WO2014202152A1 - Nouvelles compositions cosmétiques comprenant des colorants cationiques, et procédé de coloration directe de fibres de kératine - Google Patents

Nouvelles compositions cosmétiques comprenant des colorants cationiques, et procédé de coloration directe de fibres de kératine Download PDF

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WO2014202152A1
WO2014202152A1 PCT/EP2013/062997 EP2013062997W WO2014202152A1 WO 2014202152 A1 WO2014202152 A1 WO 2014202152A1 EP 2013062997 W EP2013062997 W EP 2013062997W WO 2014202152 A1 WO2014202152 A1 WO 2014202152A1
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group
amino
methyl
pyrazol
methylpyridinium
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Otto Goettel
Johann Aeby
Katiuscia GREVALCUORE
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Alfa Parf Group SpA
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Alfa Parf Group SpA
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    • 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
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • 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

Definitions

  • the invention relates to new compositions for dyeing or for lightening and dyeing keratin fibers, and in particular human keratin fibers such as the hair, comprising at least one cationic direct dye.
  • the present invention also relates to the process for direct dyeing of keratin fibers using these compositions.
  • oxidative system which has attained cosmetic significance. Keratin fibers, and in particular human hair, are dyed with dye compositions containing dye precursors, so called primary intermediates and couplers.
  • Primary intermediates are in particular para-phenylenediamines and para-aminophenols, which are generally referred to as oxidation bases.
  • Couplers are selected in particular from meta-dihydroxybenzenes, meta-aminophenols and meta- phenylenediamines to provide a wide range of different color nuances.
  • the cosmetic composition containing the oxidation bases is normally activated by the addition of hydrogen peroxide, which give rise to colored compounds by a process of oxidative condensation.
  • Another dye system which is non-oxidative is the semi-permanent system which offers the opportunity of coloring hair with colorants containing direct dyes (often referred to as toners).
  • Another type of dyes for direct coloring are cationic dyes, for example, the widely used "Arianor®-Dyes”.
  • these dyes are suffering form various deficiencies; so for instance the dyes are standardized and components may vary from one batch to another.
  • Nitro dyes and Arianor® dyes have different dye uptake properties on keratin fibers depending on the degree of hair damage. Normally nitro dyes show stronger dye uptake on the root areas whereas cationic dyes show stronger dye uptake on the lengths. Numerous compositions available on the market consist therefore of quite complex compositions of nitro and Arianor® dyes to provide more even color results.
  • the individual dyes of the above described types have the drawback that they produce irregularities when used on hair that has been damaged to different degrees or lead to quite uneven colorations; further, the endurance of the coloration is insufficient, i.e., fastness in particular with respect to shampoos; after each washing the color result becomes weaker so that the natural hair color is re-obtained after five to ten washes, depending on the individual hair type.
  • compositions for dyeing keratin fibers able to produce a broad range of colors and therefore there is still strong need for dyes which fulfill these requirements.
  • the present invention relates to new compositions for dyeing keratin fibers comprising, in a medium suitable for dyeing, one or more cationic dye of general formula (I) or (II), or a physiologically tolerated adduct thereof with an acid:
  • the invention also relates to a process for dyeing keratin fibers comprising one or more cationic dye of general formula (I) or (II), or a physiologically tolerated adduct thereof with an acid.
  • compositions for dyeing keratin fibers and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, one or more cationic direct dye of general formula (I) or (II), or a physiologically tolerated adduct thereof with an acid:
  • 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
  • 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; 15 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:
  • Rl is hydrogen
  • 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 hydroxyethyl group; or two of the RIO to R12 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.
  • 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, morpholino group or N-methylpiperazino group;
  • R13 is a methyl 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 methylene diradical
  • Q is an N-methyl pyridinium moiety.
  • Manufacturing of the cationic direct dyes of the present invention is based on commonly known chemical methods.
  • the synthesis of dyes of the present invention 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 synthesis of numerous 5-amino pyrazoles, useful for synthesis of the cationic dyes of the current invention, was described by H. Hohn, Z. Chem., 10, 386 (1970). Selected from this literature was for illustration of the current invention l-(pyridin-3-ylmethyl)-lH-pyrazol-5-amine (III). Synthesizing the dyes of the invention is especially economical if the same 5-amino-pyrazole intermediate is used for manufacturing dyes of formula (I) and formula (II).
