.1% to 10%, and even more preferably 0.5% to 5% by mass based on the total mass of Composition A and / or Composition B.

[0495] The non-carboxylic acid anionic thickener can be present in a total amount in the range of 0.01% to 20% by mass, preferably 0.1% to 10% by mass, still more preferably 0.1% to 5% by mass, and even more preferably 0.1% to 3% by mass based on the total mass of Composition A.

[0496] Next, as previously indicated, the process of decolorizing previously dyed keratinous hair fibers according to the present invention involves applying at least one decolorizing composition as defined above to the previously dyed keratinous hair fibers using at least one composition for dyeing keratinous hair fibers as defined above.

[0497] Preferably, the decolorizing composition is left for 30 seconds to 60 minutes, preferably 1 to 40 minutes, more preferably 1 to 30 minutes, and still more preferably 2 to 20 minutes.

[0498] According to a particular embodiment, the process according to the present invention also includes a step of massaging the keratinous hair fibers after application of the decolorizing composition.

[0499] During this massaging step, specific tools such as peeling gloves may be used.

[0500] Preferably, during the massage step, the finger passes along the hair bundle 5 times. The total time for the 5 passes can be in the range of, for example, 30 seconds to 2 minutes per gram of the hair bundle.

[0501] The step of massaging the keratinous hair fibers can be repeated several times, for example 2 times, optionally with an intermediate leave-on time.

[0502] The step of applying the decoloring composition can be repeated several times, optionally with an intermediate rinsing.

[0503] The time between the step of applying the composition for dyeing keratinous hair fibers and the step of applying the decoloring composition can be in the range of several minutes to several days, for example several tens of days. Preferably, the time between the step of applying the composition for dyeing keratinous hair fibers and the step of applying the decoloring composition is in the range of 1 hour to 30 days, more preferably 1 day to 15 days.

[0504] After any massage step, a step of washing the keratinous hair fibers, for example using shampoo, may follow. Then, the keratinous hair fibers may be massaged, rinsed, and dried.

[0505] Preferably, as described above, there is no step of washing, rinsing, draining, or drying the keratinous hair fibers between applying the decoloring composition and applying the tongs.

[0506] Following the application of the decoloring composition as described above, the process according to the invention includes applying the tongs as described above to the keratinous hair fibers.

[0507] The time between the step of applying the decoloring composition and the step of applying the tongs can be in the range of several seconds to several minutes, preferably 30 seconds to 60 minutes, more preferably 1 to 40 minutes, even more preferably 1 to 30 minutes, and even better 2 to 20 minutes.

[0508] Preferably, the aforementioned tongs are applied from the root to the tip of the keratinous hair fiber.

[0509] Preferably, 10 to 150 passes of the tongs as described above are applied along the keratinous hair fiber, and more preferably, 10 to 100 passes of the tongs as described above are applied along the keratinous hair fiber.

[0510] The aforementioned tongs can be applied to wet or dry keratinous hair fibers.

[0511] Preferably, the aforementioned tongs are applied to wet keratinous hair fibers.

[0512] After the step of applying the tongs as described above, a step of washing the keratinous hair fiber using, for example, shampoo may follow. Then, the keratinous hair fiber may be massaged, rinsed, and dried.

[0513] Preferably, the process according to the present invention includes a step of washing the keratinous hair fiber with, for example, shampoo after applying the tongs to the keratinous hair fiber.

