Method for coloring or lightening in the presence of inorganic base, and kit therefor

The present invention comprises an anhydrous cosmetic composition (A) containing one or more fats and one or more surfactants, an oxidizing composition (B), and at least one inorganic base, optionally one or more. The present invention relates to a method for coloring or lightening human keratin fibers in the presence of an oxidizing agent, which comprises the step of applying the composition (C) containing the dye of.

The present invention is also a kit having several compartments, the first compartment containing the above-mentioned anhydrous cosmetic composition, the second compartment containing the oxidation composition, and the third compartment. , A kit comprising a composition comprising one or more inorganic bases, optionally one or more dyes and one or more of the above-mentioned inorganic bases.

Among the methods for coloring human keratin fibers such as hair, permanent staining or oxidative staining can be mentioned. In particular, this coloring method uses one or more oxidative dye precursors, usually one or more oxidative bases, in any combination with one or more couplers.

Generally, the oxidizing base is selected from ortho- or para-phenylenediamine, ortho- or para-aminophenol and heterocyclic compounds. Such an oxidizing base is a colorless or light-colored compound, and when combined with an oxidizing agent, an oxidative condensation process gives a colored type of compound.

Very often, the tones obtained with such oxidative bases can be varied by combining the oxidative base with one or more couplers, the couplers being particularly aromatic meta-diamines, meta-aminos. It is selected from phenols, meta-diphenols and certain heterocyclic compounds such as indole compounds.

A wide range of color tones can be realized due to the wide variety of molecules used in the oxide base and the coupler.

Direct or semi-permanent staining is also known. Traditionally used methods for direct dyeing include the step of applying a direct dye on the keratin fibers, which is a colored and coloring molecule that has an affinity for the fibers, and the molecules are diffused inside the fibers. It consists of a step of waiting for penetration and then a step of rinsing.

Commonly used direct dyes are selected from direct dyes of nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane.

This type of method does not require the use of oxidants to cause coloration. However, the use of oxidants to obtain a lightening effect using dyeing is not excluded. Therefore, this is called direct staining or semi-permanent staining under the condition of lightening.

Therefore, permanent staining under lightening conditions, and even semi-permanent staining methods, use an aqueous composition containing at least one oxidant with the dye composition, most often under alkaline pH conditions. Consists of steps to do. This oxidant has the role of decomposing melanin in the hair, which may or may not make the fibers lighter, depending on the nature of the oxidant present. Therefore, for relatively slight lightening, the oxidant is generally hydrogen peroxide. If more pronounced lightening is required, a peroxide salt, such as a persulfate, is usually used, for example in the presence of hydrogen peroxide.

The method of lightening human keratin fibers consists of the step of using an aqueous composition containing at least one oxidant, most often under alkaline pH conditions. This oxidant has the role of decomposing melanin in the hair, which may or may not make the fibers lighter, depending on the nature of the oxidant present. Therefore, for relatively slight lightening, the oxidant is generally hydrogen peroxide. If more pronounced lightening is required, a peroxide salt, such as a persulfate, is usually used, for example in the presence of hydrogen peroxide.

Such coloring or lightening methods are used under alkaline conditions and a problem arises from the fact that the most commonly used alkalizing agent is ammonia. Ammonia is particularly advantageous for this type of method. In short, ammonia makes it possible to adjust the pH of the composition to alkaline pH so that the oxidant is activated. On the other hand, this agent causes swelling of keratin fibers, lifts scaly parts, promotes penetration of oxidants, and also dyes, basically oxidative dyes, if present, inside the fibers. Penetrates to, thus increasing the effect of lightening or coloring reactions.

This alkalizing agent is extremely volatile and is inconvenient for the user due to the characteristically strong, rather unpleasant odor of ammonia released during the process.

Furthermore, considering the amount of ammonia released, a higher content than required is required to compensate for this loss. This is also important for users. Not only can the user be inconvenienced by the odor, but they can also face even greater unbearable dangers, such as scalp irritation (stinging pain).

Simply stating the option of replacing ammonia in whole or in part with one or more other conventional alkalizing agents does not give a composition as effective as an ammonia-based composition. This is especially because such alkalizing agents cannot sufficiently lighten the colored fibers in the presence of an oxidizing agent.

<p><patcit num="1"><text>GB1026978</text></patcit><patcit num="2"><text>GB1153196</text></patcit><patcit num="3"><text>FR2801308</text></patcit><patcit num="4"><text>DE2359399</text></patcit><patcit num="5"><text>JP88-169571</text></patcit><patcit num="6"><text>JP05-63124</text></patcit><patcit num="7"><text>EP0770375</text></patcit><patcit num="8"><text>WO 96/15765</text></patcit><patcit num="9"><text>DE3843892</text></patcit><patcit num="10"><text>DE4133957</text></patcit><patcit num="11"><text>WO94 / 08969</text></patcit><patcit num="12"><text>WO94 / 08970</text></patcit><patcit num="13"><text>FR-A-2733749</text></patcit><patcit num="14"><text>DE19543988</text></patcit><patcit num="15"><text>FR-A-2886136</text></patcit><patcit num="16"><text>WO95 / 15144</text></patcit><patcit num="17"><text>WO95 / 01772</text></patcit><patcit num="18"><text>EP714954</text></patcit><patcit num="19"><text>FR2189006</text></patcit><patcit num="20"><text>FR2285851</text></patcit><patcit num="21"><text>FR-2140205</text></patcit><patcit num="22"><text>EP1378544</text></patcit><patcit num="23"><text>EP1674073</text></patcit><patcit num="24"><text>EP1637566</text></patcit><patcit num="25"><text>EP1619221</text></patcit><patcit num="26"><text>EP1634926</text></patcit><patcit num="27"><text>EP1619220</text></patcit><patcit num="28"><text>EP1672033</text></patcit><patcit num="29"><text>EP1671954</text></patcit><patcit num="30"><text>EP1671955</text></patcit><patcit num="31"><text>EP1679312</text></patcit><patcit num="32"><text>EP1671951</text></patcit><patcit num="33"><text>EP167952</text></patcit><patcit num="34"><text>EP167971</text></patcit><patcit num="35"><text>WO06 / 063866</text></patcit><patcit num="36"><text>WO06 / 063867</text></patcit><patcit num="37"><text>WO06 / 063868</text></patcit><patcit num="38"><text>WO06 / 063869</text></patcit><patcit num="39"><text>EP1408919</text></patcit><patcit num="40"><text>EP1377264</text></patcit><patcit num="41"><text>EP1377262</text></patcit><patcit num="42"><text>EP1377261</text></patcit><patcit num="43"><text>EP1377263</text></patcit><patcit num="44"><text>EP1399425</text></patcit><patcit num="45"><text>EP1399117</text></patcit><patcit num="46"><text>EP1416909</text></patcit><patcit num="47"><text>EP1399116</text></patcit><patcit num="48"><text>EP1671560</text></patcit><patcit num="49"><text>EP1006153</text></patcit><patcit num="50"><text>EP1433472</text></patcit><patcit num="51"><text>EP1433474</text></patcit><patcit num="52"><text>EP1433471</text></patcit><patcit num="53"><text>EP1433473</text></patcit><patcit num="54"><text>EP6291333</text></patcit></p>

<p><nplcit num="1"><text>Walter NOLL, "Chemistry and Technology of Silicones" (1968), Academic Press</text></nplcit><nplcit num="2"><text>TODD &amp; BYERS treatise "Volatile Silicone fluids for cosmetics" published in Cosmetics and Toiletries, Vol.91, Jan.76, p.27-32.</text></nplcit><nplcit num="3"><text>ASTM Standard 445 Addendum C</text></nplcit><nplcit num="4"><text>International Color Index 3rd Edition</text></nplcit><nplcit num="5"><text>CTFA (6th edition, 1995)</text></nplcit></p>

<p> One object of the present invention does not have the drawbacks of current methods due to the high content of ammonia, while with respect to lightening and uniformity or coloring in current methods. In some cases, a brightening or coloring method used in the presence of an oxidant that maintains at least as good an effect as the current method with respect to the resulting color strength, chromaticity and color uniformity along the fibers. To make a suggestion. In particular, the method according to the invention results in strong coloring.</p>

<p> Such objectives and the like are achieved by the present invention, and thus with respect to a method of coloring or brightening human keratin fibers in the presence of an oxidizing agent, the following is applied to the fibers in this method: (a) Anhydrous cosmetic composition comprising one or more fats and one or more surfactants (A), (b) Composition containing one or more oxidizing agents (B), (c) A composition containing one or more inorganic bases (C).</p><p> The present invention also comprises an anhydrous composition (A) containing one or more fats and one or more surfactants in the first compartment and one or more oxidations in the second compartment. A composition comprising a composition (B) comprising an agent, comprising one or more inorganic bases, and optionally one or more oxidative dyes and / or one or more direct dyes, in a third compartment. For kits with several compartments, including (C).</p><p> Other features and advantages of the invention will become more apparent by reading the descriptions and examples provided below.</p><p> Boundary values in a range of numbers are included in this range below, and unless otherwise stated, in that range.</p><p> Hair is preferred as the human keratin fiber treated by the method according to the invention.</p>

As previously mentioned, this method of coloring or lightening is applied in the presence of the anhydrous composition (A).

In particular, from the meaning of the present invention, the anhydrous composition has a water content of less than 0% by mass or 5% by mass, preferably less than 2% by mass, and more preferably less than 1% by mass with respect to the mass of the composition. Means a composition. It should be pointed out that water may be in the form of bound water, such as water of crystallization of salts or trace amounts of water absorbed by the raw materials used in the preparation of the compositions according to the invention.

Furthermore, when this composition is used for lightening, it does not contain or contain direct dyes or oxidative dye precursors (bases and couplers) commonly used to color human keratin fibers. Even if it is contained, its total content does not exceed 0.005% by mass with respect to the mass of the anhydrous composition containing the oxidizing agent and the aqueous composition. In fact, at such a content, only the composition will probably be colored, i.e. the coloring effect of the keratin fibers will not be observed.

The lightening method is preferably used without oxidizing bases, couplers or direct dyes.

As mentioned above, the anhydrous cosmetic composition (A) contains one or more fats.

"Fat" is an organic compound that is insoluble in water at room temperature (25 ° C) and atmospheric pressure (760 mmHg) (solubility less than 5%, preferably less than 1%, even more preferably less than 0.1% below). .. In that structure, the fat has at least one chain of at least two siloxane groups, or at least one hydrocarbon chain with at least 6 carbon atoms. In addition, fat is generally soluble in organic solvents such as chloroform, ethanol, benzene, liquid paraffin or decamethylcyclopentasiloxane under the same temperature and pressure conditions.

