JPH06199641A - Hair dye - Google Patents

Abstract

PURPOSE:To obtain a hair dye capable of preventing an oxidation polymer such as a nitro dye to be a dyeing component from autoxidizing and improving the usability without deteriorating the dyeability. CONSTITUTION:This hair dye comprises an oxidation polymer of an oxidation dye and/or a nitro dye and a polymerization suppressor. Specifically, 100g hair dye is prepared by adding 158g 2% aqueous hydrogen peroxide to 500g 2% aqueous solution of p-phenylenediamine at 40 deg.C, slowly stirring the mixture solution at 40-50 deg.C for 1hr, then spray-drying the resultant solution, providing a powdery oxidation polymer mainly composed of trimer of the p- phenylenediamine and using 5g prepared oxidation polymer, 0.5g 2-hydroxy-1,4- naphthoquinone as a polymerization suppressor, 1.0g stearyltrimethylammonium chloride as a cationic surfactant, 10g lauryldimethylacetic acid betaine, 1g lanolin and 82.5g water as optional components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hair dye capable of dyeing hair fast without damaging the hair.

[0002]

2. Description of the Related Art Oxidation type hair dye has sufficient dyeing power and fastness, but contains a strong alkaline component and has problems such as severe damage to hair and irritation to scalp and skin. is there. Therefore, as a hair dye that solves these problems, the present inventors have already found that an oxidation polymer of an oxidative dye and / or a nitro dye can satisfactorily dye hair with a specific degree of polymerization. Has applied for a hair dye containing this oxidative polymer as an active ingredient. In hair dyes set to this specific degree of polymerization, there is a phenomenon in which the oxidation polymer, which is a dyeing component, is autoxidized to increase the degree of polymerization and reduce the dyeability on hair. For the purpose of suppressing, a hair dye in a powder form or an anhydrous liquid (paste form) form containing almost no water is used.

However, since this hair dye is in the form of powder or paste, it is necessary to dilute and mix it with water immediately before dyeing and then apply it to the hair. Further, since the powdery hair dye contains air in the powder, mixing with water cannot be achieved smoothly, and there are some problems in use that the powder is scattered around. Furthermore, there is a point that the hair dye applied to the hair with the diluted and mixed hair dye is sometimes partially dried to become powder and fall off. In addition, since the affinity between hot water and the hair dye on the hair is not good at the time of rinsing after hair dyeing, there is a point that it is difficult to rinse.

On the other hand, the hair dye does not damage the hair, but it is desirable that the feel of the hair can be positively improved at the same time as the hair dye, and it is further desirable that the dyeing property can be improved. Therefore, the present inventors have found that it is effective to add a surface-active organic component as a means for improving the diluting miscibility of powder or the like with water and the dyeability with hair. A patent application has been filed for a hair dye prepared by blending the above-mentioned oxidative polymer with a cationic surfactant. However, there is a point that even if the oxidative polymer of the oxidative dye and the nitro dye is powder or the like, it absorbs water, and as a result, autoxidation occurs and the dyeing on the hair is reduced. Further, if the form of the hair dye is powder or the like, it is essential to dilute and mix with water or an aqueous solution immediately before hair dyeing, which makes the hair dyeing operation complicated. In addition, hair dyes consisting of powdered and anhydrous liquid (paste) oxidative polymers contribute significantly to stabilizing the specific degree of polymerization compared to aqueous solutions, but there is a sufficient risk of water contamination during use. Therefore, it is desirable that the stabilization of the degree of polymerization is taken even in the product form of such a hair dye.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and in the case of containing an oxidative polymerization product of the above-mentioned oxidation dye and / or nitro dye having an excellent effect as a dyeing component. It is an object of the present invention to provide a hair dye that prevents auto-oxidation that causes a decrease in dyeing performance and further improves usability.

