Use of a composition comprising an alkyl or alkylene carbonate for the decolorization of pre-colored keratinous hair fibers without damaging the keratinous hair fibers

Abstract

The present invention relates to - at least one (poly)carbodiimide compound, and - at least one colorant selected from pigments, direct dyes and mixtures thereof, for use of a composition comprising at least one alkyl or alkylene carbonate for decolorizing keratinous hair fibers without damaging the keratinous hair fibers, from keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers.

Description

Technical Field

[0001] The present invention relates to the specific use of a composition comprising at least one alkyl or alkylene carbonate for decolorizing keratinous hair fibers pre-dyed with a composition for dyeing keratinous hair fibers comprising a (poly)carbodiimide compound and at least one colorant selected from pigments, direct dyes and mixtures thereof.

Background Art

[0002] In the field of dyeing 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, penetrates into the hair fibers, and uses oxidation dyes that generate pigments via an oxidative condensation process. b) Non-permanent, semi-permanent or direct hair dyeing: It does not use an oxidative condensation process and can withstand 4 to 5 shampooing operations. This involves dyeing the keratinous fibers with a dye composition containing direct dyes. c) Temporary hair dyeing: It modifies the original color of the hair, remains from the first shampoo wash until the next shampooing operation, and serves to enhance or correct the already obtained color tone. This may be associated with the "makeup" process.

[0004] Regarding the last-mentioned type of dyeing, a technique using colored polymers produced by grafting one or more dyes having the properties of azo, triphenylmethane, azine, indamine or anthraquinone onto a polymer chain is known. Such colored polymers are not entirely satisfactory, especially with regard to the uniformity of the colored color and its resistance, and needless to say, there are problems related to their production, especially reproducibility.

[0005] Other dyeing methods consist of using pigments. Specifically, when pigments are used on the surface of keratin fibers, since the pigments on the surface hide the original color of the fibers, generally, it becomes possible to achieve coloring that can be recognized even on dark-colored hair.

[0006] Furthermore, after dyeing keratin hair fibers, a composition for decolorization can be applied. Some of these compositions for decolorization may damage the keratin hair fibers. Therefore, these compositions are not satisfactory.

[0007] Therefore, there still exists a need to use a composition for efficiently decolorizing pre-dyed keratin hair fibers with a dye composition without damaging the keratin hair fibers.

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, an object of the present invention is to use a composition for decolorizing pre-dyed keratin hair fibers with a dye composition without damaging the keratin hair fibers.

Means for Solving the Problems

[0009] Therefore, the subject of the present invention is to use a composition containing at least one alkyl or alkylene carbonate for decolorizing pre-dyed keratin hair fibers with at least one composition for dyeing keratin hair fibers without damaging the keratin hair fibers, - at least one (poly)carbodiimide compound, and - at least one colorant selected from pigments, direct dyes, and mixtures thereof.

[0010] ​By using the composition for decolorization according to the present invention, the treated keratinous hair fibers are not damaged, and in particular, have a surface finish of the keratinous hair fibers that is not decomposed and a sufficient content of endogenous lipids.

Mode for Carrying Out the Invention

[0011] Other subjects, features, aspects and advantages of the present invention will become clearer by reading the following description and examples.

[0012] The expression "at least one" used in this description is equivalent to the expression "one or more".

[0013] Unless otherwise specified, the boundary values of the value range are included in that range, especially in the expressions "between ~" and "in the range from ~ to ~".

[0014] The present invention is not limited to the exemplified embodiments. The features of various embodiments may be combined, especially within deformation modes not exemplified.

[0015] Regarding the object of the present invention and unless otherwise indicated, - The "alkyl" radical refers to, for example, a straight-chain or branched-chain saturated radical containing 1 to 20 carbon atoms, - The "aminoalkyl" radical refers to the alkyl radical defined above, where the alkyl radical contains an NH2 radical, - The "hydroxyalkyl" radical refers to the alkyl radical defined above, where the alkyl radical contains an OH group, - The "alkylene" radical represents a straight-chain or branched-chain divalent saturated C2 - C4 hydrocarbon-based group such as methylene, ethylene or propylene, - The "cycloalkyl" or "alicyclic alkyl" radical contains 1 to 3 rings, preferably 2 rings, contains 3 to 24 carbon atoms, particularly 3 to 20 carbon atoms, more specifically 3 to 13 carbon atoms, even more specifically 3 to 12 carbon atoms, preferably 5 to 10 carbon atoms, and is a cyclic saturated monocyclic or bicyclic, preferably monocyclic hydrocarbon-based group, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl. The cycloalkyl radical may be substituted with one or more (C1-C4) alkyl groups such as methyl, and in that 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 may be a preferably tolyl, xylyl or methylnaphthyl in which the aryl radical is substituted with one or more (C1-C4) alkyl groups such as methyl. 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 contains 1 to 5 atoms selected from one or more heteroatoms, preferably O, S or N, and contains 3 to 20 ring members, preferably 5 to 10 ring members, and is a saturated or unsaturated non-aromatic or aromatic monocyclic or polycyclic hydrocarbon-based radical, such as imidazolyl, pyrrolyl and furanyl, etc. - The "heterocycloalkylene" radical is a divalent heterocyclic group having the "heterocyclic" defined above. - The term "aryloxy" radical refers to an aryloxy radical having the "aryl" defined above; - The term "alkoxy" radical refers to an alkyl-oxy radical having the "alkyl" defined above, - The term "acyloxy" radical refers to an ester radical R-C(O)-O- where R is an alkyl group as defined above, - A "reactive" group is a group capable of forming a covalent bond with another identical or different group by a chemical reaction.

[0016] 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.

[0017] "Keratinous hair fibers" means hair. In other words, the expressions "keratinous hair fibers" and "hair" are equivalent in the remainder of the description.

[0018] For the purposes of the present invention, "hair" means head hair. This term does not correspond to body hair, eyebrows or eyelashes.

[0019] Polycarbodiimide compound A composition for dyeing keratinous hair fibers comprises at least one (poly)carbodiimide compound.

[0020] This composition may comprise at least two different (poly)carbodiimide compounds present as a mixture in the composition.

[0021] 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, and more preferably does not exceed 100.

[0022] The "carbodiimide group" means a divalent linear three-atom moiety represented by the general formula -(N=C=N)-.

[0023] The (poly)carbodiimide compound according to the present invention may optionally contain, in its structure, 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 group.

[0024] 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 group.

[0025] According to a particular embodiment, the (poly)carbodiimide compound has the following formula (I):

Chemical formula

Chemical formula

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

Chemical formula

[0027] Preferably, Z1 and Z2 independently represent reactive end groups. More preferably, Z1 and Z2 independently may be selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylylalkylsilyl, methacrylylalkylsilyl, crotonylalkylsilyl, carboxyanhydridealkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydealkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidealkylsilyl, sulfonylalkylsilyl, (meth)acrylylalkyl, crotonylalkyl, alkyl epoxide such as propyl epoxide or butyl epoxide and azacyclopropane groups.

[0028] Such (poly)carbodiimide compounds are sold, for example, under the name Permutex XR or RelcaLink 10 from Stahl B.V., 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 Chemicals.

[0029] Preferably, the (poly)carbodiimide compound is of the following formula (II):

Chemical formula

[0030] The term "hydrocarbon radical" means a saturated or unsaturated straight-chain or branched radical having from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon radical is a saturated straight-chain radical.

[0031] The hydrocarbon radical may contain one or more cyclic groups.

[0032] The hydrocarbon radical may in particular be intervened by one or more heteroatoms selected from O, S or N, and / or may be substituted by 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.

[0033] 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 included in the chain of the hydrocarbon radical, this heteroatom is preferably selected from oxygen O, sulfur S or nitrogen N atoms.

[0034] Preferably, X1 and X2 each independently represent an oxygen atom.

[0035] 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.

[0036] In a preferred embodiment, R1 and R2 are the following groups (i) to (iv): (i) The following formula (III): R7-O-C(O)-C(R8)(H)- (III) (In the formula, 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) of the compound (ii) The following formula (IV): R9-[O-CH2-C(H)(R 10 )] p - (IV) (In the formula, 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, R 10 is a hydrogen atom or methyl, 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 methyl) 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 methyl) of the compound is independently selected from.

[0037] Preferably, R1 and R2 independently represent a compound of formula (VI), R13 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.

[0038] 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.

[0039] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, R 10 is a hydrogen atom or methyl, and p is equal to 1.

[0040] 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.

[0041] According to another alternative embodiment, R1 and R2 are the same and 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, 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.

[0042] Preferably, n represents an integer in the range of 1 to 20, more preferably 2 to 20.

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

[0044] Preferably, w is equal to 1.

[0045] Preferably, w is equal to 1, and n + z represents an integer in the range of 4 to 10.

[0046] Preferably, L1 is a divalent C1-C such as methylene, ethylene, and propylene 18 aliphatic hydrocarbon radical, C3-C such as cyclopentylene, cycloheptylene, and cyclohexylene 15 cycloalkylene radical, C3-C such as imidazolen, pyrrolen, and furanylene 12 heterocycloalkylene group or C6-C such as phenylene 14 arylene group and mixtures thereof.

[0047] 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, and phenylene diisocyanate and mixtures thereof.

[0048] Preferably, L1 is a C3-C 15 cycloalkylene radical or a C6-C 14 arylene group and mixtures thereof, for example, the following formula (VII):

Chemical formula

[0049] Preferably, L1 is the following formula (VIII):

Chemical formula

[0050] According to another embodiment, when L1 is a C6-C 14 arylene group, L1 is not an m-tetramethylxylylene radical represented by the following formula (IX):

Chemical formula

[0051] --O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5- (wherein, R3 and R4 independently represent a divalent hydrocarbon-based radical in which one or more heteroatoms are optionally interposed, -R5 independently represents a covalent bond or a divalent saturated hydrocarbon-based radical in which one or more heteroatoms are optionally interposed, -R6 independently represents a hydrogen atom or a hydrocarbon-based radical in which one or more heteroatoms are optionally interposed) and represents a group selected from Preferably, R3 and R4 are independently selected from C6-C

[0052] arylene radicals such as phenylene in which one or more heteroatoms are optionally interposed, C3-C 14 cycloalkylene radicals such as cyclopropylene and cyclobutylene, and linear or branched C1-C 12 alkylene radicals such as methylene and ethylene, and mixtures thereof. 18 More preferably, R3 and R4 are independently selected from linear or branched C1-C

[0053] alkylene radicals such as methylene, butylene, propylene, and ethylene in which one or more heteroatoms are optionally interposed. 18 When R5 is not a covalent bond, preferably, R5 is optionally a C6-C

[0054] arylene radical such as phenylene in which one or more heteroatoms are optionally interposed, C3-C 14 cycloalkylene radicals such as cyclopropylene and cyclobutylene, and 12Selected from cycloalkylene radicals, linear or branched C1-C alkylene radicals such as methylene and ethylene, and mixtures thereof. 18 Selected from alkylene radicals and mixtures thereof.

