JPH01199906A - Method and composition for dyeing keratin fiber - Google Patents

Abstract

PURPOSE: To dye human keratin fibers to color with high gloss in various color gradations exhibiting improved resistance to external causative factors, by applying a combination of a specific oxidation dye and an indole derivative with both hydrogen peroxide and iodine ions to the keratin fibers. CONSTITUTION: Keratin fibers are dyed by applying (A) such a composition at pH 2-7 (pref. pH2-5) as to contain a combination of an indole derivative pref. of the formula (R7 is H, an alkyl, etc.; R8 and R9 are each H, an alkyl, carboxyl, etc.; R10 and R11 are each H, an alkyl, formyl, an acyl, etc.) and an oxidation dye selected from rapid oxidation dyes and couplers with iodine ion or hydrogen peroxide in a medium suitable for dyeing and (B) such another composition at pH2-12 (pref. pH2-7) containing hydrogen peroxide in a medium suitable for dyeing when the composition A contains iodine ion, or at pH3-11 containing iodine ion when the composition A contains hydrogen peroxide, to the keratin fibers, in any order.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention uses indole derivatives to dye keratin fibers, especially human keratin fibers such as hair.
The present invention relates to a new method of using in combination certain oxidation dyes selected from couplers with "fast" oxidation dyes and compositions used in the method.

(Prior Art) The applicant has filed 1. applying at least one composition (A) onto the keratin fibers, composition (A) comprising at least one oxidation dye in combination with iodine ions in a suitable medium for dyeing; The application of is carried out prior to or subsequent to the application of composition (B), and composition (B) comprises hydrogen peroxide in a suitable medium for dyeing.
A method for dyeing keratin fibers has been described which is essentially characterized by comprising i-12 to 12.

On the other hand, a number of methods are known for dyeing keratin fibers, in particular hair, using 5°6-dihydrooxindole, and in particular a method is known which consists in dyeing the hair in two different stages. The method involves applying onto the hair a composition comprising 5,6-dihydroxyindole in combination with iodine ions in a medium suitable for dyeing, and the application is carried out either before or after the application of hydrogen peroxide. It will be carried out subsequently. One such method is described, for example, in French patent application no. 25 93 061.

(WI Problem to be Decided) The applicant has proposed a sufficiently wide range of diverse colors and glosses 1 which are particularly sought after for the dyeing of hair, such as maroon and blond, in various shades of particularly fine dyeing. It has been discovered that certain oxidative dyes, as described in Luxenderg U'F Application No. 86,899, can be obtained by using in combination with 5,6-dihydroxyindole or its derivatives.

On the other hand, the applicant also claims that the various shades obtained in this way show improved resistance to external factors,
In particular, the resistance to light and washing was found to be superior compared to dyeings obtained from compositions containing the aforementioned oxidative dyes or indole derivatives. This result is particularly striking when indole derivatives are used in compositions containing oxidative dyes. Oxidative dyes by themselves provide a relatively transparent dye upon development and do not provide a ground color, whereas a ground color is generally desired in hair dyeing.

SUMMARY OF THE INVENTION The present invention therefore combines 5,6-hydroxyindole or a derivative thereof with at least one oxidation dye selected from the group consisting of so-called "fast" oxidation dyes and couplers. intended for use.

Another object of the invention consists of the composition used during this method.

The invention also describes a device or "kit" having several compartments.
The device contains various compositions suitable for carrying out the method of the invention.

Other objects of the invention will become apparent from the following description and examples.

The essential features of the method of dyeing keratin fibers, especially human keratin fibers, of the present invention are that at least one composition (A) is applied onto the fibers, and composition (A) is used in a suitable medium for dyeing. At least one indole derivative and at least one oxidation dye selected from the group consisting of so-called "fast" oxidation dyes and couplers are combined in a molecule containing (a) iodine ions, or (b) aqueous peroxide. including in combination with
The application of composition (A) is carried out prior to or subsequent to the application of composition (B), and composition (B) is in a medium suitable for dyeing, such that composition (A) contains iodine ions. When including...2 to 1
2, also preferably p) hydrogen peroxide in 12 to 7, or (b) when composition (A) contains hydrogen peroxide pi (
3 to 11, containing iodine ions.

When composition (A) contains hydrogen peroxide, composition (A)
(DPH is preferably 2-7, and especially 2-5.

The application of compositions (A) and CB) is optionally separated by a rinse.

A preferred method consists of applying onto the fiber a composition (A) containing simultaneously an indole derivative and an oxidation dye in combination with iodine ions), and the application of this composition (A) is similar to a composition containing hydrogen peroxide. It may be preceded or followed by the application of item (B).

In the method of the invention, the indole derivative corresponds to the following formula.

In the above formula, R7 is a hydrogen atom, a lower alkyl group, or -31R1,R
Represents 3R14 groups.

R8 and R represent the same or different hydrogen atoms, lower alkyl groups, carboxyl groups, lower alkoxycarbonyl groups, or -COO8i1%2R13R14 groups.

Rxo and R11 are the same or different, hydrogen atom, linear or branched C1-c2 alkyl group, ho, lumyl group, linear or branched c2C20 acyl group, linear or branched alkenoyl group of c3C20, -31R12
R13R14 groups, -P(0)(OR16) 2 groups, RII
The 50SO□ group or the R groups 0 and R11, together with the oxygen atom to which they are bonded, form a ring optionally containing a dicarbonyl group, a methylene group, a thiocarbonyl group or the following groups.

