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WO2014202150A1 - Nouveaux colorants cationiques, kits et compositions les contenant, et procédé de teinture de fibres kératiniques - Google Patents

Nouveaux colorants cationiques, kits et compositions les contenant, et procédé de teinture de fibres kératiniques Download PDF

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Publication number
WO2014202150A1
WO2014202150A1 PCT/EP2013/062983 EP2013062983W WO2014202150A1 WO 2014202150 A1 WO2014202150 A1 WO 2014202150A1 EP 2013062983 W EP2013062983 W EP 2013062983W WO 2014202150 A1 WO2014202150 A1 WO 2014202150A1
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Prior art keywords
amino
methyl
pyrazol
group
diazenyl
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English (en)
Inventor
Otto Goettel
Johann Aeby
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Alfa Parf Group SpA
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Alfa Parf Group SpA
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Priority to PCT/EP2013/062983 priority Critical patent/WO2014202150A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/432—Direct dyes
    • A61K2800/4324—Direct dyes in preparations for permanently dyeing the hair

Definitions

  • the present invention relates to new cationic dyes, kits and compositions for dyeing keratin fibers, which contain at least one of these dyes.
  • the present invention also relates to a process for dyeing keratin fibers.
  • oxidation dyes have attained substantial cosmetic significance in the field of conventional hair dyeing.
  • Keratin fibers, and in particular human hair are dyed with dye compositions containing dye precursors, generally referred to as oxidation dyes, the so called primary intermediates and couplers.
  • the color is obtained by reaction of primary intermediates with couplers in an oxidating environment.
  • Primary intermediates are in particular para-phenylenediamines, para-aminophenols and 4,5-diaminopyrazoles, which are generally referred to as oxidation bases.
  • Couplers are selected in particular from meta-dihydroxybenzenes, meta- aminophenols meta-phenylenediamines, and certain heterocyclic compounds.
  • Oxidation dye precursors are normally colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds and dyes by a process of oxidative condensation.
  • Direct dyes which are used in combination with oxidative colorants have to fulfill a number of technical requirements. Besides providing the appropriate colors, the dye uptake must be even from the roots to the tips, the direct dyes must be stable to hydrogen peroxide and they should also be stable to reducing conditions present in oxidative colorants. Further, fading must be on a very low level to avoid discoloration after several washes. Finally, in addition to the technical properties, the dyes must be safe from a toxicological and dermatological point of view.
  • hair coloring compositions currently available are not entirely satisfactory, in particular from the point of view of resistance of colorations obtained to the various attacking factors to which the hair may be subjected and, in particular, to shampoos. Therefore there is still strong need for dyes which fulfill these requirements.
  • the present invention relates to new cationic dyes of general formula (I) and
  • a further object of the invention is a ready- to use composition for dyeing keratin fibers comprising in a medium suitable for dyeing:
  • Another object of the invention is a multi-compartment dyeing kit or device or any other multi-compartment packaging system comprising at least one cationic direct dye of formula (I) or (II).
  • l is hydrogen, a straight-chain or branched (C 1 -C6)-alkyl group, a (Cl- C4)-hydroxyalkyl group, a (C 1 -C4)-aminoalkyl group, a (Cl-C8)-alkylamino group, a di-(Cl-C8)-alkylamino group, a (C1-C4)- alkylamino-(Cl-C4)-alkyl group or a di(C 1 -C4)-alkylamino-(C 1 -C4)-alkyl group, a benzyl group, an aryl group or a heteroaryl group;
  • R2 to R6 are, equal or different independently from each other, selected from hydrogen, a straight-chain or branched (C 1 -C6)-alkyl or -alkoxy group, a (Cl-C4)-hydroxyalkyl or -hydroxyalkoxy group, a methoxymethyl group, a nitro group, a halogen atom selected from chlorine, bromine, iodine and fluorine, a trifluoromethyl group, a cyano group, an acetylamino or an amino group;
