Classifications

• • 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
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • 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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
• • 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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/415—Aminophenols
• • 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

Definitions

• the present invention relates to an oxidation dyeing composition for keratin fibers, in particular human keratin fibers and more particularly for hair, comprising at least one oxidation dye and at least one cationic associative polyurethane.
• oxidation bases in particular ortho- or para-phenylenediamines, ortho - or para-aminophenols, and heterocyclic bases.
• the oxidation dye precursors are initially little or no colored compounds which develop their dyeing power within the hair in the presence of oxidizing agents, leading to the formation of colored compounds.
• the formation of these colored compounds results either from an oxidative condensation of the "oxidation bases” on themselves, or from an oxidative condensation of the "oxidation bases” on color-modifying compounds, or “couplers” , which are generally present in the dye compositions used in oxidation dyeing and are represented more particularly by metaphenylenediamines, meta-aminophenols and metadiphenols, and certain heterocyclic compounds.
• the present invention thus relates to an oxidation dye composition for keratin fibers, in particular for human keratin fibers, and in particular the hair, comprising, in a medium suitable for dyeing, at least one oxidation dye, which is characterized in that it further comprises at least one cationic associative polyurethane.
• Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers which comprises at least one oxidation dye and at least one cationic associative polyurethane and an oxidizing agent.
• ready-to-use composition is meant, within the meaning of the invention, the composition intended to be applied as it is to keratin fibers, ie it can be stored as it is before use or result of the extemporaneous mixture of two or more compositions.
• the invention also relates to a process for dyeing keratin fibers, in particular for human keratin fibers and more particularly hair, comprising: applying to the fibers at least one composition A containing, in a medium suitable for dyeing, at least one oxidation dye, the color being revealed at alkaline, neutral or acidic pH, using a composition B containing at at least one oxidizing agent which is mixed just at the time of use with composition A or which is applied sequentially without intermediate rinsing, at least one cationic associative polyurethane being present in composition A or in composition B or in each of compositions A and B.
• the invention also relates to dyeing devices or “kits” with several compartments for the oxidation dyeing of human keratin fibers and in particular of the hair.
• a device with 2 compartments comprises a compartment containing a composition A1 containing, in a medium suitable for dyeing, at least one oxidation dye, and another compartment containing a composition B1 containing, in a medium suitable for the dye, an oxidizing agent, the cationic associative polyurethane being present in composition A1 or composition B1, or in each of compositions A1 and B1.
• Another device comprises a first compartment containing a composition A2 comprising, in a medium suitable for dyeing, at least one oxidation dye, a second compartment containing a composition B2 comprising, in a medium suitable for dyeing at least one oxidizing agent, and a third compartment containing a composition C comprising, in a medium suitable for dyeing, at least one cationic associative polyurethane, composition A2 and / or composition B2 can also comprise an associative polyurethane cationic.
• Associative polymers are polymers whose molecules are capable, in the formulation medium, of associating with each other or with molecules of other compounds.
• a particular case of associative polymers are amphiphilic polymers, that is to say polymers comprising one or more hydrophilic parts which make them soluble in water and one or more hydrophobic zones (comprising at least one chain fatty) by which polymers interact and gather together or with other molecules.
• Cationic associative polyurethanes are more particularly chosen from cationic, water-soluble or water-dispersible associative amphiphilic polyurethanes.
• water-soluble or “water-soluble” relating to the associative polyurethanes of the present invention means that these polymers have a solubility in water at room temperature at least equal to 1% by weight, that is to say say that up to this concentration, no precipitate can be detected with the naked eye and the solution is perfectly clear and homogeneous.
• water-dispersible or “water-dispersible” polyurethanes means polymers which, when suspended in water, spontaneously form globules having an average size, measured by light scattering on a Coulter type, between 5 nm and 600 nm, and in particular between 5 nm and 500 nm.
• R and R ' identical or different, represent a hydrophobic group or a hydrogen atom
• X and X ′ which may be identical or different, represent a group comprising an amine function carrying or not carrying a hydrophobic group, or also the group L ";
• L, L 'and L " identical or different, represent a group derived from a diisocyanate
• P and P ' which are identical or different, represent a group comprising an amine function carrying or not a hydrophobic group;
• Y represents a hydrophilic group;
• r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25, n, m, and p are each independently of the others between 0 and 1000; the molecule containing at least one protonated or quaternized ine function and at least one hydrophobic group.