Above all, fat is a low-grade C₆~ C₁₆It is selected from non-silicone oils of alcan, animal, vegetable, mineral or synthetic origin, fatty alcohols, fatty acids, fatty acids and / or esters of fatty alcohols, non-silicone waxes, silicones or mixtures thereof.

In the sense of the present invention, alcohols, esters and fatty acids particularly contain at least one direct, containing 6 to 30 carbon atoms and particularly optionally substituted with one or more hydroxyl groups (particularly 1 to 4). Note that it has chain or branched, saturated or unsaturated hydrocarbon groups. If such compounds are unsaturated, they can contain from 1 to 3 conjugated or unconjugated carbon-carbon double bonds.

C₆~ C₁₆For lower alkanes, they are linear, branched, and optionally cyclic. Examples include hexane, undecane, dodecane, tridecane, isoparaffin, such as isohexadecane and isodecane.

Non-silicone oils of animal, vegetable, mineral or synthetic origin that can be used in the compositions of the present invention include, for example: --Animal-derived hydrocarbon oils, such as perhydrosqualene, --Plant-derived or synthetic-derived triglyceride oils, such as liquid triglycerides of fatty acids with 6 to 30 carbon atoms, such as heptanic acid or octanoic acid triglycerides, or, for example, sunflower oil, corn oil, soybean oil, gourd oil, grapes. Seed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, sunflower oil, avocado oil, etc., caprylic acid / capric acid triglycerides, such as those sold by Stearineries Dubois, or Dynamit Nobel. Sold under the names Miglyol® 810, 812 and 818, jojoba oil, shea butter oil, etc. --- Linear or branched hydrocarbons of mineral or synthetic origin with more than 16 carbon atoms, such as volatile or non-volatile paraffin oils and derivatives thereof, petrolatum, liquid paraffin, polydecene, Parleam ( Hydrocarbonized polyisobutene such as (registered trademark), preferably hydrogenated polyisobutene such as paraffin oil, petrolatum, liquid paraffin, polydecene, Parleam, etc. --Fluorinated oils such as perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, that is, sold by BNFL Fluorochemicals under the names "FLUTEC® PC1" and "FLUTEC® PC3". , Perfluoro-1,2-dimethylcyclobutane, perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, "PF 5050®" and "PF" from 3M. Sold under the name "5060®" or bromoperfluorooctanoic acid, ie, sold by Atochem under the name "FORALKYL®", nonafluoromethoxybutane and nonafluoroethoxyisobutane. , Derivatives of perfluoromorpholine, such as 4-trifluoromethylperfluoromorpholine, such as those sold by 3M under the name "PF5052®".

Fatty alcohols suitable for use in the present invention are selected, among other things, from saturated or unsaturated, linear or branched alcohols with 8 to 30 carbon atoms. Examples include cetyl alcohol, stearyl alcohol and mixtures thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol. ..

Fatty acids that can be used within the scope of the present invention are selected from among saturated or unsaturated carboxylic acids having 6 to 30 carbon atoms, in particular 9 to 30 carbon atoms. These are advantageously selected from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid.

With respect to esters of fatty acids and / or fatty alcohols, it is advantageous to differ from the triglycerides mentioned above. Aliphatic saturated or unsaturated, linear or branched C₁~ C₂₆Monoacids or polyacids and aliphatic saturated or unsaturated, linear or branched C₁~ C₂₆Esters of monoalcohols or polyalcohols can be specifically mentioned, and the total number of carbons in these esters is 10 or more.

Among the monoesters, dihydroabiethyl behenate, octyldodecyl behenate, isocetyl behenate, cetyl lactate, C lactate₁₂~ C₁₅Alkyl, isostearyl lactate, lauryl lactate, linoleil lactate, oleyl lactate, stearyl octanoate, isosetyl octanoate, octyl octylate, cetyl octanate, decyl oleate, isosetyl isostearate, isosetyl laurate, isosetyl stearate, Isodecyl octanate, isodecil oleate, isononyl isononanoate, isostearyl palmitate, methylacetyl lysinolate, myristyl stearate, octyl isononanoate, 2-ethylhexyl isononanoate, octyl palmitate, octyl pelargone, octyl stearate, erucic acid Octyldodecyl, oleyl erucate, ethyl palmitate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristate, such as isopropyl myristate, butyl myristate, cetyl myristate, 2-myristate Examples thereof include dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, etc., such as octyldodecyl, myristyl myristate, stearyl mistyrate, hexyl stearate, butyl stearate, isobutyl stearate, and the like.

Moreover, within the scope of this variant, C₄~ C₂₂Di-or tricarboxylic acid and C₁~ C₂₂Alcohol esters, and mono-, di- or tricarboxylic acids and C₂~ C₂₆Esters of di-, tri-, tetra- or pentahydroxy alcohols can also be used.

Diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, diisostearyl adipate, dioctyl maleate, glyceryl undecylate, octyldodecylstearoyl stearate, pentaerythrityl monolysinolate , Pentaerythrityl tetraisononanoate, pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraoctanoate, propylene glycol dicaprylate, propylene glycol dicaprate, tridecyl erucate, triisopropyl citrate, Especially triisostearyl citrate, glyceryl trilactic acid, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, propylene glycol dioctanoate, neopentyl glycol diheptate, diisanonate diethylene glycol and polyethylene glycol distearate. Can be mentioned.

Among the esters described above, ethyl palmitate, isopropyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristate, such as isopropyl myristate, Butyl myristate, cetyl myristate, 2-octyldecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate, etc., dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanoate, octanoic acid It is preferable to use cetyl.

The composition is also as a fatty ester, C₆~ C₃₀Of, preferably C₁₂~ C₂₂Fatty acid and sugar esters and diesters can be included. It is pointed out that "sugar" means an oxidized hydrocarbon compound having several alcohol functional groups and at least 4 carbon atoms, with or without aldehyde or ketone functional groups. I want to keep it. Such sugars may be monosaccharides, sucrose or polysaccharides.

Suitable sugars include, for example, sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose and derivatives thereof, especially alkylated, eg, methylated derivatives, such as methylglucose. ..

Esters of sugars and fatty acids are linear or branched, saturated or unsaturated, C with the previously described sugars.₆~ C₃₀, Preferably C₁₂~ C₂₂It can be specifically selected from the group comprising esters or mixtures of fatty acids. If they are unsaturated, such compounds can contain from 1 to 3 conjugated or unconjugated carbon-carbon double bonds.

Esters according to this modification can also be selected from mono-, di-, tri- and tetra-esters, polyesters and mixtures.

Such esters are, for example, esters of oleic acid, lauric acid, palmitic acid, myristic acid, bechenic acid, coconut fatty acids, stearic acid, linoleic acid, linolenic acid, capric acid, arachidonic acid, or mixtures thereof, such as, especially, It may be a mixed ester of oleic palmitic acid, oleostearic acid, palmitostearic acid or the like.

Among other things, mono- and di-esters are used, especially those of oleic acid, stearic acid, behenic acid, oleopalmitic acid, linoleic acid, linolenic acid, oleo-stearic acid of sucrose, glucose or methyl glucose. used.

An example is a product sold by Amerchol under the name Glucate® DO, which is a methylglucose dioleic acid ester.

Examples of esters or ester mixtures of sugars and fatty acids can also include: --Products sold by Crodesta under the names F160, F140, F110, F90, F70, SL40, with 73% monoester and di-, 27% tri-ester, 61% monoester and di-, respectively. Tri-, tetra-ester 39%, monoester 52% and di-, tri-, tetra-ester 48%, monoester 45% and di-, tri-, tetra-ester 55%, monoester 39% and di- , Tri-, Tetra-ester, which means palmitostearate ester of sucrose and mono-lauric acid ester of sucrose, which is formed of 61%. --For example, a product sold under the name Ryoto Sugar Ester under the reference name B370 and corresponding to the behenic acid ester of sucrose formed from 20% monoester and di-triester-80% polyester. --Tegosoft® PSE, mono-di-palmitostearate ester of sucrose commercially available from Goldschmidt.

Non-silicone waxes (s) are sold from carnauba waxes, candelilla waxes and alpha waxes, paraffin waxes, ozokelites, plant waxes such as olive waxes, rice waxes, hydrogenated jojoba waxes or flower anhydrous waxes such as BERTIN (France). Other wax or wax-like raw materials that are specifically selected from the black currant flower essential waxes, animal waxes such as beeswax, or modified beeswax (Ceraberina) and can be used according to the present invention are particularly marine. Waxes, such as products sold by SOPHIM under the reference name M82, are generally polyethylene or polyolefin waxes.

The silicone used in the cosmetic composition of the present invention is 5.10 at 25 ° C.^-6From 2.5m²/ s, preferably 1.10^-5From 1m²A volatile or non-volatile, cyclic, linear or branched, organically modified or non-modified silicone with a viscosity of / s.

The silicone that can be used according to the present invention may be in the form of oil, wax, resin or rubber.

Silicones are selected from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMS), as well as organically modified polysiloxanes having at least one functional group selected from poly (alkoxylated) groups, amine groups and alkoxy groups. Is preferable.

Organic polysiloxanes are defined in more detail in Walter NOLL's "Chemistry and Technology of Silicones" (1968), Academic Press. These may be volatile or non-volatile.

If the organic polysiloxane is volatile, the silicone is selected, among other things, from those having a boiling point between 60 ° C and 260 ° C, and more particularly from: (i) Cyclic polydialkylsiloxane having 3 to 7, preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxanes commercially available from UNION CARBIDE under the name VOLATILE SILICONE® 7207 or RHODIA under the name SILBIONE® 70045 V2. Decamethylcyclopentasiloxane and mixtures thereof, commercially available from UNION CARBIDE under the name VOLATILE SILICONE® 7158 and from RHODIA under the name SILBIONE® 70045 V5.

Cyclocopolymers of the type such as dimethylsiloxane / methylalkylsiloxane, such as SILICONE VOLATILE® FZ 3109 commercially available from UNION CARBIDE, can be mentioned below.

<chemistry num="1"><img file="JP2010143915A_D0001.tif" /></chemistry>

Furthermore, a mixture of cyclic polydialkylsiloxane and an organic compound derived from silicon, such as a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and octamethylcyclotetrasiloxane and oxy-1,1'-(hexa). A mixture of -2,2,2', 2', 3,3'-trimethylsilyloxy) bis-neopentan can also be mentioned. (ii) It has 2 to 9 silicon atoms and is 5.10 at 25 ° C.^-6m²A volatile linear polydialkyl siloxane with a viscosity of / s or less. These are, for example, decamethyltetrasiloxanes commercially available under the name "SH 200" from TORAY SILICONE. Silicones in this category are also described in the TODD &amp; BYERS paper "Volatile Silicone fluids for cosmetics" published in Cosmetics and Toiletries, Vol.91, Jan.76, p.27-32-.

