JP5339696B2 - Hair dye composition - Google Patents

Description

  The present invention relates to a hair dye composition containing an azo dye.

  As a representative example of a hair dye composition, a two-component permanent hair dye comprising a first agent containing an alkaline agent, an oxidation dye, and optionally a direct dye such as a nitro dye, and a second agent containing an oxidizing agent. And a one-component semi-permanent hair dye containing an organic acid or an alkali agent and at least one direct dye such as an acid dye, a basic dye or a nitro dye.

  Permanent hair dyes have the disadvantage that the color tone imparted by the oxidation dye is not so vivid, and attempts to obtain a vivid color by using a direct dye and an oxidation dye in general have been made. Among the dyes, nitro dyes have a problem that the dyed hair has a faint discoloration, and immediately after the hair is dyed, the color tone is very vivid, but the vividness quickly disappears.

  Further, the range of direct dyes that can be used in combination with an oxidation dye is limited in that it is required to be stable against peroxides during the hair dyeing process.

  In addition, various acid dyes, basic dyes, and nitro dyes used for permanent hair dyes and semi-permanent hair dyes, in any case, the direct dye on hair is lost relatively easily by washing and light. Therefore, it is easy to fade, which is significant in damaged hair.

  Therefore, as one method for solving the problems of resistance to light, washing, sweat, friction and heat (fastness), hair dyes using direct dyes having dissociative protons have been proposed (Patent Documents 1 and 2). reference). However, in hair dyes using direct dyes, it is widely practiced to mix a plurality of dyes having the same hue to appropriately harmonize the dyeability and discoloration at the hair tips and roots (Non-patent Document 1). And dissociable azo dyes having different structural characteristics are desired.

JP 2004-107343 A JP 2006-182653 A Clarence R. Robbins, Chemical and Physical Behavior of Human Hair 4th Ed., Pp331-334, Springer-Verlag, 2002

  An object of the present invention is a hair dye composition containing a dissociable azo dye, the dye is stable against an alkalizing agent and an oxidizing agent, does not decompose during hair dyeing, has high dyeing power, and is bright on hair. Hair dye composition that can give a solid color firmly, has excellent fastness to light, washing, sweat, friction and heat, and less fade over time, and hair dyeing using the same Is to provide a method.

  The present inventors have found that the above problem can be solved by blending a dissociable azo dye represented by the following general formula (1) into a hair dye composition.

  That is, the present invention provides a hair dye composition containing a dissociable azo dye represented by the following general formula (1).

[Wherein, R ₁ represents a hydroxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or —CH (R ₂ ) (R ₃ ) (R ₂ and R ₃ each represent a substituent having a Hammett σ value of 0.2 or more and less than 1.4. Group). W represents a sulfur atom or N—R ₄ (R ₄ represents a substituent). X, Y and Z represent a nitrogen atom or a carbon atom, and at least one of them is a nitrogen atom, but only Z is not a nitrogen atom. R ₅ and R ₆ each represent a substituent. n represents 0 to 2, and when n is 2, two R ₆ may be bonded to each other to form an aromatic ring or a heteroaromatic ring. ]

  Furthermore, this invention provides the hair dyeing method which applies said hair dye composition to hair.

  In the hair dye composition of the present invention, the dye is stable with respect to the alkalizing agent and the oxidizing agent, does not cause decomposition at the time of hair dyeing, has high dyeing power, and can firmly impart a vivid color to the hair. It has excellent fastness to light, washing, sweat, friction and heat, and there is little discoloration over time.

  The hair dye composition referred to in the present invention is not only a one-component composition but also a two-part agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, which are stored separately until just before use. In addition to the first composition and the second composition, in addition to the first composition and the second composition, a multi-part composition such as a three-part composition composed of a third composition containing an oxidizing aid is included. Refers to the entire composition mixed and actually applied to the hair.

Examples of R _{4 to} R ₆ include, for example,
・ Halogen atoms (for example, fluorine, chlorine, bromine)
・ Hydroxyl group, amino group, mercapto group, alkyl group (straight chain, branched chain or cyclic alkyl group having 1 to 15, preferably 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group , Isopropyl group, s-butyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group)
Alkenyl groups (straight chain, branched chain or cyclic alkenyl groups having 2 to 10, preferably 2 to 6 carbon atoms, such as vinyl, allyl, prenyl, cyclopenten-1-yl)
Alkynyl groups (alkynyl groups having 2 to 10, preferably 2 to 6 carbon atoms, eg ethynyl groups, propargyl groups)
Aryl group (aryl group having 6 to 16, preferably 6 to 10 carbon atoms, for example, phenyl group, o-tolyl group, p-tolyl group, naphthyl group)
A heterocyclic group (1 to 12, obtained by removing one hydrogen atom from a 5- to 10-membered, preferably 5- or 6-membered, aromatic or non-aromatic heterocyclic compound, Preferably monovalent groups having 2 to 6 carbon atoms, such as 1-pyrazolyl group, 1-imidazolyl group, 2-furyl group, 2-thienyl group, 4-pyrimidinyl group, 2-pyridyl group, 2-benzothiazolyl Group, 2-tetrahydrofuryl group, 2-morpholyl group)
Nitro group, cyano group, carbamoyl group, sulfamoyl group, acyl group (formyl group, alkylcarbonyl group having 2 to 10, preferably 2 to 6, carbon atoms, 7 to 12, preferably 7 to 9 An arylcarbonyl group having 2 or 12 carbon atoms, or a heterocyclic carbonyl group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as formyl group, acetyl group, propionyl group, pivaloyl group, benzoyl group, 2- Pyridylcarbonyl group)
Alkoxycarbonyl groups (alkoxycarbonyl groups having 2 to 10, preferably 2 to 6 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, isobutyloxycarbonyl group)
Aryloxycarbonyl group (aryloxycarbonyl group having 7 to 12, preferably 7 to 9 carbon atoms, such as phenoxycarbonyl group, naphthoxycarbonyl group)
Heterocyclic oxycarbonyl groups (heterocyclic oxycarbonyl groups having 1 to 12, preferably 2 to 6 carbon atoms, such as 1-pyrazolyloxycarbonyl group, 1-imidazolyloxycarbonyl group, 2-furyloxycarbonyl group 2-thienyloxycarbonyl group, 2-tetrahydrofuryloxycarbonyl group, 2-morpholyloxycarbonyl group)
-Imido groups (imide groups having 2 to 10, preferably 4 to 8 carbon atoms, such as N-succinimide groups and N-phthalimide groups)
Alkylsulfinyl groups (alkylsulfinyl groups having 1 to 10, preferably 1 to 6 carbon atoms, such as methylsulfinyl group, ethylsulfinyl group)
Arylsulfinyl group (arylsulfinyl group having 6 to 12, preferably 6 to 8 carbon atoms, such as phenylsulfinyl group)
Alkylsulfonyl groups (alkylsulfonyl groups having 1 to 10, preferably 1 to 6 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, cyclohexylsulfonyl group)
Arylsulfonyl group (arylsulfonyl group having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenylsulfonyl group)
-Heterocyclic sulfonyl group (heterocyclic sulfonyl group having 1 to 12, preferably 2 to 6, carbon atoms, such as 2-tetrahydropyranylsulfonyl group)
-A phosphanyl group, a phosphoryl group, and a phosphinoyl group are mentioned.