[0055] Preferably, R6 is a C6-C arylene radical such as phenylene, in which one or more heteroatoms are optionally interposed, a C3-C cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-C alkylene radical such as methylene and ethylene, and mixtures thereof. 14 Selected from alkylene radicals and mixtures thereof. 12 Selected from cycloalkylene radicals, linear or branched C1-C alkylene radicals such as methylene and ethylene, and mixtures thereof. 18 Selected from alkylene radicals and mixtures thereof.

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

[0057] More preferably, E represents an -O-R3-O- group, and R3 represents a linear or branched C1-C alkylene radical such as methylene, butylene, propylene, and ethylene, in which one or more heteroatoms are optionally interposed. 18 Represents an alkylene radical.

[0058] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from alpha-methylstyryl isocyanate of the following formula (X):

Chemical formula

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

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

[0061] In the present 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 is of 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 of formula (I) or formula (II): -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, preferably monoalkyl ethers of (poly)alkylene glycols excluding hydroxyl groups, and more preferably R 13 represents a C1-C4 alkyl group or phenyl, preferably a C1-C4 alkyl group, and 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, and is a 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, it 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 selected from C3-C 15 cycloalkylene radicals, - When -A is present, it 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 selected from C3-C 15 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 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 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 -R6 is present, it is 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 and is selected from the compounds of

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

[0066] More preferably, the (poly)carbodiimide compound is of formula (II): -X1 and X2 independently represent an oxygen atom, -R1 and R2 are independently monoalkyl ethers of (poly)alkylene glycols from which the 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 cycloalkylene radical, -E is independently --O-R3-O-;-S-R4-S-;-R5-N(R6)-R4-N(R6)-R5- (wherein R3 and R4 are independently 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, R5 is 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, -R6 is 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) representing a group selected from selected from the compounds of

[0067] Even more preferably, the (poly)carbodiimide compound is of formula (II): -X1 and X2 each independently represent an oxygen atom, -R1 and R2 each 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 each represent an integer 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 15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylenemethane, -E is a -O-R3-O- group (wherein R3 is a C6-C 14 arylene radical, a C3-C 12 cycloalkylene radical, a linear or branched C1-C 18 alkylene radical and mixtures thereof, selected from) represents selected from the compounds of

[0068] Even more preferably, the (poly)carbodiimide compound is of formula (II): -X1 and X2 each independently represent an oxygen atom, -R1 and R2 each 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 14represents 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 is a -O-R3-O- group (wherein R3 is a linear or branched C1-C alkylene radical such as methylene, propylene, butylene, ethylene, etc. with one or more heteroatoms optionally intervening) 18 represents) represents and is selected from the compounds of

[0069] According to a preferred embodiment, the (poly)carbodiimide compound is of the following formula (XII):

Chemical formula

[0070] Advantageously, the total amount of the (poly)carbodiimide compound is 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 comprises one or more colorants selected from pigments, direct dyes, and mixtures thereof.

[0072] Preferably, the dyeing composition comprises at least one pigment.

[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 weight, preferably less than 0.01% by weight.

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

[0075] These can be natural or non - natural products of natural origin.

[0076] These pigments can be in the form of pigment powders or pastes. They may or may not be coated.

[0077] The pigment can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacreous pearlescents or glitter flakes, and mixtures thereof.

[0078] 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.

[0079] The pigment can be an organic pigment. "Organic pigment" means any pigment that satisfies the definition in the chapter on organic pigments in Ullmann’s encyclopedia.

[0080] 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.

[0081] In particular, 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.

[0082] Examples of 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: Pigment Yellow 1 (CI 11680); - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105); - Cosmenyl Red R: Pigment Red 4 (CI 12085); - Cosmenyl Carmine FB: Pigment Red 5 (CI 12490); - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319); - Cosmenyl Blue A2R; Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260); - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0083] The pigments according to the present 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 material of an inorganic substance, at least one binder for binding an organic pigment to the core material, and at least one organic pigment covering at least a part of the core material.

[0084] The organic pigment can be a lake. "Lake" means a dye adsorbed on insoluble particles and the aggregate thus obtained remains insoluble during use.

[0085] The inorganic substrate on which the dye is adsorbed is, for example, alumina, silica, calcium sodium borosilicate or calcium aluminum borosilicate and aluminum.

[0086] Among the dyes, carminic acid can be mentioned. 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) can also be mentioned.

[0087] Examples of lakes include products known by the following names: D&C Red 7 (CI 15 850:1).

[0088] The pigments may be pigments having special effects. The term "pigments having special effects" means pigments that generally result in a non-uniform and color appearance (characterized by a specific hue, a specific brilliance, and a specific level of luminance) that varies based on the conditions of observation (light, temperature, angle of observation, etc.). Thereby, they are different from colored pigments that exhibit standard uniform opaque, translucent, or transparent hues.

[0089] There are several types of pigments having special effects: 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.

[0090] Examples of pigments having special effects 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 and especially 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. As pearlescent pigments, there are mentioned pearlescent agents such as 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.

[0091] 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; golden-red pearlescent pigments, especially those sold under the name Sunstone G012 (Gemtone) by BASF; peach-colored pearlescent pigments, especially those sold under the name Tan opale G005 (Gemtone) by BASF; golden-black pearlescent pigments, 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; silver-colored white pearlescent pigments, 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.;

[0092] As a further example of nacreous pearlescent agents, particles comprising a borosilicate substrate coated with titanium oxide can also be mentioned.

[0093] Particles comprising a glass substrate coated with titanium oxide are sold in particular by Toyal under the name Metashine MC1080RY.

[0094] 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) can also be mentioned. Synthetic substrates, for example, multilayer pigments based on alumina, silica, calcium sodium borosilicate, calcium aluminum borosilicate and aluminum etc. can also be envisaged.

[0095] 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 constitute it, 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 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 by appearing shiny, with sufficient intensity.

[0096] The reflective particles can be selected so as not to significantly change the color 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.

[0097] These particles can have various forms, and in particular can be in the form of small plates or small spheres, especially spherical form.

[0098] Regardless of their form, the reflective particles may or may not have a multilayer structure. In the case of a multilayer structure, they can have, for example, at least one layer of a reflective material, especially having a uniform thickness.

[0099] When the reflective particles do not have a multilayer structure, they can be composed of metal oxides, especially titanium oxide or iron oxide obtained by synthesis.

[0100] When the reflective particles have a multilayer structure, they can include, for example, a natural or synthetic substrate, especially a synthetic substrate, at least partially coated with at least one layer of a reflective material, especially at least one metal or metallic material. The substrate can be made from one or more organic materials and / or inorganic materials.

[0101] More specifically, this can be selected from, but not limited to this list, glass, ceramics, graphite, metal oxides, alumina, silica, silicates, especially aluminosilicates and borosilicates and synthetic mica and mixtures thereof.

[0102] The reflective material can include a layer of a metal or metallic material.

[0103] 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.

[0104] As a further example of reflective particles including an inorganic substrate coated with a metal layer, particles including a borosilicate substrate coated with silver can also be mentioned.

[0105] Particles of a small plate-shaped silver-coated glass substrate 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.

[0106] 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.

[0107] Examples include aluminum powder, bronze powder or copper powder coated with SiO2, sold by Eckart under the name Visionaire.

[0108] Also included are 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. Special effect pigments include fluorescent pigments (which are 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.

[0109] 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 or interference effects.

[0110] 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, more preferably from 30 nm to 50 μm.

[0111] The pigment may be dispersed in the composition by a dispersant.

[0112] The dispersant has the effect of protecting the dispersed particles from agglomerate formation or aggregation. This dispersant can be a surfactant, oligomer, polymer or some mixture thereof 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 the continuous medium or soluble in the continuous medium. In particular, 12-hydroxystearic acid, especially esters of 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 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the trade symbol Dehymyls PGPH by Henkel or other polyhydroxystearic acids, for example a product sold under the trade symbol Arlacel P100 by Uniqema and mixtures thereof are used.

[0113] 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.

[0114] The pigment used in the composition may be surface-treated with an organic agent.

[0115] Therefore, the pre-surface-treated pigments useful in connection with the present invention are pigments that have been surface-treated in whole or in part with organic agents to modify their 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 and 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 from these.

[0116] 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.

[0117] 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.

[0118] Preferably, the surface-treated pigments are coated with an organic layer.

[0119] The organic agents for treating the pigments can be deposited on the pigments by evaporating the solvent, by causing a chemical reaction between the molecules of the surface treatment agent, or by forming a covalent bond between the surface treatment agent and the pigment.

[0120] Therefore, the surface treatment can be carried out, for example, by chemically reacting a surface treatment agent with 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.

[0121] Organic agents that covalently bond to the pigment are preferably used.

[0122] 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.

[0123] Preferably, the surface treatment agent for the pigment is the following treatment agent: - PEG-silicone treatment agent, such as the AQ surface treatment agent sold by LCW; - Methicone treatment agent, such as the SI surface treatment agent sold by LCW; - Dimethicone treatment agent, such as the Covasil 3.05 surface treatment agent sold by LCW; - Dimethicone / trimethylsiloxysilicate treatment agent, such as the Covasil 4.05 surface treatment agent sold by LCW; - Magnesium myristate treatment agent, such as the MM surface treatment agent sold by LCW; - Aluminum dimyristate treatment agent, such as the MI surface treatment agent sold by Miyoshi, - Perfluoropolyisopropylmethyl ether treatment agent, such as the FHC surface treatment agent sold by LCW; - Isostearyl sebacate treatment agent, such as the HS surface treatment agent sold by Miyoshi Kasei Co., Ltd.; - Perfluoroalkyl phosphate treatment agent, such as the PF surface treatment agent sold by Daito Kasei Kogyo Co., Ltd.; - Acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment agent, 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 copolymer 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. It is selected from.

[0124] According to a specific embodiment of the present invention, the dispersant is present together with an organic or inorganic pigment in the form of submicron-sized particles.