  • R7 is a hydrogen atom, a methyl or an ethyl group, a hydroxy group, an amino group, a hydroxy-(C2-C3)-alkylamino group or a methoxy group;
  • R8 is a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine or a methyl group;
  • R9 is a hydrogen atom, an amino group, a (C 1 -C6)-alkyl group, a (Cl-C6)-alkoxy group or a (C2-C3)-hydroxyalkoxy group;
  • Y is an oxygen atom or an NR group wherein R is (C 1 -C4)-alkyl, (C2-C4)- hydroxyalkyl; or the NR group is bonded to R9 to form a benzoxazine system;
  • L is a bridging group between the pyrazole ring and the quaternary group and consists of a phenylene diradical or a (Cl-C3)-alkylene diradical;
  • Q + is a saturated cationic group selected from formula (a) or an unsaturated or aromatic cationic group selected from formula (b) to (g):
  • RIO to R12 are, equal or different and independently of each other, selected from a straight-chain or branched (Cl-C6)-alkyl group, a (C2-C4)-hydroxyalkyl group, a (C3-C6)-dihydroxyalkyl group, a (C3-C6)-polyhydroxyalkyl group or a (Cl-C6)-alkoxy-(Cl-C4)-alkyl group; or two of the groups RIO to R12 together with the nitrogen atom to which they are linked form a five-membered or six- membered heterocycle optionally containing one or more other heteroatoms (for example O, N, S) and other substituents [for example F, CI, Br, I, OH, NH2 or a straight- chain or branched (C 1 -C6)-alkyl group, a straight-chain or branched (Cl- C6)-alkoxy group, a (Cl-C6)-alkoxy-(Cl-C
  • R13 is a straight-chain or branched (Cl-C8)-alkyl group, a hydroxyethyl group or a benzyl group;
  • R14 is hydrogen, a straight-chain or branched (C 1 -C9)-alkyl group, an amino group, a mono-(Cl-C6)-alkylamino group, a di-(C 1 -C6)-alkylamino group or a pyrrolidino group;
  • R15 is a (Cl-C4)-alkyl radical, which may be substituted with a hydroxy radical
  • X is a monovalent or polyvalent anion, which may be selected from the group comprising chloride, bromide, methylsulfonate or methylsulfate, arylsulfonate, hydrogen sulfate, sulfate, phosphate, acetate or hydroxysuccinate ion.
  • the dyes may also be isolated as adduct with and acid, in particular with an inorganic acid such as hydrochloric acid or hydrobromic acid.
  • cationic dyes of general formula (I) or (II) wherein:
  • R2 to R6 are, equal or different independently from each other, selected from hydrogen, a methyl or methoxy group, a (C 1 -C2)-hydroxyalkyl group, a (C2-C3)-hydroxyalkoxy group, a methoxymethyl group, a nitro group, a chloro atom, or a trifluoromethyl group;
  • R7 is a hydroxy group, an amino group, a hydroxyethylamino group or a methoxy group
  • R8 is a hydrogen atom, a chloro atom or a methyl group
  • R9 is a methyl group, a methoxy group or a hydroxyethoxy group
  • RIO to R12 are, equal or different and independently of each other, selected from a methyl group, ethyl group or hydroxy ethyl group; or two of the RIO to Rl 2 groups together with the nitrogen atom to which they are linked form a pyrrolidino group, morpholino group or N-methylpiperazino group;
  • R13 is a methyl group or a hydroxyethyl group
  • R14 is hydrogen, a methyl group, p-dimethylamino group or p-pyrrolidino group
  • R15 is a methyl, ethyl or hydroxyethyl group
  • Y is O or NH
  • X is a chloride, bromide or methylsulfate
  • L is a (Cl-C3)-diradical
  • Q + is a (C3-C9)-trialkylammonium radical, a N-methylimidazolium radical or a N-methylpyridinium radical.
  • Most preferred are the cationic dyes of general formula (I) or (II) wherein: l is hydrogen;
  • R2-R6 are, equal or different independently from each other, selected from hydrogen, a methyl or methoxy group, a (C 1 -C2)-hydroxyalkyl group, a hydroxyethoxy group, a methoxymethyl group, a nitro group, or a chloro atom;
  • R7 is a hydroxy group, an amino group or a hydroxyethylamino group
  • R8 is a hydrogen atom or a methyl group
  • R9 is a methyl group, a methoxy group or a hydroxyethoxy group
  • RIO to R12 are, equal or different and independently of each other, selected from a methyl group, ethyl group or hydroxyethyl group; or two of the RIO to R12 groups together with the nitrogen atom to which they are linked form a pyrrolidino group, a morpholino group or a N-methylpiperazino group;
  • R13 is a methyl group
  • R14 is hydrogen, a methyl group, a p-dimethylamino group or a p- pyrrolidino group
  • R15 is a methyl, ethyl or hydroxyethyl group
  • Y is O or NH
  • X is chloride, bromide or methylsulfate
  • L is a methylene diradical
  • Q is N-methylpyridinium moiety.
