JP2002080331A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair dye composition slight in color tone change when preserved, extremely high in hair-dyeing power and having high light resistance, washing resistance, perspiration resistance, abrasion resistance and heat resistance, because of high stability of the dye to alkali agent, oxidizing agent and reducing agent. SOLUTION: This hair dye composition comprises a direct dye of the formula (1) (R1, R2, R3, R4, R5 and R6 are each a 1-4C alkyl; R7 is H or a 1-4C alkyl; and X- is an anion).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an extremely high dyeing power, capable of strongly imparting a very vivid red color to hair, little discoloration over time, and a change in color tone obtained even when stored. The present invention relates to a hair dye composition having a low content.

[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 immediately (Japanese Patent Laid-Open No. Hei 6-271435). Gazette).

Recently, there have been reports on hair dyes containing so-called cationic dyes. These cationic dyes are alkaline agents used in alkaline semi-permanent hair dyes and permanent hair dyes, and two-pack hair dyes. However, it has a disadvantage that it is unstable with respect to hydrogen peroxide used as an oxidizing agent and a reducing agent used for a permanent hair dye. In contrast, WO99 / 07334 (hereinafter referred to as WO99 / 07334) describes a hair dye containing a certain methine-type cationic dye that is stable to an oxidizing agent, a reducing agent, and the like. ing. However, according to the study of the present inventors, all of the methine-type cationic dyes specifically disclosed in the pamphlet have insufficient storage stability in the range of pH 2 to 11 generally used as a hair dye. It was something. In other words, these methine-type cationic dyes are particularly unstable with respect to alkali agents, and when a hair dye contains an alkali agent, it decomposes over time due to storage and the dyeability is significantly reduced, Further, even when the pH of the hair dye was in the acidic to neutral range, it gradually decomposed and the dyeability was reduced. Further, contrary to the description, these compounds have extremely poor stability against an oxidizing agent and a reducing agent, and when mixed with a second agent containing an oxidizing agent, they are rapidly decomposed and deteriorated in dyeability. It has been found that the dyeability is impaired by storage even in a permanent hair dye containing.

Accordingly, the present invention shows high storage stability in a wide range of pH 2 to 11, which is generally used as a hair dye,
Furthermore, a hair dye composition that is stable to all of the alkaline agent, oxidizing agent and reducing agent, has high hair dyeing power, has little discoloration over time, and has little change in dyeability and color tone even after storage. The purpose is to do.

[0006]

Means for Solving the Problems The present inventor has disclosed WO99 / 07334.
A methine-type cationic dye having a specific structure, which is included in the range of the general formula described in the claims but does not specifically disclose anything, is unexpectedly specifically disclosed in the same pamphlet. It has been found that it has remarkably high storage stability as compared with methine-type cationic dyes, particularly stability against an alkali agent, an oxidizing agent and a reducing agent. And if it is applied to hair dyes, it can strongly impart a very clear red color to hair, and is excellent in light resistance, washing resistance, sweat resistance, rub resistance, heat resistance, and immediately after production and after storage Was also found to have very little change in color tone.

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

[0008]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Represents an alkyl group having 1 to 4 carbon atoms, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 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), R ¹ , R ² ,
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. . As R ^{1 to} R ⁶ , a methyl group is most preferable from the viewpoint of ease of production of a dye and availability of production raw materials. Examples of R ^7, from the viewpoint of the stability of dyes, for R ⁷ tends to be further improved stability when there is the above alkyl group, but it can be said that the alkyl group is preferred, R ⁷ is a hydrogen atom A hydrogen atom is most preferable from the viewpoint of easy production of a dye and easy availability of a raw material because it has sufficient stability even if it is present.

[0011] In general formula (1), X ^- as the anion represented by, chloride, bromide, iodide, trichloroacetic zincate ions, tetrachlorophthalic zincate ion, sulfate ion, hydrogen sulfate ion, sulfate Methyl ion, phosphate ion, formate ion, acetate ion, perchlorate ion and the like can be mentioned.

Preferred specific examples of the direct dye (1) include:
Basic Red 12 represented by the following formula, which is known as a cationic dye for dyeing a fiber material or the like, may be mentioned.

[0013]

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One or more direct dyes (1) can be used, and other direct dyes can be used in combination. In particular, hair can be dyed deep brown or black with a deep luster and excellent gloss by a combination of yellow and blue dyes.

