JP2003113055A - Hair-dyeing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair-dyeing agent composition, having astonishingly good hair-coloring property and compatibility to hydrogen peroxide, by which bright color which is stable to hair washing and environmental influence and is retained for a long period can be realized. SOLUTION: This hair-dyeing agent composition comprises a condensed heterocyclic direct dye represented by the general formula (1) [B represents a heterocyclic group having a structure such as a pyrazolotriazole structure, a imidazoloazole structure or a pyrroloazole structure; R<2> and R<3> are each hydrogen atom, a 1-5C alkyl group, an acylamino group, an alkylsulfonylamino group or an electron-attracting group] or its salt.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a hair dye containing a specific condensed heterocyclic direct dye, capable of dyeing hair in a vivid color tone, without fading, and stable to an oxidant. Agent composition.

[0002]

Hair dye compositions containing several anionic or cationic direct dyes are well known and unlike permanent hair dye compositions containing oxidative dye intermediates,
No coupling reaction with oxidant is required. Such direct hair dye compositions are often applied to the hair in the form of so-called color shampoos with surface-active ingredients or in the form of concentrated solutions such as lotions, emulsions or gels.

However, direct hair dye compositions of this type need to be improved in terms of their color retention, and in particular their color intensity, color uniformity and color luster. Furthermore, since the above direct dyes generally have the drawback that they cannot be used with alkaline peroxides, this direct hair dye composition
Generally applied to hair without peroxides. Therefore,
Such a direct hair dye composition does not have a decolorizing effect on hair.

[0004]

The object of the present invention is to use a direct dye as a base, to have excellent dyeing properties, to be able to brilliantly color hair without fading for a long period of time, lotions, emulsions, solutions, It is to provide a hair dye composition which can be applied to the hair in the form of a gel, suspension or in the form of an aerosol by addition of a propellant.

Another object of the present invention is to provide a hair dye composition which is based on the above-mentioned direct dye and has the above-mentioned properties and hair decolorizing power.

[0006]

These objects are achieved by a hair dye composition containing at least one specific direct dye which has good hair dyeing properties as well as compatibility with peroxides.

The present inventors have surprisingly found that when the condensed heterocyclic direct dye described below is used as a hair dye, the obtained hair dye composition results in a general oxidative hair dye composition. It was found that the hair can be colored more vividly and well compared with the case of using.

Furthermore, the present inventors have found that the condensed heterocyclic direct dyes described below have excellent stability against alkaline peroxides and contain at least one of the direct dyes described below. When the composition contains at least one peroxide, and preferably has a pH of 6.5 to 12.5, the hair bleaching power derived from the alkaline peroxide imparts more vividness to the hair, so that the hair is dyed. It was found that the effect can be further improved.

The present invention provides a direct dye of the following general formula
(1):

[0010]

[Chemical 8]

[Where B is the following general formula (B-1), (B-2), (B
-3) or (B-4):

[0012]

[Chemical 9]

Represents a heterocyclic group represented by:
a, Zb, Zc, Z ^1, Z ² and Z ³ nitrogen atom or a -C (R ⁵⁾ each independently are = represents a group, at least one -C (R ⁵⁾ = group of Zb and Zc And at least one of Z ¹ , Z ² and Z ³ is a nitrogen atom,

R¹, R^FourAnd R^FiveAre independently hydrogen atoms;
Rogen atom; one or more halogen atom, hydroxyl group, alkoxy group
Si group, aryloxy group, amino group, alkylamino
Group, hydroxyalkylamino group, acyl group, acyl group
Substituted with a mino group or an alkylsulfonylamino group
May be C_1-5Alkyl group; C_1-4Alkoxy group; C
_1-4Alkylthio group; Arylthio group; Heteroaryl
Thio group; benzylthio group; one or more hydroxyl groups or amino
Acyl group which may be substituted with an amino group; acylamino
Group; alkylsulfonylamino group; acyloxy group;
Lubamoyl group; alkylaminocarbonyl group; dialky
Luaminocarbonyl group; one or more halogen atoms, nitro
Group, sulfo group, alkylsulfonyl group, C_1-4Alkyl
Base, C_1-4Alkoxy group, C_1-3Fluoroalkyl group, a
Mino group, alkylamino group, hydroxyalkylamino
Group or substituted with an alkylsulfonylamino group
Optionally a phenyl group; substituted with one or more hydroxyl groups
Good alkoxycarbonyl group; aryloxycarbo
Nyl group; Heteroaryloxycarbonyl group; Cyano
Group; nitro group; dialkylphosphinyl group; alkyls
Rufinyl group; Arylsulfinyl group; Sulfamoy
Group; alkylaminosulfonyl group; dialkylamino
Sulfonyl group; carboxy group; sulfo group; one or more al
An aryloxy group which may be substituted with a cooxy group;
Teloaryloxy group; C_1-4Alkylamino group; Ure
Id group; sulfamoylamino group; alkoxycarbonyl
Ruamino group; aryloxycarbonylamino group; or
Represents a phosphonyl group,

R ² and R ³ are each independently a hydrogen atom, C
_{1-5 represents} an alkyl group, an acylamino group, an alkylsulfonylamino group or an electron-withdrawing group, and * represents a position bonded to the nitrogen atom in the general formula (1). ] The present invention provides a hair dye composition containing a condensed heterocyclic direct dye or a salt thereof.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The group (B-1) is represented by the following general formula (B-1-1) or (B-1-2) having a pyrazolotriazole structure:

[0017]

[Chemical 10]

[In the formula, each of R ¹ , R ⁵ and * has the same meaning as described above. ] The group represented by these is preferable.

The group (B-2) is represented by the following general formula (B-2-1), (B-2-2) or (B-2-3) having an imidazoloazole structure:

[0020]

[Chemical 11]

[In the formula, each of R ¹ , R ⁵ and * has the same meaning as described above. ] The group represented by these is preferable.

The group (B-3) has the following general formula (B-3-1) or (B-3-2) having a pyrroloazole structure:

[0023]

[Chemical 12]

[In the formula, each of R ¹ , R ⁴ , R ⁵ and * has the same meaning as described above. ] The group represented by these is preferable.

The group (B-4) has the following general formula (B-4-1) or (B-4-2) having a pyrroloazole structure:

[0026]

[Chemical 13]

[In the formula, each of R ¹ , R ⁴ , R ⁵ and * has the same meaning as described above. ] The group represented by these is preferable.

Of these, a group having a pyrazolotriazole structure is provided from the viewpoints of vividness and color retention of the obtained color.
(B-1-1) and (B-1-2) are the most preferable.