[0514] Preferably, the present invention is a process for decolorizing pre-dyed keratinous hair fibers, and in particular, i) applying to the keratinous hair fiber a composition for dyeing the keratinous hair fiber as described above, and then ii) optionally, a leave-on time of 1 to 30 minutes, preferably 1 to 20 minutes, of the dyeing composition on the fiber, and then iii) optionally, a step of washing, rinsing, draining, or drying the fiber, and then iv) optionally, applying to the keratinous hair fiber a composition D containing at least one silicone compound containing at least one carboxylic acid group as described above, and then v) optionally, a leave-on time of 1 to 30 minutes, preferably 1 to 20 minutes, of the composition D on the keratinous hair fiber, and then vi) Optionally, a step of washing, rinsing, draining or drying the keratinous hair fibers vii) Applying the above-described decoloring composition to pre-dyed keratinous hair fibers viii) Optionally, a step of massaging the keratinous hair fibers, preferably the roots of the keratinous hair fibers ix) Optionally, a leave-on time of 1 to 30 minutes, preferably 1 to 20 minutes, of the dyeing composition on the fibers, then x) Applying one or more passes of the above-described tongs to the keratinous hair fibers, then xi) Optionally, a step of washing, rinsing, draining or drying the keratinous hair fibers, is included.

[0515] According to a preferred embodiment, the process for decoloring pre-dyed keratinous hair fibers is in particular i) At the time of use, immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, wherein - Composition A contains at least one (poly)carbodiimide compound as described above - Composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof, then ii) Applying the dyeing composition to the keratinous hair fibers, then iii) Optionally, applying a composition D containing at least one silicone compound containing at least one carboxylic acid group as described above to the keratinous hair fibers, then iv) Applying at least one decoloring composition as described above to the keratinous hair fibers pre-dyed with the dyeing composition, then v) Optionally, a step of massaging the keratinous hair fibers, preferably the roots of the keratinous hair fibers vi) Applying the above-described tongs to the keratinous hair fibers, then vii) Optionally, a step of washing the keratinous hair fibers, for example using a shampoo, is a process for decoloring keratinous hair fibers.

[0516] According to a preferred embodiment, the process for decolorizing pre-dyed keratinous hair fibers comprises, in particular, i) at the time of use, immediately mixing at least two compositions A and B to obtain a composition for dyeing keratinous hair fibers as defined above, - Composition A contains at least one of the (poly)carbodiimide compounds described above, - Composition B contains at least one compound having at least one carboxylic acid group other than the associative polymers described above, Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof, a step, then ii) applying the dyeing composition to the keratinous hair fibers, then iii) optionally, applying a composition D containing at least one silicone compound containing at least one carboxylic acid group as described above to the keratinous hair fibers, then, iv) applying at least one decoloring composition as described above to the keratinous hair fibers pre-dyed with the dyeing composition, then v) optionally, massaging the keratinous hair fibers, preferably the roots of the keratinous hair fibers, vi) applying tongs as described above to the keratinous hair fibers, then vii) optionally, washing the keratinous hair fibers, for example using shampoo, a process for decolorizing keratinous hair fibers.

[0517] Multi-compartment device (kit) The present invention also relates to a device for dyeing and decolorizing keratinous hair fibers such as hair, - a dyeing composition in a first compartment, - at least one of the (poly)carbodiimide compounds described above, - at least one colorant selected from pigments, direct dyes and mixtures thereof, A dyeing composition comprising, - A composition for decolorizing keratinous hair fibers pre-dyed with the said dyeing composition comprising at least one alkyl or alkylene carbonate as defined above in a second compartment; - Relates to an apparatus comprising a plurality of compartments including the aforementioned tongs.

[0518] According to a preferred embodiment, an apparatus for dyeing and decolorizing keratinous hair fibers such as hair - Composition A comprising at least one (poly)carbodiimide compound as described above in a first compartment; - Composition B comprising at least one colorant selected from pigments, direct dyes and mixtures thereof in a second compartment; - A composition for decolorizing keratinous hair fibers pre-dyed with the said dyeing composition comprising at least one alkyl or alkylene carbonate as defined above in a third compartment; - Comprising a plurality of compartments including the aforementioned tongs.