  Moreover, the group which these substituents have further 1 or 2 or more substituents can also be mentioned. In that case, the group to be substituted preferably includes the groups exemplified above as the substituent. Here, when it has two or more substituents, the substituents may be the same or different.

As such a substituent having a substituent, for example,
As an alkyl group or an aryl group with a substituent,
Aralkyl groups (aralkyl groups having 7 to 18, preferably 7 to 12 carbon atoms, such as benzyl and phenethyl groups)
Haloalkyl groups (straight, branched or cyclic alkyl groups having 1 to 15, preferably 1 to 6 carbon atoms, such as chloromethyl, 2-chloroethyl, 2-bromopropyl, 3-bromo Propyl group)
Haloaryl groups (haloaryl groups having 6 to 12, preferably 6 to 8 carbon atoms, such as p-chlorophenyl, 2,4-dichlorophenyl, 3-fluorophenyl)
Hydroxyalkyl groups (linear, branched or cyclic alkyl groups having 1 to 15, preferably 1 to 6 carbon atoms, such as hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3 -Hydroxypropyl group)

As a substituent with a hydroxyl group,
Alkoxy groups (straight chain, branched chain or cyclic alkoxy groups having 1 to 10, preferably 1 to 6 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, cyclopentyloxy )
An alkenyloxy group (a linear, branched or cyclic alkoxy group having 2 to 10, preferably 2 to 6 carbon atoms, such as a 2-buten-1-yloxy group)
Aryloxy groups (aryloxy groups having 6 to 12, preferably 6 to 10 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group)
-Silyloxy groups (silyloxy groups having 3-10, preferably 3-6 carbon atoms, such as trimethylsilyloxy group, t-butyldimethylsilyloxy group)
Heterocyclic oxy groups (heterocyclic oxy groups having 1 to 12, preferably 2 to 6, carbon atoms, such as 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group)
Alkylsulfonyloxy groups (straight chain, branched chain or cyclic alkylsulfonyloxy groups having 1 to 10, preferably 1 to 6 carbon atoms, such as methanesulfonyloxy groups, ethanesulfonyloxy groups)
Arylsulfonyloxy group (arylsulfonyloxy group having 6 to 12, preferably 6 to 10 carbon atoms, for example, phenylsulfonyloxy group)
Heterocyclic sulfonyloxy group (heterocyclic sulfonyloxy group having 1 to 12, preferably 2 to 6 carbon atoms, for example, 2-pyridylsulfonyloxy group)
Acyloxy group (acyloxy group having 1 to 12, preferably 1 to 8 carbon atoms, such as formyloxy group, acetyloxy group, pivaloyloxy group, benzoyloxy group)
Carbamoyloxy group (carbamoyloxy group having 1 to 10, preferably 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group)
Alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having 2 to 10, preferably 2 to 8 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octyloxy Carbonyloxy group)
Aryloxycarbonyloxy group (aryloxycarbonyloxy group having 7 to 12, preferably 7 to 10 carbon atoms, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group)
-Dialkylphosphinyloxy groups (phosphinyloxy groups having 2 to 12, preferably 2 to 6 carbon atoms, such as diphenoxyphosphinyloxy groups, dibutoxyphosphinyloxy groups)