[0125] "Submicron-sized" or "submicron" means a pigment having a particle diameter micronized by a micronization method and having an average particle diameter of less than 1 micrometer (μm), particularly 0.1 to 0.9 μm, preferably 0.2 to 0.6 μm.

[0126] 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.

[0127] Therefore, the dispersant may have a silicone backbone such as silicone polyether, and an amino silicone type dispersant other than the amino silicone described later. Suitable dispersants include the following: -Aminosilicones, i.e., silicones containing one or more amino groups, for example, 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, for example, Tego® RC 902, Tego® RC 922, Tego® RC 1041, and Tego® RC 1043 sold by Evonik, -Polydimethylsiloxane (PDMS) silicones having carboxylic groups, for example, X-22162 and X-22370 by Shin-Etsu Chemical Co., Ltd., epoxy silicones, for example, 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.

[0128] According to a particular embodiment, the dispersant is of the aminosilicone type other than the aminosilicones described below and is cationic.

[0129] Preferably, the pigment is selected from inorganic pigments, inorganic-organic mixed pigments, or organic pigments.

[0130] 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.

[0131] 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.

[0132] Examples of iron oxides include iron oxides sold under the trade name SunPuro® Red Iron Oxide by Sun Chemical.

[0133] Examples of pearlescent agents include mica and iron oxide sold by Sudarshan Chemical under the trade name Pearlescent Pigment Prestige soft bronze.

[0134] Direct dyes The composition for dyeing keratinous hair fibers may contain one or more direct dyes.

[0135] "Direct dyes" mean natural and / or synthetic dyes other than oxidative dyes. These are dyes that diffusely spread on the surface of the fibers.

[0136] These can be ionic or non-ionic, preferably cationic or non-ionic.

[0137] 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.

[0138] 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 formulas (XIII) to (XVI), -Het⁺ represents a cationic heteroaryl radical that is preferably optionally substituted with at least one (C1-C8) alkyl group such as methyl, and preferably has a cationic charge within the ring, for example, imidazolium, indolium, or pyridinium, etc., -Ar⁺ represents an aryl radical such as phenyl or naphthyl that has a cationic charge outside the ring, preferably ammonium, especially tri(C1-C8) alkylammonium such as trimethylammonium, -Ar is an aryl group, preferably 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 djuridinyl group, -Ar'' is 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 represent a hydrogen atom or preferably an (C1-C8) alkyl group optionally substituted with a hydroxyl 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, especially Ra and Rb represent a hydrogen atom or an (C1-C4) alkyl group optionally substituted with a hydroxyl group, -Q- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.)

[0139] In particular, azo and hydrazono direct dyes having an intra-ring cationic charge of the formulas (XIII) to (XVI) defined above, and more specifically, cationic direct dyes having an intra-ring cationic charge described in International Publication Pamphlet No. WO 95 / 15144, International Publication Pamphlet No. WO 95 / 01772, and European Patent No. 714954, preferably include the following direct dyes: [Chemical formula] (In the formulas (XVII) and (XVIII), -R 1 represents a (C1-C4) alkyl group such as methyl, -R 2 and R 3 are the same or different and each represents a hydrogen atom or a (C1-C4) alkyl group, for example, methyl, -R 4 represents a hydrogen atom or an electron-donating group, for example, optionally substituted (C1-C8) alkyl, optionally substituted (C1-C8) alkoxy, or (di)(C1-C8)(alkyl)amino in which the alkyl group is optionally substituted with a hydroxyl group. In particular, R 4 is a hydrogen atom, -Z represents a CH group or a nitrogen atom, preferably CH, -Q- is an anionic counterion as defined above, in particular a halide such as chloride, etc., or an alkyl sulfate such as methyl sulfate or mesityl, etc.)

[0140] In particular, the dyes of the 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.

[0141] The direct dye may be selected from anionic direct dyes. An anionic direct dye may be a dye generally referred to as an "acid" direct dye due to its affinity for alkaline substances. "Anionic direct dye" means a direct dye 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 its structure. The anionic dye may 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.

[0142] 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 or an alkyl or aryl group, 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 counter ion); -(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 phenylamino or phenyl group); -R’’’-S(O)2-X’- (wherein R’’’ represents an optionally substituted alkyl group 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, where M+ is as defined above; -optionally substituted heteroaryl; preferably benzothiazolyl group; -cycloalkyl, especially cyclohexyl; -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, where 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, and i) R is -NR- as defined above, or ii) represents methylene -C(Ra)(Rb)-, where Ra and Rb, which may be the same or different, each represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom bearing them form a spirocycloalkyl, and 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.

[0143] 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; 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 14is a hydrogen atom, an alkyl group or -C(O)O - , M + group (wherein M + is as defined above), represents, -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 forms a double bond with, -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 formula

[0144] 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; c) Anthraquinone dyes of formulas (XXI) and (XXI');

Chemical formula

[0145] 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; 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 selected from the groups represented, and in particular, R 30 , R 31 and R 32 represent a hydrogen atom, - Rc and Rd are the same or different and each represents 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

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

Chemical formula

[0147] Examples of the dyes of formula (XXIII) include Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50. f) Xanthene dyes of formula (XXIV):

Chemical formula

[0148] 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; g) Indole dyes of formula (XXV): [Chemical formula] (In formula (XXV), R 53 、R 54 、R 55 、R 56 、R 57 、R 58 、R 59 and R 60 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 or 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) represent a group selected from -G represents an oxygen or sulfur atom or an NRe group (wherein Re is as defined above), and in particular, G represents an oxygen atom, -Ri and Rh are the same or different and represent a hydrogen atom or an alkyl group, It is understood that formula (XXV) contains at least one sulfonate radical (O)2S(O-)-, M+ or one carboxylate radical -C(O)O-, M+, preferably sodium sulfonate.)

[0149] An example of the dye of formula (XXV) is Acid Blue 74; h) Quinoline dyes of formula (XXVI): [Chemical formula] (In formula (XXVI), -R 61 represents a hydrogen or halogen atom or an alkyl group, -R 62 , R 63 and R 64 are the same or different and represent a hydrogen atom or an (O)2S(O-)-, M+ group (wherein M+ represents a hydrogen atom or a cationic counterion), or alternatively, R 61 and R 62 or R 61 and R 64 together form a benzoyl group optionally substituted with one or more (O)2S(O-)-, M+ groups (wherein M+ represents a hydrogen atom or a cationic counterion), It is understood that formula (XXVI) contains at least one sulfonate radical (O)2S(O-)-, M+, preferably sodium sulfonate.)

[0150] Examples of dyes of formula (XXVI) include Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0151] Among the natural direct dyes that can be used according to the present invention, there may be mentioned 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, in particular poultices or extracts based on henna dyes, may be used.

[0152] Preferably, the direct dye is selected from anionic direct dyes.

[0153] The colorant may be present in a total amount in the range of 0.001% to 20% by weight, preferably 0.005% to 15% by weight, based on the total weight of the composition for dyeing keratinous hair fibers. Preferably, the colorant is selected from pigments.

[0154] The pigment may be present in a total amount of 0.05% to 20% by weight, preferably 0.1% to 15% by weight, more preferably 0.5% to 10% by weight, based on the total weight of the composition for dyeing keratinous hair fibers.

[0155] The direct dye can be present in a total amount in the range of 0.001% to 10% by weight, preferably 0.005% to 5% by weight, based on the total weight of the composition for dyeing keratinous hair fibers.

[0156] Non-carboxylic acid anionic thickener The composition for dyeing keratinous hair fibers may also contain at least one non-carboxylic acid anionic thickener.

[0157] 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 - )).

[0158] For the purposes of the present invention, a "thickener" is a compound that, when introduced at a concentration of 0.05% by weight based on the total weight 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 by 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).

[0159] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, more preferably anionic polymers having one or more sulfone groups.

[0160] For the purposes of the present invention, an "anionic polymer" means a polymer that contains one or more anionic groups or anionized groups and does not contain a cationic group or cationized group.

[0161] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers comprising at least one ethylenically unsaturated monomer having a sulfone group, in free form or in partially or fully neutralized form.

[0162] These polymers may or may not be crosslinked. They are preferably crosslinked.

[0163] These polymers can be associative or non-associative, preferably non-associative.

[0164] 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.

[0165] More particularly, their chemical structure includes at least one hydrophilic zone and at least one hydrophobic zone.

[0166] A "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.

[0167] 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).

[0168] Ethylenically unsaturated monomers carrying a sulfonic acid group are particularly vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamide(C1~C 22 )alkylsulfonic acid, N-(C1~C 22 )alkyl(meth)acrylamide(C1~C 22) It is selected from alkylsulfonic acids, such as undecylacrylamidomethanesulfonic acid and also its partially or fully neutralized form.

[0169] More preferably, (meth)acrylamide (C1 - C 22 ) alkylsulfonic acids, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2 - acrylamido - 2 - methylpropanesulfonic acid, methacrylamido - 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, and in addition, their partially or fully neutralized forms will be used.

[0170] More specifically, 2 - acrylamido - 2 - methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized form are used.

[0171] Among 2 - acrylamido - 2 - methylpropanesulfonic acid copolymers, partially or fully neutralized cross - linked copolymers of 2 - acrylamido - 2 - methylpropanesulfonic acid and acrylamide are mentioned, and the products described in Example 1 of European Patent No. 503853 may be particularly mentioned, and reference may be made to this document regarding these polymers.

[0172] Copolymers of 2 - acrylamido - 2 - methylpropanesulfonic acid or its salt and hydroxyethyl acrylate, such as the compound sold under the name Sepinov EMT10 by SEPPIC (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer), are also mentioned.

[0173] Associative AMPS polymers are especially C6 - C 22Random associative AMPS polymers modified by reaction with n-monoalkylamines or di-n-alkylamines and those described in International Patent Application Publication No. 00 / 31154 pamphlet (which forms an essential part of the content of the specification) and the like can be selected. These polymers may also include those selected from other ethylenically unsaturated hydrophilic monomers, for example, (meth)acrylic acid derivatives, such as esters with its monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinyl pyrrolidone or mixtures of its compounds.

[0174] Preferred polymers of this type are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0175] These same copolymers may also contain one or more ethylenically unsaturated monomers without aliphatic chains, for example, (meth)acrylic acid derivatives, especially esters obtained by monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinyl pyrrolidone or mixtures of its compounds.