[0519] According to a preferred embodiment, an apparatus for dyeing and decolorizing keratinous hair fibers such as hair - Composition A comprising at least one (poly)carbodiimide compound as described above in a first compartment; - Composition B comprising at least one colorant selected from pigments, direct dyes and mixtures thereof in a second compartment; - A composition for decolorizing keratinous hair fibers pre-dyed with the said dyeing composition comprising at least one alkyl or alkylene carbonate as defined above in a third compartment; - The aforementioned tongs, - Optionally, a composition D comprising at least one silicone compound comprising at least one carboxylic acid group as described above in a fourth compartment. Comprising a plurality of compartments.

[0520] According to a preferred embodiment, an apparatus for dyeing and decolorizing keratinous hair fibers such as hair - Composition A containing at least one of the aforementioned (poly)carbodiimide compounds in the first compartment, and - Composition B containing at least one compound having at least one of the aforementioned carboxylic acid groups other than the associative polymer in the second compartment (Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes, and mixtures thereof), - In the third compartment, a composition for decolorizing keratinous hair fibers pre-stained with the aforementioned dyeing composition containing at least one alkyl or alkylene carbonate as defined above, and - The aforementioned tongs, and - Optionally, in the fourth compartment, Composition D containing at least one silicone compound containing at least one of the aforementioned carboxylic acid groups, comprising a plurality of compartments.

[0521] Here, the present invention will be described more specifically using examples, but these do not limit the scope of the present invention in any way. However, the examples make it possible to support specific features, variants, and preferred embodiments of the present invention.

Examples

[0522] The (poly)carbodiimide of the present invention can be obtained via synthetic methods known to those skilled in the art, starting from commercially available products or reagents that can be synthesized according to chemical reactions also known to those skilled in the art. For example, the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D - 70469 Stuttgart, or US Patent No. 4284730 or Canadian Patent Application No. 2509861 can be mentioned.

[0523] More specifically, the process for preparing the (poly)carbodiimide of the present invention, in the first step, a diisocyanate reagent (1): O=C=N-L1-N=C=O (1) (In formula (1), L1 is as defined above), in the presence of a carboimidation catalyst (2) such as those described in US Patent No. 4,284,730, particularly a phosphorus-based catalyst, particularly phosphine oxide and phosphine sulfoxide, and those selected from diaza- and oxaaza-phospholanes, preferably in an inert atmosphere (nitrogen or argon), particularly preferably in an aprotic polar solvent such as THF, glyme, diglyme, 1,4-dioxane or DMF, at a temperature from room temperature to the reflux temperature of the solvent, preferably at approximately 140 °C, react to obtain a carbodiimide diisocyanate compound (3): O=C=N-L1-(N=C=N-L1) n -N=C=O (3) (In formula (3), L1 and n are as defined above). To deactivate the catalyst, a benzoyl halide such as benzoyl chloride can be added.

[0524] In the second step of this preparation process, when obtaining a "symmetric" (poly)carbodiimide, the compound (3) is reacted with 1 molar equivalent (1 equivalent) of a nucleophilic reagent R1-X1-H, and then with 0.5 equivalent of the reagent H-E-H (wherein R1, X1, and E are as defined above) to obtain the "symmetric" compound (4) according to the present invention: [R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)]2-E (4) (In formula (4), R1, X1, L1, n, and E are as defined above). According to one variant for obtaining compound (4) from (3), it is possible to first add 0.5 equivalent of the reagent H-E-H and then add 1 equivalent of the reagent R1-X1-H.

[0525] When obtaining an "asymmetric" (poly)carbodiimide in the second step of this preparation process, compound (3) is reacted with 1 molar equivalent (1 equivalent) of the nucleophilic reagent R1-X1-H, and then with 1 equivalent of the reagent H-E-H (wherein R1, X1, and E are as defined above), to obtain compound (5): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5) (In formula (5), R1, X1, L1, n, and E are as defined previously).

[0526] According to a variant for obtaining compound (5) from (3), it is possible to first add 1 equivalent of the reagent R1-X1-H and then add 0.5 equivalent of the reagent H-E-H.