  • Manufacturing of the cationic direct dyes of the present invention is based on commonly known chemical methods. As an example, the synthesis of a set of inventive dyes is illustrated in the following part. Selected was a starting pyrazole, substituted at the pyrazole-Nl atom with a pyridine-3-yl-methyl radical, which leads to dyes containing the substitution pattern (d).
  • the diazo process is carried out according to known methods, which are for instance described in "Methoden der Organischen Chemie (Houben Weyl)", Band X/3, Georg Thieme Verlag, Stuttgart, 1965, pp. 1-212 for the diazotation of aromatic amines, and pp. 213ff for the azo coupling.
  • cationic dyes of formula (Id) are appropriate intermediates to be converted into the cationic dyes of formula (lid).
  • Cationic pyrazole dyes of the general formula (II) can also be obtained by oxidative coupling of the isolated quaternized 4,5-diaminopyrazole; in this regard reference is expressly made to US7462204B2 where the synthesis and the isolation of quaternized 4,5-diaminopyrazoles is reported.
  • the cationic dye general formula (II) are obtained, which are brilliant orange to deep violet.
  • the cationic chromophores can be combined with various anions.
  • the type of anion is normally the result of the selected reagents used in the process, such as the alkylating agents or agents added to the dye in order to exchange the anion. The latter can be necessary for practical reasons, for instance to improve the crystallization properties of the dyes.
  • the dyes can be favorable to isolate the dyes as adduct with an acid, for instance as a 1 : 1 adduct with hydrochloric acid or with hydrobromic acid.
  • some of the dyes can contain crystal water.
  • the pyrazole azo dyes of general formula (I), which can be used, for example, in the compositions in accordance with the invention, may be selected from the group comprising:
  • the pyrazole dyes of general formula (II), which can be used, for example, in the compositions in accordance with the invention, may be selected from the group comprising:
  • the dyes may also exist in one or more tautomeric forms.
  • Most preferred cationic dyes of general formula (I) or (II), in the following case obtained from the pyrazole intermediate (III), may be selected from the group comprising: 3- ⁇ [5-Amino-4-(phenyldiazenyl)- IH-pyrazol- 1 -yljmethyl ⁇ - 1 ⁇
  • compositions for dyeing keratin fibers, in particular human hair comprising the direct cationic dyes of general formula (I) or (II), which don't have the inconveniences of the known compositions.
  • compositions according to present invention allow obtaining colorations which have good endurance and which are rich of shine and brilliant reflexes.
  • Another subject of the invention is thus a ready-to-use composition for dyeing of keratin fibers, such as hair in particular human hair.
  • the ready-to-use compositions comprise, in a medium which is suitable for dyeing:
  • the cationic direct dye(s) of formulae (I) and/or (II) in accordance with the invention are preferably present in a concentration ranging from approximately 0.001 to approximately 10% by weight relative to the total weight of the composition, and even more preferably from approximately 0.05 to approximately 2% by weight relative to the total weight of the composition.
  • the cosmetic composition comprises at least one oxidation base.
  • Suitable oxidation bases also called primary intermediates, which can be used in accordance with the invention are preferably selected from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic oxidation dyes.
  • the para-phenylenediamines may be selected, for example, from 1,4- Diamino-benzene; l,4-Diamino-2-methyl-benzene; 1 ,4-Diamino-2-(2- hydroxyethyl)-benzene; 1 ,4-Diamino-2,3-dimethyl-benzene; 1 ,4-Diamino-2,6- dimethyl-benzene; 1 ,4-Diamino-2-methoxymethyl-benzene; 1 ,4-Diamino-2- chloro-benzene; 4- [Di(2-hydroxyethyl)amino] -aniline; 2,2'-( ⁇ 2-[(4-
  • Aminophenyl)amino] ethyl ⁇ imino)diethanol (4-Aminophenyl)-(3-(imidazol- 1 - yl)propyl)amine; N,N'-bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)- 1 ,3- diaminopropanol.
  • the para-aminophenols may be selected, for example, from 4-aminophenol; 4-(methylamino)phenol, 4-Amino-3-methylphenol; 2-Aminomethyl-4- aminophenol; Bis(5-amino-2-hydroxyphenyl)methane.