Examples of direct dyes 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 46 (CI11082)
5), Basic Red 76 (CI12245), Basic Red 118 (CI12251: 1), Basic Yellow 28 (CI12245)
48054), Basic Yellow 57 (CI12719);
58-2204 gazette, JP-A-9-118832 gazette, JP-T-Hei-8-50132
And methine type cationic dyes having a cyanine structure represented by the following formula and the like.

[0016]

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The content of the direct dye (1) in the total composition (in the case of a two-pack or three-pack 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 content of the direct dye (1) is 0.05
-10% by weight, especially 0.1-5% by weight is preferred.

The hair dye composition of the present invention can be used in any pH range since the direct dye (1) exhibits high storage stability in a wide range of pH 2 to 11, which is generally used as a hair dye. Although it is possible, use at a pH of 5 or more is preferable in view of dyeability. Furthermore, since it has high stability to alkaline agents, it can have a very high dyeing power of pH 8 or more, particularly pH 8 to 11, and has a high dyeing power without direct decomposition of the dye even after long-term storage. Demonstrate. Examples of the alkaline agent include alkanolamines such as ammonia, monoethanolamine, and isopropanolamine or salts thereof, guanidinium salts such as guanidine carbonate, and hydroxide salts such as sodium hydroxide. The amount of the alkaline agent is
0.01 to 20% by weight is preferable, and 0.1 to 10% by weight is particularly preferable.
0.5 to 5% by weight is preferred.

Since the direct dye (1) has high stability to an oxidizing agent, the hair dye composition of the present invention has a form in which the oxidizing agent is mixed and then applied to the hair, that is, the direct dye (1) is used. It can be in the form of a first agent containing and a second agent containing an oxidizing agent. In this case, since the hair can be decolorized at the same time,
More vivid hair dyeing becomes possible. Examples of the oxidizing agent include hydrogen peroxide, ammonium persulfate, potassium persulfate, persulfates such as sodium persulfate, perborates such as sodium perborate, percarbonates such as sodium percarbonate, sodium bromate, and bromine. Examples include bromates such as potassium acid,
Hydrogen peroxide is particularly preferred from the viewpoints of decolorization of hair, stability of dye, availability, and the like. The content of the oxidizing agent is preferably 0.5 to 10% by weight, particularly preferably 1 to 8% by weight in the whole composition. The mixing ratio of the first agent containing the direct dye (1) and the second agent containing the oxidizing agent is preferably about 2: 1 to 1: 3 by volume.

Further, the hair dye composition of the present invention comprises a direct dye
Since (1) has high stability with respect to the reducing agent used for improving the stability of the oxidation dye during storage, the oxidation dye can be used in combination. In this case, extremely clear and intense dyeing, which is difficult to obtain with only an oxidation dye, is possible. Examples of the reducing agent include sulfite, thioglycolic acid, and ascorbic acid, and the content thereof is preferably 0.1 to 5% by weight, particularly preferably 0.3 to 3% by weight in the whole composition. As the oxidizing agent, those described above are used, and hydrogen peroxide is particularly preferable. 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 paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, and N, N-bis (2-hydroxyethyl). -Paraphenylenediamine, 2- (2-hydroxyethyl) -paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,
4'-diaminodiphenylamine, 1,3-bis (N- (2-hydroxyethyl) -N- (4-aminophenyl) amino) -2-propanol, PEG-3,2,2'-paraphenylenediamine, paraamino Phenol, paramethylaminophenol, 3-methyl
-4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (2-hydroxyethylaminomethyl) -4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6 -Methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4- Hydroxypyrimidine, 4,5
-Diamino-1- (4'-chlorobenzyl) pyrazole and the like, and salts thereof.

Examples of the coupling substance include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole, 2,4-diamino-5-methylphenetole, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diamino-5 -Fluorotoluene, 1,3-bis (2,4-diaminophenoxy) propane, metaaminophenol, 2-methyl-5-aminophenol, 2
-Methyl-5- (2-hydroxyethylamino) phenol, 2,
4-dichloro-3-aminophenol, 2-chloro-3-amino-6
-Methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-methaminophenol, 2-
Methyl-4-methoxy-5- (2-hydroxyethylamino) phenol, 2-methyl-4-fluoro-5-aminophenol, resorcin, 2-methylresorcin, 4-chlororesorcin,
1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-
Isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo
-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1- (2-hydroxyethyl) amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine , 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2, 6-diaminopyridine and the like, and salts thereof.

