HAIR COLOURING PROCESS COMPRISING THE APPLICATION OF A COMPOSITION COMPRISING A BINDING AGENT, THEN THE APPLICATION OF A COMPOSITION COMPRISING A (POLY)CARBODIIMIDE, A SPECIFIC COPOLYMER AND A COLOURING AGENT
Patent Information
- Application Number
- FR2024001590
- Authority / Receiving Office
- FR · FR
- Patent Type
- Utility models
- Current Assignee / Owner
- Filing Date
- 2024-02-19
- Publication Date
- 2025-08-22
- Estimated Expiration
- 2034-02-19
Abstract
Description
Title of the invention: HAIR COLORING PROCESS COMPRISING THE APPLICATION OF A COMPOSITION COMPRISING A BINDING AGENT, THEN THE APPLICATION OF A COMPOSITION COMPRISING A (POLY)CARBODIIMIDE, A SPECIFIC COPOLYMER AND A COLORING AGENT
[0001] The present invention relates to a hair coloring process comprising the application to the hair of at least one composition T comprising at least one binding agent; then the application to the hair of at least one hair coloring composition C comprising at least one (poly)carbodiimide compound, at least one acrylic polymer, and at least one hair coloring agent. Technical field
[0002] In the field of coloring hair keratin fibers, it is already known to color hair keratin fibers via various techniques using direct dyes or pigments for non-permanent dyes or dye precursors for permanent coloring.
[0003] There are basically three types of hair coloring processes: a. so-called permanent coloring, which has the function of bringing about a significant modification of the natural color and which uses oxidation dyes which penetrate the hair fiber and form the dye by a process of oxidative condensation; b. non-permanent, semi-permanent or direct coloring, which does not involve the oxidative condensation process and withstands 4 or 5 shampoos; it consists of dyeing the hair fibers with dye compositions containing direct dyes; c. temporary coloring that results in a change in the natural color of the hair that lasts from one shampoo to another and is used to enhance or correct an already obtained shade. It can also be compared to a "makeup" process.
[0004] Another coloring method consists of using pigments. Indeed, the use of pigments on the surface of keratinous fibers generally makes it possible to obtain visible colorings on dark hair, because the pigment on the surface masks the natural color of the fiber. However, the colorings obtained by this coloring method have the disadvantage of having low resistance to shampoos as well as to external agents, such as sebum, perspiration, brushing and / or rubbing.
[0005] Furthermore, when applying the pigment-based coloring composition, the deposition of color on the surface of the keratinous fibers may be inhomogeneous, i.e. the colored coating does not cover the fibers uniformly, which may lead to reduced visibility of the color.
[0006] There is therefore a need for a hair coloring process which has the advantage of obtaining a homogeneous and visible colored coating on the hair offering good coverage of the original color of the hair, while forming a coating resistant to shampoos and the various attacks that the hair may undergo such as brushing and / or rubbing.
[0007] Thus, the object of the present invention is to develop a hair coloring process which has the advantage of obtaining a homogeneous and smooth colored and visible coating on the hair offering good coverage of the original color of the hair, while forming a coating resistant to shampoos and to the various aggressions that the hair may undergo such as brushing and / or rubbing. DISCLOSURE OF THE INVENTION
[0008] The present invention therefore relates to a hair coloring process comprising: a. the application to the hair of at least one composition T comprising at least one binding agent chosen from amino acids with a hydrocarbon chain carrying one or more alkaline groups, dipeptides obtained from said amino acids, salts or cocrystals of said amino acids, and mixtures thereof; then b. the application to the hair of at least one hair coloring composition C comprising: i. at least one (poly)carbodiimide compound; and ii. at least one polymer comprising at least one reactive group chosen from carboxylic acids; and iii. at least one coloring agent chosen from pigments, direct dyes, and their mixtures.
[0009] Thanks to the hair coloring process according to the invention, a homogeneous colored coating is obtained on the hair to obtain good coverage of the original color of the hair and a visible coloring on all types of hair and persistent shampoos. Such a colored coating can be resistant to external aggressions that the hair can undergo such as drying with a hair dryer and perspiration.
[0010] The expression “at least one” means one or more.
[0011] Unless otherwise indicated, the limits of an interval of values are included in this interval, in particular in the expressions "between...and..." and "ranging from... to...".
[0012] The invention is not limited to the illustrated examples. In particular, the characteristics of the different examples can be combined within variants not shown.
[0013] For the purposes of the present invention and unless otherwise indicated, • an “alkyl” radical denotes a linear or branched saturated radical containing, for example, from 1 to 20 carbon atoms; • an “aminoalkyl” radical denotes an alkyl radical as defined above, said alkyl radical comprising an NH2 group; • a “hydroxyalkyl” radical denotes an alkyl radical as defined above, said alkyl radical comprising an OH group; • an “alkylene” radical denotes a divalent saturated C2-C4 hydrocarbon group, linear or branched, such as methylene, ethylene or propylene; • a “cycloalkyl” or “alicycloalkyl” radical denotes a monocyclic or polycyclic saturated cyclic hydrocarbon group, preferably monocyclic, bicyclic or tricyclic, comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 24 carbon atoms, in particular comprising from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, in particular cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl radical may be substituted by one or more alkyl groups (CrC4) such as methyl, preferably, the cycloalkyl radical is then an isobornyl group, • a “cycloalkylene” radical denotes a divalent cycloalkyl group with “cycloalkyl” as defined above, preferably C3-C12; • An “aryl” radical is a monocyclic, unsaturated, aromatic hydrocarbon cyclic radical comprising from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms, mono / bi or tri / cyclic or not, preferably the aryl group comprises 1 cycle of 6 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, it being understood that the aryl radical may be substituted by one or more alkyl groups (C1-C4) such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably the aryl group represents a phenyl; • an “arylene” radical is a divalent aryl radical with “aryl” as defined above, preferably arylene represents phenylene; • a “heterocyclic” radical designates a monocyclic or polycyclic, saturated or unsaturated, non-aromatic or aromatic hydrocarbon radical, comprising one or more heteroatoms, preferably from 1 to 5 atoms chosen from O, S or N, comprising from 3 to 20 members, preferably between 5 and 10 members, such as imidazolyl, pyrrolyl and furanyl; • a “heterocycloalkylene” radical is a divalent heterocyclic group with “heterocyclic” as defined above; • an “aryloxy” radical denotes an aryl-oxy radical with “aryl” as defined above; • an “alkoxy” radical denotes an alkyloxy radical with “alkyl” as defined above; • an “acyloxy” radical denotes an ester radical RC (O) -O- with R an alkyl group as defined above; • A “reactive” group is a group capable of forming a covalent bond with another group, identical or different, by chemical reaction.
[0014] Unless otherwise indicated, when compounds are mentioned in the present application, their optical isomers, geometric isomers, tautomers, salts, alone or in mixtures, are also understood.
[0015] By "keratinous (hair) fibers" we mean hair. In other words, the expressions "keratinous (hair) fibers" and "hair" are equivalent in the remainder of the description.
[0016] For the purposes of the present invention, the term "hair" designates the hair of the head. This term does not correspond to body hair, eyebrows or eyelashes. Binding agent
[0017] The method according to the invention comprises the application to the hair of at least one composition T comprising at least one binding agent as defined below.
[0018] Preferably, the alkali groups are chosen from amino groups, guanidine groups, imidazole groups, quaternium groups.
[0019] According to a preferred embodiment, the amino acids useful for the invention are chosen from arginine; lysine, histidine or citrulline, more preferably arginine and / or citrulline.
[0020] The term "salts" of amino acids designates the salts of amino acids with one or more organic carboxylic acids, mineral sulfonic acids; "Cocrystals" and "complexes" refer to crystalline solids composed, usually in a stoichiometric ratio, of two or more amino acids, and to compounds containing two or more amino acids held together by hydrogen bonds, noncovalent interactions such as pi stacking, or van der Waals forces.
[0021] Examples of dipeptides include citrullyl-arginine, argininyl-citrulline, argininyl-arginine, argininyl-lysine, argininyl-histinide, their salts, and mixtures thereof.
[0022] Among the amino acid salts, mention may be made of salt compounds formed between at least one amino acid and at least one organic acid, preferably chosen from organic carboxylic acids of natural origin, such as sebacic acid, azelaic acid, tartaric acid, cinnamic acid, chlorogenic acid, caffeic acid, quinic acid, ferulic acid, chicoric acid; or at least one amino acid and at least one mineral acid, such as hydrochloric acid, sulfonic acids, for example ethanesulfonic acid. These organic carboxylic acids preferably comprise from 2 to 30 carbon atoms, more preferably from 4 to 20 carbon atoms.
[0023] Advantageously, the binding agent(s) is(are) chosen from arginine, histidine, lysine, citrulline and their mixtures and the dipeptides obtained from said amino acids; preferably from arginine.
[0024] Advantageously, the amino acids are one or more dipeptides, salts or cocrystals.
[0025] Advantageously, the amino acids are chosen from citrullyl-arginine, argininyl-citrulline, argininyl-citrulline, argininyl-arginine, argininyl-lysine, lysinyl-arginine, argininyl-hystinide, hystinidyl-arginine, arginine-sebacic acid, arginine-chlorogenic acid, arginine-azelaic acid, arginine-tartaric acid, their salts, and their mixtures.
[0026] Advantageously, the binding agent(s) as defined above is (are) present in a total content ranging from 0.01 to 30% by weight, preferably from 0.05 to 25% by weight, more preferably from 0.1 to 20% by weight, even more preferably from 0.5 to 15% by weight, preferably from 1 to 10% by weight relative to the total weight of the composition T.
[0027] The composition T used in the process according to the invention may comprise water and / or one or more organic solvents.