The group represented by R ¹ , R ⁴ or R ⁵ is
From the viewpoint of hair coloring strength, a hydrogen atom; one or more hydroxyl groups,
C optionally substituted with an alkoxy group, amino group, alkylamino group or alkylsulfonylamino group
_1-5 alkyl group; C _1-4 alkoxy group; or substituted with one or more halogen atom, C _1-4 alkyl group, C _1-4 alkoxy group, amino group, alkylamino group or alkylsulfonylamino group Particularly preferred are phenyl groups. Of these, a C _1-5 alkyl group having no substituent is most preferable from the viewpoint of hair coloring strength.

The pKa value of the compound represented by the general formula (1) is preferably from 2.5 to 9, particularly preferably from 3 to 8, and most preferably from the viewpoints of hair coloring performance and coloring of the obtained color.
3.5 to 7. The hydroxyl group on the benzene ring is dissociative (dis
sociative). For this reason, R ² and R ³ are preferably electron withdrawing groups. Dyes having a dissociative group are called dissociative dyes.

The dissociative dye means a dye capable of releasing a proton and becoming anionic at a certain pH value or more. PK above
The a value can be obtained by the following method. First, the sample is dissolved in a DMF / water (volume ratio 1: 1) solution to give a final concentration of 2 × 10 ⁻⁵ mol / L. The pH of the resulting solution was 1.0 mol /
After adjusting to 2 with L hydrochloric acid, this solution is titrated with 1.0 mol / L sodium hydroxide aqueous solution. The change in the visible-ultraviolet absorption spectrum is recorded, and the inflection point is obtained by regression analysis.

Particularly preferable examples of the electron withdrawing group represented by R ² and R ³ include an electron withdrawing group having a Hammett's σ _p value of 0.1 or more, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, Examples thereof include an alkoxycarbonyl group which may be substituted with one or more hydroxyl groups, a carbamoyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, a sulfamoyl group, an alkylaminosulfonyl group, a dialkylaminosulfonyl group and an acyl group. Of these, a fluorine atom, a chlorine atom and a bromine atom are most preferable from the viewpoint of dyeing strength. The Hammett rule is an empirical rule proposed by LP Hammet in 1935 to quantitatively discuss the influence of a substituent on the reaction or equilibrium of a benzene derivative, and it is widely accepted today. There are σ _p values and σ _m values for the substituent constants obtained by the Hammett's rule, and these values are described in many general textbooks. For example, see JA Dean, “Langes Handbook of Chemist”.
ry "12th edition, 1979 (McGraw-Hill) and" Special Issue on Chemistry ", No. 122, pp. 96-103, 1979 (Nankodo), Chemica
l Review, Volume 91, pp. 165-195, 1991.

For the above reasons, the most preferable compounds represented by the general formula (1) are represented by the following general formula (2) or (3).
And a salt thereof.

[0034]

[Chemical 14]

[Wherein R ¹ and R ⁵ are each a C _1-5 alkyl group which may be substituted with one or more hydroxyl groups, alkoxy groups, amino groups, alkylamino groups or alkylsulfonylamino groups; or The above halogen atom, C _1-4 alkyl group, C _1-4 alkoxy group, amino group, phenyl group which may be substituted with alkylamino group or alkylsulfonylamino group are shown, and R ² and R ³ are respectively Fluorine atom, chlorine atom, bromine atom, iodine atom, alkoxycarbonyl group optionally substituted by one or more hydroxyl groups, carbamoyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, sulfamoyl group, alkylaminosulfonyl group, dialkylamino An electron withdrawing group that can be selected from a sulfonyl group and an acyl group is shown. ]

The definitions of the above formulas R ^{1 to} R ⁵ will be described in more detail below.

Examples of the halogen atom represented by R ¹ , R ⁴ and R ⁵ include fluorine, chlorine, bromine and iodine. Particularly, chlorine and bromine are preferable.

Examples of the C _1-5 alkyl group represented by R ¹ , R ⁴ and R ⁵ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and t-butyl group. And a pentyl group.

Examples of the substituent which may substitute the above C _1-5 alkyl group are chlorine, bromine, hydroxyl group, methoxy group, ethoxy group, phenoxy group, amino group, methylamino group, dimethylamino group, 2-hydroxyethylamino group, bis (2-hydroxyethyl) amino group, acetyl group,
An acetylamino group and a methanesulfonylamino group are mentioned. Considering the solubility of the dye, in particular, hydroxyl group, methoxy group, ethoxy group, amino group, methylamino group, dimethylamino group, 2-hydroxyethylamino group, bis (2
-Hydroxyethyl) amino group and methanesulfonylamino group are preferred.

Examples of the C _1-4 alkoxy group represented by R ¹ , R ⁴ and R ⁵ are methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group and t-butoxy group. Groups. Particularly, a methoxy group and an ethoxy group are preferable.

Examples of the C _1-4 alkylthio group represented by R ¹ , R ⁴ and R ⁵ include a methylthio group and an ethylthio group.

Examples of the arylthio group represented by R ¹ , R ⁴ and R ⁵ include a phenylthio group, a 1-naphthylthio group and a 2-naphthylthio group.

Examples of the heteroarylthio group represented by R ¹ , R ⁴ and R ⁵ include a 2-pyridylthio group, a 3-pyridylthio group, a 4-pyridylthio group, a 2-imidazolothio group and a 3-pyridylthio group.
Examples include a pyrazolothio group.

Examples of the acyl group represented by R ¹ , R ⁴ and R ⁵ which may be substituted with one or more hydroxyl groups or amino groups include formyl group, acetyl group, hydroxyacetyl group, aminoacetyl group and Examples include a propionyl group.

Examples of the acylamino group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a formylamino group, an acetylamino group and a propionylamino group.

Examples of the alkylsulfonylamino group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a methanesulfonylamino group and an ethanesulfonylamino group.

Examples of the acyloxy group represented by R ¹ , R ⁴ and R ⁵ include an acetyloxy group and a propionyloxy group.

Examples of the alkylaminocarbonyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a methylaminocarbonyl group and an ethylaminocarbonyl group.

Examples of the dialkylaminocarbonyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a dimethylaminocarbonyl group and a diethylaminocarbonyl group.

Examples of the substituent which may be substituted on the phenyl group represented by R ¹ , R ⁴ and R ⁵ are fluorine, chlorine, bromine, iodine, nitro group, sulfo group, methanesulfonyl group and ethanesulfonyl group. Group, methyl group, ethyl group, methoxy group, ethoxy group, trifluoromethyl group, amino group,
Examples thereof include a methylamino group, a dimethylamino group, a 2-hydroxyethylamino group, a bis (2-hydroxyethyl) amino group and a methanesulfonylamino group. Especially, chlorine, bromine, amino group, methylamino group, dimethylamino group, 2-
Hydroxyethylamino group, bis (2-hydroxyethyl)
Amino groups and methanesulfonyl groups are preferred.

Examples of the alkoxycarbonyl group represented by R ¹ , R ⁴ and R ⁵ which may be substituted with one or more hydroxyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and 2-hydroxyethoxy group. A carbonyl group may be mentioned.