One or more of these color developing substances and coupling substances can be used, respectively, and the content thereof is preferably 0.01 to 20% by weight, particularly 0.5 to 10% by weight in the total composition.

The hair dye composition of the present invention further comprises an autoxidative dye represented by indole, indoline and the like;
Known direct dyes such as nitro dyes and disperse dyes can also be added.

When an anionic component (anionic surfactant, anionic polymer, etc.) is added to the hair dye composition of the present invention, the ratio of “ionic activity concentration of anionic component / ionic activity of direct dye (1)” It is preferable that the density is ≦ 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.

[0027] 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, Examples include nonionic surfactants, protein derivatives, amino acids, preservatives, chelating agents, stabilizers, antioxidants, plant extracts, herbal extracts, vitamins, pigments, flavors, ultraviolet absorbers, and the like.

The hair dye composition of the present invention can be produced according to a conventional 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 persulfate. A three-part form to which a powdery oxidizing agent such as a salt is added can be used. In the case of two-pack or three-pack, direct dye
(1) may be blended in at least one 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 may be a powder, a transparent liquid, an emulsion, a cream, a gel, a paste, an aerosol, an aerosol foam, or the like. The viscosity at the stage of application to the hair (after mixing in the case of a two-part or three-part system) is preferably from 2000 to 100,000 mPa · s.

[0030]

The dyes used in each of the examples and comparative examples are shown below.

[0031]

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Example 1 and Comparative Examples 1 to 3 The following two-part hair dyes were prepared, and their stability to oxidizing and alkaline agents was evaluated. The pH of these hair dyes was 9.5 for the first agent, 4.3 for the second agent, and after mixing both.
It was 9.3.

(First agent) (% by weight) 25% by weight ammonia water 3.4 Ammonium chloride 2.7 Ethanol 10.0 Propylene glycol 10.0 Dye shown in Table 1 0.1 Deionized water Remaining amount (Second agent) (% by weight) 35% by weight Hydrogen oxide water 17.1 Ion exchange water

<Evaluation method> The first agent and the second agent are in a weight ratio of 1:
The mixture mixed in 1 was used as a test solution, and 10 g of the mixture and goat hair bundles (length: 19 cm, weight: 1 g) were placed in a test tube, left in a thermostat at 30 ° C. for 20 minutes, then rinsed with warm water, and shampooed. 2
After washing twice, it was dried. The dyed hair bundle was measured with a spectrophotometer (CM-2002, manufactured by Minolta Co., Ltd.), and based on ΔE calculated by the following equation, the dyeing power was determined according to the following evaluation criteria.
It was evaluated on a scale.

ΔE = ｛(L ₁ -L ₀ ) ² + (a ₁ -a ₀ ) ² + (b ₁ -b ₀ ) ² ｝ ^1/2 (L ₀ , a ₀ , b ₀ ): before staining Colorimetric value of goat hair bundle (L ₁ , a ₁ , b ₁ ): Colorimetric value of goat hair bundle after dyeing

<Evaluation Criteria> A: ΔE ≧ 60 ○: 60> ΔE ≧ 50 Δ: 50> ΔE ≧ 30 ×: 30> ΔE

<Results> As is evident from the results shown in Table 1, the basic red 12 (a) is more oxidizing agent than the typical methine dyes (b) to (d) disclosed in WO99 / 07334. It has high stability to alkaline agents and has excellent dyeing properties on hair.

[0038]

[Table 1]

Example 2 and Comparative Examples 4 to 6 One-part hair dyes (pH = 9.5) shown below were prepared, and their storage stability against alkaline agents was evaluated.

[0040]

<Evaluation method> Hair dye immediately after preparation and 40 ° C 3
Using 10 g of each of the hair dyes stored for months, the dyeability was evaluated by the same method and criteria as in Example 1.

<Results> As is evident from the results shown in Table 2, the storage stability of Basic Red 12 (a) with respect to alkaline agents is remarkably higher than that of methine dyes (b) to (d) described in WO99 / 07334. High and maintains excellent dyeability on hair even after storage.

[0043]

[Table 2]

Examples 3 to 5 and Comparative Examples 7 to 9 The following two-part hair dyes were prepared, and their storage stability against reducing agents and alkaline agents was evaluated. The pH of these hair dyes was 9.5 for the first agent, 4.3 for the second agent, and 9.3 after mixing both.