As an amino group with a substituent,
Alkylamino groups (alkylamino groups having 1 to 20, preferably 1 to 12 carbon atoms, such as methylamino group, dimethylamino group, cyclohexylmethylamino group, 1-pyrrolidyl group)
Arylamino groups (arylamino groups having 6 to 16, preferably 6 to 12 carbon atoms such as anilino group, N-methylanilino group, diphenylamino group)
Heterocyclic amino groups (heterocyclic amino groups having 1 to 12, preferably 2 to 6 carbon atoms such as 2-pyridylamino, pyrazol-4-ylamino, benzimidazol-2-ylamino, benzo Thiazol-2-ylamino group, benzooxazol-2-ylamino group, 2-oxazolylamino group, 1,2,4-triazol-3-ylamino group, 1,2,4-thiadiazol-2-ylamino group, 1 , 3,4-thiadiazol-2-ylamino group, 1,2,4-oxadiazol-2-ylamino group, 1,3,4-oxadiazol-2-ylamino group)
Acylamino groups (alkylcarbonylamino groups having 1-10, preferably 1-6 carbon atoms, arylcarbonylamino groups having 6-18, preferably 6-12 carbon atoms, or 2-12 , Preferably a heterocyclic carbonylamino group having 2 to 6 carbon atoms, such as formylamino group, acetylamino group, ethylcarbonylamino group, pivaloylamino group, benzoylamino group, 4-pyridylcarbonylamino group)
A ureido group (aminocarbonylamino group having 1 to 12, preferably 1 to 8 carbon atoms, for example, carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, Morpholin-4-ylcarbonylamino group)
Alkoxycarbonylamino groups (alkoxycarbonylamino groups having 2 to 10, preferably 2 to 6 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group)
Aryloxycarbonylamino group (aryloxycarbonylamino group having 7 to 12, preferably 7 to 9 carbon atoms, for example, phenoxycarbonylamino group)
A heterocyclic oxycarbonylamino group (a heterocyclic oxyamino group having 1 to 12, preferably 2 to 6 carbon atoms, such as a 2-pyridyloxycarbonylamino group)
Sulfamoylamino groups (sulfamoylamino groups having 0 to 10, preferably 0 to 6 carbon atoms, such as sulfamoylamino groups, N, N-dimethylaminosulfonylamino groups)
Alkylsulfonylamino groups (alkylsulfonylamino groups having 1 to 10, preferably 1 to 6 carbon atoms, such as methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group)
-Arylsulfonylamino group (arylsulfonylamino group having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenylsulfonylamino group)
-Phosphinylamino group (phosphinylamino group having 2 to 12, preferably 2 to 6 carbon atoms, such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group)

As a mercapto group with a substituent,
Alkylthio groups (alkylthio groups having 1 to 10, preferably 1 to 6 carbon atoms such as methylthio, ethylthio, butylthio)
Arylthio group (arylthio group having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenylthio group)
-Heterocyclic thio group (heterocyclic thio group having 2 to 10, preferably 1 to 6 carbon atoms, such as -2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group)

As a carbamoyl group with a substituent,
Alkylcarbamoyl groups (carbamoyl groups having 1 to 12, preferably 1 to 8 carbon atoms such as methylcarbamoyl group, dimethylcarbamoyl group, diethylcarbamoyl group, 1-pyrrolidylcarbonyl group)
Sulfamoylcarbamoyl groups (sulfamoylcarbamoyl groups having 1 to 12, preferably 1 to 8 carbon atoms, such as N- (sulfamoyl) carbamoyl groups, N- (N ′, N′-dimethylsulf Famoyl) carbamoyl group)

As a sulfamoyl group with a substituent,
Alkylsulfamoyl groups (alkylsulfamoyl groups having 1 to 12, preferably 1 to 6 carbon atoms, such as ethylsulfamoyl group, dimethylsulfamoyl group, dibutylsulfamoyl group, dimethyl Sulfamoyl group, diethylsulfamoyl group, N-cyclohexyl-N-methylsulfamoyl group)
Arylsulfamoyl groups (arylsulfamoyl groups having 6 to 12, preferably 6 to 8 carbon atoms, for example phenylsulfamoyl groups)
Carbamoylsulfamoyl group (carbamoylsulfamoyl group having 1 to 12, preferably 1 to 6 carbon atoms, for example, N- (carbamoyl) sulfamoyl group)

As a phosphoryl group with a substituent,
Alkyl phosphoryl groups (alkyl phosphoryl groups having 1 to 12, preferably 1 to 6 carbon atoms, such as methyl phosphoryl group, ethyl phosphoryl group)

Assuming that a substituent is attached to the substituent and further substituted therewith,
Alkoxyalkyl groups (straight, branched or cyclic alkoxyalkyl groups having 1 to 32, preferably 1 to 12 carbon atoms, such as methoxymethyl, methoxyethyl, ethoxyethyl, cyclohexyloxypropyl groups )
Alkoxyaryl groups (alkoxyaryl groups having 7 to 18, preferably 7 to 12 carbon atoms, such as p-methoxyphenyl groups, 2,4-dimethoxyphenyl groups)
An alkoxycarbonylalkyl group (an alkoxycarbonylalkyl group having 2 to 15, preferably 2 to 6 carbon atoms, for example, a methoxycarbonylethyl group, a 3-ethoxycarbonylpropyl group)
Alkylaminoalkyl groups (alkylaminoalkyl groups having 2 to 15, preferably 2 to 6 carbon atoms, such as N-methylaminomethyl group, dimethylaminoethyl group)
Alkylthioalkyl groups (alkylthioalkyl groups having 2 to 15, preferably 2 to 6 carbon atoms, such as methylthiomethyl, methylthioethyl, ethylthioethyl)
A haloalkoxyaryl group (a haloalkoxyaryl group having 7 to 18, preferably 7 to 12 carbon atoms, for example, a 2-chloro-4-methoxyphenyl group, a 2,5-dichloro-4-methoxyphenyl group )
Alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having 2 to 15, preferably 2 to 6 carbon atoms, such as methoxycarbonyloxy groups, ethoxycarbonyloxy groups)
Aryloxycarbonyloxy group (aryloxycarbonyloxy group having 7 to 18, preferably 7 to 12 carbon atoms, for example, phenoxycarbonyloxy group)
Alkoxycarbonylamino groups (alkoxycarbonylamino groups having 2 to 10, preferably 2 to 6 carbon atoms such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, isobutyloxycarbonylamino Base)
-Hydroxyalkylthio groups (hydroxyalkylthio groups having 1 to 15, preferably 1 to 6 carbon atoms, such as hydroxyethylthio group, 2-hydroxypropylthio group, etc.).

