JP2006265160A - Hair dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye composition capable of strongly dyeing the hair in a clear color tone, having high dyeability, and difficult to be discolored with time, and to provide a method for dyeing the hair using the same. <P>SOLUTION: The hair dye contains at least one kind of compound expressed by general formula (1) (X<SB>1</SB>, X<SB>2</SB>, X<SB>3</SB>and X<SB>4</SB>are each H or a substituent which has at least two hydroxy groups or two groups having a hydroxy; and V<SB>1</SB>, V<SB>2</SB>, V<SB>3</SB>and V<SB>4</SB>are each H or a substituent) as a direct dye. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hair dye having excellent dyeing power, capable of imparting a clear and wide range of colors to hair, and having little color fading due to aging.

The use of several types of anthraquinones as colorants for keratinous substrates is known. Since anthraquinones have a problem of low dyeability, attempts have been made to improve the dyeability. Japanese Patent Application Laid-Open No. 56-5409 (Patent Document 1) discloses anthraquinones having reactive groups such as CI Reactive Blue 2, CI Reactive Blue 5, and CI Reactive Blue 19. JP-A-62-277313 (Patent Document 2) and JP-A-63-501873 (Patent Document 3) disclose CISoluvent Violet 13, CIAcid Violet 43 and the like as preferred specific structures. JP-A-4-235911 (Patent Document 4) discloses specific anthraquinones having a hydroxyalkylamino group. However, none of these structures still have sufficient dyeability.
JP-A-56-5409 JP-A-62-277313 JP-T 63-501873 JP-A-4-235911

  It is an object of the present invention to strongly dye hair in a clear color tone, has excellent resistance to sunlight, hair washing, sweat, friction and heat, has high dyeability, and does not easily fade over time. The object is to provide a hair dye and a hair dyeing method using the same.

式中、Ｘ_１、Ｘ_２、Ｘ_３、及びＸ_４は水素原子若しくは置換基を表し、少なくとも２つのヒドロキシル基を表す。Ｖ_１、Ｖ_２、Ｖ_３、及びＶ_４は水素原子若しくは置換基を表す。 A hair dye comprising at least one compound represented by the following general formula (1) as a direct dye.

In the formula, X ₁ , X ₂ , X ₃ , and X ₄ represent a hydrogen atom or a substituent, and represent at least two hydroxyl groups. _{V 1, V 2, V 3} , and _{V 4} represents a hydrogen atom or a substituent.

  The staining agent of the present invention can have excellent dyeability. Moreover, the hair dye of this invention has high persistence with respect to hair washing and the exposure to sunlight. Furthermore, since the compound (1) used in the present invention is sufficiently stable against an oxide, it can be dyed in a vivid color while decolorizing the hair when used in combination with the oxide.

  The present invention will be described below. In the present invention, when a specific moiety is referred to as a “substituent”, the moiety is substituted with one or more (up to the maximum possible) substituents, even if the group itself is not substituted. Also means good. For example, an “alkyl group” as a substituent means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention includes any substituent regardless of the presence or absence of substitution.

  When the substituent is W, the substituent represented by W is not particularly limited. For example, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), and an alkenyl group (cyclo Alkenyl group, bicycloalkenyl group), alkynyl group], aryl group, heterocyclic group (also referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycar Nylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, Examples include ureido groups and other known substituents.

  More specifically, W represents a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms). Substituted bicycloalkyl groups such as bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octan-3-yl), and tricyclo structures with many ring structures are also included. . An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group and the like in addition to the above-described alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms). Cycloalkenyl groups, such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group obtained by removing one hydrogen atom, more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2- Benzothiazolyl, or a cationic heterocyclic group such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio),

  A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2- Methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl Aminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocycles having 2 to 30 carbon atoms) Oxy groups such as 1-phenyltetrazo Ru-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy (Preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably carbon number) 7-30 substituted or unsubstituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N- Methylanilino, diphenylamino), ammonio group (preferably ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, heterocyclic group substituted ammonio group such as trimethylammonio, triethylammonio, diphenylmethylammonio ), An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, Lauro Ruamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms such as carbamoylamino, N , N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonyl Amino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) Is an unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably a substituted or substituted group having 0 to 30 carbon atoms) Unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted with 1 to 30 carbon atoms) Or an unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyls Sulfonylamino, p-methylphenylsulfonylamino),

  A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms) , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyl Tetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethyl Sulfamoyl, N-acetylsulfamoy N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 Substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, 6 -30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl groups (preferably formyl group, substituted or unsubstituted 2-30 carbon atoms) An alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms, eg Methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N- Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

  Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms such as phenylazo, p-chlorophenylazo, 5-ethylthio -1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms such as dimethylphosphine Fino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyl Oxy group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphinyloxy group such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino having 2 to 30 carbon atoms). Groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phospho groups, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethyl Silyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms such as N, N-dimethylureido).

  Two Ws can be connected to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic condensed ring. For example, a benzene ring or a naphthalene ring. , Anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine Ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring, phenanthridine ring, acridine Ring, phenanthroline , Thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, also take the like are.) Are condensed structure.

  Among the above substituents W, those having a hydrogen atom may be substituted with the above substituents after removing this. Examples of such complex substituents include acylsulfamoyl groups, alkyl and arylsulfonylcarbamoyl groups. Examples thereof include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl and benzoylsulfamoyl groups.

The compound represented by the general formula (1) used in the present invention is described in detail below.
X ₁ , X ₂ , X ₃ , and X ₄ represent a hydrogen atom or a substituent, and represent at least two hydroxyl groups or a group having a hydroxyl group. The number of hydroxyl groups possessed by X ₁ , X ₂ , X ₃ and X ₄ is 0 to 4, but preferably 1 to 4. Further, it is preferably 2 to 3, particularly preferably 3. When X ₁ , X ₂ , X ₃ , and X ₄ represent a substituent other than a hydroxyl group, those exemplified as the examples of the substituent represented by W can be used, but preferably substituted or unsubstituted In which 0 to 3 amino groups are contained. The number of substituted or unsubstituted amino groups contained in X ₁ , X ₂ , X ₃ and X ₄ is 0 to 3, preferably 1 to 3. Further preferably, it is 1 to 2, particularly preferably 2. Of the substituted amino group and the unsubstituted amino group, an unsubstituted amino group is preferred.

When X ₁ , X ₂ , X ₃ , and X ₄ represent a substituted amino group, as the substituent on the amino group, those exemplified as the examples of the substituent represented by W can be used, An alkyl group, an aryl group, an acyl group, and a heterocyclic group; The above W may be further substituted on these substituents. More preferably, the substituent on the amino group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, or a heterocyclic group, and particularly preferably a methyl group, an ethyl group, or a phenyl group. Group, 2-thiazolyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2- (2′-hydroxyethyloxy) ethyl group, 3-hydroxyphenyl group, 3,5-dihydroxyphenyl group and the like.

When X ₁ , X ₂ , X ₃ , and X ₄ represent a group other than a hydroxyl group or a substituted or unsubstituted amino group, preferably a hydrogen atom, a halogen atom, a mercapto group, an alkoxy group, an alkylthio group, Group, aryloxy group, arylthio group, acyl group, cyano group, nitro group, carboxyl group, heterocyclic group, alkyl group, or arylazo group. More preferably a hydrogen atom, a halogen atom, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, a cyano group, or an arylazo group, more preferably a hydrogen atom, a halogen atom, an alkoxy group, An alkylthio group, particularly preferably a hydrogen atom.

V ₁ , V ₂ , V ₃ , and V ₄ represent a hydrogen atom or a substituent, but are preferably a hydrogen atom. When V ₁ , V ₂ , V ₃ , and V ₄ represent a substituent, this is preferably a halogen atom, hydroxyl group, amino group, mercapto group, alkoxy group, alkylthio group, aryloxy group, arylthio group. An acyl group, a cyano group, a nitro group, a carboxyl group, a heterocyclic group, an alkyl group, or an arylazo group. More preferred are halogen atom, hydroxyl group, amino group, alkoxy group, alkylthio group, aryloxy group, acyl group and cyano group, and more preferred are hydroxyl group, amino group, alkoxy group and acyl group.

The compound represented by the general formula (1) of the present invention is preferably a case where two or three of X ₁ , X ₂ , X ₃ and X ₄ represent a hydroxyl group or a group having a hydroxyl group.
More preferably, as the compound represented by the general formula (1) of the present invention, two or three of X ₁ , X ₂ , X ₃ , and X ₄ represent a hydroxyl group, and X ₁ , X ₂ , X ₃ and X ₄ other than the hydroxyl group represent one or two amino groups.
More preferably, as the compound represented by the general formula (1) of the present invention, two or three of X ₁ , X ₂ , X ₃ , and X ₄ represent a hydroxyl group, and X ₁ , X ₂ , X ₃ and X ₄ other than the hydroxyl group represents one or two amino groups, and the amino group represents an unsubstituted or substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

More preferably, as the compound represented by the general formula (1) of the present invention, two or three of X ₁ , X ₂ , X ₃ , and X ₄ represent a hydroxyl group, and X ₁ , X ₂ , X ₃ and X ₄ other than the hydroxyl group represents one or two unsubstituted monomethylamino groups.

Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereby.

  The compound represented by the general formula (1) can be synthesized based on the method described in Ullmann's Encyclopedia of Industrial Chemistry 6th edition.

  The compound represented by the general formula (1) of the present invention may be an organic or inorganic acid salt, or an organic or inorganic alkali salt. 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.

  In the present invention, the “hair dye” is not only an agent containing a specific hair dye alone, but also a mixture with other hair dye compounds or a mixture of hair dye compounds and auxiliaries, a solvent, that is, a composition, Means not only consisting of one agent as described later, but also includes a multi-component hair dye comprising two or more agents as a set.

  In addition to the compound represented by the general formula of the present invention, the hair dye of the present invention can be used in combination with other direct dyes or oxidation dyes.

Other direct dyes include, for example, Basic Blue 7 (C.I. 42595), Basic Blue 26 (C.I. 44045), Basic Blue 99 (C.I. 56059), and Basic Violet 10 (C.I. 45170). ), Basic Violet 14 (C.I. 42515), Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251), Basic Red 2 (C.I. 50240), Basic Red 12 ( C.I.48070), Basic Red 22 (C.I. 11055), Basic Red 46 (C.I. 110825), Basic Red 76 (C.I. 12245), Basic Red 118 (C.I. 12251: 1) Basic Yellow 28 (C.I. 48054), Basic yellow 57 (C.I. 12719); described in JP-A No. 58-2204, JP-A No. 9-118832, JP-A-8-501322 and JP-A-8-507545. And cationic dyes.
The content of the compound represented by the general formula (1) of the present invention is 0.0001 to 20% by weight in the total composition (after mixing each agent in the case of a two-part or three-part formula, the same applies hereinafter). More preferably, it is 0.001 to 20 weight%, More preferably, it is 0.05 to 10 weight%, Most preferably, it is 0.1 to 5 weight%. When other direct dyes are used in combination, the total content with the dissociative direct dye (1) is preferably 0.001 to 20% by weight, more preferably 0.01 to 20% in the total composition. % By weight, more preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight.

  Since the compound represented by the general formula (1) of the present invention is excellent in storage stability in a wide range of pH 2 to 11 used in ordinary hair dyes, the hair dye composition of the present invention falls within the above range. Can be used at any pH. However, use in the range of pH 5 or more is preferable from the viewpoint of dyeability.

  The hair dye of the present invention may contain various components other than the general formula (1). Examples of the alkaline agent used in the hair dye of the present invention include ammonia; alkanolamines such as monoethanolamine, isopropanolamine or salts thereof; guanidinium salts such as guanidine carbonate; hydroxides such as sodium hydroxide; Can be mentioned. The content of the alkali agent is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 5% by weight in the total composition.

  Since the compound represented by the general formula (1) used in the present invention is sufficiently stable with respect to the oxidizing agent, it can be applied to the hair after mixing with the oxidizing agent. In other words, the embodiment of the hair dye of the present invention can be made into a two-part formulation of a first agent containing a compound represented by the general formula (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; Examples thereof include bromates such as potassium bromate. Among these, hydrogen peroxide is particularly preferable from the viewpoints of depigmenting property with respect to hair and the stability and effectiveness of the compound represented by the general formula (1). Hydrogen peroxide can also be used in combination with other oxidizing agents. The content of the oxidizing agent is preferably 0.5 to 10% by weight, particularly 1 to 8% by weight in the total composition.

  The mixing ratio of the first agent containing the compound represented by the general formula (1) and the second agent containing the oxidizing agent is preferably in the range of 2: 1 to 1: 3 by volume ratio.

  In the hair dye of this invention, an oxidation dye can also be used together with the compound represented by the said General formula (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 developer and coupling substance that are usually used in oxidation hair dyes are used.

  Examples of the developer include paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, and N, N-bis (2-hydroxyethyl) -paraphenylene. Diamine, 2- (2-hydroxyethyl) -paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis (N- (2-hydroxyethyl) -N- (4-aminophenyl) amino) -2-propanol, PEG-3,2,2′-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4-aminophenol, 2-aminomethyl-4- Aminophenol, 2- (2-hydroxyethylaminomethyl) -4-a Nophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2 , 4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1- (4′-chlorobenzyl) pyrazole and the like, and salts thereof.

  Examples of coupling substances include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole, 2,4-diamino-5-methylphenetole, 2,4. -Diamino-5- (2-hydroxyethoxy) toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diamino-5-fluorotoluene 1,3-bis (2,4-diaminophenoxy) propane, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2,4-dichloro- 3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-methyl Ro-5-aminophenol, N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5- (2-hydroxyethylamino) phenol, 2-methyl-4-fluoro-5-aminophenol, resorcin, 2 -Methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5- Hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1- (2-Hydro Xylethyl) amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, Examples include 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6-diaminopyridine, and salts thereof.

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

  In the hair dye of the present invention, an auto-oxidation type dye represented by indoles and indolines, and known direct dyes such as nitro dyes and disperse dyes can be added.

  It is preferable to add polyols or polyol alkyl ethers, cationic or amphoteric polymers, and silicones to the hair dye of the present invention because uniform hair is obtained and the cosmetic effect of the hair can be improved.

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

  The hair dye of the present invention can be produced according to an ordinary method, and is a one-part type, a two-part type comprising an agent component containing an alkaline agent and an agent component containing an oxidizing agent, or a powder form such as persulfate. It can be made into the form of 3 agent type which added the oxidizing agent of. In the case of the two-part formula or the three-part formula, the compound represented by the general formula (1) may be blended with at least one of the above-described dye component. The hair dye of the present invention is used by directly applying to the hair in the case of the 1 agent type, and is used by mixing these at the time of hair dyeing and applying to the hair in the case of the 2 agent type or the 3 agent type. .

  In the case of a two-component system, typically, the compound represented by the general formula (1) and, if necessary, an oxidation dye are added to the first agent, and the pH is adjusted to 8 to 12 with an alkaline agent such as ammonia. On the other hand, the second agent contains about 2 to 6% by weight of hydrogen peroxide and is adjusted to be weakly acidic with phosphoric acid or the like. In the case of the three-agent type, persulfate is mixed with an inert substance such as talc and dextrin and a binder to form a granular material containing about 5 to 95% by weight of persulfate, It is added to the mixture with two agents at the time of use.

  Moreover, the form can be powdery, transparent liquid, emulsion, cream, gel, paste, aerosol, aerosol foam or the like. As for the viscosity in the step (after mixing in the case of 2 agent type or 3 agent type) applied to hair, 2000-100000 mPa * s is preferable. Here, the viscosity is a value measured at 20 ° C. using a Brookfield rotational viscometer (No. 5 spindle, 5 rpm).

  Example 1: Examples relating to dye properties of dye components The dyes listed in Table 1 were dissolved in a water-based composition containing an alkaline peroxide and applied to goat hair as a hair dye consisting of the following formulation: .

[Prescription]
Dye (shown in Table 1) 0.2g
Benzyl alcohol 5.0g
Sodium lauryl sulfate 0.01g
Ammonium hydroxide (25% by weight) 5.0 g
Hydrogen peroxide (50% by weight) 6.0g
The amount necessary to make the total amount of water 100g
pH 10.0

  The dye mixture was applied to intact white goat hair at 27 ° C. for 18 minutes. A composition of Formula A at 1.5-2.0 g / g of goat hair was applied. After the dyeing time (15 to 30 minutes) was completed, each hair bundle was washed with water, washed with shampoo, and dried. Thereafter, the color of the hair bundle was measured. For each example, the L, a, and b values of the hair bundle before and after the coloring process were measured with a color measuring instrument manufactured by Minolta, and the values of ΔL and ΔE were calculated according to the following well-known formulas (hereinafter, all examples) The same shall apply in

ΔE ^* ab = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^1/2
The results are shown in Table 1.
The following can be seen from the results in Table 1 below.
Hair dyes 1 and 2 have low values of ΔE ^* ab of 20 or less.
On the other hand, it can be seen that the hair dyes 3 to 6 of the present invention show high values of 29 or 30 or more.

(Washing and light fading test)
After each hair bundle colored in Example 1 was washed 20 times with shampoo, the change in ΔE ^* _ab value was equal to or greater than that of Hair Dye 1 for Hair Dye 3-7. Further, in the fading test using sunlight, the product of the present invention showed a high light fastness equivalent to or higher than that using Comparative Dyes 1 and 2.

Claims (1)

A hair dye comprising at least one compound represented by the following general formula (1) as a direct dye.

In the formula, X ₁ , X ₂ , X ₃ , and X ₄ represent a hydrogen atom or a substituent, and represent at least two hydroxyl groups or a group having a hydroxyl group. _{V 1, V 2, V 3} , and _{V 4} represents a hydrogen atom or a substituent.