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WO2011076665A1 - Agent en deux parties ou plus, sous forme d'émulsion, pour teinture et/ou blanchiment de fibres de kératine - Google Patents

Agent en deux parties ou plus, sous forme d'émulsion, pour teinture et/ou blanchiment de fibres de kératine Download PDF

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Publication number
WO2011076665A1
WO2011076665A1 PCT/EP2010/069937 EP2010069937W WO2011076665A1 WO 2011076665 A1 WO2011076665 A1 WO 2011076665A1 EP 2010069937 W EP2010069937 W EP 2010069937W WO 2011076665 A1 WO2011076665 A1 WO 2011076665A1
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weight
emulsion
hlb
chosen
agent according
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PCT/EP2010/069937
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English (en)
Inventor
Gautier Deconinck
Caroline Goget
Arnaud Huchet
Original Assignee
L'oreal
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Application filed by L'oreal filed Critical L'oreal
Priority to EP10795333A priority Critical patent/EP2516013A1/fr
Publication of WO2011076665A1 publication Critical patent/WO2011076665A1/fr

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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
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • 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
    • A61K8/31—Hydrocarbons
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/342—Alcohols having more than seven atoms in an unbroken chain
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—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
    • A61K8/86—Polyethers
    • 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
    • A61Q5/08—Preparations for bleaching the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/882—Mixing prior to application

Definitions

  • the present invention relates to an agent in two or more parts, for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair.
  • a subj ect of the present invention is also a process for dyeing and/or bleaching keratin fibres, using the agent according to the invention.
  • the present invention relates to a multi-compartment device, containing the dyeing and/or bleaching agent according to the invention, and to the use of the agent for dyeing and/or bleaching keratin fibres.
  • the first type o f dyeing is "permanent" or oxidation dyeing, which uses dye compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are co lourless or weakly coloured compounds, which, when combined with oxidizing products, can give rise to coloured compounds via a process of oxidative condensation.
  • the second type of dyeing is "semi-permanent" dyeing or direct dyeing, which consists in applying to keratin fibres direct dyes, which are co loured and co louring mo lecules that have affinity for the said fibres, in leaving them on for a time, and then in rinsing them o ff.
  • the direct dyes generally used are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine and triarylmethane direct dyes .
  • This type o f process does not require the use o f an oxidizing agent to develop the coloration. However, it is possible to use such an agent in order to obtain a lightening effect with the coloration. This is then referred to as direct or semi-permanent dyeing under lightening conditions .
  • Permanent or semi-permanent dyeing processes under lightening conditions thus consist in using, with the dye composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority o f cases.
  • the ro le o f this oxidizing agent is to degrade the melanin o f the hair, which, depending on the nature of the oxidizing agent present, leads to more or less pronounced lightening of the fibres.
  • the oxidizing agent is generally hydrogen peroxide .
  • peroxygenated salts for instance persulfates, are usually used in the presence o f hydrogen peroxide.
  • an alkaline composition in the form o f a water-in-oil inverse emulsion in the presence of certain surfactants, makes it possible to incorporate a large amount of oily compounds into compositions applied to fibres, while at the same time maintaining the stability o f these compositions .
  • an oil thickener to the system can stabilize the said system in the form of an inverse emulsion.
  • the formulation o f the dye composition as an inverse emulsion allows the generally water-soluble dyes, which are thus present in the droplets of the aqueous phase, to be better protected. As a result, the said dyes do not undergo any oxidation with atmospheric oxygen. This formulation thus leads to the production o f stronger and more chromatic co lorations.
  • One subj ect of the invention is thus an agent for dyeing and/or bleaching keratin fibres, comprising :
  • the total amount of the said oils contained in the mixture of the inverse emulsion (A) and of the direct emulsion (B) representing at least 20% by weight relative to the total weight of the said mixture.
  • the inverse emulsion (A) also comprises one or more oxidation dyes and/or one or more direct dyes .
  • the emulsions (A) and (B) do not comprise any direct dyes or any oxidation dyes (bases and couplers), or else, if they are present, their total content does not exceed 0.005 %> by weight relative to the weight of each composition. Specifically, at such a content, only the composition would be dyed, i.e . no colouring effect would be observed on the keratin fibres.
  • the dyeing and/or bleaching agent according to the present invention does not change or changes little over time during the mixing of the inverse emulsion (A) and the direct emulsion (B), or during the sequential application o f these two emulsions to the keratin fibres . It thus shows very good efficacy, especially in terms of the quality and homogeneity of the dyeing and/or bleaching.
  • the agent according to the invention is particularly efficient as regards the dyeing power obtained, and also as regards the power of the chromaticity and the selectivity o f dyeing o f the same fibre, or between differently sensitized fibres.
  • the agent according to the invention shows lightening performance qualities equivalent to or even greater than those obtained with the existing compositions, especially with those based on ammonium hydroxide.
  • the agent according to the invention also has the advantage o f limiting the evo lution o f aggressive odour during its preparation or its application to the fibres.
  • the human keratin fibres treated via the process according to the invention are preferably hair.
  • emulsion means true emulsions, which are to be distinguished from microemulsions, which are thermo dynamically stable systems, unlike true emulsions.
  • the size o f the droplets of the dispersed phase of the emulsions of the invention is preferably between 10 nm and 100 ⁇ and preferably between 200 nm and 50 ⁇ .
  • the inverse emulsion (A) and the direct emulsion (B) may be prepared via standard emulsion preparation processes that are well known to those skilled in the art.
  • the inverse emulsion (A) is in the form o f a water-in-oil emulsion, i.e . the aqueous phase is dispersed in a fatty phase.
  • the inverse emulsion (A) comprises from 40% to 70% and better still from 45% to 65%, relative to the weight of the inverse emulsion (A), of one or more oils not containing any carboxylic acid functions.
  • the amount of water ranges from 5% to 70% and better still from 10% to 50% of the total weight of the emulsion (A).
  • the aqueous phase comprising water and optionally compounds that are water-soluble at room temperature and at atmospheric pressure may range from 10% to 70% and better still from 15% to 50% of the total weight of the emulsion (A).
  • the inverse emulsion (A) comprises one or more basifying agents.
  • the basifying agent may in particular be a mineral or organic base.
  • the basifying agent is chosen from aqueous ammonia, alkali metal carbonates, alkanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (I) below:
  • W is a Ci-C 6 alkylene residue optionally substituted with a hydroxyl group or a Ci-C 6 alkyl radical
  • Rx, Ry, Rz and Rt which may be identical or different, represent a hydrogen atom or a Ci-C 6 alkyl, Ci-C 6 hydroxyalkyl or Ci-C 6 aminoalkyl radical.