ELxa and R16 represent a hydrogen atom or a lower alkyl group, R1 represents a lower alkoxy group or a mono- or dialkylamino group, R12, R13 and R
represents addition salts with the same or different radicals, linear or branched lower alkyl radicals and inorganic or organic acids, such as alkali metal, alkaline earth or corresponding amine salts.

Lower alkyl or alkoxy groups are especially C, -C.

Display the base of

Among the preferred compounds of the invention are 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, (5
or 6)-acetoxy-(6 or 5)-hydroxyindole or 2-carboxy-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,6-dimethyl-5,6-dihydroxyindole Can be mentioned.

The iodide ion is preferably an alkali metal, alkaline earth or ammonia iodide, and especially potassium iodide.

So-called "fast" oxidation dyes have a benzene structure,
It is a dye intermediate and is a molecule that is susceptible to oxidation by air in the absence of other oxidizing agents to yield a dark colored compound during the time it is left on the hair, usually one hour. It is particularly suitable for benzene trihydroxyl derivatives, diaminohydroxybenzene, aminodihydroxybenzene, triaminobenzene, aminohydro-tetraxybenzene and
-dihydroxybenzene substituted products.

1゜2.4- from benzene trihydroxyl derivatives
Trihydroxybenzene, 1.2.4-trihydroxy-5-alkylbenzene (in which the alkyl group is C1-
c), 1,2,3-trihydroxybenzene, and salts thereof.

Among diaminohydroxybenzenes, 2,4-diaminophenol, 2,5-diamino-4-methoxy-1-
Mention may be made of hydroxybenzene and their salts.

Among aminodihydroxybenzenes, 2-amino-1
, 4-dihydroxybenzene 1.1, 4-dihydroxy-2-dinithylaminobenzene, 4-7 milsorcin and their salts; 4-methyl-1,2-dihydroxybenzene and 3-methoxycatechol are particularly preferred. .

Aminohuman o+cypenzene is, for example, 2-amino-4-
Methoxyphenol, 2-aminephenol, 4,6-
Dimethoxy6-amino-1-hydroxybenzene, 2
．． 6-dimethyl-4-(N-p-hydroxyphenyl)
selected among amino-1-hydroxybenzenes and their salts.

Examples of triaminobenzene include 1,5-diamino-2-methyl-4-(N-p-hydroxyphenyl)aminobenzene and salts thereof.

Nuancers or couplers are known to react with an oxidizing base or a precursor of an oxidative dye, by an oxidative condensation reaction, giving a colored compound characteristic of the base and the coupler considered. It is a compound that has This reaction is called "coupling."

The couplers are selected from phenol, ortho-diphenol, meta-aminophenol, meta-phenylenediamine, mono- and polyhydroxyl derivatives of naphthalene and aminonaphthalene, chirazolones, benzomorpholines.

Among the couplers or answerers, mention may be made in particular of compounds that conform to the following formula:

In the above formula, R1 is a hydroxyl group, or one or more C1
-C, represents an amino group that can be substituted with a hydroxyalkyl group, and R3 and R6 are independently hydrogen, OH,
optionally) Cx can represent an amine group substituted by a lower hydroxyalkyl group of C6 or a lower alkyl group of C1-C, and R2, R4 and R,a hydrogen atoms or cl-c, It can represent an alkoxy group, a lower hydroxyalkoxy group of ClC6 or an alkyl group, and R3 and 4 can also together form a methylenedioxy group ff-j.

Among the particularly preferred couplers are 3-amino-6-methylphenol, 3-aminephenol, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2
-methoxy-5-amino phenol, 2-methoxy-
3-N(2-hydroxyethyl)aminophenol, 1
．． 6-Diami2,6-dihydroxybenzene, 2-methoxy-1-N-methylamino-4-(2-hydroxyethyloxy)aminobenzene, 1,3-diamino-6
-Methoxybenzene, 1,6-diami2-4゜6-dimethoxybenzene, 4,6-dimethoxy-1,3-diN(
2-hydroxyethyl)aminobenzene, 2,6-dimethoxy-3-N(2-hydroxyethyl)amino-1-
Aminobenzene, 2゜4-dimethoxy-5-N(2-hydroxyethylcoamino-1-aminobenzene, 2-methyl-3-N(2-hydroxyethyl)aminophenol, 1.3-dimethoxy-5-N(2-hydroxyethyl) -Hydroxyethyl)amino-
4-methoxybenzene, 3-amino-4-methoxyphenol, 3.4-methylenedioxy-1-aminobenzene, 3.4-methylene/zooxy-6-methoxy-1-aminobenzene, 2.6-dimethyl- 5-N(2-hydroxy)aminophenol, 2,6-dimethyl-3-aminephenol, 4-ethoxy-1-amino-5-N a
N-(bis-2-hydroxyethyl)aminobenzene, 2゜4-(diamino)phenoxyethanol, (2
-amino-4-N-methylamino)phenoxyethanol, 1-methoxy-2-N-(2-hydroxyethyl)
Mention may be made of amino-4-aminobenzene and salts thereof.