Examples of the aryloxycarbonyl group represented by R ¹ , R ⁴ and R ⁵ include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group and a 2-naphthyloxycarbonyl group.

Examples of the heteroaryloxycarbonyl group represented by R ¹ , R ⁴ and R ⁵ include a 2-pyridyloxycarbonyl group, a 3-pyridyloxycarbonyl group and a 4-pyridyloxycarbonyl group.

Examples of the dialkylphosphinyl group represented by R ¹ , R ⁴ and R ⁵ include a dimethylphosphinyl group and a diethylphosphinyl group.

Examples of the alkylsulfinyl group represented by R ¹ , R ⁴ and R ⁵ include a methylsulfinyl group and an ethylsulfinyl group.

Examples of the arylsulfinyl group represented by R ¹ , R ⁴ and R ⁵ include a phenylsulfinyl group.

Examples of the alkylaminosulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a methylaminosulfonyl group and an ethylaminosulfonyl group.

Examples of the dialkylaminosulfonyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a dimethylaminosulfonyl group and a diethylaminosulfonyl group.

Examples of the aryloxy group represented by R ¹ , R ⁴ and R ⁵ which may be substituted with one or more alkoxy groups include phenoxy group, 1-naphthyloxy group and 2-
Examples thereof include naphthyloxy group and dimethoxyphenoxy group.

Examples of the heteroaryloxy group represented by R ¹ , R ⁴ and R ⁵ include a 2-pyridyloxy group, a 3-pyridyloxy group and a 4-pyridyloxy group.

Examples of the C _1-4 alkylamino group represented by R ¹ , R ⁴ and R ⁵ include methylamino group, ethylamino group, propylamino group and butylamino group.

Examples of the alkoxycarbonylamino group represented by R ¹ , R ⁴ and R ⁵ include a methoxycarbonylamino group and an ethoxycarbonylamino group.

Examples of the aryloxycarbonylamino group represented by R ¹ , R ⁴ and R ⁵ include a phenoxycarbonylamino group.

Examples of the condensed heterocyclic direct dye represented by the general formula (1) of the present invention include DS-1 to DS-4 shown below.
The structure of 1 is mentioned.

[0065]

[Chemical 15]

[0066]

[Chemical 16]

[0067]

[Chemical 17]

[0068]

[Chemical 18]

The compounds represented by the general formulas (1), (2) and (3) of the present invention may be salts of organic or inorganic acids, or salts of organic or inorganic alkalis. Good. Examples of the organic or inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid and citric acid. Examples of the organic or inorganic alkali include ammonium hydroxide, 2-ethanolammonium hydroxide, sodium hydroxide and potassium hydroxide.

The preparation of the above fused heterocyclic direct dyes is in fact well known and is carried out by oxidative coupling of a substituted azoloazole with a substituted aminophenol derivative.

This oxidative coupling reaction can be carried out, for example, by the following procedure. First, the azoloazole and p-aminophenol are dissolved in an aqueous solution having a pH of 7 to 12, and then an appropriate amount of persulfate (eg, potassium persulfate) is added to this alkaline solution. The resulting solution is stirred for about 2 hours at room temperature to form the condensed heterocyclic direct dye (1).

The condensed heterocyclic direct dye (1) can be isolated, for example, by the following method. First, the obtained precipitate is collected by filtration, dried, and then extracted with acetone. After filtering the acetone solution to remove impurities,
Evaporation gives the condensed heterocyclic direct dye (1).

The color obtained is mainly dark pink to deep purple, but this color can be changed by adding one or more further dyes.

The proportion of the condensed heterocyclic direct dye in the composition according to the present invention depends on the structure of the dye and the desired chroma.
0.001 to the total composition, depending on
-5% by weight is suitable, preferably 0.01-2.5% by weight, particularly preferably 0.1-1% by weight.

A wide range of color nuances can be created by adding another direct dye for hair in addition to the fused heterocyclic direct dye represented by the formula (1).

As such a direct dye, so-called "Arianor-dyestuffs" are preferable (K. Schrader, "Grundlagen und Rezepturen der K.
osmetika ”, 2nd edition, (1989), p.811).

Particularly preferred basic (cationic) dyes are Basic Blue 6 (CI No. 51,175), Basic Blue 7 (CI No. 42,595), Basic Blue 9
(CINo.52,015), Basic Blue 26 (CINo.44,0
45), Basic Blue 41 (CINo.11,154), Basic Blue 99 (CINo.56,059), Basic Brown 4
(CINo.21,010), Basic Brown 16 (CINo.1
2,250), Basic Brown 17 (CINo.12,251), Basic Brown 7 (CINo.75,500), Basic Green 1 (CINo.42,040), Basic Red 2 (C.
I.No.50,240), Basic Red 12 (CINo.48,07)
0), Basic Red 22 (CINo.11,055), Basic Red 76 (CINo.12,245), Basic Violet 1 (CINo.42,535), Basic Violet 3
(CINo.42,555), Basic Violet 10 (CIN
o.45,170), Basic Violet 14 (CI No.42,51)
0), Basic Yellow 57 (CI No. 12,719), and the dyes disclosed in EP 0618464B1.

Naturally, vegetable direct dyes and / or
Alternatively, it is also possible to use a direct dye for anionic (acidic) hair. The following dyes can be used as suitable anionic dyes.

Acid Black 1 (CI No. 20,470),
Acid Blue 1 (CINo.42,045), Food Blue 5
(CINo.42,051), Acid Blue 9 (CINo.42,091
0), Acid Blue 74 (CINo.73,015), Acid Red 18 (CINo.16,255), Acid Red 27 (CINo.
16,185), Acid Red 87 (CINo.45,380), Acid Red 92 (CINo.45,410), Acid Orange 7
(CINo.15,510), Acid Violet 43 (CINo.
60,730), Acid Yellow 1 (CINo.10,316), Acid Yellow 23 (CINo.19,140), Acid Yellow 3 (CINo.47,005), Food Yellow 8 (CINo.1)
4,270), Acid Orange 24 (CINo.20,170), Acid Green 25 (CINo.61,570), Acid Orange 7 (CINo.15,510), Solvent Red 73 (CINo.4).
5,425: 1), Acid Red 95 (CINo.45,425), Solvent Red 43 (CINo.45,380: 2), Solvent Red 48 (CINo.45,410: 1), Acid Red 33 (CINo.
17,200), Acid Yellow 73 (CI No.45,350: 1 and
CINo.45,350), Hood Red 1 (CINo.14,700),
Food Yellow 3 (CI No.15,985).

Examples of the vegetable dyes include henna (red or black), arcana root, laccaic acid (Stocklack), indigo, logwood root powder, mud root, rhubarb powder, and the like. They can also be used alone or in combination with synthetic direct dyes.