[0006]

Means for Solving the Problems As a result of intensive studies on the dyeing stability of the oxidation polymer, the present inventors have found that
It was found that when a specific polymerization inhibiting component (polymerization inhibiting component) is added to an aqueous solution or dispersion of an oxidative dye and / or a nitro dye oxidative polymer, the progress of the degree of polymerization with time is suppressed, and the above object is achieved. The present invention has been completed by succeeding in obtaining a hair dye which can be treated. That is,

The hair dye of the present invention is characterized by containing an oxidation polymerization product of an oxidation dye and / or a nitro dye, and a polymerization inhibitor. The degree of polymerization of the oxidative polymer is preferably mainly a trimer. The polymerization inhibitor is at least one compound selected from ascorbic acid and salts thereof, thioglycolic acid and salts thereof, sulfites, hydroquinones, naphthoquinones, hydroquinone alkyl ethers, naphthoquinone alkyl ethers and nitrosoanilines. Is preferred. Further, the hair dye preferably contains a cationic surfactant and / or a nonionic surfactant.

[0008]

As described above, the oxidative dye and / or the nitro dye oxidatively polymerized product, when present in the form of a solution, causes an increase in the degree of polymerization, and the dyeing property of the solution on the hair over time (passage). Day)
However, when a polymerization-inhibiting component (polymerization-inhibiting component), for example, a naphthoquinone is added to an aqueous solution or dispersion of an oxidative polymerization product, the progress of the degree of polymerization is suppressed, so that the dyeing property is deteriorated with time. Can be prevented and the dyeing property can be secured. As described above, in order to secure stable dyeing property, the effect of the polymerization inhibitor is remarkable in the environment of an aqueous solution in which autoxidation remarkably progresses. Needless to say, it is more stable to be mixed with a powdered hair dye. It is effective in securing dyeability.

The structure of the present invention will be described in detail below. The hair dye of the present invention is characterized by containing an oxidative polymer of an oxidative dye and / or a nitro dye as a first component and a polymerization inhibitor as a second component, and further comprises a third It is characterized by containing a cationic surfactant and / or a nonionic surfactant as a component. Also, if necessary,
The hair dye containing the first component and the second component or the hair dye containing the first component to the third component may further contain optional components (1) and (2). It is a thing. Table 1 below shows the composition and amount of the components of these hair dyes.

[0010]

[Table 1]

The first component, the second component, the third component and the optional components (1) and (2) shown in Table 1 above will be described in detail below. The oxidative polymerization product of the oxidative dye and / or the nitro dye, which is the first component, is a polymer mainly composed of trimers, and is composed of one or a mixture of two or more kinds, or a copolymer. The reason why the degree of polymerization of the oxidative polymer is mainly the trimer is that only the trimer has an excellent effect as a dyeing component. A polymer of a tetramer or higher does not stain the hair, and a polymer of a dimer or lower is colorless or yellow, and cannot be a dyeing component itself unless oxidation proceeds. is there. Examples of the oxidative dyes and nitro dyes that are the subject of the present invention include the substances exemplified in Tables 2 to 7 below, but the oxidative dyes and the like used in the present invention are not limited thereto.

[0012]

[Table 2]

[0013]

[Table 3]

[0014]

[Table 4]

[0015]

[Table 5]

[0016]

[Table 6]

[0017]

[Table 7]

The oxidatively polymerized product is obtained by oxidatively polymerizing the above-mentioned oxidative dye and / or nitro dye with an oxidizing agent such as hydrogen peroxide. Oxidizing agent: Oxidizing dye and /
Alternatively, when the nitro dye is oxidized and polymerized at a molar ratio of 0.5 to 3.0, a polymer mainly composed of a trimer can be obtained. When the molar ratio is less than 0.5, a monomer which is not involved in the oxidation reaction is recognized, and when the molar ratio exceeds 3.0, a tetramer is recognized, which is not preferable. The oxidizing agent that oxidizes these dyes is not limited to hydrogen peroxide, and for example, sodium perborate, urea peroxide, sodium bromate, etc. can be used. The amount of the oxidation polymer compounded is
It is preferable that the amount of the hair dye is 0.1 to 40.0 parts with respect to the total amount. When the amount of the oxidative polymer is less than 0.1, the hair dyeing property is poor, and when it exceeds 40.0 parts, the usability such as coating property and spreadability is poor.