Other preferred couplers are 6-amino-benzomorpholine, 6-hydroxybenzomorpholine, 1-naphthol and 1-amino-7-su7thol and salts thereof.

These various oxidation dyes are used in mixtures or alone, in combination with iodide ions and indole derivatives.

A particularly preferred use of the invention is to combine at least one benzenetrihydroxyl derivative, such as 1,
2.4-trihydroxybenzene, 1*2*4-trihydroxy-5-methylbenzene, or coupler,
For example, 1゜3-dihydroxybenzene, 3-amino・
Phenol, 3-amino-6-methylphenol, 3,
It consists of using 4-methylenedioxy-6-methoxy-1-aminobenzene, 1-naphthol or mixtures thereof.

The results obtained with the combination according to the invention are particularly striking in view of the dyeing properties of these oxidative dyes in traditional systems, especially in cup 2-. In particular, the coupler is one that does not cause coloration by the process of oxidative condensation in the absence of an oxidative dye base or precursor.

The subject of the invention is also a dyeing composition intended for use in a process for dyeing keratin fibers, in particular human hair, which comprises at least 5,6-S' hydroxyindole or a derivative of formula (1) thereof; An oxidation dye selected from the group consisting of "fast" oxidation dyes and couplers and iodine ions are included in a suitable medium for dyeing. The oxidative dyes used in the compositions of the invention are particularly selected from among the preferred dyes mentioned above.

Composition (A) comprises 5,6-dihydroxyindole or its derivative of formula (1), an oxidative dye and iodine ions, generally from 0.01 to 10% by weight of oxidative dye with respect to the total weight of composition (A). , and preferably 0.25 to 5
Included in the percentage by weight. 5.6-dihydroxyindole or its derivative of formula (1) is generally present in an amount of 0.01 to 5% by weight, and preferably 0.01 to 5% by weight, relative to the total weight of composition (A).
It is present in a ratio of 0.3 to 3 times. The proportion of iodide in the same composition is in particular from 0.007 to 4% by weight, expressed in dos with respect to the total weight of composition (A), and preferably 0.0
It is 8 to 1.5% by weight.

The content of hydrogen peroxide used in composition (B) is generally from 1 to 40 volumes, preferably from 2 to 20 volumes, and even more especially from 3 to 10 volumes.

The combination of 5.6-dihydroxyindole and oxidation dye on the one hand and the iodide on the other hand, the ratio between them is preferably between 0.05 and 10, and still with a special KO of 15-2.

The method of the present invention can be applied for different compositions with a standing time of 10 seconds to 45 minutes, preferably 2 to 25 minutes, and especially 2 to 10 minutes at different step times. do.

The applicant has discovered that the method of the invention provides a variety of products in different color gradations, very shiny shades, at the same time fast and strong, penetrating well into the fibers and especially human keratin fibers without damaging them. It has actually been confirmed that this method makes it possible to achieve unique staining.

These dyes also show improved resistance to external factors, especially light and washing resistance, when using only 5,6-dihydroxyindole or its derivatives of formula (I) in combination with iodine or or exhibit improved resistance compared to methods that only use oxidative dyes in combination with iodine ions.

Applicants have also discovered that hair dyed several times after regeneration is improved by the method and composition used according to the invention compared to hair dyed using the methods and compositions of the previous art. It could be seen that it was softer, more shiny and had good mechanical properties.

Thanks to the method and composition of the invention, a relatively strong staining is obtained within a relatively short time, i.e. on the order of 5 to 15 minutes.

The compositions used to carry out the method of the invention may be in a variety of forms, such as more or less thick or gelled liquids;
It can be provided in creams, emulsions, mousses and other forms suitable for carrying out dyeing.

The dyeing compositions defined for use in the method of the invention, which contain 5,6-dihydroxyindole or its derivative of formula (1), an oxidative dye, in combination with iodine ions are generally an aqueous medium consisting of water or a water-solvent mixture, and the solvent is preferably an organic solvent,
For example, ethyl alcohol, propyl or isopropyl alcohol, t-butyl alcohol, ethylene glycol, monomethyl, monoethyl and motubutyl ethers of ethylene glycol, ethylene glycol monoethyl ether acetate, fluoropylene gellicol, propylene glycol and dipropylene glycol. selected from monomethyl ether, and methyl raftate. Particularly preferred solvents are ethyl alcohol and propylene glycol.

The indole derivative and oxidation dye can also be stored in an anhydrous solvent with the iocide, and this composition is mixed with the aqueous medium at the time of use.

When the medium is aqueous, composition (A) has a p.
H and preferably a pH of 6.5-7.

According to the present invention, anhydrous solvents refer to solvents containing 1% or less water.

When the medium consists of a water-solvent mixture, the solvent is preferably present in a concentration of 0.5 to 75% by weight with respect to the total weight of the composition, and especially 2 to 50%, and even more particularly 2 to 20%. .

The compositions of the invention may contain other additives conventionally used for dyeing keratin fibers.

When specifically applied to hair dyeing, these compositions contain 0
°05-10% aliphatic amide, 0.1-50i
ft% of anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof, thickeners, fragrances, sequestrants, film formers, treating agents, dispersants, conditioners, preservatives, It may contain opacifying agents and swelling agents for keratin fibers.