• the only hydrophobic groups are the groups R and R 'at the chain ends.
• a preferred family of cationic associative polyurethanes is that corresponding to the formula (la) described above and in which:
• R and R ' both independently represent a hydrophobic group
• X, X' each represent a group L "
• n and p are between 1 and 1000 and L
• P, P', Y and m have the meaning given above.
• Another preferred family of cationic associative polyurethanes is that corresponding to the formula (la) above in which:
• R and R ' both independently represent a hydrophobic group
• X, X' each represent a group L ", n and p are 0, and L, L ', L", Y and m have the meaning indicated above.
• n and p are equal to 0 means that these polymers do not contain units derived from an amino-functional monomer incorporated into the polymer during polycondensation.
• the protonated amino functions of these polyurethanes result from the hydrolysis of isocyanate functions, in excess, at the chain end, followed by the alkylation of the primary amine functions formed by alkylating agents with a hydrophobic group, that is to say say compounds of type RQ or R'Q, in which R and
• R ' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
• R and R ' both independently represent a hydrophobic group
• X and X ' both independently represent a group comprising a quaternary amine, n and p are zero, and
• L, L ', Y and m have the meanings indicated above.
• the number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500,000, in particular between
• hydrophobic group means a radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, which may contain one or more several heteroatoms such as P, O, N, S, or a radical with a perfluorinated or silicone chain.
• the hydrophobic group comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.
• the hydrocarbon group comes from a monofunctional compound.
• the hydrophobic group can be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.
• X and / or X' denote a group comprising a tertiary or quaternary amine
• X and / or X' can represent one of the following formulas:
• R 2 represents an alkylene radical having from 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms being able to be replaced by a heteroatom chosen from N, S, O, P;
• Ri and R 3 denote a linear or branched CC 30 alkyl or alkenyl radical, an aryl radical, at least one of the carbon atoms which can be replaced by a heteroatom chosen from N, S, O, P; A ' is a physiologically acceptable counterion.
• R represents an alkylene radical having from 1 to 20 carbon atoms, linear or branched, comprising or not a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms which can be replaced by a heteroatom chosen from N, S, O and P.
• the groups P and P ', comprising an amino function can represent at least one of the following formulas:
• R 5 and R have the same meanings as R 2 defined above;
• R 6 , R 8 and R 9 have the same meanings as Ri and R 3 defined above;
• Rio represents an alkylene group, linear or branched, optionally unsaturated and possibly containing one or more heteroatoms chosen from N, O, S and P, and A " is a physiologically acceptable counterion.
• hydrophilic group means a water-soluble group, polymeric or not. 'For example, there may be mentioned, when it is not a polymer, ethylene glycol, diethylene glycol and propylene glycol.
• a hydrophilic polymer mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers .
• the hydrophilic compound is a polyether and in particular a poly (ethylene oxide) or poly (propylene oxide).
• the cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds having functions with labile hydrogen.
• the labile hydrogen functions can be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas respectively.
• polyurethanes of the present invention encompasses these three types of polymers, namely polyurethanes themselves, polyureas and polythioureas as well as copolymers thereof.
• a first type of compound used in the preparation of the polyurethane of formula (la) is a compound comprising at least one unit with an amino function.
• This compound can be multifunctional, but preferably the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of muitifunctional compounds is low.
• this compound may comprise more than one motif with an amino function. It is then a polymer carrying a repetition of the motif with an amino function.
• This type of compound can be represented by one of the following formulas: HZ- (P) n -ZH. or HZ- (P -ZH
• N-methyldiethanolamine N-tert-butyl-diethanolamine, N-sulfofldyethanolamine.
• the second compound used in the preparation of the polyurethane of formula (la) is a diisocyanate corresponding to the formula:
• R 4 is defined above.
• methylenediphenyl diisocyanate methylene cyclohexanediisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butanediisocyanate, hexanediisocyanate.
