JP2006515006A - Cosmetic composition comprising a hydrogelling ionic amide and a dye - Google Patents

Abstract

The present invention relates to an aqueous medium or a water + solvent medium.
At least one dye, in particular a hair dye; and at least one phosphorus-free thickening molecular compound having a molecular weight of less than 2000 g / mol;
The molecular compound is
Two amide groups,
-Asymmetric carbon,
-Relates to cosmetic compositions comprising at least fatty chains comprising at least 8 carbons.

Description

The present invention relates to a cosmetic composition comprising at least one dye, in particular a hair dye, and at least one hydrogelling ionic amide.
The present invention also relates to a cosmetic dyeing method, in particular a kit, for dyeing hair, in particular using the composition.

  It is a known method to dye keratin fibers and in particular human hair with direct dyes, in particular nitrobenzene dyes, acidic azo dyes, cationic azo dyes, anthraquinone dyes and natural dyes.

These coloring methods can be achieved by applying a composition containing a direct dye to keratin fibers or by immediately mixing a composition containing a direct dye with a composition containing an oxidizing bleach, preferably an aqueous hydrogen peroxide solution. By applying the mixture obtained.
This is called lightening direct dyeing.

  Also, keratin fibers, especially human hair, dyes containing acid dye precursors commonly known as "acid bases", in particular ortho- or para-phenylenediamines, ortho- or para-amino-phenols And dyeing with heterocyclic bases are also known methods.

The acid dye precursor is initially uncolored or modestly colored and exhibits a dyeing power for hair in the presence of an oxidizing agent that forms a colored compound. Becomes a colorant. These colored compounds arise either from an oxidative condensation of “oxidation bases” or from an “oxidation base” and an oxidative condensation of a color modifying compound, ie a coupler.
These are generally present in dye compositions used in oxidative dyeing, and are represented by, among others, metaphenylenediamines, metaaminophenols, metadiphenols, and certain heterocyclic compounds.

By using various molecules consisting of an oxidation base on the one hand and a coupler on the other, a very rich color range is obtained.

  In order to localize the coloring product to the application of the hair so that the coloring product does not flow over the face or the area intended to be dyed, heretofore traditional thickeners, eg cross-linked Polyacrylic acid, hydroxyethyl cellulose, wax, or alternatively, HLB (hydrophilic lipophilic) which, if appropriately selected, increases the gelling effect when diluted with water and / or surfactant. Nonionic surfactants having a balance) have been used.

However, the Applicant, in the thickening system as described above, maintains a strong cosmetic state of the treated hair, while at the same time providing a strong and colorful color tone with low selectivity and good durability. I realized it was impossible to get.
In addition, Applicants have found that ready-to-use dye compositions, including direct dyes and prior art thickening systems, can be applied sufficiently accurately over time without fluid flow or viscosity reduction. I realized I can't.

Here, after considerable research on this case, Applicant has no fluid flow, can be localized exactly where applied, and has low selectivity and chemicals (shampoos, Permanents, etc.) or good fastness (durability) against natural effects (light, sweating, etc.), while giving a strong, colorful (shiny) color tone, and at the same time good cosmetics for the hair It has been discovered that dye compositions that can provide an effect are obtained when the following are introduced.
That is,
-In the case of direct dyeing, present simultaneously in (i) a composition comprising at least one direct dye, or (ii) an oxidizing composition used for lightening direct dyeing, or (iii) both compositions. An effective amount of at least one non-phosphorous thickening molecular compound having a molecular weight of less than 2000 g / mol-in the case of oxidative staining,
(i) a composition comprising at least one oxidative dye, or (ii) an oxidative composition, or (iii) an effective amount of at least one, having no molecular weight less than 2000 g / mol, present simultaneously. Phosphorus Ionic Thickening Molecular Compounds These discoveries are the basis of the present invention.

Thus, one subject of the present invention is at least one dye, in particular direct hair dye or oxidative hair dye, in an aqueous medium or water + solvent medium; and at least one having a molecular weight of less than 2000 g / mol Including a phosphorus-free thickening molecular compound,
Two amide groups,
-Asymmetric carbon,
-A cosmetic composition comprising at least fatty chains comprising at least 8 carbons.

  For the purposes of the present invention, the term “molecular compound” refers to those whose backbone is not produced by polymerization. This does not exclude the compound from being able to contain one or more polyoxyalkylenated or polyoxyglycerolated groups.

For the purposes of the present invention, the term “ionic molecule” means at least one quaternary nitrogen atom or CO ₂ M and SO ₃ M (M is a hydrogen atom group, an alkali metal, an alkaline earth metal, or It represents an ion derived from an organic amine).

  Another object of the invention relates to a ready-to-use composition for dyeing keratin fibers, the composition comprising at least one oxidative dye, at least one oxidant and at least one ionic enhancement. Contains viscous molecular compounds.

  For the purposes of the present invention, the term “composition ready for use” refers to a composition applied to keratin fibers without modification. That is, it may be one that can be stored before use without any modification, or one that can be obtained by immediately mixing two or more compositions.

Another subject of the present invention is a dyeing method, in particular a method for dyeing hair, in an aqueous medium or in a water + solvent medium at least one dye, in particular a direct hair dye or oxidized hair. A dye; and a molecular weight of less than 2000 g / mol and at least -2 amide groups;
-Asymmetric carbon,
-Comprising at least one phosphorus-free thickening polymer comprising a fatty chain comprising at least 8 carbons,
It includes the application of a cosmetic composition.