[0527] In the third step, compound (5) is reacted with 1 equivalent of compound (6): R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O (6) (This compound (6) is prepared in advance from compound (3’): O=C=N-L1-(N=C=N-L1) z -N=C=O(3’), where in formula (3’), L1 and z are as defined previously, and this is using 1 equivalent of the nucleophilic reagent R2-X2-H having the previously defined L1, R2, X2, and z to obtain the asymmetric compound (7): R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-C(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2(7) (In formula (7), R1, X1, L1, R2, X2, n, z, and E are as defined previously)).

[0528] 1 molar equivalent of the compound O=C=N-L1-(N=C=N-L1) z -N=C=O(3’) is reacted with 1 / w molar equivalent of H-E-H, and then with 1 equivalent of the nucleophilic reagent R2-X2-H to obtain compound (8): H-[E-C(O)-NH-L1-(N=C=N-L1) z w -NH-C(O)-X2-R2(8) (In formula (8), L1, R2, X2, z and E are as defined above, and w is an integer from 1 to 3; more preferably, w = 1) It is also possible to obtain

[0529] This final compound (8) is then reacted with 1 equivalent of compound (4'): R1-X1~C(O)-NH-L1-(N=C=N-L1) n -N=C=O(4') (This compound (4') can be synthesized by reacting 0.5 equivalent of the nucleophilic reagent R1-X1-H with 1 equivalent of compound (3)) By reacting with, the (poly)carbodiimide (9) of the present invention: R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-[E-C(O)-NH-L1-(N=C=N-L1) z w -NH C(O)-X2-R2(9) (In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined above) can be obtained.

[0530] (Poly)carbodiimide compounds and all reaction intermediates and reagents as well can be purified by conventional methods known to those skilled in the art, for example, extraction, precipitation, centrifugation, filtration and / or chromatography using water and water-immiscible organic solvents.

[0531] Example 1: Process for synthesizing (poly)carbodiimide compounds 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phosphole 1-oxide are charged with stirring into a 500 ml three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux tube.

[0532] ​​The reaction medium is heated at 140 °C for 4 hours in nitrogen while monitoring the reaction by the absorption of isocyanate groups at 2200 - 2300 cm -1 and then cooled to 120 °C.

[0533] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4 - butanediol is introduced into the reaction medium while stirring. The reaction is monitored by infrared spectroscopy at 2200 - 2300 cm -1 and the temperature is maintained at 120 °C until the isocyanate groups completely disappear, and then cooled to room temperature.

[0534] After cooling to room temperature, the reaction medium is added dropwise with vigorous stirring to a 500 - ml glass beaker containing 85 g of distilled water to obtain the desired product in the form of a translucent yellow liquid.

[0535] Example 2: The following compositions were prepared: The amounts are expressed as g / 100 g of the starting materials obtained, unless otherwise specified.

[0536] [Table 1]

[0537] [Table 2]

[0538] Composition A and Composition B are mixed at a mass ratio of 50 / 50 to obtain Dyeing Composition C.

[0539] Next, the following Composition D was prepared. The amounts are expressed as g / 100 g of the starting materials obtained.

[0540] [Table 3]

[0541] Decolorizing Composition: In parallel, a decoloring composition according to the present invention was prepared and is described in the following table. The amounts are expressed as g / 100 g of the starting material obtained.

[0542]

Table 4

[0543] Dyeing protocol: Using a small brush, apply the dyeing composition C to a tuft of dry natural hair containing 90% white hair in an amount of 0.8 g of the composition per gram of the tuft. Then, loosen the tuft and dry it with a hair dryer at medium temperature.

[0544] Next, apply the composition D to the said tuft of hair pre-treated with the composition C in an amount of 0.5 g of the composition per gram of the tuft.

[0545] Then, loosen the tuft and dry it with a hair dryer at medium temperature.

[0546] Next, subject the tuft of hair to a process that promotes aging by placing it in an oven at a temperature of 60 °C for 48 hours before applying the decoloring composition.