  • 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 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: 3 -( ⁇ 5 - Amino-4- [(2-amino-3 , 5 -dimethyl-4-oxocyclohexa-2, 5 -dien- 1 - ylidene)amino]- IH-pyrazol- 1 -yl ⁇ methyl)- 1 -methylpyridinium chloride;
  • the dyes may also exist in one or more tautomeric forms.
  • Most preferred cationic dyes of general formula (I) or (II), obtainable from the pyrazole intermediate (III), may be selected from the group comprising:
  • compositions of the invention comprising, in a medium suitable for dyeing, one or more cationic dye of general formula (I) or (II), as defined above, may further comprise one or more known conventional direct dye(s), different from those of general formula (I) and (II).
  • the color range of the cationic direct dyes of general formula (I) and (II) can be extended, for example, by the addition of one or more conventional cationic direct dye which is a cationic direct blue dye.
  • cationic anthraquinone blue dyes of the general formula (VIII) are highly compatible with the dyes of general formula (I) and (II) and fulfill the requirements in an outstanding manner:
  • 16 is a hydrogen atom, a C1-C6 alkyl group which may be substituted by one or two hydroxy groups, a di-(Cl-C2)alkylamino-(C2-C3)alkyl group, a phenyl or a tolyl group;
  • R17 is a hydrogen atom, a methyl or a methoxy group
  • Z is a (C2-C3)-alkylene diradical
  • G+ is a cationic group selected from formula (a) or (b) wherein R10-R12 and R13 are as defined for general formula (I) and (II);
  • X is an anion as defined for general formula (I) and (II), preferably it is chloride, bromide, methylsulfonate or methyl sulfate.
  • the anthraquinone dyes of general formula (VIII) HC Blue 16 and HC Blue 17 (INCI names) are the most preferred.
  • the cationic dye(s) of general formula (I) or (II) according to the invention are preferably used in a concentration of from 0.001 to 10% by weight, and even more preferably from 0.05 to 5% by weight, relative to the total weight of the ready-to-use composition.
  • cationic dyes of general formula (I) and (II) and optionally (VIII) are able to produce a broad range of colors further conventional direct dyes may be added, which may be cationic, nonionic or anionic or mixtures thereof.
  • Cationic direct dyes which can be used in combination with cationic dyes of general formula (I) or (II) are for instance the dyes Basic Yellow 57, Basic Brown 16, Basic Brown 17, Basic Red 76, Basic Red 1 18, and Basic Blue 99.
  • Useful cationic dyes of the triphenylmethane type are for instance Basic Violet 2 and Basic Blue 77.
  • Non ionic dyes which may be used in combination with cationic dyes of general formula (I) or (II) are of the nitro dye type which can be selected from 2- Amino-3-nitrophenol; 2-[(2-Hydroxyethyl)amino]-l-methoxy-5-nitrobenzene; 1- (2-Hydroxyethoxy)-3-methylamino-4-nitrobenzene; 2,3-(Dihydroxypropoxy)-3- methylamino-4-nitrobenzene; 1 -[(2-Ureidoethyl)amino]-4-nitrobenzene; 4-[(2- Hydroxyethyl)amino]-3-nitro- 1 -methylbenzene; 1 -[(2-Hydroxyethyl)amino]-2- nitrobenzene (HC Yellow No.
  • Anionic dyes in combination with cationic dyes of general formula (I) or (II) and optionally (VIII) may be used to obtain very specific effects; such as, for example, Acid Yellow 1, Acid Yellow 23, Acid Red 52, Acid Red 92 and Acid Violet 43.
  • nonionic dyes and anionic dyes are preferably used in a concentration of from 0.001 to 5% by weight, and even more preferably from 0.05 to 2.5% by weight, relative to the total weight of the composition.
  • compositions for dyeing keratin fibers in accordance with the invention can be in various forms, such as in form of a liquid, a cream, a gel, a liquid able to produce foam, or in any other form which is appropriate for dyeing keratin fibers, in particular human hair.
  • compositions for dyeing keratin fibers can therefore comprise various adjuvants used conventionally in compositions for dyeing hair, such as solvents, fatty alcohols, fatty acids, cationic, nonionic, anionic, amphoteric surfactants or mixtures thereof, cationic, nonionic, anionic, amphoteric polymers or mixtures thereof, inorganic or organic thickeners, inorganic or organic acids and bases for adjusting the pH to the desired range, buffers, penetrating agents, sequestering agents, dispersing agents, film-forming agents, preserving agents, opacifiers and fragrances.