These direct dyes are usually used in an amount of 0.005 to 5% by weight, preferably 0.05 to 2.5% by weight, particularly preferably 0.1 to 1% by weight, based on the total composition, and they are used as solutions, dispersions and emulsions. , Gel or aerosol form.

The composition according to the invention may comprise at least one oxidative dye intermediate (ie developer and / or coupler substance).

As developers, in particular, 1,4-diaminobenzene, 2,5-diaminotoluene, tetraaminopyrimidine, triaminohydroxypyrimidine, 1,2,4-triaminobenzene, 2- (2,5-diamino) Examples thereof include phenyl) ethanol, 2- (2-hydroxyethylamino) -5-aminotoluene, 1-amino-4-bis- (2-hydroxyethyl) aminobenzene and water-soluble salts thereof.

As the coupler, resorcin, 2-methylresorcin, 4-chlororesorcin, 2-amino-4-chlorophenol, 4- (N-methylamino) phenol, 2-aminophenol, 3-aminophenol, 1- Methyl-2-hydroxy-4-aminobenzene, 3- (N, N-dimethylamino) phenol, 4-amino-3-methylphenol, 5-amino-2-
Methylphenol, 6-amino-3-methylphenol, 3-
Amino-2-methylamino-6-methoxypyridine, 2-amino
-3-hydroxypyridine, 4-aminodiphenylamine,
4,4-diaminodiphenylamine, 2-dimethylamino-5-
Aminopyridine, 2,6-diaminopyridine, 1,3-diaminobenzene, 1-amino-3- (2-hydroxyethylamino) benzene, 1-amino-3- [bis (2-hydroxyethyl) amino] benzene, α-naphthol, 1,4-diamino-2-chlorobenzene, 4,6-dichlororesorcin, 1,3-diaminotoluene, 1-hydroxynaphthalene, 4-hydroxy-1,2-methylenedioxybenzene, 1,5- Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4-hydroxy-1,2-methylenedioxybenzene, 2,4-diamino-3-chlorophenol and / or 1-methoxy-2-amino -4- (2-hydroxyethylamino) benzene is mentioned. However, the present invention is not limited to the compounds exemplified above.

The developer and coupler substances are preferably contained in a molar ratio of 1: 3 to 5: 1, in particular 1:
1 to 3: 1 is preferable. The proportion of these components to be blended in the hair dye composition of the present invention depends on the desired color, but is preferably 0.05 to 5% by weight based on the entire composition.

Since the condensed heterocyclic direct dye (1) has excellent stability against alkaline peroxides, it can be used together with peroxides and can be bleached and colored at the same time. Therefore, the hair dye composition of the present invention can contain at least one peroxide and at least one condensed heterocyclic direct dye (1).

The peroxide used in the hair dye composition may be a diluted solution of hydrogen peroxide, an emulsion or a gel. Further, for example, an alkaline earth peroxide such as magnesium peroxide. , Urea peroxide, melamine peroxide, etc. can be used in suitable stoichiometric amounts. In addition, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, among others, can be included to increase the degree to which the hair is bleached. From the viewpoint of providing excellent bleaching power, it is preferable to use hydrogen peroxide and persulfate together. In particular, the pH value of the composition is 6.5-1
It is preferably adjusted to 2.5, more preferably 8 to 11.

Hair-Compone Containing Persulfate
nts), for example, K. Schrader's paper “Grundlagen
und Rezepturen der Kosmetika ”, 2nd edition, (1989), p.
Hydrogen peroxide solution (for example, 6 wt% of p.815-823)
A powder used by mixing with H ₂ O ₂ aqueous solution) is particularly preferable.

The hair dye composition of the present invention may further contain a surfactant. Anionic, nonionic, cationic, amphoteric or zwitterionic surfactants can be blended in the hair dye composition of the present invention, and when these surfactants are used in combination,
They have an affinity for each other.

Examples of the anionic surfactant include sulfate-based surfactants, sulfonate-based surfactants, carboxylate-based surfactants and alkylphosphate-based surfactants which are usually used in shampoos.

For example, as the sulfate type anionic surfactant, well-known C _10-18 alkyl sulfate, C _12-14 alkyl ether sulfate and lauryl ether sulfate (especially 1 to 4 ethylene oxide groups in the molecule) are used. With lauryl ether sulphate)
Suitable ether sulphates such as Furthermore,
Monoglyceride (ether) sulphate, fatty acid amide sulphate produced by introducing sulfate after ethoxylation of the corresponding fatty acid alkanolamide, their alkali metal salts and a typical mild detergent that can be applied to the skin. Certain long chain mono and dialkyl phosphate salts can be used.

Suitable sulfonate anionic surfactants include α-olefin sulfonates or salts thereof, especially sulfosuccinic acid half salts such as disodium salt of monooctyl sulfosuccinate, long chain monoalkyl ethoxy sulphosuccinate and the like. Examples include alkali metal salts of esters (half-ester).

Suitable carboxylate-based surfactants include alkyl polyether carboxylic acids represented by the following general formula (4) or salts thereof and alkamide polyethers represented by the following general formula (5). Examples thereof include carboxylic acids or salts thereof.

[0094]

[Chemical 19]

(Wherein R ⁶ is a C _8-20 alkyl group, preferably a C _12-14 alkyl group, X is a hydrogen atom or an ammonium cation which may be substituted with a sodium, potassium, magnesium or hydroxyalkyl group, a represents a number of 1 to 20, preferably 2 to 17, and b represents 1 to
It indicates a number of 10, preferably 2.5 to 5. )

Such products are well known and have been commercially available for a long time under the trade names of "AKYPO" and "AKYPO-SOFT".

Further, as a mixture with other surfactants,
_C8-20 acyl isethionates and sulfo fatty acids and their esters can also be used.

Mixtures of several anionic surfactants, for example mixtures of α-olefin sulphates with sulfosuccinates (preferably 1: 3 to 3: 1) or ether sulphates with polyether carboxylic acids or alkylamido ether carboxylic acids. And the like can be used.

Further, anionic surfactants which are usually used in liquid body cleansing agents can be used. An outline of these surfactants can be found in K. Schrader's monograph ["G
rundlagen und Rezepturen der Kosmetika ”, 2nd edition,
(1989, Huethig Buchverlag), pp.683-691].

Regarding the concentration of the anionic surfactant, 5
.About.50% by weight, especially 10 to 25% by weight are preferred. It is preferable to add these anionic surfactants to the color shampoo of the present invention, preferably 5 to 30% by weight, more preferably 7.5 to 25% by weight, particularly preferably 1% by weight based on the total composition.
It is compounded in an amount of 0 to 20% by weight.

Examples of the nonionic surfactant include alkyl polyglucosides represented by the following general formula (6).