R ₁ represents a hydroxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or —CH (R ₂ ) (R ₃ ), preferably an alkylsulfonylamino group, —CH (R ₂ ) (R ₃ ), preferably carbon The numbers and specific examples are the same as those described in the description of the substituents represented by R _{4 to} R ₆ .

R ₂ and R ₃ represent electron withdrawing groups having Hammett's substituent constant σ value of 0.2 or more and less than 1.4. Hammett's rule is an empirical rule proposed by LP Hammet in 1935 to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives and is widely accepted today. Substituent constants obtained by Hammett's rule include σ _p value and σ _m value, and these values are found in many general books. For example, JA Dean edition “Lange's Handbook of Chemistry” 12th edition , 1979 (McGraw-Hill) and “Chemical Fields Extra”, 122, 96-103, 1979 (Nanedo), Chemical Review, 91, 165-195, 1991. However, R ₂ and R ₃ are not limited to the substituents described in these documents as substituents having a σ value of 0.2 or more and less than 1.4. Even if the values are unknown, the Hammett's rule is used. Of course, it is included as long as it is included in the range when measured based on the above. Specific examples of electron withdrawing groups having a σ value of 0.2 or more and less than 1.4 include chlorine atom, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group And sulfamoyl group. R ₂ and R ₃ may be the same or different, but are preferably the same, preferably a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, or a cyano group, and a carbamoyl group, an alkyl group More preferred is an oxycarbonyl group or a cyano group. The preferable number of carbon atoms and specific examples of these groups are the same as those described in the description of the substituents represented by R _{4 to} R ₆ .

R ₄ is preferably an alkyl group, an acyl group, or an aryl group, more preferably an alkyl group or an aryl group, and most preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a t-butyl group.

R ₅ is preferably an alkyl group, an acylamino group, an aryl group, an amino group, an alkyloxycarbonylamino group, or an alkylaminocarbonyloxy group, more preferably an alkyl group or an aryl group, and most preferably an alkyl group having 1 to 4 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, and an isopropyl group.

R ₆ is preferably an alkyl group, an aryl group, an alkylthio group, an arylthio group or an alkyloxy group, more preferably an alkyl group or an alkylthio group, and most preferably an alkyl group having 1 to 3 carbon atoms. Specific examples include a methyl group and an ethyl group.

Preferred combinations of X, Y, and Z include a combination in which X is a carbon atom, Y and Z are nitrogen atoms, and a combination in which X and Z are nitrogen atoms and Y is a carbon atom. Examples of the group consisting of a heterocycle formed by a combination of X, Y, and Z and one or two R ₆ include Het-1 to Het-13 shown below. Among these, Het-4 to Het— 13 is an example in which two R ₆ are bonded to form an aromatic ring or a heterocyclic ring. In the following formula, R ₆ has the same meaning as described above, and R _{7 to} R _{14 each} represent a substituent. Examples of the substituent for R _{7 to} R ₁₄ include the groups exemplified as the aforementioned R _{4 to} R ₆ , and two or more adjacent groups are bonded to each other to form a saturated or unsaturated 5-membered or 6-membered group. A ring structure may be formed.

  Specific examples of the dissociable azo dye used in the present invention are shown below, but are not limited to the following examples.

Preferred dissociable azo dyes (1) include compounds in which R ₁ is an alkylsulfonylamino group, W is a sulfur atom, and n is 1.

  The dissociable azo dye (1) used in the hair dye composition of the present invention can be used alone or in combination of two or more, and its content is preferably 0.0001 to 25% by mass in the total composition. More preferably, it is 0.001-20 mass%, More preferably, it is 0.05-15 mass%, Most preferably, it is 0.1-10 mass%.

  The dissociable azo dye (1) used in the hair dye composition of the present invention is excellent in storage stability in a wide range of pH 2 to 14 used in ordinary hair dyes, and has any pH within the above range. However, from the viewpoint of hair dyeing / bleaching effect and skin irritation, the pH of the entire composition at the time of use (mixing) is preferably 8 to 14 (25 ° C.), and particularly preferably pH 8 to 13. Moreover, when the hair dye composition of this invention is a multi-drug type, the pH of the 1st agent before mixing has preferable pH 8-14, and the pH of the 2nd agent before mixing has preferable 2-5. As pH adjusters, in addition to the alkaline agents shown below, inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid and lactic acid, hydrochlorides such as monoethanolamine hydrochloride, monopotassium dihydrogen phosphate Further, phosphates such as disodium monohydrogen phosphate can be used.

〔Oxidant〕
Since the dissociable azo dye (1) is very stable against an oxidizing agent, it can be applied to hair after mixing with the oxidizing agent. In other words, the hair dye composition of the present invention can be of a two-part type composed of a first agent containing the dissociable azo dye (1) and a second agent containing an oxidizing agent. In this case, dyeing and decoloring are performed simultaneously, and a more vivid dyeing is obtained.

  Examples of the oxidizing agent include hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; perborates such as sodium perborate; percarbonates such as sodium percarbonate; sodium bromate; And bromates such as potassium bromate. Among these, hydrogen peroxide is preferable from the viewpoint of decolorization to hair and the stability and effectiveness of the oxidizing agent itself. In addition to hydrogen peroxide, other oxidizing agents can be used in combination as an oxidizing aid. Of these, it is preferable to use a combination of hydrogen peroxide and persulfate.

  When using an oxidizing agent, an oxidizing agent can be used individually or in combination of 2 or more types, The content is 0.5-30 mass% in the whole composition, Furthermore, 1-20 mass% is preferable. When hydrogen peroxide and persulfate are used in combination, the hydrogen peroxide content is 0.5-10% by mass in the total composition, and the persulfate content is 0.5-25% in the total composition. %, And the total content of both is preferably 1 to 30% by mass.