The polymerization inhibitor as the second component is used to prevent the deterioration of the dyeing property of an oxidation polymer such as an oxidation dye or a nitro dye with the passage of time and to secure the dyeing property.
That is, when an oxidation polymer such as an oxidative dye or a nitro dye is present in the form of a solution, the degree of polymerization is increased (autooxidation, etc.) and the dyeing property of the solution on the hair is changed with time (passage). Although it decreases with the addition of a second component, a polymerization inhibiting component (polymerization inhibiting component), for example, when a naphthoquinone is added to an aqueous solution or dispersion of an oxidation polymer, the progress of the degree of polymerization with time is suppressed. The deterioration of the dyeability with time can be prevented and the dyeability can be secured. As a typical example of a naphthoquinone that serves as a polymerization inhibitor, 2-hydroxy 1,4-naphthoquinone (a henna dyeing component which is a kind of plant dye) is used to stabilize the dyeing property over time by preventing natural oxidative polymerization. The effect was examined by the following test.

Test Method 200 ml of a hair dye solution comprising 5% by weight of p-phenylenediamine trimer, 1% by weight of 2-hydroxy-1,4-naphthoquinone and naphthoquinone, and 94% by weight of water was prepared. The solution was filled in a light-shielding bottle, sealed and stored. Using 200 ml of the hair dye solution for each storage period (1 day, 1 week, ..., 17 weeks), a sample [hair bundle containing sun hair (11 cm
(Length) 1.0 g, wool muslin 0.2] was dyed for 60 minutes at a temperature of 20 ° C., then washed with shampoo, rinsed with running water, naturally dried, and then subjected to measurement.
Deterioration of the dyeing property of this hair dye solution over time (each storage period) was shown by the reflectance of wool muslin Z% (a substitute special value for the degree of dyeing on white hair). Wool muslin reflectance Z%
Was measured with the following measuring device. Measuring instrument; Color measuring instrument: Suga Test Instruments SM color computer S
M-3 Color system: Z value of XYZ system (The smaller the Z value, the more dyed in black.) Filter: Equipped with an ultraviolet cut filter. Original fabric reflectance: 94.58% Z value (85.83% X value, 8
7.07% Y value)

Each storage period (1 day, 1 week, ..., 1
The relationship between the reflectance of wool muslin after 7 weeks) and Z% is shown in FIG. As shown in FIG. 1, it can be seen that the dyeing property of the hair dye solution containing no naphthoquinone deteriorates with time. On the other hand, in the hair dye solution containing naphthoquinone, it is found that the dyeing property does not deteriorate over time. As described above, the deterioration of the dyeing property is due to the increase in the degree of polymerization of p-phenylenediamine, and naphthoquinone exhibits the effect of suppressing the increase in the degree of polymerization of trimers or higher.

As described above, as an example of the polymerization inhibitor to which the present invention is applied, a typical example of naphthoquinones is 2-
Although hydroxy 1,4-naphthoquinone has been shown, examples of the polymerization inhibitor as the second component include ascorbic acid and its salt, thioglycolic acid and its salt, and sulfite.
At least one compound selected from hydroquinones, naphthoquinones, hydroquinone alkyl ethers, naphthoquinone alkyl ethers and nitrosoanilines can be mentioned. These compounds are dyes of an oxidation dye such as an oxidative dye and a nitro dye with the passage of time. It has the effect of preventing the deterioration of the dyeability and ensuring the dyeability. The amount of the polymerization inhibitor blended is 0.000 based on the total amount of the hair dye.
It is preferably about 5 to 20.0 parts. When the amount of the polymerization inhibitor is less than 0.0005, the effect of suppressing the increase in the degree of polymerization of the oxidized polymer is low, and when it exceeds 20.0 parts, it is economically undesirable.

Specific examples of the polymerization inhibitor are shown below. Examples of ascorbic acid and salts thereof include ascorbic acid, sodium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, and diethanolamine ascorbate. Examples of thioglycolic acid and its salts include thioglycolic acid and
Examples include sodium thioglycolate, ammonium thioglycolate, thioglycolic acid monoethanolamine, and thioglycolic acid diethanolamine. Examples of sulfites include sodium sulfite, ammonium sulfite, monoethanolamine sulfite, and diethanolamine sulfite. As hydroquinones,
Examples thereof include hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, and tertiary butyl hydroquinone. Examples of the naphthoquinones include naphthoquinone and hydroxynaphthoquinone. Examples of hydroquinone alkyl ethers include hydroquinone monopyropyr ether. Examples of naphthoquinone alkyl ethers include naphthoquinone monomethyl ether. Examples of the nitrosoanilines include N-methyl-N-nitrosoaniline, N-ethyl-N-nitrosoaniline, ammonium N-nitrosophenylhydroxyaniline, and aluminum N-nitrosophenylhydroxyaniline.