  • Examples of such compounds of formula (I) that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.
  • the basifying agents that are particularly preferred are alkanolamines, and in particular monoethanolamine, diethanolamine and triethanolamine.
  • the basifying agent is monoethanolamine.
  • the inverse emulsion (A) contains as basifying agent at least one organic amine and preferably at least one alkanolamine.
  • the emulsion contains several basifying agents, including an alkanolamine and aqueous ammonia or a salt thereo f, the organic amine(s) are preferably in weight majority relative to the amount of ammonia.
  • the inverse emulsion (A) does not contain any aqueous ammonia.
  • the inverse emulsion (A) when the inverse emulsion (A) contains aqueous ammonia, it also contains one or more alkanolamines, and the weight amount of alkanolamine(s) in the inverse emulsion (A) is greater than the weight amount of ammonia in this same emulsion.
  • the inverse emulsion (A) has a content of basifying agent(s) ranging from 0. 1 % to 40% by weight and preferably from 0.5 %) to 20%o by weight relative to the weight of this emulsion.
  • the inverse emulsion (A) and/or the aqueous phase of the inverse emulsion (A) has a pH greater than or equal to 8 and more preferentially a pH ranging from 8.5 to 1 1 .5.
  • This pH may also be adjusted to the desired value by using, in addition to the basifying agent, one or more acidifying agents.
  • acidifying agents examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids .
  • the inverse emulsion (A) according to the present invention also comprises one or more surfactants with an HLB o f greater than or equal to 8.
  • HLB hydrophilic-lipophilic balance of a surfactant
  • the HLB or hydrophilic-lipophilic balance of the surfactant(s) used according to the invention is the HLB according to Griffin, defined in the publication J. Soc . Cosm. Chem. 1954 (volume 5), pages 249-256.
  • Non-limiting examp les o f surfactants with an HLB of greater than or equal to 8 are especially given in the publication entitled McCutcheon 's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, in the chapter entitled "HLB Index”.
  • the surfactant(s) that may be used in the inverse emulsion (A) are preferably chosen from nonionic surfactants and anionic surfactants, and preferably from nonionic surfactants .
  • the anionic surfactants are more especially chosen from the salts, in particular alkali metal salts, especially sodium salts, ammonium salts, amine salts, amino alcohol salts or alkaline-earth metal salts such as magnesium salts, of the fo llowing compounds :
  • alkyl sulfates alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates;
  • alkylsulfonates alkylamidesulfonates, alkylarylsulfonates, a-olefin sulfonates, paraffin sulfonates;
  • alkylsulfosuccinates alkyl ether sulfosuccinates, alkylamidesulfosuccinates; alkylsulfo succinamates;
  • fatty acids such as oleic acid, ricinoleic acid, palmitic acid or stearic acid, coconut oil acid or hydrogenated coconut oil acid;
  • alkyl or acyl radical of these various compounds advantageously contains from 6 to 24 carbon atoms and preferably from 8 to 24 carbon atoms, and the aryl radical preferably denotes a phenyl or benzyl group .
  • the nonionic surfactants are preferably chosen from oxyalkylenated or glycerolated surfactants, preferably oxyalkylenated surfactants .
  • oxyalkylenated nonionic surfactants means nonionic surfactants that bear in their mo lecule one or more groups chosen from the following groups: -CH 2 -CH 2 -0- -CH 2 -CH 2 -CH 2 -0-, -CH 2 -CH(CH 3 )-0-, or mixtures thereof.
  • the oxyalkylenated nonionic surfactants with an HLB o greater than or equal to 8 may belong, in a non-limiting manner, to th following families:
  • oxyethylenated fatty alcoho ls with an HLB of greater than or equal to 8 are preferred.
  • the concentration of these surfactants with an HLB of greater than or equal to 8 is preferably between 1 % and 20%, more preferentially from 1 % to 15 % and better still from 2% to 10% by weight relative to the total weight of the inverse emulsion (A) .
  • the inverse emulsion (A) according to the invention comprises one or more oils not containing any carboxylic acid functions contained in the continuous phase o f the inverse emulsion
  • the direct emulsion (B) according to the invention comprises one or more oils not containing any carboxylic acid functions contained in the dispersed phase of the direct emulsion.
  • oil means an organic compound that is inso luble in water at ordinary temperature (25 °C) and at atmospheric pressure (760 mmHg; i. e. 1013. 1 05 Pa) (water solubility o f less than 5 % by weight, preferably 1 % and even more preferentially 0. 1 %) .
  • These compounds have in their structure at least one hydrocarbon-based chain comprising at least six carbon atoms or a sequence o f at least two siloxane groups.
  • oils are soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol or benzene.
  • oils are liquid at ordinary temperature (25 °C) and at atmospheric pressure (760 mmHg; i.e . 1013. 105 Pa) .
  • oil not containing any carboxylic acid functions means an oil containing no -COOH groups and no -COO- groups .
  • the oil(s) not containing any carboxylic acid functions, used in the emulsion (A) and in the emulsion (B), which may be identical or different, may be chosen especially from hydrocarbons, non-silicone oils o f animal, plant, mineral or synthetic origin, fatty alcohols, fatty acid esters and/or fatty alcoho l esters, and silicones, and mixtures thereo f.
  • the fatty alcoho ls more particularly contain one or more linear or branched, saturated or unsaturated hydrocarbon-based groups, comprising 6 to 30 carbon atoms, which are optionally substituted, in particular with one or more (in particular 1 to 4) hydroxyl groups . I f they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds .
  • liquid hydrocarbons are chosen from:
  • C 6 - C i 6 lower alkanes examples include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane,
  • liquid hydrocarbon(s) are chosen from liquid paraffins and liquid petroleum j elly.
  • the silicone is cho sen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group .
  • liquid polydialkylsiloxanes especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group .
  • silicones may also be organomodified.
  • organomodified silicones that may be used in accordance with the invention are liquid silicones as defined previously, comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group .
  • They may be vo latile or non-vo latile.
  • the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C , and even more particularly from cyclic polydialkylsiloxanes containing from 3 to 7 and preferably 4 to 5 silicon atoms .
  • Non-volatile polydialkylsiloxanes may also be used.
  • silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.
  • polydialkylsiloxanes mention may be made, in a nonlimiting manner, of the following commercial products: - the Silbione® oils of the 47 and 70047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70047 V 500000;
  • oils of the 200 series from the company Dow Corning such as DC200 with a viscosity of 60000 mm 2 /s;
  • CFA dimethiconol
  • silicones containing aryl groups are polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes. Examples that may be mentioned include the products sold under the following names:
  • the liquid fatty esters are preferably liquid esters of saturated or unsaturated, linear or branched Ci-C 26 aliphatic mono- or polyacids and of saturated or unsaturated, linear or branched Ci-C 26 mono- or polyalcohols, the total number of carbon atoms in the esters being greater than or equal to 10.