[0547] This step of accelerated aging makes it possible to simulate the natural aging of the colored coating on the hair in vivo, and this aging corresponds to 2 weeks at room temperature in vivo.

[0548] Protocol for decolorization: Three different processes were carried out to decolor the tuft of hair colored with the composition C+D: - Comparative process 1 in which only the decoloring composition E is applied to the tuft of hair that has been dyed; - Comparative process 2 in which only the tongs as described above are applied to the tuft of hair that has been dyed (Brosse Pince Ceramik Defrisage from Anself); Process 3 according to the invention (Brosse Pince Ceramik Defrisage from Anself), in which the decoloring composition E is applied to the dyed tress of hair, followed by the tongs described above being applied to the tress of hair.

[0549] In Comparative Process 1, the coloring and decoloring composition E is applied to the dyed tress of hair using the fingers, in an amount of 2 g of the composition per 1 g of the tress of hair.

[0550] Then, in order to correctly distribute the composition E over the tress of hair, the tress is combed 6 times using a comb.

[0551] After leaving the tress of hair at room temperature for 4 minutes, the shampoo protocol described below is carried out.

[0552] In Comparative Process 2, 2 g of water per 1 g of the tress of hair is applied to the dyed tress of hair using the fingers.

[0553] Then, in order to accurately distribute the water over the tress of hair, the locks are combed 6 times using a comb.

[0554] Then, the tress of hair is grasped between arm A and arm B of the tongs according to the invention, and then 100 passes of the tongs along the tress of hair from the root to the tip are carried out.

[0555] Then, the shampoo protocol described below is carried out.

[0556] In Process 3 according to the invention, the coloring and decoloring composition E is applied to the dyed tress of hair using the fingers, in an amount of 2 g of the composition per 1 g of the tress of hair.

[0557] Then, in order to correctly distribute the composition E over the tress of hair, the tress is combed 6 times using a comb.

[0558] Then, the tress of hair is grasped between arm A and arm B of the tongs according to the invention, and then 100 passes of the tongs along the tress of hair from the root to the tip are carried out.

[0559] Next, execute the shampoo protocol described below.

[0560] Shampoo protocol: Comb the hair bundle, wet it with water at 35°C, and then pass it through your fingers 5 times for 5 seconds. Then, wring the hair bundle between two fingers to dry it.

[0561] Apply a standard shampoo (Garnier Ultra Doux) uniformly to the dyed hair bundle in an amount of 0.4 g of the standard shampoo per 1 g of the hair bundle, and gently knead it along the longitudinal direction of the hair bundle from the roots to the tips for 15 seconds (6 times).

[0562] Then place the hair bundle in a watch glass and leave it for 1 minute.

[0563] Then, rinse the hair bundle with water while passing it through your fingers (15 times). Then, wring the hair bundle between two fingers to dry it before the next shampoo wash.

[0564] Subsequently, comb the hair bundle and dry it with a hair dryer.

[0565] Results The color persistence of the hair bundle was evaluated in the CIE L*a*b* system using a Minolta Spectrophotometer CM3600A colorimeter (D65 light source, angle 10°, including the specular component).

[0566] In this L*a*b* system, L* represents the color intensity, a* indicates the green / red axis, and b* indicates the blue / yellow axis.

[0567] The color persistence was evaluated by the color difference ΔE between the hair bundles dyed before the decolorization process, and then evaluated after the hair bundles dyed beforehand described above underwent the protocol for decolorization. The lower the value of ΔE, the more persistent the color in terms of the protocol for decolorizing the hair bundles dyed beforehand.

[0568] The ΔE value is obtained according to the following formula.

Number

[0569] In this formula, L*a*b* represents the value measured after dyeing the hair and after the bleaching step, and L0*a0*b0* represents the value measured after dyeing the hair but before the bleaching step.

[0570]

Table 5

[0571] The process for bleaching dyed keratinous hair fibers according to the present invention is observed to have an excellent ability to bleach from keratinous hair fibers as compared to a comparative process.