  • the ortho-aminophenols may be, for example, 2-Amino-5-ethylphenol or 2-
  • the heterocyclic oxidation bases may be selected, for example, from 4,5- Diamino- 1 -(2-hydroxyethyl)- 1 H-pyrazole; 4,5-Diamino-4-methylbenzyl- 1 H- pyrazole; 2,3-Diaminodihydroxypyrazolo pyrazolone dime tho sulfonate; 2,5- Diaminopyridine; 2,4,5,6-Tetraaminopyrimidine.
  • the coupler components that may be used are, for example, m- phenylenediamine derivatives, resorcinol and resorcinol derivatives, m-amino- phenol and m-amino-phenol derivatives, naphthols as well as heterocyclic couplers, such as pyridines, pyrazolones, indoles.
  • Suitable coupler substances of the resorcinol type may be for instance:
  • Suitable coupler substances may be m-aminophenol and derivatives thereof, such as 3-Aminophenol; 5-Amino-2-methylphenol; 5-Amino-4-chloro-2- methylphenol; 3-Amino-2,6-dimethylphenol; 2-Methyl-5- hydroxyethylaminophenol; 3-Amino-2,4-dichlorophenol; 3,4-Dihydro-2H- 1 ,4- benzoxazin-6-ol; Hydroxyethyl-3,4-methylenedioxyaniline; 3,4-Dihydro-6- hydroxy-2H- 1 ,4-benzoxazine; 6-Amino-3,4-dihydro-2H- 1 ,4-benzoxazine.
  • Suitable coupler substances of the m-phenylenediamine type may be for instance:
  • Suitable coupler substances of the naphthol type may be for example:
  • Suitable heterocyclic coupler substances may be for example:
  • Oxidation bases and couplers containing unsubstituted or substituted amino groups may be used as free bases or in form of their acid-addition salts.
  • the acid- addition salts may be selected in particular from the hydrochlorides, hydrobromides, sulphates, phosphates and hydroxysuccinates.
  • the oxidation dye(s) are preferably present in a concentration ranging from approximately 0.0001 to approximately 10% by weight relative to the total weight of the composition, and even more preferably from approximately 0.001 to approximately 5% by weight relative to the total weight of the composition.
  • composition besides the cationic dyes of formula (I) and/or (II), primary intermediates and couplers, comprises at least one oxidizing agent.
  • the oxidizing agent present in the dye composition may be selected from oxidizing agents used conventionally in oxidation dyeing and preferably from hydrogen peroxide, urea peroxide, alkali or ammonium persulphates or alkali perborates. Hydrogen peroxide is particularly preferred.
  • the pH of the composition generally ranges from approximately 5 to approximately 12.
  • the preferred range is from 6.5 to 1 1.5. It can be adjusted to the desired value using acidifying or basifying agents usually used in hair color technology.
  • the acidifying agents may be, for example, inorganic or organic acids, such as hydrochloric acid, sulphuric acid, orthophosphoric acid and carboxylic acids, such as hydroxysuccinic acid, citric acid or lactic acid.
  • inorganic or organic acids such as hydrochloric acid, sulphuric acid, orthophosphoric acid and carboxylic acids, such as hydroxysuccinic acid, citric acid or lactic acid.
  • the basifying agents may be , for example, aqueous ammonia, alkaline carbonates, alkanolamines, such as monoethanolamine (MEA), l-amino-2- propanol, 2-amino-2-methyl-propanol (AMP), 2-amino-2-methyl-l,3-propanediol, 2-amino-2-ethyl- 1 ,3-propanediol and tris(hydroxymethyl)-aminomethane (Tromethamine, Tris).
  • MEA monoethanolamine
  • AMP 2-amino-2-methyl-propanol
  • 2-amino-2-ethyl- 1 ,3-propanediol 2-amino-2-ethyl- 1 ,3-propanediol and tris(hydroxymethyl)-aminomethane (Tromethamine, Tris).
  • composition may contain amino acids, preferably a-amino acids such as Arginine, Glycine, Ornithine, Lysine Serine and Histidine; most preferred are Arginine and Glycine.
  • amino acids preferably a-amino acids such as Arginine, Glycine, Ornithine, Lysine Serine and Histidine; most preferred are Arginine and Glycine.
  • compositions in accordance with the current invention make it possible to obtain colorations in brilliant shades which exhibit excellent stability to everyday conditions, in particular to shampoos.
  • the medium which is suitable for dyeing (or the support) for the composition in accordance with the invention generally comprises water or a mixture of water and at least one organic solvent in order to dissolve the compounds which would not be sufficiently soluble in water.
  • the organic solvent may be, for example, Q -C 4 lower alkanols such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxy-ethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether; and aromatic alcohols such as benzyl alcohol or phenoxyethanol; and mixtures thereof.
