JP2001288056A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair dye composition having extremely high hair dye power, slight color fading with days and a slight change in color tone even in preservation. SOLUTION: This hair dye composition contains a direct dye of formula (1) [A is a (substituted or ring condensation) cationic nitrogen-containing heterocyclic aromatic group; B is a (substituted) phenylene group or a (substituted) naphthylene group; R is H, cyano group, a (substituted) 1-6C alkyl group or a group capable of forming 5- or 6-membered ring with a substituent group of N on the ring of A; K is a coupling component residue such as a phenol base, an aniline base or the like; X- is an anion].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an extremely high dyeing power and can strongly impart a very vivid greenish yellow to orange color to hair. The present invention relates to a hair dye composition having a small change in color tone of the agent even when the hair dye composition is used.

[0002]

2. Description of the Related Art Hair dyes are classified according to the dye used and whether or not melanin has a decolorizing effect. Typical examples include direct dyes such as alkaline agents, oxidation dyes and nitro dyes. It contains a two-part permanent hair dye consisting of a first agent and a second agent containing an oxidizing agent, and an organic acid or alkali agent and a direct dye such as an acid dye, a basic dye, or a nitro dye. Single-agent semi-permanent hair dyes are known.

[0003]

However, in the above-mentioned permanent hair dye, the color tone of the oxidation dye is not so vivid,
Vivid nitro dyes, which are generally used as direct dyes, are vivid immediately after hair dyeing, but have a drawback in that they lose color over time and dull in color immediately (Japanese Patent Laid-Open No. Hei 6-271435). Gazette).

Recently, there have been reports on hair dyes containing a so-called cationic dye having a structure in which a cationic group is contained in a conjugated system as a direct dye (Japanese Unexamined Patent Publication No. 8-507545 and Japanese Unexamined Patent Publication No. 8-501322). JP, JP-T10-502946,
JP-A-10-194942) decomposes when mixed with hydrogen peroxide which is generally used as an oxidizing agent at the time of hair dyeing, so that the desired hair dyeing effect cannot be obtained or permanent dyeing is performed. It has been found that it has a drawback that it is unstable with respect to alkaline agents and reducing agents, which are essential components of hair preparations.

[0005] Accordingly, an object of the present invention is to provide a hair dye composition having high hair dyeing power, little discoloration over time, excellent storage stability, and little change in color tone of the agent upon storage. I do.

[0006]

Means for Solving the Problems The present inventor has disclosed a technique disclosed in
In Japanese Patent No. 11362, if the following compound known as a cationic dye for dyeing and printing paper is applied to a hair dye, the dye was not decomposed at the time of hair dyeing, and the hair became extremely vivid greenish. It can strongly impart a color from yellow to orange, and has excellent light resistance, washing resistance,
It has been found that the composition exhibits sweat resistance, rub resistance and heat resistance, is stable in the composition, and has little change in color tone immediately after production and after storage.

That is, the present invention relates to a direct dye represented by the following general formula (1):

[0008]

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[In the formula, A represents a cationic nitrogen-containing heterocyclic aromatic group which may have a substituent and may be condensed with an aromatic ring, and B represents a group having a substituent. A phenylene group or a naphthylene group which may have a substituent;
Is a hydrogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a nitrogen atom on the ring of A in cooperation with a substituent of the nitrogen atom and an adjacent carbon atom together with 5 or A group capable of forming a 6-membered ring;
Aniline, acylacetoarylamide, pyridone, quinoline, pyrazole, indole, diphenylamine, aminopyridine, pyrimidine, pyrimidone, naphthol, naphthylamine, aminothiazole, thiophene or hydroxypyridine represents a residue of a coupling component, X ^- represents an anion. And a hair dye composition comprising the compound represented by the formula:

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), examples of the cationic nitrogen-containing heterocyclic aromatic group represented by A include those represented by the following general formula.

[0011]

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(R ¹ and R ² are an alkyl group having 1 to 6 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent.
An alkenyl group of 1 to 6 or a group forming a ring with R of the general formula (1), and R ³ has 1 to 6 carbon atoms which may have a substituent.
And an alkenyl group having 2 to 6 carbon atoms which may have a substituent or a phenyl group which may have a substituent. )

As the alkyl group having 1 to 6 carbon atoms represented by R in the general formula (1) and represented by R ¹ , R ² and R ³ in the cationic nitrogen-containing heterocyclic aromatic group A,
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclohexyl group.Examples of the groups that may be substituted include an aryl group, an alkoxy group, an amino group, a hydroxyl group, a cyano group, and a halogen atom. .