• a third compound used in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the hydrophobic end groups of the polymer of formula (la).
• This compound consists of a hydrophobic group and a function containing labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
• this compound can be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol, decyl alcohol.
• this compound may, for example, be hydrogenated - hydroxylated polybutadiene.
• the hydrophobic group of the polyurethane of formula (la) can also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit.
• the hydrophobic group is introduced by the quaternizing agent.
• This quaternizing agent is a compound of type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
• the cationic associative polyurethane can also comprise a hydrophilic block.
• This sequence is provided by a fourth type of compound used in the preparation of the polymer.
• This compound can be multifunctional. It is preferably difunctional. It is also possible to have a mixture where the percentage of multifunctional compound is low.
• the labile hydrogen functions are alcohol, primary or secondary amine, or thiol functions. This compound can be a polymer terminated at the ends of the chains by one of these functions containing labile hydrogen.
• hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers.
• the hydrophilic compound is a polyether and in particular a poly (ethylene oxide) or poly (propylene oxide).
• the hydrophilic group noted Y in formula (la) is optional. Indeed, the units with a quaternary or protonated amine function may be sufficient to provide the solubility or the hydrodispersibility necessary for this type of polymer in an aqueous solution.
• hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are however preferred.
• Said cationic associative polyurethanes are water-soluble or water-dispersible.
• the cationic associative polyurethane (s) is preferably used in an amount which can vary from approximately 0.01 to 10% by weight of the total weight of the composition. More preferably, this amount varies from about 0.1 to 5% by weight.
• oxidation dyes which can be used according to the invention are chosen from oxidation bases and / or couplers.
• compositions according to the invention contain at least one oxidation base.
• the oxidation bases can be used in the frame "the present invention are chosen from those conventionally known in oxidation dyeing, and among which the ortho- and para-phenylenediamines can be mentioned in particular, double bases, ortho- and para - aminophenols, the following heterocyclic bases and their addition salts with an acid, for example:
• Ri represents a hydrogen atom, a CC 4 alkyl, monohydroxyalkyl radical.
• CrC l polyhydroxyalkyl C 2 -C 4 alkoxy (C ⁇ -C) alkyl (CrC 4 ), alkyl C r C 4 substituted by a nitrogen group, phenyl or 4'-aminophenyl;
• R 2 represents a hydrogen atom, a CC 4 alkyl radical, a monohydroxyalkyl radical
• R 3 represents a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl radical in CC 4 , sulfo, carboxy, monohydroxyalkyl in CC 4 or hydroxyalkoxy in CC 4 , acetylaminoalkoxy in C r C 4 , C r C mesylaminoaicoxy or Cr C carbamoylamino alkoxy, 5 R 4 represents a hydrogen or halogen atom or a CC 4 alkyl radical.
• a halogen atom such as a chlorine atom
• an alkyl radical in CC 4 sulfo, carboxy, monohydroxyalkyl in CC 4 or hydroxyalkoxy in CC 4 , acetylaminoalkoxy in C r C 4 , C r C mesylaminoaicoxy or Cr C carbamoylamino alkoxy
• 5 R 4 represents a hydrogen or halogen atom or a
• N-phenyl-paraphenylenediamine 2- ⁇ -hydroxyethyloxy-paraphenylenediamine, 2- ⁇ -5 acetylaminoethyloxy-paraphenylenediamine, N- ( ⁇ -methoxyethyl) - paraphenylenediamine, 2-methyl-1-N- ⁇ -hydroxyethyl-paraphenylenediamine, and their addition salts with an acid.
• para-phenylenediamines of formula (I) above very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl-para-phenylenediamine, 2- ⁇ -hydroxyethyl-para-phenylenediamine,
• double bases is intended to mean compounds comprising at least two aromatic rings on which are carried amino and / or hydroxyl groups.