The present invention is also directed to a method of oxidative dyeing of keratin fibers, more particularly human keratin fibers, such as hair, which comprises at least one dye composition comprising at least one oxidative dye in a suitable dyeing medium. Including applying to the fiber, the color appears in alkaline, neutral, or acidic with an oxidizing composition comprising at least one oxidizing agent, and the oxidizing composition is mixed with the dye composition at the time of use Or sequentially without intermediate rinsing. Having a molecular weight of less than 2000 g / mol and at least:
Two amide groups,
-Asymmetric carbon,
The fatty chain-containing at least one phosphorus-free thickening molecular compound containing at least 8 carbons is present in the dye composition or in the oxidizing composition or in each of the two compositions.

  The subject of the present invention also relates to a staining device, ie a “kit”, which is divided into a plurality of compartments.

  The two-compartment apparatus of the present invention comprises an oxidizing composition comprising a dye composition comprising at least one acid dye in a suitable dyeing medium and at least one oxidizing agent in a suitable dyeing medium. The molecular compound of the present invention is contained in a dye composition, an oxidation composition, or each composition.

Another device of the present invention includes three compartments,
The first compartment comprises a dye composition comprising at least one oxidation dye in a suitable dye medium;
The second compartment contains an oxidizing composition comprising at least one oxidizing agent in a suitable dye medium;
The third compartment contains a composition comprising at least one molecular compound of the invention as described above in a suitable dye medium. The dye composition and / or the oxidation composition may also contain the molecular compound of the present invention.

  Another subject of the invention is thus directed to a direct dye composition used for keratin fibers, in particular human keratin fibers, in particular hair, and in a suitable dyeing medium at least one direct dye And the composition further comprises at least one molecular compound of the present invention.

  Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers comprising at least one direct dye, at least one oxidizing agent and at least one molecular compound of the invention. .

  Another subject of the invention relates to a method for direct dyeing of keratin fibres, in particular human keratin fibres, in particular hair, in a suitable dyeing medium, at least one direct dye and at least one present invention. The present invention relates to the application of a composition containing the molecular compound of

  The invention also relates to a keratin fiber, in particular a human keratin fiber, in particular a lightening direct lightening method for hair, comprising a dyeing composition comprising at least one dye in a suitable dyeing medium, and at least The present invention relates to the application of an instant mixture with an oxidizing composition comprising one oxidizing agent to the fibers, wherein the dye composition and / or the oxidizing composition comprises at least one molecular compound according to the invention.

  The subject of the present invention also relates to an apparatus for direct dyeing and lightening direct dyeing of keratin fibers or a “kit” consisting of two compartments.

  A two-compartment device for direct dyeing according to the present invention comprises a first compartment containing at least one direct dye and an at least one molecular compound according to the invention in a suitable dyeing medium. Includes two compartments.

  Another device comprising two compartments for lightening direct dyeing according to the invention comprises a first compartment containing a dye composition comprising at least one direct dye in a suitable dyeing medium, and suitable dyeing. In the medium is included another compartment containing an oxidizing composition comprising an oxidizing agent and at least one molecular compound of the invention.

  However, other features, aspects, subject matter, and advantages of the present invention will become more apparent from the description and examples that follow.

[Thickening molecular compound]
According to the invention, the phosphorus-free thickening molecular compound has a molecular weight of less than 2000 g / mol, and
Two amide groups,
-Asymmetric carbon,
At least a fatty chain comprising at least 8 carbons.

  The ionic molecular compound is preferably cationic.

  More preferably, the fatty chain contains between 8 and 30 carbon atoms, more preferably between 8 and 22 carbon atoms.

  Preferably, the thickening molecular compound has a molecular weight of less than 1000 g / mol, more preferably a molecular weight of less than 800 g / mol.

  Preference is given to those in which at least one fatty chain is bound to an amide group, in particular those in which at least one fatty chain is bound to the amide group via a carbonyl group. More preferably, the thickening molecular compound contains at least two carbon chains, more preferably at least one fatty chain forms part of the ester group.

  According to a preferred embodiment of the present invention, the thickening molecule compound contains at least two —CONH— bonds.

  In particular, the thickening compound is present in an aqueous medium at a weight concentration of between 0.1 and 60% by weight, preferably between 0.25 and 25% by weight, based on the total weight of the cosmetic composition. Exists.

  Preferably, the composition forms a film after drying. In one preferred embodiment, the film is insoluble in pure water at room temperature. However, it may be soluble at acidic or alkaline pH.

  Thickening molecular compounds that may be mentioned are 1- (11-(((1S) -1-ethoxycarbonyl-5-((1-oxo-dodecyl) amino) pentyl) amino) -11-oxoundecyl) pyridinium bromide. is there.

[Direct dye]
Preferably, the direct dyes used for the present invention are: neutral, acidic or cationic nitrobenzene direct dye; neutral, acidic or cationic, azo direct dye; neutral, acidic or cationic A quinone; or, in particular; an anthraquinone direct dye; an azine direct dye; a triallylmethane direct dye; an indoamine direct dye; and a natural direct dye.

  The direct dye may be soluble or insoluble in the dye composition. In the latter case, it is called a dye pigment. The direct dye is preferably soluble in the composition.