[0572] Therefore, the process for bleaching from keratinous hair fibers according to the present invention enables efficient bleaching from pre-dyed tresses using a composition for dyeing keratinous hair fibers comprising a (poly)carbodiimide compound and a colorant selected from pigments, direct dyes and mixtures thereof.

Claims

1. - at least one (poly)carbodiimide compound, and - at least one colorant selected from pigments, direct dyes and mixtures thereof, A method for decolorizing keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers, comprising The method comprising i) applying to the keratinous hair fibers pre-dyed with the dyeing composition - at least one decolorizing composition comprising at least one alkyl or alkylene carbonate ; and ii) applying a tong (1) having two arms A and B to the keratinous hair fibers, the keratinous hair fibers passing between the two arms Each of the arms A and B comprises a support part (2) and an active part (3), The arms A and B are movable between a spaced position in which the active parts (3) are spaced apart from each other and a cooperating position in which the active parts (3) are close to each other, The active part (3) comprises an active surface (4) and a facing surface (5), the active surface (4) having bristles (6), In the cooperating position of the active part (3), the bristles (6) of the arms A and B are intermingled so as to grip the keratinous hair fibers without blocking them.

2. The (poly)carbodiimide compound is of the following formula (I): 【Chemical 1】 (wherein -X １ and X ２ each independently represents an oxygen atom O, a sulfur atom S or an NH group, -R １ and R ２ each independently represents a hydrocarbon radical optionally intervened by one or more heteroatoms, preferably a group selected from alkyl, alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane group, and a hydrocarbon radical optionally intervened by one or more heteroatoms and one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acryloalkylsilyl, methacryloalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acryloalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane group, preferably a group selected from alkyl. - n represents an integer in the range of 1 to 1000, - A is a monomer selected from the following compounds: 【Chemical 2】 ) The method according to claim 1, characterized in that it is selected from compounds of the formula (I).

3. The (poly)carbodiimide compound is of the following formula (II): 【Chemical 3】 (wherein -X １ and X ２ each independently represents an oxygen atom O, a sulfur atom S or an NH group, -R １ and R ２ each independently represents a hydrocarbon radical optionally intervened by one or more heteroatoms, - n and z represent integers in the range of 1 to 20, n + z ≧ 2, and w represents an integer in the range of 1 to 3, -L １ is, independently, a divalent C １ -C １８ aliphatic hydrocarbon radical, C ３ -C １５ cycloalkylene radical, C ３ -C １２ heterocycloalkylene group or C ６ -C １４ arylene group and mixtures thereof, and - E is independently -O-R ３ -O-; -S-R ４ -S-; -R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - (wherein, R ３ and R ４ each independently represents a divalent hydrocarbon radical in which one or more heteroatoms may optionally be interposed) -R ５ independently represents a divalent saturated hydrocarbon radical with a covalent bond or one or more heteroatoms intervening optionally, -R ６ is independently selected from a group consisting of a hydrogen atom or a hydrocarbon radical optionally intervened by one or more heteroatoms), the method according to claim 1, characterized in that it is selected from compounds of).