  • adjuvants used conventionally in compositions for dyeing hair, such as solvents, fatty alcohols, fatty acids, cationic, nonionic, anionic, amphoteric surfactants or mixtures thereof, cationic, nonionic, anionic, amphoteric polymers or mixtures thereof, inorganic or organic thickeners, inorganic or organic acids and bases for adjusting the pH to the
  • the medium which is suitable for dyeing 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 in case they are not sufficiently soluble in water.
  • the organic solvent may be, for example, an alcohol 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 an aromatic alcohol such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents can be present in a concentration preferably ranging from approximately 1 to approximately 40% by weight relative to the total weight of the composition, and even more preferably from approximately 2 to approximately 20% by weight relative to the total weight of the composition.
  • Fatty alcohols may be aliphatic alcohols usually consisting of a chain of 8 to
  • Fatty alcohols usually have even number of carbon atoms and a single hydroxy group attached to the terminal carbon. Some are unsaturated and some are branched.
  • Examples are for instance cetyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, lanolin alcohol, lauryl alcohol, oleyl alcohol, behenyl alcohol, and mixtures thereof.
  • the preferred surfactants will ensure maximum compatibility of the cosmetic medium with the variety of dyes, optionally added oxidizing agents, conditioning materials typically present in such compositions.
  • Suitable anionic surfactants for the hair colorants according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may also be present in the molecule.
  • acyl sarcosides containing 10 to 18 carbon atoms in the acyl group
  • acyl taurides containing 10 to 18 carbon atoms in the acyl group
  • acyl isethionates containing 10 to 18 carbon atoms in the acyl group
  • sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups
  • linear alkane sulfonates containing 12 to 18 carbon atoms
  • linear a-olefm sulfonates containing
  • esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • Zwitterionic surfactants are surface active compounds which contain at least one quaternary ammonium group and at least one -COO (_) or -SO 3 (_) group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3- carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropy
  • Ampholytic surfactants are surface-active compounds which, in addition to a Cs-18 alkyl or acyl group, contain at least one free amino group and at least one— COOH or— SO 3 H group in the molecule and which are capable of forming inner salts.
  • ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N- hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacyl aminoethyl aminopropionate and CI 2- C18 acyl sarcosine.
  • Nonionic surfactants contain, for example, a polyol group, a poly-alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are:
  • cationic surfactants suitable for use in compositions according to the invention are, in particular, quaternary ammonium compounds.
  • ammonium halides such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride; in some cases the anion of the cationic surfactant may be different and consists of an alkylsufate anion.
  • Other cationic surfactants suitable for use in accordance with the invention are for instance the quaternized protein hydrolyzates.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80);
  • alkyl amidoamines particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid®S 18, are distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability;
  • esterquats such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex® and the products marketed under the trade name of Dehyquart® - such as Dehyquart® AU-46 and Dehyquart® L-80 - are also readily biodegradable.
  • the esterquats are the particularly preferred surfactants for the purposes of the invention.
  • quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat®100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).
  • compositions of the present invention may further comprise one or more thickeners in an amount sufficient to provide the composition with the required viscosity so that it can be readily applied to the hair without unduly dripping off the hair.
  • thickeners such as xanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose, ethyl cellulose (available as AQUACOTETM), hydroxyethyl cellulose (NAT OSOLTM), carboxymethyl cellulose, hydroxypropylmethyl cellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose, hydroxypropyl cellulose (available as KLUCELTM), hydroxyethyl ethyl cellulose, cetyl hydroxyethyl cellulose (available as NATROSOLTM Plus 330), N-vinylpyrrolidone (available as POVIDONETM), Acrylates/Ceteth-20 Itaconate Copolymer (available as STRUCTURETM 300
  • PEG- 150/Decyl/SMDI copolymer available as ACULYNTM 44
  • PEG- 150/Stearyl/SMDI copolymer available as ACULYNTM 46
  • Acrylates/Beheneth- 25 Methacrylate Copolymer available as ACULYNTM 28
  • Acrylate s/Vinyl Neodecanoate Crosspolymer available as ACULYNTM 38
  • Acrylates/Steareth-20 Methacrylate Crosspolymer available as ACULYNTM 88
  • PEG- 150 Distearate available as ACULYNTM 60
  • trihydroxystearin available as THIXCINTM
  • acrylates copolymer e.g.
  • ACULYNTM 33 or hydrophobically modified acrylate copolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer (available as ACULYNTM 22), non-ionic amphophilic polymers comprising at least one fatty chain and at least one hydrophilic unit selected from polyether urethanes comprising at least one fatty chain.