It is preferable to use non-volatile polydialkylsiloxanes, rubbers and resins of polydialkylsiloxanes, the above-mentioned polyorganicsiloxanes modified with organic functional groups, and mixtures thereof.

Such silicones are selected from polydialkylsiloxanes in particular, and among polydialkylsiloxanes, polydimethylsiloxanes having a trimethylsilyl terminal group can be mainly mentioned. Silicone viscosities are measured at 25 ° C according to ASTM Standard 445 Appendix C.

Among such polydialkylsiloxanes, the following commercially available products can be mentioned without limitation: --47 and 70 047 series of SILBIONE® oils commercially available from RHODIA, or MIRASIL® oils, such as 70 047 V 500 000 oils, --MIRASIL® series oils commercially available from RHODIA, --DOW CORNING 200 series oil, for example viscosity 60000mm²DC200 with / s, etc. --VISCASIL® oil from GENERAL ELECTRIC and some oils from the SF series from GENERAL ELECTRIC (SF96, SF18).

Polydimethylsiloxane having a dimethylsilanol terminal group such as RHODIA's 48 series oil (known as dimethiconol in the CTFA name) can also be mentioned.

Examples of this type of polydialkyl siloxane include products marketed by GOLD SCHMIDT under the names "ABIL WAX® 9800 and 9801", which are polydialkyl (C).₁~ C₂₀) Siloxane.

Silicone rubbers that can be used in accordance with the present invention are particularly polydialkylsiloxanes, preferably polydimethylsiloxanes with high number average molecular weights between 200,000 and 1000000, used alone or in admixture in solvents. .. The solvent can be selected from volatile silicone, polydimethylsiloxane (PDMS) oil, polyphenylmethylsiloxane (PPMS) oil, isoparaffin, polyisobutylene, methylene chloride, pentane, dodecane, tridecane or a mixture thereof.

According to the present invention, more particularly usable products are mixtures such as: --A mixture of polydimethylsiloxane or dimethiconol (CTFA) with hydroxylated chain ends and cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as product Q21401 commercially available from DOW CORNING. --A mixture of polydimethylsiloxane rubber and cyclic silicone, such as GENERAL ELECTRIC's product SF1214 Silicone Fluid, which has a number average molecular weight of 500000 dissolved in the oil SF1202 Silicone Fluid, which corresponds to decamethylcyclopentasiloxane. , Rubber SF30 equivalent to dimethicone, --Two PDMS with different viscosities, especially a mixture of PDMS rubber and PDMS oil, eg, GENERAL ELECTRIC product SF 1236. This product SF 1236 is 20m²Rubber SE 30 as described above with a viscosity of / s and a viscosity of 5.10^-6m²A mixture of oil SF96 with / s. The product preferably contains 15% rubber SE 30 and 85% oil SF 96.

The organic polysiloxane resin that can be used according to the present invention has the following units: R₂SiO_2/2, R₃SiO_1/2, RSiO_3/2And SiO_4/2(In the formula, R represents an alkyl having 1 to 16 carbon atoms), which is a crosslinked siloxane system. Among such products, R is C₁~ C₄Lower alkyl groups, especially those meaning methyl, are particularly preferred.

Among such resins, products marketed under the name "DOW CORNING 593" or products marketed by GENERAL ELECTRIC under the names "SILICONE FLUID SS 4230 and SS 4267" can be mentioned. These are silicones with a dimethyl / trimethylsiloxane structure.

Examples include trimethylsiloxysilicate type resins commercially available from SHINETSU under the names X22-4914, X21-5034 and X21-5037.

Organically modified silicones that can be used in accordance with the present invention are, as previously defined, silicones that contain one or more organic functional groups immobilized with hydrocarbon groups in their structure.

Apart from the silicones described above, the organically modified silicones are polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organic functional groups described above.

Polyalkylarylsiloxanes are linear and / or branched and 1.10 at 25 ° C.^-5From 5.10^-2m²It is particularly selected from polydimethyl / methylphenylsiloxane and polydimethyl / diphenylsiloxane, which have viscosities in the range of / s.

Among such polyalkylarylsiloxanes, examples include products marketed under the following names: . RHODIA SILBIONE® 70 641 Series Oils, RHODIA RHODORSIL® 70 633 and 763 series oils, .DOW CORNING 556 COSMETIC GRADE FLUID oil made by DOW CORNING, .BAYER PK series silicones, such as product PK20, .BAYER PN, PH series silicones, such as PN1000 and PH1000 products, etc. Some oils in the SF series from GENERAL ELECTRIC, such as SF 1023, SF 1154, SF 1250, SF 1265.

Among the organically modified silicones, the following polyorganic siloxanes can be mentioned. --C₆-C₂₄Polyethylene oxy having an optional alkyl group and / or having a polypropylene oxy group, for example, commercially available from DOW CORNING under the name DC 1248, or SILWET® L 722, L 7500 manufactured by UNION CARBIDE. , L 77, L 711 oil and other products called dimethicone copolypropylene, and alkyl (C) marketed by DOW CORNING under the name Q2 5200.₁₂)-Meticconco polyol etc. --Products with substituted or unsubstituted amine groups, for example, products marketed by GENESEE under the names GP4 Silicone Fluid and GP7100, or by DOW CORNING under the names Q2 8220 and DOW CORNING 929 or 939. Product. Substituted amine groups are especially C₁~ C₄It is an aminoalkyl group. --Products with an alkoxylated group, for example, products marketed by SWS SILICONES under the name "SILICONE COPOLYMER F-755" and by GOLD SCHMIDT under the names ABIL WAX (registered trademarks) 2428, 2434 and 2440.

Fat is C₂~ C₃It is preferable that it does not contain an alkoxylated unit and does not contain a glycerol unit.

Among other things, fats are selected from compounds that are liquid or pasty at room temperature and atmospheric pressure.

The fat is preferably a compound that is liquid at a temperature of 25 ° C. and at atmospheric pressure.

Fat is C₆~ C₁₆Selected from lower alkanes, non-silicone oils derived from mineral oils with more than 16 carbon atoms, non-silicone oils derived from plants or synthetics, fatty alcohols, esters of fatty acids and / or fatty alcohols, silicones or mixtures thereof. Is preferable.

The fat is preferably selected from liquid paraffin, polydecene, fatty acids and / or fatty alcohol liquid esters, or mixtures thereof.

The fat (s) of the composition according to the invention are preferably non-silicone.

The anhydrous cosmetic composition is preferably between 10 and 99% by weight, preferably between 20 and 90% by weight, and more particularly between 25 and 80% by weight, based on the weight of the anhydrous composition (A). Has a content.

Anhydrous cosmetic composition (A) also comprises one or more surfactants.

In particular, surfactants or surfactants are selected from nonionic surfactants or anionic surfactants.

Anionic surfactants are even more special from salts of the following compounds, especially alkali metal salts, especially sodium salts, ammonium salts, amine salts, amino alcohol salts or alkaline earth metal salts such as magnesium. Selected: --Alkyl sulphate, alkyl ether sulphate, alkyl amide ether sulphate, alkylaryl-polyether sulphate, monoglyceride sulphate, --Alkyl sulfonate, alkyl amide sulfonate, alkylaryl sulfonate, α-olefin-sulfonate, paraffin sulfonate, --Alkyl phosphate, alkyl ether phosphate, --Alkyl sulfosuccinate, alkyl ether sulfosuccinate, alkylamide-sulfosuccinate, alkyl sulfosuccinate, --Alkyl sulfoacetate, --Acyl sarcosinate, acyl acetylate and N-acyl taurate, --Salts of fatty acids, such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, coconut oil or hydrogenated coconut oil, --Alkyl D galactoside uronic acid salt, --Acyl-lactilate, --- Salts such as polyalkoxylated alkyl ether carboxylic acids, polyalkoxylated alkaline ether carboxylic acids, polyalkoxylated alkylamide ether carboxylic acids, especially those having 2 to 50 ethylene oxide groups, --And a mixture of these.

The alkyl or acyl groups of such various compounds preferably have 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, and the aryl group preferably means a phenyl or benzyl group. It should be noted that

The nonionic surfactant is selected, among other things, from mono- or polyalkoxylated, mono- or polyglycerolized nonionic surfactants. The alkoxylated unit is, among other things, an ethoxylated, propoxylated unit, or a combination thereof, preferably ethoxylated.

Examples of alkoxylated nonionic surfactants include: -Alkoxylated alkyl (C)₈~ C₂₄) Phenol, Saturated or unsaturated, linear or branched, alkoxylated C₈~ C₃₀alcohol, Saturated or unsaturated, linear or branched, alkoxylated C₈~ C₃₀Amide, Saturated or unsaturated, linear or branched C₈~ C₃₀Acid and polyethylene glycol ester, Saturated or unsaturated, linear or branched C₈~ C₃₀Acid and ester of polyethoxylated sorbitol, Saturated or unsaturated, ethoxylated vegetable oils, Above all, ethylene oxide condensates and / or propylene oxide condensates (used alone or in admixture).

Surfactants have several molar numbers of ethylene oxide and / or propylene oxide between 1 and 100, preferably between 2 and 50. It is advantageous that the nonionic surfactant does not contain propoxylated units.

According to a preferred embodiment of the present invention, the alkoxylated nonionic surfactant is an ethoxylated C.₈~ C₃₀Alcoholic, saturated or unsaturated, linear or branched C₈~ C₃₀It is selected from the ester of the acid and the ester of polyethoxylated sorbitol.

As an example of a nonionic mono- or polyglycerol surfactant, preferably C₈~ C₄₀Mono- or polyglycerol alcohols are used.

Especially C₈~ C₄₀Mono-or polyglycerol alcohols correspond to the following formula: RO- [CH₂-CH (CH)₂OH) -O]_m-H (In the equation, R is linear or branched, C₈~ C₄₀Of, preferably C₈~ C₃₀Represents an alkyl or alkenyl group of, m represents a number in the range 1 to 30, preferably 1 to 10).

Examples of suitable compounds within the scope of the present invention are lauryl alcohol with 4 mol glycerol (INCI name: polyglyceryl-4 lauryl ether), lauryl alcohol with 1.5 mol glycerol, oleyl alcohol with 4 mol glycerol. (INCI name: POLYGLYCERYL-4OLEYL ETHER), oleyl alcohol with 2 mol of glycerol (INCI name: POLYGLYCERYL-2OLEYL ETHER), cetearyl alcohol with 2 mol of glycerol, cetearyl alcohol with 6 mol of glycerol, 6 mol Oreocetyl alcohol with glycerol and octadecanol with 6 mol of glycerol can be mentioned.