  When the hair dye composition of the present invention is of a two-component type, the mixing ratio of the first agent containing the dissociable azo dye (1) and the second agent containing the oxidizing agent is 2: 1 by volume. A range of ˜1: 3 is preferred.

[Other dyes]
The hair dye composition of the present invention can be mixed with other direct dyes or oxidation dyes to change the color tone.

  As other direct dyes, known direct dyes such as acid dyes, basic dyes, nitro dyes, disperse dyes, and cationic dyes can be used. Examples of direct dyes include blue No. 1, purple No. 401, black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203, yellow No. 403 (1), acidic orange 3, 2- Nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitro-o-phenylenediamine, 4-amino-3-nitrophenol, 4 -Hydroxypropylamino-3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis (2-hydroxyethyl)- 2-nitro-p-phenylenediamine, dispersed purple 1, dispersed blue 1, dispersed black 9, basic blue 99, basic brown 16, basic brown 17, basic red 76, basic yellow 76, basic yellow 57 , Basic orange 31, basic red 51, and a methine-type cationic dye having a cyanine structure represented by the following formula.

  Also, for example, JP 2002-275040 A, JP 2003-107222 A, JP 2003-107223 A, JP 2003-113055 A, JP 2003-342139 A, JP 2004-107343 A, etc. Direct dyes described in JP-A-2004-155746 and JP-A-2006-182653 can also be added.

  When other direct dyes are used in combination, the total content of the dissociable azo dye (1) and other direct dyes is preferably 0.0001 to 20% by mass, more preferably 0.001 to 20% by mass in the total composition, More preferably, it is 0.05-15 mass%, Most preferably, it is 0.1-10 mass%.

  In the hair dye composition of the present invention, an oxidative dye can be used in combination with the dissociable azo dye (1). Such a combination enables extremely clear and strong dyeing that cannot be obtained with an oxidation dye alone. As the oxidation dye, a known precursor and a known coupler which are usually used for an oxidation type hair dye are used.

  Examples of the precursor include paraphenylenediamine, toluene-2,5-diamine, orthochloroparaphenylenediamine, N-phenylparaphenylenediamine, N, N-bis (hydroxyethyl) paraphenylenediamine, and 3-methyl-4- Examples include aminophenol, 2-hydroxyethyl paraphenylenediamine, paraaminophenol, paramethylaminophenol, 4-amino-methcresol, orthoaminophenol, and salts thereof.

  Examples of couplers include resorcin, 2-methylresorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, metaphenylenediamine, metaaminophenol, 2,4-diaminophenoxyethanol, 2,6-diamino. Examples thereof include pyridine, 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine, and salts thereof.

  Two or more precursors and couplers may be used in combination, and their content is preferably 0.0005 to 20% by mass, more preferably 0.001 to 15% by mass, and further 0.5 to 10% by mass in the total composition. % Is preferred.

  To the hair dye composition of the present invention, an auto-oxidation dye represented by indoles, indolines and the like can be further added.

  The total content of the dissociable azo dye (1), other direct dyes, oxidation dyes and auto-oxidation dyes is 0.001 to 25% by mass, further 0.01 to 20% by mass, and further 0.1 to 15% by mass in the total composition. %, Particularly 0.5 to 10% by mass is preferred.

[Other ingredients]
When the hair dye composition of the present invention is a two-part or three-part type, the first agent contains an alkaline agent. Alkaline agents such as ammonia and salts thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and salts thereof; alkanediamines such as 1,3-propanediamine and the like Salts: carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Of these alkali agents, ammonia, alkanolamines and salts thereof are preferred. As the ammonium salt, ammonium carbonate and ammonium hydrogen carbonate are preferable, and as the alkanolamine and its salt, monoethanolamine and its salt are preferable.

  Of the above alkaline agents, ammonia, alkanolamines and salts thereof are preferred. As the ammonium salt, ammonium carbonate and ammonium hydrogen carbonate are preferable, and as the alkanolamine and its salt, monoethanolamine and its salt are preferable. Furthermore, the content of these is most preferably in the following range. The sum of the content (X) when ammonia and its salt in all compositions are converted as ammonia and the content (Y) when monoethanolamine and its salt are converted as monoethanolamine is sufficient. From the viewpoint of hair / bleaching effect and reduction of hair damage, scalp stimulation, and olfactory stimulation, it is preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, particularly 0.2 to 5% in the total composition. It is preferable that it is weight%. The weight ratio of X / Y is preferably 0.01: 1 to 2: 1, more preferably 0.02: 1 to 1: 1, and particularly preferably 0.05: 1 to 0.5: 1.

  The hair dye composition of the present invention can contain a conditioning component suitable for application to hair. Conditioning ingredients are usually polymers or oils that can be dissolved or dispersed in the hair dye composition and adhere to the hair when rinsed or diluted with water or shampoo.

  When using a conditioning component, the compounding quantity is 0.01-30 mass% in the whole composition, Preferably it is 0.05-20 mass%, More preferably, it is 0.1-10 mass%.

  Suitable conditioning components for use in the hair dye compositions of the present invention are conditioning agents generally characterized as cationic polymers, silicones, organic conditioning oils (eg, hydrocarbon oils, polyolefins, fatty acid esters), and the like It is a combination. Furthermore, in addition to these, it is a conditioning agent that forms dispersed liquid particles in an aqueous surfactant.