As the third component, a cationic surfactant, a nonionic surfactant or both of these surfactants can be used. By incorporating the third component such as the cationic surfactant, the dyeability can be further improved. That is, the hair dye containing a cationic surfactant and / or a nonionic surfactant in the oxidative polymerization product of the oxidative dye and / or nitro dye as the first component and the polymerization inhibitor as the second component is The following effects will be exhibited. (1) Since it has an appropriate viscosity, when applied to hair, the flow of the liquid is small and the liquid is uniformly held on the hair surface, so that the hair is effectively dyed. (2) The inclusion of a third component such as a cationic surfactant has an appropriate viscosity and suppresses the evaporation of water, so that the applied part does not become tight and the hair dyeing component does not fall off, and therefore the dyeing Easy hair operation. (3) Rinse is easy because it has a good affinity with hot water.
In addition, since the cationic surfactant and / or the nonionic surfactant has a property of accepting an electron, they are dyed to the hair by the oxidation polymer of the oxidative dye and / or the nitro dye during coating dyeing. It is possible to improve the dyeability to hair by suppressing the formation of a further polymer that deteriorates. (4) Cationic surfactants and the like are adsorbed to the hair to give the hair softness, smoothness, moisturizing feeling, antistatic effect, and the like, and the feel of the hair without damaging the hair,
You can dye hair while improving the condition.

Examples of the cationic surfactant include monoalkyltrimethylammonium salt having an alkyl group having 12 to 22 carbon atoms, dialkyldimethylammonium salt, alkylbenzylammonium salt, alkylpyridinium salt and the like.

As the nonionic surfactant, for example, polyoxyethylene alkyl (having 12 to 18 carbon atoms) is used.
Ether, polyoxyethylene alkyl (C8-
9) Ether, polyoxyethylene alkyl (C1
2-18) thioether, polyoxyethylene alkyl (C12-18) ester, polyoxyethylene sorbitan monoalkyl (C12-18) ester,
Polyoxyethylene alkyl (C12-18) amine, polyoxyethylene alkyl (C12-18)
Amide, polyoxyethylene polyoxypropylene,
Polyoxyethylene sorbitan alkyl (C12-
18) Monoester and polyoxyethylene fatty acid (C12-18) monoglycerin ester are mentioned.

The amount of the cationic surfactant and / or the nonionic surfactant to be blended is 0.1 to 4 with respect to the total amount of the hair dye.
It is 0.0 part. When the content of the third component is less than 0.1 part, the usability and the finished condition of hair are deteriorated, and when it exceeds 40.0 parts, the dyeability is deteriorated.

In addition to the above components, the hair dye of the present invention may further contain 1 to 60 parts of the optional component (1) based on the total amount of the hair dye, if necessary. As the optional component (1), the following anionic surfactants, amphoteric surfactants, protein hydrolysates and their derivatives, other polymer compounds, nitrogen-containing chelate compounds, water-soluble proteins and amino acids are used. . However, the anionic surfactant cannot be used when the cationic surfactant is used as the third component. These optional components (1) contribute to the improvement of miscibility, the ease of coating, the prevention of dry dropout, and the ease of rinsing.

Examples of the anionic surfactant include the following ethanolamine salts, ammonium salts, sodium salts and potassium salts. That is, carbon number 12 to
18 fatty acid salt, C 12-18 alkyl acid salt, polyoxyethylene alkyl (C 12-18) ether sulfate, N- having a C 12-18 fatty acid residue
Acyl amino acid salt, N-acyl-N-methyl taurine salt having a fatty acid residue having 12 to 18 carbon atoms, 12 to 12 carbon atoms
Examples thereof include polyoxyethylene alkyl ether phosphate having 18 alkyl groups.

Examples of the amphoteric surfactant include N-alkyl (C12 to C18) N-carboxymethylammonium betaine, N-alkyl (C12 to C18).
Examples thereof include N-carboxyethylammonium betaine and N-alkyl (C12 to C18) amidopropyl.