The alkenyl group having 2 to 6 carbon atoms represented by R ¹ , R ² and R ³ in the cationic nitrogen-containing heterocyclic aromatic group A includes an ethenyl group and a propenyl group. Examples of the group that may be used include a cyano group and a phenyl group.

The group which may be substituted with the phenyl group represented by R ³ in the ring B and the cationic nitrogen-containing heterocyclic aromatic group A in the general formula (1) includes an alkyl group, an aryl group, an alkoxy group, Examples include an amino group, a dialkylamino group, a hydroxyl group, a cyano group, a nitro group, a halogen atom and the like, and specific examples include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a diethylamino group, a chlorine atom and a bromine atom.

In the general formula (1), examples of the residue of the coupling component represented by K include the following general formulas (2) to (9)
And tautomers thereof.

[0017]

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(Y ¹ , Y ² and Y ^{4 each} represent an oxygen atom or an NH group; Y ³ represents an oxygen atom, an NH group or an N—CN group; R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8, R 10, R 11,} R 14, R
^15, R ¹⁸ and R ¹⁹ represents a hydrogen atom or an alkyl group having carbon atoms of 1 to 6 optionally having a substituent, R ⁹ represents a cyano group, a carbamoyl group or a sulfamoyl group, R ^12,
R ^13, R ^{1 6} and R ¹⁷ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, Z ¹ and Z ² may have a substituent Good carbon number 1
And 6 represents an alkyl group or an amino group which may have a substituent. However, in the formula (8), R ¹⁴ and R ¹⁵ may jointly form a 5- or 6-membered ring with an adjacent nitrogen atom, and R ¹⁴ and R ¹⁶ or R ¹⁵ and R ¹⁷ may jointly form A 5- or 6-membered ring may be formed together with the adjacent nitrogen atom and carbon atom. )

At residue K of the coupling component:
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ ,
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁸ , R ¹⁹ , Z ¹ and Z ² include a methyl group, an ethyl group, a propyl group, an isopropyl group and a cyclohexyl group. Examples of the good group include an aryl group, an alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, a hydroxyl group, a cyano group, and a halogen atom.

In the residue K, the group which may be substituted with the amino group represented by Z ¹ and Z ² includes an alkyl group such as a methyl group and an ethyl group; a halogen atom, an alkyl group and an alkoxy group. And the like.

In the formula (8), examples of the 5- or 6-membered ring which R ¹⁴ and R ¹⁵ can form together with an adjacent nitrogen atom include a pyrrolidine ring, a piperidine ring, a morpholine ring and a piperazine ring. Further, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and the like may be substituted, but unsubstituted is preferable.

In the formula (8), R ¹⁴ and R ¹⁶ or R
^{When 15} and R ¹⁷ form a 5- or 6-membered ring with adjacent nitrogen and carbon atoms, these rings may further contain other heteroatoms such as oxygen or sulfur, and , An alkoxy group, an alkyl group, a halogen atom or a cyano group may be substituted, and may further have one condensed ring. As such a 5- or 6-membered ring, a pyrroline ring, a dihydrooxazine ring and a di- or tetrahydropyridine ring having 0 to 4 methyl groups are preferred.

[0023] In general formula (1), X ^- as the anion represented by, chloride, bromide, iodide, tetrachlorophthalic zincate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, formate ion , Acetate ions and the like.

The direct dye (1) used in the present invention is described below.
The following shows a specific example.

[0025]

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[0026]

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One or more direct dyes (1) can be used, and other direct dyes can also be used in combination. In particular, hair can be dyed in deep brown with excellent gloss and dark brown or black by combination with reddish and bluedish dyes.

Examples of the direct dye other than the direct dye (1) include Basic Blue 7 (CI42595), Basic Blue 26 (CI44045), and Basic Blue 99 (CI5605).
9), Basic Violet 10 (CI45170), Basic Violet 14 (CI42515), Basic Brown 16 (CI12250), Basic Brown 17 (CI1225)
1), Basic Red 2 (CI50240), Basic Red 22 (CI11055), Basic Red 76 (CI1224)
5), Basic Red 118 (CI12251: 1), Basic Yellow 57 (CI12719); JP-B-58-2204, JP-A-9-118832, JP-A-8-501322, and JP-A-8-210
And basic dyes described in JP-A-507545 and the like.