[0176] These copolymers are described in particular in European Patent Application Publication No. A750899 specification, U.S. Patent No. 5089578 specification 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。

[0177] Among these polymers, the following are included: -Crosslinked or non-crosslinked, neutralized or non-neutralized copolymers containing 15% to 60% by mass of AMPS units and 40% to 85% by mass of (C8-C 16 ) alkyl (meth) acrylamide or (C8-C 16 ) alkyl (meth) acrylate units with respect to the polymer, for example, those described in European Patent Application Publication No. A750899; -10 mol% to 90 mol% of acrylamide units, 0.1 mol% to 10 mol% of AMPS units, 5 mol% to 80 mol% of n-(C6-C 18) A terpolymer containing alkyl acrylamide units, for example, those described in U.S. Patent No. 5,089,578.

[0178] Also included are copolymers of fully neutralized AMPS and dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and n-dodecyl methacrylamide, for example, those described in the above Morishima paper.

[0179] 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.

[0180] Advantageously, the total amount of the non-carboxylic acid anionic thickener is in the range of 0.01% to 20% by weight, preferably 0.1% to 10% by weight, more preferably 0.1% to 5% by weight, and even more preferably 0.1% to 3% by weight based on the total mass of the composition for dyeing keratinous hair fibers.

[0181] Silicone The composition for dyeing keratinous hair fibers may also contain at least one silicone.

[0182] The silicone is other than a compound having at least one carboxylic acid group as defined below.

[0183] Preferably, the dyeing composition contains at least one silicone selected from non-amino silicones, amino silicones, and mixtures thereof.

[0184] 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.

[0185] The silicones that can be used can be soluble or insoluble in the dyeing composition, and they may be in the form of oils, waxes, resins or gums, with silicone oils being preferred.

[0186] Silicones are described in detail, in particular, in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0187] Preferably, the dyeing composition contains one or more silicones that are liquid at atmospheric pressure (1.013×10 5 Pa) at 25°C.

[0188] Volatile silicones can have a boiling point of 60°C to 260°C (under atmospheric pressure) and can more particularly be selected from the following: i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5 silicon atoms, such as the following: - Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

[0189] Products sold under the name Volatile Silicone 7207 by Union Carbide or under the name Silbione 70045 V 2 by Rhodia, under the name Volatile Silicone 7158 by Union Carbide or under the name Silbione 70045 V 5 by Rhodia; - Cyclic copolymers of dimethylsiloxane / methylalkylsiloxane type having the following chemical structure:

Chemical formula

[0190] Preferably, they are cyclomethicone.

[0191] Mention may be made of Volatile Silicone FZ 3109 sold by Union Carbide. - A mixture of a cyclic silicone and a silicon-based organic compound, such as a mixture (50 / 50) of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol, and a mixture of octamethylcyclotetrasiloxane and 1,1'-oxy(2,2,2',2',3,3'-hexatrimethylsilyloxy)bisneopentane; ii) Generally, a linear polydialkylsiloxane 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.

[0192] 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 products sold under the name SH 200 by Toray Silicone Co., Ltd. can be mentioned.

[0193] Among non-volatile silicones, polydialkylsiloxanes, especially polydimethylsiloxane (PDMS), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and organopolysiloxanes (or organomodified polysiloxanes or alternatively organomodified silicones) containing one or more organic functional groups generally bonded via a hydrocarbon group in their structure and preferably selected from aryl groups, amine groups, alkoxy groups and polyoxyethylene or polyoxypropylene groups, either alone or as a mixture, can be mentioned. Preferably, the non-volatile silicone is optionally selected from oxyethylenated and oxypropylenated polydimethyl / methylsiloxanes.

[0194] The organically modified silicone may be a polydiarylsiloxane, particularly a polydiphenylsiloxane, and a polyalkylarylsiloxane modified with the above-described organic functional groups. The polyalkylarylsiloxane is particularly selected from linear and / or branched polydimethyl / methylphenylsiloxanes and polydimethyl / diphenylsiloxanes.

[0195] Among the organically modified silicones, organopolysiloxanes including the following may be mentioned: - Polyoxyethylene and / or polyoxypropylene groups optionally containing a C6-C 24 alkyl group, for example, dimethicone copolyol, particularly those sold under the name DC 1248 by Dow Corning or the oils Silwet® L 722, L7500, L77 and L711 from Union Carbide, or (C12) alkyl methicone copolyol, particularly those sold under the name Q2 5200 by Dow Corning; - Substituted or unsubstituted amine groups, particularly C1-C4 aminoalkyl groups, products sold under the names GP4 Silicone Fluid and GP7100 by Genesee, or products sold under the names Q2-8220, DC929 or DC939 by Dow Corning may be mentioned; - 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 a hydroxyalkyl group. - Acryloyloxyalkyl groups; for example, the polyorganosiloxanes described in U.S. Patent No. A-4957732. - Carboxylic acid - type anionic groups, for example, those described in European Patent No. 186507 or alkylcarboxylic acid - type anionic groups, for example, products from Shin - Etsu such as X - 22 - 3701E 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, 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, DC200 with a viscosity of 60000 mm 2 / s; - Viscasil® oils from General Electric and specific oils of the SF series from General Electric (SF 96, SF 18).

[0197] Polydimethylsiloxanes having dimethylsilanol end - groups, known under the name dimethiconol (CTFA), for example, oils of series 48 from Rhodia can also be mentioned.

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

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

[0200] 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 (registered trademark) oil of Rhodia's 70 641 series; - 70633 and 763 series of Rhodosil (registered trademark) oil from Rhodia; - Dow Corning's oil Dow Corning 556 Cosmetic Grade Fluid; - PK series of silicones from Bayer, for example, product PK20; - Silicones of the PN and PH series from Bayer, such as products PN1000 and PH1000; - Specific 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 aminosilicone. "Aminosilicone" means any silicone containing at least one primary, secondary, or tertiary amine, or quaternary ammonium group.

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

[0204] Preferably, the aminosilicones 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 a first embodiment, the amino silicone corresponding to formula (B) is of formula (C):

Chemical formula

[0207] According to a second embodiment, the amino silicone corresponding to formula (B) is the following formula (D): [Chemical formula] (wherein -m and n are numbers such that the sum (n + m) ranges from 1 to 1000, particularly 50 to 250, more particularly 100 to 200, n can represent a number from 0 to 999, particularly 49 to 249, more particularly 125 to 175, and m can represent a number from 1 to 1000, particularly 1 to 10, more particularly 1 to 5, -R1, R2 and R3 are the same or different and represent a hydroxyl or C1 - C4 alkoxy radical, and at least one of the R1 - R3 radicals represents an alkoxy radical) is selected from silicones of .

[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 particularly 0.3:1.

[0210] The mass average molecular weight (Mw) of these silicones is preferably in the range of 2000 to 1000000, more particularly in the range of 3500 to 200000.

[0211] According to a third embodiment, the amino silicone corresponding to formula (B) is the following formula (E): [Chemical formula] (wherein - p and q are numbers such that the sum (p + q) ranges from 1 to 1000, particularly from 50 to 350, and more particularly from 150 to 250, and p can represent a number from 0 to 999, particularly from 49 to 349, and more particularly from 159 to 239, and q can represent a number from 1 to 1000, particularly from 1 to 10, and more particularly from 1 to 5; - R1 and R2 are different and represent a hydroxyl or a C1 - C4 alkoxy radical, and at least one of the R1 radical or the R2 radical represents an alkoxy radical) is selected from silicones of the following 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 particularly is 1:0.95.

[0214] The mass average molecular weight (Mw) of the silicone is preferably in the range of 2000 to 200000, even more particularly in the range of 5000 to 100000, and more particularly in the range of 10000 to 50000.

[0215] Commercially available products containing the silicone of structure (D) or (E) may contain one or more other amino silicones 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 aminosilicones 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 aminosilicone of formula (E), a microemulsion with an average particle diameter in the range of 5 nm to 60 nm (including both end values), more specifically in the range of 10 nm to 50 nm (including both end values), is utilized. Thus, the aminosilicone microemulsion of formula (E) sold by the company Wacker under the name Finish CT 96 E (registered trademark) or SLM 28020 (registered trademark) can be used.

[0219] According to a fourth embodiment, the aminosilicone 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, especially from 50 to 150, and n can represent a number from 0 to 1999, especially from 49 to 149, and m can represent a number from 1 to 2000, especially 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 the silicones. This radical is preferably linear.

[0220] The weight average molecular weight (Mw) of these aminosilicones preferably ranges from 2000 to 1000000, more specifically from 3500 to 200000.

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

[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, and more particularly in the range of 1000 to 200,000.

[0224] The silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning. c) Formula (H):

Chemical formula

[0225] Such amino silicones are described, in particular, in U.S. Patent No. 4,185,087. d) Formula (I):

Chemical formula

[0226] These silicones are described, for example, in European Patent Application Publication No. A0530974; e) Formula (J):

Chemical formula

[0227] 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 - 200, more particularly 10 - 100, - b is an integer in the range of 0 - 200, preferably 4 - 100, more particularly 5 - 30, - x is an integer in the range of 1 - 10000, more particularly 10 - 5000, - R’’ is a hydrogen atom or methyl, - R is the same or different and is a linear or branched divalent C2 - C 12represents a hydrocarbon radical, preferably, R represents an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical, preferentially, R represents a -CH2CH2CH2OCH2CH(OH)CH2- radical, -R’ is the same or different and represents a linear or branched divalent C2-C hydrocarbon optionally containing one or more heteroatoms such as oxygen 12 represents a hydrocarbon radical, preferably, R’ represents an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a -CH2CH2CH2OCH2CH(OH)CH2- radical, preferentially, R’ represents a -CH(CH3)-CH2- radical), and is formed from repeating units having

[0228] The siloxane block preferably represents 50 mol% to 95 mol%, more particularly 70 mol% to 85 mol% based on the total mass of the silicone.

[0229] The amine content is preferably 0.02 to 0.5 meq / g, more particularly 0.05 to 0.2 in a solution containing 30% of the copolymer in dipropylene glycol.

[0230] The mass average molecular weight (Mw) of the silicone is preferably 5000 to 1000000, more particularly 10000 to 200000.

[0231] In particular, silicones sold under the names Silsoft A-843 or Silsoft A+ from Momentive are mentioned. g) and mixtures thereof.

[0232] Preferably, the aminosilicone of formula (B) is selected from aminosilicones corresponding to formula (E).