[0102]

[Chemical 20]

[In the formula, R⁷Is C_8-20Alkyl group, preferred
Kuha C_10-14Represents an alkyl group, Z is C _5-6Saccharide
, P is a number from 0 to 10, q is a number from 1 to 5, preferably
Specifically, it indicates a number of 1.1 to 2.5. ]

Further preferred nonionic surfactants for use in the compositions of the present invention are C _10-22 aliphatic alkyl ethoxylates. C _10-22 aliphatic alcohol ethers are “Laureth” according to the CTFA nomenclature,
"Myristeth", "Oleth",
"Ceteth", "Deceth", "Steareth" and "Cetearet"
h) ”is known by a trade name in which the number of ethylene oxide is added (for example, Laureth-16), and the average number of ethylene oxide is 2.5 to 25, and 10 to 20 is appropriate.
Is preferred.

Examples of the nonionic surfactant that can be used in combination include sorbitan esters such as polyethylene glycol-sorbitan stearate, fatty acid polyglycol esters or fatty acid esters, and mixed polymerization of ethylene oxide and propylene oxide.
lymerized) polyglycol. These are "P
It is marketed under the trade name of "luronics".

Further usable surfactants are amineoxy.
It is Such amine oxides have always been the latest technology.
The technique is, for example, lauryl dimethylamine oxide, etc.
C _12-18Alkyldimethylamine oxide, C_12-18A
Lukylamidopropylamine oxide or alkyl
Amidoethylamine oxide, C_12-18Alkyldi
Droxyethyl) amine oxide or alkyldi
(Hydroxypropyl) amine oxide or alkyl chain
Ethylene oxide group and / or propylene oxide group
Amine oxides having Suitable Amine
Kisido is, for example, "Ammonyx", "Aromox", "Genam
It is marketed under the trade name such as "inox".

Further optional surfactant components include fatty acid mono and dialkanol amides such as coco fatty acid monoethanolamide and myristic acid isopropanolamide.

Suitable zwitterionic (zwitterionic) surfactants include, among others, known betaines such as fatty acid amidoalkyl betaines and sulfobetaines (eg, lauryl hydroxysulfobetaine). Further, long-chain alkyl amino acids such as cocoaminoacetic acid and cocoaminopropionic acid, sodium cocoamphopropionate and sodium cocoamphoacetate are also preferred examples. In particular, betaine or sulfobetaine represented by the following formulas (7) to (10) can be used.

[0109]

[Chemical 21]

[In the formula, R ⁸ represents a C _8-18 alkyl group,
n shows 1-3. ]

As preferred fatty acid amidoalkyl betaines, cocoamidopropyl betaine, cocoamphoacetic acid and cocoamphopropionate, and their sodium salts are particularly preferable. In particular, the mixing ratio of cocoamidopropyl betaine and cocoamphoacetic acid is 3: 1 by weight.
It is preferably 1: 3, particularly 2: 1 to 1: 1.

Suitable cationic surfactants include cetyltrimethylammonium chloride, dimethylstearylammonium chloride, trimethylcetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldihydrogenated tallow ammonium. Chloride, lauryl dimethyl benzyl ammonium chloride, behenyl trimethyl ammonium chloride,
Examples thereof include long-chain quaternary ammonium compounds such as lauryltrimethylammonium chloride, tris (oligooxyethyl) alkylammonium phosphate, and cetylpyridinium chloride, and these can be used alone or as a mixture. In addition, the European Patent Application Publication No.
The quaternary ammonium salts disclosed in 472,107 are also useful.

Other suitable long chain ammonium compounds include esters or amides of quaternary ammonium compounds represented by the general formula (11) or (12).

[0114]

[Chemical formula 22]

[Wherein, R ⁹ and R ¹⁰ each independently represent a C _8-22 alkyl group or alkenyl group which may be substituted with a hydroxyl group, and R ¹¹ and R ¹² each independently represent C _{1 -3} represents an alkyl or _{-CH 2 -CH 2 -O- (CH 2} CH 2 O) z -H , a group represented by, x, y and z each independently represents a 0 to 5, Y ^-
Represents an anion. ]

The anion Y ⁻ is preferably a halide ion such as Cl ⁻ or Br ⁻ , a lower alkylsulfate anion such as methylsulfate anion and ethylsulfate anion, or an alkylphosphate anion, but various general anions can also be used. Can be used.

Particularly preferably, in the formula (11), R ⁹ and R ¹⁰ are each independently an oleyl group or a C _12-18 alkyl group, R ¹¹ is a methyl group, and R ¹² is —CH ₂ —CH ₂ — O- (CH ₂ CH ₂ O) _z-
It is a compound represented by H. These compounds are already well known, for example "Schercoquat", "D
It is commercially available under trade names such as "ehyquart F30" and "Tetranyl". The use of these "esterquats" in hair conditioning agents is well known in practice, for example:
It is disclosed in WO 93/10748, 92/06799 and 94/16677 pamphlets.

If the composition according to the invention is not a color shampoo, it is preferred to use nonionic, amphoteric, zwitterionic and cationic surfactants in amounts of 0.5 to 5% by weight, based on the total composition.

[0119] The hair dye composition of the present invention preferably further comprises a C _3-6 alkane diol or an ingredient thereof ether (especially C _{1 -3} monoalkyl ether). The preferred solvent used in the composition of the present invention is 1,2-
Propanediol, 1,3-propanediol, 1-methoxy
-2-propanol, 1-ethoxy-2-propanol, 1,3-butanediol, 1,4-butanediol, diethylene glycol and their monomethyl- and monoethyl ethers and dipropylene glycol and their monomethyl- and monoethyl ethers Is mentioned. The content of these diols is preferably 0.5 to 3 with respect to the entire composition.
It is 0% by weight, more preferably 1 to 15% by weight, particularly preferably 5 to 10% by weight. Other than C _3-6 alkene diols and their ethers, monoalcohols such as ethanol, 1-propanol and 2-propanol; polyalcohols such as glycerin and hexanetriol; ethylcarbitol, benzyl alcohol, benzyloxyethanol. , Propylene carbonate (4-methyl-1,3-
Dioxan-2-one), N-alkylpyrrolidone, urea and the like are also suitable and useful.

As other components, cationic, anionic, nonionic and amphoteric polymers may be added,
They are preferably 0.1 to 5 relative to the entire hair dye composition.
It can be incorporated in an amount of% by weight, particularly preferably 0.25 to 2.5% by weight.

The hair dye composition of the present invention may further contain a conditioning agent such as oil and fat.
Sunflower oil, almond oil, peach kernel oil, malt oil, macadamia nut oil, evening primrose oil, jojoba oil, castor oil,
Examples are olive oil, soybean oil, lanolin and their derivatives, and mineral oils such as paraffin oil and petrolatum.

The compositions of the present invention may also include synthetic oils and waxes such as silicone oils and polyethylene glycols.

