TW202412739A - Hair dye composition - Google Patents

Abstract

The present invention provides a hair dye composition that can improve skin cleansing performance while maintaining hair dyeing performance. The hair dye composition of the present invention comprises (A) an oxidation dye and (B) an oxidation dye that meets predetermined conditions, wherein (A) the oxidation dye is 6-methoxy-2-methylamino-3-aminopyridine, etc., and (B) the oxidation dye is typically an oxidation dye without a benzene ring, etc.

Description

Hair dye ingredients

The present invention relates to a hair dye composition containing 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof.

Existing oxidative hair dyes are composed of a first agent containing, for example, an alkaline reagent and an oxidative dye, and a second agent containing an oxidizing agent such as hydrogen peroxide. The alkaline reagent promotes the action of the oxidizing agent contained in the second agent and makes the hair swell to increase the permeability of the dye into the hair. The oxidizing agent decomposes the melanin in the hair and forms oxidative dye polymers inside the hair. When the alkaline reagent is removed, the hair's stratum corneum closes, sealing the oxidative dye polymers inside the hair.

Generally speaking, from the perspective of excellent hair dyeing ability, highly reactive dye intermediates such as p-phenylenediamine and toluene-2,5-diamine are applicable to oxidation dyes. Among them, from the perspective of excellent hair dyeing ability, these dye intermediates are used in a wide variety of hair colors. For example, the oxidation hair dye composition disclosed in Patent Document 1 contains a dye intermediate such as toluene-2,5-diamine as the main component of the dye.

Prior art documents Patent documents Patent document 1: Japanese Patent Publication No. 2003-40747

Problem to be solved by the invention However, although oxidative hair dye compositions using p-phenylenediamine and the like have excellent hair dyeing power, they are difficult to remove from the skin.

Means for solving the problem The present invention is based on the following discovery: by containing 6-methoxy-2-methylamino-3-aminopyridine or its salt and a specific oxidative dye as a dye, it is possible to improve the ease of removal from the skin while maintaining the hair dyeing ability (hereinafter referred to as "skin cleansing property").

To solve the above problems, a hair dye composition according to one aspect of the present invention is characterized in that: it comprises (A) an oxidation dye and (B) an oxidation dye; (A) the oxidation dye comprises 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof; (B) the oxidation dye comprises any one or more of (1) to (6); (1) an oxidation dye without a benzene ring; (2) an oxidation dye without an amine group; (3) an oxidation dye with a benzene ring and a heterocyclic ring, wherein the benzene ring and the heterocyclic ring are directly bonded, bonded through one covalent bond, or bonded through two or three consecutive covalent bonds; 4) Oxidative dyes having a benzene ring and an amine group, wherein all the amine groups are diamines or tertiary amines and are substituted by a carbon chain having more than two carbon atoms; (5) Oxidative dyes having a benzene ring and a primary amine group, wherein all the primary amine groups have the following functional groups: functional groups that are bonded to carbons on both sides of the carbon to which the primary amine group is bonded, or functional groups that are bonded to carbons adjacent to the carbon to which the primary amine group is bonded and have two or more consecutive covalent bonds; (6) Oxidative dyes having a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes the meta position.

In the hair dye composition, the (B) oxidation dye may include any one or more of the following oxidation dyes: an oxidation dye satisfying the requirement of (1), an oxidation dye satisfying the requirement of (2), and an oxidation dye satisfying any two or more of the requirements of (3) to (6).

In the hair dye composition, the oxidation dye (B) may be 4-chlororesorcinol, 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, 2-amino-4-hydroxyethylaminoanisole, hydroxyethyl-3,4-methylenedioxyaniline, 2,6-dihydroxy-3,4-dimethylpyridine, 2, 6-dimethoxy-3,5-pyridinediamine, 2-amino-3-hydroxypyridine, 2,5,6-triamino-4-pyrimidinol, 1-hydroxyethyl-4,5-diaminopyrazole, resorcinol, 1,5-naphthalene diol, 1-naphthol, 2-methyl-5-hydroxyethylaminophenol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and any one or more of their salts.

In the hair dye composition, the (B) oxidation dye may contain at least 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof.

The pH of the hair dye composition during use may be 10.5 or less.

The hair dye composition may further contain (D) a polymerization accelerator.