[0028] Preferably, the composition T comprises water, in particular in a total content of 20% to 99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, relative to the total weight of the composition T.
[0029] When composition T is aqueous, it can have a pH ranging from 1 to 5, more preferably from 2 to 4, even more preferably from 2 to 3.
[0030] Acidifying and / or alkalizing agents may be added to the aqueous composition to correct the pH of the composition T.
[0031] Composition T may further comprise an organic solvent.
[0032] Examples of organic solvents that may be mentioned include lower C1-C4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol propylene glycol, pentylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether diethylene glycol, and aromatic alcohols, including aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.
[0033] Preferably, the composition T comprises at least one monoalcohol, preferably ethanol and / or isopropanol.
[0034] The organic solvents may be present in a total content ranging from 0% to 70% by weight, preferably from 0% to 60% by weight and more preferably from 0% to 50% by weight, relative to the total weight of the composition T. Composition C
[0035] Composition C used in the context of the process according to the invention comprises one or more (poly)carbodiimide compound(s).
[0036] The composition may comprise at least two different (poly)carbodiimide compounds, present in the form of a mixture in the composition.
[0037] The expression “(poly)carbodiimide compound” designates a compound comprising one or more carbodiimide groups, preferably at least two carbodiimide groups, more preferably at least three carbodiimide groups; in particular, the number of carbodiimide groups does not exceed 200, preferably 150, more preferably 100.
[0038] The term "carbodiimide group" denotes a divalent linear triatomic moiety of general formula -(N=C=N)-.
[0039] The (poly)carbodihnide compound(s) according to the invention may optionally comprise in its structure one or more reactive groups other than the carbodiimide groups, chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vi-nylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydri-doalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercap-toalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sul-fonylakylsilyl, (meth)acrylkalkyl, crotonoylalkyl, alkylepoxide such as propylepoxide or butylepoxide groups and azacyclopropane.
[0040] The reactive group(s) other than carbodiimide groups may be side or terminal groups. Preferably, the (poly)carbodiimide compound(s) comprises one or more terminal groups other than the carbodiimide groups, preferably one or more terminal groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, al-dehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide groups and azacyclopropane.
[0041] According to a particular embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) below: OO lri A A4—bT x'X? H l J„ H
[0042] in which: • Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; • R 1 and R 2 independently represent a group selected from a hydrocarbon group, preferably alkyl, optionally interrupted by one or more heteroatoms, a group selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylal-kylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyal-kylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornenylsilyl, acyl-pentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide and azacyclopropane groups, and a hydrocarbon group, preferably alkyl, optionally interrupted by one or more heteroatoms and with one or more groups selected from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hy-droxyalkylsilyl, aldehydoalkylsilyl,mercaptoalkylsilyl, norbomenylsilyl, acetylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide groups and azacyclopropane; , • n denotes an integer ranging from 1 to 1000; and
[0043] - A is a monomer chosen from the compounds below:
[0044] According to another embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I1) below:
[0045] (D in which: • Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; • Yi and Y2 independently represent a divalent organic radical selected from a C1-C36 saturated aliphatic group or a C6-C24 aromatic or al-alkylaromatic group, the aliphatic or aromatic group optionally comprising one or more non-pendant heteroatoms, such as a nitrogen atom, an oxygen atom, a sulfur atom, or combinations thereof; • Zi and Z2 independently represent a reactive terminal group or an inert terminal group; • as an inert terminal group, Z1 and Z2 may independently represent a saturated, linear or branched or cyclic aliphatic group of C1 to C50, or an aromatic group of C6 to C[8, said aliphatic and aromatic groups optionally comprising from 1 to 10 heteroatoms chosen from nitrogen, oxygen, sulfur and combinations thereof, and the aliphatic or aromatic group may be partially or totally fluorinated; in this variant, Z i and Z2 comprise a CG linking group connecting Zi to Yi and Z2 to Y2, the CG group optionally being a single covalent bond, a saturated CC bond, an unsaturated covalent CC bond, an amide group, an ester group, a carbonate group, a thioester group, an ether group, a urethane group, a thiourethane group or a urea group; • as a reactive terminal group, Zi and Z2 may be chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylal-kylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoal-kylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mer-captoalkylsilyl, norbornesylsilyl, acylpentadienylalkylsilyl, maleimidoal-kylsilyl, sulfonylalkylsilyl, (meth)acryalkyl, crotonylalkyl, alkylepoxide groups such as propylepoxide or butylepoxide and azacyclopropane groups; • Q represents an organopolymer or an organooligomer comprising repeating units of saturated, linear or branched or cyclic aliphatic groups, or of aromatic or alkylaromatic groups, coupled via repeated carbonate, ester, ether, amide, urethane or urea bonds or combinations thereof; • A represents a divalent, saturated, branched or cyclic aliphatic, aromatic, alkylaromatic or linear radical containing from 2 to 30 carbon atoms, which may optionally include one or more non-pendant heteroatoms such as a nitrogen atom, an oxygen atom, a sulfur atom, or combinations thereof, in the aliphatic chain or the aromatic chain; • r denotes an integer equal to 0 or 1; • m denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1; • m' denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1; • n denotes an integer ranging from 0 to 1000, preferably equal to 0 or 1, with m + (m'*n ) > 2.
[0046] Preferably, Zi and Z2 independently represent a reactive terminal group; more preferably, Zi and Z2 independently represent a group chosen from alkoxysilyl, hydroxysilyl, acetoxysilyl, vinylsilyl, acrylalkylsilyl, methacrylalkylsilyl, crotonylalkylsilyl, carboxyanhydridoalkylsilyl, carboxyalkylsilyl, hydroxyalkylsilyl, aldehydoalkylsilyl, mercaptoalkylsilyl, norbornesylsilyl, acylpentadienylalkylsilyl, maleimidoalkylsilyl, sulfonylalkylsilyl, (meth)acrylalkyl, crotonylalkyl, alkylepoxide such as propylepoxide or butylepoxide groups and azacyclopropane.
[0047] Such (poly)carbodiimide compounds are sold, for example, by the company Stahl BV, under the name Permutex XR, or under the name RelcaLink10. or under the name Picassian XL and by the company Nisshinbo under the name Carbodilite with the V- ranges 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.
[0048] Preferably, the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) below:
[0049] in which: • Xi and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group; • R1 and R2 independently represent a hydrocarbon group optionally interrupted by one or more heteroatoms; • n and z independently denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3; • Li independently represents a C1-C18 divalent aliphatic hydrocarbon group, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof; • E independently represents a group chosen from:
[0050] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;
[0051] wherein R3 and R4 independently represent a divalent hydrocarbon group optionally interrupted by one or more heteroatoms; • R5 independently represents a covalent bond or a saturated divalent hydrocarbon group, optionally interrupted by one or more heteroatoms; • R6 independently represents a hydrogen atom or a hydrocarbon group, optionally interrupted by one or more heteroatoms.
[0052] The term “hydrocarbon radical” or “hydrocarbon group” designates a saturated or unsaturated, linear or branched radical containing from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based radical (or the hydrocarbon group) is a saturated linear radical.
[0053] The hydrocarbon group may comprise one or more cyclic groups.
[0054] The hydrocarbon group may be interrupted by one or more heteroatoms, in particular chosen from O, S or N and / or 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 comprising a metal ion which may be incorporated in the form of a salt.
[0055] The term "heteroatom(s)" denotes an oxygen O, sulfur S or nitrogen N atom, and also halogen atoms such as Cl, F, Br and I. If the heteroatom is included in the chain of the hydrocarbon-based radical (or hydrocarbon group), the heteroatom is preferably chosen from oxygen O, sulfur S or nitrogen N atoms.
[0056] Preferably, X1 and X2 independently represent an oxygen atom.
[0057] Preferably, R1 and R2 are independently selected from dialkylamino alcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which one hydroxyl group has been removed, and mixtures thereof.
[0058] In a preferred embodiment, R1 and R2 are independently selected from groups (i) to (iv) below: i. the compound of formula (III) below:
[0059] R7-OC(O)-C(R8)(H)-(III),
[0060] wherein R7 represents a C1-C3 alkyl group and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is a methyl and R8 is a hydrogen atom or a methyl. i. the compound of formula (IV) below:
[0061] R9-[0-CH2-C(H)(Rio)]p-(IV),
[0062] in which R9 represents a C1-C4 alkyl group, R10 represents a hydrogen atom or a C1-C4 alkyl group and p denotes an integer ranging from 1 to 3; preferably, R9 is methyl, ethyl or butyl, R10 is a hydrogen atom or methyl and p is equal to 1. i. the compound of formula (V) below:
[0063] (Rn)2N-CH2-C(H)(Ri2)- (V),
[0064] wherein Ru represents a C1-C4 alkyl group and R[2 represents a hydrogen atom or a C1-C4 alkyl group; preferably, Ru is methyl, ethyl or butyl and R[2 is a hydrogen atom or methyl. i. the compound of formula (VI) below:
[0065] R13-[O-CH2-C(H)(R14)]q- (VI),
[0066] in which Rn represents a C1-C4 alkyl group or a phenyl, RM represents a hydrogen atom or a C1-C4 alkyl group and q denotes an integer ranging from 4 to 30; preferably, Rn is a methyl, ethyl or butyl and Ru is a hydrogen atom or a methyl.
[0067] Preferably, R1 and R2 independently represent a compound of formula (VI) in which Rn represents a Cr-C4 alkyl group or a phenyl, preferably a Cr-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.
[0068] According to an alternative embodiment, R 1 and R 2 are different and one of the radicals R 1 or R 2 represents a compound of formula (IV) as described above and the other radical R 1 or R 2 represents a compound of formula (VI) as described above.