Alcohol may represent a mixture of a plurality of alcohols, and the numerical value of m represents a statistical value, which means that several kinds of polyglycerol fatty alcohols can coexist as a mixture in a commercial product.

Among mono- or polyglycerol alcohols, C with 1 mole of glycerol₈/ C₁₀Alcohol, C with 1 mole of glycerol₁₀/ C₁₂C with alcohol and 1.5 moles of glycerol₁₂It is particularly preferable to use alcohol.

The surfactant contained in the anhydrous composition is preferably a nonionic surfactant.

The content of the surfactant in the anhydrous composition (A) is, in particular, 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the mass of the anhydrous composition.

The cosmetic composition (A) also contains various additives conventionally used in the composition for coloring or lightening hair, such as anionic, cationic, nonionic, amphoteric, amphoteric ionic. Polymers or mixtures thereof, mineral thickeners, especially fillers such as clay and talc, organic thickeners, especially anionic, cationic, nonionic and amphoteric polymer binding thickeners, antioxidants, penetrations It can contain agents, sequestrants, air fresheners, dispersants, film-forming agents, humidity control agents, ceramides, preservatives, and opalescent agents.

The additives are generally present in an amount between 0.01 and 20% by weight, respectively, with respect to the mass of composition (A).

The composition can include one or more mineral thickeners selected from organic compatible clays, fumed silica, or mixtures thereof.

The organically compatible clay can be selected from montmorillonite, bentonite, hectorite, attapargite, sepiolite, and mixtures thereof. The clay is preferably bentonite or hectorite.

These clays can be modified with chemicals selected from quaternary amines, tertiary amines, aminoacetic acids, imidazolines, amine sequens, fatty sulfates, alkaline sulfonates, amine oxides and mixtures thereof.

As organically compatible clays, quaternium-18 bentonite, for example, those sold by Rheox under the names Bentone 3, Bentone 38, Bentone 38V, Tixogel VP sold by United Catalyst, and sold by Southern Clay. Claytone 34, Claytone 40, Claytone XL, and other stearalconium bentonites, such as those sold by Rheox under the name Bentone 27, Tixogel LG sold by United Catalyst, and sold by Southern Clay. Claytone AF, Claytone APA, etc., Quotanium-18 / Benzarconium Bentonite, eg Claytone HT, Claytone PS, sold by Southern Clay, Quotanium-18 Hectorite, eg Bentone Gel DOA, Bentone Gel ECO5, Bentone Gel EUG, Bentone Gel IPP, Bentonite Examples include those sold by Rheox under the names of Gel ISD, Bentone Gel SS71, Bentone Gel VS8, Bentone Gel VS38, and Simagel M and Simagel SI345 sold by Biophil.

Fused silica can be obtained by high temperature hydrolysis of volatile silicon compounds in an oxyhydrogen flame to produce fine silica. This method makes it possible, in particular, to obtain hydrophilic silica having a large number of silanol groups on its surface. Such hydrophilic silicas are, for example, "AEROSIL 130 (registered trademark)", "AEROSIL 200 (registered trademark)", "AEROSIL 255 (registered trademark)", "AEROSIL 300 (registered trademark)", "AEROSIL 380 (registered trademark)". Under the name of "Registered Trademark", "CAB-O-SIL HS-5 (Registered Trademark)", "CAB-O-SIL EH-5 (Registered Trademark)", "CAB-O-SILLM-130" from Degussa It is commercially available from Cabot under the names of "(registered trademark)", "CAB-O-SIL MS-55 (registered trademark)", and "CAB-O-SIL M-5 (registered trademark)".

The surface of silica can be chemically modified by a chemical reaction to reduce the number of silanol groups. In particular, the silanol group can be replaced with a hydrophobic group. This gives hydrophobic silica.

Hydrophobic groups may be: Obtained by high temperature treatment in the presence of trimethylsilokyl groups, especially hexamethyldisilazane. Silica treated in this way is called "silica sililate" according to CTFA (6th edition, 1995). These are marketed, for example, by Degussa under the reference name "AEROSIL R812®" and by Cabot under the reference name "CAB-O-SIL TS-530®". --Dimethylsilyloxyl or polydimethylsiloxane groups, these are obtained by treating fumed silica, in particular in the presence of polydimethylsiloxane or dimethyldichlorosilane. The silica treated in this way is called "silica dimethyl silylate" according to CTFA (6th edition, 1995). These are, for example, "AEROSIL R972 (registered trademark)" and "AEROSIL R974 (registered trademark)" from Degussa, "CAB-O-SIL TS-610 (registered trademark)" and "CAB-O-SIL". "TS-720 (registered trademark)" is commercially available from Cabot.

The fumed silica preferably has a particle size that can range from nanometers to micrometers, for example in the range of about 5 to 200 nm.

The composition preferably comprises hectorite, organically modified bentonite or fumed silica, optionally modified.

If present, the mineral thickener accounts for 1 to 30% by weight of the amount of constituent material.

The composition is favorably in the form of a gel or cream.

As previously mentioned, the method according to the invention is carried out in the presence of composition (B) containing one or more oxidizing agents.

Among other things, the oxidants or agents are hydrogen peroxide, urea peroxide, bromates or ferricides of alkali metals, peroxidized salts such as alkali metal or alkaline earth metal persulfates, peroxides and percarbonates. , And peracids and their precursors. One or more oxidoreductases, such as laccase, peroxidase and oxidoreductase with two electrons (such as uricase) can also be optionally used as oxidants in the presence of their respective donors or cofactors. it can.

It is advantageous that this oxidizing agent is composed of hydrogen peroxide, particularly in an aqueous solution (hydrogen peroxide), and the concentration is particularly preferably 0.1 to 50% by mass with respect to the oxidizing composition (B). May vary from 0.5 to 20% by weight, even more preferably between 1 and 15% by weight.

Depending on the desired degree of lightening, the oxidant may also include an oxidant preferably selected from the peroxide salts.

The oxidant is preferably not selected from salts and peracids and precursors.

The oxidation composition may be aqueous or non-aqueous. The aqueous composition means a composition having more than 5% by weight water, preferably more than 10% by weight water, and even more preferably more than 20% by weight water.

The composition (B) is preferably an aqueous composition.

The composition (B) can also contain one or more organic solvents.

As an organic solvent, for example, linear or branched C₂~ C₄Ethers of glycerol, polyols and polyols such as alkanols such as ethanol and isopropanol, such as 2-butoxyethanol, propylene glycol, dipropylene glycol, monomethyl ethers of propylene glycol, monoethyl ethers and monomethyl ethers of diethylene glycol, and aromatic alcohols such as Benzyl alcohol or phenoxyethanol and the like, as well as mixtures thereof and the like can be mentioned.

The solvent (s) usually have a content in the range of 1 to 40% by weight, preferably 5 to 30% by weight, based on the mass of the oxidation composition (B), when they are present.

The oxidation composition (B) can contain one or more acidifying agents.

Among the acidifying agents, mineral or organic acids such as hydrochloric acid, ortholic acid, sulfuric acid and the like, and carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulfonic acid can be mentioned as examples.

Generally, the pH of the oxidation composition (B) is less than 7 when aqueous.

The oxidizing composition (B) can also contain other components conventionally used in the art, such as the anhydrous composition (A), particularly those previously detailed with respect to fats.

Finally, the oxidizing composition (B) can take various forms, such as solutions, emulsions or gels.

The method according to the invention, if this is a coloring method, is carried out in the presence of the composition (C) containing one or more oxidation dyes and / or one or more direct dyes.

Oxidizing dyes are generally selected from oxidative bases, which are optionally combined with one or more couplers.

For example, the oxidizing base is selected from para-phenylenediamine, bis-phenylalkylene diamine, para-aminophenol, ortho-aminophenol, heterocyclic bases and addition salts thereof.

Among the paraphenylenediamines, for example, paraphenylenediamine, paratrylenediamine, 2-chloroparaphenylenediamine, 2,3-dimethylparaphenylenediamine, 2,6-dimethylparaphenylenediamine, 2,6-diethylpara Phenylene diamine, 2,5-dimethylparaphenylenediamine, N, N-dimethylparaphenylenediamine, N, N-diethylparaphenylenediamine, N, N-dipropylparaphenylenediamine, 4-amino N, N-diethyl3- Methylaniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (β) -Hydroxyethyl) Amino-2-chloroaniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoroparaphenylenediamine, 2-isopropylparaphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxy Methylparaphenylenediamine, N, N-dimethyl 3-methylparaphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenylenediamine, N-( 4'-Aminophenyl) paraphenylenediamine, N-phenylparaphenylenediamine, 2-β-hydroxyethyloxyparaphenylenediamine, 2-β-acetylaminoethyloxyparaphenylenediamine, N- (β-methoxyethyl) paraphenylene Diamine, 4-aminophenylpyrrolidin, 2-thienylparaphenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene, 3-hydroxy1- (4'-aminophenyl) pyrrolidine and additional salts with these acids Can be mentioned.

Among the above-mentioned paraphenylenediamines, paraphenylenediamine, paratrylenediamine, 2-isopropylparaphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxyparaphenylenediamine, 2,6- Dimethylparaphenylenediamine, 2,6-diethylparaphenylenediamine, 2,3-dimethylparaphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloroparaphenylenediamine, 2-β- Acetylaminoethyloxyparaphenylenediamines and addition salts with these acids are particularly preferred.

Among the bis-phenylalkylenediamines, for example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diaminopropanol, N, N' -Bis- (β-Hydroxyethyl) N, N'-Bis- (4'-Aminophenyl) Ethylenediamine, N, N'-Bis- (4-Aminophenyl) Tetramethylenediamine, N, N'-Bis-( β-Hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) ) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane and their addition salts Can be mentioned.

Among the para-aminophenols, for example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxy Methylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β) -Hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol and addition salts with these acids can be mentioned.

Among the ortho-aminophenols, for example, 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido2-aminophenol and addition salts with these acids are used. Can be mentioned.

Among the heterocyclic bases, examples thereof include pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, for example, the compounds described in the patents GB1026978 and GB1153196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 3,4-diaminopyridine and their additions. You can mention salt.