The pigments can be white or colored, inorganic and / or organic, coated or uncoated, and can take the form of spheres, plates or other forms.
These are used to color and / or make the composition opaque. Examples of inorganic pigments include titanium dioxide (which may be surface-treated), zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, and ferric blue. There is. Organic pigments that may be mentioned include lakes based on carbon black and cochineal carmine or barium, strontium, calcium or aluminum.
The pigment is present in the composition in a proportion of 0.05 to 40%, preferably 2 to 25% by weight of the final composition for non-powder compositions. For powder compositions, it accounts for up to 70% of the total weight of the composition.

  Pearlescent agents or pearlescent pigments are: white pearlescent pigments such as mica coated with titanium or bismuth oxychloride; mica titanium coated with iron oxide, in particular ferric blue or oxidized It may be selected from colored pearlescent pigments such as mica titanium coated with chromium or mica titanium coated with organic pigments of the type described above. There may also be mentioned liquid crystal or multilayer interference pigments. The pearlescent pigment may be included in the composition in a proportion of 0.01% to 20% of the total weight of the composition, preferably in a proportion of 1% to 15% of the composition. It may be.

The composition may comprise an inert filler that is insoluble in a physiologically acceptable medium. These fillers may be organic or inorganic, and may have a lamellar shape, an elongated shape, or a spherical shape. Talc, mica, silica, kaolin, polyamide or nylon® powder (especially Orgasol® sold by Atochem), poly-β-alanine powder, and polyethylene powder, polytetrafluoroethylene (Teflon ( (Registered trademark)) hollow microspheres such as powder, lauroyl lysine, starch, boron nitride, hollow polyvinylidene chloride spheres, etc., for example, Expandel (registered trademark) (Nobel Industry), acrylic particles, such as polytrap ( (Registered trademark) (Dow Corning), or silicone resin microbeads (for example, Toshiba Tospearl (registered trademark)), precipitated calcium carbonate, magnesium carbonate, magnesium hydrocarbon, hollow silica microspheres (to Maprecos) Silica beads) and glass or ceramic microcapsules.
The filler may be included in a proportion of 0.01% to 35%, preferably 0.5% to 15% of the total weight of the composition.

  The composition may comprise a dye that is soluble in a physiologically acceptable medium, such as a fat-soluble dye and a water-soluble dye.

Examples of the benzene-based direct dye that can be used in the present invention include, but are not limited to, the following compounds.
1,4-diamino-2-nitrobenzene 1-amino-2-nitro-4- (α-hydroxyethylamino) -benzene 1-amino-2-nitro-4-bis (α-hydroxyethyl) amino-benzene 1, 4-bis (α-hydroxyethylamino) -2-nitrobenzene 1-α-hydroxyethylamino-2-nitro-4-bis (α-hydroxyethylamino) benzene 1-α-hydroxyethylamino-2-nitro-4 -Aminobenzene 1-α-hydroxyethylamino-2-nitro-4- (ethyl)-(α-hydroxyethyl) aminobenzene 1-amino-3-methyl-4-α-hydroxyethylamino-6-nitrobenzene 1- Amino-2-nitro-4-α-hydroxyethylamino-5-chlorobenzene 1,2-diamino-4-nitrobenzene -Amino-2-α-hydroxyethylamino-5-nitrobenzene 1,2-bis (α-hydroxyethylamino) -4-nitrobenzene 1-amino-2- [tris (hydroxymethyl) methylamino] -5-nitrobenzene 1 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-α 1-hydroxyethyloxy-2-α-hydroxyethylamino-5-nitrobenzene 1-methoxy-2-α-hydroxyethylamino-5-nitro-benzene 1-α-hydroxyethyloxy-3-methylamino-4-nitrobenzene 1 -Α, α'-dihydroxypropyloxy-3-methylamino-4- Trobenzene 1-α-hydroxyethylamino-4-α, α-dihydroxypropyloxy-2-nitrobenzene 1-α, α'-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene 1-α-hydroxyethylamino -4-trifluoromethyl-2-nitrobenzene 1-α-hydroxyethylamino-3-methyl-2-nitrobenzene 1-α-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 (α-hydroxyethyl) amino] -3-nitrobenzene 1-α-hydroxyethylamino-2 -Nitrobenzene 1-hydroxy-4-α-hydroxyethyla Mino-3-nitrobenzene

  Examples of the azo direct dye that can be used in the present invention include the cationic azo dyes described in International Application WO95 / 15144, WO 95/01772 or European Patent Application 714955, and these contents are indispensable for the present invention. Make up part.

Further azo direct dyes that may be mentioned include those listed in the third edition of the International Color Index.
Disperse Red 17
Acid Yellow 9
Acid Black 1
Basic Red 22
Basic Red 76
Basic Yellow 57
Basic Brown 16
Acid Yellow 36
Acid Orange 7
Acid Red 33
Acid Red 35
Basic Brown 17
Acid Yellow 23
Acid Orange 24
Disperse Black 9

1- (4′-aminodi-phenylazo) -2-methyl-4- [bis (β-hydroxyethyl) amino] benzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene-sulfonic acid are also used. Can be mentioned.