Thickeners are particularly suitable for biopolymers such as sodium alginate, arabic yam, guarco-glucan, xanthan gum or scleroglucan, cellulosics such as methylcellulose, hydroxyethylcellulose, hydroxyglobil methylcellulose, the sodium salt of calxymethylcellulose, etc. It can be chosen among derivatives and polymers of acrylic acid. Inorganic thickeners such as bentonite can also be used as well. These thickeners, alone or in mixtures, preferably represent from 0.1 to 5% by weight, and advantageously from 0.5 to 6%, relative to the total weight of the composition.
present in a proportion of

The acidifying agent that can be used in a preferred embodiment of the method of using the composition in an acidic manner can be selected from lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid, citric acid.

The pH can also be adjusted, in particular by alkalinizing agents selected from amines (e.g. alkanolamines, alkylamines), alkalis or ammonium hydroxides or carbonates, e.g. when the precursor is used in the form of a salt of a strong acid. It can be adjusted if necessary.

When the composition is used in the form of a mousse, it can be prepared under pressure in an aerosol device in the presence of a propellant and at least 1P of mousse generator. Mousse formers can be anionic, cationic, nonionic, amphoteric foaming polymers or surfactants of the type mentioned above.

In order to use the method of the invention, various compositions can be prepared in a device having several compartments, also called a "kit" or dyeing toolbox, which device is used for dyeing keratin fibers. All the components to which the dyeing is to be applied are premixed or unmixed for successive application. Such a device is known per se and comprises a first compartment containing composition (A) (an indole derivative, an oxidative dye as described above, in the presence of iodine in a suitable medium for dyeing); A second compartment containing a hydrogen peroxide solution can be included.

If the medium containing the indole derivative, oxidation dye and iodide ion is an anhydrous medium, it is mixed with an aqueous support suitable for dyeing, optionally present in a third compartment, before use.

Compositions containing indole derivatives, oxidative dyes and iodine ions in an anhydrous medium can optionally be applied directly onto human hair.

If the composition (A) applied onto the fibers contains hydrogen peroxide, the dyeing tool box preferably contains in the first compartment an indole derivative and an oxidation dye as defined above suitable for dyeing. Composition (A) in a medium! &, containing a composition (B) containing iodide ions in a second compartment, an aqueous composition of hydrogen peroxide in a third compartment, and
The contents of the second compartment are intended to be mixed with the contents of the first compartment immediately prior to use.

If the suitable medium for dyeing is aqueous, the composition of the first compartment preferably has a pH of 2 to 7, and especially 6.5.
Showing a pH of ~7. - of the composition containing hydrogen peroxide is 2 to
12, but it is preferably acidic and between 2 and 7;
More particularly, it is 2-5.

The multi-compartment apparatus which can be used according to the invention is the mixing means in use and can have facilities known per se and regulated under an inert atmosphere.

The methods and compositions used in accordance with the present invention may be applied to natural or previously dyed hair, permanent or non-permanent or decurled hair, or hair that has been heavily or lightly bleached and then optionally dyed. Can be used to dye permanent hair. It is likewise possible to use it for dyeing fur or wool.

The following examples are provided to illustrate the invention but are not intended to be of a limiting nature.

Example 1 Prepare the following composition.

Composition A1 -5,6-dihydroxyindole 0.59/1
-L2,4-)lyhydroxybenzene 1.00
g-potassium milate 1.0
0g-ethyl alcohol io, oo
y - Preservative required amount - natural - = 5.8 one water sufficient amount 100.00
9 Composition B (contains 12.5 volumes of hydrogen peroxide solution) -
Hydrogen peroxide 5.759-lacryl ammonium sulfate 6.70? - Gum Arabic 1.00? - stabilizer
0.03 F-Fragrance Required Amount-2-Amino-2-Methyl-1-Propatur Required Amount p
) I-4 Sufficient amount of water ioo, o
Dyeing of oy90fs gray natural hair is carried out by applying composition (A1).

The composition (AI) is left for 15 minutes. After rinsing with water, 12.5 volumes of composition (B) of hydrogen peroxide solution are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a bright chestnut brown with a reddish sheen.

Example 2 Prepare the following composition.

Composition A2 -5,6-cyhydroxyynol 0.60
．． P-1,6-cyhydroxybenzene 0
．． 055'-6-aminophenol 0
．． 40 P-potassium iodide i, o
oy-ethyl alcohol 10.0Oli
' - Preservative required amount - Natural pH - 6,5 - Water Sufficient amount ioo, o
Permanently dyed 90-year-old gray hair is dyed by applying composition (A2).

Leave for 15 minutes. After rinsing with water, 12.5 volumes of composition (B) of hydrogen peroxide solution are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, your hair will be dyed a deep chestnut color with a natural shine.

Example 3 Prepare the following composition.

Composition A3-5, 6-dihydroxyindole 0.20
g-6-aminophenol 0.10
g - Potassium iodide 1.00 g - Ethyl alcohol io, oo & - Preservative Necessary amount - Natural - = 7 One Water Sufficient amount 100.0
For dyeing 990% gray natural hair, apply composition (A3) and leave it for 5 minutes for 15 minutes. After rinsing with water, 12.5 volumes of hydrogen peroxide solution composition (B) are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, your hair will be dyed a natural shiny golden-blonde color.

Example 4 Prepare the following composition.