  • the organic solvent(s) can be present in a concentration preferably ranging from approximately 1 to approximately 40% by weight relative to the total weight of the dye composition, and even more preferably from approximately 5 to approximately 30% by weight relative to the total weight of the dye composition.
  • compositions in accordance with the invention can also contain various adjuvants used conventionally in compositions for dyeing the hair, such as anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof; anionic, cationic, nonionic or amphoteric polymers or mixtures thereof; inorganic or organic thickeners; antioxidants; penetration agents; sequestering agents; fragrances; buffers; dispersing agents; packaging agents; film-forming agents; preserving agents and opacifiers.
  • adjuvants used conventionally in compositions for dyeing the hair, such as anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof; anionic, cationic, nonionic or amphoteric polymers or mixtures thereof; inorganic or organic thickeners; antioxidants; penetration agents; sequestering agents; fragrances; buffers; dispersing agents; packaging agents; film-forming agents; preserving agents and opacifiers.
  • Surfactants that may be used in hair colorants of the current invention may be from the classes of anionic, cationic, amphoteric (including zwitterionic surfactants) or nonionic surfactant.
  • Suitable surfactants, other than cationic surfactants include fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylated alkylphenols, block polymers of ethylene and/or propylene glycol, glycerol esters, phosphate esters, fatty acid alkanol amides and ethoxylated fatty acid esters, alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulf
  • sodium and ammonium alkyl sulfates sodium and ammonium ether sulfates having 1 to 3 ethylene oxide groups and nonionic surfactants sold as Tergitols, e.g., C1 1-C15 Pareth-9 and Neodols, e.g. C12-C15 Pareth-3. They may be included for various reasons, e.g. to assist in thickening, for forming emulsions, to help in wetting hair during application of the hair dye product composition, etc.
  • Amphoteric surfactants include, for example, the asparagine derivatives as well as betaines, sultaines, glycinates and propionates having an alkyl or alkylamido group of from about 10 to about 20 carbon atoms.
  • amphoteric surfactants suitable for use in this invention include lauryl betaine, lauroamphoglycinate, lauroamphopropionate, lauryl sultaine, myristamidopropyl betaine, myristyl betaine, stearoamphopropylsulfonate, cocamidoethyl betaine, cocamidopropyl betaine, cocoamphoglycinate, cocoamphocarboxypropionate, cocoamphocarboxyglycinate, cocobetaine, and cocoamphopropionate.
  • Suitable conditioning materials include silicones and silicone derivatives; hydrocarbon oils; monomeric quaternary compounds and quaternized polymers.
  • Monomeric quaternary compounds are typically cationic compounds, but may also include betaines and other amphoteric and zwitterionic materials that provide a conditioning effect.
  • Suitable monomeric quaternary compounds include behentrialkonium chloride, behentrimonium chloride, benzalkonium bromide or chloride, benzyl triethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride, CI 2- 18 dialkyldimonium chloride, cetalkonium chloride, ceteartrimonium bromide and chloride, cetrimonium bromide, chloride and methosulfate, cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate, cocamidopropyl ethosulfate, cocoethyldimonium ethosulfate, cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride, dicetyldi
  • Quaternized polymers are typically cationic polymers, but may also include amphoteric and zwitterionic polymers.
  • Useful polymers are exemplified by polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10, polyquaternium-22, polyquaternium-32, polyquaternium-39, polyquaternium-44 and polyquaternium-47.
  • Silicones suitable to condition hair are dimethicone, amodimethicone, dimethicone copolyol and dimethiconol.
  • Suitable silicones are also disclosed in WO99/34770.
  • compositions of the present invention may also contain at least one silicone quaternary compound selected from silicone quaternium- 1 , silicone quaternium-2, silicone quaternium-2 panthenol succinate, silicone quaternium-3, silicone quaternium-4, silicone quaternium-5, silicone quaternium-6, silicone quaternium-7, silicone quaternium-8, silicone quaternium-9, silicone quaternium- 10, silicone quaternium- 1 1 , silicone quaternium- 12, silicone quaternium- 15, silicone quaternium- 16, silicone quaternium- 16/glycidoxy dimethicone crosspolymer, silicone quaternium- 17, silicone quaternium- 18, silicone quaternium-20 and silicone quaternium-21.