  • At least one from among the alcohol and the acid from which the esters of the invention are derived is branched.
  • ethyl palmitate isopropyl palmitate
  • alkyl myristates such as isopropyl myristate or ethyl myristate
  • isocetyl stearate 2-ethylhexyl isononanoate
  • isodecyl neopentanoate isostearyl neopentanoate.
  • Esters of C4-C22 dicarboxylic or tricarboxylic acids and of Ci- C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C 4 - C26 di-, tri-, tetra- or pentahydroxy alcohols may also be used.
  • diethyl sebacate diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.
  • the emulsion (A) or (B) may also comprise, as liquid fatty ester, C6-C30 and preferably C12-C22 fatty acid esters and diesters of sugars.
  • sucrose means oxygenous hydrocarbon-based compounds that contain several alcohol functions, with or without aldehyde or ketone functions, and that comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.
  • suitable sugars include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or non-conjugated carbon-carbon double bonds.
  • esters according to this variant may also be chosen from mono-, di-, tri-, tetraesters and polyesters, and mixtures thereof.
  • esters may be chosen, for example, from oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleo-palmitate, oleo-stearate and palmito-stearate mixed esters.
  • Monoesters and diesters and especially sucrose, glucose or methylglucose mono- or dio leates, stearates, behenates, oleopalmitates, lino leates, lino lenates and oleostearates are more particularly used.
  • esters of mono-, di- or triacids with glycerol may also be used.
  • oils o f plant origin or synthetic triglycerides that may be used in the emulsions that are useful for the agent according to the invention, as liquid fatty esters
  • examples that may be mentioned include triglyceride oils of plant or synthetic origin, such as liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those so ld by the company Stearineries Dubois or those sold under the names Miglyo l® 8 10, 8 12 and 8 1 8 by the company Dynamit Nobel, jojoba oil and shea butter oil.
  • Liquid fatty esters derived from monoalcohols will preferably be used as esters according to the invention. Isopropyl myristate and isopropyl palmitate are particularly preferred.
  • liquid unsaturated fatty alcoho ls of the invention comprise from 8 to 30 carbon atoms.
  • the liquid fatty alcohols may be unsaturated.
  • liquid unsaturated fatty alcohols contain in their structure at least one double or triple bond.
  • the fatty alcoho ls o f the invention bear in their structure one or more double bonds. When several double bonds are present, there are preferably 2 or 3 of them, and they may be conjugated or unconjugated.
  • These fatty alcoho ls may be linear or branched.
  • liquid unsaturated fatty alcohols are chosen from o leyl alcoho l, lino lenyl alcohol, lino lenyl alcoho l and undecylenyl alcohol.
  • Oleyl alcoho l is mo st particularly preferred.
  • the liquid fatty alcoho ls may also be branched saturated fatty alcoho ls. More particularly, the liquid branched saturated fatty alcoho ls o f the invention are chosen from isostearyl alcoho l and octyldodecanol.
  • the oil(s) not containing any carboxylic acid functions, present in the emulsions (A) and (B), do not comprise any oxyalkylene units or any glycerol units .
  • the oil(s) not containing any carboxylic acid functions, present in the emulsions (A) and (B), are non-silicone.
  • the oil(s) not containing any carboxylic acid functions, present in the emulsions (A) and (B), are chosen from hydrocarbons, non-silicone oils o f animal, plant, mineral or synthetic origin, fatty alcohols, fatty acid esters and/or fatty alcoho l esters, and silicones, and mixtures thereof; preferably from liquid petroleum j elly, polydecenes, liquid esters o f fatty acids and/or of fatty alcoho ls, and liquid fatty alcoho ls, and mixtures thereof; and more preferably from liquid petroleum j elly, polydecenes and liquid fatty alcoho ls, and mixtures thereof.
  • the oil not containing any carboxylic acid functions is liquid petroleum j elly.
  • the inverse emulsion (A) according to the present invention preferably comprises one or more oil-thickening agents .
  • the thickener may be chosen from po lymeric thickeners, non- polymeric agents, mineral thickeners and organic thickeners, and mixtures thereof.
  • thickener means a compound that modifies the rheo logy of the medium into which it is incorporated.
  • the oily-medium thickener may be chosen from:
  • - alkyl guar gums (with a C 1 -C6 alkyl group), such as tho se described in EP-A-708 1 14;
  • - oil-gelling polymers for instance triblock polymers or star polymers resulting from the po lymerization or copolymerization o f at least one monomer containing an ethylenic group, for instance the polymers so ld under the name Kraton;
  • 100 000 comprising a) a polymer backbone containing hydrocarbon- based repeating units containing at least one heteroatom, and optionally b) at least one pendent fatty chain and/or at least one terminal fatty chain, which are optionally functionalized, containing from 6 to 120 carbon atoms and being linked to these hydrocarbon- based units, as described in patent applications WO-A-02/056847 and WO-A-02/47619, the content of which is incorporated by way o f reference; in particular, polyamide resins (especially comprising alkyl groups containing from 12 to 22 carbon atoms) such as those described in US-A-5 783 657, the content of which is incorporated by way o f reference;
  • the thickener may be an organic gelling agent, i. e. an agent comprising at least one organic compound.
  • the organogelling agents may be chosen from those described in patent application WO-A-03/ 105 788 , the content of which is incorporated by way o f reference.
  • the polymeric thickener present in the emulsion that is useful for the agent according to the invention is an amorphous polymer formed by polymerization o f an o lefin.
  • the olefin may especially be an elastomeric ethylenically unsaturated monomer.
  • olefins examples include ethylenic carbide monomers especially containing one or two ethylenic unsaturations, containing from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene or isoprene.
  • the po lymeric thickener is capable of thickening or gelling the composition.
  • amorphous polymer means a polymer that does not have a crystalline form.
  • the polymeric thickener may also be film-forming.
  • the polymeric thickener may especially be a diblock, triblo ck, multiblock, radial or star copolymer, or mixtures thereof.
  • the polymeric thickener is an amorphous blo ck copolymer of styrene and of olefin.
  • the polymeric thickener is preferably hydrogenated to reduce the residual ethylenic unsaturations after po lymerization o f the monomers.
  • the po lymeric thickener is an optionally hydrogenated copolymer, containing styrene blocks and ethylene/C 3 - C 4 alkylene blocks .
  • Diblock copolymers preferably hydrogenated, that may be mentioned include styrene-ethylene/propylene copolymers and styrene- ethylene/butadiene copolymers .