4. The (poly)carbodiimide compound is selected from compounds of the formula (II), wherein -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently selected from a dialkylamino alcohol from which a hydroxyl group has been removed, an alkyl ester of a hydroxycarboxylic acid, and a monoalkyl ether of (poly)alkylene glycol and mixtures thereof, - n and z represent integers in the range of 1 to 20, n + z ≧ 2, and w is equal to 1, - L1 is a divalent C １ ~C １８ aliphatic hydrocarbon radical, C ３ ~C １５ cycloalkylene group, C ３ ~C １２ heterocycloalkylene group or C ６ ~C １４ arylene group and mixtures thereof, selected from - E is independently --O--R ３ --O--; --S--R ４ --S--; --R ５ --N(R ６ )--R ４ --N(R ６ )--R ５ -- (wherein R3 and R4 are independently selected from an arylene radical having one or more heteroatoms optionally intervening therein, a C ６ -C １４ arylene radical, a C ３ -C １２ cycloalkylene radical, a linear or branched C １ -C １８ alkylene radical, and mixtures thereof) -R ５ When it is not a covalent bond, R ５ is selected from an arylene radical in which one or more heteroatoms are optionally interposed, a C ６ ~C １４ arylene radical, a C ３ ~C １２ cycloalkylene radical, a linear or branched C １ ~C １８ alkylene radical, and mixtures thereof, -R ６ represents a group selected from (wherein R ６ is an arylene radical in which one or more heteroatoms are optionally interposed, a C ６ -C １４ cycloalkylene radical, a linear or branched C １ -C １８ alkylene radical, and mixtures thereof). The method according to claim 3, characterized in that. ６ -C １４ arylene radical, C ３ -C １２ cycloalkylene radical, linear or branched C １ -C １８ alkylene radical and mixtures thereof). It should be noted that the original text seems a bit fragmented and might need further context clarification for a more seamless and accurate translation. This translation attempts to make sense of the overall structure based on the provided rules.

5. The (poly)carbodiimide compound is selected from compounds of the formula (II), wherein -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently a monoalkyl ether of a (poly)alkylene glycol from which a hydroxyl group has been removed, - n and z represent integers in the range of 1 to 20, n + z ≧ 2, and w is equal to 1, -L １ is a C ３ -C １５ cycloalkylene radical, - E is independently -O-R ３ -O-; -S-R ４ -S-; -R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - (wherein R ３ and R ４ are independently selected from an arylene radical having one or more heteroatoms optionally intervening therein, a C ６ -C １４ arylene radical, a C ３ -C １２ cycloalkylene radical, a linear or branched C １ -C １８ alkylene radical, and mixtures thereof) -R ５ When it is not a covalent bond, R ５ is selected from an arylene radical in which one or more heteroatoms are optionally interposed, a C ６ ~C １４ arylene radical, a C ３ ~C １２ cycloalkylene radical, a linear or branched C １ ~C １８ alkylene radical, and mixtures thereof, -R ６ represents a group selected from (wherein R is a C to C arylene radical, a C to C cycloalkylene radical, a linear or branched C to C alkylene radical, and mixtures thereof, in which one or more heteroatoms may optionally be interposed). The method according to claim 3 or 4, characterized in that it represents a group selected from the above. ６ to C １４ arylene radical, C ３ to C １２ cycloalkylene radical, linear or branched C １ to C １８ alkylene radical and mixtures thereof). It should be noted that the original text seems a bit fragmented and might need some further context clarification for a more seamless and accurate translation. The translation attempts to make sense of the overall structure and meaning as best as possible.

6. The (poly)carbodiimide compound is selected from compounds of the formula (II), wherein -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently the following formula (VI): R １３ - [O - CH ２ - C(H)(R １４ )] ｑ - (VI) (wherein R １３ represents a C １ -C ４ alkyl group or phenyl, preferably a C １ -C ４ alkyl group, more preferably methyl, R １４ represents a hydrogen atom or a C １ -C ４ alkyl group, preferably a hydrogen atom, and q represents an integer in the range of 4 to 30). represents a compound of -n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, w is equal to 1, -L １ is a C such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ to C １５ cycloalkylene radical, -E is -O-R ３ -O-group (wherein R ３ is a C to which one or more heteroatoms are optionally interposed ６ to C １４ arylene radical, C ３ to C １２ cycloalkylene radical, linear or branched C １ to C １８ alkylene radical and mixtures thereof), characterized in that the method according to any one of claims 3 to 5.