To solve the above problems, another aspect of the hair dye composition of the present invention is characterized in that: it does not contain an oxidizing agent; it comprises (A) an oxidation dye and (B) an oxidation dye; (A) the oxidation dye comprises 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof; (B) the oxidation dye comprises any one or more of (1) to (6): (1) an oxidation dye without a benzene ring; (2) an oxidation dye without an amine group; (3) an oxidation dye with a benzene ring and a heterocyclic ring, wherein the benzene ring and the heterocyclic ring are directly bonded, bonded by one covalent bond, or bonded by two or three consecutive covalent bonds. (4) an oxidation dye having a benzene ring and an amine group, wherein all the amine groups are diamines or tertiary amines and are substituted by a carbon chain having more than two carbon atoms; (5) an oxidation dye having a benzene ring and a primary amine group, wherein all the primary amine groups have the following functional groups: a functional group that is bonded to the carbons on both sides of the carbon to which the primary amine group is bonded, or a functional group that is bonded to the carbon adjacent to the carbon to which the primary amine group is bonded and has two or more consecutive covalent bonds; (6) an oxidation dye having a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes the meta position.

In the hair dye composition, the oxidation dye (B) may be any one or more of 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, isatin, 1,5-naphthalene diol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, 5-amino-6-chloro-o-cresol, and salts thereof.

In the hair dye composition, the (B) oxidation dye may be any one or more of 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and salts thereof.

When the hair dye composition further selectively contains (C) oxidation dye, the mass ratio (A/C) of the content of the (A) oxidation dye to the total content of the (C) oxidation dye is 1 or more; the (C) oxidation dye (excluding the (B) oxidation dye) has a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes ortho-position or para-position.

In the hair dye composition, the mass ratio of the content of the alkaline agent to the content of the oxidation dye (A) (alkaline agent/A) may be 0.1 or more.

Invention Efficacy According to the invention, it is possible to improve skin cleansing performance while maintaining hair dyeing performance.

The expression "one or more of A, B, C, ..." used in this case does not mean that when the total number of the listed members A, B, C, ... is n, it refers to the listed members themselves, but to any combination of 2, 3, ..., and n among the n members. For example, "one or more of A, B, and C" means "only A, only B, only C, A and B, A and C, B and C, or A, B, and C".

(First embodiment) The first embodiment of the hair dye composition of the present invention is described below. The hair dye composition of this embodiment is a multi-agent hair dye composition, for example, a two-agent hair dye composition consisting of a first agent having an oxidative dye, etc., and a second agent containing an oxidizing agent, etc. The components of the two-agent hair dye composition are exemplified below. The numerical value of mass % representing the content of the component refers to the numerical value in the dosage form containing the same when a solubilizing agent such as water is used.

(The first agent of the two-agent hair dye composition) The first agent of the hair dye composition may preferably contain an alkaline reagent, (D) a polymerization accelerator, etc. in addition to the above-mentioned oxidation dye.

((A) Oxidation dyes) Oxidation dyes are classified into colorants and dye intermediates, and usually develop color through polymerization of dye intermediates with each other or dye intermediates with colorants. In this embodiment, the dye contains (A) 6-methoxy-2-methylamino-3-aminopyridine or its salt as an essential dye. Specific examples of salts include hydrochlorides, sulfates, hydrobromates, etc. The (A) oxidation dyes may be used alone or in combination of two (A) oxidation dyes. Among them, 6-methoxy-2-methylamino-3-aminopyridine dihydrochloride (HC Blue7) is preferred from the viewpoint of excellent dye stability.

The lower limit of the content of the oxidation dye (A) in the mixture of the first agent and the second agent, i.e., the hair dye composition for hair dyeing, can be appropriately set to preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. When the content of the oxidation dye (A) is 0.1% by mass or more, the hair dyeing power and skin cleansing property can be further improved.

The upper limit of the content of the oxidation dye (A) in the mixture can be appropriately set, and is preferably 2 mass % or less, more preferably 1.4 mass % or less, and further preferably 1 mass % or less from the viewpoint of the solubility of the oxidation dye (A). The range may also be any combination of the upper and lower limits.

((B) Oxidative dye) In the hair dye composition of this embodiment, the oxidative dye includes the following (B) oxidative dye. The (B) oxidative dye may be used alone or in combination of two or more (B) oxidative dyes. Among them, the (B) oxidative dye does not include the (A) oxidative dye.

(B) The oxidation dye is selected from the specific examples shown below, and satisfies any one or more of the following conditions (1) to (6).