[0233] Preferably, the dyeing composition comprises at least one aminosilicone having the INCI name amodimethicone, preferably introduced in the form of an emulsion or microemulsion, together with a surfactant.

[0234] Preferably, the dyeing composition comprises at least one aminosilicone having the INCI name amodimethicone, as an emulsion or microemulsion, together with a surfactant having the INCI names trideceth-5 and trideceth-10.

[0235] The silicone may be present in a total amount in the range of 0.01% to 20% by weight, preferably 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, and even more preferably 0.5% to 5% by weight, based on the total weight of the dyeing composition.

[0236] The aminosilicone may 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 weight, based on the total weight of the dyeing composition.

[0237] Associative polymer The composition for dyeing keratinous hair fibers may also comprise at least one associative polymer other than the aforementioned non-carboxylic acid anionic thickener.

[0238] 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.

[0239] More specifically, their chemical structure includes at least one hydrophilic zone and at least one hydrophobic zone.

[0240] 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 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0241] 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).

[0242] The associative polymer can be nonionic, anionic, cationic or amphoteric.

[0243] Preferably, the associative polymer is selected from anionic associative polymers.

[0244] Among the anionic associative polymers that can be mentioned 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.

[0245] Among these anionic associative polymers, particularly preferred are polymers formed from 20% to 60% by mass of acrylic acid and / or methacrylic acid, 5% to 60% by mass of lower alkyl (meth)acrylate, 2% to 50% by mass of fatty chain allyl ether and 0% to 1% by mass of a crosslinking agent (a well-known copolymerizable unsaturated polyethylene monomer, for example, diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylene bisacrylamide).

[0246] Among the latter polymers, in particular, a cross-linked terpolymer of methacrylic acid, ethyl acrylate, and polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular, a cross-linked terpolymer of methacrylic acid, ethyl acrylate, and steareth-10 allyl ether (40 / 50 / 10) in the form of a 30% aqueous emulsion sold under the names Salcare SC 80 (registered trademark) and Salcare SC 90 (registered trademark) by Ciba is most preferred. -(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 and the like.

[0247] 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.

[0248] This type of anionic polymer is described and prepared, for example, in U.S. Patent No. 3,915,921 and U.S. Patent No. 4,509,949.

[0249] Among this type of anionic associative polymer, more specifically, those described above, etc., composed of 95% by mass to 60% by mass of acrylic acid (hydrophilic unit), 4% by mass to 40% by mass of C 10 ~C 30 alkyl acrylate (hydrophobic unit) and 0% by mass to 6% by mass of a cross-linkable monomer, or alternatively 98% by mass to 96% by mass of acrylic acid (hydrophilic unit), 1% by mass to 4% by mass of C 10 ~C 30Those composed of an alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by mass of a crosslinkable monomer are used.

[0250] Among the above 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).

[0251] Also included is an acrylic acid / lauryl methacrylate / vinyl pyrrolidone terpolymer sold by ISP under the name of Acrylidone LM. -(c) Maleic anhydride / C30 - C38 α-olefin / alkyl maleate terpolymers, for example, products sold by Newphase Technologies under the trade name of Performa V 1608 (registered trademark) (maleic anhydride / C30 - C38 α-olefin / isopropyl maleate copolymer); -(d) Acrylic terpolymers containing the following: i) Approximately 20% to 70% by mass of an 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) Approximately 0.5% to 60% by mass of a nonionic monourethane which is a reaction product of a surfactant having one hydroxyl group and a monoethylenically unsaturated monoisocyanate, For example, those described in European Patent Application Publication No. A0173109, more specifically, the terpolymer described in Example 3, i.e., an aqueous 25% dispersion of a terpolymer of methacrylic acid / methyl acrylate / behenyl alcohol dimethyl-meth-isopropenylbenzyl isocyanate ethoxylate (40 EO). -(e) Among these monomers, a copolymer containing an ester of an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol with an oxyalkylenated fatty alcohol.

[0252] Preferably, these compounds further contain, as monomers, an ester of an α,β-monoethylenically unsaturated carboxylic acid and a C1-C4 alcohol.

[0253] Examples of this type of compound include Aculyn 22 (registered trademark) sold by Roehm & Haas, which is a terpolymer of methacrylic acid / ethyl acrylate / stearyl oxyalkylenated methacrylate, and also Aculyn 88 sold by Roehm & Haas.

[0254] Advantageously, the associative polymers other than the non-carboxylic acid anionic thickeners are selected from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0255] Particularly preferably, the associative polymers are selected from copolymers containing an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol among their monomers.

[0256] Advantageously, the total amount of the associative polymer ranges from 0.05% to 15% by mass, preferably from 0.05% to 10% by mass, more preferably from 0.1% to 5% by mass, and even more preferably from 0.1% to 1% by mass, based on the total mass of the dyeing composition.

[0257] Compound having at least one carboxylic acid group The composition for dyeing keratinous hair fibers may also contain at least one compound other than the aforementioned associative polymer, which has at least one carboxylic acid group.

[0258] Preferably, the compound other than the associative polymer having at least one carboxylic acid group is selected from a silicone compound, a polyurethane, an acrylic polymer, and a mixture thereof, each containing at least one carboxylic acid group.

[0259] Polyurethane and acrylic polymer According to a preferred embodiment, the composition for dyeing keratinous hair fibers comprises one or more compounds other than the associative polymer having at least one carboxylic acid group, selected from a polyurethane, an acrylic polymer, and a mixture thereof.

[0260] 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 a polyurethane, an acrylic polymer, and a mixture thereof.

[0261] Preferably, the composition for dyeing keratinous hair fibers comprises one or more compounds other than the associative polymer having at least one carboxylic acid group, in the form of an aqueous dispersion of polymer particles selected from a polyurethane, an acrylic polymer, and a mixture thereof.

[0262] Thus, in this embodiment, the polymer used in the aqueous dispersion of polymer particles is other than the associative polymer.

[0263] This dispersion can be a simple dispersion in which the cosmetic composition is dispersed in an aqueous medium. A specific example of the dispersion is latex.

[0264] The aqueous dispersion of polymer particles can be selected from an aqueous dispersion of polyurethane particles.

[0265] More specifically, the polyurethane present in the aqueous dispersion used in the present invention is - The following formula (A):

Chemical formula

[0266] 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 high molecular weight dihydroxylated compounds include polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compound is selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0267] The polyisocyanates that can be used according to the present invention are particularly selected from organic diisocyanates having a molecular weight of approximately 112 to 1000, preferably approximately 140 to 400.

[0268] Preferably, the polyisocyanate is selected from diisocyanates, more particularly from those of the general formula R2(NCO)2, where 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.

[0269] Preferably, R2 represents an organic diisocyanate. As examples of organic diisocyanates, 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.

[0270] 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.

[0271] 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.

[0272] Preferably, R3 represents a low molecular weight diol having more than 20 carbon atoms, more preferably selected from 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.

[0273] 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 US Pat. 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.

[0274] 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.

[0275] The prepolymer is extended by two families of chain extenders. The first group of chain extenders corresponds to compounds of the general formula (B).

[0276] 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, isophoronediamine, 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.

[0277] 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 reactive with isocyanate groups and one group that is ionic or capable of forming an ionic group.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] 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 more preferably less than 1000. Even more preferably, the glass transition temperature of the aqueous dispersion of polyurethane particles is less than 0 °C.

[0282] 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 more preferably 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 more preferably 30% to 50% by mass with respect to the total mass of the dispersion.

[0283] 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.

[0284] The polyurethane particles can have an average diameter in the range of up to approximately 1000 nm, such as approximately 50 nm to approximately 800 nm, and more preferably approximately 100 nm to approximately 500 nm. These particle sizes can be measured using a laser particle size distribution measuring device (e.g., Brookhaven BI90).

[0285] Non-limiting examples of the aqueous polyurethane dispersion include those sold under the name Baycusan® by Bayer, such as 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).

[0286] Aqueous polyurethane dispersions of isophthalic acid / adipic acid copolymer / hexylene glycol / neopentyl glycol / dimethylol acid / isophorone diisocyanate (INCI name: Polyurethane-1, e.g., Luviset® PUR from BASF), polyurethane of polycarbonate, polyurethane of aliphatic polyester, and aliphatic polyurethane (e.g., the Neorez® series from DSM, such as Neorez® R989, Neorez® and R-2202) are also included.

[0287] According to a preferred embodiment, the aqueous dispersion of polyurethane particles can be selected from an aqueous dispersion of particles of a compound having the INCI name Polyurethane-35 or a compound having the INCI name Polyurethane-34.

[0288] Preferably, 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 an acrylic polymer, and more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0289] 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.

[0290] "Film-forming polymer" means a polymer that can form a macroscopically continuous film, preferably an adhesive film, on a support, in particular on a keratinous material, either alone or in the presence of an auxiliary film-forming agent.

[0291] 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)acrylamides.

[0292] Units derived from the (meth)acrylic acid monomers of the polymer can optionally be in the form of salts, in particular alkali metal salts, alkaline earth metal salts or ammonium salts or organic base salts.

[0293] (Meth)acrylic acid esters (also known as (meth)acrylates) are preferably alkyl (meth)acrylates, in particular C1-C 30 , preferably C1-C 20 , more preferably C1-C 10 alkyl (meth)acrylates, aryl (meth)acrylates, in particular C6-C 10 aryl (meth)acrylates and hydroxyalkyl (meth)acrylates, in particular C2-C6 hydroxyalkyl (meth)acrylates.

[0294] 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 can be mentioned.

[0295] Among hydroxyalkyl (meth)acrylates, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate can be mentioned.

[0296] Among aryl (meth)acrylates, benzyl acrylate and phenyl acrylate can be mentioned.

[0297] 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 specifically C1-C4 alkyl (meth)acrylates.

[0298] According to the present invention, the alkyl group of the ester can be fluorinated or further perfluorinated, that is, some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0299] 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 can be mentioned.

[0300] The acrylic polymer can be a homopolymer or a copolymer, preferably a copolymer, even more preferably a copolymer of (meth)acrylic acid and (meth)acrylic acid ester.

[0301] Preferably, the acrylic polymer 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 comprises one or more units derived from C1-C4 alkyl (meth)acrylate.

[0302] Preferably, the aqueous dispersion of acrylic polymer particles does not contain a surfactant.

[0303] "Surfactant" means any agent that can modify the surface tension between two surfaces.