  The cationic polymer refers to a polymer having a cationic group or a group that can be ionized into a cationic group, and includes an amphoteric polymer that becomes cationic as a whole. That is, as the cationic polymer, an aqueous solution containing an amino group or an ammonium group in the side chain of the polymer chain or containing a diallyl quaternary ammonium salt as a structural unit, such as a cationized cellulose derivative, a cationic starch, a cationization Examples include guar gum derivatives, diallyl quaternary ammonium salt polymers or copolymers, and quaternized polyvinylpyrrolidone derivatives. Among these, diallyl quaternary ammonium salt is included as a structural unit particularly in terms of softness during shampooing, smoothness and ease of fingering, ease of packing during drying and moisturizing effect, and stability of the agent. Polymers, quaternized polyvinylpyrrolidone derivatives, and cationized cellulose derivatives are preferred, and polymers or copolymers of diallyl quaternary ammonium salts and cationized cellulose derivatives are more preferred.

  Specific examples of the polymer or copolymer of diallyl quaternary ammonium salt include dimethyldiallylammonium chloride polymer (polyquaternium-6, such as Marquat 100; Nalco), dimethyldiallylammonium chloride / acrylic acid copolymer (polyquaternium- 22, for example, Marquat 280, 295; Nalco), dimethyldiallylammonium chloride / acrylic acid amide copolymer (polyquaternium-7, for example, Marquat 550; Nalco), and the like.

  Specific examples of the quaternized polyvinylpyrrolidone derivative include a quaternary ammonium salt (polyquaternium-11 such as Guffcoat 734, 755, and 755) obtained from a copolymer of vinylpyrrolidone (VP) and dimethylaminoethyl methacrylate and diethyl sulfate. 755N (above, IPS Japan Ltd.)).

  Specific examples of the cationized cellulose derivative include a polymer of quaternary ammonium salt obtained by adding glycidyltrimethylammonium chloride to hydroxyethylcellulose (polyquaternium-10, such as Leogard G, GP (above, Lion)), polymer JR -125, same JR-400, same JR-30M, same LR-400, same LR-30M (above, Amerchol)), hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (polyquaternium-4, eg, Cellcoat H-100) , L-200 (National Starch and Chemical Co., Ltd.)).

  Two or more cationic polymers may be used in combination. The effect of the cationic polymer increases as the content increases. However, when the content is too large, the stability is poor, and the viscosity of the agent alone or at the time of mixing is reduced. From these points and the point of touch improvement, the content of the cationic polymer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.05 to 5% by mass in the total composition.

  The hair dye composition of the present invention preferably contains polysilicones in order to give an excellent feeling of use. Examples of the polysilicone include polyalkoxysilanes and modified silicones (for example, amino-modified silicone, fluorine-modified silicone, alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, and alkyl-modified silicone). Silanes, polyether-modified silicones, and amino-modified silicones are preferred.

  Polyalkoxysilanes may be cyclic or acyclic dimethylsiloxane polymers, such as SH200 series, BY22-019, BY22-020, BY11-026, BY22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (above, Toray Dow Corning) KF-9008, KM-900 series, MK-15H, MK-88 (above, Shin-Etsu Chemical) Can be mentioned.

  The polyether-modified silicone may be any silicone having a polyoxyalkylene group, and examples of the group constituting the polyoxyalkylene group include an oxyethylene group and an oxypropylene group. More specifically, for example, KF-6015, KF-945A, KF-6005, KF-6009, KF-6013, KF-6019, KF-6029, KF-6017, KF-6043, KF-353A, KF- 354A, KF-355A (Shin-Etsu Chemical Co., Ltd.), FZ-2404, SS-2805, FZ-2411, FZ-2412, SH3771M, SH3772M, SH3773M, SH3775M, SH3749, SS-280X series, BY22-008M, BY11- 030, BY25-337 (above, Toray Dow Corning).

  The amino-modified silicone may be any silicone having an amino group or an ammonium group, for example, an amino-modified silicone oil in which all or part of the terminal hydroxyl groups are blocked with methyl groups or the like, or amodimethicone in which the terminals are not blocked. and so on. Preferred amino-modified silicones include those represented by the following general formula (S).

[In the formula, R ′ represents a hydroxyl group, a hydrogen atom or R ^X , R ^X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, D represents R ^X , a group R ″ — (NHCH ₂ CH ₂ ) _m NH ₂ , a group OR ^X or a hydroxyl group, R ″ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, m represents a number of 0 to 3, and p and q are The number average is 10 or more and less than 20000, preferably 20 or more and less than 3000, more preferably 30 or more and less than 1000, and still more preferably 40 or more and less than 800. ]

  Specific examples of suitable commercially available amino-modified silicones include SF8452C, SS-3551 (above, Toray Dow Corning), KF-8004, KF-867S, KF-8015 (above, Shin-Etsu Chemical Co., Ltd.), etc. Examples thereof include amino-modified silicone oils and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671, and FZ-4672 (above, Toray Dow Corning).

  The total content of these silicones in the hair dye composition of the present invention is preferably 0.02 to 40% by mass, more preferably 0.1 to 20% by mass in the total composition, from the viewpoint of sufficient effect and suppression of stickiness. 0.2-15 mass% is especially preferable.

  When the hair dye composition of the present invention contains silicones and a cationic polymer, the mass ratio of the cationic polymer (active amount): silicones in the total composition is preferably 100: 1 to 1:50, 50 : 1-1: 10 is more preferable.

  The hair dye composition of the present invention preferably contains a higher alcohol in one or more of the first agent, the second agent, and the third agent from the viewpoint of improving touch and stability. The inclusion of the higher alcohol has the effect of forming a structure with the surfactant to prevent separation of the hair dye composition and improving the feel during rinsing.

  As the higher alcohol, those having 8 to 22 carbon atoms, particularly 16 to 22 carbon atoms are preferable, and specific examples thereof include cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like, and mixtures thereof.

  Two or more higher alcohols may be used in combination, and the content thereof is preferably 0.01 to 20% by mass, particularly 0.1 to 10% by mass, based on the total composition.