(First agent) (% by weight) 25% by weight aqueous ammonia 3.4 Ammonium chloride 2.7 Ethanol 10.0 Propylene glycol 10.0 Dye shown in Table 3 0.05 Reducing agent shown in Table 3 0.5 Deionized water Agent) (wt%) 35 wt% hydrogen peroxide solution 17.1 ion exchange water

<Evaluation Method> For the hair dye (first agent: agent 2 agent = 1: 1 (weight)) immediately after preparation and after storage at 40 ° C. for 3 months, the same method and standard as in Example 1 were used. The dyeability was evaluated.

<Results> As can be seen from the results shown in Table 3, the storage stability of Basic Red 12 (a) with respect to an alkali agent and a reducing agent is significantly higher than that of the methine dye (b) described in WO99 / 07334. Even after storage, it maintains excellent dyeing properties on hair.

[0048]

[Table 3]

Examples 6 to 11 and Comparative Examples 10 to 13 Hair dyes shown in Table 4 (single-part formula) and Table 5 (two-part formula) were prepared, and their stability to alkali, oxidizing and reducing agents was obtained. Was evaluated.

<Evaluation method> For the one-part hair dye, the composition itself was used, and for the two-part hair dye, the first part and the second part of the first part were used.
Dyeing was carried out by applying one mixture (weight ratio) to the hair. (1) Regarding the dyeing power, 10 g of the above composition was applied to a gray hair bundle (weight 10 g) and left in a thermostat at 30 ° C. for 20 minutes. Next, it was rinsed with warm water, washed with shampoo and dried, and its dyeability was observed and evaluated according to the following criteria. (2) For discoloration, compare the color tone of the hair bundle after repeating shampoo washing 20 times with the color tone of the hair bundle before treatment,
Evaluation was made according to the following criteria. (3) The color tone change was evaluated according to the following criteria by comparing the color tone immediately after the production of the hair dye containing the direct dye (first agent in the case of the two-part system) and after storage at 40 ° C. for 6 months.

<Evaluation Criteria> (1) Dyeing power ：: Uniform and very good dyeing ○: Uniform and good dyeing △: Not much dyeing X: Almost no dyeing

(2) Discoloration A: Almost the same as before the treatment O: Slightly discolored by the treatment Δ: Discolored considerably by the treatment X: Discolored by the treatment

(3) Change in color tone ：: Almost the same as the color tone before storage ：: The color tone was slightly lightened by storage Δ: The color tone was considerably lightened by storage ×: The color tone was lightened by processing

<Results> As is evident from the results shown in Tables 4 and 5, Basic Red 12 (a) was compared with the methine dyes (b) and (c) described in WO99 / 07334 in terms of an alkali agent, an oxidizing agent, It has remarkably high stability to reducing agents, has excellent dyeing properties for hair, and maintains its dyeing properties even after storage.

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

The hair dye composition of the present invention has a high stability of the dye to an alkali agent, an oxidizing agent and a reducing agent, so that the color tone change of the agent upon storage is small and the hair dyeing power is extremely high. It is high and shows excellent light resistance, washing resistance, sweat resistance, rub resistance and heat resistance.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Sou Miyabe 2-1-3 Bunka, Sumida-ku, Tokyo F-term in Kao Corporation Research Laboratories 4C083 AB012 AB032 AB332 AB352 AB412 AC072 AC102 AC122 AC182 AC482 AC532 AC552 AC642 AC692 AC772 AC851 AC852 AD642 BB04 BB24 BB43 BB44 BB45 BB48 CC36 DD01 DD08 DD22 DD23 DD28 DD31 DD41 EE01 EE26 4C204 BB09 CB03 DB06 EB10 FB03 GB01

Claims (5)

[Claims] 1. A direct dye represented by the following general formula (1): [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 each} have 1 carbon atom
And R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ⁻ represents an anion. ] The hair dye composition containing the compound represented by these. 2. The hair dye composition according to claim 1, which has a pH of 5 or more. 3. The hair dye composition according to claim 1, which has a pH of 8 or more. 4. The hair dye composition according to claim 1, which is applied to hair after being mixed with an oxidizing agent. 5. The hair dye composition according to claim 1, further comprising an oxidation dye.