Composition A4 -5,6-dihydroxyindole 0
．． 70 g-1,2,4-1lihydroxy-5-methyl 6. oog benzene monoiodide potassium
2.00 &-ethyl alcohol
io, oog)
i, oogMA) 5.00 gm - preservative
Necessary amount - Natural - = 5.4 One water Sufficient amount IQo,
00990 Permanently gray hair is dyed by applying composition (A4).

Leave for 15 minutes. After rinsing with water, 12.5 volumes of hydrogen peroxide solution composition (B) is applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a deep auburn blonde.

Example 5 Prepare the following composition.

Composition A5 -5.6-dihydroxyindole 0
．． 50 E/-1,6-cyhydroxybenzene
0.50 g-potassium iodide
i,ooy-ethyl alcohol
10.00 g)
1.00g 5.00g1-
Preservative Required amount - Triethanolamine Required amount - = 6 - Water
Enough amount 100.00,! ii
'Dyeing of 90% gray, permanent hair is carried out by applying composition (A5).

Leave for 15 minutes. After rinsing with water, 12.5 volumes of hydrogen peroxide solution composition (B) are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a deep chestnut color with a hint of gray.

Example 6 Prepare the following composition.

Composition A6 -5.6-dihydroxyindole 0.2
09-6-aminephenol o
, iog, -1,2,4-trihydroxybenzene
0.40 g-Iodide power Ilium
0.50 g-ethyl alcohol
io, oo g-preservative required amount - natural one = 6.6 one water tenth it 10
0.00g 90% gray hair, natural hair dye (A
6) is applied.

Leave for 15 minutes. After rinsing with water, the composition (B) of 12.5 ml of hydrogen peroxide solution is applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a pale silvery-golden blonde.

Example 7 Prepare the following composition *J.

Composition A7 -5,6-dihydroxyindole o,6
o g-3-amino-6-methylphenol o
, so g-1,2,4-tri and V-roxybenzene
o,6o g-potassium iodide
0.80 g-ethyl alcohol
10.009 - Preservative required amount - natural - = 6.7 1 water 100.
00990% gray hair, natural hair dyeing composition (A7)
Do this using

Leave for 15 minutes. After rinsing with water, 12.5 caps of hydrogen peroxide solution composition (B) are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a reddish-brown-chestnut color.

Implementation 9'lJ 8 Prepare the following composition.

Composition A3 -5,6-dihydroxyindole (L4
0 g-1-s7 toll 0
．． 40 g-potassium iodide
0.809-ethyl alcohol
io, oo g-preservative required amount-triethanolamine required i p) J=8.5-water sufficient amount 100.00
Coloring of #90 gray, natural hair is carried out using composition (A8).

Leave for 15 minutes. After rinsing with water, 12.5 volumes of hydrogen peroxide solution composition (B) is applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a bright maroon color with a silvery sheen.

Example 9 Prepare the following composition.

Composition A9 -5,6-dihydroxyindole 0.30
g-6,4-methylenedioxy-6-medoxy1-
Aminobenzey D, 3[1
,! i'-potassium iodide
0.50,! i'-ethyl alcohol
70.00 g - Preservative Required - Triethanolamine Required amount... = 6 - Water
Sufficient amount ioo,oo g90%
Dyeing of gray, natural hair is carried out by applying composition (A,).

Leave for 15 minutes. After rinsing with water, 12.5 volumes of hydrogen peroxide solution composition CB) are applied and allowed to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a bright maroon color.

Example 10 Prepare the following composition.

Composition A0° monopotassium iodide 0.4
0 g-ethyl alcohol
5. []01-Propylene glycol
5.009 - Preservatives Required amount - Triethanolamine Required f pH = 6.5 - Deionized water Sufficient amount 1oo, oo y Composition B 5,6-dihy V loxindole 1.0
0g-6-amino-6-methylphenol
0.509-ethyl alcohol 12
．． 00 g-Triethanolamine Required amount...=6.
5- Theory Ionized water Sufficient amount 100.
00 g Apply the composition AIO on natural gray hair containing 90% gray hair for 15 minutes. Rinse.

Then, for 15 minutes, an equal weight mixture of pH 5 hydrogen peroxide solution containing 20 g of composition B0 is applied. This mixing is carried out just at the time of use. Next, rinse your hair and dry it. Her hair is a thin, silvery, natural blonde color.

Example 11 Prepare the following composition.

Composition Al1 -5.6-dihydroxyindole 0.4
5 Q-6-hydroxybenzomorpholine
0.4511-x ethylene glycol monoethyl ether 8.50 g-potassium iodide
0.50 g-Tartaric acid required amount −=
5 One theory Ionized water Tenko 100.00
Natural gray hair with 90% gray hair is pretreated for 10 minutes with composition B2 containing 60 volumes of...3 hydrogen peroxide solution. After rinsing with water, the composition (All) is applied for 20 minutes. After rinsing and drying, the hair is dyed a very silvery-white-light pronto shade. If you omit the intermediate rinse, the resulting shade will be a deep blonde with pearlescent silvery white.

Example 12 Prepare the following composition.