Further, as suitable hydrophobic compounds, particularly isopropyl myristate, isopropyl palmitate,
Isopropyl stearate, isopropyl isostearate, oleyl oleate, isocetyl stearate,
Hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate, oleyl erucate, fatty acid esters such as polyethylene glycol, PE
G-7-glyceryl cocoate, polyglycerin fatty acid ester such as cetyl palmitate, and the like can also be used.

When the hair dye composition of the present invention is used in the form of emulsion, it may contain an emulsifier usually used. Emulsifying agents include long chain fatty acids. As the fatty acid, a C _10-24 fatty acid, particularly a C _12-22 fatty acid is preferable, and these can be contained in an amount of 0.5 to 15% by weight, particularly 1 to 10% by weight based on the whole composition. Behenic acid and stearic acid are particularly preferred, but other fatty acids, for example myristic acid, palmitic acid, oleic acid, and mixtures of natural or synthetic fatty acids such as coco fatty acids can also be incorporated.

The hair dye composition according to the present invention was prepared by using a Brookfield rotational viscometer (No. 5 spindle, 5 rpm).
Measured at 20 ° C, preferably 1,000-60,000 mPa · s, especially
It has a viscosity of 5,000 to 50,000 mPa · s, especially 10,000 to 40,000 mPa · s.

The pH of the composition of the present invention is preferably 6.5 to 12.
The pH is adjusted to a neutral or alkaline range of 5, for example, 7.8 to 12, and particularly preferably to pH 8 to 11 at which the phenolic hydroxyl group is dissociated to obtain a good hair dyeing effect. Preferred alkalizing agents include ammonia, monoethanolamine; alkali metal carbonates and hydrogen carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Further, various alkalizing agents such as diethanolamine, triethanolamine, and hydroxyalkanolamines can be used.

When the composition of the present invention is a color shampoo, an anionic surfactant can be contained in addition to the above-mentioned surfactant.

In a preferred embodiment of the color shampoo according to the invention, a mixture of at least one of the abovementioned anionic surfactants and C _8-22 acylaminocarboxylic acids or their water-soluble salts is added to the overall composition. It is preferably included in an amount of 0.5 to 10% by weight, especially 1 to 7.5% by weight.

A particularly preferred N-acylaminocarboxylic acid or its water-soluble salt is N-lauroyl glutamate, especially its sodium salt. Other suitable N-acylaminocarboxylic acids are, for example, N-lauroyl sarcosinate, C
_12-18 N-acyl aspartic acid, N-myristoyl sarcosinate, N-oleoyl sarcosinate, N-lauroylmethylalanine, N-lauroyl lysine and N-lauroyl aminopropylglycine, preferably water-soluble thereof Alkali metal salt or ammonium salt, particularly preferably sodium salt.

The composition of the present invention further comprises a thickener, a fragrance,
Known cosmetic additives such as stabilizers, solubilizers, natural and / or synthetic polymers, chelating agents and the like can be included. The composition of these substances is basically known and is described, for example, in the monograph of K. Schrader (pp. 796-798).

The hair dye composition of the present invention can be applied in the form of any well-known hair coloring media, specifically, solutions, creams, emulsions, pastes, gels, (Foaming) aerosol and the like.

The hair dye composition of the present invention comprises a one-part composition, a two-part composition comprising a first part containing an alkalizing agent and a second part containing an oxidizing agent, and the above two-part composition according to a conventional method. In addition to the agent, it can be prepared as a three-part composition comprising a powdered oxidizing agent such as persulfate. Fused heterocyclic direct dyes (1)
Can be added to one or both of the first agent and the second agent in the two-part and three-part composition.

When dyeing hair, the one-part type is applied to the hair as it is, while the two-part or three-part type is applied to the hair after mixing the respective agents.

The treatment time with the present hair dye composition is preferably 10 to 60 minutes, but it can be shortened by the heat effect. The hair is then washed, rinsed and dried.

[0135]

The present invention will be described in detail below with reference to examples.

Dyes and Dyes DS- Obtained in Synthesis Examples I-III
Examples using 1 to DS-41 belong to the scope of the present invention. On the other hand, the dyes NDS-1 and NDS-2 obtained in Synthetic Examples IV and V and the examples using them are outside the scope of the present invention and are for comparison purposes only.

Synthesis Example I 3-Methyl-6-phenyl-1H-pyrazolo [5,1-c] [1,2,4] triazole (0.5 g) was added to an alkaline aqueous solution of pH 12 (50 ml).
Dissolved in. 4-amino-2,6 was added to the obtained aqueous solution with stirring.
-Dichlorophenol (0.5g) was added. When potassium persulfate (0.2g) was added to the obtained mixture, it turned dark purple. After stirring this mixture for 2 hours, the formed precipitate was collected by filtration. The recovered dark brown precipitate was dried and then dissolved in acetone. This acetone solution was filtered to remove impurities, and acetone was distilled off to obtain pyrazolotriazole direct dye DS-2 as a dark brown crystalline powder.

[0138]

[Chemical formula 23]

Synthesis Example II 6- (2-chlorophenyl) -3-methyl-1H-pyrazolo [5,1-c]
[1,2,4] Triazole (0.5 g) was dissolved in an alkaline aqueous solution (50 ml) having a pH of 12. To the obtained aqueous solution, under stirring, 4-
Amino-2,6-dichlorophenol (0.5g) was added.
When potassium persulfate (0.2g) was added to the obtained mixture, it turned dark purple. After stirring the mixture for 2 hours,
The formed precipitate was collected by filtration. The recovered dark brown precipitate was dried and then dissolved in acetone. This acetone solution was filtered to remove impurities, and acetone was distilled off to obtain pyrazolotriazole direct dye DS-1 as a dark brown crystalline powder.

[0140]

[Chemical formula 24]

Synthesis Example III 7-chloro-2,6-dimethyl-1H-pyrazolo [5,1-b] [1,2,4] triazole (24.4 g) and potassium carbonate (98.8 g)
Water (100 ml), ethyl acetate (120 ml) and ethanol (60
ml). Here, under stirring, 4-amino
-2,6-Dichlorophenol (27.9g) was added. To this mixture, aqueous ammonium persulfate solution (39.3g / 100ml water)
Was slowly added over 40 minutes, and the solution turned dark purple. After stirring the mixture for 2 hours, water (500 ml) was added. When concentrated hydrochloric acid (75 ml) was slowly added here,
The solution was brownish yellow. After stirring this mixture for 30 minutes,
The precipitate was collected by filtration. The damp brown-yellow precipitate was added to acetonitrile. Acetonitrile solution 20
After refluxing for a minute, it was cooled to room temperature. The resulting precipitate was collected by filtration and dried. Pyrazolotriazole direct dye DS-3 was obtained as a yellow powder (39.6 g, yield 89
%).

[0142]

[Chemical 25]

Dyes DS-3 to DS-41 were prepared by a procedure similar to Synthesis Examples I, II and III.