(1) Oxidation dyes without benzene rings; (2) Oxidation dyes without amine groups; (3) Oxidation dyes with benzene rings and heterocyclic rings, wherein the benzene rings and heterocyclic rings are directly bonded, bonded through one covalent bond, or bonded through two or three consecutive covalent bonds; (4) Oxidation dyes with benzene rings and amine groups, wherein all amine groups are diamines or tertiary amines and are substituted by carbon chains having two or more carbon atoms; (5) An oxidation dye having a benzene ring and a primary amine group, wherein all the primary amine groups have the following functional groups: a functional group bonded to carbons located on both sides of the carbon to which the primary amine group is bonded, or a functional group bonded to a carbon adjacent to the carbon to which the primary amine group is bonded and has two or more consecutive covalent bonds; (6) An oxidation dye having a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes the meta position.

In the above (6), when there are multiple amino groups or hydroxyl groups, as long as some of them satisfy the requirements of (6), it is regarded as (6) oxidation dye.

Among these, oxidation dyes satisfying at least one of (1) and (2) and at least two of (3) to (6) are preferred.

In addition, more preferred are any one or more of (1) and (2), or any one or more of hydroxyethyl-3,4-methylenedioxyaniline (HYDROXYETHYL-3,4-METHYLENEDIOXYANILINE), 3-amino-2,4-dichlorophenol (3-AMINO-2,4-DICHLOROPHENOL), 2-amino-4-hydroxyethylaminoanisole (2-AMINO-4-HYDROXYETHYLAMINOANISOLE), and 2-methyl-5-hydroxyethylaminophenol (2-METHYL-5-HYDROXYETHYLAMINOPHENOL).

(B) Specific examples of the above (1) in the oxidation dye include 2,6-dihydroxy-4-methyl-pyridine, 2,4,5,6-tetraaminepyrimidine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 2,6-dimethoxy-3,5-pyridinediamine, 2,6-dihydroxy-4-methyl-pyridine, 2,4,5,6-tetraaminepyrim ...hydroxy-4-methyl-pyridine, 2,4,5,6-tetraaminepyrimidine, 2,4,5,6-tetraaminepyrimidine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 2,6-dihydroxy-4-methyl-pyridine, 2,4,5,6-tetraaminepyrimidine, 2,4,5,6-tetraaminepyrimidine, 2,4,5 AMINE), 2,6-bis-(2-hydroxyethyl)-3,5-pyridinamine (2,6-BIS-(2-HYDROXYETHYL)-3,5-PYRIDINEDIAMINE), 5-AMINO-2,6-DIMETHOXY-3-HYDROXYPYRIDINE, 4,5-DIAMINO-1-METHYLPYRAZOLE, 2-AMINO-3-HYDROXYPYRIDINE RIDINE), 2-Dimethyl-amino-5-amino-pyridine, 2,3-Diamino-6-methoxy-pyridine, 2,6-DIAMINOPYRIDINE, 3-Oxa-5-(3,5-diamino-2-pyridyloxy)pentanol, 3-(3 ,5-Diamino-2-pyridyloxy)-2-hydroxypropanol (3-(3,5-Diamino-2-pyridyloxy)-2-hydroxypropanol), 2,5,6-triamino-4-pyrimidinol (2,5,6-TRIAMINO-4-PYRIMIDINOL), 1-hydroxyethyl-4,5-diaminopyrazole (1-HYDROXYETHYL-4,5-DIAMINOPYRAZOLE), 2,3-DIAMINODIHYDROPYRAZOLO PYRAZOLONE DIMETHOSULFONATE), HYDROXYETHOXY AMINOPYRAZOLOPYRIDINE, 1-HEXYL-1H-PYRAZOLE-4,5-DIAMINE HEMISULFATE, DIMETHYLPIPERAZINIUM AMINOPYRAZOLOPYRIDINE, and their salts.