  • silicone quaternary compound selected from silicone quaternium- 1 , silicone quaternium-2, silicone quaternium-2 panthenol succinate, silicone quaternium-3, silicone quaternium-4, silicone quaternium-5, silicone quaternium-6
  • Concentration of the polyquaternium or silicone quaternary compound may vary in the range of 0.01 to 10%, preferably 0.05 to 7.5%, more preferably 0.1 to 5% and most preferably 0.1 to 3% by weight calculated to the weight of the composition.
  • Suitable thickeners may be for example higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil, fatty acids and anionic and nonionic polymeric thickeners based on polyacrylic and polyurethane polymers.
  • cellulose derivatives such as hydroxyalkylcelluloses, preferentially hydroxymethyl and hydroxyethylcellulose; carboxyalkylcellulose, such as carboxymethylcellulose; hydrophobically modified anionic polymers and nonionic polymers, particularly such polymers having both hydrophilic and hydrophobic moieties (i.e. amphiphilic polymers).
  • Useful nonionic polymers include polyurethane derivatives such as PEG-150/stearyl alcohol/SDMI copolymer.
  • Suitable polyether urethanes are Aculyn® 22, Aculyn® 44, and Aculyn® 46 polymers sold by Rohm & Haas. Other useful amphiphilic polymers are disclosed in US6010541.
  • anionic polymers that can be used as thickeners are acrylates copolymer, acrylates/ceteth-20 methacrylates copolymer, acrylates/ceteth-20 itaconate copolymer, and acrylates/beheneth-25 acrylates copolymers.
  • associative type of thickeners e.g.
  • the polymer may be included in one of either the hair dye composition or the developer composition of the hair dye product and the surfactant material in the other.
  • the requisite viscosity is obtained upon mixing of the hair dye and developer compositions.
  • the thickeners are provided in an amount to provide a suitably thick product as it is applied to the hair.
  • Such products generally have a viscosity of from 1000 to 100000 cps, and often have a thixotropic rheology.
  • Another subject of the invention is a multi-compartment dyeing "kit- 1 " or device or any other multi-compartment packaging system, comprising:
  • a first compartment which contains, in a medium suitable for dyeing, at least one primary intermediate, at least one coupler and at least one cationic direct dye selected from the compounds of formulae (I) or (II), and
  • a second compartment which contains, in a medium suitable for dyeing, the oxidizing composition.
  • Another subject of the invention is a multi-compartment dyeing "kit-2" or device or any other multi-compartment packaging system, comprising:
  • a first compartment which contains, in a medium suitable for dyeing, at least one primary intermediate and at least one coupler,
  • a second compartment which contains, in a medium suitable for dyeing, at least one cationic direct dye selected from compounds of formulae (I) or (II), and
  • a third compartment which contains, in a medium suitable for dyeing, the oxidizing composition.
  • compositions in accordance with the invention can be in various forms, such as in the form of liquids, creams, gels or foams or in any other form which is appropriate for dyeing keratin fibers, and in particular human hair.
  • Another subject of the invention is a process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, using at least one cationic dye of general formula (I) or (II) as defined above.
  • the process for dyeing keratin fibers comprises:
  • composition comprising, in a medium suitable for dyeing, at least one cationic dye of general formula (I) or (II) as defined above, at least one primary intermediate and optionally at least one coupler,
  • a process for dyeing keratin fibers comprises:
  • composition comprising, in a medium suitable for dyeing, at least one cationic dye of general formula (I) or (II) as defined above,
  • composition comprising at least one primary intermediate and optionally at least one coupler, - separately preparing a developer composition comprising, in a medium suitable for dyeing, at least one oxidizing agent,
  • the ready-to-use composition for dyeing keratin fibers is obtained by mixing together the components, for example the components of the kits as defined above.
  • the cosmetic composition thus obtained is applied to the keratin fibers and is left on them for an exposure time preferably ranging from approximately 5 to approximately 45 minutes, more preferably from approximately 10 to approximately 30 minutes, after which the fibers are rinsed, optionally washed with shampoo, rinsed again and dried.
  • Step 1 General procedure for the preparation of 4-(aryldiazenyl)-l - pyrazol-5-amines
  • the obtained diazonium salt solution is then added to a mechanically stirred solution of the corresponding 5-amino-lH-pyrazole (100 mmol) and 20.5g (250 mmol) sodium acetate dissolved in 150 ml water/methanol 2: 1 (v/v).
  • the spontaneously obtained orange-yellow, paste-like dye suspension is stirred for lh; then the product is filtered off, washed with water and dried.