Synthesis Example IV (outside the scope of the present invention) 6- (2-chlorophenyl) -3-methyl-1H-pyrazolo [5,1-c]
[1,2,4] Triazole (0.5 g) was dissolved in an alkaline aqueous solution (50 ml) having a pH of 12. The resulting aqueous solution, while stirring, 2,
5-Diaminotoluene (0.5g) was added. When potassium persulfate (0.2g) was added to the obtained mixture, it turned dark purple. After stirring this mixture for 2 hours, the formed precipitate was collected by filtration. The recovered dark brown precipitate was dried and then dissolved in acetone. This acetone solution was filtered to remove impurities, and acetone was distilled off to obtain pyrazolotriazole direct dye NDS-1 as a dark brown crystalline powder.

[0145]

[Chemical formula 26]

Synthesis Example V (outside the scope of the present invention) 6- (2-chlorophenyl) -3-methyl-1H-pyrazolo [5,1-c]
[1,2,4] Triazole (0.5 g) was dissolved in an alkaline aqueous solution (50 ml) having a pH of 12. The resulting aqueous solution was stirred with N,
N-diethyl-p-phenylenediamine (0.5g) was added. When potassium persulfate (0.2g) was added to the obtained mixture, it turned dark purple. After stirring this mixture for 2 hours, the formed precipitate was collected by filtration. The recovered dark brown precipitate was dried and then dissolved in acetone. This acetone solution was filtered to remove impurities, and acetone was distilled off to obtain pyrazolotriazole direct dye NDS-2 as a dark brown crystalline powder.

[0147]

[Chemical 27]

Examples 1 to 4 Dyeing In Examples 1 to 4, 1 bundle of undamaged white goat hair was dipped in the solution shown in Table 1 (30 ° C.) for 20 minutes. The goat hair was then shampooed, rinsed and dried. For each example, the L value, a value, and b value of the dyed hair were measured with a Minolta color measuring device, and the ΔE value, which is a well-known measure of chroma, was measured by a usual method. It calculated (it is the same also in each following example).
The results are shown in Table 2.

[0149]

[Table 1]

[0150]

[Table 2]

The compositions of Examples 1 and 2 gave a bright and bright magenta color, while the compositions of Examples 3 and 4 gave only a faint pink dull color. From the comparison of these respective examples, in contrast to the structure-similar direct dyes having no dissociative protons (Examples 3 and 4), the direct dyes according to the present invention having a dissociative proton (Examples 1 and 2) were used. ) Shows a surprising advantage.

Examples 5 to 6 Staining Each composition shown in Table 3 was prepared and applied (50 ° C., 15 minutes) to an undamaged white goat hair bundle and an undamaged human blonde. Thereafter, the hair tresses were shampooed, rinsed and dried. The results are shown in Tables 4 and 5.

[0153]

[Table 3]

[0154]

[Table 4]

[0155]

[Table 5]

The compositions of Examples 5 and 6 imparted a bright and vivid magenta color to both undamaged white goat hair tresses and to undamaged human blond hair.

Examples 7 to 15 Goat Hair and Human Hair
Dyeing Pyrazolotriazole direct dye DS-3, DS-4, DS-6, DS-7
And any one of DS-12 to DS-16, and a composition having a general composition shown in Table 6 was prepared. Each composition was applied to one bundle of undamaged white goat hair (50 ° C, 20 minutes, one bundle of hair).
coated with 1.5-2 g of composition per gram). After 20 minutes, the hair tresses were rinsed, washed with shampoo and dried. After that, color evaluation was performed. The results are shown in Table 7.

[0158]

[Table 6]

[0159]

[Table 7]

Examples 16 and 17 Staining with hydrogen peroxide One bundle of undamaged white goat hair was immersed in the solutions shown in Table 8 (30 ° C) for 20 minutes. The goat hair was then shampooed, rinsed and dried. The results are shown in Table 9.

[0161]

[Table 8]

[0162]

[Table 9]

The compositions of Examples 16 and 17 impart a bright magenta color.

Examples 18-21 Compatibility with Hydrogen Peroxide Compositions containing the pyrazolotriazole direct dye DS-4 or DS-6 and having the general composition shown in Table 10 below were prepared. Each composition was applied to one bun of undamaged human blonde (50
℃, 20 minutes). After 20 minutes, the tresses were rinsed, shampooed and dried. After that, color evaluation was performed. Red (a
Table 11 shows the changes in the values.

[0165]

[Table 10]

[0166]

[Table 11]

Since the dyes DS-4 and DS-6 were stable to alkaline peroxides, the compositions of Examples 20 and 21 containing hydrogen peroxide were the same as those of Examples 18 and 19 containing no hydrogen peroxide.
It gave a more vivid red color than the composition.

Examples 22-25 Compatibility with Peroxides The compositions of Examples 22-25 shown in Table 12 were applied to Chinese black hair tresses and left at 50 ° C. for 30 minutes. Thereafter, the hair tresses were shampooed, rinsed and dried. The results are shown in Table 13.

[0169]

[Table 12]

[0170]

[Table 13]

The compositions of Examples 22-24 impart a bright magenta color. These compositions provided a pronounced bleaching effect and a strong red coloring effect.

Examples 26 and 27 Compatibility with Oxidative Dyes Both compositions shown in Table 14 were applied (50 ° C., 15 minutes) to a white goat hair bundle. Thereafter, the hair tresses were shampooed, rinsed and dried. The results are shown in Table 15.

[0173]

[Table 14]

[0174]

[Table 15]

The composition of Example 26 imparted a red gold brown color while the composition of Example 27 imparted a light brown color with no reddish tone.

The hair dye composition according to the present invention also provides a long-lasting bright color based on the characteristics of the condensed heterocyclic direct dye. Compared with conventional direct dyes, this color is more durable against environmental effects such as hair washing, sunlight, sweat and rain.

Examples 28 and 29 The wash fastness of DS-4 dyed damaged hair was compared to a conventional oxidative dye combination. Apply the composition of the formula shown in Table 16 to a human blonde with a perm (50 ° C, 15 minutes)
did. Both hair bundles were dyed dark magenta. Then, it was subjected to a shampoo washing protocol and the degree of discoloration due to washing was measured. The shampoo washing protocol consists of applying 0.1 g of shampoo per 1 g of hair, massaging the hair for 30 seconds and rinsing with warm water at 40 ° C. for 30 seconds. Repeat this process 20 times. The L value, a value, and b value before and after this processing cycle and the color change after the processing cycle were calculated. The results are shown in Table 17.

[0178]

[Table 16]

[0179]

[Table 17]

Surprisingly, the dyestuffs according to the invention show almost no fading by washing, as compared with conventional oxidative dyeing results.