[0069] Preferably, in formula (IV), R9 is methyl, ethyl or butyl and Rio is hydrogen or methyl and p is 1.
[0070] Preferably, in formula (VI), Rb is methyl, ethyl or butyl and R[4 is hydrogen or methyl and q denotes an integer ranging from 4 to 30.
[0071] According to another alternative embodiment, R1 and R2 are identical and represent a compound of formula (VI) in which Rn represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, R[4 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30.
[0072] Preferably, n denotes an integer ranging from 1 to 20, more preferably from 2 to 20.
[0073] Preferably, z denotes an integer ranging from 1 to 20, more preferably from 2 to 20.
[0074] Preferably, w is equal to 1.
[0075] Preferably, w is equal to 1, n+z denotes an integer ranging from 4 to 10.
[0076] Preferably, Li is selected from a C1-C18 divalent aliphatic hydrocarbon group such as methylene, ethylene and propylene, a C3-C6 cycloalkylene radical such as cyclopentylene, cycloheptylene and cyclohexylene, a C3-C12 heterocycloalkylene group such as imidazolene, pyrrolene and furanylene, or a C6-C14 arylene group such as phenylene, and mixtures thereof.
[0077] For example, Li may be selected from a radical derived from tolylene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, 1,5-napthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and dii-
[0078] phenylene cyanate, and mixtures thereof. Preferably, Li is chosen from a C3-C15 cycloalkylene radical or a C6-C14 arylene group, and mixtures thereof, such as the compounds of formula (VII) below:
[0079] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to formula (VIII) below: .... (wine).
[0080] According to another embodiment, when L1 is a C6-C14 arylene group, Li is not the m-tetramethylxylylene radical represented by formula (IX) below: (IX).
[0081]
[0082]
[0083] As previously indicated, E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 independently represent a divalent hydrocarbon group optionally interrupted by one or more heteroatoms; • R5 independently represents a covalent bond or a hy- group saturated divalent carbon, optionally interrupted by one or more heteroatoms; and • R6 independently represents a hydrogen atom or a hydrocarbon group, optionally interrupted by one or more heteroatoms.
[0084] Preferably, R3 and R4 are independently selected from a C6-CM arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0085] More preferably, R3 and R4 are independently chosen from a linear or branched CrCi8 alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms.
[0086] Preferably, when R5 is not a covalent bond, R5 is selected from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0087] Preferably, R6 is chosen from a C6-Ci4 arylene radical such as phenylene, a C3-Ci2 cycloalkylene radical such as cyclopropylene and cyclobutylene, a linear or branched C1-Ci8 alkylene radical such as methylene and ethylene, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0088] Preferably, E represents a group -O-R3-O- in which R3 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0089] More preferably, E represents a group -O-R3-O- in which R3 represents a linear or branched CrCi8 alkylene radical such as methylene, butylene, propylene or ethylene, optionally interrupted by one or more heteroatoms.
[0090] According to a particular embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyryl isocyanates of formula (X) below: (X),
[0091] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms, and • n denotes an integer ranging from 2 to 100.
[0092] In this embodiment, the expression “alkyl group” is as defined above.
[0093] In this embodiment, the expression “cycloalkyl group” is as defined above.
[0094] In this embodiment, n can designate an integer ranging from 2 to 50, preferably from 3 to 30 and even more preferably from 5 to 10.
[0095] According to another particular embodiment, the (poly)carbodiimide compound is a compound of formula (XI) below: (XI), Z
[0096] wherein R independently represents an alkyl group containing from 1 to 24 carbon atoms, a cycloalkyl group containing from 3 to 24 carbon atoms or an aryl group containing from 6 to 24 carbon atoms.
[0097] “Alkyl group”, “cycloalkyl group” and “aryl group” are as defined above.
[0098] According to a preferred embodiment, the (poly)carbodiimide compound is chosen from the compounds of formula (I) or of formula (II) in which: • Xi and X2 independently represent an oxygen atom; • R1 and R2 are independently selected from dialkylamino alcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which a hydroxyl group has been removed, and mixtures thereof, preferably (poly)alkylene glycol monoalkyl ethers, in which a hydroxyl group has been removed, more preferably compound of formula (VI) as described above in which Rn represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, Ru represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom, and q denotes an integer ranging from 4 to 30; • n and z, when present, denote an integer ranging from 1 to 20, with n+z > 2 and w equal to 1; • Lb when present, is chosen from a divalent C1-C18 aliphatic hydrocarbon group, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical; • A, when present, is chosen from a C1-C18 divalent aliphatic hydrocarbon group, a C3-C15 cycloalkylene radical, a C3-C12 heterocycloalkylene group or a C6-C14 arylene group, and mixtures thereof, preferably a C3-C15 cycloalkylene radical; • E, when present, independently represents a group selected from:
[0099] - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;
[0100] wherein R3 and R4 are independently selected from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; • when R5 is not a covalent bond, R5, when present, is chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; and • R6, when present, is chosen from a C6-C14 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1-Ci8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0101] Preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which: • Xi and X2 independently represent an oxygen atom; • R1 and R2 are independently selected from dialkylamino alcohols, hydroxycarboxylic acid alkyl esters and (poly)alkylene glycol monoalkyl ethers, in which one hydroxyl group has been removed, and mixtures thereof; • n and z independently denote an integer ranging from 1 to 20, with n+z > 2 and w equal to 1; • Li is selected from a divalent aliphatic hydrocarbon group C1 to C18,
[0102]
[0103]
[0104]
[0105]
[0106]
[0107] a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group or a C6-Ci4 arylene group, and mixtures thereof; • E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; • when R5 is not a covalent bond, R5 is chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; and • R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1Ci8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof. More preferably, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which: • Xi and X2 independently represent an oxygen atom; • R1 and R2 are, independently, monoalkyl ethers of (poly)alkylene glycol, in which a hydroxyl group has been removed; • n and z independently denote an integer ranging from 1 to 20, with n+z > 2 and w equal to 1; • Li is a C3 to C15 cycloalkylene radical; • E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; • when R5 is not a covalent bond, R5 is chosen from a C6-C14 arylene radical, a C3-C12 cycloalkylene radical, a linear or branched C1-C18 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof; and • R6 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C1Ci8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof. More preferably still, the (poly)carbodiimide compound is chosen from the compounds of formula (II) in which: Xi and X2 independently represent an oxygen atom; R1 and R2 independently represent the compound of formula (VI) above- below:
[0108] R13-[O-CH2-C(H)(R14)]q- (VI),
[0109] in which Rn represents a C1-C4 alkyl group or a phenyl, preferably a C1-C4 alkyl group, more preferably a methyl, RM represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30; • n and z independently denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w equal to 1; • Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4'-dicyclohexylene methane; and • E represents a group -O-R3-O- in which R3 is chosen from a C6-Ci4 arylene radical, a C3-Ci2 cycloalkylene radical, a linear or branched C rCi8 alkylene radical, optionally interrupted by one or more heteroatoms, and mixtures thereof.
[0110] More preferably still, the (poly)carbodihnide compound is chosen from the compounds of formula (II) in which: • Xi and X2 independently represent an oxygen atom; • R1 and R2 independently represent the compound of formula (VI) above- below:
[0111] R13-[O-CH2-C(H)(R14)]q- (VI)
[0112] in which R13 represents a Cr-C4 alkyl group or a phenyl, preferably a Cr-C4 alkyl group, more preferably a methyl, R14 represents a hydrogen atom or a Cr-C4 alkyl group, preferably a hydrogen atom and q denotes an integer ranging from 4 to 30; • n and z independently denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10 and w equal to 1; • Li is a C3-C15 cycloalkylene radical such as cyclopentylene, cycloheptylene cyclohexylene and 4,4'-dicyclohexylene methane, preferably 4,4'-dicyclohexylene methane; and • E represents a group -O-R3-O- in which R3 represents a linear or branched C1-C18 alkylene radical such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms.
[0113] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of formula (XII) below:
[0114] wherein Li is 4,4-dicyclohexylene methane, n and z each independently denote an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E independently represents -O-R3-0 wherein R3 is a straight or branched C1-C18 alkylene group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms, and r and s are each independently an integer ranging from 4 to 30.
[0115] Advantageously, the total amount of the (poly)carbodiimide compound(s) ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% and better still from 1% to 6% by weight relative to the total weight of composition C.
[0116] Polymers comprising at least one reactive group chosen from carboxylic acids
[0117] Composition C used in the process according to the invention comprises at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably an acrylic polymer.
[0118] Preferably, the polymer comprising at least one reactive group chosen from carboxylic acids, preferably one or more acrylic polymers, is in the form of aqueous dispersions of particles of acrylic polymer(s).
[0119] Thus, preferably, composition C comprises at least one polymer comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymers, in the form of aqueous dispersions.
[0120] The dispersion(s) may be simple dispersions in the aqueous medium of the cosmetic composition. As a special case of dispersions, latex may be mentioned.
[0121] More preferably, the acrylic polymer(s) are in the form of aqueous dispersions of film-forming acrylic polymer particles.
[0122] For the purposes of the invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from known compounds called monomers). This reason or these reasons will be repeated at least twice and preferably at least 3 times.
[0123] By "film-forming polymer" is meant a polymer which is capable of forming, alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous film on a support, in particular on the hair, and preferably a cohesive film.
[0124] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer chosen from (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide.
[0125] The unit(s) derived from the (meth)acrylic acid monomers of the polymer may optionally be in the form of salt(s), including alkali metal, alkaline earth metal, ammonium or organic base.