• - Zi and Z 2 identical or different, represent a hydroxyl radical or -NH 2 which can be substituted by an alkyl radical in C, -C 4 or by a link arm Y;
• the link arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals in CC s ;
• R 5 and R 6 represent a hydrogen or halogen atom, an alkyl radical in CC, monohydroxyalkyl in C ⁇ -C 4 , polyhydroxyalkyl in C 2 -C, aminoalkyl in CC 4 ' or a link arm Y; - R 7 , R 8 , R 9 , Rio, Ru and R ⁇ 2) identical or different, represent a hydrogen atom, a link arm Y or a CC alkyl radical; it being understood that the compounds of formula (H) have only one linking arm
• nitrogen groups of formula (II) above mention may in particular be made of the amino, monoalkyl (CC 4 ) amino, dialkyl (CC 4 ) amino, trialkyl (CC 4 ) amino, monohydroxyalkyl (CC 4 ) arnino radicals, imidazolinium and ammonium.
• N, N'-bis- ( ⁇ -hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propanol, 1, 8 -bis- (2,5-diaminophenoxy) -3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred,
• R 1 3 represents a hydrogen atom, a halogen atom such as fluorine, an alkyl radical in CC 4 , monohydroxyalkyl in CC, alkoxy (C., - C) alkyl (CC) or aminoalkyl in CC 4 , or hydroxyalkyl (C t -C 4 ) C, -C 4 aminoalkyl
• R 1 represents a hydrogen atom or a halogen atom such as fluorine, an alkyl radical -C 4l CC monohydroxyalkyl, polyhydroxyalkyl, C 2 -C 4 aminoalkyl, C r -C 4 cyanoalkyl or alkoxy CC 4 (C r C) alkyl (C ⁇ -C 4 ).
• para-aminophenols of formula (III) above there may be mentioned more particularly para-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluoro-phenol, 4-amino - 3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-methoxymethyl-phenoI, 4-amino-2-aminomethyl-phenol , 4-amino- 2- ( ⁇ -hydroxyethyl-a ⁇ inomethyl) -phenol, and their addition salts with an acid.
• ortho-aminophenols which can be used as oxidation bases in the context of the present invention, are in particular chosen from 2-amino-phenol, 2-amino-1-hydroxy-5-methyl- benzene, 2-amino-1-hydroxy-6-methyl-benzene, 5-acetamido-2-amino-phenol, and their addition salts with an acid.
• heterocyclic bases which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may more particularly be made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.
• pyridine derivatives mention may more particularly be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3- amino-pyridine, 2,3-diar ⁇ ino-6-methoxy-, pyridine, 2- ( ⁇ -methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino-pyridine, and their salts 'addition with an acid.
• pyrimidine derivatives mention may be made more particularly of the compounds described for example in German patents DE 2,359,399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-Hydroxy-5,6-diaminopyrimidine, 2, 5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7- diamine; 2,5-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-
• the oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the composition and even more preferably from 0.005 to 8% by weight approximately of this weight.
• the couplers which can be used in the dyeing process according to the invention are those conventionally used in oxidation dyeing compositions, that is to say meta-aminophenols, meta-phenylenediamines, metadiphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, ' sesamol and its derivatives, pyridine derivatives, derivatives
• pyrazolotriazo.es pyrazolones, indazoles, benzimidazoles, benzothia ⁇ oles, benzoxazoles, 1, 3-benzodioxoles, quinolines and their addition salts with an acid.
• couplers are more particularly chosen from 2,4-diamino 1 - ( ⁇ -hydroxyethyloxy) - benzene, 2-methyl-5-amino-phenol, 5-N- ( ⁇ -hydroxyethyl) amino-2-methyl- phenol, 3-amino-phenol, 1, 3-dihydroxy-benzene, 1, 3-dihydroxy-2-methyl-benzene, 4-chloro-1, 3-dihydroxy-benzene, 2-amino 4- ( ⁇ -hydroxyethylamino) -1-methoxy-benzene, 1, 3-diamino-benzene, 1, 3-bis- (2,4-diaminophenoxy) -propane, sesamol, 1 ⁇ amino-2-methoxy- 4,5-methylenedioxy benzene, ⁇ -naphthol, 6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl indole, 6-hydroxy-indoline, 2,6-dihydroxy -4-methyl-
• these couplers preferably represent from 0.0001 to 10% by 'weight of the total weight of the composition, and even more preferably from 0.005 to 5% by weight.