[0304] Among acrylic polymers, copolymers of (meth)acrylic acid and methyl or ethyl (meth)acrylate, especially copolymers of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or polyacrylate-2 cross-polymer, which is the compound sold by Lubrizol under the trade name Fixate Superhold Polymer, or acrylate copolymer, which is the compound sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000VP3, or acrylate polymer, which is the compound sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000 SLPN-PE1 can be mentioned.

[0305] 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.

[0306] Examples of additional monomers would include, for example, styrene monomers, especially styrene and α-methylstyrene, preferably styrene.

[0307] In particular, the acrylic polymer can be 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.

[0308] 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.

[0309] Examples of the acrylic polymer 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.

[0310] Preferably, the dyeing composition comprises at least one aqueous dispersion of acrylic polymer particles.

[0311] More preferably, the dyeing composition comprises the following monomers: a) (meth)acrylic acid, and b) C1-C 30 , more preferably C1-C 20 , even better C1-C 10 , more specifically at least one aqueous dispersion of acrylic polymer particles containing one or more units derived from C1-C4 alkyl (meth)acrylate.

[0312] Preferably, the acrylic polymer (or active substance or dry matter) content of the aqueous dispersion of acrylic polymer particles is 20% to 60% by mass, more preferably 22% to 55% by mass, even better 25% to 50% by mass based on the mass of the dispersion.

[0313] 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% by mass to 35% by mass, more preferably 0.5% by mass to 30% by mass, still better 1% by mass to 25% by mass, and even more preferably 3% by mass to 15% by mass based on the total mass of the dyeing composition.

[0314] The total amount of the aqueous dispersion of the particles of the polymer other than the aforementioned associative polymer selected from polyurethane, acrylic polymer, and mixtures thereof is preferably in the range of 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 30% by mass, still better 1% by mass to 25% by mass, and even more preferably 2% by mass to 20% by mass based on the total mass of the dyeing composition.

[0315] According to a specific embodiment, the total amount of the aqueous dispersion of the particles of the acrylic polymer other than the aforementioned associative polymer is preferably in the range of 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 30% by mass, still better 1% by mass to 25% by mass, and even more preferably 2% by mass to 20% by mass based on the total mass of the dyeing composition.

[0316] organic solvent The composition for dyeing keratinous hair fibers may contain one or more organic solvents.

[0317] Examples of the organic solvent include lower C1 - C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2 - butoxyethanol, 1,2 - hexanediol, propylene glycol, propylene glycol monomethyl ether, and diethylene glycol monoethyl ether and monomethyl ether, and in addition, aromatic alcohols, particularly aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.

[0318] The organic solvent may be present in a total amount of 0.01% by mass to 60% by mass, preferably 0.05% by mass to 50% by mass based on the total mass of the composition for dyeing keratinous hair fibers.

[0319] The composition for dyeing keratinous hair fibers may be aqueous. The water content may range from 10% to 99% by mass, preferably from 20% to 98% by mass, more preferably from 30% to 95% by mass, based on the total mass of the composition for dyeing keratinous hair fibers.

[0320] Additive The dyeing composition may contain any conventional adjuvant or additive.

[0321] Among the additives that may be contained in the composition, there may be mentioned reducing agents, softening agents, antifoaming agents, moisturizing agents, ultraviolet screening agents, peptidizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, preservatives, non-silicone oils and mixtures thereof.

[0322] The dyeing composition 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.

[0323] Based on general knowledge, a person skilled in the art can select, in addition to the appropriate form of delivery, a method for preparing it, first considering the nature of the components used, in particular their solubility in their carriers, and then considering the intended use of the composition.

[0324] Decolorizing composition As shown above, a composition for decolorizing keratinous hair fibers containing at least one alkyl or alkylene carbonate is used.

[0325] Alkyl or alkylene carbonate The term "alkyl carbonate" means an alkyl or dialkyl carbonate.

[0326] Preferably, the alkyl or alkylene carbonate is C1-C 30 , preferably C1-C6 alkyl carbonate or C1-C 30 , preferably C1-C6 alkylene carbonate, and more preferably, the alkyl or alkylene carbonate is selected from alkylene carbonates, even more preferably propylene carbonate, butylene carbonate, pentylene carbonate, and mixtures thereof.

[0327] Particularly preferably, the alkyl carbonate or alkylene carbonate is selected from propylene carbonate.

[0328] Advantageously, the total content of the alkyl or alkyl carbonate is in the range of 10% to 60% by mass, preferably 15% to 50% by mass, based on the total mass of the decolorizing composition.

[0329] Glycol ether The composition for decolorizing keratinous hair fibers may also contain at least one glycol ether.

[0330] The term "glycol ether" means one or more glycol ethers with or without a hydroxyl group.

[0331] Preferably, the glycol ether is of the formula R 11 (-O-CH(CH3)-CH2) n OH (wherein R 11 represents a C1-C 30 , preferably C1-C6, even more preferably C1-C4 alkyl radical, and n is 1-50, preferably 2-50, even more preferably 2-10, preferably 2-5).

[0332] Advantageously, the glycol ether is of the formula CH3(-O-CH(CH3)-CH2) nThose of OH (wherein n is 2 to 50, preferably 2 to 10, more preferably 2 to 5).

[0333] 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.

[0334] Advantageously, the total content of the glycol ether is at least 5% by mass, preferably 5% to 40% by mass, more preferably 5% to 20% by mass based on the total mass of the decoloring composition.

[0335] Polyol The composition for decolorizing keratinous hair fibers may also contain at least one polyol other than the aforementioned glycol ether.

[0336] 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, saturated or unsaturated.

[0337] More specifically, the polyol contains 2 to 30 hydroxyl groups, more preferably 2 to 10 hydroxyl groups, and even more preferably 2 to 3 hydroxyl groups.

[0338] 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, sugars such as sorbitol, glucose and mixtures thereof.

[0339] Particularly preferably, the polyol is selected from propylene glycol.

[0340] The content of the polyol is advantageously in the range of 10% to 80% by mass, preferably 20% to 70% by mass, more preferably 30% to 60% by mass, based on the total mass of the bleaching composition.

[0341] The composition for bleaching keratinous hair fibers may also contain at least one non-carboxylic acid anionic thickener as described above.

[0342] The composition for bleaching keratinous hair fibers may contain water.

[0343] According to another specific embodiment, the composition for bleaching keratinous hair fibers does not contain water.

[0344] Furthermore, the above-mentioned additives may be included in the bleaching composition.

[0345] Process of application to keratinous hair fibers The process for bleaching keratinous hair fibers may include the application of a composition for bleaching as defined above to keratinous hair fibers pre-dyed with a composition for dyeing keratinous hair fibers as defined above.

[0346] The step of applying composition D containing at least one silicone compound containing at least one carboxylic acid group to keratinous hair fibers may be carried out, and the application of the composition D is carried out before the application of the bleaching composition.

[0347] Preferably, the silicone compound containing at least one carboxylic acid group is a silicone compound other than the aforementioned silicones.

[0348] The term "carboxylic acid group" means COOH or COO - functional group, and COO -The counter ion of the base can be selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0349] The silicone that can be used can be soluble or insoluble in Composition D, and these can be in the form of oil, wax, resin or rubber, and silicone oil and rubber are preferred.

[0350] Silicone is particularly described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.

[0351] Preferably, the silicone compound containing at least one carboxyl group has the following formula (XXVII):

Chemical formula

[0352] In particular, the silicone compound containing at least one carboxylic acid group is an organosiloxane of the following formula (XXVIII):

Chemical formula

Chemical formula

[0353] 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.

[0354] 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.

[0355] 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.

[0356] Among the organosiloxanes of formula (XXXI), 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) can be mentioned.

[0357] The silicone compound containing a carboxyl group may correspond to, for example, the compound described in European Patent No. 186507 in the name of Chisso Corporation, which is hereby incorporated by reference into this specification.

[0358] Preferably, the silicone compound containing at least one carboxyl group is selected from organopolysiloxanes of formula (XXVIII), organopolysiloxanes of formula (XXIX), and mixtures thereof.

[0359] More preferably, the silicone compound containing at least one carboxyl group is the following formula (XXVIII): [Chemical Formula] (In the formula, -R1 independently represents a linear or branched alkyl group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and preferably methyl. -R4 independently represents a linear or branched alkylene group having 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms, in which at least one heteroatom selected from sulfur atoms, nitrogen atoms, oxygen atoms, and mixtures thereof is optionally interposed; or a divalent group R a -(OR b ) x -(wherein R a represents a linear or branched alkylene group having 1 to 4 carbon atoms, R b represents an alkylene group having 1 to 4 carbon atoms, and x is an integer in the range of 1 to 200). -M independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium NR'3 (wherein R' represents, identically or differently, H or an alkyl having 1 to 4 carbon atoms). -n represents an integer in the range of 1 to 1000) and is selected from organosiloxanes.

[0360] 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 more preferably 1% to 5% by mass based on the total mass of Composition D.

[0361] oil Composition D may contain one or more oils other than the silicone compound containing at least one carboxylic acid group described above.

[0362] Preferably, composition D contains one or more oils other than the silicone compound containing at least one carboxylic acid group described above. More preferably, composition D contains one or more oils selected from alkanes.

[0363] "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).

[0364] The oil can be volatile or non-volatile.

[0365] "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 volatile oil has an evaporation rate between 0.01 and 200 mg / cm 2 / min, including the limit value.

[0366] "Non-volatile oil" means an oil that remains on the skin or keratinous fibers at room temperature and atmospheric pressure. More specifically, the non-volatile oil has an evaporation rate strictly less than 0.01 mg / cm2 / min.

[0367] Preferably, the composition contains one or more oils selected from C6-C 16 alkanes and / or mixtures thereof.

[0368] C6-C 16 Regarding alkanes, these can be straight-chain or branched and optionally cyclic.

[0369] In particular, branched C8-C 16 alkanes, such as C8-C 16Examples include isoparaffins (also known as isoparaffins), isododecane, isodecane or isohexadecane, oils sold under the trade names Isopar or Permethyl, for example, and mixtures thereof.

[0370] Also included are linear alkanes, preferably of plant origin, containing 7 to 15 carbon atoms, particularly 9 to 14 carbon atoms, and more particularly 11 to 13 carbon atoms.

[0371] 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, a patent application by Cognis.

[0372] In addition to n-dodecane (C12) and n-tetradecane (C14), sold by Sasol under the product symbols Parafol 12-97 and Parafol 14-97 respectively, mixtures thereof are also included.