(B) Specific examples of the above (2) in the oxidation dye include 5-hydroxy-1,4-benzodioxane, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 1,7-naphthalenediol, pyrocatechool, resorcinol, 4-chlororesorcinol, pyrogalloinol, 1-naphthol, 1,5-naphthalenediol, 1,7 ... Alcohol (1,5-NAPHTHALENEDIOL), 2,7-naphthalene diol (2,7-NAPHTHALENEDIOL), Hydroquinone (HYDROQUINONE), 1-Methyl-2,4,5-trihydroxy-benzene (1-Methyl-2,4,5-trihydroxy-benzene), 1,2,4-trihydroxybenzene (1,2,4-TRIHYDROXYBENZENE), 2-METHYLRESORCINOL, 2,3-naphthalene diol (2,3-NAPHTHALENEDIOLE), Thymol (THYMOL), 2,3-dihydroxy-1,4-naphthoquinone (2,3-Dihydroxy-1,4-naphthoquinone), Naphtholsulfonic acid (NAPHTHOL SULFONATE), 1-Acetoxy-2-methylnaphthalene, 2-METHYL-1-NAPHTHOL, phloroglucinol, 4-FORMYL-1-METHYLQUINOLINIUM-p-TOLUENESULFONATE, and their salts.

(B) Specific examples of the above (3) in the oxidation dye include 3,4-methylenedioxyaniline, 4,5-diamino-1-((4-chlorophenyl)methyl)-1H-pyrazole, 5-hydroxy-1,4-benzodioxane, 3,4-methylenedioxyphenol, NOL), 2-Bromo-4,5-methylene-dioxy-phenol, HYDROXYBENZOMORPHOLINE, 4-HYDROXYINDOLE, 5,6-DIHYDROXYINDOLE, 6-HYDROXYINDOLE, 5,6-DIHYDROXYINDOLINE, PHENYL-PYRAZOLIDE METHYL PYRAZOLONE), HYDROXYETHYL-3,4-METHYLENEDIOXYANILINE, 7-Hydroxyindole, 5-Hydroxyindole, ISATIN, 4-FORMYL-1-METHYLQUINOLINIUM-p-TOLUENESULFONATE, and their salts.

(B) Specific examples of the above (4) in the oxidation dye include hydroxybenzomorpholine, 4-hydroxyindole, 5,6-dihydroxyindole, 6-hydroxyindole, 5,6-dihydroxyindoleline, 2-methyl-5-hydroxyethylaminophenol, 3-ethylamino-p-cresol, 2-methyl-5-hydroxyethylaminophenol ... LAMINO-p-CRESOL), N,N-diethyl-m-aminophenol (N,N-DIETHYL-m-AMINOPHENOL), 2,6-hydroxyethylaminotoluene (2,6-HYDROXYETHYLAMINOTOLUENE), 5-(2-Hydroxyethyl)-amino-4-methoxy-2-methylphenol (5-(2-Hydroxyethyl)-amino-4-methoxy-2-methylphenol), 3,3'-dihydroxydiphenylamine (3,3'-DIHYDROXYDIPHENYLAMINE), phenylmethylpyrazole (PHENYL METHYL PYRAZOLONE), HYDROXYETHYL-3,4-METHYLENEDIOXYANILINE, 7-Hydroxyindole, 5-Hydroxyindole, ISATIN, DIPHENYLAMINE, 4-FORMYL-1-METHYLQUINOLINIUM-p-TOLUENESULFONATE, and their salts.

(B) Specific examples of the above (5) in the oxidation dye include 3-amino-2,4-dichlorophenol (3-AMINO-2,4-DICHLOROPHENOL), 2-amino-4-hydroxyethylaminoanisole (2-AMINO-4-HYDROXYETHYLAMINOANISOLE), 4,6-bis-(2-hydroxyethoxy)-m-phenylenediamine (4,6-BIS(2-HYDROXYETHOXY)-m-PHENYL ENEDIAMINE), 2,4-Dimethoxy-1,3-diamino-benzene, N-CYCLOPENTYL-m-AMINOPHENOL, 5-Amino-4-methoxy-2-methyl-phenol, and their salts.