Composition A 2 -Resorcinol 0.40 g-
2-7 minophenol 0.109
-6-amino-6-methylphenol 0.25
g-potassium iodide 0.6()
g-Ethyl alcohol-guar gum (CELANESB Co., Ltd.)
) Sold under the name UARHP60J)
i, oog-triethanolamine required amount −
= 6 - required amount of preservative - sufficient amount of deionized water ioo, o
o gThese compositions are applied for 20 minutes on natural gray hair that is 90% gray. After rinsing, composition B3 containing 12.5 volumes of -3 hydrogen peroxide solution is applied for 10 minutes. After rinsing and drying, the shade obtained is an off-white-gold light deronde.

Example 16 Example 12 is repeated, but the - of the hydrogen peroxide solution used is brought to 8.5 with 2-amino-2-methyl-1-f lovanol before use. A very bright ZOLON R with a gold-tinged gray-white luster is obtained in the finished color.

Example 14 Prepare the following composition.

Composition A15 -5-7 Setoxy 6-hydroxyindole 0.6
0 g-6-aminobenzomorpholine hydrochloride o, so
g-1,2,4-) Lich V roxybenzene
0.40 g-potassium iodide i
, oog-ethyl alcohol 15.
00 g60% MA)
5.009 force.

)
1.5011-Preservative 0
- 15 g - Triethanolamine Required - Near deionized water Enough thiioo, oog Apply this composition on 90% gray natural gray hair for 12 minutes, then rinse. Furthermore, this hair is 12.5
Hydrogen peroxide composition B containing pJ-15 for 98 minutes. After rinsing and drying, the hair is dyed a natural light blonde shade with a pale golden-gray sheen.

Example 15 Example 14 is repeated, except that - of the hydrogen peroxide solution used is converted to i) 8 with triethanolamine before use. The same final dyeing result as in Example 14 is obtained, ie a natural light blond shade with a pale golden-gray shine.

Example 16 Prepare the following composition.

Composition A□.

-5,6-dihydroxyindole 0.5
0 g-1,2,4-trihydroxybenzene
0.50 g-3-7 minophenol
0.15 g-potassium iodide
0.40 g-Ethylene glycol heptanoethyl ether 7+50g-Hydrochloric acid Required amount -=
5 Preservatives Required amount Deionized water Sufficient amount 1oo, oo
g-Hydrogen peroxide solution 3.75 g
-2-uryl ammonium sulfate 6.7
011-Thickener 1.DOg
-Stabilizer 0.03 g-
Fragrance Required amount - Monoethanolamine Required tp [(=8.5-Water
Sufficient amount 100.00.
Apply composition A for 15 minutes on natural gray hair that is 990% gray.
14 shall apply. After rinsing, apply hydrogen peroxide composition B for 10 minutes. After rinsing and drying,
Get a natural light blonde dye with a sheer off-white sheen.

Example 17 Prepare the following composition.

Composition A15 -5,6-dihydroxyindole o, i
og-4-methyl-1,2-dihydroxybenzene 1
．． 00f! -potassium iodide
1.009-ethyl alcohol
io, oo y is falling)
Sold at 1.00g60% MA) 5.00 fi Kite - Triethanolamine Required fpH = 7 - Preservative Required amount 1 water Sufficient amount ioo, o
o g 90% gray natural gray hair by applying composition A115 and leaving for 15 minutes. After rinsing with water, composition B5 of 10 volumes of hydrogen peroxide solution with pH=5.8.
Apply and let act for 5 minutes. After rinsing with water and shampooing, the hair turns reddish-brown-gray blonde.

Claims (31)