  • ACULYNTM 22 hydrophobically modified acrylate copolymers
  • non-ionic amphophilic polymers comprising at least one fatty chain and at least one hydrophilic unit selected from polyether urethanes comprising at least one fatty chain.
  • the added amount may be at least 0.05%, preferably at least 0.5% to 1%, by weight of thickener relative to the total weight of the composition.
  • the thickener may be present in any of the components.
  • the composition may further optionally comprise a cationic polymer or a combination of cationic polymers.
  • Preferred cationic polymers are Polyquaternium-7, Polyquaternium-22, Polyquaternium-37 and Polyquaternium- 87. Particularly preferred are Polyquaternium-22 and Polyquaternium-37 and mixtures thereof.
  • the compositions of the present invention may comprise at least about 0.05%, preferably from about 0.5% to 2% by weight of the composition of a cationic polymer.
  • compositions of the present invention may also comprise conditioning agents.
  • Conditioning agents suitable for use may be selected from silicone materials, amino silicones, polymeric resins, polyol carboxylic acid esters, cationic surfactants, water-insoluble oils, oil derived materials and mixtures thereof.
  • Useful silicone conditioning materials can be selected from polyalkylsilioxane oils, linear polydiemthylsiloxane oils containing trimethylsilyl or hydroxydimethylsiloxane end groups, polymethylphenylsiloxane polydimethylphenylsiloxane or polydimethyldiphenylsiloxane oils, silicone resins, organofunctional siloxanes having in their general structure one or a number of organofunctional group(s), the same or different, attached directly to the siloxane chain.
  • Said organofunctional group(s) are selected from polyethyleneoxy and/or polypropyleneoxy groups, (per)fluorinated groups, thiol groups, substituted or unsubstituted amino groups, carboxylate groups, hydroxylated groups, alkoxylated groups, quaternium ammonium groups, amphoteric and betain groups.
  • the silicone can either be used as a neat fluid or in the form of a pre-formed emulsion.
  • the conditioning agent may generally be used at levels of from about 0.05% to about 20% by weight of the composition, preferably of from about 0.1% to about 15%, more preferably of from about 0.2% to about 10%, even more preferably of from about 0.2% to about 2%.
  • phosphate -based conditioning and emulsifying wax comprising a mixture of cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), dicetyl phosphate and ceteth-10 phosphate (e.g. available as C ODAFOSTM CES).
  • Another useful raw material may be beheneth 30 phosphate, cetostearyl alcohol, mono and dicetyl phosphate (e.g. available as CRODAFOSTM BES-70).
  • the preferred amount of such materials is at least 0.1%, preferably from 0.1% to about 20%, preferred for the current application is an amount between 0.5% and 5% by weight.
  • compositions may further comprise ingredients which have antistatic or film forming properties such as polyamines, for example PEG- 15 Cocopolyamine and Chitosan.
  • ingredients which have antistatic or film forming properties such as polyamines, for example PEG- 15 Cocopolyamine and Chitosan.
  • compositions may also comprise extracts, for instance plant extracts or vegetable oils, for example in amounts from 0.1 to 5%, more preferably from 0.5 to 2.5% by weight.
  • the pH of the composition may generally range from approximately 2 to approximately 12, preferably the pH is from 7 to 1 1.
  • the pH can be adjusted to the desired value using acidifying or basifying agents usually used in the dyeing of keratin fibers.
  • Acidifying agents may be inorganic or organic acids such as hydrochloric acid, phosphoric acid, carboxylic acids such as malic acid, citric acid or lactic acid, and sulphonic acids.
  • Basifying agents may be, for example, aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine (MEA) and triethanolamine, l-amino-2-propanol, 2-amino-2-methyl-propanol (AMP), 2-amino-2-methyl-l,3- propanediol, 2-amino-2-ethyl-l,3-propanediol and tris(hydroxymethyl)- aminomethane (tromethamine, Tris), sodium hydroxide, potassium hydroxide or mixtures thereof.
  • alkanolamines such as monoethanolamine (MEA) and triethanolamine
  • MEA monoethanolamine
  • AMP 2-amino-2-methyl-propanol
  • 2-amino-2-methyl-propanol 2-amino-2-methyl-propanol
  • 2-amino-2-methyl-propanol 2-amino-2-methyl-propanol
  • the amount of basifying agents can range between 0.1 and 10% by weight, preferably between 1 and 5% by weight.
  • the ready-to-use composition also contains an ammonium salt such as ammonium chloride.