(B) Specific examples of the above (6) in the oxidation dye include hydroxybenzomorpholine, 4-hydroxyindole, 5,6-dihydroxyindole, 6-hydroxyindole, 5,6-dihydroxyindoleline, 2-methyl-5-hydroxyethylaminophenol, 3-ethylamine, 3-ETHYLAMINO-p-CRESOL、N,N-DIETHYL-m-AMINOPHENOL、2,6-HYDROXYETHYLAMINOTOLUENE、5-(2-Hydroxyethyl)-amino-4-methoxy-2-methylphenol、3,3'-DIHYDROXYDIPHENOL、 HENYLAMINE), 3-amino-2,4-dichlorophenol (3-AMINO-2,4-DICHLOROPHENOL), 2-amino-4-hydroxyethylaminoanisole (2-AMINO-4-HYDROXYETHYLAMINOANISOLE), 4,6-bis-(2-hydroxyethoxy)-m-phenylenediamine (4,6-BIS(2-HYDROXYETHOXY)-m-PHENYLENEDIAMINE), 2,4-dimethoxy-1,3-diamino-benzene (2,4-Dimethoxy-1,3-diamino-benzene zene), N-cyclopentyl-m-aminophenol (N-CYCLOPENTYL-m-AMINOPHENOL), 5-Amino-4-methoxy-2-methyl-phenol, m-PHENYLENEDIAMINE, 1-Methyl-2,4-diamino-benzene, 1-Methoxy-2,4-diamino-benzene, m -aminophenol (m-AMINOPHENOL), 2,4-diaminophenol (2,4-DIAMINOPHENOL), 1-Methyl-2-hydroxy-4-(carbamoylmethylamino)benzene (1-Methyl-2-hydroxy-4-(carbamoylmethylamino)benzene), 1-Hydroxy-3-carbamoylmethylamino-benzene, 4-AMINO-2-HYDROXY-TOL UENE), 2,4-DIAMINOPHENOXYETHANOL, 4-ETHOXY-m-PHENYLENEDIAMINE, 1-Methyl-2,6-diamino-benzene, 1,3-bis(2,4-DIAMINOPHENOXY)PROPANE, 1-β-Hydroxyethyl-2,4-diamino-benzene yl-2,4-diamino-benzene), 5-AMINO-6-CHLORO-o-CRESOL, 2,4-DIAMINO-5-METHYL-PHENETOLE, 2,4-DIAMINO-5-METHYLPHENOXYETHANOL, 5-AMINO-4-CHLORO-o-CRESOL, 2-AMINO-5-ACETYL-AMIDE- 2-Amino-5-acetamido-phenol, 5-AMINO-4-FLUORO-2-METHYLPHENOL, m-DIMETHYLAMINOPHENYLUREA, 4-FLUORO-6-METHYL-m-PHENYLENEDIAMINE, 3-AMINO-2,6-DIMETHYLPHENOL, and their salts.

Specific examples of the salt include hydrochlorides, sulfates, hydrobromides, etc. (B) The oxidation dye is selected from at least one of the specific examples.

Among the specific examples, preferred are 4-chlororesorcinol, 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, 2-amino-4-hydroxyethylaminoanisole, hydroxyethyl-3,4-methylenedioxyaniline, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 2-amino-3-hydroxypyridine, 2,5,6-triamino-4-pyrimidinol, 1-hydroxyethyl-4,5-diaminopyrazole, resorcinol, 1,5-naphthalene diol, 1-naphthol, 2-methyl-5-hydroxyethylaminophenol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and any one or more of their salts.

From the viewpoint of further improving the hair dyeing ability, it is preferred that the (B) oxidation dye includes an oxidation dye having a (B-1) heterocyclic structure. Examples of the oxidation dye having a (B-1) heterocyclic structure include 1-hydroxyethyl-4,5-diaminopyrazole, 2,4,5,6-tetraaminopyrimidine, hydroxyethyl-3,4-methylenedioxyaniline, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and salts thereof.

From the viewpoint of excellent hair dyeing power and hot water fading inhibition effect, it is preferred that (B) oxidation dye contains 1-hydroxyethyl-4,5-diaminopyrazole or its salt. Among them, since 1-hydroxyethyl-4,5-diaminopyrazole or its salt has a high chroma and presents a warm color such as a bright red, it is not easy to obtain a tone with low chroma and suppressed red. However, even in this case, by combining it with 6-methoxy-2-methylamino-3-aminopyridine or its salt of (A) oxidation dye, it is still possible to suppress red and present a low chroma purple tone.

In addition, (B) the oxidation dye is preferably a combination of 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof and 2,6-dihydroxy-3,4-dimethylpyridine or a salt thereof. According to this composition, red color can be suppressed and yellow color can be expressed.

In addition, (B) oxidation dyes are preferably used in combination with 1-hydroxyethyl-4,5-diaminopyrazole or its salt and 2,4,5,6-tetraaminopyrimidine, 2,7-naphthalene diol, or their salts. According to this composition, redness can be suppressed and yellowness can be expressed. By expressing yellowness, a natural sense of harmony can be expressed when dyeing blond hair, bleaching hair, or dyeing white hair.

The lower limit of the content of the oxidation dye (B) in the mixture can be appropriately set, preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and further preferably 1 mass % or more. When the content of the oxidation dye (B) is 0.1 mass % or more, the hair dyeing power and the hot water fading inhibition effect can be further improved.