The quinone direct dyes that may be mentioned are the following dyes:
Disperse Red 15
Solvent Violet 13
Acid Violet 43
Disperse Violet 1
Disperse Violet 4
Disperse Blue 1
Disperse Violet 8
Disperse Blue 3
Disperse Red 11
Acid Blue 62
Disperse Blue 7
Basic Blue 22
Disperse Violet 15
Basic Blue 99
And the following compounds:
1-N-methylmorpholiniumpropylamino-4-hydroxy-anthraquinone 1-aminopropylamino-4-methylaminoanthraquinone 5-α-hydroxyethyl-1,4-diaminoanthraquinone 2-aminoethylaminoanthraquinone 1, 4- Bis (α, α'-dihydroxypropylamino) anthraquinone

Examples of azine dyes include the following.
Basic Blue 17
Basic Red 2

Examples of the triarylmethane dye that can be used in the present invention include the following.
Basic Green 1
Acid Blue 9
Basic Violet 3
Basic Violet 14
Basic Blue 7
Basic Violet 49
Basic Blue 26
Acid Blue 7

Examples of indoamine dyes that can be used in the present invention include the following.
2-α-hydroxyethylamino-5- [bis (α-4′-hydroxyethyl) amino] anilino-1,4-benzoquinone;
2-α-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) phenylureido-6-methyl-1,4-benzoquinoneimine;
3- [4′-N- (Ethylcarbamylmethyl) amino] phenylureido-6-methyl-1,4-benzoquinoneimine

Examples of natural dyes used in the present invention include Lawson, juglone, alizarin, perpurin, carminic acid, kermesic acid, perprogalin, protocatechualdehyde, indigo, isatin, curcumin, spinurosine, and apigenidin.
An extract containing these natural dyes or a decoction can also be used. In particular, henna-based shipping agents or extracts are also used.

[Oxidative dye]
The oxidation dyes that can be used for the present invention are selected from oxidation bases and / or couplers.

  Preferably, the composition according to the invention comprises at least one oxidation base.

  The oxidation base that can be used in the context of the present invention is selected from those known in the art for oxidation dyeing, in particular ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols and complex. Cyclic bases, as well as addition salts that occur between these with acids.

  The oxidation dye used in the present invention is selected from oxidation bases and / or couplers.

  The composition of the present invention preferably comprises at least one oxidation base.

  The oxidation base that can be used in the context of the present invention is selected from conventionally known ones in the oxidation dyeing. And among them, in particular, the following ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols and heterocyclic bases, and between these and acids Addition salts are mentioned.

［式中、
R₁ は、水素原子、C_１−C_４アルキル基、C_１−C₄モノヒドロキシアルキル基、C_２−C₄ポリヒドロキシアルキル基、（C_１−C_４）アルコキシ（C_１−C_４）アルキル基、又は、窒素を含む基、フェニル基、もしくは、４´−アミノフェニル基により置換されたC_１−C_４アルキル基を表し；
R_２ は、水素原子、C_１−C_４アルキル基、C_１−C₄ モノヒドロキシアルキル基、C_２−C₄ ポリヒドロキシアルキル基 （C_１−C_４）アルコキシ（C_１−C_４）アルキル基、又は、窒素を含む基により置換されたC_１−C_４アルキル基を表し；
R₁及びR_２は、その一部となる窒素原子と共に５又は６員環の窒素を含む複素環式化合物を形成でき、それらは１以上のアルキル、ヒドロキシ、ウレイド基により任意に置換されていてよい；
R_３は、水素原子、塩素原子等のハロゲン原子、C_１−C_４アルキル基、スルホ基、カルボキシ基、C_１−C_４モノヒドロキシアルキル基、C_１−C_４ヒドロキシアルコキシル基、アセチルアミノ（C_１−C_４）アルコキシル基、メシルアミノ（C_１−C_４）アルコキシル基、又は、カルバモイルアミノ（C_１−C_４）アルコキシル基を表し；
R_４は水素、ハロゲン原子、又は、C_１−C_４アルキル基を表す］。 In particular, the following may be mentioned:
-(I) paraphenylenediamines of the following formula (I) and addition salts thereof with acids;

[Where:
R ₁ is a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ). alkyl group, or a group containing a nitrogen, phenyl or represents C ₁ -C ₄ alkyl group substituted by a 4'-aminophenyl group;
R ₂ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₂ -C ₄ polyhydroxyalkyl group (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl. group, or represents C ₁ -C ₄ alkyl group substituted with a group containing a nitrogen;
R ₁ and R ₂ can form a heterocyclic compound containing a 5- or 6-membered nitrogen with a nitrogen atom that is part of it, and they are optionally substituted with one or more alkyl, hydroxy, ureido groups. Good;
R ₃ is a hydrogen atom, a halogen atom such as a chlorine atom, a C ₁ -C ₄ alkyl group, a sulfo group, a carboxy group, a C ₁ -C ₄ monohydroxyalkyl group, a C ₁ -C ₄ hydroxyalkoxyl group, an acetylamino ( C ₁ -C ₄₎ alkoxyl group, mesylamino (C ₁ -C ₄₎ alkoxy group, or represents a carbamoylamino (C ₁ -C ₄₎ alkoxy group;
R ₄ represents hydrogen, a halogen atom, or a C ₁ -C ₄ alkyl group].

Among the groups containing nitrogen of the above formula (I), in particular, amino, mono (C ₁ -C ₄₎ alkylamino, di (C ₁ -C ₄₎ alkylamino, tri (C ₁ -C ₄₎ alkyl amino, monohydroxy (C ₁ -C ₄₎ alkylamino, imidazolinium, and, and ammonium group.