[0373] Examples of alkanes suitable for the present invention include those described in WO 2007 / 068371 and WO 2008 / 155059, patent applications. These alkanes are obtained from fatty alcohols, which themselves are obtained from coconut kernel oil or palm oil.

[0374] According to a particular embodiment, the composition contains isododecane. Compounds of this kind are, for example, isododecane sold by Ineos under the product symbol Isododecane.

[0375] Preferably, composition D is C8 - C 16It contains one or more oils selected from alkanes, more preferably isododecane, isohexadecane, tetradecane and / or mixtures thereof.

[0376] More preferably, Composition D contains isododecane.

[0377] Composition D may contain one or more oils other than silicone compounds containing at least one carboxylic acid group, 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.

[0378] Composition D may contain at least one colorant selected from the pigments, direct dyes and mixtures thereof described above.

[0379] Protocol The composition for dyeing keratinous hair fibers described above and any of the above Composition D can be used on dry or wet keratinous hair fibers, and on any type of fair or dark, natural or colored, permanently waved, bleached or hair straightening treated keratinous hair fibers.

[0380] According to a preferred embodiment, the dyeing composition and Composition D are applied simultaneously to the keratinous hair fibers.

[0381] According to another preferred embodiment, after the dyeing composition is applied to the keratinous hair fibers, Composition D is applied to the keratinous hair fibers.

[0382] According to another preferred embodiment, Composition D is applied to the keratinous hair fibers before the composition for dyeing keratinous hair fibers is applied.

[0383] According to a particular embodiment, the keratinous hair fibers are washed before applying the composition for dyeing keratinous hair fibers and any Composition D.

[0384] Preferably, after the dyeing composition has been applied to the keratinous hair fibers and before composition D is applied to the keratinous hair fibers, a washing, rinsing, draining or drying step is carried out.

[0385] More preferably, after the dyeing composition has been applied to the keratinous hair fibers and before composition D is applied to the keratinous hair fibers, a drying step is carried out.

[0386] Application to the keratinous hair fibers may be carried out by any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

[0387] The application of the composition for dyeing keratinous hair fibers and of any composition D to the keratinous hair fibers is generally carried out at room temperature (15 °C to 25 °C).

[0388] After applying the dyeing composition to the keratinous hair fibers, it is possible to wait for 1 minute to 6 hours, in particular 1 minute to 2 hours, more particularly 1 minute to 1 hour, more preferably 1 minute to 30 minutes, for example before applying composition D to the keratinous hair fibers or before a washing, rinsing, draining or drying step.

[0389] 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.

[0390] 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.

[0391] A step of applying heat to the keratinous hair fibers using a heating appliance may be carried out.

[0392] The heat application step of the process can be carried out using a hood, a hair dryer, a straightening iron, a curling iron, a Climazon.

[0393] Preferably, the heat application step of the process is carried out using a hair dryer.

[0394] When carrying out the step of applying heat to keratinous hair fibers, the step of applying heat to keratinous hair fibers is carried out after applying a composition for dyeing keratinous hair fibers and any optional composition D to the keratinous hair fibers.

[0395] During the implementation of the step of applying heat to keratinous hair fibers, mechanical actions such as combing, brushing or using a hairbrush can be applied to the hair bundle.

[0396] When the step of applying heat to keratinous hair fibers is carried out using a hood dryer or a hair dryer, the temperature is preferably 30°C to 110°C, and preferentially 50°C to 90°C.

[0397] When the step of applying heat to keratinous hair fibers is carried out using a straight iron, the temperature is preferably 110°C to 220°C, preferably 140°C to 200°C.

[0398] In a specific variant, in the process of the present invention, the step (b1) of applying heat using a hood dryer, a hair dryer or a climazon, preferably a hair dryer, can be carried out, and the step (b2) of applying heat using a straight iron or a curling iron, preferably a straight iron, can be carried out.

[0399] Step (b1) may be carried out before step (b2).

[0400] During the implementation of step (b1), also referred to as the drying step, the keratinous hair fibers may be dried at a temperature of, for example, 30°C or higher. According to a specific embodiment, this temperature exceeds 40°C. According to a specific embodiment, this temperature exceeds 45°C and is less than 110°C.

[0401] Preferably, when drying keratinous hair fibers, drying is carried out by using an air flow in addition to the supply of heat. By using an air flow during drying in this way, it becomes possible to improve the separation of the coating of the hair bundle.

[0402] During drying, a mechanical action such as combing, brushing or hand-combing can be applied to the hair bundle.

[0403] The temperature when sliding the straight iron or curling iron during the implementation of step (b2) can preferably be in the range of 110 °C to 220 °C, preferably 140 °C to 200 °C.

[0404] 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.

[0405] Preferably, in connection with the prior dyeing of keratinous hair fibers, the following may in particular exist: i) Application of the composition for dyeing the keratinous hair fibers to the keratinous hair fibers, then ii) Optionally, a leave-on time of 1 to 30 minutes, preferably 1 to 20 minutes, of the dyeing composition on the fibers, then iii) Optionally, a step of washing, rinsing, draining or drying the fibers, then iv) Optionally, application of composition D containing at least one silicone compound containing at least one carboxylic acid group as described above to the keratinous hair fibers, 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 fibers, then vi) Optionally, a step of washing, rinsing, draining or drying the keratinous hair fibers.

[0406] Preferably, the step of applying the dyeing composition to the keratinous hair fibers is repeated several times.

[0407] According to a preferred embodiment, in connection with the pre - dyeing of keratinous hair fibers, at the time of use, a step of immediately mixing at least two compositions A and B is carried out to obtain a composition for dyeing the keratinous hair fibers as defined above, and the said dyeing composition is applied to the keratinous hair fibers, - 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, Composition A and / or Composition B optionally contains at least one silicone as defined above.

[0408] According to another preferred embodiment, at the time of use, a step of immediately mixing at least two compositions A and B is carried out to obtain a composition for dyeing the keratinous hair fibers as defined above, and the said dyeing composition is applied to the keratinous hair fibers, - Composition A contains at least one (poly)carbodiimide compound as described above, - Composition B contains at least one compound having at least one carboxylic acid group other than the aforementioned associative polymer, Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof, Composition A and / or Composition B optionally contains at least one silicone as defined above.

[0409] 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, and even better less than 5 minutes before application.

[0410] 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. In a particular embodiment, the mass ratio of composition A to composition B is equal to 1.

[0411] According to a preferred embodiment, in connection with the pre - dyeing of keratinous hair fibers, at the time of use, a step is carried out of immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, and the said dyeing composition is applied 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, Composition A and / or Composition B optionally contains at least one silicone as defined above, The aforementioned Composition D is applied to the keratinous hair fibers before and / or after, preferably after, applying the mixture of Compositions A and B to the keratinous hair fibers.

[0412] According to a preferred embodiment, at the time of use, a step is carried out of immediately mixing at least two compositions A and B to obtain a composition for dyeing the keratinous hair fibers as defined above, and the said dyeing composition is applied 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 aforementioned associative polymer, Composition A and / or Composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof, Composition A and / or Composition B optionally contains at least one silicone as defined above, The aforementioned Composition D is applied to the keratinous hair fibers before and / or after, preferably after, applying the mixture of Compositions A and B to the keratinous hair fibers.

[0413] Next, as previously shown, the process of decolorizing from keratinous hair fibers may involve applying at least one decolorizing composition as defined above to keratinous hair fibers that have been pre-dyed using at least one composition for dyeing keratinous hair fibers as defined above.

[0414] Preferably, the decolorizing composition is then rinsed after any leave-on time, optionally followed by a shampooing operation.

[0415] Preferably, the decolorizing composition is left for 30 seconds to 60 minutes, preferably 1 to 30 minutes, more preferably 1 to 15 minutes, even better 2 to 10 minutes, before rinsing.

[0416] This process may also include a step of massaging the keratinous hair fibers after application of the decolorizing composition.

[0417] During this massaging step, specific tools such as peeling gloves may be used.

[0418] Preferably, during the massaging step, the fingers are passed along the hair tress at least 5 times, for example 6 times. The total time of passing may be in the range of 30 seconds to 2 minutes, for example, for 1 g of hair tress.

[0419] The step of massaging the keratinous hair fibers may be repeated several times, for example 2 times, optionally with an intermediate leave-on time.

[0420] The step of applying the decolorizing composition may be repeated several times, optionally with an intermediate rinse.

[0421] The time between the step of applying the composition for dyeing keratinous hair fibers and the step of applying the decolorizing composition may range from 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 decolorizing composition ranges from 1 hour to 30 days, more preferably from 1 day to 15 days.

[0422] After any massaging step, a step of washing the keratinous hair fibers may follow, for example using shampoo. The keratinous hair fibers may then be massaged, rinsed and dried.

[0423] Here, the present invention will be described more specifically using examples, which in no way limit the scope of the present invention. However, the examples make it possible to support specific features, variants and preferred embodiments of the present invention.

Examples

[0424] 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.

[0425] More specifically, the process for preparing the (poly)carbodiimide of the present invention, in a first step, a diisocyanate reagent (1): O = C = N - L1 - N = C = O (1), (In formula (1), L1 is as defined above) is reacted, in the presence of a carbodiimidation catalyst (2) such as those described in U.S. 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, 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) is obtained. To deactivate the catalyst, a benzoyl halide such as benzoyl chloride may be added.

[0426] In the second step of this preparation process, when obtaining a "symmetric" (poly)carbodiimide, 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 a "symmetric" compound (4): [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) is obtained. According to a 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.

[0427] In the second step of this preparation process, when obtaining an "asymmetric" (poly)carbodiimide, compound (3) is reacted with 1 molar equivalent (1 equivalent) of a 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 above) is obtained.

[0428] According to one variant for obtaining compound (5) from (3), first 1 equivalent of reagent R1-X1-H can be added, and then 0.5 equivalent of reagent H-E-H can be added.

[0429] In the third step, compound (5) reacts 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 compound (3’): O=C=N-L1-(N=C=N-L1) z -N=C=O(3’), (In formula (3’), L1 and z are as defined above, and this is using 1 equivalent of the nucleophile R2-X2-H having L1, R2, X2 and z defined above 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 above) is obtained.

[0430] 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 1 equivalent of the nucleophile 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

[0431] 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.

[0432] (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.

[0433] 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.