The upper limit of the content of the oxidation dye (B) in the mixture can be appropriately set, preferably 6% by mass or less, more preferably 5% by mass or less, and further preferably 4% by mass or less. When the content of the oxidation dye (B) is 6% by mass or less, the skin cleansing property can be further improved, and the stability of the preparation can also be improved. In addition, when the oxidation dye (B) is 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof, redness can be suppressed. It can also be a range of any combination of the above upper and lower limits.

The lower limit of the total content of the oxidation dye (A) and the oxidation dye (B) in the mixture can be appropriately set, preferably 0.5 mass% or more, more preferably 1 mass% or more, and further preferably 1.5 mass% or more. When the mass is 0.5 mass% or more, the hair dyeing power and the hot water fading inhibition effect can be further improved.

The upper limit of the total content of the oxidation dye (A) and the oxidation dye (B) in the mixture can be appropriately set, preferably 7.5% by mass or less, more preferably 5.5% by mass or less, and further preferably 4.8% by mass or less. When the mass is 7.5% by mass or less, the skin cleansing property can be particularly improved, and the stability of the preparation can be improved. In addition, when the oxidation dye (B) is 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof, redness can be suppressed. The range may also be any combination of the upper and lower limits mentioned above.

The lower limit of the mass ratio (B/A) of the content of the oxidation dye (B) to the content of the oxidation dye (A) in the mixture can be appropriately set, preferably 0.2 or more, more preferably 1 or more, and further preferably 2 or more. When the mass ratio is 0.2 or more, hot water fading can be particularly suppressed, thereby improving hair dyeing power.

The upper limit of the mass ratio (B/A) of the content of the oxidation dye (B) to the content of the oxidation dye (A) in the mixture can be appropriately set, preferably 9 or less, more preferably 6 or less, and further preferably 3 or less. When the mass ratio is 9 or less, the skin cleansing property can be further improved. In addition, when the oxidation dye (B) is 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof, redness can be suppressed. It can also be a range of any combination of the upper and lower limits mentioned above.

((C) Oxidative dye) The hair dye composition of this embodiment may also selectively include (C) oxidative dyes, wherein the (C) oxidative dyes (excluding the above-mentioned (B) oxidative dyes) have a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes ortho or para. The (C) oxidative dyes may be a single (C) oxidative dye or a combination of two or more (C) oxidative dyes.

(C) Specific examples of oxidation dyes include 1,2-diamino-benzene, toluene-2,5-diamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, N-phenyl-p-phenylenediamine, o-aminophenol, p-aminophenol, p-methylaminophenol, 3,4-diaminobenzoic acid, and benzoic acid. ACID), 2-methoxy-p-phenylenediamine (2-METHOXY-p-PHENYLENEDIAMINE), N,N-diethyl-p-phenylenediamine (N,N-DIETHYL-p-PHENYLENEDIAMINE), N-methoxyethyl-p-phenylenediamine (N-METHOXYETHYL-p-PHENYLENEDIAMINE), N,N-dimethyl-p-phenylenediamine (N,N-DIMETHYL-p-PHEN YLENEDIAMINE), N,N-bis(2-hydroxy-ethyl)-p-phenylene-diamine (N,N-BIS(2-HYDROXY-ETHYL)-p-PHENYLENE-DIAMINE), 4-amino-m-cresol (4-AMINO-m-CRESOL), 6-amino-m-cresol (6-AMINO-m-CRESOL), HYDROXYETHYL-p-PHENYLENE DIAMINE), 4,4'-diaminodiphenylamine (4,4'-DIAMINODIPHENYLAMINE), 2,6-dimethyl-p-phenylenediamine (2,6-DIMETHYL-p-PHENYLENEDIAMINE), 6-amino-o-cresol (6-AMINO-o-CRESOL), 2-aminomethyl-p-aminophenol (2-AMINOMETHYL-p-AMINOPHENOL), hydroxyethylaminomethyl-p-aminophenol (HYDROXYETHYLAMINOMETHYL-p-AMINO PHENOL), 2-methoxymethyl-p-aminophenol (2-METHOXYMETHYL-p-AMINOPHENOL), hydroxypropylbis(N-hydroxyethyl-p-phenylenediamine) (HYDROXYPROPYL BIS (N-HYDROXYETHYL-p-PHENYLENEDIAMINE), 2-Methyl-4-dimethyl-amino-aniline, 5-Amino-salicylic acid, PEG-3,2’,2’-di-p-phenylenediamine, 2,2’-methylenebis-4-aminophenol, 2-AMINO-5-ETHYLPHENOL, 2-METHOXY-METHYL-p-PHENYLENEDIAMINE, HYDROXYPROPYL p-PHENYLENEDIAMINE), METHYLIMIDAZOLIUMPROPYL p-PHENYLENEDIAMINE, TOLUENE-3,4-DIAMINE, and salts thereof. Specific examples of the salt include hydrochlorides, sulfates, and hydrobromides.