  Among the paraphenylenediamines of the above formula (I), para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6- Dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (β-hydroxyethyl) -para-phenylenediamine, 4-N, N- Bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-alkyl Roaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) -para-phenylenediamine, 2-hydroxymethyl -Para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl-β-hydroxyethyl) -para-phenylenediamine, N- (β, γ-dihydroxypropyl)- Para-phenylenediamine, N- (4′-aminophenyl) -para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy -Para-phenylenediamine, N- (β-methoxyethyl)- La - phenylenediamine and 2-methyl -1-N-beta-hydroxyethyl - p - phenylenediamine, and the addition salts thereof with acids, and the like in particular.

  Examples of the paraphenylenediamines of the above chemical formula (I) include para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β- Hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (β- Hydroxyethyl) -para-phenylenediamine, 2-chloro-para-phenylenediamine and addition salts of these with acids are very particularly preferred.

  -(II) According to the invention, the term double base refers to a compound comprising at least two aromatic nuclei having at least amino and / or hydroxyl groups.

［式中、
− Z₁及びZ₂は、同一か又は異なっており、水酸基、又は、C_１−C_４アルキル基、若しくは、架橋基（linker arm）Yによって置換されることができるNH₂基、を表し；
− 架橋基Yは、１から１４個の炭素鎖原子を含む直鎖または分岐のあるアルキレン鎖を表し、１以上の窒素基、及び/又は、酸素、硫黄、又は、窒素原子などのヘテロ原子が挿入され、又は、末端封止されていることができ、さらに、１以上の水酸基、または、C_１−C_６アルコキシ基により、任意に置換されていることができる；
−R_５及びR_６は、水素、又は、ハロゲン原子、C_１−C_４アルキル基、C_１−C_４モノヒドロキシアルキル基、C_２−C_４ポリヒドロキシアルキル基、C_１−C_４アミノアルキル基、又は、架橋基Yを表す；
−R_７、R₈、R_９、R_１０、R_１１、及びR_１２は、同一又は異なることができ、水素原子、架橋基Y、又は、C_１−C_４アルキル基を表し；
式（II）の化合物は、１分子当たり１つのみの架橋基Yを含むことがわかる。 Double bases that can be used as the oxidation base of the dye composition of the present invention include:
Particular mention is made of compounds corresponding to the following formula (II) and addition salts formed between them and acids. ;

[Where:
-Z ₁ and Z ₂ are the same or different and represent a hydroxyl group or a C ₁ -C ₄ alkyl group or an NH ₂ group that can be substituted by a linker arm Y;
The bridging group Y represents a linear or branched alkylene chain containing 1 to 14 carbon chain atoms, wherein one or more nitrogen groups and / or heteroatoms such as oxygen, sulfur or nitrogen atoms are present Can be inserted or end-capped and can be optionally substituted with _one or more hydroxyl groups or C ₁ -C ₆ alkoxy groups;
-R ₅ and _{R 6} is hydrogen or halogen atom, C ₁ -C ₄ alkyl group, C ₁ -C ₄ monohydroxyalkyl radical, C ₂ -C ₄ polyhydroxyalkyl radical, C ₁ -C ₄ aminoalkyl Represents a group or a bridging group Y;
_{-R 7, R 8, R 9} , R 10, R 11, and _{R 12} are the same or different can represent a hydrogen atom, a bridging group Y, or, a C ₁ -C ₄ alkyl group;
It can be seen that the compound of formula (II) contains only one bridging group Y per molecule.

Among the nitrogen-containing groups of the above formula (II), in particular, amino, mono (C ₁ -C ₄ ) alkylamino, di (C ₁ -C ₄ ) alkylamino, tri (C ₁ -C ₄ ) alkylamino Monohydroxy (C ₁ -C ₄ ) alkylamino, imidazolinium and ammonium groups.

  For the double base of the above formula (II), in particular, 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-methylaminophenyl) tetramethylenediamine, N, N′-bis (ethyl)- N, N′-bis (4′-amino-3′-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane, and these and acids The addition salt of is mentioned.

  Among the double bases of formula (II), N, N′-bis (β-hydroxyethyl) -N, N′-bis (4′-aminophenyl) -1,3-diaminopropanol, and 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane or one of these and an acid addition salt is particularly preferred.

［式中、
R_１３は、水素原子、フッ素等のハロゲン原子、又は、C_１−C_４アルキル、C_１−C_４モノヒドロキシアルキル、（C_１−C_４）アルコキシ（C_１−C_４）アルキル、C_１−C_４アミノアルキル、又は、ヒドロキシ（C_１−C_４）アルキルアミノ（C_１−C_４）アルキルを表し；
R_１４は、水素原子、フッ素等のハロゲン原子、又は、C_１−C_４アルキル、C_１−C_４モノヒドロキシアルキル、C_２−C_４ポリヒドロキシアルキル、C_１−C_４アミノアルキル、C_１−C_４シアノアルキル、又は、（C_１−C_４）アルコキシ（C_１−C_４）アルキル基を表す］。 In particular, the following may be mentioned:
-(III) Paraaminophenols of the following formula (III) and addition salts thereof with acids;

[Where:
R ₁₃ is a hydrogen atom, a halogen atom such as fluorine, or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl, C ₁ -C ₄ aminoalkyl, or hydroxy (C ₁ -C ₄₎ alkylamino (C ₁ -C ₄₎ alkyl;
R ₁₄ represents a hydrogen atom, a halogen atom such as fluorine, or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, C ₁ -C ₄ aminoalkyl, C _1. —C ₄ cyanoalkyl or (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) represents an alkyl group].