• addition salts with an acid of the oxidation bases and couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.
• composition according to the invention may also contain, in addition to the oxidation dyes defined above, direct dyes to enrich the shades with reflections.
• direct dyes can in particular then be chosen from nitro, azo or anthraquinone, neutral, cationic or anionic dyes in the weight proportion of approximately 0.001 to 20% and preferably from 0.01 to 10% of the total weight of the composition.
• Composition A and / or composition B can also more particularly contain, at least one amphoteric or cationic substantive polymer different from the cationic associative polyurethanes of the invention.
• cationic polymer designates any polymer containing cationic groups and / or groups which can be ionized into cationic groups.
• the cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in patent application EP-A-337 354 and in French patents FR- 2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.
• the preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly connected thereto.
• the cationic polymers used generally have a number-average molecular mass of between 500 and 5J0 6 approximately, and preferably between 10 3 and 3J0 6 approximately.
• cationic polymers mention may more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type.
• R3 identical or different, denote a hydrogen atom or a CH3 radical
• A identical or different, represent an alkyl group, linear or branched, from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group from 1 to 4 carbon atoms;
• R and R2, identical or different, represent hydrogen or an alkyl group having
• X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.
• the polymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1-C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
• comonomers can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1-C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
• guar gums containing groups cationic trialkylammonium such as guar gums containing groups cationic trialkylammonium.
• Guar gums modified with a salt (eg chloride) of 2,3-epoxypropyl trimethylammonium are used, for example.
• Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.
• Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride; an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or also by an oligomer resulting from the reaction of a reactive bifunctional compound vis- with respect to a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydrin, a diepoxide or a bis- derivative unsaturated; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amino group of the polyaminoamide; these polyaminoamides can be al
• 'Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents Mention may be made, for example, of the adipic acid-diacoylaminohydroxyalkoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Such polymers are described in particular in French patent 1,583,363. Among these derivatives, there may be mentioned more particularly the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.
• the molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1.
• Such polymers are described in particular in the patents American 3,227,615 and 2,961,347.
• Polymers of this type are in particular sold under the name "Hercosett 57” by the company Hercules Inc. or else under the name of "PD 170” or “Delsette 101” by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine.
• Rg denotes a hydrogen atom or a methyl radical
• R7 and RQ independently of one another, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1 -C4), or R7 and Rg may denote jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl;
• R7 and Rg independently of one another preferably denote an alkyl group having from 1 to 4 atoms of carbon;
• Y ' is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate.
• R 10 > R 11 - R 12 and R 13 represent a linear or branched C-
• R-14-D where R14 is alkylene and D is a quaternary ammonium group
• A1 and B1 represent polymethylenic groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
• X denotes an anion derived from a mineral or organic acid
• R-10 and R-12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group -
• x and y denote an integer from 1 to 4 , representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical
• X is an anion such as chloride or bromide.
• R These polymers have an average molecular mass generally of between 1000 and 100,000.
• Quaternary polyammonium polymers consisting of recurring units of formula (IX): (CH 2 ) 2 - O - (CH 2 ) 2 - (IX)
• D may be zero or may represent a group - (CH2) r -CO- in which r denotes a number equal to 4 or 7, X "is an anion;
• Such polymers can be prepared according to the methods described in US Pat. Nos. 4,157,388, 4,702,906, 4,719,282 . They are described in particular in patent application EP-A-122 324.
• Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the company BAS. F.
• Mention may more particularly a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride (20/80 by weight) as a dispersion 'containing 50 wt% of said copolymer in mineral oil.
• This dispersion is marketed under the name of "SALCARE® SC 92" by the company ALLIED
• colloids It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names of "SALCARE® SC 95" and “SALCARE® SC 96" by the company ALLIED COLLOIDS.
• cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.
• cationic polymers capable of being used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers with recurring units of formulas (W) and (U) below:
• CH 3 C 2 H 5 and in particular those whose molecular weight, determined by gel permeation chromatography, is approximately 1200.
• the concentration of cationic polymer in the composition according to the present invention can vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.