7. The (poly)carbodiimide compound is selected from the compounds of the formula (II), wherein -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently the following formula (VI): R １３ - [O - CH ２ - C(H)(R １４ )] ｑ - (VI) (wherein, R １３ is a C １ - C ４ alkyl group or phenyl, preferably a C １ - C ４ alkyl group, more preferably represents methyl, R １４ is a hydrogen atom or a C １ - C ４ alkyl group, preferably represents a hydrogen atom, and q represents an integer in the range of 4 to 30) represents a compound of -n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, w is equal to 1, -L １ is a C such as cyclopentylene, cycloheptylene, cyclohexylene, and 4,4-dicyclohexylenemethane ３ to C １５ cycloalkylene radical, preferably 4,4-dicyclohexylenemethane, -E is -O-R ３ -O-group (wherein R ３ represents a linear or branched C such as methylene, propylene, butylene, ethylene, etc. in which one or more heteroatoms are optionally interposed １ ~C １８ represents an alkylene radical). The method according to any one of claims 3 to 6, characterized in that.

8. The (poly)carbodiimide compound is the following formula (XII): 【Chemical Formula 4】 (wherein L １ is 4,4-dicyclohexylenemethane, n and z represent integers in the range of 2 to 20, n + z is in the range of 4 to 10, and E is -O-R ３ -O-group (wherein R ３ is a linear or branched C １ to C １８ alkylene radical in which one or more heteroatoms are optionally interposed), and r and s represent integers in the range of 4 to 30), which is selected from the compounds of, the method according to any one of claims 3 to 7.

9. The total amount of the (poly)carbodiimide compound is in the range of 0.01% by mass to 20% by mass, preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, still more preferably 0.5% by mass to 8% by mass, and even better 1% by mass to 6% by mass, based on the total mass of the dyeing composition. The method according to any one of claims 1 to 8, characterized in that.

10. The total amount of the colorant is in the range of 0.001% by mass to 20% by mass, preferably 0.005% by mass to 15% by mass, based on the total mass of the dyeing composition, and preferably the colorant is selected from pigments. The method according to any one of claims 1 to 9, characterized in that.

11. wherein the alkyl or alkylene carbonate is C １ to C ３０ , preferably C １ to C ６ alkyl carbonate or C １ to C ３０ , preferably C １ to C ６ alkylene carbonate, and more preferably, the alkyl or alkylene carbonate is selected from alkylene carbonates, still more preferably propylene carbonate, butylene carbonate, pentylene carbonate, and mixtures thereof, the method according to any one of claims 1 to 10.

12. The total content of the alkyl or alkylene carbonate is in the range of 10% by mass to 60% by mass, preferably 15% by mass to 50% by mass, based on the total mass of the decoloring composition. The method according to any one of claims 1 to 11, characterized in that.

13. The two arms A and B perform articular movement around the articular axis (Z), and move at an angle towards each other so that the active parts (3) of the arms A and B are in contact with each other. The method according to any one of claims 1 to 12, characterized in that.

14. The bristles (6) are preferably arranged in the form of a tuft of bristles made of a natural material, such as natural silk, or animal hair, such as the hair of a squirrel, wild boar or goat. The method according to any one of claims 1 to 13, characterized in that.

15. The active surfaces of the arms A and B have rows (7) of tufts of bristles (6) separated by a free space (8), and the rows (7) of tufts of bristles (6) of the active parts (3) are arranged parallel to each other. The method according to claim 14, characterized in that.

16. The method according to any one of claims 1 to 15, characterized in that it comprises a step of washing the keratinous hair fibers after application of the tongs thereto, for example, by means of shampoo.

17. An apparatus for dyeing and then decolorizing keratinous hair fibers such as hair, - Composition A containing at least one (poly)carbodiimide compound as defined in any one of claims 2 to 8 in a first compartment, - Composition B containing at least one colorant selected from pigments, direct dyes and mixtures thereof in a second compartment, - A composition for decolorizing keratinous hair fibers pre-dyed with the dyeing composition containing at least one alkyl or alkylene carbonate as defined in claim 11 or 12 in a third compartment, - The tongs (1) as defined in any one of claims 1 and 13 to 15, An apparatus comprising a plurality of compartments, including.

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