  • the oxidizing agent present in the composition may be selected from oxidizing agents used conventionally in oxidation dyeing and preferably from hydrogen peroxide, urea peroxide, alkali metal bromates and persalts such as a percarbonate salt, a bromate salt, a perborate salt or a persulfate salt. Hydrogen peroxide is particularly preferred.
  • the ready-to-use compositions in accordance with the invention lead from weakly colored to intense, from colorations of low chromaticity to chromatic colorations. Therefore the compositions according to the invention are useful to provide natural shades as well as fashioned shades. Besides the chromatic properties the ready-to-use compositions show very good evenness and excellent properties of resistance with respect to atmospheric factors such as light and bad weather and with respect to perspiration and the various treatments to which the hair may be subjected (washing, blow-drying, combing, or permanent-waving).
  • Another object of the invention is a process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, using a ready-to-use composition as defined above.
  • the ready-to-use composition is applied to the hair fibers and is left on them for an exposure time preferably ranging from approximately 3 to approximately 40 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)-lH- pyrazol-5-amine intermediates
  • 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, fine 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)-lH-pyrazol-5- amine
  • Arylamine p-toluidine
  • Arylamine methyl p-aminobenzoate
  • Example 1 d 4- [(2-methyl-4-nitrophenyl)diazenyl] -1 -(py ridin-3- ylmethyl)-lH-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 2c 4-[(5-amino-4- ⁇ [2-(hydroxymethyl)phenyl]diazenyl ⁇ -lH- pyrazol-l-yl)methyl]-l-methylpyridinium methyl sulfate (I-iii)
  • the product on TLC is uniform and shows the expected characteristics of a cationic dye.
  • the dye crystallizes out as hydrobromide and contains two equivalents of crystal water.
  • Example 2e 3-( ⁇ 5-Amino-4-[(4-methylphenyl)diazenyl]-lH-pyrazol-l- yl ⁇ methyl)-l-(2-hydroxyethyl)pyridinium bromide hydrobromide (dye I-v)
  • a mixture of 4-[(4-Methylphenyl)diazenyl]-l-(pyridin-3-ylmethyl)-lH- pyrazol-5-amine (example lb, lOOmmol, 29.24g) and 2-bromoethanol (500mmol, 65.77g) is heated to 100°C in 350 ml 3-methoxypropionitrile for 6 hours.
  • Methyl 4- ⁇ [5-amino- 1 -(pyridin-3-ylmethyl)- 1 H-pyrazol-4- yl]diazenyl ⁇ benzoate (example lc, 6.6g, 19.6mmol) is suspended in 100ml 3- methoxypropionitrile and heated to 100°C.
  • Dimethylsulfate (2.6g, 20.6mmol) 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 20-30ml, 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 3a 3-( ⁇ 5-Amino-4-[(2-amino-3,5-dimethyl-4-oxocyclohexa-2,5- dien-l-ylidene)amino]-lH-pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride (Il-i) is obtained from 3-amino-2,6-dimethylphenol (3.34g, 89% yield).
  • the compound is identical with the reference manufactured by the general method.
  • Example 3b 3- ⁇ [5-Amino-4-( ⁇ 2-[(2-hydroxyethyl)amino]-5-methyl-4- oxocyclohexa-2,5-dien-l-ylidene ⁇ amino)-lH-pyrazol-l-yl] methyl ⁇ -l- methylpyridinium chloride ( ⁇ -ii) 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]-lH-pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride (II-iii) 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]-lH-pyrazol-l-yl ⁇ methyl)-l-methylpyridinium chloride (Il-iv) is obtained from 2,4-diaminoanisole sulfate (3.29g, 88% yield).
  • Example 3e 3- ⁇ [5-amino-4-( ⁇ 2-[(2-hydroxyethyl)amino]-4-imino-5- methoxycyclohexa-2,5-dien-l-ylidene ⁇ amino)-lH-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 ⁇ -lH-pyrazol-l-yl)methyl]-l- methylpyridinium chloride (II-vi) is obtained from 2,4-diaminophenoxyethanol 2HC1 (2.95g, 73% yield).
  • Colorants are prepared by dissolving the dyes of formula (I) and/or (II) in the following composition:
  • the colorant which is in form of a gel is applied to white Yak hair. After a processing time of 30 min at 30°C, the hair is washed with water and dried. The colors are of intense, vivid shades as indicated in Table 1.
  • the stock solutions containing the dyes are prepared with the proportions indicated in the Table 2 (numbers in grams).
  • the obtained colorants are applied to white Yak hair in a sufficient amount. After a processing time of 30 min at 30°C, the hair was washed with water and dried. The nuances are as indicated in Table 2.