  • Example la 4-(Phenyldiazenyl)-l-(pyridin-3-ylmethyl)-l -pyrazol-5- amine
  • Example lb 4- [(4-methylphenyl)diazenyl] -l-(pyridin-3-ylmethyl)-l - pyrazol-5-amine
  • Arylamine p-toluidine
  • Arylamine methyl p-aminobenzoate
  • Example le 4- ⁇ [2-(methoxymethyl)-4-nitrophenyl]diazenyl ⁇ -l-(pyridin- 3-ylmethyi)-l//-pyrazol-5-amine
  • Arylamine 2-aminobenzylalkohol
  • Arylamine 2-aminobenzylalkohol
  • Step 2 Quaternization of the Intermediates from Step 1
  • the dye crystallizes out as hydrochloride and contains one equivalent of crystal water.
  • Example 2b 3-( ⁇ 5-Amino-4- [(4-methylphenyl)diazenyl] -l//-pyrazol-l- yl ⁇ methyl)-l-methylpyridinium bromide hydrobromide
  • reaction mixture is evaporated, then the residue is dissolved in 150 ml ethanol and 25 ml of an ammonium bromide solution (180 mmol, 17.63 g) is added followed by the addition of a solution of hydrobromic acid with external cooling (33% in acetic acid, 132 mmol, 32.37 g). Precipitation occurs and a thick suspension is obtained.
  • the mixture is diluted with 50 ml ethanol and stirring is continued at room temperature for a further hour. The solid is filtered off and recrystallized from 450 ml ethanol/water 9: 1 (v/v). Filtration and drying gives 34.72 g (57.4% of th.) orange needles.
  • Example 2c 3-( ⁇ 5-Amino-4-[(4-(methoxycarbonyl)phenyl)diazenyl]-lH- pyrazol-l-yl ⁇ methyl)-l-methylpyridinium methyl sulfate
  • Methyl 4- ⁇ [5-amino-l-(pyridin-3-ylmethyl)-lH-pyrazol-4- yl]diazenyl ⁇ benzoate (example lc, 6.6 g, 19.6 mmol) is suspended in 100 ml 3- methoxypropionitrile and heated to 100°C.
  • Dimethylsulfate (2.6 g, 20.6 mmol) is added over a 15 min period whereby a red solution is obtained. Stirring is continued for an additional hour; then the reaction mixture is allowed to cool to room temperature.
  • the solution is concentrated to a volume of 20-30 ml, then an identical volume of isopropanol is added to precipitate the dye. After stirring for 30 min the dye is filtered off, washed with isopropanol and dried to give 7.8g (86% of th.) mustard-yellow solid.
  • Example 2d 3-( ⁇ 5-Amino-4- [(2-methyl-4-nitrophenyl)diazenyl] -1H- pyrazol-l-yl ⁇ methyl)-l-methylpyridinium methyl sulfate
  • Example 2e 3-[(5-Amino-4- ⁇ [2-(methoxymethyl)-4- nitrophenyl]diazenyl ⁇ -l -pyrazol-l-yl)methyl]-l-methylpyridinium methyl sulfate
  • Example 2g 4- [(5-amino-4- ⁇ [2-(hydroxymethyl)phenyl] diazenyl ⁇ -l - pyrazol-l-yl)methyl]-l-methylpyridinium methyl sulfate
  • Example 3a 3-( ⁇ 5-Amino-4-[(2-amino-3,5-dimethyl-4-oxocyclohexa-2,5- dien-l-ylidene)amino]-l -pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride is obtained from 3-amino-2,6-dimethylphenol (3.34g, 89% yield).
  • Example 3b 3- ⁇ [5-Amino-4-( ⁇ 2- [(2-hy droxyethyl)amino] -5-methyl-4- oxocyclohexa-2,5-dien-l-ylidene ⁇ amino)-l -pyrazol-l-yl]methyl ⁇ -l- methylpyridinium chloride is obtained from 2-methyl-5- hydroxyethylaminophenol (1.59g, 39.5% yield).
  • Example 3c 3-( ⁇ 5-Amino-4-[(2-amino-4-imino-5-methylcyclohexa-2,5- dien-l-ylidene)amino]-l -pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride is obtained from 2,4-diaminotoluene (3.28g, 92% yield).
  • Example 3d 3-( ⁇ 5-Amino-4-[(2-amino-4-imino-5-methoxycyclohexa- 2,5-dien-l-ylidene)amino]-l -pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride is obtained from 2,4-diaminoanisole sulfate (3.29g, 88% yield).