Other pyridine oxidizing bases that can be used in the present invention are, for example, the 3-aminopyrazolo [1,5-a] pyridine oxidizing base described in the patent application FR2801308 or an addition salt thereof. As an example, pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylaminopyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5- a] Pyridine-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino- Pyrazolo [1,5-a] Pyridine-7-yl) -Methanol; 2- (3-Amino-Pyrazolo [1,5-a] Pyridine-5-yl) Ethanol; 2- (3-Amino-Pyrazolo [1 , 5-a] Pyridine-7-yl) ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-Diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridine- 3-Ilamine; Pyrazolo [1,5-a] Pyridine-3,5-Diamine; 5-Morphorin-4-yl-Pyrazolo [1,5-a] Pyridine-3-ylamine; 2-[(3-Amino- Pyrazolo [1,5-a] Pyridine-5-yl)-(2-Hydroxyethyl) Amino] Ethanol; 2-[(3-Amino-Pyrazolo [1,5-a] Pyridine-7-yl)-(2) -Hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [ 1,5-a] Pyridine-6-ol; 3-amino-pyrazolo [1,5-a] Pyridine-7-ol; and their addition salts can be mentioned.

Among the pyrimidine derivatives, for example, the compounds described in patents DE2359399, JP88-169571, JP05-63124, EP0770375 or patent application WO 96/15765, such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2 , 5,6-triaminopyrimidine, 2-hydroxy4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their additions, and When there is a remutable equilibrium, a remutable morphology and the like can be mentioned.

Among the pyrazole derivatives, the compounds described in patents DE3843892, DE4133957 and patent applications WO94 / 08969, WO94 / 08970, FR-A-2733749 and DE19543988, such as 4,5-diamino1-methylpyrazole, 4,5- Diamino1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino1- (4'-chlorobenzyl) pyrazole, 4,5-diamino1,3-dimethylpyrazole, 4,5- Diamino-3-methyl1-phenylpyrazole, 4,5-diamino1-methyl3-phenylpyrazole, 4-amino1,3-dimethyl5-hydradinopyrazole, 1-benzyl4,5-diamino-3-methylpyrazole , 4,5-diamino-3-tert-butyl1-methylpyrazole, 4,5-diamino1-tert-butyl3-methylpyrazole, 4,5-diamino1- (β-hydroxyethyl) 3-methylpyrazole, 4,5-diamino1-ethyl3-methylpyrazole, 4,5-diamino1-ethyl3- (4'-methoxyphenyl) pyrazole, 4,5-diamino1-ethyl3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl 1-methylpyrazole, 4,5-diamino-3-hydroxymethyl 1-isopropylpyrazole, 4,5-diamino-3-methyl 1-isopropylpyrazole, 4-amino-5- (2'- Aminoethyl) Amino 1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl 3,4,5-triaminopyrazole, 3,5-diamino1-methyl4-methylaminopyrazole, 3, Examples thereof include 5-diamino4- (β-hydroxyethyl) amino1-methylpyrazole, and addition salts thereof. 4,5-Diamino1- (β-methoxyethyl) pyrazole can also be used.

Preferably, 4,5-diaminopyrazole will be used, and even more preferably, 4,5-diamino-1- (β-hydroxyethyl) pyrazole and / or a salt thereof will be used.

Pyrazole derivatives can also include diamino-N, N-dihydropyrazolopyrazolone and, in particular, those described in the patent application FR-A-2886136, such as the following compounds and their addition salts: 2,3-. Diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2 -a] pyrazole-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one, 2-amino-3- (pyrrolidin) -1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazole- 3-one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazole-3-one, 4,5-diamino-1,2-di (2-hydroxyethyl) -1,2- Dihydro-pyrazole-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one, 2-amino- 3-Dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridadino [1,2-a] Pyrazole-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5 -(3-Dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazole-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one.

Use of 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole-1-one and / or a salt thereof is preferred.

As heterocyclic bases, 4,5-diamino-1- (β-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazole- The use of 1-one and / or this salt is preferred.

The composition according to the invention can optionally include one or more couplers that are advantageously selected from those conventionally used for dyeing keratin fibers.

Among such couplers, particular examples include meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene coupler, heterocyclic coupler and their addition salts.

For example, 1,3-dihydroxybenzene, 1,3-dihydroxy2-methylbenzene, 4-chloro 1,3-dihydroxybenzene, 2,4-diamino1- (β-hydroxyethyloxy) benzene, 2-amino4 -(β-Hydroxyethylamino) 1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureidaniline, 3-ureido1-dimethylaminobenzene, Sesamole, 1-β-hydroxyethylamino-3,4-methylendioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxyN-methylindole, 2 -Amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylenedioxybenzene, 2,6 -Bis- (β-Hydroxyethylamino) toluene, 6-hydroxyindolin, 2,6-dihydroxy4-methylpyridine, 1-H3-methylpyrazole-5-one, 1-phenyl3-methylpyrazole-5-one, 2,6-Dimethylpyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1,2,4-triazole, 6-methylpyrazolo [1, 5-a] Benzeneimidazole, addition salts with these acids and mixtures thereof can be mentioned.

In general, the addition salt with an oxidizing base and the addition salt with a coupler that can be used within the scope of the present invention are addition salts with an acid, for example, hydrochloride, hydrobromide, sulfate, citric acid. It is particularly selected from salts, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and the like.

It is advantageous that the base oxides (s) each account for 0.0001 to 10% by weight, preferably 0.005 to 5% by weight, based on the total weight of the composition.

The content of the coupler (s), if present, accounts for 0.0001 to 10% by weight, preferably 0.005 to 5% by weight, based on the total weight of the composition, respectively. Is advantageous.

For direct dyes, these are selected from among ionic or nonionic varieties, preferably cationic or nonionic varieties.

Examples of suitable direct dyes include azo, methine, carbonyl, azine, (hetero) arylnitro, tri (hetero) arylmethane direct dyes, mottled rocks, phthalocyanines and natural direct dyes (alone or mixed). And use).

In particular, the azo dye contains a functional group -N = N-, in which two nitrogen atoms are not incorporated into the ring at the same time. However, it is not excluded that one of the two nitrogen atoms in the -N = N-chain is incorporated into the ring.

Methine dyes are, among other things, compounds containing at least one chain selected from&gt; C = C &lt;and N = C &lt;, and two atoms of these chains are not simultaneously incorporated into the ring. However, it is clearly stated that one of the nitrogen or carbon atoms of the chain can be incorporated into the ring. Among other things, dyes of this lineage include, for example, methine, azomethine, mono- and diarylmethane, indamine (or diphenylamine), indophenol, indaniline, carbocyanine, azacarbocyanine and their isomers, diazacarbocyanine and these. Derived from compounds such as the isomers of, tetraazacarbocyanine, hemicianin.

Regarding carbonyl dyes, for example, acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthraquinone, pyrantron, pyrazolanthrone, pyrimidinoanthrone, flavantron, idantron, flavon, (iso) biolantron, isoindrinone, benzimidazole Dyes selected from lon, isoquinolinone, anthraquinone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapidone, diketopyrrolopyrrole, and coumarin can be mentioned.

Examples of cyclic azine dyes include azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine and pyronin.

(Hetero) aromatic nitro dyes are, among other things, benzenenitro or pyridinenitro direct dyes.

For dyes of the porphyrin or phthalocyanine type, cationic or non-cationic compounds can be used, which include one or more metals or metal ions, such as alkaline and alkaline earth metals, zinc and silicon. Optionally included.

Examples of particularly suitable direct dyes are benzene-based nitro dyes, azo, azomethine, methine direct dyes, azacarbocyanins, such as tetraazacarbocyanine (tetraazapentamethine), and quinones and especially anthraquinone, naphthoquinone or benzoquinone direct dyes. , Adin, xanthene, triarylmethane, indamine, indigoid, phthalocyanine, porphyrin direct dyes and natural direct dyes (used alone or in combination).

Such dyes may be monochromophore dyes (ie, containing only one colorant) or polychromophores, preferably di- or trichromophores, which may be the same or different. Often, they may or may not be in the same chemical family. It should be noted that polychromophore dyes contain several groups derived from molecular absorbent substances in the visible region between 400 and 800 nm. Moreover, this light absorption of the dye does not require prior oxidation of the dye or combination with other species.

In the case of polychromophore dyes, the chromophores are linked together by at least one link, which may be cationic or non-cationic.

The connection is preferably linear, branched or cyclic C.₁~ C₂₀It is an alkyl chain, which is at least one heteroatom (nitrogen, oxygen, etc.) and / or at least one group containing these (CO, SO).₂) Arbitrarily interrupted by at least one heterocycle (this heterocycle is uncondensed or condensed with a phenyl nucleus and contains at least one quaternized nitrogen atom incorporated into the ring. Included, optionally interrupted by at least one other heteroatom (optionally containing oxygen, nitrogen, sulfur, etc.), optionally interrupted by at least one substituted or unsubstituted phenyl or naphthyl group, or optional Two Cs replaced by₁~ C₁₅Arbitrarily interrupted by at least one quaternary ammonium group substituted with an alkyl group, this linkage is free of nitro, nitroso or peroxo groups.

If the heterocycle or aromatic nucleus is substituted, these may be, for example, one or more Cs.₁~ C₈Alkyl group (hydroxyl, C₁~ C₂Alkoxy, C₂~ C₄Hydroxyalkoxy, acetylamino, or amino group (1 or 2 Cs)₁~ C₄This can be substituted with an alkyl group (optionally having at least one hydroxyl group), or these two groups can form a 5- or 6-membered heterocycle with the nitrogen atom to which they are attached. The heterocycle is optionally substituted with another heteroatom that is the same as or different from nitrogen); halogen atom; hydroxyl group; C₁~ C₂Alkoxy group; C₂~ C₄Hydroxyalkoxy group; amino group; 1 or 2 C₁~ C₄It is substituted with an alkyl group (which may be the same or different) and is substituted with an amino group which optionally has at least one hydroxyl group;

Among the benzene substantive dyes that can be used in accordance with the present invention, the following compounds can be mentioned without limitation: - 1,4-Diamino-2-nitrobenzene, - 1-Amino-2-nitro-4-β-hydroxyethylaminobenzene - 1-Amino-2-nitro-4-bis (β-hydroxyethyl) aminobenzene - 1,4-Bis (β-Hydroxyethylamino) -2-nitrobenzene - 1-β-Hydroxyethylamino-2-nitro-4-bis (β-hydroxyethylamino) benzene - 1-β-Hydroxyethylamino-2-nitro-4-aminobenzene - 1-β-Hydroxyethyl Amino-2-nitro-4- (Ethyl) (β-Hydroxyethyl) Aminobenzene - 1-Amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene - 1-Amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene - 1,2-Diamino-4-nitrobenzene - 1-Amino-2-β-Hydroxyethylamino-5-Nitrobenzene - 1,2-Bis (β-Hydroxyethylamino) -4-nitrobenzene --- 1-Amino-2-tris (Hydroxymethyl) Methylamino-5-Nitrobenzene - 1-Hydroxy-2-amino-5-nitrobenzene - 1-Hydroxy-2-amino-4-nitrobenzene - 1-Hydroxy-3-nitro-4-aminobenzene - 1-Hydroxy-2-amino-4,6-dinitrobenzene - 1-β-Hydroxyethyloxy-2-β-Hydroxyethylamino-5-nitrobenzene - 1-Methoxy-2-β-Hydroxyethylamino-5-nitrobenzene - 1-β-Hydroxyethyloxy-3-methylamino-4-nitrobenzene - 1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene - 1-β-Hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene - 1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene - 1-β-Hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene --- 1-β-Hydroxyethylamino-3-methyl-2-nitrobenzene - 1-β-Aminoethylamino-5-methoxy-2-nitrobenzene - 1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene - 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene - 1-Hydroxy-6-bis (β-hydroxyethyl) amino-3-nitrobenzene - 1-β-Hydroxyethylamino-2-nitrobenzene - 1-Hydroxy-4-β-Hydroxyethylamino-3-nitrobenzene.