[0126] The (meth)acrylic acid esters (also called (meth)acrylates) are advantageously chosen from alkyl (meth)acrylates, in particular C1 to C30 alkyl, preferably C1 to C20, preferably C1 to C10, aryl (meth)acrylates, in particular C6 to C10 aryl, hydroxyalkyl (meth)acrylates, in particular C2 to C6 hydroxyalkyl.
[0127] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.
[0128] Hydroxyalkyl (meth)acrylates include hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.
[0129] Aryl (meth)acrylates include benzyl acrylate and phenyl acrylate.
[0130] The particularly preferred (meth)acrylic acid esters are alkyl (meth)acrylates, preferably C1 to C30 alkyl, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.
[0131] According to the present invention, the alkyl group of the esters can be fluorinated or even perfluorinated, that is to say that all or part of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.
[0132] As (meth)acrylic acid amides, mention may be made, for example, of (meth)acrylamides, as well as N-alkyl (meth)acrylamides, in particular of alkyl C2 to C12. N-alkyl (meth)acrylamides include N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide, and N-undecylacrylamide.
[0133] The acrylic polymer according to the invention may be a homopolymer or a copolymer, preferably a copolymer, even better a copolymer of (meth)acrylic acid and (meth)acrylic acid esters.
[0134] Preferably, the acrylic polymer(s) according to the invention comprise(s) one or more units derived from the following monomers: a. (meth)acrylic acid; and b. C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10 and even more particularly C1 to C4.
[0135] Preferably, the aqueous dispersion of acrylic polymer particles does not comprise a surfactant.
[0136] The term “surfactant” designates any agent capable of modifying the surface tension between two surfaces.
[0137] Among the acrylic polymers according to the invention are copolymers of (meth)acrylic acid and methyl acrylate or ethyl acrylate, in particular copolymers of methacrylic acid and ethyl acrylate such as the compound sold under the trade name LUVIMER MAE by BASF, or the crosslinked polymer compound of polyacrylate-2 sold under the trade name FIXATE SUPERHOLD POLYMER by LUBRIZOL, or the acrylate copolymer compound sold under the trade name DAITOSOL 3000VP3 by the company DAITO KASEI KOGYO, or the acrylate copolymer compound sold under the trade name DAITOSOL 3000SLPN-PE1 by the company DAITO KASEI KOGYO.
[0138] The acrylic polymer may optionally comprise one or more additional monomers, other than the (meth)acrylic acid and / or (meth)acrylic acid ester and / or (meth)acrylic acid amide monomers.
[0139] Additional monomers include, for example, styrenic monomers, particularly styrene and alpha-methylstyrene, and preferably styrene.
[0140] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer chosen from copolymers resulting from the polymerization of at least one styrene monomer and at least one C1 to C20, preferably C1 to C10, alkyl (meth)acrylate monomer.
[0141] The C1 to C10 alkyl (meth)acrylate monomer may be chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate.
[0142] Acrylic polymers include styrene / (meth)acrylate copolymers sold under the name JONCRYL 77 by BASF, under the name YODOSOL GH41F by AKZO NOBEL and under the name SYNTRAN 5760 CG by INTERPOLYMER.
[0143] Preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles.
[0144] More preferably, composition C comprises at least one aqueous dispersion of acrylic polymer particles comprising one or more units of the following monomers: a. (meth)acrylic acid; and b. C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10 and even more particularly C1 to C4.
[0145] Preferably, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active ingredient, or dry matter) content relative to the weight of the dispersion of 20 to 60% by weight, more preferably of 22 to 55% by weight and better still of 25 to 50% by weight.
[0146] Advantageously, the acrylic polymer(s) as defined above is (are) present in a total content ranging from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, even more preferably from 1 to 15% by weight, preferably from 2 to 10% by weight, relative to the total weight of composition C.
[0147] According to a particular embodiment, the total content of the aqueous dispersion(s) of acrylic polymer particles preferably ranges from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, preferably from 1 to 25% by weight, and even more preferably from 2 to 20% by weight, relative to the total weight of composition C. Coloring agent
[0148] Composition C used in the process according to the present invention comprises at least one coloring agent chosen from pigments, direct dyes, and mixtures thereof.
[0149] Preferably, the composition C used in the process according to the invention comprises at least one pigment.
[0150] Preferably, the composition C used in the process according to the invention comprises at least one pigment.
[0151] By "pigment" is meant all pigments providing color to keratinous materials. Their solubility in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.
[0152] The pigments which can be used are chosen from organic and / or mineral pigments known in the art, including those described in Kirk-Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of Industrial Chemistry.
[0153] They can be natural, of natural origin or not.
[0154] These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.
[0155] The pigments may for example be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as mother-of-pearl or flakes, and mixtures thereof.
[0156] The pigment may be a mineral pigment. A mineral pigment means any pigment meeting the definition in Ullmann's encyclopedia in the chapter on inorganic pigments. Among the mineral pigments used in the present invention, mention may be made of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.
[0157] The pigment may be an organic pigment. “Organic pigment” means any pigment meeting the definition in Ullmann's Encyclopedia in the chapter on organic pigments.
[0158] The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane, quinophthalone.
[0159] In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.
[0160] For example, we can also cite organic pigment pigment pastes, such as the products sold by the company Hoechst under the names:
[0161] - COSMENYL IOG YELLOW: Pigment YELLOW 3 (Cl 11710);
[0162] - COSMENYL YELLOW G: Pigment YELLOW 1 (Cl 11680);
[0163] - ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
[0164] - COSMENYL RED R: Pigment RED 4 (Cl 12085);
[0165] - CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
[0166] - VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
[0167] - COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
[0168] - COSMENYL GREEN GG: Pigment GREEN 7 (Cl 74260);
[0169] - COSMENYL BLACK R: Pigment Black 7 (CI 77266).
[0170] The pigments according to the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixing of organic pigments on the core, and at least one organic pigment at least partially covering the core.
[0171] The organic pigment may also be a lake. By "lake" is meant dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.
[0172] The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, sodium calcium borosilicate or aluminum calcium borosilicate, and aluminum.
[0173] Dyes include carminic acid. Other names include D&C Red 21 (CI 45380), D&C Orange 5 (CI 45370), D&C Red 27 (CI 45410), D&C Orange 10 (CI 45425), D&C Red 3 (CI 45430), D&C Red 4 (CI 15510), D&C Red 33 (CI 17200), D&C Yellow 5 (CI 19140), D&C Yellow 6 (CI 15985), D&C Green (CI 61570), D&C Yellow 1 O (CI 77002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090).
[0174] Examples of lakes include the product known as D&C Red 7 (CI 15850:1).
[0175] The pigment may also be a special effect pigment. Special effect pigments are pigments that generally create a colored appearance (characterized by a certain shade, vibrancy and clarity) that is non-uniform and changes depending on the viewing conditions (light, temperature, viewing angles, etc.). They are therefore opposed to colored pigments that provide a conventional uniform opaque, semi-transparent or transparent shade.
[0176] There are several types of special effect pigments, those with a low refractive index, such as fluorescent or photochromic pigments, and those with a high refractive index, such as pearlescent pigments, interference pigments or flakes.
[0177] Examples of special effect pigments include pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, mica coated with iron oxide, mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, as well as pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include Cellini mother-of-pearl marketed by BASF (Mica-TiO 2 lake), Prestige marketed by Eckart (Mica-TiO 2), Prestige Bronze marketed by Eckart (Mica-Fe 2 O 3) Colorona marketed by Merck (Mica-TiO 2-Fe2 O3).
[0178] Mention may also be made of the golden mother-of-pearls marketed by BASF under the names Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze mother-of-pearls marketed in particular by Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super bronze (Cloisonne); the orange mother-of-pearls marketed in particular by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion orange (Colorona) and Matte Orange (17449) (Microna); brown mother-of-pearl marketed by BASF under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite);copper-tinted mother-of-pearl, in particular marketed by BASF under the name Copper 340A (Timica), red-tinted mother-of-pearl, in particular marketed by Merck under the name Sienna fine (17386)(Colorona); yellow-tinted mother-of-pearl, in particular marketed by BASF under the name Yellow (4502) (Chromalite); red golden-tinted mother-of-pearl, in particular marketed by BASF under the name Sunstone G012 (Gemtone); pink mother-of-pearl, in particular marketed by BASF under the name Tan opale G005 (Gemtone);black mother-of-pearl with a golden hue, in particular marketed by BASF under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl in particular marketed by Merck under the name Matte blue (17433) (Microna), white mother-of-pearl with a silver hue, in particular marketed by Merck under the name Xirona Silver, and green-gold and pinkish-orange mother-of-pearl in particular marketed by Merck under the name Indian summer (Xirona), and mixtures thereof.;
[0179] Still as examples of nacres, we can also cite particles including a borosilicate substrate coated with titanium oxide.
[0180] The particles comprising a titanium oxide coated glass substrate are sold under the name METASHINE MC1080RY by TOYAL.
[0181] Finally, examples of nacre include polyethylene terephthalate flakes, including those marketed by Meadowbrook Inventions under the name Silver IP 0.004X0.004 (silver flakes). Multi-layer pigments based on synthetic substrates such as alumina, silica, sodium calcium borosilicate or aluminum calcium borosilicate and aluminum may also be considered.
[0182] The special effect pigments may also be chosen from reflective particles, that is to say in particular particles whose size, structure, including the thickness of the layer(s) which constitute it and their physical and chemical nature, as well as the surface state, enable them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create at the surface of the composition or mixture, when applied to the support to be made up, highlights visible to the naked eye, that is to say brighter points which contrast with their environment by appearing to sparkle.
[0183] The reflective particles may be chosen so as not to significantly modify the coloring effect generated by the coloring agents with which they are associated, and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or copper color.