Examples of the protein hydrolyzate and its derivative include hydrolyzed collagen (for example, a molecular weight of 80).
0-1200, MP-1000 manufactured by Nippi), hydrolyzed silk, hydrolyzed keratin, hydrolyzed gelatin, hydrolyzed collagen ethyl, hydrolyzed collagen ethyl / resin acid condensate, hydrolyzed collagen ethyl / resin acid condensate /
Aminomethylpropanediol liquid, hydrolyzed collagen ethyl hexadecyl, coconut oil fatty acid hydrolyzed collagen, lauryl hydrolyzed collagen, myristyl hydrolyzed collagen, palmityl hydrolyzed collagen, stearyl hydrolyzed collagen, oleyl hydrolyzed collagen,
Isostearyl hydrolyzed collagen, its sodium,
Examples thereof include potassium and ethanolamine salts.

Other high molecular compounds include, for example:
Cationized cellulose (eg, VCC, polymer J
R), diethylaminoethylated cellulose, diisopropylaminoethylated cellulose, dimethylaminoethylated cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone-vinyl acetate copolymer, vinylpyrrolidone-diethylaminoacrylate copolymer quaternary ammonium salt (eg, GAF). Co., Ltd., Gafquat), poly N-vinyl carbazole, acrylic acid-acrylamide copolymer (for example, Sumifloc FN-12, Sumitomo Chemical Co., Ltd.), N methacryloylethyl N, N-dimethylammonium α-N-methylcarboxybetaine-methacryl. Acid alkyl ester copolymer (molecular weight of 1,000 to 100,000, for example, Yukaformer manufactured by Mitsubishi Petrochemical), chitosan derivative (molecular weight of 100)
Up to 800,000), chitosan lactic acid, hydrochloric acid, sulfate, carboxymethyl chitosan hydrochloride, phosphorylated chitosan lactate, sulfated chitosan acetate and the like.

As the nitrogen-containing chelate compound, for example,
Ethylenediaminetetraacetic acid and 1-, 2-, 3-, 4-sodium, potassium salt, ethylenetriaminepentaacetic acid and 1-, 2-, 3-, 4-, 5-sodium, potassium salt, nitrilotriacetic acid and 1- , 2-, 3-sodium,
Potassium salt, N-hydroxyethylethylenediaminetriacetic acid and 1-, 2-, 3-sodium, potassium salt, ethylenediaminetetrapropionic acid and ammonium,
Sodium, potassium salt, triethylenetetracyclohexaacetic acid and ammonium, sodium, potassium salt,
Examples thereof include ethylene glycol diethyl ether diamine tetraacetic acid and potassium salt, cyclohexane 1,2 diamine tetraacetic acid diethanol amine salt, ethylene diamine, and tetraacetyl ethylene diamine.

Examples of the water-soluble protein include albumin, casein, sodium caseinate, gelatin and the like.

In the hair dye of the present invention, in addition to the above components, 0.001 to 10.0 parts of the optional component (2) may be added to the total amount of the hair dye, if necessary. . Optional component (2)
As, for example, viscosity modifiers, hydrotopes, preservatives, bactericides, ultraviolet absorbers, PH modifiers, pigments, fragrances (coumarin, oak moss resin, lavender oil, cedarwood oil, vetiver oil, patchouli oil, amyl salicylate, Bornyl acetate, lemon oil, anisaldehyde, heliotrobin, musk T, etc., conditioning agents (oil components; lanolin, squalane, jojoba oil,
Liquid paraffin, higher alcohols, esters, silicone oil, castor oil, olive oil, and other moisturizing ingredients; glycerin, propylene glycol, 2-pyrrolidone-5-carboxylic acid sodium sorbitol, urea, etc., bulking ingredients (starch, egg white powder, sulfuric acid) Sodium and the like).

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Example 1 500 g of a 2% aqueous solution of p-phenylenediamine at 40 ° C.
To the above, 158 g of 2% hydrogen peroxide water was added, and the mixture was slowly stirred at 40 to 50 ° C. for 1 hour, and then spray-dried to obtain a powdery oxidative polymer mainly composed of a trimer of p-phenylenediamine. Obtained. 5 g of this oxidation polymer, 0.5 g of 2-hydroxy-1,4-naphthoquinone as a polymerization inhibitor, 1.0 g of stearyltrimethylammonium chloride as a cationic surfactant and 10 g of betaine lauryldimethylaminoacetate as an optional component, 1 g of lanolin, purification Water 8
100 g of a hair dye consisting of 2.5 g was prepared.