The content of (C) oxidation dye in the mixture can be appropriately set, preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less. When it is 1% by mass or less, the skin cleansing property can be particularly improved, and the stability of the preparation can also be improved. In addition, when (C) oxidation dye is not added to the mixture, the skin cleansing property can be further improved.

The lower limit of the mass ratio (A/C) of the content of the oxidation dye (A) to the content of the oxidation dye (C) in the mixture can be appropriately set, preferably 1 or more, more preferably 1.5 or more, and further preferably 2 or more. When the mass ratio is 1 or more, the skin cleansing property can be improved.

The lower limit of the mass ratio of the total content of the (A) oxidation dye and the (B) oxidation dye to the content of the (C) oxidation dye in the mixture ((A+B)/C) can be appropriately set, and is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. When the mass ratio is 2 or more, the skin cleansing property can be further improved.

(Reducing agent) The first agent may contain a reducing agent as appropriate. The reducing agent can improve the stability of the dye. In addition, the stability of the dye can be maintained during storage, and the hair dyeing effect after opening can be maintained. Examples of reducing agents include ascorbic acid, thioglycolic acid, cysteine, hydroxyl compounds, sulfites, hydrogen sulfites, thiosulfates, etc.

Examples of ascorbic acid include ascorbic acid, isoascorbic acid, salts thereof, and derivatives thereof. Specific examples of salts include sodium salts, potassium salts, calcium salts, ammonium salts, monoethanolamine salts, and diethanolamine salts. Specific examples of the derivatives include disodium ascorbate sulfate, disodium isoscorbate sulfate, magnesium ascorbate phosphate, palmitic acid ascorbate, stearic acid ascorbate, dipalmitoyl ascorbate, tetra-2-hexyldecanoic acid ascorbate, myristic acid ascorbate, lauric acid ascorbate, acetic acid ascorbate, propionic acid ascorbate, tartaric acid ascorbate, and citric acid ascorbate. Ascorbic acid ester citrate, ascorbic acid succinate, ascorbic acid benzoate, (ascorbic acid/tocopherol) potassium phosphate, ethyl ascorbate, allantoin ascorbic acid, ascorbic acid chitosan, methylsilanol ascorbic acid, tetradecylhexyl ascorbate, aminopropyl ascorbic acid phosphate, ascorbic acid polypeptide, ascorbic acid glucoside, methylsilanol ascorbic acid jelly, etc.

Specific examples of thioglycolic acids include thioglycolic acid, thioglycolic acid salts, esters of thioglycolic acid, etc. Specific examples of cysteine acids include cysteine, cysteine hydrochloride, N-acetyl-L-cysteine, etc. Specific examples of hydroxyl compounds include thioglycerol, thiolactic acid, thiomalonic acid, cysteamine, etc. Specific examples of sulfites include sulfurous acid, ammonium sulfite, sodium sulfite, etc. Specific examples of hydrogen sulfites include ammonium hydrogen sulfite, sodium hydrogen sulfite, etc. Specific examples of thiosulfates include thiosulfuric acid, sodium thiosulfate, etc. Among them, ascorbic acid, ammonium sulfite, and sodium sulfite are preferred. These reducing agents may be used alone or in combination of two or more reducing agents.

The lower limit of the content of the reducing agent in the mixture can be appropriately set, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and further preferably 0.1 mass % or more. When the content of the reducing agent is 0.01 mass % or more, the stability of the dye can be further improved.

The upper limit of the content of the reducing agent in the mixture can be appropriately set, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less. When the content of the reducing agent is 10% by mass or less, the hair dyeing power can be further improved. It can also be a range of any combination of the above upper and lower limits.