• K and M can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or although K and M form part of a chain of a polymer with an ⁇ , ⁇ -dicarboxylic ethylene unit, one of the carboxylic groups of which has been caused to react with a polyamine comprising one or more primary or secondary amine groups.
• amphoteric polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:
• the vinyl compound can also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride.
• the copolymers of acrylic acid and of the latter monomer are offered under the names MERQUAT 280, MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.
• Polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reagents, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
• the N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups whose alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide , N-octylacrylamide, N-decyiacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides,
• the acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of the mayic or fumaric acids or anhydrides.
• the preferred basic comonomers are aminoethyl methacrylates, butylaminoethyl, N, N ' ⁇ dimethylaminoethyl, N-tert-butylaminoethyl.
• Copolymers are particularly used whose name CTFA (4th Ed., 1991) is.
• Octylacryiamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
• Rj ⁇ represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of any one of said acids with a primary bis or secondary bis amine
• Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the radical
• Phexamethylenediamine these polyaminoamines being crosslinked by the addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts.
• a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives
• the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
• the alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
• R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
• y and z represent an integer from 1 to 3
• R21 and R22 represent a hydrogen, methyl, ethyl or propyl atom
• R23 and R24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.
• the polymers comprising such units can also comprise units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates; acrylamides or methacrylamides or vinyl acetate.
• non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates; acrylamides or methacrylamides or vinyl acetate.
• non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates
• acrylamides or methacrylamides or vinyl acetate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
• R 25 represents a radical of formula:
• R 27 e * R 28 identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkoyiamine residue or a dialkoylamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R26.
• R2g represents a hydrogen atom, a CH3O radical, CH3CH2O, phenyl
• R30 denotes hydrogen or a lower alkyl radical such as methyl, ethyl
• R3-I denotes hydrogen or a lower alkyl radical such as methyl, ethyl
• R32 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R33-N (R3- ⁇ ) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3) -, R31 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms,
• r is such that the molecular weight is between 500 and 6,000,000 and preferably between 1,000 and 1,000,000.
• X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is a straight or branched chain alkylene radical comprising up to 7 carbon atoms in the main chain which are unsubstituted or substituted by hydroxyl groups and which may additionally contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane;
• E denotes the symbol E or E 'and at least once E';
• E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in (a main chain, substituted or not by one or more hydroxyl radicals and comprising one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with the acid chloroacetic acid or sodium chloroacetate.
• N, N-dimethylaminopropylamine or by semiesterification with an N.N-diaicanolamine is N, N-dimethylaminopropylamine or by semiesterification with an N.N-diaicanolamine.
• copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
• amphoteric polymers which are particularly preferred according to the invention are those of the family (1).
• the amphoteric polymer (s) can represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and even more preferably from 0.1% to 3% by weight , of the total weight of the composition.
• compositions of the invention preferably comprise one or more surfactants.
• the surfactant (s) can be chosen either, alone or as a mixture, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.
• surfactants which are suitable for carrying out the present invention are in particular the following:
• anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, there may be mentioned in particular (non-limiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates, monoglycerides sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, ⁇ -olefin-sulfonates, paraffin-sulfonates; (C 6 -C 2 ) alkyl sulfosuccinates, (C 6 - alkyl)
• alkyl esters C 6 -C 2
• carboxylic polyglycosides such as alkyl glucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside sulfosuccinates., alkylsulfosuccinatnes; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group.
• anionic surfactants that can still be used, there may also be mentioned the salts of fatty acids such as the salts of oleic, ricinoleic, palmitic, stearic acids, acids of coconut oil or hydrogenated coconut oil; acyl-lactylates whose acyl radical contains 8 to 20 carbon atoms.
• alkyl D galactoside uronic acids and their salts the polyoxyalkylene carboxylic (C 6 -C 2 ) ether acids, the polyoxyalkylene (C 6 -C 24 ) alkyl aryl ether carboxylic acids, the alkyl (C 6 -C 24 ) polyoxyalkylene carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.
• Non-ionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants” by MR PORTER, editions Blackie & Son (Glasgow and London), 1991, pp 116-178) and their nature is not, within the framework of the present invention, of critical nature. Thus, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, polyethoxylated, polypropoxylated alkylphenols, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide which can range in particular from 2 to 50.