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that can be used in accordance with the present invention, the cations described in the patent applications WO95 / 15144, WO95 / 01772 and EP714954, FR2189006, FR2285851, FR-2140205, EP1378544, EP1674073. Sex dyes can be mentioned.

Therefore, in particular, dyes of formulas (I) to (IV), preferably compounds of formulas (I) to (III), can be mentioned:

<chemistry num="2"><img file="JP2010143915A_D0002.tif" /></chemistry>

During the ceremony D represents a nitrogen atom or -CH group R₁And R₂Are the same or different, hydrogen atoms; C₁~ C₄Alkyl groups (-CN, -OH or -NH₂May be substituted with a group, or with a carbon atom of the benzene ring, a heterocycle (optionally oxygen- or nitrogen-containing, with one or more Cs.₁~ C₄(May be substituted with an alkyl group)); represents a 4'-aminophenyl group, R₃And R'₃Are the same or different, hydrogen atoms, or halogen atoms selected from chlorine, bromine, iodine and fluorine, cyano, C₁~ C₄Alkyl, C₁~ C₄Represents an alkoxy or acetyloxy group X^-Represents an anion preferably selected from chloride ion, methyl sulfate ion and acetate ion. A represents a group selected from the following structures A1 to A18, more preferably A1, A4, A7, A13 and A18.

<chemistry num="3A"><img file="JP2010143915A_D0003.tif" /></chemistry><chemistry num="3B"><img file="JP2010143915A_D0004.tif" /></chemistry>

Where R₄May be substituted with hydroxyl radicals C₁~ C₄Represents an alkyl group, R₅Is the following C₁~ C₄Represents an alkoxy group

<chemistry num="4"><img file="JP2010143915A_D0005.tif" /></chemistry>

here, R₆Is a hydrogen atom or C₁~ C₄Represents an alkyl group R₇Represents a hydrogen atom, an alkyl group optionally substituted with a -CN group or an amino group, a 4'-aminophenyl group, or R₆With a heterocycle (optionally oxygen-containing and / or nitrogen-containing, C₁~ C₄(May be substituted with an alkyl group), R₈And R₉Are the same or different, hydrogen atoms, halogen atoms such as bromine, chlorine, iodine or fluorine, C₁~ C₄Alkyl or C₁~ C₄Represents an alkoxy group, -CN group, X^-Represents an anion preferably selected from chloride ion, methyl sulfate ion and acetate ion. B represents a group selected from the following structures B1 to B6,

<chemistry num="5"><img file="JP2010143915A_D0006.tif" /></chemistry>

Where R₁₀Is C₁~ C₄Represents an alkyl group, R₁₁And R₁₂Are the same or different, hydrogen atom or C₁~ C₄Represents an alkyl group

<chemistry num="6"><img file="JP2010143915A_D0007.tif" /></chemistry>

here, R₁₃Is a hydrogen atom, C₁~ C₄Represents a halogen atom such as an alkoxy group, bromine, chlorine, iodine or fluorine, R₁₄Is a hydrogen atom, C₁~ C₄Represents an alkyl group, or with a carbon atom of the benzene ring, a heterocycle (optionally containing oxygen and / or one or more Cs₁~ C₄(Substituted with an alkyl group) to form R₁₅Represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine. R₁₆And R₁₇Are the same or different, hydrogen atom or C₁~ C₄Represents an alkyl group D₁And D₂Represents the same or different nitrogen atom or -CH group, m = 0 or 1, preferably 1. R₁₃When represents an unsubstituted amino group, D₁And D₂At the same time represents the -CH group and is understood to be m = 0, X^-Represents an anion preferably selected from chloride ion, methyl sulfate ion and acetate ion. E represents a group selected from the following structures E1 to E8, especially E1, E2 and E7.

<chemistry num="7A"><img file="JP2010143915A_D0008.tif" /></chemistry><chemistry num="7B"><img file="JP2010143915A_D0009.tif" /></chemistry>

Where R'is C₁~ C₄Represents an alkyl group If m = 0, then D₁Represents a nitrogen atom and E can also mean a group having the following structure E9,

<chemistry num="8"><img file="JP2010143915A_D0010.tif" /></chemistry>

Where R'is C₁~ C₄Represents an alkyl group

<chemistry num="9"><img file="JP2010143915A_D0011.tif" /></chemistry>

here, The symbol G is the following structure G₁~ G₃Represents a group selected from

<chemistry num="10"><img file="JP2010143915A_D0012.tif" /></chemistry>

Structure G₁~ G₃In R₁₈Is C₁~ C₄Alkyl group, C₁~ C₄Means a phenyl group that may be substituted with an alkyl group or a halogen atom selected from chlorine, bromine, iodine and fluorine. R₁₉Is C₁~ C₄Means an alkyl group or a phenyl group R₂₀And R₂₁Are the same or different, C₁~ C₄Represents an alkyl group, a phenyl group, or G₁Together in a benzene ring (one or more Cs)₁~ C₄Alkyl, C₁~ C₄Alkoxy, or NO₂(Substituted with a group), or G₂Together in a benzene ring (one or more Cs)₁~ C₄Alkyl, C₁~ C₄Alkoxy, or NO₂Forming (arbitrarily substituted with a group), R₂₀Can also mean a hydrogen atom, Z is an oxygen atom, a sulfur atom or -NR₁₉Means the group M is -CH, -CR group (R is C₁~ C₄(Meaning alkyl), or -NR₂₂(X^-)_rRepresents K is -CH, -CR group (R is C₁~ C₄(Meaning alkyl), or -NR₂₂(X^-)_rRepresents P is -CH, -CR group (R is C₁~ C₄(Meaning alkyl) or -NR₂₂(X^-)_rRepresents r means zero or one R₂₂Is O^-Atom, C₁~ C₄Alkoxy group, or C₁~ C₄Represents an alkyl group R₂₃And R₂₄May be the same or different, a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, C₁~ C₄Alkyl, C₁~ C₄Alkoxy group, -NO₂Represents a group X^-Represents an anion preferably selected from chloride ion, iodide ion, methyl sulfate ion, ethyl sulfate ion, acetate ion and perchlorate ion. However, R₂₂Is 0^-When we mean, r means zero, K or P or M is -N-alkyl C₁~ C₄X^-If it means R₂₃Or R₂₄Is preferably a non-hydrogen atom K is -NR₂₂(X^-)_rMeans M = P = -CH, -CR, M is -NR₂₂(X^-)_rWhen it means, K = P = -CH, -CR, P is -NR₂₂(X^-)_rWhen we mean, K = M, which means -CH or -CR, Z means sulfur atom, R₂₁Is gC₁~ C₄When it means alkyl, R₂₀Is a non-hydrogen atom, Z is -NR₂₂Means R₁₉Is C₁~ C₄When meaning alkyl, structure G₂R of the base₁₈, R₂₀Or R₂₁At least one of the groups is C₁~ C₄Other than alkyl groups, This symbol J represents: (a) The following structure J₁Group with:

<chemistry num="11"><img file="JP2010143915A_D0013.tif" /></chemistry>

(This structure J₁During, R₂₅Is a halogen atom selected from hydrogen atom, chlorine, bromine, iodine and fluorine, C₁~ C₄Alkyl group, C₁~ C₄Alkoxy, -OH, -NO₂, -NHR₂₈, -NR₂₉R₃₀, C₁~ C₄-Represents an NHCO alkyl group, or R₂₆Together with form a 5- or 6-membered ring (containing or not containing one or more heteroatoms selected from nitrogen, oxygen or sulfur), R₂₆Is a halogen atom selected from hydrogen atom, chlorine, bromine, iodine and fluorine, C₁~ C₄Alkyl, C₁~ C₄Represents an alkoxy group Or R₂₇Or R₂₈Together with form a 5- or 6-membered ring (containing or not containing one or more heteroatoms selected from nitrogen, oxygen or sulfur), R₂₇Is a hydrogen atom, a group of -OH, -NHR₂₈Based on, -NR₂₉R₃₀Represents the basis of R₂₈Is a hydrogen atom, C₁~ C₄Alkyl group, C₁~ C₄Monohydroxyalkyl group, C₂~ C₄Represents a polyhydroxyalkyl group, a phenyl group, R₂₉And R₃₀Can be the same or different, C₁~ C₄Alkyl group, C₁~ C₄Monohydroxyalkyl group, C₂~ C₄(Representing a polyhydroxyalkyl group), -(B) May contain other heteroatoms and / or carbonyl groups, one or more Cs₁~ C₄A 5- or 6-membered, nitrogen-containing heterocyclic group optionally substituted with an alkyl, amino or phenyl group. In particular, the following structure J₂Group with:

<chemistry num="12"><img file="JP2010143915A_D0014.tif" /></chemistry>

(This structure J₂During, R₃₁And R₃₂Can be the same or different, hydrogen atom, C₁~ C₄Represents an alkyl group or a phenyl group Y is the group of -CO- or

<chemistry num="13"><img file="JP2010143915A_D0015.tif" /></chemistry>

Means the basis of If n = 0 or 1 and n means 1, U means the group of -CO-).

In structures (I) to (IV) defined above, C₁~ C₄The alkyl or alkoxy group preferably means methyl, ethyl, butyl, methoxy, ethoxy.

Among the compounds of formulas (I) and (III), the following compounds are preferable.