  • Example 3e 3- ⁇ [5-amino-4-( ⁇ 2- [(2-hy droxyethyl)amino] -4-imino-5- methoxycyclohexa-2,5-dien-l-ylidene ⁇ amino)-l -pyrazol-l-yl]methyl ⁇ -l- methylpyridinium chloride is obtained from 2-amino-4- hydroxyethylaminoanisole sulfate (3.6g, 86% yield).
  • Example 3f 3-[(5-Amino-4- ⁇ [2-amino-5-(2-hydroxyethoxy)-4- iminocyclohexa-2,5-dien-l-ylidene] amino ⁇ -l -pyrazol-l-yl)methyl]-l- methylpyridinium chloride is obtained from 2,4-diaminophenoxyethanol 2HC1 (2.95g, 73% yield).
  • Example 3g Alternative route - 3-( ⁇ 5-Amino-4-[(2-amino-3,5-dimethyl-
  • a standard oxidative hair color composition as example shade 7/0, to which a 0.5% amount of the cationic dyes of the invention according to Table 1 was added, was mixed, at the time of use, with an equal amount of a developer composition containing hydrogen peroxide solution (6% by weight).
  • composition in accordance with the invention was applied at 30°C for 30 minutes to 50% human grey hair.
  • the hair was then rinsed, washed with a standard shampoo and dried.
  • the hair swatches were intensely dyed with the indicated reflexes. The obtained shades were substantially resistant to washout.
  • Example 4 The cosmetic compositions of Example 4, containing the inventive dyes, were stored at various conditions (4°C, 20°C, 50°C) for 4 weeks. Then dye-outs were performed as indicated. The obtained color results showed no visual differences to the dye outs performed before the storage test.
  • composition is prepared as part of a 3 component kit.
  • the composition containing the inventive dyes (I) or (II) is useful to provide more fashioned nuances to a conventional oxidative colorant; various glints are obtained according to the color of the cationic dye and the used amounts.
  • component 1 of the kit can be added the composition indicated in the table below (component 2 of the kit) in various amounts, for example in an amount of 10-20% w/w.
  • component 2 of the kit a developer composition containing hydrogen peroxide is added and mixed to obtain the ready-to-use composition.
  • component 3 of the kit containing hydrogen peroxide is added and mixed to obtain the ready-to-use composition.
  • Component 2 of the kit and composition is
  • the order of mixing the kit components is arbitrary.
  • the ready-to-use composition is applied to the hair in a sufficient amount and processed for 30 minutes.
  • the hair was then rinsed, washed with a standard shampoo and dried.
  • the hair swatches were intensely dyed with the reflexes indicated in Table 1.

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Abstract

Cette invention concerne de nouveaux colorants cationiques de formule générale (I) et (II), ainsi que des kits et des compositions contenant au moins un desdits colorants pour teindre des fibres kératiniques, et un procédé de teinture de fibres kératiniques utilisant au moins un desdits colorants.
PCT/EP2013/062983 2013-06-21 2013-06-21 Nouveaux colorants cationiques, kits et compositions les contenant, et procédé de teinture de fibres kératiniques Ceased WO2014202150A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUA20161586A1 (it) * 2016-03-11 2017-09-11 Beauty & Business S P A Composizione per colorare la fibra cheratinica
WO2020258731A1 (fr) * 2019-06-28 2020-12-30 L'oreal Composition pour colorer des fibres de kératine

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DE4234885A1 (de) 1992-10-16 1994-04-21 Wella Ag Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten, deren Verwendung zum Färben von Haaren sowie neue Pyrazol-Derivate
WO1998027941A1 (fr) 1996-12-23 1998-07-02 The Procter & Gamble Company Compositions de coloration
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUA20161586A1 (it) * 2016-03-11 2017-09-11 Beauty & Business S P A Composizione per colorare la fibra cheratinica
WO2020258731A1 (fr) * 2019-06-28 2020-12-30 L'oreal Composition pour colorer des fibres de kératine
WO2020258732A1 (fr) * 2019-06-28 2020-12-30 L'oreal Composition pour colorer des fibres de kératine
US11752082B2 (en) 2019-06-28 2023-09-12 L'oreal Cosmetic composition for the oxidative dyeing of keratin fibres
US12144880B2 (en) 2019-06-28 2024-11-19 L'oreal Cosmetic composition for the oxidative dyeing of keratin fibres

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