  Among the para-aminophenols of the above formula (III), para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4- Amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, and 4-amino-2- (β-hydroxyethyl) Aminomethyl) phenol, and addition salts of these with acids.

  -(IV) In the context of the invention, ortho-aminophenols which can be used as oxidation base are 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy. It is selected from -6-methylbenzene and 5-acetamido-2-aminophenol and their addition salts with acids.

  -(V) Among the heterocyclic bases that can be used as the oxidation base in the dye composition according to the present invention, in particular, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and addition salts thereof with acids Is mentioned.

  Examples of pyridine derivatives include compounds described in British Patent Nos. 1026978 and 1153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2 , 3-diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine, and 3,4-diaminopyridine, and addition salts thereof with acids.

  Among the pyrimidine derivatives, among others, the compounds described in German Patent DE 2 359 339 or Japanese Patent JP 88-169571 and JP 91-10659 or International Application WO 96/15765, for example 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 pyrazolopyrimidine derivatives such as the compounds described in French patent application FR-A-2750048, among which pyrazolo [1,5-a] Pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; Lazolo [1,5-a] pyrimidine-3,7-diamine; 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazolo [1,5-a] pyrimidine- 7-ol; 3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazolo [1, 5- [A] pyrimidin-3-ylamino) ethanol; 2-[(3-Aminopyrazolo [1,5-a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol; 2-[(7-aminopyrazolo [ 1,5-a] pyrimidin-3-yl) (2-hydroxyethyl) -amino] ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7diamine; 2,6-dimethyl Tilpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5, N7, N7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; and 3-amino-5 Examples include methyl-7-imidazolyl-propylaminopyrazolo [1,5-a] pyrimidine, addition salts thereof, and tautomers thereof. When tautomeric equilibrium exists, addition salts with these acids are also included.

  Among the pyrazole derivatives, in particular, compounds described in German Patent Nos. 3843892, 4133957, and International Applications WO94 / 08969, WO94 / 08970, French Patent Application Publication No. 2733749 and German Patent No. 19543388, For example, 4,5-diamino-1-methyl-pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4′-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl -4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-buty -1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β -Hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl -3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-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′-amino) Ethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole And 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole, and addition salts thereof with acids.

  According to the present invention, the oxidation base is preferably present in the range of approximately 0.0005 to 12% by weight, more preferably approximately 0.005 to 8% by weight, based on the total weight of the total composition.

  The couplers that can be used in the dyeing method of the present invention are those conventionally used in oxidation dye compositions, that is, metaaminophenols, metaphenylenediamines, metadiphenols, naphthols, heterocyclic couplers. For example, indole derivatives, indoline derivatives, sesamol, and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzo Examples include dioxoles and quinolines, and addition salts thereof with acids.

  As these couplers, in particular, 2,4-diamino-1- (β-hydroxyethyloxy) benzene, 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol , 3-aminophenol, 2-methyl-3-amino-6-methylphenol, 3,5-diamino-2,6-dimethoxypyridine, 6-hydroxybenzomorpholine, 1-β-hydroxyethylamino-3,4 -Methylenedioxybenzene, 1-methyl-2,6-bis (β-hydroxyethylamino) benzene, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3- Dihydroxybenzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino , 1,3-bis (2,4-diaminophenoxy) propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindole, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2 -Amino-3-hydroxypyridine, 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole, and 2,6-dimethylpyrazolo [1,5-b] -1, Selected from 2,4-triazoles, and addition salts with these acids.

  When present, the coupler is preferably present in the range of approximately 0.0001 to 10% by weight, more preferably approximately 0.005 to 5% by weight, based on the total weight of the composition. .

  The direct dye or oxidative dye is preferably present in the range of approximately 0.001 to 20% by weight, more preferably approximately 0.005% to 10%, based on the total weight of the ready-to-use composition. Is preferred.

[Medium]
The medium suitable for dyeing the composition is preferably an aqueous medium composed of water, and may further advantageously contain a cosmetically acceptable organic solvent. Organic solvents include in particular alcohols (eg ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol) or glycols or glycol ethers (eg ethylene glycol monomethyl, monoethyl or monobutyl ether), propylene glycol Or ethers thereof (for example, propylene glycol monoethyl ether), butylene glycol, dipropylene glycol, and diethylene glycol alkyl ether (for example, diethylene glycol monoethyl ether or diethylene glycol monobutyl ether). The solvent may be present at a concentration of between about 0.5% and 20%, more preferably between about 2% and 10% by weight relative to the total mass of the composition.

  The composition may comprise an effective amount of other reagents already known for use in direct dyes, such as various common adjuvants. Specifically, metal ion sealants such as EDTA and editronic acid, UV screening agents, waxes, volatile or non-volatile substances, cyclic, linear or branched (especially by amine groups) ) Organically modified or non-organically modified silicones, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, provitamins such as vitamins or panthenol, opacifiers, And a binding polymer.