  The hair dye composition of the present invention can contain a surfactant. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Counterions of the anionic residues of these surfactants include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; alkanol groups having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  The surfactants can be used alone or in combination of two or more thereof, and the content thereof is not particularly limited, but is preferably 0.05 to 20% by weight, more preferably 0.1 to 18% by weight, particularly 0.5 to It can be 15 mass%.

  In the hair dye composition of the present invention, water and, if necessary, an organic solvent are used as a medium. Examples of organic solvents include lower aliphatic alcohols such as ethanol, propanol and isopropanol; aromatic alcohols such as benzyl alcohol and benzyloxyethanol; polyols such as propylene glycol, 1,3-butanediol, diethylene glycol and glycerin; Cellosolves such as cellosolve and butylcellosolve; and carbitols such as ethylcarbitol and butylcarbitol.

  Although content in particular of an organic solvent is not restrict | limited, For example, it is 0.05-20 mass% in a whole composition, Furthermore, 0.1-15 mass%, It can be 0.5-10 mass% especially.

  In addition to the above components, other components that are normally 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, natural or synthetic polymers, ethers, protein derivatives, hydrolyzed proteins, amino acids, preservatives, chelating agents, stabilizers, oxidation Examples include inhibitors, botanical extracts, herbal extracts, vitamins, fragrances, and UV absorbers.

  The hair dye composition of the present invention is a two-component formula comprising a first agent containing a dissociable azo dye (1) and an alkali agent and a second agent containing an oxidizing agent such as hydrogen peroxide. In order to improve decolorization power, it is provided as a three-part formula that combines a powdery oxidizer consisting of granules such as persulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.) as a third agent. It is preferable.

  The one-part formula can be, for example, liquid, emulsion, cream, gel, paste, mousse, etc., and can also be in aerosol form. In the case of the two-part type (or three-part type), the dosage form of the first agent and the second agent can be, for example, liquid, emulsion, cream, gel, paste, mousse, etc. It can also be in the form. It is desirable that the first agent and the second agent (the third agent in the case of the three-agent type) are mixed and applied to the hair so that the viscosity becomes difficult to spill, and the hair dye composition of the present invention The viscosity of all compositions measured with a B-type rotational viscometer with a helical stand at 25 ° C. (B8R type viscometer, Tokimec) in either one agent type, two agent type, or three agent type is 2000 to 10 It is preferably 10,000 mPa · s. Here, the viscosity is a value obtained by rotating the rotor T-C at 10 rpm for 1 minute.

  Further, as a booster liquid for changing the color tone of these oxidized hair dyes to a known two-part oxidized hair dye or three-part oxidized hair dye, a solution containing a dissociable azo dye (1) is used. A combined form is also possible. Specifically, a known two-component oxidation type comprising a first agent containing an alkali agent (which may include an arbitrary oxidation dye intermediate or direct dye) and a second agent containing an oxidant. A dissociable azo dye (1) is added to a known three-part oxidative hair dye, which is a combination of a hair dye or a third agent containing an oxidizing aid in addition to the first and second agents. It can be set as the form which combined the booster liquid to contain. Further, for example, before or during use of the one-component hair dye composition containing the dissociable azo dye (1), the two-component oxidation hair dye or the three-component oxidation hair dye as described above. Combinations of agents can also be used.

<Hair dyeing method>
For the hair dyeing treatment using the composition of the present invention, for example, the first agent and the second agent of the composition of the present invention (or the third agent in the case of the three-component type) are mixed immediately before use, and then the hair. Applying to the above, after leaving for a predetermined time within 1 hour, it may be washed away and dried. The application temperature to the hair is preferably 15 to 45 ° C., the application time is 3 to 50 minutes, more preferably 5 to 40 minutes, and particularly preferably 10 to 30 minutes. In this case, first, the hair dye is lightly washed with water, then washed with a shampoo containing an anionic surfactant, and then washed with water, the cationic polymer flows out moderately, and the silicones remain in the hair moderately. And a good conditioning effect. As the shampoo, a general aqueous shampoo containing about 5 to 20% by weight of an anionic surfactant such as sodium laureth-1 sulfate, sodium laureth-2 sulfate or sodium laureth-3 sulfate is suitable.

Synthesis example 1
A dissociable azo dye D-23 was synthesized according to the following reaction formula.

(1) Synthesis of Compound C 16.2 g (0.08 mol) of Compound A and 6.2 g (0.08 mol) of Compound B were suspended in 80 mL of isopropyl alcohol and stirred at an internal temperature of 25 ° C. for 3 hours. Next, a solution obtained by dissolving 6.9 g (0.082 mol) of sodium hydrogen carbonate in 200 mL of water was added dropwise. The precipitated crystals were filtered, washed thoroughly with water and dried to obtain 14.0 g of Compound C as colorless crystals. Yield 99%.

(2) Synthesis of Compound E 10.0 g (0.055 mol) of Compound C was dissolved in 100 mL of tetrahydrofuran, and then 18.9 g (0.165 mol) of methanesulfonyl chloride was added. Next, 8.9 g of sodium hydride (oiliness, content 50 to 72%) was added, and the mixture was stirred at a reaction temperature of 65 ° C. for 5 hours. To the reaction solution, 10 mL of methanol, 1000 mL of ethyl acetate and 500 mL of saturated brine were added and allowed to stand. After removing the aqueous layer, the ethyl acetate layer was washed with 500 mL of saturated brine, and water was dried over anhydrous magnesium sulfate. Subsequently, the filtrate obtained by filtering magnesium sulfate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. 5.5 g of compound E was obtained as colorless fine crystals. Yield 39%.