  • the diblock polymers are especially so ld under the name Kraton® G 1 70 1 E by the company Kraton Polymers.
  • Triblock copolymers which are preferably hydrogenated, that may be mentioned include styrene-ethylene/propylene-styrene copolymers, styrene-ethylene/butadiene-styrene copolymers, styrene- isoprene-styrene copolymers and styrene-butadiene-styrene copolymers .
  • Triblo ck po lymers are especially sold under the names Kraton® G 1 650, Kraton® G 1652, Kraton® D 1 1 01 , Kraton® D 1 102 and Kraton® D 1 160 by the company Kraton Polymers.
  • a mixture of hydrogenated styrene-butadiene/ethylene-styrene triblo ck copolymer and of hydrogenated ethylene-propylene-styrene star polymer may also be used, such a mixture especially being in isododecane .
  • Such mixtures are sold, for example, by the company Penreco under the trade names Versagel® M5960 and Versagel® M5670.
  • a diblock copolymer such as those described above, in particular a styrene-ethylene/propylene diblo ck copolymer, is advantageously used as polymeric thickener.
  • organophilic clays are clays modified with chemical compounds that make the clay able to swell.
  • Clays are products that are already well known per se, which are described, for example, in the publication Mineralogie des argiles [Mineralo gy o f clays] , S . Caillere, S . Henin, M. Rautureau, 2nd Edition 1982, Masson, the teaching of which is included herein by way of reference.
  • Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereo f.
  • Examples o f such products that may be mentioned include clays of the smectite family such as montmoriUonites, hectorites, bentonites , beidellites and saponites, and also of the vermiculite, stevensite and chlorite families .
  • Clays may be o f natural or synthetic origin. Clays that are cosmetically compatible and acceptable with keratin materials are preferably used.
  • the organophilic clay may be chosen from optionally modified montmorillonite, bentonite, hectorite, attapulgite and sepio lite, and mixtures thereof.
  • the clay is preferably a bentonite or a hectorite.
  • These clays may be modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof.
  • Organophilic clays that may be mentioned include quaternium- 1 8 bentonites such as those sold under the names Bentone 3 , Bentone 38 and Bentone 38V by the company Rheox, Tixogel VP by the company United Catalyst, Claytone 34, Claytone 40 and Claytone XL by the company Southern Clay; stearalkonium bentonites such as those so ld under the names Bentone 27 by the company Rheox, Tixogel LG by the company United Catalyst and Claytone AF and Claytone APA by the company Southern Clay; quaternium- 1 8/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by the company Southern Clay.
  • Fumed silicas may be obtained by high-temperature hydrolysis of a vo latile silicon compound in an oxhydric flame, producing a finely divided silica. This process makes it possible especially to obtain hydrophilic silicas having a large number of silanol groups at their surface.
  • Such hydrophilic silicas are sold, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by the company Degussa, and Cab-O-Sil HS-5®, Cab-O- Sil EH-5®, Cab-O-Sil LM- 130®, Cab-O-Sil MS-55® and Cab-O-Sil M-5® by the company Cabot.
  • the hydrophobic groups may be :
  • silica in the presence o f hexamethyldisilazane .
  • Silicas thus treated are known as "silica silylate” according to the CTFA (6th Edition, 1995) . They are so ld, for example, under the references Aerosil R8 12® by the company Degussa and Cab-O-Sil TS-530® by the company Cabot.
  • silica thus treated are known as "silica dimethyl silylate" according to the CTFA (6th Edition, 1995) . They are so ld, for example, under the references Aerosil R972® and Aerosil R974® by the company Degussa and Cab- O-Sil TS-610® and Cab-O-Sil TS-720® by the company Cabot.
  • the fumed silica preferably has a particle size that may be nanometric to micrometric, for examp le ranging from about 5 to 200 nm.
  • An organomodified bentonite or hectorite is preferably used as mineral thickener.
  • the thickener used is a distearyldimethylammonium-modified hectorite .
  • the mineral thickeners are combined with carbonates, for instance propylene carbonate.
  • the thickener is preferably present in the inverse emulsion (A) in a total content ranging from 0. 1 % to 10% by weight, preferably ranging from 0.5 % to 7% by weight and more preferentially ranging from 1 % to 5 % by weight relative to the total weight of the emulsion.
  • the direct emulsion (B) is in the form o f an oil-in-water emulsion, i. e. with a fatty phase dispersed in an aqueous phase.
  • the direct emulsion (B) preferably comprises 5 % to 50%> and more preferentially 10% to 30% by weight, relative to the total weight of the direct emulsion (B), of one or more oils not containing any carboxylic acid functions as described previously.
  • the direct emulsion (B) comprises one or more oxidizing agents .
  • This oxidizing agent may be chosen from the oxidizing agents conventionally used for the bleaching and oxidation dyeing o f keratin fibres, and among which mention may be made o f hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, and peroxygenated salts, for instance persulfates, perborates and percarbonates of alkali metals or alkaline-earth metals such as sodium, potassium or magnesium.
  • One or more redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), optionally in the presence of the respective donor or cofactor thereof, may also be used as oxidizing agent.
  • the use o f hydrogen peroxide is particularly preferred. It may be advantageously used as an aqueous solution (aqueous hydrogen peroxide so lution) whose concentration may vary more particularly from 0. 1 % to 50% by weight, even more preferentially from 0.5 % to 20% by weight and better still from 1 % to 15 % by weight relative to the total weight of the direct emulsion (B) .
  • the oxidizing agent may also comprise one or more compounds preferably chosen from peroxygenated salts .
  • the pH of the aqueous phase of the direct emulsion (B) is less than 7.
  • This pH may be adjusted to the desired value by using one or more acidifying agents, which may be chosen especially from those described previously.
  • the mixture o f emulsions (A) and (B) contains an amount of oil(s) not containing any carboxylic acid functions of at least 20% by weight and preferably between 20.5 %> and 75 % by weight relative to the total weight of the said mixture.
  • the mixture of emulsions (A) and (B) contains an amount of oil(s) not containing any carboxylic acid functions o f at least 25 % by weight, more particularly between 25.5 % and 75 % by weight, even more preferentially o f at least 30% by weight and more particularly between 30.5 % and 75 % by weight, relative to the total weight of the said mixture.
  • the emulsions (A) and/or (B) according to the invention may also contain one or more additional fatty substances other than oils not containing any carboxylic acid functions defined previously, in particular such as solid fatty alcoho ls such as cetyl alcoho l, stearyl alcoho l or mixtures thereof. These additional fatty substances are free of carboxylic acid functions.
  • the inverse emulsion (A) is in the form of a gel or a cream.