The amount of the direct dye (1) to be compounded in the total composition (in the case of a two-part or three-part system, after mixing of the respective agents; the same applies hereinafter).
It is preferably from 01 to 20% by weight, more preferably from 0.05 to 10% by weight, especially from 0.
1-5% by weight is preferred. When other direct dyes are used in combination, the total amount of the direct dyes (1) is 0.05
-10% by weight, especially 0.1-5% by weight is preferred.

The pH of the hair dye composition of the present invention is preferably from 6 to 11, and particularly preferably from 8 to 11. Examples of the alkaline agent for adjusting the pH include commonly used ones, for example, ammonia, organic amines and salts thereof. The amount of the alkali agent is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, particularly 0.5 to 5% by weight in the whole composition.
Is preferred.

The hair dye composition of the present invention can also contain an oxidizing agent. In this case, the hair can be decolorized at the same time, so that more vivid hair dyeing is possible. As the oxidizing agent, those usually used, for example, hydrogen peroxide, ammonium persulfate, potassium persulfate, persulfates such as sodium persulfate, perborate such as sodium perborate, percarbonate such as sodium percarbonate, Examples thereof include bromates such as sodium bromate and potassium bromate, and hydrogen peroxide is particularly preferable. The compounding amount of the oxidizing agent is 0.5 to 10 in the total composition.
% By weight, especially 1 to 8% by weight.

The hair dye composition of the present invention may further contain an oxidation dye. In this case, extremely vivid and strong dyeing, which is difficult to obtain with the oxidation dye alone, is possible. As the oxidizing agent in this case, those described above are used, and hydrogen peroxide is particularly preferable. Alternatively, an oxidase such as laccase can be used instead. As the oxidation dye, known developers and coupling substances commonly used for oxidation hair dyes can be used.

Examples of the color developing substance include, for example, p-phenylenediamine, p-toluylenediamine, N-methyl-p-phenylenediamine, chloro-p-phenylenediamine, 2- (2'-hydroxyethylamino) -5- Amino toluene, N, N-bis-
(2-hydroxyethyl) -p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, 2,6-dimethyl-p-
Phenylenediamine, methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-
Methyl-p-phenylenediamine, 6-methoxy-3-methyl-p
-Phenylenediamine, 2,5-diaminoanisole, N- (2-
One or several types of NH ₂ — groups, NHR— groups or NHR ₂ — groups (R represents 1 carbon atom), such as hydroxypropyl) -p-phenylenediamine, N-2-methoxyethyl-p-phenylenediamine and the like;
Having 4 to 4 alkyl groups or hydroxyalkyl groups)
-Phenylenediamines; 2,5-diaminopyridine derivatives, 4,5-diaminopyrazole derivatives; p-aminophenol, 2-methyl-4-aminophenol, N-methyl-p-aminophenol, 3-methyl-4- P- such as aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, and 2,5-dimethyl-4-aminophenol Aminophenols, o
-Aminophenols, o-phenylenediamines, 4,4'-
Diaminophenylamine, hydroxypropylbis (N-
Hydroxyethyl-p-phenylenediamine) and the like.

As the coupling substance, for example,
1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 5-
Amino-2-methylphenol, 5- (2'-hydroxyethylamino) -2-methylphenol, 2,4-diaminoanisole, m-toluylenediamine, resorcinol, m-phenylenediamine, m-aminophenol, 4- Chlororesorcin,
2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 4-hydroxyindole, 6-hydroxyindole, 2,4-diamino-6-hydroxypyrimidine, 2 , 4,6-
Triaminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6
-Diamino-2-hydroxypyrimidine, 1,3-bis (2,4-diaminophenoxy) propane and the like, and salts thereof.

One or more of these color-developing substances and coupling substances can be used each, and the compounding amount is 0.01 to 20% by weight, particularly 0.5 to 10% by weight in the total composition.
Is preferred.

The hair dye composition of the present invention may further contain known direct dyes such as autoxidation dyes represented by indoles and indolines, nitro dyes and disperse dyes.

When an anionic base (anionic activator, anionic polymer, fatty acid, etc.) is added to the hair dye composition of the present invention, "anionic base ion activity concentration / cationic direct dye ( It is preferable that the ion activity concentration of 1) ≦ 8 ”. Here, the ion activity concentration means “molar concentration × ion valence”.

The addition of polyols or polyol alkyl ethers, cationic or amphoteric polymers, or silicones to the hair dye composition of the present invention provides uniform hair dyeing and improves the cosmetic effect of hair. Is preferred.