  • the cream composition is mixed 1 : 1 (w/w) with hydrogen peroxide 6% and applied to hair swatches of different degree of damage.
  • the hair fibers were
  • the standard processing time was 30 min at 30°C.
  • the hair swatches were rinsed with warm water, shampooed and dried. In both cases the color result was identical, medium brown.
  • the grey coverage which was 100%, was evaluated by means of the 50% human grey hair swatch.

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Abstract

La présente invention concerne de nouvelles compositions pour la coloration de fibres de kératine, comprenant, dans un milieu approprié pour la coloration, un ou plusieurs colorants cationiques de formule générale (I) ou (II), ou un adduit physiologiquement toléré de celui-ci ayant un acide: (II), ainsi qu'un procédé pour colorer des fibres de kératine, comprenant un ou plusieurs colorants cationiques de formule générale (I) ou (II), ou un adduit physiologiquement toléré de celui-ci ayant un acide.
PCT/EP2013/062997 2013-06-21 2013-06-21 Nouvelles compositions cosmétiques comprenant des colorants cationiques, et procédé de coloration directe de fibres de kératine Ceased WO2014202152A1 (fr)

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US20220362137A1 (en) * 2019-07-05 2022-11-17 L'oreal Composition comprising a natural dye, a hydrazono and/or azo cationic synthetic direct dye and an aromatic compound
US20230363994A1 (en) * 2020-06-30 2023-11-16 L'oreal Dyeing composition comprising an anthraquinone cationic direct dye, a polyol, an anionic surfactant and a nonionic polysaccharide

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FR1391408A (fr) * 1963-04-24 1965-03-05 Geigy Ag J R Procédé de teinture de matières à base de polyamides
US4308205A (en) * 1976-11-17 1981-12-29 Montedison S.P.A. Water-soluble monoazo cationic dyestuffs derived from 1-phenyl-3-aminopyrazoles
WO1995001772A1 (fr) * 1993-07-05 1995-01-19 Ciba-Geigy Ag Procede de teinture de fibres keratiniques
WO2005051918A1 (fr) * 2003-11-21 2005-06-09 Wella Aktiengesellschaft Diaminopyrazoles cationiques, procede pour leur production et colorants contenant ces composes
US20060005327A1 (en) * 2004-06-23 2006-01-12 Andrew Greaves Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor
FR2925052A1 (fr) * 2007-12-14 2009-06-19 Oreal Colorants directs azomethiniques ou precurseurs reduits de colorants directs azomethiniques obtenus a partir du 4,5-diamino-pyrazole, procede de coloration capillaire a partir de ces colorants ou precurseurs
EP2246038A1 (fr) * 2009-04-30 2010-11-03 L'Oréal Composés de type azométhinique à motif pyrazolopyridine cationique pour la coloration des fibres kératiniques

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FR1391408A (fr) * 1963-04-24 1965-03-05 Geigy Ag J R Procédé de teinture de matières à base de polyamides
US4308205A (en) * 1976-11-17 1981-12-29 Montedison S.P.A. Water-soluble monoazo cationic dyestuffs derived from 1-phenyl-3-aminopyrazoles
WO1995001772A1 (fr) * 1993-07-05 1995-01-19 Ciba-Geigy Ag Procede de teinture de fibres keratiniques
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WO2005051918A1 (fr) * 2003-11-21 2005-06-09 Wella Aktiengesellschaft Diaminopyrazoles cationiques, procede pour leur production et colorants contenant ces composes
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US20060005327A1 (en) * 2004-06-23 2006-01-12 Andrew Greaves Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor
FR2925052A1 (fr) * 2007-12-14 2009-06-19 Oreal Colorants directs azomethiniques ou precurseurs reduits de colorants directs azomethiniques obtenus a partir du 4,5-diamino-pyrazole, procede de coloration capillaire a partir de ces colorants ou precurseurs
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220362137A1 (en) * 2019-07-05 2022-11-17 L'oreal Composition comprising a natural dye, a hydrazono and/or azo cationic synthetic direct dye and an aromatic compound
US20230363994A1 (en) * 2020-06-30 2023-11-16 L'oreal Dyeing composition comprising an anthraquinone cationic direct dye, a polyol, an anionic surfactant and a nonionic polysaccharide
US12544322B2 (en) * 2020-06-30 2026-02-10 L'oréal Dyeing composition comprising an anthraquinone cationic direct dye, a polyol, an anionic surfactant and a nonionic polysaccharide

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