[0434] The reaction medium is heated at 140 °C for 4 hours in nitrogen and then cooled to 120 °C while monitoring the reaction by the absorption of isocyanate groups at 2200 - 2300 cm -1 by infrared spectroscopy.​

[0435] 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. By infrared spectroscopy, 2200 - 2300 cm -1 is monitored, and the temperature is maintained at 120 °C until the isocyanate groups completely disappear, and then it is cooled to room temperature.

[0436] 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.

[0437] Example 2 The following compositions A and B were prepared: The amounts are expressed as g / 100 g of the starting materials obtained unless otherwise specified. In Table 1 below, "am" means the active substance.

[0438]

Table 1

[0439] (1) Synthesized according to the synthesis process described in Example 1 (containing 40% active substance in water) (2) Sold under the name Sepinov EMT10 (containing 90% active substance) by SEPPIC. (3) Sold under the name Belsil ADM LOG 1 (containing 15% active substance) by Wacker.

[0440]

Table 2

[0441] (4) Sold under the trade name Daitosol 3000SLPN-PE1 by Daito Kasei Kogyo (aqueous dispersion containing 30% active substance) (5) Sold under the trade name Aculyn 22 (registered trademark) by Rohm & Haas (an oxyalkylenated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active substance).

[0442] Next, one mixture was prepared. Composition A was mixed with Composition B in a 50 / 50 mass ratio to obtain Composition C.

[0443] Next, the following Composition D was prepared. The amounts are expressed as g / 100g of the starting materials obtained.

[0444]

Table 3

[0445] (6) Sold under the trade name Silform INX by Momentive Performance Materials.

[0446] Decolorizing composition In parallel, Decolorizing composition E was prepared and described in the following table. The amounts are expressed as g / 100g of the starting materials obtained.

[0447]

Table 4

[0448] (7) Sold by Clariant under the trade name Hostacerin AMPS.

[0449] Protocol for dyeing a tuft of hair Apply 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 of hair. Next, loosen the tuft of hair, dry it with a hair dryer, and then comb it. The length of the tuft of hair is 20 cm and the weight of the tuft of hair is 1 g.

[0450] Next, Composition D was applied to the said bundle of hair pre-treated with Composition C in an amount of 0.5 g of the composition per 1 gram of the hair bundle.

[0451] Next, the hair bundle was dried with a hair dryer and then stored at a temperature of 22 °C and a humidity of 35% for 24 hours.

[0452] Protocol for decolorizing pre-dyed hair bundles Composition E was applied to the dyed hair bundles at a rate of 2 g of the composition per one hair bundle. The hair bundle was pinched from the root to the tip (6 times) using, for example, peeling gloves and then massaged for 4 minutes (the fingers were passed along the hair bundle 6 times). Next, the hair bundle was rinsed.

[0453] Shampoo protocol Next, the hair bundles were washed using a standard shampoo (L’Oreal Paris Elseve Multivitamine). The shampoo was uniformly applied to the dyed hair bundles in an amount of 0.4 g of the standard shampoo per 1 gram of the hair bundle and gently kneaded along the longitudinal direction of the hair bundle from the root to the tip for 15 seconds (6 times).

[0454] Next, the hair bundles were placed in a watch glass and left for 1 minute.

[0455] Next, the hair bundles were rinsed with water while passing them through the fingers (15 times). Next, the hair bundles were wrung out to remove moisture and then dried using a hair dryer.

[0456] Next, the surface finish of the wet hair bundles was evaluated.

[0457] The principle of the method used here to enable the evaluation of the surface finish of the hair bundles is to measure the frictional force of the hair bundles between two contacts (simulation of the human perception of the feel between two fingers).

[0458] To conduct the test, the hair bundle was fixed to the force sensor of an LS1EH tensile compressor manufactured by Lloyd Instruments.

[0459] Place the tuft of hair between two contacts applying a constant pressure. In the vertical tension movement, measure the frictional force over the length of the tuft of hair.

[0460] The test was performed on three tufts of hair. Therefore, an average value can be shown.

[0461] Denote the data as "Work Total" (WT). This is a measurement unit representing the force applied to the tuft of hair to move over the distance L. The greater the force, the worse the aesthetic result.

[0462] The test was carried out on tufts of hair treated with compositions C, D and E and then shampooed, and this protocol was repeated 5 times. Therefore, these tufts of hair are the tufts of hair according to the invention.

[0463] At the same time, the test was carried out on non - dyed tufts of hair, which were then shampooed and this protocol was repeated 5 times as described above. Therefore, these tufts of hair are comparative tufts of hair.

[0464] Summarize the results in the following table.

[0465]

Table 5

[0466] It is clear that the forces applied to the two types of tufts of hair are equivalent. This means that the feel is equivalent between the comparative tufts of hair and the tufts of hair according to the invention.

[0467] Therefore, the use of the dyeing composition as described above and the subsequent application of the decolorizing composition E do not affect the surface finish of the hair. The use of the decolorizing composition E does not damage the keratinous hair fibers.

[0468] The content of endogenous lipids on the tuft of hair was also evaluated.

[0469] Endogenous lipids (lauric acid, myristic acid, palmitic acid, monounsaturated C16 Fatty acids, monounsaturated C 18 Chemical analysis of the composition of the hair tufts was performed with respect to fatty acids, stearic acid, squalene, cholesterol).

[0470] The higher the concentration of endogenous lipids, the "healthier" the hair was.

[0471] The tests were carried out on hair tufts treated with compositions C, D and E and then shampooed, and this protocol was repeated 5 times. Therefore, these hair tufts are hair tufts according to the invention.

[0472] At the same time, the tests were carried out on unstained hair tufts, which were then shampooed and this protocol was repeated 5 times as described above. Therefore, these hair tufts are comparative hair tufts.

[0473] At the same time, tests were carried out on unstained, unshampooed hair tufts. Therefore, these hair tufts are control hair tufts.

[0474] The results are summarized in the following table. In the following table, the content of each of the listed endogenous lipids is shown and is expressed in μg / g of hair.

[0475]

Table 6

[0476] It is clear that the decrease in the content of endogenous lipids on the hair tufts according to the invention is relatively low compared to that on the control hair tufts. In any case, this decrease in content is more easily gradual than that observed in the comparative hair tufts. Therefore, the content of endogenous lipids on the hair tufts according to the invention is satisfactory.

[0477] Therefore, the use of the staining composition as described above followed by the application of the decolorizing composition E does not damage the keratinous hair fibers and is only a conventional treatment of the hair by the shampooing operation.

Claims

1. - at least one (poly)carbodiimide compound, and - at least one colorant selected from pigments, direct dyes, and mixtures thereof, Use of a composition comprising at least one alkyl or alkylene carbonate for decolorizing keratinous hair fibers pre-dyed with at least one composition for dyeing keratinous hair fibers, without damaging said keratinous hair fibers.

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] ) Use according to claim 1, characterized in that it is selected from compounds of.

3. The (poly)carbodiimide compound is of the following formula (II): [Chemical Formula 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 independently represents a group selected from -O-R ３ -O-; -S-R ４ -S-; -R ５ -N(R ６ )-R ４ -N(R ６ )-R ５ - (In the formula, R ３ and R ４ each independently represent a divalent hydrocarbon radical in which one or more heteroatoms may optionally intervene, -R ５ independently represents a divalent saturated hydrocarbon radical having a carbon-carbon single bond or a divalent saturated hydrocarbon radical in which one or more heteroatoms are optionally interposed, -R ６ each independently represents a hydrogen atom or a hydrocarbon radical optionally intervened by one or more heteroatoms) ) Use according to claim 1, characterized in that it is selected from compounds of.

4. The (poly)carbodiimide compound is of the formula (II): -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently selected from a dialkylaminoalcohol 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 independently represents a group selected from --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 is a C in which one or more heteroatoms are optionally interposed ６ ~C １４ arylene radical, C ３ ~C １２ cycloalkylene radical, linear or branched C １ ~C １８ alkylene radical and mixtures thereof selected from) Use according to claim 3, characterized in that it is selected from compounds of.

5. The (poly)carbodiimide compound is of the formula (II): -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 C ３ to C １５ a cycloalkylene radical, - E independently represents a group selected from -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 of C ６ to C １４ optionally interrupted by one or more heteroatoms, a cycloalkylene radical of C ３ to C １２ a linear or branched alkylene radical of C １ to C １８ optionally interrupted by one or more heteroatoms, 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 is a C in 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). Use according to claim 3 or 4, characterized in that it is selected from compounds of.

6. The (poly)carbodiimide compound is of the formula (II): -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, and 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) representing 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, -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 in which one or more heteroatoms are optionally interposed ６ ~C １４ arylene radical, C ３ ~C １２ cycloalkylene radical, linear or branched C １ ~C １８ alkylene radical and mixtures thereof). Use according to any one of claims 3 to 5, characterized in that it is selected from compounds of.

7. The (poly)carbodiimide compound is of the formula (II): -X １ and X ２ each independently represents an oxygen atom, -R １ and R ２ are each independently represented by 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) representing 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, -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 of methylene, propylene, butylene, ethylene, etc. in which one or more heteroatoms are optionally interposed １ ~C １８ represents an alkylene radical) Use according to any one of claims 3 to 6, characterized in that it is selected from compounds of.

8. The (poly)carbodiimide compound is of the following formula (XII): 【Chemical Formula 4】 (wherein, L １ is 4,4-dicyclohexylene methane, 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) The use according to any one of claims 3 to 7, characterized in that it is selected from the compounds of

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, even 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 composition C. The use according to any one of claims 1 to 8, characterized in that it is in the range of

10. The content 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 composition for dyeing keratinous hair fibers. Preferably, the colorant is selected from pigments. The use according to any one of claims 1 to 9, characterized in that it is

11. 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. Use according to any one of claims 1 to 10, characterized in that.

12. The total content of 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 bleaching composition. The use according to any one of claims 1 to 11, characterized in that it is

13. The composition for bleaching keratinous hair fibers contains at least one glycol ether. The use according to any one of claims 1 to 12, characterized in that it is

14. wherein the glycol ether is of the formula CH ３ ( - O - CH(CH ３ ) - CH ２ ) ｎ OH (wherein n is 2 to 50, preferably 2 to 10, more preferably 2 to 5), and is preferably selected from tripropylene glycol methyl ether, The use according to claim 13, characterized in that.

15. The content of the glycol ether is at least 5% by mass, preferably 5% by mass to 40% by mass, more preferably 5% by mass to 20% by mass, based on the total mass of the bleaching composition. The use according to claim 13 or 14, characterized in that it is

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