The hair dye composition of the present invention may contain, in addition to the above components, other components which are usually used as cosmetic raw materials. Such optional components include hydrocarbons, animal and vegetable fats and oils, higher fatty acids, organic solvents, penetration enhancers, cationic surfactants, natural or synthetic polymers, higher alcohols, ethers, amphoteric surfactants , Nonionic surfactants, protein derivatives, amino acids, preservatives, chelating agents, stabilizers, antioxidants, plant extracts, herbal extracts, vitamins, pigments, fragrances, UV absorbers .

The hair dye composition of the present invention can be produced according to a usual method, and can be produced in a one-part system, a two-part system comprising a composition containing an alkali agent and a composition containing an oxidizing agent, or And a powdery oxidizing agent such as persulfate. In the case of the two-part or three-part system, the direct dye (1) can be blended in one or both of the above compositions. The hair dye composition of the present invention is used by directly applying it to the hair in the case of the one-part type, and is used by mixing and applying it to the hair in the case of the two- or three-part type. Is done.

The form is not particularly limited.
It can be in the form of powder, transparent liquid, emulsion, cream, gel, paste, aerosol, aerosol foam or the like. Viscosity, at the stage of applying to the hair, 2000-10
0000 mPa · s is preferred.

[0042]

The compounds used in the following examples are as follows.

[0043]

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Examples 1 to 5 Hair dyes shown in Table 1 were prepared according to a conventional method.

[0045]

[Table 1]

Examples 6 to 9 Hair dyes shown in Table 2 were prepared according to a conventional method.

[0047]

[Table 2]

Examples 10 to 12 Hair dyes shown in Table 3 were prepared according to a conventional method.

[0049]

[Table 3]

Example 13 The following hair dye was prepared according to a conventional method. (First agent) (% by weight) Paraaminophenol 1 Paraaminoorthocresol 1.1 Compound (a) 0.1 28% by weight aqueous ammonia 5 Monoethanolamine 2 Cetanol 8.5 Polyoxyethylene (40) cetyl ether 3 Polyoxyethylene (2) cetyl ether 3.5 Stearyltrimethylammonium chloride 2 Liquid paraffin 0.5 Sodium sulfite 0.05 Ascorbic acid 0.5 Tetrasodium edetate 0.1 Perfume Appropriate amount Ammonium chloride Amount to adjust to pH10 Water Balance

(Second agent) (% by weight) 35% by weight aqueous hydrogen peroxide 17.1 Methyl paraben 0.1 Phosphoric acid Amount to be adjusted to pH 3.5 Water Balance

[0052]

EFFECT OF THE INVENTION The hair dye composition of the present invention has an extremely high hair dyeing power, exhibits excellent light resistance, washing resistance, sweat resistance, rub resistance and heat resistance, and even when stored. Little change in color tone of the agent.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yukihiro Ohashi 2-1-3 Bunka, Sumida-ku, Tokyo Inside Kao Corporation Research Laboratory (72) Inventor Shintaro Toki 2-1-3 Bunka, Sumida-ku, Tokyo Within Kao Corporation Research Laboratory (72) Inventor Yoshinori Saito 2-1-3 Bunka, Sumida-ku, Tokyo F-term within Kao Corporation Research Laboratory 4C083 AB012 AB032 AB052 AB352 AB412 AC022 AC072 AC122 AC182 AC472 AC482 AC532 AC542 AC552 AC692 AC851 AC852 AD132 AD152 AD162 AD352 AD642 BB24 CC36 DD27 EE26 4H057 AA01 BA01 BA03 BA04 BA24 CA07 CB34 CB45 CB46 CB52 CB55 CB59 CC02 DA01 DA21

Claims (3)

[Claims] 1. A direct dye represented by the following general formula (1): [In the formula, A represents a cationic nitrogen-containing heterocyclic aromatic group which may have a substituent and may be condensed with an aromatic ring, and B is a phenylene which may have a substituent. R represents a hydrogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or substitution of a nitrogen atom on a ring of A, which represents a naphthylene group which may have a group or a substituent; Together with the nitrogen atom and adjacent carbon atom
Or a group capable of forming a 6-membered ring; K is a phenolic, aniline, acylacetoarylamide, pyridone, quinoline, pyrazole,
Indole, diphenylamine, amino pyridine, pyrimidine, pyrimidone based, naphthol, naphthylamine, aminothiazole system, represents a residue of a coupling component of the thiophene or hydroxypyridine system, X ^- represents an anion. ] The hair dye composition containing the compound represented by these. 2. The hair dye composition according to claim 1, further comprising an oxidizing agent. 3. The method according to claim 1, further comprising an oxidation dye.
The hair dye composition according to the above.