• copolymers of ethylene oxide and of propylene, condensates of ethylene oxide and of propylene on fatty alcohols polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1, 5 to 4; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide; esters of oxyethylenated sorbitan fatty acids having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethyleneglycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as amino (C-ig - C14) alkyl oxides or N-acylaminopropylmorpholine oxides.
• the alkylpolyglycosides constitute nonionic surfactants which
• Amphoteric or zwitterionic surfactants can in particular be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulfobetaines, (C8-C20) alkyl amidoalkyl (C-j-Ce) betaines or (C8-C20) amidoalkyl (C-J-CQ) alkyl sulfobetaines.
• aliphatic secondary or tertiary amines in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxy
• B represents -CH2CH2OX '
• C represents - (CH2) Z -Y'
• z 1 or 2
• X 'de notes the group -CH2CH2-COOH or a hydrogen atom
• Y denotes -COOH or the radical -CH 2 - CHOH - SO 3 H
• R2 'de notes an alkyl radical of an acid Rg -COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, especially in C7, Cg, C ⁇ or C-13 , a C17 alkyl radical and its iso form, an unsaturated C-17 radical.
• Disodium Caprylamphodiacetate Disodium Capryloamphodiacetate, Disodium Coco- amphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylampho- dipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic acid, Coco-
• amphodipropionic acid By way of example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA CHIMIE,
• cationic surfactants that may be mentioned in particular (nonlimiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or amine oxides of a cationic nature.
• the amounts of surfactants present in the composition according to the invention may vary from 0.01 to 40% and preferably from 0.5 to 30% of the total weight of the composition.
• the compositions according to the invention may also contain other rheology adjusting agents such as cellulosic thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylceliulose, etc.), guar gum and its derivatives (hydroxypropylguar, etc.), microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid and ionic or nonionic associative polymers such as the polymers sold under the names PEMULEN TR1 or TR2 by the company GOODRICH, SALCARE SC90 by the company ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the company AK
• These additional thickeners can represent from 0.01 to 10% by weight of the total weight of the composition.
• the medium of the composition suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, monoethyl ether or diethylene glycol monobutyl ether.
• the solvents can then be present in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition.
• composition A may further comprise an effective amount of other agents, 'moreover previously known in oxidation dyeing, such as various common adjuvants, sequestrants such as EDTA and etidronic acid, UV-screening agents, waxes , volatile or non-volatile, cyclic or linear or branched, organomodified silicones
• agents 'moreover previously known in oxidation dyeing, such as various common adjuvants, sequestrants such as EDTA and etidronic acid, UV-screening agents, waxes , volatile or non-volatile, cyclic or linear or branched, organomodified silicones
• preservatives in particular by amino groups or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or
• compositions may also include reducing or antioxidant agents. These can be chosen in particular from sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, ter-butyl- hydroquinone and homogentisic acid, and they are then generally present in amounts ranging from approximately 0.05 to 1.5% by weight relative to the total weight of the composition.
• the oxidizing agent is preferably chosen from urea peroxide, bromates or ferricyanides of alkali metals, persalts such as perborates and persulfates.
• the use of hydrogen peroxide is particularly preferred.
• This oxidizing agent advantageously consists of a solution of hydrogen peroxide, the titer of which can vary, more particularly, from approximately 1 to 40 volumes, and even more preferably from approximately 5 to 40. It is also possible to use as an agent oxidizing one or more redox enzymes such as laccases, peroxidases and oxidoreductases with 2 electrons (such as uricase), where appropriate in the presence of their respective donor or cofactor.
• the pH of the ready-to-use composition applied to the keratin fibers is generally between the values 4 and 11. It is preferably between 6 and 10, and can be adjusted to the desired value by means of acidifying or basifying agents well known from the state of the art in dyeing keratin fibers.
• basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, hydroxyalkylamines and ethylenediamines oxyethylenated and / or oxypropylenes, sodium or potassium hydroxides and the compounds of formula (XIX) below:
• R is a propylene residue optionally substituted by a hydroxyl group or a CC 4 alkyl radical
• R 38 , R 39 , R 0 and ' R identical or different, represent a hydrogen atom, an alkyl radical in CC or hydroxyalkyl in CC 4 .
• the acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or acids sulfonic.
• the dyeing process according to the invention preferably consists in applying the ready-to-use composition, produced extemporaneously at the time of use from compositions A and B described above, on the dry or wet keratin fibers. , and to let it act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, to rinse the fibers, then optionally to wash them in shampoo, then to rinse them again, and dry them.
• a variant of this process consists in taking a composition A ′ comprising at least one oxidation dye but without cationic associative polyurethane, a composition A ′′ comprising at least one cationic associative polyurethane, and in mixing these compositions A at the time of use. ', A "with composition B, then apply and allow the mixture obtained to act as above.
• compositions A, A ′ and / or B can also comprise at least one cationic or amphoteric polymer and at least one surfactant.
• compositions were prepared:
• Oxidizing composition 2.3 fatty alcohol Oxyethylenated fatty alcohol 0.6
• Polymer 1 is the following polymer:
• R 4 methylenedicyclohexyl against ion: CH 3 SO 4 "
• Polymer 2 is the following polymer: C 18 H 37 N + (CH 3 ) (CH 3 ) - (CH 2 ) 2 -O-CONHR 4 NHCO-O (POE) O- CONHR 4 NHCO-O (CH 2 ) 2 -N + (CH 3 ) (CH 3 ) C ⁇ 8 H 37 with:
• the coloring compositions were mixed, at the time of use, in a plastic bowl and for 2 minutes, with the oxidizing composition given above, at a rate of
• the hair was dyed in both cases in a powerful purple-red shade.

Priority Applications (12)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8856184

Family Applications (1)

Country Status (20)

Cited By (8)

Families Citing this family (12)

Citations (3)

Family Cites Families (89)

• 2000
  • 2000-11-08 FR FR0014319A patent/FR2816207B1/fr not_active Expired - Fee Related
• 2001
  • 2001-11-06 JP JP2002540706A patent/JP4065196B2/ja not_active Expired - Fee Related
  • 2001-11-06 EP EP01993449A patent/EP1335695B1/fr not_active Expired - Lifetime
  • 2001-11-06 PL PL01361594A patent/PL361594A1/xx not_active Application Discontinuation
  • 2001-11-06 ES ES01993449T patent/ES2222404T3/es not_active Expired - Lifetime
  • 2001-11-06 AU AU2375802A patent/AU2375802A/xx active Pending
  • 2001-11-06 BR BR0115461-3A patent/BR0115461A/pt not_active IP Right Cessation
  • 2001-11-06 DE DE60103661T patent/DE60103661T2/de not_active Expired - Lifetime
  • 2001-11-06 MX MXPA03003948A patent/MXPA03003948A/es active IP Right Grant
  • 2001-11-06 CN CNB01818586XA patent/CN1243534C/zh not_active Expired - Fee Related
  • 2001-11-06 CA CA002427466A patent/CA2427466A1/fr not_active Abandoned
  • 2001-11-06 WO PCT/FR2001/003428 patent/WO2002038116A1/fr active IP Right Grant
  • 2001-11-06 AU AU2002223758A patent/AU2002223758B2/en not_active Ceased
  • 2001-11-06 AT AT01993449T patent/ATE268154T1/de not_active IP Right Cessation
  • 2001-11-06 PT PT01993449T patent/PT1335695E/pt unknown
  • 2001-11-06 US US10/415,952 patent/US7101405B2/en not_active Expired - Fee Related
  • 2001-11-06 KR KR1020037006249A patent/KR100540619B1/ko not_active IP Right Cessation
  • 2001-11-06 RU RU2003117010/15A patent/RU2238714C1/ru not_active IP Right Cessation
  • 2001-11-06 DK DK01993449T patent/DK1335695T3/da active
  • 2001-11-06 TR TR2004/01525T patent/TR200401525T4/xx unknown
  • 2001-11-07 AR ARP010105204A patent/AR031299A1/es unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events