  In the ready-to-use composition or the oxidizing composition, the oxidizing agent is preferably selected from peracid salts such as urea peroxide, alkali metal bromate, iron cyanide, sodium perborate, persulfate and the like. .

  An oxidoreductase such as laccase, peroxidase, or two-electron oxidoreductase (eg, uricase) may suitably be used as an oxidant in the presence of the respective donor or cofactor.

  The pH of ready-to-use compositions [compositions obtained by mixing dye compositions and oxidizing compositions] applied to keratin fibers is generally between 4 and 11. Preferably, it is between 6 and 10, and can be adjusted to the desired value using acidifying or alkalizing agents well known in the keratin fiber dyeing art.

  Among the above basifying agents, for example, aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and their derivatives, oxyethylenated, and / or oxypropylene Hydroxyalkylamines and ethylenediamines, sodium hydroxide, potassium hydroxide, and compounds represented by the formula (XIX) may be mentioned.

In the formula, R is an propylene residue optionally substituted by hydroxyl or C ₁ -C ₄ alkyl group;
R ₃₈ , R ₃₉ , R ₄₀ and R ₄₁ may be the same or different and each represents a hydrogen atom or a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group. ]

  The acidifying agent is usually an inorganic acid or an organic acid, such as hydrochloric acid, orthophosphoric acid, carboxylic acid (for example, tartaric acid, citric acid, or lactic acid), or sulfonic acid.

  In the dyeing method of the present invention, preferably, the ready-to-use composition prepared immediately at the time of use is applied to wet or dry keratin fibers from the above-described dye composition and oxidation composition, and the composition is applied. Preferably from about 1 to 60 minutes, more preferably from about 10 to 45 minutes, to leave it to act, rinse the fibers, and optionally wash the fibers with shampoo, then rinse again, and then It is to dry.

  One variation of this method includes a first composition that includes at least one oxidative dye but does not include a molecular compound of the present invention, a second composition that includes an oxidizing agent, and at least one of the present invention. Take a third composition containing the molecular compound, and in use, immediately mix these three compositions together.

  According to the above method, each of the composition group or several composition groups can comprise at least one cationic or amphoteric polymer and at least one surfactant.

  The direct dyeing method of the present invention preferably comprises a ready-to-use composition that does not contain an oxidizing agent, or a composition prepared immediately upon use from the above-described dye composition and oxidizing composition. Apply to dry keratin fibers, leave the composition to act for a standing time of preferably about 1 to 60 minutes, more preferably about 10 to 45 minutes, rinse the fibers, and optionally further Washing with shampoo, then rinsing the fibers again and further drying them.

  One variation of this direct dyeing method uses at least one direct dye but does not contain the molecular compound of the invention and another composition containing at least one molecular compound, these The two compositions are mixed with the oxidizing composition at the time of use and then the mixture is applied and left to act as described above.

  In the direct dyeing method of the present invention, in the case of direct dyeing (using a dye composition) or light-colored direct dyeing using (dye composition and oxidizing composition), the dye composition and / or oxidation The composition comprises at least one cationic or amphoteric polymer and at least one surfactant.

According to the present invention, the oxidation dyeing method is immediately adjusted at the time of use from the above-described dye composition and oxidation composition,
A ready-to-use composition comprising at least one oxidizing agent and at least one direct dye (the dye composition and / or oxidizing composition has a molecular weight of less than 2000 g / mol, and at least
Two amide groups,
-Asymmetric carbon,
-Applying at least one non-ionic thickening molecular compound containing at least 8 carbon fatty chains, to wet or dry keratin fibers, preferably about 1 to 60 minutes, more preferably Allow the composition to act for a standing time in the range of about 10 to 45 minutes, rinse the fibers, then optionally wash the fibers with a shampoo, then rinse the fibers, and dry the fibers This is an oxidation dyeing method comprising:

  Of course, those skilled in the art will recognize that any of the additional compounds described above are such that the beneficial effects inherently associated with the dye compositions of the present invention are not adversely affected or substantially adversely affected. You will pay attention to choose.

  The invention also relates to a cosmetic method comprising the application of the composition according to the invention.

The composition may take the form of a fluid or thickened liquid, gel, cream, mousse, W / O or O / W emulsion, or multilayer emulsion.
For example, they may be used as shampoos, care products that are washed away or left in place, deep care masks, or lotions or creams for treating the scalp and skin. They are used in particular for hair.

These compositions may be packed into aerosol devices in the presence of one or more propellants. These propellants are preferably dimethyl ether, C _3-5 alkane, 1,1-difluoroethane, a mixture of dimethyl ether and C _3-5 alkane, 1,1-difluoroethane and a mixture of dimethyl ether and / or C _3-5 alkane. More selected.

  The composition of the present invention is a makeup product for skin, lips or keratin fibers, such as a foundation, makeup applege, eye shadow, mascara, eyeliner, lipstick or body makeup product (semi-permanent tattoo). ). These products may contain one or more cosmetically and dermatological active ingredients and add a care aspect to the makeup. These makeup compositions preferably contain only soluble or insoluble direct dyes as dyes.

  Furthermore, by applying these compositions topically, protective agents, treatments or care cosmetics, dermatological, hygienic, or used on the human face, neck, hands, body It may be a medicinal composition. For example, a care cream, sunscreen, artificial sunscreen, lip protection, or care balsam, dermatological pomade, or dermatological pomade or ointment may be constructed.