This hair dye was stored at room temperature for 2 months.
Then, the hair dye was applied to the hair with a brush and left for 60 minutes. After leaving it to stand, rinse it, wash the hair with a shampoo, and dry it with a hair dryer. , No gloss, no damage to hair), safety (no stain to scalp and skin, no irritation), fastness (hair wash resistance, perm treatment resistance) and usability (miscibility) , Coating property, spreadability) was evaluated based on the following evaluation index. The results are shown in Table 8 below. Evaluation index ◎: Very good, ○: Good △: Somewhat inferior ×: Inferior

[0039]

[Table 8]

As is clear from the results in Table 8, Example 1
The hair dye prepared in 1) can obtain good results in all respects of the evaluation items even after storage for 2 months, can not damage the hair, can dye the hair firmly, and is also irritating. It turns out that it is excellent in usability.

Examples 2 to 7 Hair dyes were prepared in the composition ratios shown in Tables 9 and 10 and applied to hair in the same manner as in Example 1 to evaluate the dyeing state and the like based on the above-mentioned evaluation indexes. evaluated. The results are shown in Tables 9 and 10 below.

[0042]

[Table 9]

[0043]

[Table 10]

As is clear from the results of Tables 9 and 10, the hair dyes of Examples 2 to 7 also give good results in all points of evaluation items, like the hair dye of Example 1. It can be seen that even after storage for 2 months, the hair can be dyed firmly without damaging the hair, and the hair is not irritating and is excellent in usability.

Comparative Examples 1 to 3 Hair dyes having the compositional ratios shown in Table 11 (however, not containing a polymerization inhibitor as the second component) were prepared and applied to hair in the same manner as in Example 1. The dyed state and the like were evaluated based on the above-mentioned evaluation index. The results are shown in Table 11 below.
Shown in.

[0046]

[Table 11]

As is clear from the results shown in Table 11, the hair dyes of Comparative Examples 1 to 3 are particularly inferior in the dyed state. This is considered to be because the hair dyes of Comparative Examples 1 to 3 did not contain a polymerization inhibitor, and thus the degree of polymerization of the oxidation polymer progressed and the dyeing property deteriorated after storage for 2 months. On the other hand, as is clear from the above results, the hair dyes of the present invention (Examples 1 to 7) have a dyed state, a finished state, safety, fastness and use even after storage for 2 months. It is satisfactory in all respects such as sex.

[0048]

The hair dye of the present invention comprises an oxidation dye and / or an oxidation dye having an excellent effect as a dyeing component by containing a polymerization inhibitor.
Or, since it suppresses the progress of the degree of polymerization over time of the oxidized polymer of the nitro dye, it is possible to prevent the deterioration of dyeing property over time,
Moreover, the dyeing property is secured. Further, a hair dye obtained by further adding a cationic surfactant and / or a nonionic surfactant to an oxidation polymerization product of an oxidative dye and / or a nitro dye and a polymerization inhibitor has an appropriate viscosity. Therefore, when this hair dye is applied to hair, the flow of the liquid is small, the liquid is uniformly held on the hair surface and the hair is effectively dyed, and since the evaporation of water is suppressed, the applied part may be tight. The hair dyeing component does not fall off, so that the hair dyeing operation is easy, and the affinity with hot water is good, rinsing is easy, and further, the cationic surfactant and / or
Or, by using nonionic surfactants alone or in combination, cationic surfactants or the like can be adsorbed to the hair to give the hair effects such as softness, smoothness, moist feeling, and antistatic properties.
It has the advantage that hair can be dyed while improving the feel and condition of the hair without damaging the hair.

[Brief description of drawings]

FIG. 1 is a drawing showing the relationship between the storage period and the reflectance Z% of wool muslin.

Claims (4)

[Claims] 1. A hair dye comprising an oxidative dye and / or an nitro dye oxidatively polymerized product, and a polymerization inhibitor. 2. The hair dye according to claim 1, wherein the degree of polymerization of the oxidized polymer is mainly trimer. 3. The polymerization inhibitor is ascorbic acid and its salt,
The hair dye according to claim 1, which is at least one compound selected from thioglycolic acid and its salts, sulfites, hydroquinones, naphthoquinones, hydroquinone alkyl ethers, naphthoquinone alkyl ethers and nitrosoanilines. 4. The hair dye according to claim 1, which contains a cationic surfactant and / or a nonionic surfactant.