  • the direct emulsion (B) is in the form o f a so lution, an emulsion or a gel.
  • the inverse emulsion (A) also comprises one or more oxidation dyes .
  • the agent according to the invention is advantageously used for the oxidation dyeing o f keratin fibres.
  • oxidation dyes that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers .
  • the oxidation bases may be chosen especially from para- phenylene diamines, bis (phenyl) alky lene diamines, para-aminophenols, ortho-aminopheno ls and heterocyclic bases, and the addition salts thereo f.
  • para-phenylenediamines that may be mentioned, for example, are para-phenylenediamine, para-tolylenediamine, 2-chloro- para-phenylenediamine, 2,3 -dimethyl-para-phenylenediamine, 2,6- dimethyl-para-phenylene diamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N- dimethyl-par a-phenylene - diamine, ⁇ , ⁇ -diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4 - amino -N,N- diet hy 1-3 -met hylaniline, N,N-bis( - hydro xy ethyl) -par a-phenylene diamine, 4 -N,N-bis( - hydroxy ethyl) - amino-2-
  • the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N'-bis( -hydroxyethyl)-N,N'-bis(4'- aminophenyl)-l ,3-diaminopropanol, N,N'-bis( -hydroxyethyl)-N,N'- bis (4 '-amino phenyl) ethylene diamine, N,N'-bis(4-aminophenyl)tetra- methylene diamine, N, N'-bis( -hydroxy ethyl) -N,N'-bis(4- aminophen- yl)tetramethylene diamine, N,N'-bis(4-methylaminophenyl)tetramethyl- ene diamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3 '-methylphenyl)- ethylene diamine and 1 ,8-bis((
  • para-aminophenols that may be mentioned, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3- fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethyl- phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4- amino-2-( -hydroxyethylaminomethyl)phenol and 4-amino-2-fluoro- phenol, and the addition salts thereof with an acid.
  • ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6- methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof.
  • heterocyclic bases that may be mentioned, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2-(4-methoxyphenyl)- amino-3-aminopyridine and 3,4-diaminopyridine, and the addition salts thereof.
  • pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo[l,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2801 308.
  • Examples that may be mentioned include pyrazolo[l,5- a]pyrid-3-ylamine, 2-acetylaminopyrazolo[ 1 ,5-a]pyrid-3-ylamine, 2-morpholin-4-ylpyrazolo[ 1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo- [1 ,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[ 1 ,5-a]pyrid-3- ylamine, (3-aminopyrazolo[ 1 ,5-a]pyrid-7-yl)methanol, 2 -(3 -amino - pyrazolo[l ,5-a]pyrid-5-y
  • pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2 359 399; JP 88-169 571; JP 05-63124; EP 0770375 or patent application WO 96/15765, for instance 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6- triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, and the addition salts thereof, and the tautomeric forms thereof, when a tautomeric equilibrium exists.
  • pyrazole derivatives that may be mentioned are the compounds described in patents DE 3843892 and DE 4 133 957, and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 19543988, for instance 4,5-diamino- 1 -methylpyrazole, 4,5- diamino- l-( -hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5- diamino- 1 -(4 '-chlorobenzyl)pyrazole, 4,5-diamino - 1 ,3 -dimethyl- pyrazole, 4,5-diamino-3-methyl- 1 -phenylpyrazole, 4,5-diamino- 1 - methyl- 3 -phenylpyrazole, 4 -amino - 1 ,3-dimethyl-5-hydrazinopyrazole, 1 -b en
  • a 4,5-diaminopyrazole will preferably be used, and even more preferentially 4,5-diamino- 1 -(P-hydroxyethyl)pyrazole and/or a salt thereof.
  • Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones and especially those described in patent application FR-A-2886 136, such as the following compounds and the addition salts thereof: 2,3-diamino-6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3-ethylamino-6,7- dihydro-lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3-isopropyl- amino-6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2-amino-3- (pyrrolidin-l-yl)-6,7-dihydro-lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one,
  • the couplers that may be used in the present invention may be chosen from those conventionally used for the dyeing of keratin fibres.
  • couplers mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.
  • addition salts o f the oxidation bases and couplers that may be used in the context of the invention are especially chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates .
  • the oxidation base(s) may each advantageously represent an amount greater than 0.005 % to 1 0% by weight relative to the total weight of the inverse emulsion (A), and preferably an amount greater than 0.005 % to 5 % by weight relative to the total weight of this emulsion.
  • the coupler(s), if they are present, may each advantageously represent an amount greater than 0.005 % to 10% by weight relative to the total weight of the inverse emulsion (A), and preferably an amount greater than 0.005 % to 5 % by weight relative to the total weight of this emulsion.
  • the inverse emulsion (A) comprises one or more direct dyes .
  • the inverse emulsion (A) may comprise one or more oxidation dyes and, as additional dye, one or more direct dyes .
  • the inverse emulsion (A) does not comprise any oxidation dyes, and the agent according to the invention is then advantageously used for the lightening direct dyeing of keratin fibres.
  • the direct dyes that may be used in the inverse emulsion (A) are more particularly chosen from ionic and nonionic species, preferably cationic or nonionic species .
  • direct dyes that are suitable for use, mention may be made o f azo; methine; carbonyl; azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanin direct dyes; and natural direct dyes, alone or as mixtures .
  • the dyes of this family are derived from compounds of the type such as methines, azomethines, mono- and diarylmethanes, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanins, azacarbocyanins and isomers thereo f, diazacarbocyanins and isomers thereo f, tetraazacarbocyanins and hemicyanins .
  • compounds of the type such as methines, azomethines, mono- and diarylmethanes, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanins, azacarbocyanins and isomers thereo f, diazacarbocyanins and isomers thereo f, tetraazacarbocyanins and hemicyanins .
  • dyes of the carbonyl family examples that may be mentioned include dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazo lanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquino linone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole and coumarin.
  • dyes chosen from acridone benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthron
  • dyes of the cyclic azine family mention may be made especially of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine and pyronin.
  • nitro (hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes .
  • cationic or non-cationic compounds optionally comprising one or more metals or metal ions, for instance alkali metals, alkaline-earth metals, zinc and silicon.
  • Examples of particularly suitable direct dyes include nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanin direct dyes, for instance tetraazacarbocyanins (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine; xanthene; triarylmethane; indoamine; indigoid; phthalocyanin direct dyes, porphyrins and natural direct dyes, alone or as mixtures .
  • These dyes may be monochromophoric dyes (i .e . comprising only one dye) or polychromophoric, preferably di- or trichromophoric; the chromophores possibly being identical or different, and from the same chemical family or otherwise.
  • a polychromophoric dye comprises several radicals each derived from a mo lecule that absorbs in the visible region between 400 and 800 nm. Furthermore, this absorbance of the dye does not require any prior oxidation thereo f, or combination with any other chemical species.
  • the chromophores are connected together by means of at least one linker, which may be cationic or non-cationic.
  • the linker is a linear, branched or cyclic C 1 - C20 alkyl chain, optionally interrupted with at least one heteroatom (such as nitrogen or oxygen) and/or with at least one group comprising such an atom (CO, S0 2 ), optionally interrupted with at least one heterocycle that may or may not be fused to a phenyl nucleus and comprising at least one quaternized nitrogen atom engaged in said ring and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted with at least one substituted or unsubstituted phenyl or naphthyl group, optionally at least one quaternary ammonium group substituted with two optionally substituted C 1 - C 1 5 alkyl groups; the linker not comprising any nitro, nitroso or peroxy groups .
  • the linker not comprising any nitro, nitroso or peroxy groups .
  • heterocycles or aromatic nuclei are substituted, for example, with one or more C i -Cs alkyl radicals optionally substituted with a hydroxyl, C 1 - C2 alkoxy, C2 - C4 hydroxyalkoxy, acetylamino , or amino group substituted with one or two C 1 - C4 alkyl radicals, optionally bearing at least one hydroxyl group , or the two radicals possibly forming, with the nitrogen atom to which they are attached, a 5 - or 6-membered heterocycle optionally comprising another heteroatom identical to or different than nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C1-C4 alkyl radicals optionally bearing at least one hydroxyl group.
  • benzenic direct dyes that may be used according to the invention, mention may be made in a nonlimiting manner of the following compounds:
  • azo, azomethine, methine and tetraazapentamethine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2 189006, FR 2285 851, FR 2 140205, EP 1 378544 and EP 1 674073.
  • D represents a nitrogen atom or a -CH group
  • Ri and R 2 which may be identical or different, represent a hydrogen atom; a C 1 -C 4 alkyl radical which may be substituted with a -CN, -OH or -NH 2 radical, or form, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen or nitrogen, which may be substituted with one or more C 1 -C 4 alkyl radicals; a 4'- aminophenyl radical,
  • R3 and R'3 which may be identical or different, represent a hydrogen atom or a halogen atom chosen from chlorine, bromine, iodine and fluorine, or a cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or acetyloxy radical,
  • X " represents an anion preferably chosen from chloride, methyl sulfate and acetate
  • A represents a group chosen from structures Al to A18, preferably Al, A4, A7, A13 and A18, below:
  • R 6 represents a hydrogen atom or a C1-C4 alkyl radical
  • R 7 represents a hydrogen atom, an alkyl radical which may be substituted with a -CN radical or with an amino group, a 4'- aminophenyl radical, or forms with R 6 a heterocycle optionally containing oxygen and/or nitrogen, which may be substituted with a C1-C4 alkyl radical,
  • R9 which may be identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, or a -CN radical,
  • X " represents an anion preferably chosen from chloride, methyl sulfate and acetate
  • B represents a group chosen from structures Bl to B6 below:
  • R 10 represents a C1-C4 alkyl radical
  • Rn and R12 which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical
  • Ri3 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino radical,
  • Ri4 represents a hydrogen atom, a C1-C4 alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen and/or substituted with one or more C1-C4 alkyl groups,
  • Ri5 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,
  • Ri6 and Ri7 which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical
  • Di and D 2 which may be identical or different, represent a hydrogen atom or a -CH group
  • n 0 or 1, preferably 1,
  • X " represents an anion preferably chosen from chloride, methyl sulfate and acetate
  • E represents a group chosen from structures El to E8, in particular El, low:
  • R' represents a C 1 -C 4 alkyl radical
  • E may also denote a group of structure E9 below:
  • R' represents a C 1 -C 4 alkyl radical.
  • Ri8 denotes a C 1 -C 4 alkyl radical, a phenyl radical which may be substituted with a C 1 -C 4 alkyl radical, or a halogen atom chosen from chlorine, bromine, iodine and fluorine;
  • Ri9 denotes a C 1 -C4 alkyl radical or a phenyl radical
  • R20 and R21 which may be identical or different, represent a C1-C 4 alkyl radical, a phenyl radical, or form together in Gi a benzene ring substituted with one or more C1-C 4 alkyl, C1-C 4 alkoxy or N0 2 radicals, or form together in G 2 a benzene ring optionally substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or N0 2 radicals;
  • R20 may also denote a hydrogen atom
  • Z represents an oxygen or sulfur atom or a group -NR19
  • M represents a group -CH, -CR (R denoting C1-C 4 alkyl) or - NR 22 (X-) r ;
  • K represents a group -CH, -CR (R denoting C1-C 4 alkyl) or -
  • P represents a group -CH, -CR (R denoting C1-C 4 alkyl) or - NR 22 (X " ) r ;
  • r denotes 0 or 1
  • R 22 represents an O " atom, a C1-C 4 alkoxy radical or a C1-C 4 alkyl radical
  • R 2 3 and R 2 4 which may be identical or different, represent a hydrogen atom or a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C 4 alkyl or C1-C 4 alkoxy radical, or an -N0 2 radical;
  • X " represents an anion preferably chosen from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate;
  • R 23 or R 24 is preferably different than a hydrogen atom
  • R 2 o is other than a hydrogen atom
  • At least one of the radicals Ris, R 2 o or R 2 i of the group of structure G 2 is other than a C1-C 4 alkyl radical;
  • R25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, an -OH, -N0 2 , -NHR 28 , -NR 29 R3o or C1-C4 -NHCOalkyl radical, or forms with R 26 a 5- or 6-membered ring optionally containing one or more heteroatoms chosen from nitrogen, oxygen and sulfur;
  • R 2 6 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, or forms with R 27 or R 2 s a 5- or 6-membered ring optionally containing one or more heteroatoms chosen from nitrogen, oxygen and sulfur;
  • R 27 represents a hydrogen atom, an -OH radical, a radical -NHR 28 or a radical -NR 29 R3o;
  • R 2 8 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl, C 2 -C4 polyhydroxyalkyl radical or a phenyl radical;
  • R 2 9 and R30 which may be identical or different, represent a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl or C 2 -C4 polyhydroxyalkyl radical;
  • -(b) a 5- or 6-membered nitrogenous heterocyclic group, which may contain other heteroatoms and/or carbonyl groups and may be substituted with one or more C1-C4 alkyl, amino or phenyl radicals, and especially a group of structure J 2 below: in which structure J 2 :
  • R31 and R3 2 which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical; CH,
  • n 0 or 1 , with, when n denotes 1 , U denoting a -CO- radical.