(3) Synthesis of Compound G After 13.3 g (0.1 mol) of Compound F was suspended in 20 mL of isopropyl alcohol and 15 mL of water, 6.6 g of 85% potassium hydroxide was added and dissolved. Under ice cooling, 16.4 g (0.105 mol) of ethyl iodide was added dropwise while maintaining the reaction temperature at 25 ° C. or lower. Next, stirring was performed for 2 hours at a reaction temperature of 60 ° C., and this reaction solution was poured into 400 mL of cold water, and further stirred for 30 minutes. The precipitated crystals were filtered, sufficiently washed with water and dried to obtain 15.2 g of Compound G as pale yellow crystals. Yield 94%.

(4) Synthesis of D-23 Compound G 2.8 g (0.017 mol) was dissolved in phosphoric acid 350 mL, and sodium nitrite 1.3 g (0.19 mol) was gradually added while maintaining the internal temperature at 5 ° C. or lower for 30 minutes. Stir. A solution prepared by dissolving 4.8 g (0.19 mol) of compound E in 50 mL of acetic acid was added dropwise to the reaction solution, and the mixture was stirred at 10 ° C. for 5 hours. 2 L of water was added to the reaction solution and stirred for 1 hour, and the precipitated crystals were filtered and thoroughly washed with water. The obtained crystals were dried and purified by silica gel column chromatography. Crystallization with 150 mL of methanol / water = 1/1 (volume mixing ratio), filtration, washing with 50 mL of the same mixed solvent and drying gave 2.8 g of dissociable azo dye D-23 as orange crystals. Yield 39%.
Mp two hundred fifty-seven to two hundred fifty-eight ° C. maximum absorption lambda _max 546.1 nm in DMF, the molar absorption coefficient ε41,200, DMF / water = 1/1 pK _a (volume mixing ratio) in the 2.91.

Synthesis example 2
A dissociable azo dye D-26 was synthesized according to the following reaction formula.

(1) Synthesis of Compound J Compound J was obtained in the same manner as in Synthesis Example 1 except that Compound A was changed to Compound H in the methods of (1) and (2).

(2) Synthesis of Compound L 10.5 g (0.13 mol) of sodium thiocyanate was dissolved in 100 mL of methanol, and then 13.9 g (0.05 mol) of Compound K was added under ice / methanol cooling. Next, 15.4 mL (0.11 mol) of triethylamine was added, and 14 mL (0.1 mol) of triethylamine and 16.3 g (0.102 mol) of bromine were simultaneously added dropwise while maintaining the internal temperature at 5 ° C. or lower. After reacting for 2 hours at room temperature, the reaction solution was poured into 1000 mL of cold water and stirred for 30 minutes. The precipitated crystals were filtered, sufficiently washed with water and dried to obtain 10.0 g of Compound L as pale yellow crystals. Yield 68%.

(3) Synthesis of D-26 A dissociable azo dye D-26 was obtained in the same manner as in Synthesis Example 1 (4) except that Compound G was changed to Compound L and Compound E was changed to Compound J.

Synthesis example 3
A dissociable azo dye D-1 was synthesized according to the following reaction formula.

  A dissociable azo dye D-1 was obtained in the same manner except that Compound J was changed to Compound E in the method of Synthesis Example 2 (3).

Example 1
A two-component hair dye first agent shown in Table 1 and a second agent A shown in Table 2 are prepared, and the first agent: second agent: purified water is mixed at a mass ratio of 4: 7: 1 to dye hair. An agent composition was obtained. 1 g of each hair dye composition was applied to 1 g of goat wool at 30 ° C., allowed to stand for 30 minutes, washed with water and shampooed, and dried.

After dyeing in this way, the chromaticity of the hair bundle was measured. For each example, the chromaticity of the hair bundle before and after the coloring process was measured with a color difference meter CR-400 manufactured by Konica Minolta, and the color values were expressed in the L ^* a ^* b ^* color system. When the chromaticity change amount ΔE ^* was calculated according to the well-known equation, ΔE ^* was 50.6.

Examples 2 to 4 (these are reference examples and are not included in the scope of the claims)
A foam type one-piece hair dye shown in Table 3 is prepared. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 5-8
A creamy two-component hair dye first agent shown in Table 4 and a common second agent shown in Table 5 were prepared, and the first agent: common second agent were mixed at a mass ratio of 1: 1 to prepare a hair dye composition. It is a thing. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 9-12
A two-component hair dye first agent shown in Table 6 is prepared, and the first agent: common second agent is mixed at a mass ratio of 1: 1 to obtain a hair dye composition. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 13-16
A two-component hair dye first agent and a booster solution shown in Table 7 are prepared, and a first agent: booster solution: common second agent is mixed at a mass ratio of 1: 1: 0.1 to obtain a hair dye composition. . Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 17-19
According to a conventional method, the creamy three-component hair dye first agent and third agent shown in Table 8 are prepared, and the first agent: common second agent: third agent is mixed at a mass ratio of 1: 1: 0.3. A hair dye composition is obtained. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Claims (6)

Hair dye containing at least one azo dye selected from the group consisting of the following compounds D-1, D-3, D-6, D-11, D-23, D-26 and D-27, and an oxidizing agent Agent composition.

The hair dye composition according to claim 1, wherein the oxidizing agent comprises hydrogen peroxide. The hair dye composition according to claim 1 or 2, wherein the hair dye composition is a two-part composition comprising a first agent containing the azo dye and a second agent containing an oxidizing agent. The hair dye composition according to claim 3, wherein a mixing ratio of the first agent and the second agent is 2: 1 to 1: 3 by volume ratio. The hair dye composition according to any one of claims 1 to 4, wherein an oxidative dye is used in combination with the azo dye. The hair dyeing method which applies the hair dye composition of any one of Claims 1-5 to hair.