  The invention will now be described by reference to examples.

[Example]
Example 1
The following dye composition is prepared:
Solution A:
1- (11-(((1S) -1-ethoxycarbonyl-5-((1-oxo-dodecyl) amino) pentyl) amino) -11-oxoundecyl) -pyridinium bromide
0.5% am
p-Phenylenediamine 0.25%
2-Methyl-5-aminophenol 0.35%
Sequestering agent appropriate amount reducing agent appropriate amount pH adjusting agent 20% aqueous ammonia solution 10%
Water up to 100%
Solution B: Aqueous hydrogen peroxide solution 20 parts by weight Solutions A and B are mixed in equal amounts before application to the hair.

(Example 2)
The following dye composition is prepared:
1- (11-(((1S) -1-ethoxycarbonyl-5-((1-oxo-dodecyl) amino) pentyl) amino) -11-oxoundecyl) -pyridinium bromide
0.5% am
Basic Red 51 0.2%
pH adjusting agent in an appropriate amount, pH 8 and adjusting water up to 100%

After application to the hair, these compositions are 1- (11-(((1S) -1-ethoxycarbonyl-5-((1-oxo-dodecyl) amino) pentyl) amino) -11-oxoundecyl) -It gave a stronger shade than the comparative composition without pyridinium bromide.

Claims (21)

In an aqueous medium or water + solvent medium,
At least one dye, in particular a hair dye; and at least one phosphorus-free thickening molecular compound having a molecular weight of less than 2000 g / mol;
The molecular compound is
Two amide groups,
-Asymmetric carbon,
A cosmetic composition comprising at least fatty chains comprising at least 8 carbons.   The composition according to claim 1, wherein the ionic molecular compound is preferably cationic.   The composition according to claim 1, wherein the thickening molecule compound contains at least two —CONH— bonds.   4. Composition according to any one of claims 1 to 3, characterized in that the fatty chain contains between 8 and 30, preferably between 8 and 22. carbon atoms.   The composition according to any one of claims 1 to 4, wherein the thickening molecular compound has a molecular weight of less than 1000 g / mol, preferably less than 800 g / mol.   The composition according to any one of claims 1 to 5, wherein at least one fatty chain is directly bonded to the amide group.   6. The composition according to claim 1, wherein at least one fatty chain is bonded to the amide group via a carbonyl functional group.   The composition according to any one of claims 1 to 7, wherein the thickening molecular compound comprises at least two fatty chains.   9. Composition according to any one of the preceding claims, characterized in that at least one fatty chain constitutes part of an ester group. The thickening compound is present in the aqueous medium at a weight concentration of between 0.1 and 60% by weight, preferably between 0.25 and 25% by weight, based on the total weight of the cosmetic composition. The composition according to any one of claims 1 to 9, wherein   The composition according to any one of claims 1 to 10, wherein the hair dye is a direct dye that is soluble or insoluble in the composition.   The composition according to claim 11, wherein the direct dye is soluble in the composition.   Said direct dyes are neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinones and in particular anthraquinone direct dyes The composition according to claim 11, wherein the composition is selected from azine direct dyes, triallylmethane direct dyes, indoamine direct dyes, and natural direct dyes.   The composition according to any one of claims 1 to 13, wherein the oxidation dye is selected from an oxidation base and / or a coupler.   15. The composition of claim 14, comprising at least one oxidation base.   The oxidation base is selected from ortho- or para-phenylenediamines, double bases, ortho- or para-aminophenols and heterocyclic bases, and addition salts of these with acids. The composition according to claim 14.   15. The coupler according to claim 14, wherein the coupler is selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers, and addition salts of these with acids. Composition. Having a molecular weight of less than 2000 g / mol and at least −2 amide groups,
-Asymmetric carbon,
A fatty chain comprising at least 8 carbons,
At least one phosphorus-free thickening molecular compound comprising
Including the application of a cosmetic composition comprising
Especially a dyeing method for dyeing hair.   The dyeing method according to claim 18, wherein a composition comprising at least one direct dye is applied. Keratin fibers, in particular human keratin fibers, in particular a method for direct dyeing of hair, comprising a dye composition comprising at least one direct dye in a suitable dyeing medium and an oxidizing composition comprising at least one oxidizing agent Applying an instant mixture with the object to the fiber,
The dye composition and / or the oxidation composition is:
Having a molecular weight of less than 2000 g / mol and at least:
Two amide groups,
-Asymmetric carbon,
A fatty chain comprising at least 8 carbons,
Dyeing method containing phosphorus-free thickening molecular compound containing
From the above-described dye composition and oxidizing composition, it is immediately adjusted at the time of use,
A ready-to-use composition comprising at least one oxidizing agent and at least one direct dye (the dye composition and / or oxidizing composition has a molecular weight of less than 2000 g / mol, and at least
Two amide groups,
-Asymmetric carbon,
-Applying at least one non-ionic thickening molecular compound containing at least 8 carbon fatty chains, to wet or dry keratin fibers, preferably about 1 to 60 minutes, more preferably Allow the composition to act for a standing time in the range of about 10 to 45 minutes, rinse the fiber, then optionally wash the fiber with a shampoo, then rinse the fiber, and then dry the fiber An oxidation dyeing method comprising: