KR100851614B1 - Cationic azo dyes with julolidine units, dyeing composition containing them, method of dyeing - Google Patents

Abstract

A cationic azo dye containing a julolidine unit or its addition salt or solvate a dye composition for dyeing a keratin fiber(hair) containing the azo dye, a method for dyeing a keratin fiber by using the composition, and a dyeing kit using the composition are provided to improve the resistance against light and weather and to reduce toxicity profile. A cationic azo dye containing a julolidine unit is represented by the formula I, wherein A is a cationic aromatic heterocycle group represented by the formula IIa, IIb or IIc; R1 is independently a linear or branched saturated or unsaturated C1-C16 hydrocarbon group which is optionally interrupted by at least one group selected from a hetero atom such as O, N or S and a carbonyl group, can be substituted and can be condensed with an aromatic ring to form a three to seven-membered carbon ring; R2 are independently a linear or branched saturated or unsaturated C1-C16 hydrocarbon group referred above, a hydroxyl group, a C1-C4 alkoxy group, a C2-C4 (poly)hydroxyalkoxy group, etc.; m is an integer of 0-4; e is an integer of 0-2; p is 0 or 1; x is an integer of 0-2; y is an integer of 0-6; and z is an integer of 0-6.

Description

Cationic azo dyes having julolidine units, compositions for dyeing comprising the same, and dyeing methods {CATIONIC AZO DYES WITH JULOLIDINE UNITS, DYEING COMPOSITION CONTAINING THEM, METHOD OF DYEING}

The present invention relates to the use of cationic azo compounds having a julolidine unit, the use as a direct dye for dyeing keratin fibers, in particular human keratin fibers such as hair; A dyeing composition comprising the azo compound; And a novel cationic azo compound having a compartment and a zololidine unit.

As a method for dyeing keratin fibers, especially human hair, a dyeing composition comprising an oxidizing dye precursor (commonly referred to as an oxidation base), such as ortho-phenylenediamine, para-phenylenediamine, ortho Dyeing using aminophenols, para-aminophenols, and heterocycle compounds is known. The base for oxidation is a colorless or pale colored compound, and when combined with the oxidation product, it can be converted into a colored compound by oxidative condensation.

By using such a base for oxidation in combination with a dyeing coupling agent or a modifier, it is known that the color tone obtained when using only the base for oxidation can be changed. Especially as the modifier, aromatic meta-diamine, meta-aminophenol, meta- Modifiers selected from diphenols and heterocycle compounds such as indole compounds can be used.

Various colors can be obtained by various molecules used as the base for oxidation and the coupling agent.

The so-called "permanent" dyeings obtained using such oxidizing dyes must meet several requirements. That is, it should not cause toxic problems, should be able to achieve the desired intensity of hue, and exhibit good resistance to external factors such as sunlight, weather, cleaning, permanent waving, sweat, and friction.

In addition, the dye should be capable of dyeing white hair and ultimately have minimal selectivity, that is, the dyed keratin fibers are typically sensitized to different levels between the hair tip and the hair root (i.e. , Damaged state), and the difference in the degree of coloring in one keratin fiber and in the same keratin fiber should be minimized.

In addition, a method of dyeing keratin fibers by direct dyeing or semi-permanent dyeing is known. The conventional direct dyeing method includes applying a dye directly to keratin fibers to color pigment molecules having affinity for the fibers; Leaving the pigment molecules for a time to penetrate into the hair by diffusion; And rinsing the fibers in water.

When using the composition for direct dyeing or semi-permanent dyeing, unlike the case of the oxidative dyeing composition, it is not necessary to use an oxidant as an essential component. This staining method can be performed repeatedly without damaging the keratin fibers.

Illustrative direct dyes usable in the aforementioned dyeing methods include nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, or triarylmethane direct dyes.

Such dyeing may impart color to the keratin fibers, but due to the binding properties between the direct dye and the keratin fibers, a temporary or semipermanent dye is obtained. That is, by this interaction between the dye and the fiber, the dye is easily separated from the surface and / or core of the keratinous fiber. The color obtained by the above-mentioned dyeing method is generally poor in washing or sweat resistance.

Accordingly, color uniformity of the quality of dyed hair, resistance to shampoo and resistance after shampooing (strength), limit of scouring which can cause partial discoloration, color developing dyes having different strengths In the combination of these, the development of a dye having a better performance, such as improved discoloration with time is required.

In addition, when using a conventional cationic direct dye can obtain a good color development, there is a disadvantage that the range of color is limited to a single color (yellow, orange, red). Therefore, there is also a need for the development of dyes that can be dyed in colors outside the conventional color range.

The Applicant has discovered that by using a cationic azo direct dye having a so-called “Julolidine” unit, the aforementioned properties can be improved.

U.S. Patent No. 4,341,853 describes the use of cationic direct dyes having such zololidine units as photosensitive agents for electrophotography.

The azo compounds of the present invention provide dyes that are resistant to external factors (daylight, climate), including shampooing, and sweating. The dyeing compositions of the present invention have a good toxicity profile. In addition, the dyes of the present invention can impart a vivid color, in particular blue and purple hues. According to the present invention, a wide range of colors can be obtained even when the dye of the present invention is used alone or in combination with other conventional direct dyes or oxide dyes.

It is an object of the present invention to provide the use of a cationic azo compound having a zololidine unit as a dye directly to keratin fibers, in particular human keratin fibers such as hair.

Another object of the present invention is a dyeing composition for dyeing keratin fibers, in particular human keratin fibers, such as hair, wherein at least one cationic azo compound having a zololidine unit according to the invention in a suitable dyeing medium It provides a dyeing composition comprising a.

It is also an object of the present invention to provide a dyeing method comprising the step of using a dyeing composition of the present invention as a method for dyeing keratin fibers, particularly human keratin fibers, such as hair.

Another object of the present invention is to provide a use of the composition for dyeing keratin fibers, in particular human keratin fibers, such as hair.

Still another object of the present invention is to provide a kit having a compartment containing the dyeing composition of the present invention.

Another object of the present invention is to provide a cationic azo compound having a zololidine unit.

Hereinafter, the characteristics, aspects, objects, and effects of the present invention will be described in more detail with reference to the detailed description of the present invention.

Unless stated otherwise in the following description, the boundary values in the numerical range are included in the above range.

The cationic azo compound having a zololidine unit of the present invention is a compound represented by the following general formula (I), or an addition salt or solvate of the compound:

In the general formula (I),

A represents a cationic aromatic heterocycle selected from compounds represented by the following general formulas (IIa) to (IIc):

(In each of the above general formulas (IIa) to (IIc),

Each R ₁ is independently of the other,

Optionally interrupted by one or more groups selected from a hetero atom, such as oxygen, nitrogen, or sulfur, and a carbonyl group, optionally substituted, optionally condensed with an aromatic ring, and one or more 3 to 7 Linear or branched, saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, capable of forming a cyclic carbon ring,

R ₁ is

 Without nitro bonds, nitroso bonds, peroxide bonds, and diazo bonds,

 Directly bonded to a quaternized or unquaternized nitrogen atom of the aromatic heterocycle A,

Each R ₂ is independently of the other,

Optionally disconnected, optionally substituted, by one or more heteroatoms, or by one or more groups having one or more heteroatoms, preferably one or more heteroatoms selected from oxygen and nitrogen; Linear or branched saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, which can form cyclic aromatic or non-aromatic carbon rings,

 Hydroxyl groups,

C ₁ -C ₄ alkoxy groups,

C ₂ -C ₄ (poly) hydroxyalkoxy groups,

An alkoxycarbonyl group (R ₁₁ O-CO-), wherein R ₁₁ represents a C ₁ -C ₄ alkyl radical,

Alkylcarbonyloxy radicals (R ₁₂ CO-O-), wherein R ₁₂ represents a C ₁ -C ₄ alkyl radical,

Amino groups; Or an amino group optionally substituted with one or two C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the two alkyl radicals may be the same or different from each other, wherein the alkyl radicals are the alkyl radicals Together with the bonded nitrogen atom, a 5 or 6 membered cyclic heterocycle can be optionally formed, and the heterocycle is a second hetero atom, nitrogen, or a hetero atom other than nitrogen, for example, oxygen, or May have sulfur),

Alkylcarbonylamino groups (R ₁₃ CO-NR _13- ) and / or (R ₁₃ CO-NH-), wherein each R ₁₃ radical independently of _one another represents a C ₁ -C ₄ alkyl radical,

Carbamoyl groups ((R ₁₄ ) ₂ N-CO), wherein each R ₁₄ radical, independently of one another, represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, which may be the same or different from each other,

A ureido group ((R ₁₅ ) ₂ N-CO-NR _16- ), wherein the R ₁₅ and R ₁₆ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical,

Sulfonamide groups ((R ₁₇ ) ₂ N-SO _2- ), wherein each R ₁₇ radical independently of one another represents a hydrogen atom or a C ₁ -C ₄ alkyl radical,

Alkylsulfonylamino groups (R ₁₈ SO ₂ -NR _19- ), wherein the R ₁₈ and R ₁₉ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical,

- guanidinyl nyumgi _{((R 20) 2 NC (} = NH 2 +) - NR 21 -) ( wherein, R ₂₀ and R ₂₁ radicals are independently of each other, hydrogen atom or a C ₁ ~C ₄ alkyl refers to the radical ),

 -Nitro groups,

 Cyano groups, or

 Halogen atoms, preferably chlorine, or fluorine

 Indicates,

Two R ₂ radicals together with the carbon atom to which each R ₂ radical is bonded may form an aromatic or non-aromatic fused ring,

 m is an integer from 0 to 4,

 e is an integer from 0 to 2,

 p is an integer from 0 to 1,

D represents a CR ₂ group or a nitrogen atom,

Q represents an NR ₁ group, an oxygen atom, or a sulfur atom,

 In each of the general formulas (IIa), (IIb), and (IIc), a bond is a bond formed between the azo group and the A group,

In each of the above general formulas (IIa), (IIb), or (IIc), when two R ₂ radicals bonded to two adjacent carbon atoms form an aromatic ring together with the carbon atom, the a bond is Through the aromatic ring formed, which may be formed between the azo group and the A group),

The electroneutrality of the compound is provided by one or more anions An ⁻ which may be cosmetically acceptable and may be the same or different from one another, and such anions include chloride, methylsulfate, methosulfate, tosylate, Acetate is included,

Each of X, Y, and Z means a substituent of a three-ring nucleus that is substituted for the alkyl and the aryl ring,

x is an integer from 0 to 2, y is an integer from 0 to 6, z is an integer from 0 to 6;

The compound is not known 2- (9-julolidilazo) -3-methylbenzothiazolium perchlorate, and 2- (9-julolidilazo) -3-ethylthiazolium perchlorate, which are known electrophotographic photosensitizers .

In this specification, unless stated otherwise, the contents are considered as follows:

When the alkyl radical in the general formula, or the alkyl portion of the radical is "substituted", said alkyl radical, or said alkyl portion, comprises one or more substituents selected from the following groups:

Hydroxyl groups,

C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and

Amino groups; Or an amino group optionally substituted with one or more C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the one or more alkyl radicals may be the same or different from one another and the alkyl radicals are bonded to the alkyl radicals. Together with the nitrogen atom, it is possible to form a 5 or 6 membered cyclic heterocycle, which heterocycle optionally has one or more hetero atoms other than nitrogen or nitrogen as the second hetero atom.

When the aryl or heteroaryl radical in the general formula or the aryl or heteroaryl portion of the radical is "substituted", for example, when the substituent X is substituted on the aromatic ring of the tricycle, the aryl or hetero An aryl radical, or said aryl or heteroaryl moiety, comprises one or more substituents bonded to a carbon atom, said substituents being selected from the following groups:

Hydroxy, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) -hydroxyalkoxy, acylamino, and amino substituted with one or two C ₁ -C ₄ alkyl radicals, wherein said alkyl The radicals may be the same or different from one another and optionally have one or more hydroxy groups, said alkyl radicals being 5 or 7 membered, preferably 5 or 6 membered hetero, together with the nitrogen atom to which the two radicals are bonded It can form a cycle, and wherein the heterocycle is a nitrogen, or it is optionally C ₁ ~C _16, preferably which is substituted with a second hetero atom other than the nitrogen by one or more radicals, which is optionally has) selected from C ₁ ~ C ₈ alkyl radical,

Halogen atoms such as chlorine, fluorine or bromine,

Hydroxyl groups,

C ₁ -C ₂ alkoxy radicals,

C ₂ -C ₄ (poly) -hydroxyalkoxy radicals,

Amino radicals,

Amino radicals substituted with one or two C ₁ -C ₄ alkyl radicals (which may be the same or different from each other), optionally having one or more hydroxy groups,

Acylamino radicals (-NR ₃₁ -COR ₃₂ ), wherein R ₃₁ radicals are hydrogen atoms; or C ₁ -C ₄ alkyl radicals optionally having one or more hydroxy groups, and R ₃₂ radicals are C ₁ -C ₂ alkyl Radicals),

Carbamoyl radicals ((R ₃₃ ) ₂ N—CO—), wherein each R ₃₃ radical may be the same or different from one another and is a hydrogen atom; or C ₁ to C ₄ optionally having one or more hydroxy groups Alkyl radicals),

Alkylsulfonylamino radicals (R ₃₄ SO ₂ -NR _35- ), wherein R ₃₄ radicals represent a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, wherein the R ₃₅ radical represents C _{1 to} C ₄ alkyl radical, or phenyl radical), and

Aminosulfonyl radicals ((R ₃₆ ) ₂ N-SO _2- ), wherein each R ₃₆ radical may be the same or different from one another and is a hydrogen atom; or C ₁ -C optionally having one or more hydroxy groups ₄ alkyl radical).

The non-aromatic radical when the ring or heterocyclic portion of the non-aromatic radical in the general formula is "substituted", for example, when substituents Y and Z are substituted on the aliphatic heterocycle of the tricyclic nucleus. The ring or heterocyclic moiety of comprises one or more substituents bonded to a carbon atom, said substituents being selected from the following groups:

Hydroxyl groups,

C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and

Alkylcarbonylamino (R ₄₁ CO-NR _42- ), wherein the R ₄₂ radical is a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, and the R ₄₁ radical is C ₁ -C _2-alkyl radical, a group or one or more hydroxy group (wherein substituted by two C ₁ ~C ₄ alkyl group optionally having, the alkyl group, which may be the same or different from each other, together with the nitrogen atom to which said alkyl group , Or a 5 or 6 membered cyclic heterocycle, which heterocycle optionally comprises one or more second hetero atoms, other than nitrogen).

If the ring does not have the maximum number of substituents, hydrogen is present in the unsubstituted position.

R ₁ in said general formula is preferably a C ₁ ~C ₈ alkyl group, or hydroxyalkyl group.

According to a first variant of the invention, each cationic aromatic heterocycle represented by the general formulas (IIa), (IIb), and (IIc) comprises two R ₂ radicals bonded to carbon atoms adjacent to each other. The radical may, together with the carbon atom to which the radical is bonded, form an optionally substituted aromatic fused ring.

According to the second modification of the present invention, e, m, and p in the general formula are each 0.

Preferably, when X in the said general formula represents an alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, or an acylamino group (wherein alkyl is a C _1- optionally substituted C ₆ chain, acyl represents alkylcarbonyl), x is 0 or 1.

Examples of the compound represented by the general formula (I) according to the present invention include compounds represented by the following structural formulas:

.

.

The dyes represented by the above general formulas can be prepared according to, for example, the following synthesis methods A, B, C, and D respectively different from each other.

In each of the following schemes, B is a noncationic precursor of A, represented by the following three structural formulas:

Hereinafter, HAL represents a halogen group bonded to R ₁ by one of R ₁ carbon atoms, preferably a chloro group, a bromo group, or an iodo group, and according to another embodiment of the present invention , HAL represents an alkylsulphato group, preferably methyl sulfato group or ethyl sulfato group, and according to another embodiment of the present invention, methylsulfonato group (mesylate group), or arylsulfonato (tosyl) Rate group).

1. Synthesis Method A

The compound represented by general formula (I) is obtained by a series of three step reactions as in the following scheme:

First, the conventional method (H Zollinger, Color Chemistry, Wiley VCH Ed 2003 and The Chemistry of synthetic dyes, Academic Press, London, vol II, 1952), diazonium salts of hetero aromatic amine BNH ₂ (1) ₍₂ in accordance with the ). The diazonium salt ( 2 ) is reacted with compound ( 3 ) to form compound ( 4 ) (aromatic amine with julolidine units). Reference may be made to the aforementioned references for this type of coupling reaction .

The third step of this synthesis process involves reacting compound ( 4 ) with an alkyl sulfate, such as an alkyl halide, alkyl alkylsulfonate, or alkyl arylsulfonate, thereby providing a compound ( 5 ), i.e., a cation having a julolidine unit. St. Azo directly dyes.

Such alkylation reactions are carried out, for example, at temperatures lower than 150 ° C. and in halogenated solvents (dichloromethane) or ester solvents (ethyl acetate), preferably with refluxing of the solvents. For these reaction conditions, reference may be made to the contents described in the aforementioned documents. In addition, with regard to this type of reaction, reference may be made to the contents described in Advanced Organic Synthesis 5th Ed M. Smith and J. March John Wiley & Sons Ed, 2001, and International Patent Application WO 03/060015.

2. Synthesis Method B

The compound represented by the general formula (I) can be obtained according to the reaction shown in the following scheme. First, the dia-amination of the para-aminoated derivative ( 6 ) of an aromatic amine with a zololidine unit is performed. Compound ( 8 ) is obtained by coupling-reacting the obtained diazonium salt ( 7 ) with a heterocycle. Then, by alkylating the heterocycle functional group of compound ( 8 ), compound ( 9 ) (cationic azo direct dye with julolidine units) is obtained:

All reaction steps according to this synthesis method can be referred to in the references, and reference of the synthesis method A can be referred to.

In particular, the second stage coupling reaction of the present synthesis process involves reacting the obtained diazonium salt ( 7 ) with heterocycle BH, where BH is hydrogen bonded to B present at the position of the azo group to be formed later. Represents an atom).

3. Synthesis Method C

The compound represented by the general formula (I) may be obtained by a two-step reaction as follows: First, a cationic heterocycle by a para-hydrazino compound of aromatic amine ( 10 ) having a zololidine unit Compound ( 12 ) is obtained by performing a nucleophilic attack on the carbon atom of [11], and compound ( 13 ) (cationic azo direct dye having a zololidine unit) is obtained by oxidizing the obtained compound ( 12 ). . In the above reaction, for example, a pyridinium type cationic heterocycle, preferably compound 11 , can be used as shown in the following scheme:

The formation reaction of compound ( 12 ) can be carried out at temperatures lower than 150 ° C. and in polar solvents, preferably alcohols or DMF, if necessary, in the presence of a base having a lower nucleophilicity than the selected hydrazine ( J. Med. Chem . 1996, 39 (2), 570-581). In addition, the oxidation reaction is preferably carried out in the presence of an acid, a conventional oxidizing agent such as N-bromosuccinimide, ferric chloride, manganese oxide, chromium oxide, hydrogen peroxide, or peracid ( peracid), at a temperature lower than 100 ° C. for less than 24 hours.

4. Synthesis Method D

In addition, the compound represented by the said general formula (I) may be synthesize | combined by an oxidative coupling reaction. This synthesis method can be referred to in the references. For example, reference is made to Angew. Chem. 1958, 70, 215; Angew. Chem., Int. Ed. , 1962, 1,640 and H Zollinger, Color Chemistry 3rd Ed, VCH Wiley, 2003. The reaction according to the present synthetic method is carried out using pyridinium as a heterocycle, more particularly with compound ( 14 ), as shown in the following scheme, whereby compound ( 17 ) (julolidine Cationic azo direct dyes with units) can be synthesized:

As the starting reactants used in the present invention, commercially available products or materials prepared according to methods known in the art can be used, and commercially available compounds are used.

The present invention also provides the use of a cationic azo compound, or an addition salt of said compound, or a solvent compound thereof, represented by the following general formula (I):

In the general formula (I),

A represents a cationic aromatic heterocycle selected from compounds represented by the following general formulas (IIa) to (IIc):

(In each of the above general formulas (IIa) to (IIc),

Each R ₁ is independently of the other,

Optionally interrupted by one or more groups selected from a hetero atom, such as oxygen, nitrogen, or sulfur, and a carbonyl group, optionally substituted, optionally condensed with an aromatic ring, and one or more 3 to 7 Linear or branched, saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, capable of forming a cyclic carbon ring,

R ₁ is

 Without nitro bonds, nitroso bonds, peroxide bonds, and diazo bonds,

 Directly bonded to a quaternized or unquaternized nitrogen atom of the aromatic heterocycle A,

Each R ₂ is independently of the other,

Optionally disconnected, optionally substituted, by one or more heteroatoms, or by one or more groups having one or more heteroatoms, preferably one or more heteroatoms selected from oxygen and nitrogen; Linear or branched saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, which can form cyclic aromatic or non-aromatic carbon rings,

 Hydroxyl groups,

C ₁ -C ₄ alkoxy groups,

C ₂ -C ₄ (poly) hydroxyalkoxy groups,

An alkoxycarbonyl group (R ₁₁ O-CO-), wherein R ₁₁ represents a C ₁ -C ₄ alkyl radical,

Alkylcarbonyloxy radicals (R ₁₂ CO-O-), wherein R ₁₂ represents a C ₁ -C ₄ alkyl radical,

Amino groups; Or an amino group optionally substituted with one or two C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the two alkyl radicals can be the same or different from one another, and the alkyl radicals are Together with the nitrogen atom to which the radical is bonded, a 5 or 6 membered cyclic heterocycle may be optionally formed, and the heterocycle is a second hetero atom, nitrogen, or a hetero atom other than nitrogen, for example, oxygen, or May have sulfur),

Alkylcarbonylamino groups (R ₁₃ CO-NR _13- ) and / or (R ₁₃ CO-NH-), wherein each R ₁₃ radical independently of _one another represents a C ₁ -C ₄ alkyl radical,

Carbamoyl groups ((R ₁₄ ) ₂ N-CO), wherein each R ₁₄ radical, independently of one another, represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, which may be the same or different from each other,

A ureido group ((R ₁₅ ) ₂ N-CO-NR _16- ), wherein the R ₁₅ and R ₁₆ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical,

Sulfonamide groups ((R ₁₇ ) ₂ N-SO _2- ), wherein each R ₁₇ radical independently of one another represents a hydrogen atom or a C ₁ -C ₄ alkyl radical,

Alkylsulfonylamino groups (R ₁₈ SO ₂ -NR _19- ), wherein the R ₁₈ and R ₁₉ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical,

- guanidinyl nyumgi _{((R 20) 2 NC (} = NH 2 +) - NR 21 -) ( wherein, R ₂₀ and R ₂₁ radicals are independently of each other, hydrogen atom or a C ₁ ~C ₄ alkyl refers to the radical ),

 -Nitro groups,

 Cyano groups, or

 Halogen atoms, preferably chlorine, or fluorine

 Indicates,

Two R ₂ radicals together with the carbon atom to which each R ₂ radical is bonded may form an aromatic or non-aromatic fused ring,

 m is an integer from 0 to 4,

 e is an integer from 0 to 2,

 p is an integer from 0 to 1,

D represents a CR ₂ group or a nitrogen atom,

Q represents an NR ₁ group, an oxygen atom, or a sulfur atom,

 In each of the general formulas (IIa), (IIb), and (IIc), a bond is a bond formed between the azo group and the A group,

In each of the above general formulas (IIa), (IIb), or (IIc), when two R ₂ radicals bonded to two adjacent carbon atoms form an aromatic ring together with the carbon atom, the a bond is Through the aromatic ring formed, which may be formed between the azo group and the A group),

The electroneutrality of the compound is provided by one or more anions An ⁻ which may be cosmetically acceptable and may be the same or different from one another, and such anions include chloride, methylsulfate, methosulfate, tosylate, Acetate,

Each of X, Y, and Z means a substituent of a three-ring nucleus that is substituted for the alkyl and the aryl ring,

x is an integer from 0 to 2, y is an integer from 0 to 6, z is an integer from 0 to 6.

In this specification, unless stated otherwise, the contents are considered as follows:

When the alkyl radical in the general formula, or the alkyl portion of the radical is "substituted", said alkyl radical, or said alkyl portion, comprises one or more substituents selected from the following groups:

Hydroxyl groups,

C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and

Amino groups; Or an amino group optionally substituted with one or more C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the one or more alkyl radicals may be the same or different from one another and the alkyl radicals are bonded to the alkyl radicals. Together with the nitrogen atom, it is possible to form a 5 or 6 membered cyclic heterocycle, which heterocycle optionally has one or more hetero atoms other than nitrogen or nitrogen as the second hetero atom.

When the aryl or heteroaryl radical in the general formula or the aryl or heteroaryl portion of the radical is "substituted", for example, when the substituent X is substituted on the aromatic ring of the tricycle, the aryl or hetero An aryl radical, or said aryl or heteroaryl moiety, comprises one or more substituents bonded to a carbon atom, said substituents being selected from the following groups:

Hydroxy, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) -hydroxyalkoxy, acylamino, and amino substituted with one or two C ₁ -C ₄ alkyl radicals, wherein said alkyl The radicals may be the same or different from one another and optionally have one or more hydroxy groups, said alkyl radicals being 5 or 7 membered, preferably 5 or 6 membered hetero, together with the nitrogen atom to which the two radicals are bonded It can form a cycle, and wherein the heterocycle is a nitrogen, or it is optionally C ₁ ~C _16, preferably which is substituted with a second hetero atom other than the nitrogen by one or more radicals, which is optionally has) selected from C ₁ ~ C ₈ alkyl radical,

Halogen atoms such as chlorine, fluorine or bromine,

Hydroxyl groups,

C ₁ -C ₂ alkoxy radicals,

C ₂ -C ₄ (poly) -hydroxyalkoxy radicals,

Amino radicals,

Amino radicals substituted with one or two C ₁ -C ₄ alkyl radicals (which may be the same or different from each other), optionally having one or more hydroxy groups,

Acylamino radicals (-NR ₃₁ -COR ₃₂ ), wherein R ₃₁ radicals are hydrogen atoms; or C ₁ -C ₄ alkyl radicals optionally having one or more hydroxy groups, and R ₃₂ radicals are C ₁ -C ₂ alkyl Radicals),

Carbamoyl radicals ((R ₃₃ ) ₂ N—CO—), wherein each R ₃₃ radical may be the same or different from one another and is a hydrogen atom; or C ₁ to C ₄ optionally having one or more hydroxy groups Alkyl radicals),

Alkylsulfonylamino radicals (R ₃₄ SO ₂ -NR _35- ), wherein R ₃₄ radicals represent a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, wherein the R ₃₅ radical represents C _{1 to} C ₄ alkyl radical, or phenyl radical), and

Aminosulfonyl radicals ((R ₃₆ ) ₂ N-SO _2- ), wherein each R ₃₆ radical may be the same or different from one another and is a hydrogen atom; or C ₁ -C optionally having one or more hydroxy groups ₄ alkyl radical).

The non-aromatic radical when the ring or heterocyclic portion of the non-aromatic radical in the general formula is "substituted", for example, when substituents Y and Z are substituted on the aliphatic heterocycle of the tricyclic nucleus. The ring or heterocyclic moiety of comprises one or more substituents bonded to a carbon atom, said substituents being selected from the following groups:

Hydroxyl groups,

C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and

Alkylcarbonylamino (R ₄₁ CO-NR _42- ), wherein the R ₄₂ radical is a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, and the R ₄₁ radical is C ₁ -C _2-alkyl radical, a group or one or more hydroxy group (here, which is substituted with two C ₁ ~C ₄ alkyl group optionally having, the alkyl group, which may be the same or different from each other, together with the nitrogen atom to which said alkyl group , 5 or 6 membered cyclic heterocycle, which heterocycle optionally includes one or more second hetero atoms, other than nitrogen or nitrogen.

If the ring does not have the maximum number of substituents, hydrogen is present in the unsubstituted position.

R ₁ in said general formula is preferably a C ₁ ~C ₈ alkyl group, or hydroxyalkyl group.

According to a first variant of the invention, each cationic aromatic heterocycle represented by the general formulas (IIa), (IIb) and (IIc) comprises two R ₂ radicals bonded to carbon atoms adjacent to each other. The radical may, together with the carbon atom to which the radical is bonded, form an optionally substituted aromatic fused ring.

According to the second modification of the present invention, e, m, and p in the general formula are each 0.

Preferably, when X in the said general formula represents an alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, or an acylamino group (wherein alkyl is a C _1- optionally substituted C ₆ chain, acyl represents alkylcarbonyl), x is 0 or 1.

Examples of the compound represented by the general formula (I) according to the present invention include compounds represented by the following structural formulas:

.

.

In addition, the present invention provides a dyeing composition for dyeing keratin fibers, in particular human keratin fibers, such as hair, comprising at least one cationic azo compound described above as a direct dye in a suitable dyeing medium.

The dyeing composition of the present invention comprises a cationic azo direct dye represented by the general formula (I) in an amount of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, based on the total weight of the composition. do.

The dyeing composition may further include one or more bases for oxidation.

Examples of such a base for oxidation include phenylenediamine, bis-phenylalkylenediamine, para-aminophenol, ortho-aminophenol, heterocyclic base, and addition salts thereof.

Specific examples of what can be used as the phenylenediamine include paraphenylenediamine, paratoluenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, and 2,6-dimethyl paraphenylenediamine. , 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl para Phenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl ) Amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloro aniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine , 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine, 2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl parape Rendiamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylene Diamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-β hydroxyethylamino 5-amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine, and acids thereof Addition salts may be mentioned.

Examples of the paraphenylenediamine preferably used include paraphenylenediamine, paratoluenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, and 2-β-. Hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxy Oxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, and acid addition salts thereof.

Preferred examples of the bis-phenylalkylenediamine include N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino. Propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3, 6-dioxaoctane, and addition salts thereof.

Illustrative examples of the para-aminophenol that are preferably used include para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino-3-chlorophenol, and 4-amino 3-. Hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β- Hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol, and acid addition salts thereof.

Preferred examples of the ortho-aminophenol are preferably 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and addition thereof. Salts.

Examples of the heterocycle base include pyridine derivatives, pyrimidine derivatives, and pyrazole derivatives.

Examples of the pyridine derivatives include compounds described in British Patent 1 026 978 and British Patent 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 3,4- Diamino pyridine and addition salts thereof.

In addition to the foregoing, examples of the pyridine oxidation base usable in the present invention include 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases, or addition salts thereof, as described in French Patent Application 28013083. Can be. Specific examples of such pyridine oxidation bases include pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridine-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; Pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; Pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2-[(3-amino-pyrazolo [1,5-a] pyridin-5-yl)-(2-hydroxyethyl) -amino] -ethanol; 2-[(3-amino-pyrazolo [1,5-a] pyridin-7-yl)-(2-hydroxyethyl) -amino] -ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol, and addition salts thereof.

As an example of the said pyrimidine derivative, German patent # 2359399; Japanese Patent No. 88-169571; Japanese Patent Application No. 05-63124; Each compound described in European Patent 0770375, or International Patent Application 96/15765, such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2- Hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and addition salts thereof and tautomers thereof (However, when the tautomer equilibrium state is achieved).

Examples of the pyrazole derivatives include the compounds described in German Patent 3843892, German Patent # 4133957, and International Patent # 94/08969, International Patent # 94/08970, French Patent A-2 733 749, and German Patent 195 43 988, for example, 4,5-diamino 1-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4 ' -Chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole , 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4 , 5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyra Sol, 4,5-diamino 1-ethyl 3- (4'-methoxyphenyl) pyrazole, 4,5-diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-di Mino 3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1 -Methyl 4-methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and addition salts thereof. 4,5-diamino 1- (β-methoxyethyl) pyrazole may also be used as the pyrazole derivative.

The base for oxidation is included in the dyeing composition of the present invention, typically in an amount of 0.001 to 20% by weight, preferably 0.005 to 6% by weight based on the total weight of the composition.

When the dyeing composition of the present invention comprises at least one base for oxidation, the composition preferably comprises at least one coupling agent commonly used for dyeing keratin fibers. Examples of the coupling agent that can be used include meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene coupling agent, heterocycle coupling agent, and addition salts thereof.

Specific examples of coupling agents usable in the present invention include 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4- Diamino 1- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis- (2, 4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β-hydroxyethylamino-3,4- Methylenedioxybenzene, α-naphthol, 2 methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6- Hydroxy benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- ( (beta) -hydroxyethylamino) toluene and these addition salts are mentioned.

The coupling agent is included in the dyeing composition of the present invention in an amount of about 0.001 to 20% by weight, preferably 0.005 to 6% by weight based on the total weight of the composition.

Generally, examples of the addition salt of the oxidizing base and the addition salt of the coupling agent, which can be used in the present invention, include hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate and tosylate. Acid addition salts such as benzenesulfonate, phosphate, and acetate; And base addition salts such as sodium salts, potassium salts, ammonia, amines, or alkanolamines.

In addition to the cationic azo direct dye represented by the general formula (I), the dyeing composition of the present invention may further include one or more second direct dyes. For example, the second direct dye may be neutral, acidic, or Cationic benzene-based nitro dyes; Neutral, acidic, or cationic azo direct dyes; Quinone direct dyes, preferably neutral, acidic, or cationic anthraquinone direct dyes; Azine direct dyes; Direct dyes selected from triarylmethane direct dyes, indoamino direct dyes, and natural direct dyes. Specific examples of such a second direct dye include benzene nitro dye, azo dye, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenothiazine indigoid, and xanthene. (xanthene), phenanthridine, phthalocyanine dyes, dyes derived from triarylmethane, and dyes selected from natural dyes, but are not limited to the foregoing, and the dyes may be used alone or as a mixture. It can also be used in combination.

Illustrative dyes usable in the present invention as the benzene direct dyes include, but are not limited to, the following compounds:

1,4-diamino-2-nitrobenzene,

1-amino-2 nitro-4-β-hydroxyethylaminobenzene,

1-amino-2 nitro-4-bis (β-hydroxyethyl) -aminobenzene,

1,4-bis (β-hydroxyethylamino) -2-nitrobenzene,

1-β-hydroxyethylamino-2-nitro-4-bis- (β-hydroxyethylamino) -benzene,

1-β-hydroxyethylamino-2-nitro-4-aminobenzene,

1-β-hydroxyethylamino-2-nitro-4- (ethyl) (β-hydroxyethyl) -aminobenzene,

1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene,

1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene,

1,2-diamino-4-nitrobenzene,

1-amino-2-β-hydroxyethylamino-5-nitrobenzene,

1,2-bis- (β-hydroxyethylamino) -4-nitrobenzene,

1-amino-2-tris- (hydroxymethyl) -methylamino-5-nitrobenzene,

1-hydroxy-2-amino-5-nitrobenzene,

1-hydroxy-2-amino-4-nitrobenzene,

1-hydroxy-3-nitro-4-aminobenzene,

1-hydroxy-2-amino-4,6-dinitrobenzene,

1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene,

1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene,

1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene,

1-β, γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene,

1-β-hydroxyethylamino-4-β, γ-dihydroxypropyloxy-2-nitrobenzene,

1-β, γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene,

1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene,

1-β-hydroxyethylamino-3-methyl-2-nitrobenzene,

1-β-aminoethylamino-5-methoxy-2-nitrobenzene,

1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene,

1-hydroxy-2-chloro-6-amino-4-nitrobenzene,

1-hydroxy-6-bis- (β-hydroxyethyl) -amino-3-nitrobenzene,

1-β-hydroxyethylamino-2-nitrobenzene,

1-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Illustrative dyes usable in the present invention as the azo direct dyes include cationic azo dyes described in International Patent No. 95/15144, International Patent 95/01772, and European Patent 714954. The entirety of which is incorporated herein by reference.

Among the aforementioned dye compounds, it is particularly preferable to use the following dyes:

1,3-dimethyl-2-[[4- (dimethylamino) phenyl] azo] -1 H-imidazolium chloride,

1,3-dimethyl-2-[(4-aminophenyl) azo] -1 H-imidazolium chloride,

1-methyl-4-[(methylphenylhydrazino) methyl] -pyridinium methyl sulfate.

As the second direct dye, the following dyes described in the Color Index International Third Edition may also be used:

Disperse Red 17,

Acid Yellow 9,

Acid Black 1,

Basic Red 22,

Basic Red 76,

Basic Yellow 57,

Basic Brown 16,

Acid Yellow 36,

Acid Orange 7,

Acid Red 33,

Acid Red 35,

Basic Brown 17,

Acid Yellow 23,

Acid Orange 24,

Disperse Black 9.

In addition, 1- (4'-aminodiphenylazo) -2-methyl-4-bis- (β-hydroxyethyl) aminobenzene, and 4-hydroxy-3- (2-methoxyphenylazo)- 1-naphthalene sulfonic acid can also be used.

Illustrative dye compounds preferably used in the direct dyes are as follows:

Disperse Red 15,

Solvent Violet 13,

Acid violet 43,

Disperse Violet 1,

Disperse Violet 4,

Disperse Blue 1,

Disperse Violet 8,

Disperse Blue 3,

Disperse Red 11,

Acid blue 62,

Disperse Blue 7,

Basic Blue 22,

Disperse Violet 15,

Basic Blue 99,

1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone,

1-aminopropylamino-4-methylaminoanthraquinone,

1-aminopropylaminoanthraquinone,

5-β-hydroxyethyl-1,4-diaminoanthraquinone,

2-aminoethylaminoanthraquinone,

1,4-bis- (β, γ-dihydroxypropylamino) -anthraquinone.

Further, exemplarily used as the azine dye is as follows:

Basic Blue 17,

Basic Red 2.

Illustrative ones usable as the triarylmethane dyes are as follows:

Basic Green 1,

Acid blue 9,

Basic violet 3,

Basic violet 14,

Basic Blue 7,

Acid Violet 49,

Basic Blue 26,

Acid Blue 7.

Illustrative ones usable as the indoamino dyes are as follows:

2-β-hydroxyethylamino-5- [bis- (β-4′-hydroxyethyl) amino] anilino-1,4-benzoquinone,

2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone,

3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine,

3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine,

3- [4'-N- (ethyl, carbamylmethyl) -amino] -phenyl-ureido-6-methyl-1,4-benzoquinone imine.

Illustrative examples of those usable as the tetraazapentamethine type dyes include compounds represented by the following general formulas:

In addition, examples of the natural dyes that can be used in the present invention include lawsonone, juglone, alizarin, purpurin, carminic acid, and kermesic acid. ), Purpurogallin, protocatechaldehyde, indigo, isatitin, curcumine, spinulosine, and apigenidine Can be. It is also possible to use extracts or decoctions containing the above-mentioned natural dyes, and well-known henna-based poultices or extracts.

The aforementioned second direct dye is different from the compound represented by the general formula (I) and is included in the composition of the present invention in an amount of about 0.001 to 20% by weight, preferably about 0.005 to 10% by weight.

In addition, the dyeing composition of the present invention is one or more oxidizing agents commonly used for the oxidative dyeing of keratin fibers, such as hydrogen peroxide, urea peroxide, alkali metal bromate, persalt (e.g. perborate and fur) Sulfate), peracids, and oxidases (e.g. peroxidase, two-electron oxidase-reductases such as uricase, and four-electron oxygenases, e.g. For example, laccases may be further included. In particular, it is preferable to use hydrogen peroxide as said oxidizing agent.

As the dyeing medium, so-called dyeing support, it is common to use a cosmetic medium including water or a mixture of one or more organic solvents and water used to dissolve a compound that is not sufficiently soluble in water. desirable. Examples of the organic solvent include C _{1 to} C ₄ lower alkanols such as ethanol and isopropanol; Ethers of polyols and polyols, for example 2-butoxyethanol, propylene glycol, glycerol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, and aromatic alcohols such as benzyl alcohol Or phenoxyethanol, and mixtures thereof.

The organic solvent is included in the dyeing composition of the present invention in an amount of about 1 to 40% by weight based on the total weight of the composition, preferably in an amount of about 5 to 30% by weight.

The dyeing composition of the present invention is a variety of additives commonly used in hair dyeing compositions, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants. , Zwitterionic surfactants, or mixtures thereof; Anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers, zwitterionic polymers, or mixtures thereof; Mineral thickeners and organic thickeners, preferably associative polymeric thickening agents, antioxidants, penetrating agents, metal ion sequestering agents having anionic, cationic, nonionic, and amphoteric properties agents, perfumes, buffers, dispersants, conditioners such as volatile or nonvolatile modified or unmodified silicones, film formers, ceramides, preservatives, opacifiers have.

The various additives may be included in the amount of 0.01 to 20% by weight in the dyeing composition of the present invention, respectively.

Those skilled in the art will appreciate that one or more additional compounds may be selected and added within a range that does not inhibit the desirable properties inherent in the dyeing composition of the present invention, that is, within a range that does not substantially impair.

The dyeing composition of the present invention usually has a pH value of 3 to 12, preferably 5 to 11, and more preferably 6 to 10.5. The pH of the composition for dyeing can be adjusted to a desired value using an acidifying agent or an alkalizing agent commonly used for dyeing keratin fibers or using a conventional buffering system.

Examples of those which can be used as the acidifying agent include mineral acids or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid and sulfonic acid.

Examples of those usable as the basicizing agent include sodium hydroxide or potassium hydroxide in addition to ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and the following general formula The compound represented by (II), and its derivative (s) are mentioned:

(In the general formula (II),

W is a propylene moiety optionally substituted with a hydroxy group or a C ₁ -C ₄ alkyl radical; Each of R _a , R _b , R _c , and R _d represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, or a C ₁ -C ₄ hydrocyalkyl radical, which may be the same or different from each other).

The dyeing compositions of the present invention can be used in various forms, such as liquids, creams, gels, or keratin fibres, in particular other forms suitable for dyeing human hair.

The dyeing method of the present invention comprises applying the composition of the present invention to keratinous fibers and then rinsing the fibers in water.

According to one embodiment of the present invention, the composition of the present invention is applied to keratinous fibers in the presence of an oxidizing agent, and this dyeing is called highlighting dyeing. When used, the oxidant may be added to the composition of the present invention, or may be added as a composition for oxidation containing the oxidant, or after providing the composition of the present invention.

According to a preferred embodiment of the present invention, the dyeing composition of the present invention comprises at least one base for oxidation.

According to the dyeing method of an embodiment of the present invention, the dyeing composition of the present invention with or without an oxidizing agent is applied to a keratin material, and then, with the composition applied, for about 3 minutes to 1 hour, preferably about 15 After leaving for 45 minutes, the keratin fibers are rinsed with water, then rinsed with shampoo, then rinsed with water and dried.

The oxidation composition may further include various additives commonly used in hair dyeing compositions, and examples of such additives are as described above.

The pH of the oxidizing composition comprising the oxidizing agent is, after mixing with the dyeing composition, the pH of the composition obtained for dyeing keratin fibers is about 3 to 12, preferably 5 to 11, more preferably 6 To 10.5. The pH of the oxidizing composition may be adjusted to a desired value using an acidifying agent or an alkalizing agent commonly used for dyeing keratin fibers, and examples of such an acidifying agent and a basicizing agent are as described above.

The final dyeing composition to be finally applied to the keratinous fibers can take various forms, such as in the form of liquids, creams, gels, or other forms suitable for dyeing keratinous fibers, in particular human hair.

The present invention further relates to the use for keratin fiber dyeing of the dyeing composition of the present invention.

In addition, the present invention, a kit or a kit for dyeing having a plurality of compartments, comprising: a first compartment comprising a dyeing composition of the present invention; And a second compartment comprising an oxidant. The kit may be provided with means for supplying a suitable mixture to the hair, such as in the kit described in Applicant's French Patent 2 586 913.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Preparation Examples of Compounds of the Invention

Example 1 Preparation of Compounds of the Invention According to Synthesis Method A

To 200 μg of a 40% w / v nitrosilsulfate solution in sulfuric acid was added 100 mL mL of acetic anhydride and 500 mL mL propionic anhydride, and the resulting mixture was cooled to a temperature lower than 5 ° C., followed by 50 μg of 4- Aminopyridine was added slowly. The mixture obtained was diluted by adding 200 mL of propionic acid and 40 mL of acetic acid, followed by diluting a solution obtained by dissolving 50 μg of gluolidine in 200 mL of methanol while maintaining the reaction temperature at a temperature lower than 10 ° C. Added. After 16 hours, the mixture was neutralized by adding 500 mL mL of water, 300 mL g ice and then 30 mL of soda at a temperature lower than 5 ° C. to the reaction mixture. The resulting product (A) was extracted with ethyl acetate and then purified by silica gel chromatography.

5 mL of dimethylsulfate was added to the purified product (A), and then diluted in 50 mL of dichloromethane, and the reaction mixture obtained was stirred for 2 hours. The mixture was then concentrated by distilling the solvent under vacuum, then the residue was dissolved and purified in methyl ethyl ketone and then precipitated using heptane. As a result, 7.12 g of blue powder was obtained. As a result of analyzing the obtained final product, it was confirmed that it is compound [i].

Example 2: Preparation of Compounds of the Invention According to Synthesis Method A

30 mL of 35% sulfuric acid was added to 13.21 mL of the suspension obtained by suspending aminoimidazole in 100 mL of water, and the resulting mixture was cooled to -5 ° C, and then the reaction temperature was maintained at a temperature lower than 0 ° C. A solution obtained by dissolving 7 g of sodium nitrite in mL water was added dropwise. Then, after adding 5 μg of sulfanilic acid, the obtained mixture was mixed with 8.75 μg of gluolidine, 175 mL of water, 225 mL of acetic acid, and 40 g of sodium acetate. It was added to the obtained acid solution of gluolidine, at which time the reaction temperature was maintained at 0 ° C. After 2 hours at 5 ° C., the reaction mixture was diluted and the pH value was adjusted to 8 using soda. The precipitated product (B) was filtered off and washed with water.

5 g of product (B) was dissolved in 50 mL mL of dichloromethane, and then 5 mL mL of dimethylsulfate, and 1.53 mL of sodium acetate were added successively. The resulting mixture was stirred for 2 hours, then concentrated in vacuo, then the product was obtained in 100 mL of methyl ethyl ketone and then 100 mL of heptane was added to the product. The precipitate thus obtained was washed with heptane to obtain 4.5 g of violet-black powder. After treating the powder with an ion exchange resin, the expected product [ii] was obtained in the form of hydrochloride (2.56 g). As a result of analyzing the expected product, it was identified that it is Compound [ii].

Example 3: Preparation of Compounds of the Invention According to Synthesis Method A

In a 500 mL three-necked flask, 6.3 μg of 3-aminopyridine, 17 mL of 35% hydrochloric acid, and 65 μg of ice were mixed. Then, while maintaining the temperature of the obtained mixture at 0 ° C., a solution obtained by dissolving 5.08 μg of sodium nitrite in 20 mL of water was added dropwise. After the addition was completed, the resulting mixture was stirred at 0 ° C. for 20 minutes, and then a solution obtained by dissolving 400 mg mg of urea in 10 mL mL water was added. Then, 11.6 얻어진 g of gluolidine was dissolved in a mixture of ethanol (25 mL), 35% hydrochloric acid (16 mL) and ice (22 g) while maintaining the temperature of the obtained mixture at a temperature lower than 10 ° C. The obtained solution was added dropwise. After 3 hours at 5 ° C., the mixture was neutralized by addition of ammonia until the pH of the reaction mixture reached 9.5. It extracted using ethyl acetate, adding water to the paste thus obtained. The organic phase obtained was dried and then concentrated in vacuo. The resulting product was purified by chromatography (silica gel, eluting solvent: heptane / ethyl acetate), and then a pure fraction of the dark red powder was collected (4.3 g), which fractionated to the expected compound (Compound (C)). It is a corresponding compound.

The product (127 mg) obtained in the above step was dissolved in toluene (5 mL), then 86 of dimethylsulfate was added, and the reaction mixture obtained was stirred for 72 hours. After the toluene was removed under vacuum, the resulting product was treated with water at room temperature for 4 hours and then dried under vacuum to give a dark purple solid (170 mg). The solid was analyzed and found to be the expected compound [iii].

Example 4: Preparation of Compounds of the Invention According to Synthesis Method A

10 g of 2-amino-1-methyl benzimidazole was dissolved in a high temperature mixture of 60 mL mL of orthophosphoric acid and 20 mL mL of acetic acid to obtain a first solution.

In a 250 mL three-necked flask equipped with a thermometer and an argon inlet, dilute 26 μg of nitrosulfuric acid (40% in sulfuric acid) to 25 mL of 98% phosphoric acid at a temperature of 10 ° C. Got it.

The first solution was added dropwise to the second solution for 30 minutes while maintaining the reaction temperature in the range of 2-5 ° C. The mixture thus obtained was stirred for 15 minutes. Then, after adding 3.3 g of sulfamic acid, the obtained mixture was stirred for 15 minutes.

13 g of gluolidine premelted was dissolved in 25 mL of DMF and 9 g of acetic acid to obtain a solution.

The diazonium salt obtained in the above-mentioned process was added dropwise to the solution while maintaining the reaction temperature at a temperature lower than 10 ° C. The resulting mixture was diluted with 50 mL of water and then left at 0 ° C. for 18 hours. Then, 500 g of ice was added, followed by 100 mL of 30% soda, followed by 500 g of ice, and 150 mL of 30% soda. The mixture thus obtained was diluted again with 2 L of water, and then the pH value of the dilution was adjusted to 7 by addition of sodium bicarbonate (190 g).

The precipitate obtained was filtered off (9.6 g) and then dried. Then 1 g was purified by chromatography (silica, elution solvent: dichloromethane / methanol). As a result, 100 mg of red powder was obtained. The powder was analyzed and found to be the expected compound (D).

100 mg of Compound (D) was dissolved in 20 mL of dichloromethane, and then 500 of dimethyl sulfate was added dropwise at room temperature. The resulting solution was stirred for 5 minutes and then added to 250 mL of ethyl ether. The resulting precipitate was filtered off and washed with 4 × 50 mL mL of ethyl ether. After drying, 50 mg of black paste was recovered. The paste was analyzed and found to be the expected compound [iv].

Example 5: Preparation of Compounds of the Invention According to Synthesis Method A

An acid solution of zulolidine was obtained by adding 5.7 mL of 35% hydrochloric acid to 100 mL of water, and then dissolving 11.8 g of gluolidine at 40 ° C. in the resulting mixture. Meanwhile, 17.4 mL of 35% hydrochloric acid was added to 100 mL of water, and then 10 g of pyridin-2-amine 1-oxide (prepared according to the method described in Synth. Commun . 1977, 509-514) to the resulting mixture. Was added. While maintaining the temperature of the resulting mixture at 0 ° C., a solution consisting of 10 mL of water and 4.7 g of sodium nitrite was added. The mixture thus obtained was stirred at 0 ° C. for 30 minutes. The mixture was then added to the acid solution of zulolidine while maintaining the reaction temperature below 10 ° C. The temperature of the resulting mixture was raised to room temperature for 2 hours. The pH of the mixture was adjusted to 4.2 by adding 70 g of sodium acetate to the mixture. Then, the mixture was extracted with dichloromethane, washed with water, dried over sodium sulfate, filtered and concentrated in vacuo, triturated in ether, and then the obtained powder was filtered and then dried in vacuo. , 10 g of dark purple powders were obtained. Analysis of the powder confirmed that it was a compound corresponding to the expected product (E) with a small amount of impurities.

5 g of product (E) was dissolved in 20 mL mL of N-methylpyrrolidone (NMP), and then the resulting solution was heated to 60 ° C. Then, 4.05 lg of dimethylsulfate was added. After 2 hours 30 minutes, the solution was cooled to room temperature. 50 mL of 20% ammonia solution was added to the cooled solution. The resulting mixture was left at room temperature for 15 hours, extracted with dichloromethane (2 x 100 mL), washed with water, dried and concentrated in vacuo. The resulting dark blue oil was washed twice with isopropyl ether and then triturated in the third fraction. The milled product was filtered off, washed with ether and then dried under vacuum to give 2 g of brown powder. The brown powder was analyzed and found to be the expected compound [v].

Examples regarding dyeing (non-highlighting conditions):

Each dyeing composition was prepared in the following proportions:

Solution 1

  Hydroxyethylcellulose Natrosol 250MR   0.72 g   Alkyl C8 / C10 (50:50) hydroxyethylcellulose CG110   5 g   Benzyl alcohol   4 g   Polyethylene Glycol 400   4 g   water   qs 100 g

Solution 2: Buffer pH 9.5

Ammonium Chloride (NH ₄ Cl)   5.4 g   Ammonia Solution (20%)   qs pH 9.5 (about 4 mL)   Demineralized water   qs 100 mL

Solution 3: buffer pH 7

KH ₂ PO ₄   0.026 mol / L Na ₂ PO ₄   0.041 mol / L   Demineralized water   qs 500 mL

Each dyeing composition was prepared by dissolving each of the following dyes (5 × 10 ⁻³ mol / L) in Solution 1 and then adding equal volume of Buffer 2 or Buffer 3 (pH 9.5 or pH 7). .

Each composition was applied to gray hair with 90% gray hair (applied in an amount of 6 g of the solution per gram of hair). After leaving for 30 minutes with the composition applied, the hair was rinsed in water, then washed using a standard shampoo, rinsed again in water, and then dried.

The results of applying the respective dyeing compositions are as follows:

pH 7 pH 9.5 Dyes [i] Vivid blue color Vivid blue color Dyes [ii] Vivid purple color Vivid purple color Dyes [iii] Vivid fuchsia develops Vivid reddish purple color Dyes [iv] Vivid blue color Vivid blue color Dyes [v] Vivid blue-violet is developed Vivid blue purple color

Examples on Dyeing (Highlighting Conditions):

Each dyeing composition was prepared in the following proportions:

  dyes   0.25 g   Hydroxyethylcellulose Natrosol 250MR   0.72 g   Alkyl C8 / C10 (50:50) hydroxyethylcellulose CG110   5 g   Benzyl alcohol   4 g   Polyethylene Glycol 400   4 g   Ammonium hydroxide   13 g   water   qs 100 g

When using the composition, each composition was mixed with 40 vol. Applies). After leaving for 30 minutes with the composition applied, the hair was rinsed with water, then washed with a standard shampoo, then rinsed with water again and dried.

The results of applying the respective dyeing compositions are as follows:

  NW   PW   Dyes [i]   Vivid blue color   Vivid blue color   Dyes [ii]   Vivid purple color   Vivid purple color

For each hair dyed, 12 shampoo treatments (using a standard shampoo) were performed to evaluate the color after 12 shampoo treatments to test the wash-resistance of each of the dyeing compositions. After 12 shampoos of each dyed hair, each hair was still colored.

According to the present invention, it is possible to provide a dye that is resistant to external factors (daylight, climate), including shampooing and sweating. The dyeing compositions of the present invention have a good toxicity profile. In addition, the dyes of the present invention can impart a vivid color, in particular blue and purple hues. According to the present invention, a wide range of colors can be obtained even when the dye of the present invention is used alone or in combination with other conventional direct dyes or oxide dyes.

Claims (27)

Staining for dyeing keratinous fibers, represented by the following general formula (I) and comprising at least one cationic azo compound having a julolidine unit, or an addition salt or solvate of said compound Composition for:

In the general formula (I), A represents a cationic aromatic heterocycle selected from compounds represented by the following general formulas (IIa) to (IIc):

(In each of the above general formulas (IIa) to (IIc), Each R ₁ is independently of the other, Optionally interrupted by one or more groups selected from a hetero atom, such as oxygen, nitrogen, or sulfur, and a carbonyl group, optionally substituted, optionally condensed with an aromatic ring, and one or more 3 to 7 Linear or branched, saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, capable of forming a cyclic carbon ring, R ₁ is  Without nitro bonds, nitroso bonds, peroxide bonds, and diazo bonds,  Directly bonded to a quaternized or unquaternized nitrogen atom of the aromatic heterocycle A, Each R ₂ is independently of the other, Optionally disconnected, optionally substituted by one or more heteroatoms, or by one or more groups having one or more heteroatoms, to form one or more 3- to 6-membered aromatic or non-aromatic carbon rings Linear or branched saturated or unsaturated C ₁ to C ₁₆ hydrocarbon chain,  Hydroxyl groups, C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, An alkoxycarbonyl group (R ₁₁ O-CO-), wherein R ₁₁ represents a C ₁ -C ₄ alkyl radical, Alkylcarbonyloxy radicals (R ₁₂ CO-O-), wherein R ₁₂ represents a C ₁ -C ₄ alkyl radical, Amino groups; Or an amino group optionally substituted with one or two C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the two alkyl radicals may be the same or different from each other, wherein the alkyl radicals are the alkyl radicals Together with the nitrogen atom to which it is attached, may optionally form a 5 or 6 membered cyclic heterocycle, which heterocycle may have nitrogen as the second hetero atom, or a hetero atom other than nitrogen), An alkylcarbonylamino group (R ₁₃ CO-NR _13- ) or (R ₁₃ CO-NH-), wherein each R ₁₃ radical independently of _one another represents a C ₁ -C ₄ alkyl radical, Carbamoyl groups ((R ₁₄ ) ₂ N-CO), wherein each R ₁₄ radical, independently of one another, represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, which may be the same or different from each other, A ureido group ((R ₁₅ ) ₂ N-CO-NR _16- ), wherein the R ₁₅ and R ₁₆ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical, Sulfonamide groups ((R ₁₇ ) ₂ N-SO _2- ), wherein each R ₁₇ radical independently of one another represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, Alkylsulfonylamino groups (R ₁₈ SO ₂ -NR _19- ), wherein the R ₁₈ and R ₁₉ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical, - guanidinyl nyumgi _{((R 20) 2 NC (} = NH 2 +) - NR 21 -) ( wherein, R ₂₀ and R ₂₁ radicals are independently of each other, hydrogen atom or a C ₁ ~C ₄ alkyl refers to the radical ),  -Nitro groups,  Cyano groups, or  Halogen atoms Indicates, Two R ₂ radicals together with the carbon atom to which each R ₂ radical is bonded may form an aromatic or non-aromatic fused ring,  m is an integer from 0 to 4,  e is an integer from 0 to 2,  p is an integer from 0 to 1, D represents a CR ₂ group or a nitrogen atom, Q represents an NR ₁ group, an oxygen atom, or a sulfur atom,  In each of the general formulas (IIa), (IIb), and (IIc), a bond is a bond formed between the azo group and the A group, In each of the above general formulas (IIa), (IIb), or (IIc), when two R ₂ radicals bonded to two adjacent carbon atoms form an aromatic ring together with the carbon atom, the a bond is Through the aromatic ring formed, which may be formed between the azo group and the A group), The electroneutrality of the compound is provided by one or more anions An ⁻ which are cosmetically acceptable and can be the same or different from each other, Each of X, Y, and Z means a substituent of a three-ring nucleus that is substituted for the alkyl and the aryl ring, x is an integer from 0 to 2, y is an integer from 0 to 6, z is an integer from 0 to 6; When the alkyl radical or alkyl portion of the radical is "substituted", the alkyl radical, or alkyl portion of the radical, comprises one or more substituents selected from the following groups: Hydroxyl groups, C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and Amino groups; Or an amino group optionally substituted with one or more C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the one or more alkyl radicals may be the same or different from one another and the alkyl radicals are bonded to the alkyl radicals. Together with the nitrogen atom, it is possible to form a 5 or 6 membered cyclic heterocycle, said heterocycle optionally having one or more hetero atoms other than nitrogen or nitrogen as the second hetero atom); When the aryl or heteroaryl radical or aryl or heteroaryl portion of the radical is "substituted", the aryl or heteroaryl radical, or aryl or heteroaryl portion of the radical, may be substituted with one or more substituents bonded to a carbon atom. Wherein the substituents are selected from the following groups: Hydroxy, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) -hydroxyalkoxy, acylamino, and amino substituted with one or two C ₁ -C ₄ alkyl radicals, wherein said alkyl The radicals may be the same or different from one another, optionally have one or more hydroxy groups, the alkyl radicals together with the nitrogen atom to which the two radicals are bonded, to form a five or seven membered cyclic heterocycle, the hetero The cycle is a C ₁ -C ₁₆ alkyl radical optionally substituted with one or more radicals selected from nitrogen or a second hetero atom other than nitrogen), Halogen atoms, Hydroxyl groups, C ₁ -C ₂ alkoxy radicals, C ₂ -C ₄ (poly) -hydroxyalkoxy radicals, Amino radicals, Amino radicals substituted with one or two C ₁ -C ₄ alkyl radicals (which may be the same or different from each other), optionally having one or more hydroxy groups, Acylamino radicals (-NR ₃₁ -COR ₃₂ ), wherein R ₃₁ radicals are hydrogen atoms; or C ₁ -C ₄ alkyl radicals optionally having one or more hydroxy groups, and R ₃₂ radicals are C ₁ -C ₂ alkyl Radicals), Carbamoyl radicals ((R ₃₃ ) ₂ N—CO—), wherein each R ₃₃ radical may be the same or different from one another and is a hydrogen atom; or C ₁ to C ₄ optionally having one or more hydroxy groups Alkyl radicals), Alkylsulfonylamino radicals (R ₃₄ SO ₂ -NR _35- ), wherein R ₃₄ radicals represent a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, wherein the R ₃₅ radical represents C _{1 to} C ₄ alkyl radical, or phenyl radical), and Aminosulfonyl radicals ((R ₃₆ ) ₂ N-SO _2- ), wherein each R ₃₆ radical may be the same or different from one another and is a hydrogen atom; or C ₁ -C optionally having one or more hydroxy groups ₄ alkyl radical); When the ring or heterocyclic portion of a non-aromatic radical is "substituted", the ring or heterocyclic portion of the non-aromatic radical comprises one or more substituents bonded to a carbon atom, the substituents being among the following groups Being selected: Hydroxyl groups, C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and Alkylcarbonylamino (R ₄₁ CO-NR _42- ), wherein the R ₄₂ radical is a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, and the R ₄₁ radical is C ₁ -C _2-alkyl radical, a group or one or more hydroxy group (wherein substituted by two C ₁ ~C ₄ alkyl group optionally having, the alkyl group, which may be the same or different from each other, together with the nitrogen atom to which said alkyl group , May form a 5 or 6 membered cyclic heterocycle, wherein the heterocycle optionally comprises one or more second hetero atoms, other than nitrogen; If the ring does not have the maximum number of substituents, hydrogen is present in the unsubstituted position. The method of claim 1, R ₁ is a C ₁ -C ₈ alkyl group or a hydroxyalkyl group. The method of claim 1, Each cationic aromatic heterocycle represented by the general formulas (IIa), (IIb), and (IIc) includes two R ₂ radicals bonded to carbon atoms adjacent to each other, The radical is a dyeing composition, characterized in that together with the carbon atom bonded to the radical can form an optionally substituted aromatic fused ring. The method of claim 1, e, m, and p are each 0, the composition for dyeing. The method of claim 1, When X represents an alkyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, or an acylamino group, x is 0 or 1, The composition for dyeing. The method of claim 1, Dyeing composition characterized in that the compound represented by the general formula (I) is represented by one of the following structural formula:

. The method of claim 1, A dyeing composition, wherein the cationic azo compound is contained in a suitable dyeing medium. The method of claim 1, Based on the total weight of the composition, a dyeing composition comprising a direct dye represented by the general formula (I) in an amount of 0.001 to 20% by weight. The method of claim 1, Comprising an oxidation base selected from para-phenylenediamine, bis-phenylalkylenediamine, para-aminophenol, ortho-aminophenol, heterocyclic base, and addition salts thereof Dyeing composition characterized in. The method of claim 9, Based on the total weight of the composition, the composition for dyeing comprising a base for oxidation in an amount of 0.001 to 20% by weight. The method of claim 1, A dyeing composition, further comprising a coupling agent selected from meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene coupling agent, heterocycle coupling agent, and addition salts thereof. The method of claim 11, The coupling agent, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino 1- (β-hydroxyethyloxy) benzene , 2-amino 4- (β-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureido 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl- 1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine, 3,5-diazino- 2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene, and addition thereof A dyeing composition, characterized in that selected from salts. The method of claim 11, Based on the total weight of the composition, the composition for dyeing, characterized in that it comprises the coupling agent or agent in an amount of 0.001 to 20% by weight. The method of claim 1, As a 2nd direct dye different from the compound represented by the said general formula (I), Neutral, acidic, or cationic benzene-based nitro dyes; Neutral, acidic, or cationic azo direct dyes; Quinone direct dyes; Azine direct dyes; A composition for dyeing, further comprising at least one direct dye selected from triarylmethane direct dyes, tetraazapentamethine direct dyes, indoamino direct dyes, and natural direct dyes. The method of claim 14, Based on the total weight of the composition, the composition for dyeing, characterized in that it comprises at least one second direct dye in an amount of 0.001 to 20% by weight. The method of claim 1, A dyeing composition comprising at least one oxidizing agent selected from hydrogen peroxide, urea peroxide, alkali metal bromate, persalt, peracid, and oxidase. The method of claim 1, A dyeing composition comprising at least one hydroxylated solvent selected from ethanol, propylene glycol, glycerol, and mono ethers of polyols. The method of claim 1, Anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, or mixtures thereof; Anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers, zwitterionic polymers, or mixtures thereof; Choose from mineral thickeners and organic thickeners, antioxidants, penetrating agents, metal ion sequestering agents, fragrances, buffers, dispersants, conditioners, film formers, ceramides, preservatives, opacifiers Dyeing composition, characterized in that it further comprises one or more additives. Applying a dyeing composition according to any one of claims 1 to 18 to keratin fibers; Leaving the composition applied for 3 minutes to 1 hour; And Rinsing the keratin fibers in water Keratin fiber staining method comprising a. A method for dyeing keratinous fibers, characterized by using the dyeing composition according to any one of claims 1 to 18. A kit having a plurality of compartments or a kit for dyeing, A first compartment comprising a composition for dyeing according to any one of claims 1 to 18; And a second compartment comprising a composition containing an oxidizing agent. A cationic azo compound represented by the following general formula (I) and having a zololidine unit, or an addition salt or solvent compound of the compound:

In the general formula (I), A represents a cationic aromatic heterocycle selected from compounds represented by the following general formulas (IIa) to (IIc):

(In each of the above general formulas (IIa) to (IIc), Each R ₁ is independently of the other, Optionally interrupted by one or more groups selected from a hetero atom, such as oxygen, nitrogen, or sulfur, and a carbonyl group, optionally substituted, optionally condensed with an aromatic ring, and one or more 3 to 7 Linear or branched, saturated or unsaturated C ₁ -C ₁₆ hydrocarbon chains, capable of forming a cyclic carbon ring, R ₁ is  Without nitro bonds, nitroso bonds, peroxide bonds, and diazo bonds,  Directly bonded to a quaternized or unquaternized nitrogen atom of the aromatic heterocycle A, Each R ₂ is independently of the other, Optionally disconnected, optionally substituted by one or more heteroatoms or by one or more groups having one or more heteroatoms, to form one or more 3-6 membered cyclic aromatic or non-aromatic carbon rings Linear or branched saturated or unsaturated C ₁ to C ₁₆ hydrocarbon chain,  Hydroxyl groups, C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, An alkoxycarbonyl group (R ₁₁ O-CO-), wherein R ₁₁ represents a C ₁ -C ₄ alkyl radical, Alkylcarbonyloxy radicals (R ₁₂ CO-O-), wherein R ₁₂ represents a C ₁ -C ₄ alkyl radical, Amino groups; Or an amino group optionally substituted with one or two C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the two alkyl radicals may be the same or different from each other, wherein the alkyl radicals are the alkyl radicals Together with the nitrogen atom to which it is attached, may optionally form a 5 or 6 membered cyclic heterocycle, which heterocycle may have nitrogen as the second hetero atom, or a hetero atom other than nitrogen), An alkylcarbonylamino group (R ₁₃ CO-NR _13- ) or (R ₁₃ CO-NH-), wherein each R ₁₃ radical independently of _one another represents a C ₁ -C ₄ alkyl radical, Carbamoyl groups ((R ₁₄ ) ₂ N-CO), wherein each R ₁₄ radical, independently of one another, represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, which may be the same or different from each other, A ureido group ((R ₁₅ ) ₂ N-CO-NR _16- ), wherein the R ₁₅ and R ₁₆ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical, Sulfonamide groups ((R ₁₇ ) ₂ N-SO _2- ), wherein each R ₁₇ radical independently of one another represents a hydrogen atom or a C ₁ -C ₄ alkyl radical, Alkylsulfonylamino groups (R ₁₈ SO ₂ -NR _19- ), wherein the R ₁₈ and R ₁₉ radicals independently of one another represent a hydrogen atom or a C ₁ -C ₄ alkyl radical, - guanidinyl nyumgi _{((R 20) 2 NC (} = NH 2 +) - NR 21 -) ( wherein, R ₂₀ and R ₂₁ radicals are independently of each other, hydrogen atom or a C ₁ ~C ₄ alkyl refers to the radical ),  -Nitro groups,  Cyano groups, or  Halogen atoms  Indicates, Two R ₂ radicals together with the carbon atom to which each R ₂ radical is bonded may form an aromatic or non-aromatic fused ring,  m is an integer from 0 to 4,  e is an integer from 0 to 2,  p is an integer from 0 to 1, D represents a CR ₂ group or a nitrogen atom, Q represents an NR ₁ group, an oxygen atom, or a sulfur atom,  In each of the general formulas (IIa), (IIb), and (IIc), a bond is a bond formed between the azo group and the A group, In each of the above general formulas (IIa), (IIb), or (IIc), when two R ₂ radicals bonded to two adjacent carbon atoms form an aromatic ring together with the carbon atom, the a bond is Through the aromatic ring formed, which may be formed between the azo group and the A group), The electroneutrality of the compound is provided by one or more anions An ⁻ which are cosmetically acceptable and can be the same or different from each other, Each of X, Y, and Z means a substituent of a three-ring nucleus that is substituted for the alkyl and the aryl ring, x is an integer from 0 to 2, y is an integer from 0 to 6, z is an integer from 0 to 6; When the alkyl radical or alkyl portion of the radical is "substituted", the alkyl radical, or alkyl portion of the radical, comprises one or more substituents selected from the following groups: Hydroxyl groups, C ₁ -C ₄ alkoxy groups, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and Amino groups; Or an amino group optionally substituted with one or more C ₁ -C ₄ alkyl radicals, optionally having one or more hydroxy groups, wherein the one or more alkyl radicals may be the same or different from one another and the alkyl radicals are bonded to the alkyl radicals. Together with the nitrogen atom, it is possible to form a 5 or 6 membered cyclic heterocycle, said heterocycle optionally having one or more hetero atoms other than nitrogen or nitrogen as the second hetero atom); When the aryl or heteroaryl radical or aryl or heteroaryl portion of the radical is "substituted", the aryl or heteroaryl radical, or the aryl or heteroaryl portion, includes one or more substituents bonded to a carbon atom; , The substituent is selected from the following groups: Hydroxy, C ₁ -C ₂ alkoxy, C ₂ -C ₄ (poly) -hydroxyalkoxy, acylamino, and amino substituted with one or two C ₁ -C ₄ alkyl radicals, wherein said alkyl The radicals may be the same or different from one another, optionally have one or more hydroxy groups, the alkyl radicals together with the nitrogen atom to which the two radicals are bonded, to form a 5 or 7 membered cyclic heterocycle, the hetero The cycle is a C ₁ -C ₁₆ alkyl radical optionally substituted with one or more radicals selected from nitrogen or a second hetero atom other than nitrogen), Halogen atoms, Hydroxyl groups, C ₁ -C ₂ alkoxy radicals, C ₂ -C ₄ (poly) -hydroxyalkoxy radicals, Amino radicals, Amino radicals substituted with one or two C ₁ -C ₄ alkyl radicals (which may be the same or different from each other), optionally having one or more hydroxy groups, Acylamino radicals (-NR ₃₁ -COR ₃₂ ), wherein R ₃₁ radicals are hydrogen atoms; or C ₁ -C ₄ alkyl radicals optionally having one or more hydroxy groups, and R ₃₂ radicals are C ₁ -C ₂ alkyl Radicals), Carbamoyl radicals ((R ₃₃ ) ₂ N—CO—), wherein each R ₃₃ radical may be the same or different from one another and is a hydrogen atom; or C ₁ to C ₄ optionally having one or more hydroxy groups Alkyl radicals), Alkylsulfonylamino radicals (R ₃₄ SO ₂ -NR _35- ), wherein R ₃₄ radicals represent a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, wherein the R ₃₅ radical represents C _{1 to} C ₄ alkyl radical, or phenyl radical), and Aminosulfonyl radicals ((R ₃₆ ) ₂ N-SO _2- ), wherein each R ₃₆ radical may be the same or different from one another and is a hydrogen atom; or C ₁ -C optionally having one or more hydroxy groups ₄ alkyl radical); When the ring or heterocyclic portion of a non-aromatic radical is "substituted", the ring or heterocyclic portion of the non-aromatic radical comprises one or more substituents bonded to a carbon atom, the substituents being among the following groups Being selected: Hydroxyl groups, C ₁ -C ₄ alkoxy, C ₂ -C ₄ (poly) hydroxyalkoxy groups, and Alkylcarbonylamino (R ₄₁ CO-NR _42- ), wherein the R ₄₂ radical is a hydrogen atom; or a C ₁ -C ₄ alkyl radical optionally having one or more hydroxy groups, and the R ₄₁ radical is C ₁ -C _2-alkyl radical, a group or one or more hydroxy group (wherein substituted by two C ₁ ~C ₄ alkyl group optionally having, the alkyl group, which may be the same or different from each other, together with the nitrogen atom to which said alkyl group , May form a 5 or 6 membered cyclic heterocycle, wherein the heterocycle optionally comprises one or more second hetero atoms, other than nitrogen; If the ring does not have the maximum number of substituents, hydrogen is present in the unsubstituted position, The compound is, 2- (9-zololidylazo) -3-methylbenzothiazolium perchlorate, and Not 2- (9-Joololidilazo) -3-ethylthiazolium perchlorate. The method of claim 22, R ₁ is a C ₁ -C ₈ alkyl group or a hydroxyalkyl group. The method of claim 22, Each cationic aromatic heterocycle represented by the general formulas (IIa), (IIb), and (IIc) includes two R ₂ radicals bonded to carbon atoms adjacent to each other, And said radical, together with the carbon atom to which said radical is bonded, can form an optionally substituted aromatic fused ring. The method of claim 22, and e, m, and p are each 0. The method of claim 22, X represents 0 or 1 when X represents an alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an amino group, an alkylamino group, a dialkylamino group, or an acylamino group. The method according to any one of claims 22 to 26, Compounds characterized in that the compound represented by the general formula (I) is represented by one of the following structural formula:

.