[0184] These particles can have various shapes, including a platelet or globular shape, in particular spherical.
[0185] The reflective particles, whatever their shape, may or may not have a multi-layer structure and, in the case of a multi-layer structure, may have, for example, at least one layer of uniform thickness, including a reflective material.
[0186] When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, in particular of titanium or iron oxides obtained by synthesis.
[0187] When the reflective particles have a multi-layer structure, they may comprise, for example, a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, including at least one metal or metallic material. The substrate may be monomaterial, multi-material, organic and / or inorganic.
[0188] More particularly, it can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, including aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being exhaustive.
[0189] The reflective material may comprise a layer of metal or metallic material.
[0190] Reflective particles are in particular described in documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.
[0191] Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a borosilicate substrate coated with silver.
[0192] Silver-coated glass substrate particles, in platelet form, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by TOYAL. Nickel / chromium / molybdenum alloy coated glass substrate particles are sold under the names CRYSTAL STAR GF 550, GF 2525 by the same company.
[0193] Particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being 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 oxides, and mixtures thereof.
[0194] Examples include SiO2 coated aluminum, bronze or copper powders sold under the name VISIONAIRE by ECKART.
[0195] Also mentioned are pigments having an interference effect that are not fixed on a substrate, for example, liquid crystals (Helicones HC from Wacker) and holographic interference flakes (geometric pigments or Spectra f / x from Spectratek). Special effect pigments also include fluorescent pigments, whether they are substances that fluoresce in daylight or that produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed, for example, by the Quantum Dots Corporation.
[0196] The variety of pigments that can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic and interference effects.
[0197] The size of the pigment used in the composition according to the present invention is generally between 10 nm and 200 microns, preferably between 20 nm and 80 microns, and more preferably between 30 nm and 50 microns.
[0198] The pigments can be dispersed in the composition using a dispersing agent.
[0199] The dispersing agent is used to protect the dispersed particles from being ag glomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer, or a mixture of several of these, carrying one or more functionalities with a strong affinity for the surface of the particles to be dispersed. In particular, they can attach physically or chemically to the surface of the pigments. These dispersants also have at least one functional group compatible with the continuous medium or soluble in it.In particular, esters of 12-hydroxystearic acid and C8 to C20 fatty acid and polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g / mol, such as that sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxy stearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof, are used.
[0200] As another dispersant used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17,000 sold by Avecia, and polydimethylsiloxane / oxypropylene blends such as those sold by Dow Corning under the references DC2-5185, DC2-5225 C.
[0201] The pigments used in the composition may be surface treated with an organic agent.
[0202] Thus, the previously surface-treated pigments useful in the context of the invention are pigments which have undergone entirely or partially a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as those described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53 to 64, before being dispersed in the composition according to the invention.These organic agents may be chosen, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.
[0203] The surface-treated pigments useful in the composition may also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.
[0204] The surface-treated pigments useful in the context of the present invention may be prepared according to surface treatment techniques well known to those skilled in the art, or commercially available as is.
[0205] Preferably, the surface-treated pigments are covered with an organic layer.
[0206] The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the surfactant molecules or creation of a covalent bond between the surfactant and the pigments.
[0207] The surface treatment can thus be carried out, for example, by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or fillers. This method is described in particular in US patent 4,578,266.
[0208] Preferably, an organic agent bound to the pigments will be used covalently.
[0209] The agent for surface treatment may represent from 0.1 to 50% by weight per relative to the total weight of the surface-treated pigment, preferably from 0.5 to 30% by weight and even more preferably from 1 to 20% by weight of the total weight of the surface-treated pigment.
[0210] Preferably, the surface treatments of the pigments are chosen from the following treatments: • a PEG-silicone treatment such as the AQ surface treatment marketed by LCW; • a methicone treatment such as the SI surface treatment marketed by LCW; • a dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW; • a dimethicone / trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW; • a magnesium myristate treatment such as the MM surface treatment marketed by LCW; • an aluminum dimyristate treatment, such as the MI surface treatment marketed by Miyoshi; • a perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW; • an isostearyl sebacate treatment such as the HS surface treatment marketed by Miyoshi; • a perfluoroalkyl phosphate treatment such as the PF surface treatment marketed by Daito; • an acrylate / dimethicone copolymer and perfluoroalkyl phosphate treatment as an FSA surface treatment marketed by Daito; • a polymethylhydrogensiloxane / perfluoroalkyl phosphate treatment such as the FS01 surface treatment marketed by Daito; • an acrylate / dimethicone copolymer treatment, for example the ASC surface treatment marketed by Daito; • an isopropyl titanium triisostearate treatment such as the ITT surface treatment marketed by Daito; • an acrylate copolymer treatment such as the APD surface treatment marketed by Daito; • a perfluoroalkyl phosphate / isopropyl titanium triisostearate treatment such as the PF + ITT surface treatment marketed by Daito.
[0211] According to a particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in the form of submicron-sized particles.
[0212] By "submicronic" is meant pigments whose particle size has been micronized by a micronization process and whose average particle size is less than one micrometer (micron), in particular between 0.1 and 0.9 microns, and preferably between 0.2 and 0.6 microns.
[0213] According to one embodiment, the dispersing agent and the pigment(s) is (are) present in an amount (dispersant:pigment), according to a weight ratio, between 1: 4 and 4: 1, in particular between 1.5: 3.5 and 3.5: 1 or better between 1.75: 3 and 3: 1.
[0214] The dispersing agent(s) may therefore have a silicone backbone, such as silicone polyether and amino-silicone dispersants. Suitable dispersing agents include: • aminosilicones, i.e. silicones comprising one or more amino groups such as those marketed under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1, marketed by Genesee Polymers, • silicone acrylates such as Tego RC 902, Tego RC 922, Tego RC 1041, and Tego RC 1043, marketed by Evonik, • polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 by Genesee Polymers, or Tego ® RC 1401, Tego ® RC 1403, Tego ® RC 1412 by Evonik.
[0215] According to a particular embodiment, the dispersing agent(s) is (are) of aminosilicone type and is (are) cationic.
[0216] Preferably, the pigment(s) is(are) chosen from mineral, mixed mineral-organic or organic pigments.
[0217] In one variant of the invention, the pigment(s) is(are) organic pigments, preferably organic pigments surface-treated with an organic agent chosen from silicone compounds. In another variant of the invention, the pigment(s) is(are) mineral pigments.
[0218] Preferably, the pigment(s) are chosen from iron oxides, in particular red, brown or black. As an example of iron oxide, mention may be made of iron oxide sold by Sun Chemical under the name SunPuro® Red Iron Oxide.
[0219] Direct dyeing
[0220] Composition C used in the process according to the invention may comprise one or more direct dyes.
[0221] By "direct dyeing" we mean natural and / or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber. They can be ionic, for example cationic or anionic, or non-ionic.
[0222] They can be ionic or non-ionic, preferably cationic or non-ionic.
[0223] Examples of suitable direct dyes that may be cited include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in mixtures.
[0224] The direct dyes may be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances. Anionic direct dye is understood to mean any direct dye comprising in its structure at least one CO2R or SO3 R substituent in which R denotes a hydrogen atom or a cation of a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from acid nitrate direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and natural acid dyes.
[0225] Comme exemples : 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 ou sunset yellow ; ou Acid Red 111, Acid Red 134, Acid yellow 38 ;
[0226] (b) les teintures azo-anioniques pyrrazolone incluant Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, ou Acid Yellow 17 ;
[0227] (c) anthraquinone dyes including: 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; Purple EXT No. 2; and Acid Black 48;
[0228] (d) nitrated dyes including: Acid Brown 13; Acid Orange 3; Yellow Acid 1, salt 2,4-Dinitro-l-naphthol-7-sulfonic acid sodium, 2-piperidino 5-nitro benzene sulfonic acid, 2 (4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-[3-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7 ;
[0229] (e) triarylmethane dyes including: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50.
[0230] (f) xanthene-derived dyes including: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;
[0231] (g) indole-derived dyes: Acid Blue 74;
[0232] (h) quinoline-derived dyes, including: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
[0233] The natural direct dyes used according to the invention include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocate-chaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orceins. Extracts or decoctions containing these natural dyes can also be used, including poultices or extracts based on henna.
[0234] Advantageously, the coloring agent(s) is (are) a pigment present in a content ranging from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight relative to the total weight of composition C, preferably, the coloring agent(s) is (are) chosen from pigments.
[0235] The pigment(s) may be present in a total content ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, preferably from 0.5% to 10% by weight, relative to the total weight of the composition.
[0236] The direct dye(s) may be present in a total content ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, relative to the total weight of composition C. Solvents
[0237] Composition C according to the invention may comprise one or more organic solvents.
[0238] Examples of organic solvents that may be mentioned are C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol propylene glycol, pentylene glycol, propylene glycol monomethyl ether, monoethyl ether and monomethyl ether diethylene glycol, and aromatic alcohols, including aromatic monoalcohols such as benzyl alcohol, phenoxyethanol, and mixtures thereof.
[0239] The organic solvents may be present in a total content of between 0.01 and 60% by weight, preferably between 0.05 and 50% by weight and more preferably including between 0.1 and 45% by weight relative to the total weight of composition C.
[0240] The composition C used in the context of the process according to the invention may be aqueous. The moisture content may range from 1% to 90% by weight, preferably 10% to 80% by weight, more preferably 20% to 70% by weight, relative to the total weight of composition C. Additives
[0241] Composition C used in the context of the process according to the invention may contain any adjuvant or additive usually used.