[Claims] (1) A method for dyeing keratin fibers, which comprises applying at least one composition (A) onto the fibers;
) comprises at least one indole derivative and at least one oxidation dye selected from fast oxidation dyes and couplers in a medium suitable for dyeing, (a) with iodide ions, or (b) with hydrogen peroxide. pH 2-7 in combination with
, preferably at a pH of 2 to 5, the application of composition (A) is carried out either before or after the application of composition (B), and composition (B) is present in a suitable medium for dyeing (a). )
When the composition (A) contains iodine ions, the pH is 2 to 12;
A method for dyeing keratin fibers, preferably containing hydrogen peroxide at a pH of 2 to 7, or (b) iodine ions at a pH of 3 to 11 when the composition (A) contains hydrogen peroxide. (2) A composition (A) containing an indole derivative and an oxidation dye in combination with iodine ions is applied onto the fiber, and the composition (A) is applied before the composition (B) containing hydrogen peroxide is applied. 2. The method according to claim 1, wherein the method is performed as follows. (3) Indole derivatives have the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_7 represents a hydrogen atom, a lower alkyl group, or -SiR_1_2R_1_3R_1_4 group, and R
_8 and R_9 are the same or different, and are a hydrogen atom, a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group, or -COOSiR_1_2R_1_3R_1
_4 group, R_1_0 and R_1_1 are the same or different, hydrogen atom, linear or branched C_1-C_2_0 alkyl group, formyl group, linear or branched C_2-C_2_0
acyl group, linear or branched C_3-C_2_0 alkenoyl group, -SiR_1_2R_1_3R_1_
4 groups, -P(O)(OR_1_5)_2 groups, R_1_5
Represents OSO_2 groups, or R_1_0 and R_1_
1 is a carbonyl group, methylene group, thiocarbonyl group, or the following group, along with the oxygen atom that binds them ▲ There is a mathematical formula, chemical formula, table, etc.
There are chemical formulas, tables, etc. ▼ Forms a ring containing R_1_5 and R_1_6 represent a hydrogen atom or a lower alkyl group, R_1_7 represents a lower alkoxy group or a mono- or dialkylamino group, R_1_2,
R_1_3 and R_1_4 are the same or different and represent a linear or branched lower alkyl group and an addition salt with an inorganic or organic acid, for example an alkali metal, alkaline earth or corresponding amine salt. ) The method according to claim (1) or (2). (4) Indole derivatives include 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole,
5-methoxy-6-hydroxyindole, (5 or 6)-acetoxy-(6 or 5)-hydroxyindole, 2-carboxy-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole and 2, Process according to any one of claims (1) to (3), selected from among 3-dimethyl-5,6-dihydroxyindoles. (5) A method for dyeing keratin fibers, which comprises applying at least one composition (A) onto the fibers;
) comprises in a medium suitable for dyeing at least 5,6-dihydroxyindole and at least one oxidation dye selected from fast oxidation dyes and couplers in combination with iodine ions, and the application of composition (A) is composition (B)
and subsequent application of the composition (B).
) is a method for dyeing keratin fibers containing hydrogen peroxide at a pH of 2 to 12 in a medium suitable for dyeing. (6) The method according to any one of claims (1) to (5), wherein the iodide is an alkali metal, alkaline earth or ammonium iodide. (7) Applying on the fibers, in a first step, a composition (A) comprising iodide ions in the form of alkali metal, alkaline earth or ammonium iodides, indole derivatives and oxidative dyes in a medium suitable for dyeing. Apply, and in the second step,
7. A method according to claim 1, characterized in that a composition (B) containing hydrogen peroxide in a suitable medium for dyeing is applied. (8) Process according to any one of claims (1) to (7), characterized in that from 1 to 40 volumes, preferably from 2 to 20 volumes of the aqueous composition of hydrogen peroxide are used. (9) in separate compositions for 10 seconds to 45 minutes, preferably 2 to 45 minutes;
Claims (1) to 1 applied with a standing time of 25 minutes.
The method according to any one of (8). (10) At least one indole derivative as defined in any one of claims (1) to (5) and at least one oxidation dye selected from fast oxidation dyes and couplers are combined with iodine. A composition for dyeing keratin fibers, characterized in that it contains in combination with ions. (11) The composition according to claim (10), which contains only a coupler as the oxidation dye. (12) The fast oxidation dye is selected from benzene trihydroxyl derivatives, diaminohydroxybenzene, aminodihydroxybenzene, aminohydroxybenzene, triaminobenzene and 1,2-dihydroxybenzene substitutes. Composition. (13) Fast oxidation dyes include 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-alkyl (
C_1-C_6) Benzene, 1,2,3-trihydroxybenzene, 4-aminoresorcinol, 2-amino-1,
4-dihydroxybenzene, 2-amino-4-methoxyphenol, 2,4-diaminophenol, 2-amino-phenol, 4-methyl-1,2-dihydroxybenzene, 3-methoxycatechol, 1,4-dihydroxy-2 -diethylaminobenzene, 2,5-diamino-4
-methoxy-1-hydroxybenzene, 4,6-dimethoxy-3-amino-1-hydroxybenzene, 2,6-
selected from dimethyl-4-(N-p-hydroxyphenyl)amino-1-hydroxybenzene, 1,5-diamino-2-methyl-4-(N-p-hydroxyphenyl)aminobenzene and salts thereof; Claim (1)
2) The composition described. (14) The coupler is selected from phenol, ortho-diphenol, meta-aminophenol, meta-phenylene diamine, mono- or polyhydroxyl derivatives of naphthalene and aminonaphthalene, pyrazolone, benzomorpholine, or claim (10) or (11). The composition according to any one of the above. (15) The coupler has the following formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 is an OH group, or one or more C
_1-C_6 represents an amino group that can be substituted with a hydroxyalkyl group, and R_3 and R_5 are independently substituted with hydrogen, an OH group, or optionally a C_1-C_6 lower alkyl group or a C_1-C_6 lower hydroxyalkyl group. represents an amino group, R_2, R_4 and R_6 are hydrogen, C_1-C_6 lower alkoxy group,