<chemistry num="14"><img file="JP2010143915A_D0016.tif" /></chemistry>

Among the azo direct dyes, the following dyes listed in the International Color Index 3rd Edition can also be mentioned: --Disperse Red17 --Basic Red 22 --Basic Red76 --Basic Yellow 57 --Basic Brown 16 --Basic Brown17 --Disperse Black 9.

Furthermore, 1- (4'-aminodiphenylazo) -2-methyl-4-bis (β-hydroxyethyl) aminobenzene can also be mentioned.

Among the quinone substantive dyes, the following dyes: --Disperse Red15 --Solvent Violet13 --Disperse Violet1 --Disperse Violet4 --Disperse Blue1 --Disperse Violet8 --Disperse Blue3 --Disperse Red 11 --Disperse Blue7 --Basic Blue22 --Disperse Violet15 --Basic Blue99 And the following compounds can be mentioned: - 1-N-Methylmorpholinium propylamino-4-hydroxyanthraquinone - 1-Aminopropylamino-4-methylaminoanthraquinone - 1-Aminopropylaminoanthraquinone --5-β-Hydroxyethyl-1,4-diaminoanthraquinone --2-Aminoethylaminoanthraquinone - 1,4-Bis (β, γ-dihydroxypropylamino) anthraquinone.

Among the azine dyes, the following compounds can be mentioned: --Basic Blue17 --Basic Red 2.

Among the triarylmethane dyes that can be used according to the present invention, the following compounds can be mentioned: --Basic Green1 --Basic Violet3 --Basic Violet14 --Basic Blue7 --Basic Blue 26.

Among the Indianamine dyes that can be used according to the present invention, the following compounds can be mentioned: - 2-β-Hydroxyethylamino-5 [bis (β-4'-hydroxyethyl) amino] Anilino-1,4-benzoquinone - 2-β-Hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone --3-N- (2'-Chloro-4'-Hydroxy) Phenylacetylamino-6-Methoxy-1,4-benzoquinoneimine --3-N- (3'-Chloro-4'-Methylamino) Phenylureide-6-Methyl-1,4-benzoquinoneimine --3- [4'-N- (ethyl, carbamilmethyl) amino] Phenyl-ureido-6-methyl-1,4-benzoquinoneimine.

Among the tetraazapentamethine dyes that can be used according to the present invention, the compounds shown in the following table can be mentioned.

<chemistry num="15"><img file="JP2010143915A_D0017.tif" /></chemistry>

X^-Represents an anion preferably selected from chloride ion, iodide ion, methylsulfate ion, ethylsulfate ion, acetate ion and perchlorate ion.

Among the polychromophore dyes are, among other things, symmetric or asymmetric, bi- or tri-chromophore azo and / or azomethine (hydrazone) dyes, which, on the one hand, are optionally fused. Contains at least one 5- or 6-membered aromatic heterocycle, the aromatic heterocycle containing at least one quaternized nitrogen atom incorporated into the heterocycle and at least one other. It optionally contains a hetero atom (nitrogen, sulfur, oxygen, etc.) and, on the other hand, contains at least one phenyl or naphthyl group, of which the phenyl or naphthyl group is optionally substituted and at least one OR group (R is). , Hydrogen atom, optionally substituted C₁~ C₆Alkyl group, representing optionally substituted phenyl nuclei), or at least one N (R')₂Group (R'is (same or different), hydrogen atom, optionally substituted C₁~ C₆Arbitrarily having an alkyl group (representing an optionally substituted phenyl nucleus), the R'group forms a saturated, 5- or 6-membered heterocycle with the nitrogen atom to which they are attached. Can, or instead, one and / or both R'groups form a 5- or 6-membered saturated heterocycle with the carbon atom of the aromatic ring, which is located in the ortho position with respect to the nitrogen atom, respectively. can do.

Preferred examples of the cationic aromatic heterocycle include a 5- or 6-membered ring containing 1 to 3 nitrogen atoms, preferably 1 or 2 nitrogen atoms (one of which is quaternized). The heterocycle is further optionally fused with the benzene ring. It should be pointed out that this heterocycle can optionally contain other heteroatoms other than nitrogen, such as sulfur or oxygen.

If the heterocycle or phenyl or naphthyl group is substituted, these may be, for example, one or more Cs.₁~ C₈Alkyl group (hydroxy, C₁~ C₂Alkoxy, C₂~ C₄Hydroxyalkoxy, acetylamino, amino group (1 or 2 Cs)₁~ C₄It is substituted with an alkyl group (optionally having at least one hydroxyl group), or these two groups can form a 5- or 6-membered heterocycle with the nitrogen atom to which they are attached. , This heterocycle is optionally substituted with another heteroatom that is the same as or different from nitrogen); halogen atom; hydroxyl group; C₁~ C₂Alkoxy group; C₂~ C₄Hydroxyalkoxy group; amino group; one or two C₁~ C₄It is substituted with an alkyl group (which may be the same or different) and is substituted with an amino group which optionally has at least one hydroxyl group;

Such polychromophores are formed by at least one linkage that optionally contains at least one quaternized nitrogen atom that may or may not be incorporated into a saturated or unsaturated, optionally aromatic heterocycle. , Are combined together.

Preferably, the linkage is a linear, branched or cyclic C₁~ C₂₀It is an alkyl chain, which is at least one heteroatom (nitrogen, oxygen, etc.) and / or at least one group containing them (CO, SO).₂) Arbitrarily interrupted by at least one heterocycle (this heterocycle is fused or unfused with the phenyl nucleus and contains at least one quaternized nitrogen atom incorporated into the ring. Containing and optionally interrupted by at least one other heteroatom (optionally containing oxygen, nitrogen or sulfur, etc.) and optionally interrupted by at least one substituted or unsubstituted phenyl or naphthyl group, Two Cs that are arbitrarily replaced₁~ C₁₅Arbitrarily interrupted by at least one quaternary ammonium group substituted with an alkyl group, this linkage is free of nitro, nitroso or peroxo groups.

The linkage and the bond between each chromophore are usually made by a heteroatom that replaces the phenyl or naphthyl nucleus, or by a quaternized nitrogen atom of the cationic heterocycle.

The dye can contain the same or different chromophores.

Examples of such dyes are the patent applications EP1637566, EP1619221, EP1634926, EP1619220, EP1672033, EP1671954, EP1671955, EP1679312, EP1671951, EP167952, EP167971, WO06 / 063866, WO06 / 063867, WO06 / 063868, WO06 / 063869, EP1408919. , EP1377264, EP1377262, EP1377261, EP1377263, EP1399425, EP1399117, EP1416909, EP1399116, EP1671560 can be specifically mentioned.

It is also possible to use a cationic direct dye as described in EP1006153 of the patent application, which EP1006153 describes a dye containing two anthraquinone-based chromophores that are bound by a cationic linkage. , Patent applications EP1433472, EP1433474, EP1433471 and EP1433473 describe dyes of the same or different chromophores that are bound by a cationic or non-cationic linkage, and patent EP6291333 describes three chromophores. One of the chromophores is the anthraquinone chromophore, to which two azo or diazacarbocyanine chromophores or their isomers bind. ..

Among the natural substantive dyes that can be used according to the present invention include Lawson, Juglone, Alizarin, Perpurine, Carminic Acid, Kermesic Acid, Perprogalin, Protocatecaldehyde, Indigo, Isatin, Curcumin, Spinulosin, Apigenidine, Orcein. .. Extracts or decoctions containing such natural dyes, especially henna-based paps or extracts, can also be used.

If present, the direct dyes (s) account for 0.0001 to 10% by weight, preferably 0.005 to 5% by weight, of the total mass of the composition, among others.

The composition (C) can also contain one and / or other types of dyes. The composition (C) can also be optionally derived from a mixture of the two dyeing compositions, one containing an oxidative dye (s) and the other a direct dye or a direct dye (s). Including.

Another component of the composition (C) is represented by one or more inorganic bases.

In the meaning of the present invention, an inorganic compound has one or more elements other than hydrogen in groups 1 to 13 of the Periodic Table of the Elements in its structure, and simultaneously contains carbon and hydrogen atoms (s). Means any compound that does not.

According to certain embodiments of the present invention, the inorganic base contains one or more elements other than hydrogen in groups 1 and 2 of the Periodic Table of the Elements.

In a preferred variant, the inorganic base has the following structure: (Z₁^x-)_m(Z₂^{y +})_n(During the ceremony, Z₂Means groups 1 to 13, preferably groups 1 or 2 of the Periodic Table of the Elements, such as sodium or potassium. Z₁^x-Is C0₃^2-, OH^-, HCO₃^2-, SiO₃^2-, HPO₄^2-, P0₄^3-, B₄0₇^2-Ion, preferably CO₃^2-, OH-, SiO₃^2-Means an anion selected from the ions of x means 1, 2 or 3 y means 1, 2, 3 or 4 m and n mean 1, 2, 3 or 4 independently of each other, ny = mx).

Preferably, the inorganic base is represented by the following formula (Z):₁^x-)_m(Z₂^{y +})_n(In the formula, Z₂Means Group 1 and Group 2 metals in the Periodic Table of the Elements, Z₁^x-Is AEON CO₃^2-, OH^-, SiO₃^2-Means the anion selected from, x means the value of 1, y means 1 or 2, m and n mean 1 or 2 independently of each other, at ny = mx There is).

Examples of the inorganic base that can be used according to the present invention include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, and potassium metasilicate. The inorganic base is preferably an alkaline carbonate.

The content of the inorganic base (s) of the composition (C) is preferably in the range of 0.01 to 30% by mass, preferably in the range of 0.1 to 20% by mass, based on the mass of the composition.

The composition (C) can also contain one or more additional organic amines, the pKb of this organic amine at 25 ° C of less than 12, preferably less than 10, even more preferably less than 6. is there.

Organic amines of the formula below are suitable:

<chemistry num="16"><img file="JP2010143915A_D0018.tif" /></chemistry>

(In the formula, W is a hydroxyl group or C₁~ C₆Arbitrarily substituted with an alkyl group, C₁~ C₆The alkylene residues, Rx, Ry, Rz and Rt (which may be the same or different) are hydrogen atoms, C.₁~ C₆Alkyl group or C₁~ C₆Hydroxyalkyl, C₁~ C₆Represents aminoalkyl).

Examples of such amines include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine, spermidine.

According to the second variant, organic amines are selected from amino acids.

Among other things, the amino acids that can be used are of natural or synthetic origin in the L, D, or racemic form, and in particular at least one selected from the functional groups of carboxylic acids, sulfonic acids, phosphonic acids or phosphoric acids. It has an acid functional group. Amino acids may be in neutral or ionic form.

Amino acids that can be used in the present invention include aspartic acid, glutamic acid, alanine, arginine, ornitine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, Specific examples include taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acid is a basic amino acid containing another amine functional group optionally contained within the ring or within the ureido functional group.

Such a basic amino acid is described by the following formula (I):

<chemistry num="17"><img file="JP2010143915A_D0019.tif" /></chemistry>

(In the formula, R means a group selected from the following.) It is preferable to select from those corresponding to.

<chemistry num="18"><img file="JP2010143915A_D0020.tif" /></chemistry>

The compounds corresponding to formula (I) are histidine, lysine, arginine, ornithine and citrulline.

According to the preferred variant of the invention, the organic amine is selected from basic amino acids. Particularly preferred amino acids are arginine, lysine, histidine or mixtures thereof.

According to the third variant, the organic amine is selected from heterocyclic organic amines. In addition to the histidines already mentioned as amino acids, pyridine, piperidine, imidazole, triazole, tetrazole, benzimidazole can be specifically mentioned.

According to the fourth variant, organic amines are selected from amino acid dipeptides. Carnosine, anserine and ophidine can be specifically mentioned as amino acid dipeptides that can be used in the present invention.

According to the fifth modification of the present invention, the organic amine is selected from compounds having a guanidine functional group. As this type of amine that can be used in the present invention, in addition to arginine previously mentioned as an amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycosiamine, metformin, agmatine, n-amidino Alanin, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino (imino) methyl] amino) ethane-1-sulfonic acid can be specifically mentioned.

When using additional organic amines, it is preferred to choose from basic amino acids or monoethanolamines.

If additional organic amines are present in the composition (C), their content is preferably 0.01 to 30% by weight, preferably 0.1 to 20% by weight, based on the weight of the composition.

The composition (C) can be an anhydrous composition or an aqueous composition. The aqueous composition means a composition comprising more than 5% by weight water, preferably more than 10% by weight water, more preferably more than 20% by weight water.

The composition (C) is preferably an aqueous composition.

The composition can optionally contain one or more solvents. What is stated within the description of the aqueous composition (B) may be suitable for the composition (C) at the stated concentration levels.

The composition (C) can also include conventional additives, such as those previously mentioned, and these additives can also be mentioned.

The pH of the composition (C) is between 2 and 12, preferably between 8 and 11 when aqueous. The pH is adjusted with an oxidizing agent or alkalizing agent (inorganic or organic amine) such as those previously mentioned.

When the composition applied to hair (including the compositions (A), (B) and (C)) contains ammonia, the content thereof is 0.03% by mass or less of the final composition with respect to the final composition. (NH₃(When expressed as), it is specified that it is particularly preferable that it is 0.01% by mass or less. It is stated that the final composition is obtained by mixing the compositions (A), (B) and (C), either before application to the keratin fibers (mixed at the time) or Either before applying directly to the keratin fibers (even with or without premixing, apply sequentially without intermediate rinsing).

According to the first modified method of the present invention, the compositions (A), (B) and (C) are sequentially applied to dry or moist keratin fibers without intermediate rinsing. In particular, the composition (A) is followed by (C), then (B), or (C) is followed by (A), then (B).

In one particular embodiment of this modification, the composition obtained by mixing the compositions (A) and (C) and then the oxidizing composition (B) prior to application is applied sequentially without intermediate rinsing. Equivalent to doing.

According to the second modification of this method, the composition obtained by mixing the compositions (A), (B) and (C) at the time of use before application is applied to dried or moist keratin fibers. To do. This variant is preferred.

In each of these modifications, the mass ratio R1 [(A) + (C)] / (B) of the amount of the composition and the mass ratio R2 (A) / (C) of the amount of the composition were 0.1 to 10, It preferably varies between 0.3 and 3.

Moreover, regardless of the modification used, the mixture present on the fiber (obtained either by mixing the composition at the time of use or by sequential application of the composition) is generally about 1 minute to 1 hour, preferably about 1 minute to 1 hour. It is left for 5 to 30 minutes.

While performing this method, the temperature is customarily between room temperature (15-25 ° C) and 80 ° C, preferably between room temperature and 60 ° C.

At the end of the treatment, human keratin fibers are optionally rinsed with water, optionally washed with shampoo, then rinsed with water, then dried or left to dry.

Another object of the present invention is a kit having several compartments, the first containing the above-mentioned anhydrous composition (A) containing one or more fats and one or more surfactants. Includes a compartment, a second compartment containing the composition (B) containing one or more oxidants, and a third compartment containing the composition (C) containing one or more inorganic bases. Regarding the kit.

According to a modification, the composition (C) comprises one or more oxidative dyes and / or one or more direct dyes.

The following examples are for exemplifying the present invention and do not limit the scope thereof.

<p> Prepare the following composition (amount represents the active ingredient in grams).</p><p> Composition A1</p><p><tables num="1"><img file="JP2010143915A_D0021.tif" /></tables></p><p> Composition C1</p><p><tables num="2"><img file="JP2010143915A_D0022.tif" /></tables></p><p> Mix the following at the time of use. --Composition A1, 10 parts by mass --Composition C1, 4 parts by mass --Oxidizing agent (Platinium international 20 Volumes) (hydrogen peroxide) (composition B), 15 parts by mass</p><p> The resulting mixture (pH = 9.4) is then applied to a pristine tuft of 90% gray hair and a permed tuft of 90% gray hair.</p><p> The bath ratio of "mixture / hair tress" is 10/1 (g / g) respectively.</p><p> The leaving time is 30 minutes at 27 ° C.</p><p> At the end of the standing time, rinse the hair tress and then wash with Elseve Multivitamin Shampoo.</p><p> No irritating odor was observed during the preparation of the dye mixture or during application to the hair tress.</p><p> In addition, strong coloring is obtained with low selectivity, as shown in the table below.</p><p> The selectivity was calculated after measuring the coloration of the hair tresses with the CIE system l * a * b * using the Minolta spectrocolorimeter CM2600D.</p><p> The selectivity is expressed by ΔE * and calculated from the numerical value of L * a * b * according to the following equation.</p><p><maths num="1"><img file="JP2010143915A_D0023.tif" /></maths></p><p> (In the formula, L *, a * and b * represent the values measured on the pristine hair tress, L._{o o}*, a_{o o}* And b_{o o}* Represents the value measured on the tuft of permed hair).</p><p> The lower the value of ΔE *, the higher the uniformity of the obtained coloring.</p><p><tables num="3"><img file="JP2010143915A_D0024.tif" /></tables></p>

<p> Prepare the following composition (amount represents active ingredient in grams):</p><p> Composition A1</p><p><tables num="4"><img file="JP2010143915A_D0025.tif" /></tables></p><p> Composition C2</p><p><tables num="5"><img file="JP2010143915A_D0026.tif" /></tables></p><p> Mix the following at the time of use. --Composition A1, 10 parts by mass --Composition C2, 4 parts by mass --Oxidizing agent (Platinium international 20 Volumes) (hydrogen peroxide) (composition B), 15 parts by mass</p><p> The resulting mixture (pH 9.5) is then applied to a pristine hair tress with 90% gray hair and a permed hair tress with 90% gray hair.</p><p> The bath ratio of "mixture / hair tress" is 10/1 (g / g) respectively.</p><p> The leaving time is 30 minutes at 27 ° C.</p><p> At the end of the standing time, the hair tress is rinsed and then washed with Elseve Multivitamin Shampoo.</p><p> No irritating odor was observed during the preparation of the dye mixture or during application to the hair tress.</p><p> Further, as shown in the table below (numerical values and calculated values are obtained as in Example 1), a strong dark purple coloration is obtained with low selectivity.</p><p><tables num="6"><img file="JP2010143915A_D0027.tif" /></tables></p>

<p> The following compositions are prepared.</p><p> Composition A1</p><p><tables num="7"><img file="JP2010143915A_D0028.tif" /></tables></p><p> Composition B3</p><p><tables num="8"><img file="JP2010143915A_D0029.tif" /></tables></p><p> Mix the following at the time of use. --Composition A1, 9 parts by mass --Composition B3, 1 part by mass --Oxidizing agent (20 Volumes) (6% hydrogen peroxide), 10 parts by mass</p><p> In parallel, it is prepared by the formulation of the prior art.</p><p><tables num="9"><img file="JP2010143915A_D0030.tif" /></tables></p><p> At the time of use, the composition of the prior art and the oxidant 20 Volumes (containing 6% hydrogen peroxide) are mixed on a mass ratio basis.</p><p> The final concentration of sodium hydroxide in the mixture of the prior art is the same as that of the mixture of the present invention, i.e. 1 g%. The pH value of the mixture of these two is 10.9 ± 0.2.</p><p> Each mixture is then applied to a pristine maroon (height of shade 5) hair tress. The bath ratio of "mixture / hair tress" is 10/1 (g / g) respectively. The application time is 45 minutes at 27 ° C. At the end of the application time, rinse the hair tress and then wash with Elseve multivitamin shampoo.</p><p> The table below shows that the method according to the present invention provides better lightening than the method according to the prior art.</p><p><tables num="10"><img file="JP2010143915A_D0031.tif" /></tables></p>

<p> The following compositions are prepared.</p><p> Composition A1</p><p><tables num="11"><img file="JP2010143915A_D0032.tif" /></tables></p><p> Composition B4</p><p><tables num="12"><img file="JP2010143915A_D0033.tif" /></tables></p><p> Mix the following when using: --Composition A1, 9 parts (mass) --Composition B4, 1 part --Oxidizing agent 20 Volumes (containing 6% hydrogen peroxide), 10 parts.</p><p> In parallel, it is prepared by the formulation of the prior art.</p><p><tables num="13"><img file="JP2010143915A_D0034.tif" /></tables></p><p> At the time of use, the oxidant 20 Volumes (containing 6% hydrogen peroxide) is mixed with the composition of the prior art based on the mass ratio.</p><p> The final concentration of potassium carbonate in the mixture of the present invention is the same as that of the mixture of the prior art, i.e. 1 g%. The pH value of the mixture of these two is 9.4 ± 0.2.</p><p> Each mixture is then applied to a pristine maroon (height of shade 5) hair tress. The bath ratio of "mixture / hair tress" is 10/1 (g / g) respectively. The application time is 45 minutes at 27 ° C. At the end of the application time, rinse the hair tress and then wash with Elseve multivitamin shampoo.</p><p> The table below shows that the method according to the present invention provides better lightening than the method according to the prior art.</p><p><tables num="14"><img file="JP2010143915A_D0035.tif" /></tables></p>