[0242] Among the additives which may be contained in the composition are reducing agents, softeners, antifoaming agents, moisturizing agents, clays, mineral fillers, UV filters, peptizers, perfumes, anionic, cationic, non-ionic or amphoteric surfactants, vitamins, polymers other than the polymers described above, preservatives, oils, silicones other than the silicones described above, various silicone waxes in wax form, and mixtures thereof.
[0243] The composition C used in the context of the process according to the invention 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 multiple (W / W / W or polyol / O / W or O / W / O), in the form of a cream, mousse, stick, dispersion of vesicles including or not ionic lipids, two-phase or multi-phase lotion.
[0244] A person skilled in the art can choose the appropriate dosage form, as well as its preparation process, on the basis of his general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support, and, on the other hand, the application envisaged for the composition.
[0245] The above additives may generally be present in a content between 0% and 20% by weight, relative to the total weight of composition C. Process
[0246] The application to the hair of composition T comprising at least one binding agent as defined above can be carried out on dry or damp hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.
[0247] Preferably, a washing or rinsing, spinning and / or drying step is carried out after application of the composition T comprising at least one binding agent as defined above. More preferably, a rinsing and / or drying step is carried out after application of the composition T as defined above.
[0248] The application of the composition T comprising at least one binding agent as defined above can be carried out at room temperature (between 15 and 25°C).
[0249] After application of the composition T comprising at least one binding agent as defined above, a setting time can be applied between 1 minute and 6 hours, in particular between 1 minute and 3 hours, more particularly between 1 minute and 2 hours, more preferably between 1 minute and 90 minutes, before applying composition C to the hair. During this waiting time, the hair can be dried or left to dry, for example at a temperature greater than or equal to 30°C.
[0250] Preferably, the exposure time is between 1 minute and 1 hour after the application of composition T to the hair and before a possible washing or rinsing, wringing and / or drying step.
[0251] Composition C described above can be used on dry or damp hair, as well as on all types of hair, light or dark, natural or colored, permed, bleached or straightened.
[0252] Preferably, a rinsing, wringing and / or drying step is carried out after applying composition C to the hair. More preferably, a drying step is carried out after applying composition C to the hair.
[0253] Application to the hair can be carried out by any conventional means, in particular by means of a comb, a brush, a brush, a sponge or the fingers.
[0254] The application of composition C to the hair is generally carried out at room temperature (between 15 and 25°C).
[0255] After applying composition C, the hair can be left to dry or dried, for example at a temperature greater than or equal to 30°C.
[0256] The method according to the invention can thus comprise a step of applying heat to keratinous fibers using a heating tool.
[0257] The heat application step of the method of the invention can be carried out using a helmet, a hair dryer, a straightening or curling iron, a climazon, etc. Preferably, the heat application step of the method of the invention is carried out using a hair dryer.
[0258] During the step of applying heat to the hair, a mechanical action can be exerted on the strands such as by combing, brushing, or passing the fingers through.
[0259] When the step of applying heat to the hair is carried out using a helmet or a hair dryer, the temperature is preferably between 30 and 110°C, preferably between 50 and 90°C.
[0260] Preferably, if the hair is dried, it is dried, in addition to a heat supply, with an air flow. This air flow during drying improves the individualization of the coating.
[0261] Preferably, the invention is a hair coloring process comprising: i. the application to the hair of at least one composition T comprising at least one binding agent as defined above, then ii. a time for leaving said composition T on the hair ranging from 1 minute to
[0262]
[0263]
[0264]
[0265]
[0266]
[0267]
[0268]
[0269] 90 minutes, preferably 1 minute to 1 hour, optionally at a temperature greater than or equal to 30°C; then iii. optionally, a step of washing, rinsing, wringing and / or drying the hair; then iv. the application to the hair of at least one composition C comprising: 1. at least one (poly)carbodiimide compound as defined above; 2. at least one polymer comprising at least one reactive group chosen from: carboxylic acids as defined above, preferably at least one acrylic polymer as defined above; and 3. at least one coloring agent as defined above; i. optionally, a step of washing, rinsing, wringing and / or drying said hair. Advantageously, in the hair coloring process according to the invention, step b) consists of mixing extemporaneously at the time of use at least two compositions A and B to obtain a composition C and applying composition C to the hair, with: - composition A comprising (i) at least one (poly)carbodiimide compound as defined above; - composition B comprising: (ii) at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined above, preferably at least one acrylic polymer as defined above; and (iii) at least one coloring agent as defined above. According to a preferred embodiment, the hair coloring process according to the invention is a hair coloring process comprising: i. the application to the hair of at least one composition T comprising at least one binding agent as defined above, then ii. a time for leaving said composition T on the hair ranging from 1 minute to 90 minutes, preferably from 1 minute to 1 hour, at room temperature or at a temperature greater than or equal to 30°C; then iii. optionally, a step of washing, rinsing, wringing and / or drying the hair; then iv. a step of extemporaneous mixing at the time of use of at least two compositions A and B to obtain composition C and of application of composition C to the hair, with: - a composition A comprising (i) at least one (poly)carbodiimide compound as defined above; - a composition B comprising: (ii) at least one polymer comprising at least a reactive group chosen from carboxylic acids as defined above, preferably at least one acrylic polymer as defined above; and (iii) at least one coloring agent as defined above; then (v) optionally, a step of washing, rinsing, wringing and / or drying said hair.
[0270] Preferably, composition A does not comprise a coloring agent as defined above.
[0271] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes before application to the hair, more preferably less than 10 minutes before application, better still less than 5 minutes before application.
[0272] The weight ratio between composition A and composition B is preferably from 0.1 to 10, preferably from 0.2 to 5, preferably from 0.5 to 2, or even from 0.6 to 1.5. In a particular embodiment, the weight ratio between composition A and composition B is equal to 1.
[0273] The total content of the (poly)carbodiimide compound(s) preferably ranges from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, even more preferably from 0.5 to 20% by weight, preferably from 1 to 15% by weight, relative to the total weight of composition A.
[0274] The total content of the polymer(s) comprising at least one reactive group chosen from carboxylic acids, preferably acrylic polymer(s), is preferably from 0.2 to 60% by weight, more preferably from 1 to 40% by weight, even more preferably from 1 to 30% by weight, preferably from 2 to 20% by weight relative to the total weight of composition B. Multi-compartment device (required)
[0275] The present invention also relates to a hair coloring device comprising several compartments containing:
[0276] * in a first compartment, a composition T comprising at least one agent binder as defined above,
[0277] * in a second compartment, a composition A comprising (i) at least one (poly)carbodiimide compound as defined above,
[0278] * in a third compartment, a composition B comprising:
[0279] (ii) at least one polymer comprising at least one reactive group chosen from carboxylic acids as defined above, preferably at least one acrylic polymer as defined above; and
[0280] (iii) at least one coloring agent as defined above.
[0281] The present invention will now be described more specifically by examples, which in no way limit the scope of the invention. However, the examples serve to reinforce specific features, variants and embodiments. preferred features of the invention. EXAMPLES
[0282] The (poly)carbodiimide(s) of the invention are accessible by the synthesis methods known to those skilled in the art from commercial products or reagents synthesizable according to chemical reactions also known to those skilled in the art. Examples include Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D-70469 Stuttgart, or US patent 4,284,730 or Canadian application CA 2,509,861.
[0283] More particularly, the process for preparing the (poly)carbodiimides of the invention firstly uses a diisocyanate reagent (1):
[0284] O=C=N-LrN=C=O (1),
[0285] formula (1) in which L1 is as defined above which reacts in the presence of a carboimidation catalyst (2) such as those described in US 4,284,730, in particular phosphorus catalysts particularly chosen from phospholene oxides and phospholene sulfoxides, diaza and oxazaphospholanes, preferably under an inert atmosphere (nitrogen or argon), and in particular in a polar solvent preferably aprotic such as THF, glyme, diglyme, 1,4-dioxane and DMF, at a temperature between room temperature and reflux of the solvent, preferably around 140 °C; to yield the carbodiimide diisocyanate compound (3):
[0286] O=C=N-L1-(N=C=N-L1)nN=C=O (3),
[0287] formula (3) wherein L1 and n are as defined above. A benzoyl halide such as benzoyl chloride may be added to deactivate the catalyst.
[0288] To obtain “symmetrical” (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent R 1-X 1-H, then 0.5 eq. of HEH reagent with R 1, X 1 and E as defined above, to lead to the “symmetrical” compound according to the invention (4):
[0289] [R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)]2-E (4),
[0290] formula (4) in which R 1, X 1, L i, net E are as defined above. According to a variant to obtain compound (4) from (3), it is possible to first add 0.5 eq. of reagent HEH, then 1 eq. of reagent R 1-X 1-H.
[0291] To obtain “asymmetric” (poly)carbodiimides, in the second step of the preparation process, compound (3) reacts with 1 molar equivalent (1 eq) of nucleophilic reagent R 1-X 1-H then 1 eq. of HEH reagent with R 1, X 1 and E as defined above, to lead to compound (5):
[0292] R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EH (5),
[0293] formula (5) in which Rl,Xl,Ll,netE are as defined above.
[0294] According to a variant for obtaining compound (5) from (3), it is possible to first add 1 eq. of reagent R 1-X bH, then 0.5 eq. of reagent HEH.
[0295] In a third step, compound (5) reacts with 1 eq. of compound (6 R2-X2 -C(O)-NH-L1-(N=C=N-L1)ZN=C=O,
[0296] said compound (6) is prepared beforehand from compound (3'):
[0297] O=C=N-L1-(N=C=N-L1)ZN=C=O (3'),
[0298] formula (3') in which L 1 and z are as defined above, and react with 1 eq of nucleophilic reagent R 2-X 2-H with Ll, R 2, X 2, and z as defined above, to lead to the asymmetric compound (7):
[0299] R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-EC(O)-NH-L1--(N=C=N-L1)z-NH-C(O) -X2-R2 (7),
[0300] formula (7) in which R 1, X 1, L i, R 2, X2, n, z and E are as defined above.
[0301] It is also possible to react 1 molar equivalent of compound
[0302] O=C=N-Ll-(N=C=N-Ll)zN=C=O (3') with 1 / w molar equivalent of HEH, then 1 eq. of nucleophilic reagent R 2-X 2-H to lead to compound (8):
[0303] H-[EC(O)-NH-L1-(N=C=N-L1)z]w-NH-C(O)-X2-R2 (8),
[0304] formula (8) in which L 1, R 2, X2, z and E are as defined above, and w is an integer between 1 and 3, more preferably w = L
[0305] This last compound (8) can then react with 1 eq of compound (4 '):
[0306] R1-X1-C(O)-NH-L1-(N=C=N-L1)nN=C=O (4'),
[0307] (said compound (4 ') can be synthesized by reaction of 0.5 eq. of nucleophilic reagent R 1-X1-H with 1 equivalent compound (3)), to yield the (poly) carbodiimide of the invention (9): R1-X1-C(O)-NH-L1-(N=C=N-L1)n-NH-C(O)-[EC(O)-NH-L1 -(N=C=N-L1)Z]W-NH C(O)-X2-R2 (9), formula (9) in which L 1, R 1, X i R2 X2, n, z, w, and E are as defined above.
[0308] The (poly)carbodiimide compounds as well as all reaction intermediates and reagents can be purified by conventional methods known to those skilled in the art, such as extraction with water and a water-immiscible organic solvent, precipitation, centrifugation, filtration and / or chromatography.
[0309] Example 1: Process for the synthesis of the compound (poly) carbodiimide
[0310] In a 500 mL three-necked flask equipped with a thermometer, a stirrer and a reflux tube, 50 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-l-phenyl-lH-phosphole 1-oxide were introduced with stirring.
[0311] The reaction medium was heated to 140°C under nitrogen for 4 hours at the end of the reaction by infrared spectroscopy by the absorption of the isocyanate functions between 2200 and 2300 cm-1, then cooled to 120°C.
[0312] 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 with stirring. The temperature of 120 °C is maintained until the isocyanate functions have completely disappeared, followed by infrared spectroscopy at 2200-2300 cm-1, then cooling to room temperature.
[0313] After cooling to room temperature, the reaction medium is poured dropwise with vigorous stirring into a 500 mL glass beaker containing 85 g of distilled water to yield the desired product in the form of a translucent yellow liquid.
[0314] Example 2: Process for the synthesis of dipeptide salt L-Arginine-R-Citrulline
[0315] 536 g defluorenylmethoxycarbonyl-arginine (2,2,4,6,7-p entamethyldihydro- benzofuran-5-sulfonyl)-OH (abbreviated Fmoc-Arg(Pbf)-OH hereinafter) were added under nitrogen to a solution of 355 g of (2,4-b est (octadecyloxy)phenyl)methanol (hereinafter referred to as OH-Tag) in 3.5 L of THF. 3.4 g of 4-dimethylaminopyridine and 128 mL of N,N'-diisopropylcarbodiimide (DIC) were added and the medium was mixed for 30 minutes, before being concentrated under reduced pressure, and the residue (Fmoc-Arg(Pbf)OH-Tag) was dried under vacuum.
[0316] 76 mL of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 76 mL of piperidine were added to 650 g of Fmoc-Arg(Pbf)OH-Tag solution in 6.5 L of THF / DMF. The obtained solid (H-Arg(Pbf)OH-Tag) was filtered and dried under vacuum.
[0317] 216 g of Fmoc-Citrulline-OH (Fmoc-Cit-OH ) was added to 440 g of H-Arg (Pbf) OH-Tag in 6.5 L of THF, then 276 g of hexafluorophosphate (1-Cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium and 240 mL of N,N-diisopropylethylamine were added. The medium was mixed for 15 minutes and then concentrated in vacuo. The resulting residue (Fmoc-Cit-Arg(Pbf)OH-Tag) was filtered and dried in vacuo.
[0318] 56 mL of DBU was added to 540 g of Fmoc-Cit-Arg (Pbf) OH-Tag solution in 5.5 L of THF / DMF. Then, 56 mL of piperidine was added and the medium was mixed for 10 minutes. The obtained solid (H-Cit-Arg (Pbf) OH-Tag) was filtered and dried under vacuum.
[0319] 456 g of H-Cit-Arg (Pbf) OH-Tag were diluted in 9 L of TFA:H2O (95:5) and
[0320]
[0321]
[0322]
[0323] mixed for 3 hours. The reaction medium was filtered and the filtrate concentrated under reduced pressure. The residue was added to 68 mL of cold methyl tert-butyl ether. The solid residue obtained was dried. 140 mL of ethanesulfonic acid in 200 mL of water were stirred under nitrogen for 2 hours, filtered, and then poured into 700 g of ion exchange resin previously rinsed with water. 70 g of dipeptide dissolved in 200 mL of water were stirred under nitrogen for 2 hours, filtered, and then poured into the ion exchange resin, previously rinsed with water. The filtrates were lyophilized for 48 hours to give 70 g of ethanesulfonic acid salt and the dipeptide. Its structure was confirmed by HPLC, ion exchange chromatography, infrared spectroscopy, LC-MS, colorimetric titration, and 'H NMR (400 MHz). Synthesis of sebacic acid and arginine salt / cocrystal: hHÿ \ 0 H N • “\ P K. H0-7 arginine Sebacic acid O. "" : q ON arginine PM: 5+8.63 Molecular formula C22H44NSOg Synthesis: Sebacic acid (~1 eq) and L-arginine (~2.0 eq) were mixed with water:ethanol (4:1) and stirred at 60-700 C for 2 h. Then, the solution was left at room temperature and the volatiles were removed and the residue subjected to freeze-drying to obtain Sbc-Arg salt as an off-white foam (Yield: >95%) which is hygroscopic in nature. Sebacic acid and arginine salt derivatives in various proportions of 1:1 and 2:1 are synthesized following the similar protocol described above. Synthesis of chlorogenic acid arginine amide (CAA)
[0324] Step 1:
[0325] Acid (3aR,5S,7R,7aR)-7-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy]-5-hydroxy-2,2-dimethyl-hexahydro-2H-l,3-benzodioxole-5-carboxylic acid (2):
[0326] Chlorogenic acid 1 (165.0 g; 0.465 mol; 1 eq) in acetone (1.4 L) was added to dimethoxypropane (1.0 L) and p-toluenesulfonic acid (1.65 g) and the reaction mixture was stirred at room temperature for 3 h. The volatiles were removed by vacuum distillation to obtain compound 2 (150.0 g) as a solid and which was taken for the next step reaction.
[0327] Step 2:
[0328] (2S)-2-{ [(3aR,5S,7R,7aR)-7-{ [(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy}-5-hy droxy-2,2-dimethyl-hexahydro-2H-l,3-benzodioxol-5-yl]formamido}-5-carbamimida ethyl midopentanoate (3):
[0329] A mixture of compound 2 (80.0 g; 0.202 mol; 1.0 eq) was dissolved in N,N-dimethylformamide (1200 mL), to which were added H-Arg-OEt. 2HC1 (58.36 g; 1.05 eq), BOP reagent ((1H-Benzo[d][l,2,3]triazol-1-I)oxy)tris(dimethylamino)phosphonium hexafluorophosphate (V) (89.34 g; 1.0 eq) followed by di-isopropyl ethylamine (78.325 g; 3.0 eq). The resulting reaction mixture was stirred at room temperature for 16 h and diluted with water, extracted with ethyl acetate, then the solvent was removed in vacuo and the resulting residue was further purified by silica gel chromatography to obtain compound 3 (58.0 g). Steps 3 and 4
[0330] Acid (2S)-5-carbamimidamido-2-{[(lS,3R,4R,5R)-3-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2 -enoyl]oxy}-1,4,5-trihydroxycyclohexyl]formamido}pentanoic acid (5)
[0331] Compound 3 (25.0 g; 0.043 mol; 1.0 eq) was dissolved in tetrahydrofuran (500 mL), the mixture was cooled to 5 °C, water (250 mL) was added, followed by lithium hydroxide monohydrate (4.53 g; 2.5 eq). The resulting reaction mixture was stirred for 14 h at room temperature. The pH was acid corrected with stirring of the aqueous hydrochloric acid contents for 30 min. and the volatiles were removed in vacuo and the material was purified by chromatography (Cl8 silica gel) to obtain compound 5 as a solid (6.8 g). Example 3
[0332] The following compositions, as described in Tables 1, 2 and 3 below, were prepared: the quantities are expressed in g of raw material as is / 100 g, unless otherwise indicated.
[0333] [Table 1] Table 1 Composition Tl (invention) T2 (invention) dipeptide salt L-Arginine-R-Citrulline(1) 5 - L-Arginine salt(2) - 5 Ethanol - 47.5 Hydrochloric acid - Qs pH 2.6 Water Qsp 100 Qsp 100
[0334] (1) ethanesulfonic acid salt and (2S)-2-[(2R)-2-amino-5- (carbamoylamino) pentanamido] -5- carbamimidamidopentanoic acid, as synthesized in Example 2,
[0335] (2) salt of sebacic acid (decanedioic acid) and acid (2S)-2-amino-5-carbamimidamidopentanoic acid.
[0336] Compositions T1 and T2 each have a pH of 2.6.