Example 30 Measurement of pKa Value The pKa values of the dyes DS-3 to DS-5, DS-7 and DS-10 were determined by the following method. The dye was dissolved in a solution of DMF / water (volume ratio 1: 1) to give a final concentration of 2 × 10 ⁻⁵ mol / L. The pH of the obtained solution was adjusted to pH 2 with 1.0 mol / L hydrochloric acid, and then the solution was titrated with 1.0 mol / L sodium hydroxide aqueous solution. The change in the visible-ultraviolet absorption spectrum was recorded and the inflection point was determined by regression analysis. The results are shown in Table 18.

[0182]

[Table 18]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 7, 2002 (2002.6.7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0141

[Correction method] Change

[Correction content]

Synthesis Example III 7-Chloro-2,6-dimethyl-1H-pyrazolo [1,5-b] [1,2,4] triazole (24.4 g) and potassium carbonate (98.8 g) were added.
Water (100 ml), ethyl acetate (120 ml) and ethanol (60
ml). Here, under stirring, 4-amino
-2,6-Dichlorophenol (27.9g) was added. To this mixture, aqueous ammonium persulfate solution (39.3g / 100ml water)
Was slowly added over 40 minutes, and the solution turned dark purple. After stirring the mixture for 2 hours, water (500 ml) was added. When concentrated hydrochloric acid (75 ml) was slowly added here,
The solution was brownish yellow. After stirring this mixture for 30 minutes,
The precipitate was collected by filtration. The damp brown-yellow precipitate was added to acetonitrile. Acetonitrile solution 20
After refluxing for a minute, it was cooled to room temperature. The resulting precipitate was collected by filtration and dried. Pyrazolotriazole direct dye DS-3 was obtained as a yellow powder (39.6 g, yield 89
%).

   ─────────────────────────────────────────────────── ─── Continued front page    (31) Priority claim number Japanese Patent Application No. 2001-231327 (P2001-231327) (32) Priority date July 31, 2001 (July 31, 2001) (33) Priority claiming country Japan (JP) (72) Inventor Toshio Kawagishi             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Hui             Inside Rum Co., Ltd. F-term (reference) 4C083 AB082 AB411 AB412 AC102                       AC152 AC472 AC552 AC782                       AC851 AC852 BB24 DD23                       DD27 EE01 EE05 EE07 EE26                       FF05                 4H057 AA01 BA04 CA07 CA12 CB16                       CB21 CB45 CB46 CC02 DA01                       DA21

Claims (6)

[Claims] 1. A direct dye of the following general formula (1): [Chemical 1] [In the formula, B is the following general formula (B-1), (B-2), (B-3) or (B-
Four): [Chemical 2] Represents a heterocyclic group represented by, where Za, Zb, Zc,
Z¹, Z²And Z³Are each independently a nitrogen atom or -C (R^Five)
= Group and at least one of Zb and Zc is -C.
(R^Five) = Group and Z¹, Z²And Z³At least one of
One is a nitrogen atom, R¹, R^FourAnd R^FiveAre independently hydrogen atom; halogen atom;
One or more halogen atom, hydroxyl group, alkoxy group, aryl
Luoxy group, amino group, alkylamino group, hydroxy
Alkylamino group, acyl group, acylamino group or
C optionally substituted with an alkylsulfonylamino group
_1-5Alkyl group; C_1-4Alkoxy group; C _1-4Alkylchi
Group; arylthio group; heteroarylthio group; benzyl
Ruthio group; substituted with one or more hydroxyl or amino groups
Optionally substituted acyl group; acylamino group; alkylsulfur
Honylamino group; Acyloxy group; Carbamoyl group;
Rukylaminocarbonyl group; dialkylaminocarbonyl
Group; one or more halogen atom, nitro group, sulfo group,
Rukylsulphonyl group, C_1-4Alkyl group, C_1-4Arcoki
Shi group, C_1-3Fluoroalkyl group, amino group, alkyl
Amino group, hydroxyalkylamino group or alk
Phenyl optionally substituted with a sulfonylamino group
Group; alkoxy optionally substituted with one or more hydroxyl groups
Carbonyl group; Aryloxycarbonyl group; Heteroa
Reel oxycarbonyl group; cyano group; nitro group; dia
Rucylphosphinyl group; Alkylsulfinyl group; Ali
Sulphinyl group; sulfamoyl group; alkylami
Nosulfonyl group; dialkylaminosulfonyl group; cal
Boxy group; sulfo group; substituted with one or more alkoxy groups
Optionally substituted aryloxy group; heteroaryloxy
Group; C_1-4Alkylamino group; ureido group; sulfamo
Ilamino group; alkoxycarbonylamino group; aryl
Or a phosphonyl group
Then R²And R³Are each independently a hydrogen atom, C_1-5Alkyl
A group, an acylamino group, an alkylsulfonylamino group or
Shows an electron-withdrawing group, * Indicates the position of bonding with the nitrogen atom in formula (1). ]
Dyes containing condensed heterocyclic direct dyes or salts thereof
Agent composition. 2. A group having a pyrazolotriazole structure and represented by the following formula (B-1-1) or (B-1-2): [In the formula, R ¹ , R ⁵ and * each have the same meaning as described in claim 1. ], A group having an imidazoloazole structure and represented by the following formula (B-2-1), (B-2-2) or (B-2-3): [In the formula, R ¹ , R ⁵ and * each have the same meaning as described in claim 1. ], A group having a pyrroloazole structure and represented by the following formula (B-3-1) or (B-3-2): [In the formula, R ¹ , R ⁴ , R ⁵ and * each have the same meaning as described in claim 1. ] Or a group having a pyrroloazole structure and represented by the following formula (B-4-1) or (B-4-2): [Wherein, R ¹ , R ⁴ , R ⁵ and * each have the same meaning as described in claim 1. ] The hair dye composition according to claim 1. 3. A condensed heterocyclic direct dye (1) has the following general formula (2) or (3): [Wherein each of R ¹ and R ⁵ is a C _1-5 alkyl group which may be substituted with one or more hydroxyl groups, alkoxy groups, amino groups, alkylamino groups or alkylsulfonylamino groups; or one or more halogens. Atom, C _1-4 alkyl group,
C _1-4 represents a phenyl group which may be substituted with an alkoxy group, an amino group, an alkylamino group or an alkylsulfonylamino group, R ² and R ³ are each a fluorine atom, a chlorine atom, a bromine atom,
It may be selected from an iodine atom, an alkoxycarbonyl group which may be substituted with one or more hydroxyl groups, a carbamoyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, a sulfamoyl group, an alkylaminosulfonyl group, a dialkylaminosulfonyl group or an acyl group. An electron withdrawing group is shown. ] The hair dye composition of Claim 1 which is a compound represented by these. 4. At least one fused heterocyclic direct dye
The hair dye composition according to any one of claims 1 to 3, which comprises 0.001 to 5% by weight of (1) based on the entire composition. 5. The hair dye composition according to claim 1, further comprising at least one oxidative dye intermediate. 6. The hair dye composition according to claim 1, further comprising at least one peroxide.