JP2001288059A - 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) or formula (2) [Y is a group of formula (y1), (y2), (y3), (y4) which may contain a substituent group or a (substituted) benzene ring condensed with a quinoline ring; Z is a polyfunctional crosslinkable group; Q is N+R1R2R3 (R1 to R3 are each a (substituted) 1-6C alkyl group or two or three of R1 to R3 form a heterocyclic ring with N') ; Y' is a group of formula (y1'), (y2'), (y3') or (y4') which may contain a substituent group or a (substituted) benzene ring condensed with a quinoline ring; X is a -N= group or a -N+R= (R is a (substituted) 1-6C alkyl group; (m) and (n) are each 1 or 2; ring A and ring B each may contain a substituent group; An- is an anion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an ink composition having an extremely high dyeing power, capable of strongly imparting a very vivid greenish yellow color to hair, having little discoloration over time, and having an effect even when stored. The present invention relates to a hair dye composition having a small change in color tone.

[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. When a conjugate group based on (-N = N-) contains a cationic group, it has a disadvantage that it is unstable with respect to an alkali agent and a reducing agent, which are essential components of a permanent hair dye. I understood.

[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]

The present inventor has disclosed in Japanese Patent Application Laid-Open No. 58-1
In 85651, fiber materials, paper, for dyeing and printing leather, or the following compounds known as cationic dyes for ink production, if applied to hair dye, the dye will be decomposed during hair dyeing Without giving a very vivid greenish yellow to the hair,
It has been found that it shows excellent light resistance, washing resistance, 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) or (2):

[0008]

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[Wherein Y is a group represented by the formula (y
1), (y2), (y3) or (y4)

[0010]

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A benzene ring which may have a substituent condensed at the 5/6 or 7/8 position of the quinoline ring, Z represents a polyvalent cross-linking group, Q is-
N ⁺ R ¹ R ² R ³ (R ¹ , R ² and R ³ each represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, or two or three of them represent a quaternary nitrogen atom; May form a heterocyclic ring with
And m and n each represent 1 or 2, the A ring and the B ring may have a substituent, and An ⁻ represents an anion. ]

[0012]

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[In the formula, Y ′ is a group which may have a substituent.
(y1 '), (y2'), (y3 ') or (y4')

[0014]

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And a benzene ring which may have a substituent condensed at the 5/6 or 7/8 position of the quinoline ring, wherein X is a -N = group or -N ⁺ R = group (R
Represents an alkyl group having 1 to 6 carbon atoms which may have a substituent), n represents 1 or 2, and A ring and B ring are
It may have a substituent, and An ⁻ represents an anion. And a hair dye composition comprising the compound represented by the formula:

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formulas (1) and (2), R,
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ^2, and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclohexyl group, and the like. Examples thereof include an aryl group, an alkoxy group, an amino group, a hydroxyl group, a cyano group, and a halogen atom.

In the general formulas (1) and (2), the groups which may be substituted on the rings A and B include alkyl, aryl, alkoxy, amino, hydroxyl, cyano, nitro, halogen and the like. Examples of the atom include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom, and a bromine atom.

In the general formulas (1) and (2), the group which may be substituted with the group Y and the group Y 'includes an alkyl group, an alkoxy group, an amino 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 chlorine atom and a bromine atom.

In the general formula (1), as the polyvalent crosslinking group represented by Z,

[0020]

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[Wherein R ⁴ represents a hydrogen atom or a hydroxyl group,
A halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a group selected from an amino group and an alkyleneimino group, and R ⁵ is a group selected from a hydroxyl group, a halogen atom, an amino group and an alkyleneimino group. It represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may be substituted. ] Are represented.

[0022] In the general formula (1) and (2), An ^- as the anion represented by, chloride, bromide, iodide, tetrachlorophthalic zincate ion, sulfate ion, hydrogen sulfate ion, phosphate Ion, formate ion, acetate ion and the like.

The direct dye (1) used in the present invention is described below.
Specific examples of (2) and (2) are shown below.

[0024]

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[0025]

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One or more of the direct dyes (1) and (2) 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.

The direct dyes other than the direct dyes (1) and (2) include, for example, Basic Blue 7 (CI42595), Basic Blue 26 (CI44045), and Basic Blue 99 (C.I.
I.56059), Basic Violet 10 (CI45170),
Basic Violet 14 (CI42515), Basic Brown 16 (CI12250), Basic Brown 17 (C.
I.12251), Basic Red 2 (CI50240), Basic Red 22 (CI11055), Basic Red 76 (C.
I.12245), Basic Red 118 (CI12251: 1), Basic Yellow 57 (CI12719); JP-B-58-2204, JP-A-9-118832, JP-A-8-501322, and JP-T-8 And basic dyes described in JP-A-507545.

The compounding amount of the direct dyes (1) and (2) is preferably 0.01 to 20% by weight in the total composition (after mixing the respective components in the case of the two-part or three-part system, the same applies hereinafter). Further, the content is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight. When other direct dyes are used in combination, the total amount of the direct dyes (1) and (2) is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight.

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, and 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 color developing substances 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, respectively, 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, it is preferable that “anionic base ion activity concentration / cationic direct dye ( 1) and (2) ion activity concentration ≤
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.

[0038] In addition to the above components, other components commonly used as cosmetic raw materials can be added to the hair dye composition of the present invention. 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 an ordinary method, and can be prepared 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) or (2) 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.

[0041]

The compounds used in the following examples are as follows.

[0042]

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

[0044]

[Table 1]

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

[0046]

[Table 2]

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

[0048]

[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) (wt%) 35 wt% aqueous hydrogen peroxide 17.1 methyl paraben 0.1 phosphoric acid Amount adjusted to pH 3.5 Water Balance

[0051]

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 Kao Corporation Research Laboratory (72) Inventor Yoshiki Saito 2-1-3 Bunka Sumida-ku, Tokyo Kao Corporation Research Laboratory F-term (reference) 4C083 AB082 AB102 AB282 AB352 AB412 AC022 AC072 AC102 AC122 AC172 AC182 AC472 AC482 AC532 AC542 AC552 AC692 AC841 AC842 AC851 AC852 AC861 AC862 AD162 AD352 AD642 BB21 BB53 CC36 DD08 DD17 DD22 DD23 DD31 DD41 EE01 EE26 4H057 AA01 BA01 BA03 BA04 CA07 CB03 CB45 CB46 CC02 DA01 DA21

Claims (3)

[Claims] 1. A direct dye represented by the following general formula (1) or (2): Wherein Y is a group represented by the formula (y1), (y2), (y
3) or (y4) Or the 5/6 or 7 / position of the quinoline ring
Z represents a benzene ring which may have a substituent fused to the 8-position; Z represents a polyvalent crosslinking group; and Q represents -N ⁺ R ¹ R ² R ³ (R ¹ , R ² and R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, or two or three of them may form a heterocyclic ring with a quaternary nitrogen atom), and m and n Represents 1 or 2, ring A and ring B may have a substituent, and An ⁻ represents an anion. [Chemical formula 3] Wherein Y ′ is a group represented by the following formula (y1 ′),
2 '), (y3') or (y4 ') Or the 5/6 or 7 / position of the quinoline ring
X represents a benzene ring which may have a substituent condensed at the 8-position, and X represents a -N = group or a -N ⁺ R = group (R represents a C1-6 group which may have a substituent. A represents an alkyl group); n represents 1 or 2; A ring and B ring may have a substituent; and An ^- 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.