[0337] [Table 2] Table 2 Composition A Polycarbodiimide(3) 17.5 Ethanol 20 Water Qsp 100
[0338] (3) synthesized according to the synthesis process described in Example 1 (40% of active ingredient in water),
[0339] [Table 3] Table 3 Composition B Acrylates Copolymer (4) 29.2 Aminosilicone 8.8 Iron Oxide CI 77491 12 Divinyldimethicone / Dimethicone Copolymer (and) Ci2-b Pareth-3 (and) C12-13 Pareth-23 (5) 10.2 Ethanol 3.75 Preservative(s) qs Water Qsp 100
[0340] (4) acrylic polymer: sold by DAITO KASEI KOGYO under the name commercial DAITOSOL 3000SLPN-PE1 (aqueous dispersion with 30% active ingredient),
[0341] (5) sold by DOW CORNING under the name DOW CORNING HMW 2220 NON- IONIC EMULSION (divinyldimethicone / dimethicone block copolymer in aqueous emulsion) (60% active ingredient)).
[0342] Composition A was then mixed with composition B at a 1:1 ratio to obtain composition C according to the invention. Protocol
[0343] Three different processes were implemented.
[0344] Compositions T1 or T2 were respectively applied to locks of hair of different types: natural hair with 90% white hair (BN90) and damaged hair (SA20). Each of these compositions was applied to locks of hair, at a rate of 0.5 g of composition per gram of lock. The hair was wrapped in cellophane and the treatment was left to act for 1 hour at a temperature of 39°C. The locks were then rinsed and dried using a hair dryer.
[0345] Composition C was then applied to the locks previously treated with composition T1 or composition T2, at a rate of 0.5 g of composition per gram of hair. The locks of hair were then untangled and dried using a hair dryer.
[0346] The processes using compositions T1 or T2, then composition C, are therefore processes according to the invention. In the following, they are designated respectively by processes 1 and 2.
[0347] According to process 3, no application of composition T1 or composition T2 was carried out. Only composition C was applied to strands of different types of natural hair with 90% white hair (BN90) and damaged hair (SA20), at a rate of 0.5 g of composition per gram of hair. Hair strands were then detangled and dried using a hair dryer.
[0348] The hair strands were then stored at room temperature and 35% humidity for 24 hours.
[0349] Processes 1 to 3 are summarized in Table 4 below:
[0350] [Table 4] Table 4 Process 1 (invention) 2 (invention) 3 (comparison) Application of compositions Tl +C T2 + CC
[0351] The strands of hair treated by processes 1 to 3 were then subjected to several repeated shampoos (protocol below) in order to evaluate the longevity of the coloring. Shampoo protocol
[0352] The colored hair strands are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands are then wrung out between two fingers.
[0353] A standard shampoo (Ultra Doux by Garnier) is applied evenly to the colored strands at a rate of 0.4 g of standard shampoo per gram of strands, gently kneading the strands of hair along their length (6 passes) for 15 seconds.
[0354] The strands of hair are then placed in a watch glass and left for 1 minute.
[0355] Then, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then wrung out between two fingers before the next shampoo.
[0356] After 5 shampoos, the hair strands are combed and dried with a hairdryer. Results
[0357] Colorimetric measurements were performed using a KONICA MINOLTA-3600 spectrophotometer (illuminant D65, angle 10°, specular component included) in the CIELab system.
[0358] In this system, L*a*b*, L* represents the lightness of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.
[0359] The longevity of the coloring is evaluated by the difference in AE color between the colored strands before shampooing, then after 5 shampoos according to the protocol described above. The lower the AE value, the longer the color lasts between shampoos.
[0360] The value of AE is calculated according to the following equation:
[0361] ....... AE =^L -L o + j + (a'-a0*) + (b -bo"J
[0362] In this equation, L*, a* and b* represent the values measured after coloring the hair and after having undergone 5 shampoos, and Lo*, a0* and b0* represent the values measured after coloring the hair but before the 5 shampoos.
[0363] The results are grouped in Tables 5 and 6 below, respectively for each type of hair tested (BN90 (natural hair) and SA20 (damaged hair)):
[0364] [Table 5] Table 5 Process - natural hair Number of shampoos L* a* b* AE 3 (comparison) 0 35.5 25.1 19.6 - 5 55.8 6.2 13.2 28.5 1 (invention) 0 36.4 25.3 19.6 - 5 45.0 17.6 15.2 12.3 2 (invention) 0 37.2 25.2 19.8 - 5 43.0 15.9 13.8 12.5
[0365] [Table 6] Table 6 Process - damaged hair Number of shampoos L* a* b* AE 1 (invention) 0 40.6 24.9 24.3 5 43.4 24.3 23.8 2.9 2 (invention) 0 39.0 23.6 22.5 5 39.6 22.8 22.8 1.0 3 (comparison) 0 37.8 26.6 23.6 5 43.9 21.7 22.7 7.9
[0366] For each hair type, hair treated with processes 1 and 2 according to the invention has a lower AE value than hair treated with comparative process 3.
[0367] Thus, the colored hair obtained with the process according to the invention has improved resistance to shampooing.
Claims
Claims
1. A hair coloring process comprising: a) applying to the hair at least one composition T comprising at least one binding agent selected from amino acids with a hydrocarbon chain carrying one or more alkaline groups, dipeptides obtained from said amino acids, salts or cocrystals of said amino acids, and mixtures thereof; then b) applying to the hair at least one hair coloring composition C comprising: i) at least one (poly)carbodiimide compound; ii) at least one polymer comprising at least one reactive group selected from carboxylic acids; and iii) at least one coloring agent selected from pigments, direct dyes and mixtures thereof.
2. Process according to claim 1, characterized in that the binding agent(s) is (are) chosen from arginine, histidine, lysine, ci-trulline and their mixtures and dipeptides obtained from said amino acids; preferably from arginine.
3. Process according to claim 1 or 2, characterized in that the amino acids are one or more dipeptides, salts or cocrystals.
4. Process according to any one of the preceding claims, characterized in that the amino acids are chosen from citrullyl-arginine, argininyl-citrulline, argininyl-citrulline, argininyl-arginine, argininyl-lysine, lysinyl-arginine, argininyl-hystinide, hystinidyl-arginine, arginine-sebacic acid, arginine-chlorogenic acid, arginine-azelaic acid, arginine-tartaric acid, their salts, and their mixtures.
5. Process according to any one of the preceding claims, characterized in that the total content of the binding agent ranges from 0.01 to 30% by weight, preferably from 0.05 to 25% by weight, more preferably from 0.1 to 20% by weight, even more preferably from 0.5 to 15% by weight, preferably from 1 to 10% by weight relative to the total weight of the composition T.
6. Process according to any one of claims 1 to 5, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) below: (II) in which - Xi and X2 each independently represent O, S or NH; - R1 and R2 each independently represent a hydrocarbon group optionally interrupted by one or more heteroatoms, - n and z independently denote an integer ranging from 1 to 20, with n+z > 2 and w denotes an integer ranging from 1 to 3; - Li independently represents a divalent C1 to C[8] aliphatic hydrocarbon group, a C3-Ci5 cycloalkylene radical, a C3-Ci2 heterocycloalkylene group or a C6-Ci4 arylene group, and mixtures thereof; - E independently represents a group chosen from: - -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 each independently represent a divalent hydrocarbon group optionally interrupted by one or more heteroatoms; - R5 independently represents a covalent bond or a saturated divalent hydrocarbon group, optionally interrupted by one or more heteroatoms; - R6 independently represents a hydrogen atom or a hydrocarbon group, optionally interrupted by one or more heteroatoms.
7. Process according to claim 6, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (II) in which: - Xi and X2 each independently represent O; - Ri and R2, are each independently represented by the following formula (VI): r13 -[O-CH2 -C(H)(R14 )]q- (VI) in which Ri3 is a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group> more preferably a methyl, Ri4 is a hydrogen atom or a C1-C4 alkyl group> preferably a hydrogen atom and q is an integer equal to 4 to 30; - n and z independently denote an integer equal to 1 to 20 with n+z ranging from 4 to 10 and w equal to 1; - Li is a C3 to C15 cycloalkylene radical such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4'-dicyclohexylene methane, preferably 4,4'-dicyclohexylene methane; and - E independently represents -O-R3-0 in which R3 is a linear or branched C1 to C18 alkylene radical such as methylene, propylene, butylene, ethylene, optionally interrupted by one or more heteroatoms.
8. Process according to any one of claims 6 or 7, characterized in that the (poly)carbodiimide compound(s) is (are) chosen from the compounds of formula (XII) following: (XII), in which Lx is 4,4-dicyclohexylene methane, n and z denote each independently an integer ranging from 1 to 20, with n+z ranging from 4 to 10, E independently represents -O-R3-0 wherein R3 is a straight or branched C1-C8 alkylene group such as methylene, propylene, butylene or ethylene, optionally interrupted by one or more heteroatoms, and r and s are each independently an integer ranging from 4 to 30.
9. Process according to any one of the preceding claims, characterized in that the polymer comprising at least one reactive group chosen from carboxylic acids is an acrylic polymer, preferably an acrylic polymer comprising one or more units derived from the following monomers: (a) (meth)acrylic acid; and (b) C1 to C30 alkyl (meth)acrylate, more preferably C1 to C20, even better C1 to C10, and even more particularly C1 to C4.
10. Process according to any one of the preceding claims, characterized in this step b) consists in extemporaneously mixing at the time of use at least two compositions A and B to obtain a hair coloring composition C and in applying the hair coloring composition C to the hair, with: - composition A comprising i) at least one (poly)carbodiimide compound as defined in any one of claims 1 and 7 to 8; - composition B comprising: ii) at least one polymer comprising at least one reactive group chosen from the carboxylic acids according to claims 1 and 9; and iii) at least one coloring agent as defined in claim 1.
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