C_1-C_6 represents a lower alkyl group or hydroxyalkoxy group, and R_3 and R_4 can also form a methylenedioxy group together. ) Claim (10), (11) or (14)
The composition according to any one of the above. (16) The coupler of formula (I) is 3-aminophenol, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 3-amino-6-methylphenol, 2
-methoxy-5-aminophenol, 1,3-diamino-4,6-methoxybenzene, 2-methoxy-5-N(
2-hydroxyethyl)aminophenol, 1,3-diamino-2,6-dimethoxybenzene, 2-methoxy-
1-N-methylamino-4-(2-hydroxyethyloxy)aminobenzene, 1,3-diamino-6-methoxybenzene, 4,6-dimethoxy-1,3-diN(2-
hydroxyethyl)aminobenzene, 2,6-dimethoxy-3-N(2-hydroxyethyl)amino-1-aminobenzene, 2,4-dimethoxy-3-N(2-hydroxyethyl)amino-1-aminobenzene, 2-methyl-5-N(2-hydroxyethyl)aminophenol,
4-methoxy-1,3-diN(2-hydroxyethyl)
Aminobenzene, 3-amino-4-methoxyphenol, 3,4-methylenedioxy-1-aminobenzene, 3
, 4-methylenedioxy-6-methoxy-1-aminobenzene, 2,6-dimethyl-3-N(2-hydroxyethyl)aminophenol, 2,6-dimethyl-3-aminophenol, 4-ethoxy-1 -amino-3-N,N
-(bis-2-hydroxyethyl)aminobenzene, 2
, 4-(diamino)phenoxyethanol, (2-amino-4-N-methylamino)phenoxyethanol, 1
Composition according to claim (15), selected from -methoxy-2-N-(2-hydroxyethyl)amino-4-aminobenzene and salts thereof. (17) Composition (A) includes 6-aminobenzomorpholine, 6-hydroxybenzenemorpholine,
The composition according to any one of claims (10) or (11), comprising 1-naphthol, 1-amino-7-naphthol or a salt thereof. (18) The composition for dyeing keratin fibers includes 5,6-dihydroxyindole or a derivative thereof defined in claim (3), 1,2,4-trihydroxybenzene,
1,2,4-trihydroxy-5-methylbenzene, 1
, 3-dihydroxybenzene, 3-aminophenol,
Claim (1) containing at least one oxidation dye selected from 3-amino-6-methylphenol, 3,4-methylenedioxy-6-methoxy-1-aminobenzene, and 1-naphthol and iodine ion. 10) The composition for dyeing keratin fibers as described above. (19) The oxidation dye is from 0.01 to 0.01 with respect to the total weight of the composition.
10% by weight, preferably 0.25-5% by weight, and the indole derivative as defined in claim (3) is present in a proportion of 0.01-5% by weight, preferably 0.003-3% by weight. Claim (1) is present in a proportion of % by weight.
The composition according to any one of items 0) to (18). (20) The proportion of iodide is I^- with respect to the total weight of the composition.
0.007 to 4% by weight and preferably 0.08 to 1.5% by weight expressed as ions.
The composition according to any one of (19). (21) The indole derivative and oxidation dye are on one side, and the iodide is on the other hand, and the weight ratio between them is 0.0.
5 to 10, and preferably 0.5 to 2.
The composition according to any one of claims (10) to (20). (22) A suitable medium for dyeing consists of water or a water-solvent mixture and has a pH of 2 to 7, and preferably 3.5 to 7.
Claims (10) to (2) which are an aqueous medium having a pH of
The composition according to any one of 1). (23) Any one of claims (10) to (22), wherein the composition is present in the form of a solution in one or more anhydrous solvents.
The composition described in Section. (24) Solvents include ethyl alcohol, propyl or isopropyl alcohol, t-butyl alcohol, ethylene glycol, monomethyl, monoethyl and monobutyl ether of ethylene glycol, ethylene glycol monoethyl ether acetate, propylene glycol,
Composition according to any one of claims (22) or (23), selected from monomethyl ethers of propylene glycol and dipropylene glycol, and methyl lactate. (25) The composition (A) used is defined in claims (10) to (
24) as defined in any one of paragraphs 24)
The method for dyeing keratin fibers according to any one of claims (1) to (9). (26) aliphatic amide in a proportion of 0.05-10%, 0.
anions and cations present in a proportion of 1 to 50% by weight;
Nonionic, amphoteric surfactants or mixtures thereof, 0.
1 selected from thickeners, fragrances, sequestrants, film-forming agents, treating agents, dispersants, conditioners, preservatives, opacifiers, swelling agents for keratin fibers in a proportion of 1 to 5% by weight; 26. A method according to claim 1, characterized in that a composition comprising one or more additives is used. (27) Claims (1) to (9) for dyeing human hair.
), and application of the method according to any one of (25) and (26). (28) A device having several compartments, in the first compartment containing a group of indole derivatives, fast oxidation dyes or couplers as defined in any one of claims (3) to (5). an oxidative dye selected from among them in the presence of iodine ions in a medium suitable for dyeing as defined in any one of claims (7) to (20); A device or "kit" for dyeing as described above, characterized in that it contains therein an aqueous composition of hydrogen peroxide. (29) The device according to claim (28), wherein the aqueous composition of hydrogen peroxide has a pH of 2 to 12, and preferably 2 to 7. (30) A device having several compartments, the first compartment containing an oxidizing dye selected from the group consisting of an anhydrous solvent, an iodide ion, an indole derivative, and a fast oxidizing dye and a coupler; an aqueous medium suitable for dyeing in a compartment, and in a third compartment an aqueous composition of hydrogen peroxide of 1 to 40 volumes at a pH of 2 to 12, preferably at a pH of 2 to 7; Device or "kit" for dyeing keratin fibers as defined above, characterized in that the composition contained in the second compartment is intended to be mixed with the contents of the first compartment on use. (31) A device having several compartments, in the first compartment containing an indole derivative and an oxidation dye selected from the group consisting of fast oxidation dyes and couplers in a medium suitable for dyeing. a second compartment contains a composition comprising iodine ions in a medium suitable for dyeing, and a third compartment contains hydrogen peroxide in an aqueous medium. A device as described above, characterized in that the contents of the third compartment are intended to be mixed with the contents of the first compartment immediately before use.