  • the C 1 - C 4 alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.
  • azo direct dyes that may also be mentioned are the fo llowing dyes, described in the Colour Index International, 3rd edition:
  • quinone direct dyes that may be mentioned are the following dyes:
  • azine dyes that may be mentioned are the following compounds:
  • triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds:
  • indoamine dyes that may be used according to the invention, mention may be made of the following compounds:
  • X " represents an anion preferably chosen from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate.
  • po lychromophoric dyes mention may be made more particularly of symmetrical or non-symmetrical azo and/or azomethine (hydrazone) di- or trichromophoric dyes comprising, on the one hand, at least one optionally fused 5 - or 6-membered aromatic heterocycle, comprising at least one quaternized nitrogen atom engaged in said heterocycle and optionally at least one other heteroatom (such as nitrogen, sulfur or oxygen), and, on the other hand, at least one optionally substituted phenyl or naphthyl group , optionally bearing at least one group OR with R representing a hydrogen atom, an optionally substituted C i -C 6 alkyl radical, an optionally substituted phenyl nucleus, or at least one group N(R' ) 2 with R' , which may be identical or different, representing a hydrogen atom, an optionally substituted C i -C 6 alkyl radical or an optionally substituted phenyl nucleus; the radical
  • Aromatic cationic heterocycles that may preferably be mentioned include 5 - or 6-membered rings containing 1 to 3 nitrogen atoms and preferably 1 or 2 nitrogen atoms, one being quaternized; said heterocycle moreover being optionally fused to a benzene nucleus . It should similarly be noted that the heterocycle may optionally comprise another heteroatom other than nitrogen, for instance sulfur or oxygen.
  • heterocycles or phenyl or naphthyl groups are substituted, for example, with one or more C i -Cs alkyl radicals optionally substituted with a hydroxyl, C1-C2 alkoxy, C2-C4 hydroxyalkoxy, acetylamino or amino group substituted with one or two C1-C4 alkyl radicals optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another heteroatom identical to or different than nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl group.
  • polychromophores are connected together by means of at least one linker optionally comprising at least one quaternized nitrogen atom that may or may not be engaged in a saturated or unsaturated, optionally aromatic heterocycle.
  • the linker is a linear, branched or cyclic C1-C20 alkyl chain, optionally interrupted with at least one heteroatom (such as nitrogen or oxygen) and/or with at least one group comprising such a heteroatom (CO or SO2), optionally interrupted with at least one heterocycle that may or may not be fused to a phenyl nucleus and comprising at least one quaternized nitrogen atom engaged in said ring and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted with at least one substituted or unsubstituted phenyl or naphthyl group, optionally at least one quaternary ammonium group substituted with two optionally substituted C1-C15 alkyl groups; the linker not comprising any nitro, nitroso or peroxy groups.
  • a heteroatom such as nitrogen or oxygen
  • CO or SO2 heteroatom
  • the linker is a linear, branched or cyclic C1-C20 alkyl chain, optionally interrupted with at
  • the bonding between the linker and each chromophore generally takes place via a heteroatom substituent on the phenyl or naphthyl nucleus or via the quaternized nitrogen atom of the cationic heterocycle.
  • the dye may comprise identical or different chromophores.
  • EP 1 006 153 which describes dyes comprising two chromophores of anthraquinone type connected via a linker o f cationic type
  • EP 1 433 472, EP 1 433 474, EP 1 433 471 and EP 1 433 473 which describe identical or different dichromophoric dyes, connected via a cationic or non-cationic linker
  • EP 6 291 333 which especially describes dyes comprising three chromophores, one of them being an anthraquinone chromophore, to which are attached two chromophores of azo or diazacarbocyanin type or an isomer thereo f.
  • the direct dye(s) advantageously represent an amount greater than 0.0001 % to 1 0% by weight and preferably an amount greater than 0.005 % to 5 % by weight relative to the total weight of the inverse emulsion (A) .
  • the emulsions (A) and (B) do not comprise any direct dyes or any oxidation dyes (bases and couplers), or else, if they are present, their total content does not exceed 0.005 % by weight relative to the total weight of each emulsion.
  • the agent according to the invention is advantageously used for bleaching keratin fibres.
  • the inverse emulsion (A) may advantageously comprise one or more solid or pasty adjuvants, which are preferably pulverulent.
  • the adjuvants may then be chosen from clays, salts other than ammonium salts, anionic, nonionic, cationic or zwitterionic surfactants, natural or synthetic thickeners, optionally modified starch, glass beads, silica, Nylon, alumina, titanium dioxide, zeo lites, poly(methyl methacrylate) (PMMA), chitosan, maltodextrin, cyclodextrin, monosaccharides or disaccharides, for instance glucose, sucrose, sorbito l or fructose, zinc oxide, zirconium oxide, silica beads, talc, borosilicates, especially of calcium, polyethylene, polytetrafluoroethylene (PTFE), cellulo se and derivatives thereo f, superabsorbent compounds, magnesium or calcium carbonates, polyacrylamide,
  • the emulsions (A) and (B) constitute a cosmetically acceptable medium optionally comprising one or more organic so lvents.
  • Examples o f organic so lvents that may be mentioned include linear or branched C 2 - C 4 alkano ls, such as ethano l and isopropano l; glycerol; polyo ls and polyol ethers, for instance 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcoho ls, such as benzyl alcohol or phenoxyethano l, and mixtures thereof.
  • Such organic so lvents may be present in proportions preferably of between 1 % and 40% by weight and more preferentially between 5 % and 30% by weight relative to the total weight of each composition in which they are contained.
  • the emulsions (A) and/or (B) according to the present invention may also comprise one or more adjuvants, chosen from those conventionally used in compositions for dyeing and/or bleaching keratin fibres, such as conditioning po lymers, in particular cationic polymers, organic thickeners other than the oil thickeners defined previously, with, in particular, anionic, cationic and nonionic polymeric associative thickeners, surfactants with an HLB of less than 8 , antioxidants; penetrants; sequestrants; fragrances; dispersants; film- forming agents; ceramides; preserving agents; opacifiers .
  • adjuvants chosen from those conventionally used in compositions for dyeing and/or bleaching keratin fibres, such as conditioning po lymers, in particular cationic polymers, organic thickeners other than the oil thickeners defined previously, with, in particular, anionic, cationic and nonionic polymeric associative thickeners, surfactants with an H
  • the direct emulsion (B) may also comprise thickeners as described above for the inverse emulsion (A), and also anionic, cationic, amphoteric and nonionic surfactants such as those described above for the inverse emulsion (A).
  • the above adjuvants may generally be present in an amount for each o f them o f between 0.01 % and 20% by weight relative to the weight of each composition.
  • a subj ect of the present invention is also a process for dyeing and/or bleaching keratin fibres, comprising the application to the said fibres of the agent as described above.
  • the agent applied to the keratin fibres results from the mixing of the emulsions (A) and (B), this mixing being performed either before application to the keratin fibres (extemporaneous preparation) or directly on the keratin fibres (successive application to the fibres o f the emulsions (A) and (B) without intermediate rinsing) .
  • the emulsions (A), and then (B), are applied to the wet or dry keratin fibres, successively and without intermediate rinsing.
  • a composition obtained by extemporaneous mixing, before application, of the emulsions (A) and (B) is applied to the wet or dry keratin fibres.
  • the time between the mixing of the emulsions (A) and (B) and the application of the mixture to the hair then preferably does not exceed 30 minutes, preferably 10 minutes and more preferably 5 minutes .
  • the weight ratio of the amount of inverse emulsion (A) used to the amount of direct emulsion (B) used may range from 0.2 to 3 and preferably from 0.3 to 1 .
  • the mixture present on the fibres (resulting either from the extemporaneous mixing of the emulsions (A) and (B), or from the successive application o f these compositions) is left in place for a time, generally from about 1 minute to 1 hour and preferably from 5 minutes to 30 minutes.
  • the temperature during the process is conventionally between room temperature (between 15 and 25 °C) and 80°C and preferably between room temperature and 60° C .
  • the human keratin fibres are optionally rinsed with water, optionally washed with a shampoo and then rinsed with water, before being dried or left to dry.
  • a subj ect of the invention is also a multi-compartment dyeing and/or bleaching device or "kit", comprising a first compartment containing an inverse emulsion (A), and a second compartment containing a direct emulsion (B), the emulsions (A) and (B) being as described above.
  • This device may also comprise one or more compositions for washing and/or conditioning keratin fibres, which are intended to be applied before and/or after the dyeing and/or bleaching treatment according to the invention.
  • This device may advantageously be equipped with a means for dispensing the desired mixture on the hair, such as the devices described in patent FR 2 586 913.
  • the invention relates to the use of the agent as defined above for dyeing and/or bleaching keratin fibres, in particular human keratin fibres such as the hair.
  • the oxidation dyeing inverse emulsion (A) below was prepared (in the table below, the amounts are expressed as weight percentages) :
  • one part by weight of the direct emulsion C I is mixed with one part by weight of the inverse emulsion C2.
  • the mixture is then applied to locks o f natural hair containing 90% white hairs .
  • a leave-on time of 30 minutes at room temperature (23 °C) the hair is rinsed, washed with a standard shampoo and then dried. An ash-golden very light blond co loration is then obtained.

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Abstract

La présente invention concerne un agent pour teinture et/ou blanchiment de fibres de kératine qui comprend les éléments suivants : - une émulsion inverse d'eau dans l'huile (A) qui comporte 30 % à 70 % en poids (par rapport au poids de l'émulsion inverse (A)) d'une ou de plusieurs huiles ne contenant aucune fonction d'acide carboxylique, de l'eau, un ou plusieurs tensioactifs dont la valeur HLB est supérieure ou égale à 8, et un ou plusieurs agents alcalinisants ; et une émulsion directe d'huile dans l'eau (B) qui comprend de l'eau, une ou plusieurs huiles ne contenant aucune fonction d'acide carboxylique, un ou plusieurs agents d'oxydation, la quantité totale desdites huiles contenues dans le mélange des émulsions (A) et (B) représentant au moins 20 % en poids par rapport au poids total dudit mélange. La présente invention porte également sur un procédé de teinture et/ou de blanchiment de fibres de kératine au moyen d'un agent, et sur un kit les contenant.
PCT/EP2010/069937 2009-12-22 2010-12-16 Agent en deux parties ou plus, sous forme d'émulsion, pour teinture et/ou blanchiment de fibres de kératine WO2011076665A1 (fr)

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EP10795333A EP2516013A1 (fr) 2009-12-22 2010-12-16 Agent en deux parties ou plus, sous forme d'émulsion, pour teinture et/ou blanchiment de fibres de kératine

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FR0959378 2009-12-22
FR0959378A FR2954113B1 (fr) 2009-12-22 2009-12-22 Agent de coloration et/ou de decoloration des fibres keratiniques en deux parties ou plus, sous forme d'emulsion.
US29896910P 2010-01-28 2010-01-28
US61/298,969 2010-01-28

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Cited By (3)

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WO2011131676A3 (fr) * 2010-04-22 2012-06-07 L'oreal Procédé de coloration ou d'éclaircissement et émulsion inverse pour le traitement des cheveux comprenant un solvant particulier
FR3052971A1 (fr) * 2016-06-23 2017-12-29 Oreal Composition cosmetique oxydante sous forme d'une nanoemulsion comprenant un tensioactif non-ionique polyoxyethylene
JP2022510502A (ja) * 2018-10-31 2022-01-26 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 人工的な毛髪染色のための２成分システム

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FR3002438B1 (fr) * 2013-02-28 2016-08-19 Oreal Composition cosmetique oxydante sous forme d'une nanoemulsion huile-dans-eau destinee a la coloration et/ou la decoloration des fibres keratiniques
FR3059547B1 (fr) * 2016-12-01 2019-06-21 L'oreal Composition de coloration comprenant un colorant direct de structure triarylmethane, sous forme d'emulsion eau-dans-huile et procede de coloration et de decoloration simultanees mettant en oeuvre cette composition

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FR2801308A1 (fr) 1999-11-19 2001-05-25 Oreal COMPOSITIONS DE TEINTURE DE FIBRES KERATINIQUES CONTENANT DE DES 3-AMINO PYRAZOLO-[1,(-a]-PYRIDINES, PROCEDE DE TEINTURE, NOUVELLES 3-AMINO PYRAZOLO-[1,5-a]-PYRIDINES
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WO2002056847A1 (fr) 2001-01-17 2002-07-25 L'oreal Composition cosmetique contenant un polymer et une huile fluoree
EP1377263A2 (fr) 2001-04-02 2004-01-07 L'oreal Composition tinctoriale pour la teinture des fibres keratiniques comprenant un colorant diazoique dicationique particulier
EP1377262A1 (fr) 2001-04-02 2004-01-07 L'oreal Composition tinctotiale pour la teinture des fibres keratiniques comprenant un colorant azoique cationique
EP1377261A1 (fr) 2001-04-02 2004-01-07 L'oreal Composition tinctoriale pour la teinture des fibres keratiniques comprenant un colorant azoique cationique
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