(Alkaline reagent) The first agent may also preferably contain an alkaline reagent. The role of the alkaline reagent is to promote the action of the oxidizing agent contained in the second agent, thereby improving the hair dyeing power. One alkaline reagent may be used alone, or two or more alkaline reagents may be used in combination. Examples of alkaline reagents include ammonia, alkanolamines, silicates, carbonates, bicarbonates, carbamates, metasilicates, phosphates, organic amines, alkaline amino acids, and the like. Specific examples of alkanolamines include monoethanolamine, triethanolamine, and the like. Specific examples of silicates include sodium silicate, potassium silicate, calcium silicate, and the like. Specific examples of carbonates include sodium carbonate, ammonium carbonate, magnesium carbonate, etc. Specific examples of bicarbonates include sodium bicarbonate, ammonium bicarbonate, etc. Specific examples of carbamates include ammonium carbamate, etc. Specific examples of metasilicates include sodium metasilicate, potassium metasilicate, etc. Specific examples of phosphates include triammonium phosphate, diammonium hydrogen phosphate, etc. Specific examples of organic amines include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, guanidine, etc. Specific examples of alkaline amino acids include arginine, lysine, etc. Among them, ammonia, monoethanolamine and carbonate are preferred.

The lower limit of the content of the alkaline reagent in the mixture can be appropriately set, and it is preferably contained in an amount that makes the lower limit of the pH of the mixture 7 or more, more preferably 7.5 or more, further preferably 8 or more, particularly preferably 8.5 or more, and most preferably 9 or more. In addition, the upper limit of the content of the alkaline reagent can be appropriately set, and it is preferably contained in an amount that makes the upper limit of the pH of the mixture 12 or less. By making the pH of the mixture 7 or more, the action of the oxidizing agent contained in the second agent can be further promoted, and the hair dyeing power can be further improved. By making the pH of the mixture 12 or less, the damage of the hair can be further suppressed. The pH of the mixture refers to the pH measured at 25°C when the mixture of each agent is diluted 10 times with water and dissolved at a concentration of 10 mass%.

Furthermore, when the above-mentioned (B) oxidation dye contains 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof, the pH is preferably below 10.5, more preferably below 10, and further preferably below 9.5. By making the pH below 10.5, the chroma can be significantly reduced, and the red color can be suppressed, so that the color tone can be dyed into purple to blue-black. Especially in the field of popular hair colors, it is preferably pH 10.5 or below, and when dyeing white hair, it is preferably pH 9.8 or below. When the pH is below 10.5, the lightness is higher, and a bright color tone can be expressed, mainly in hair colors for black hair such as bleaching or popular hair colors, or for dyeing white hair. Bright colors can also be expressed. In addition, when the pH is below 9.8, the lightness is low and a dark tone can be shown, so it is mainly suitable for dyeing white hair.

The content of the alkaline reagent in the mixture described in this specification refers to the content of the pure alkaline reagent after removing the solvent in the raw material reagent. The lower limit of the content of the alkaline reagent in the mixture can be appropriately set, preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and further preferably 0.5 mass% or more. The upper limit of the content of the alkaline reagent in the mixture can be appropriately set, preferably 7 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less. It can also be a range of any combination of the above upper and lower limits.

The lower limit of the mass ratio of the content of the alkaline reagent to the content of the oxidation dye (A) in the mixture (alkaline reagent/A) can be appropriately set, preferably 0.1 or more, more preferably 0.5 or more, and further preferably 1 or more. When the mass ratio is 0.1 or more, the hair dyeing ability and skin cleansing property can be further improved. In addition, the upper limit of the mass ratio (alkaline reagent/A) can be appropriately set, preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. When the mass ratio is 15 or less, the hair dyeing ability and skin cleansing property can be further improved. It can also be a range of any combination of the above upper and lower limits.

The lower limit of the mass ratio of the content of the alkaline reagent in the mixture to the total content of the oxidation dye (A) and the oxidation dye (B) can be appropriately set, preferably 0.05 or more, more preferably 0.1 or more, and further preferably 0.4 or more. When the mass ratio is 0.05 or more, the hair dyeing power can be further improved. In addition, the upper limit of the mass ratio can be appropriately set, preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. When the mass ratio is 4 or less, the hair dyeing power can be further improved. It can also be a range of any combination of the above upper and lower limits.

((D) polymerization accelerator) The first agent may further contain a (D) polymerization accelerator. By adding a (D) polymerization accelerator, the hair dyeing power and skin cleansing property are improved. In addition, redness can be further suppressed. Examples of (D) polymerization accelerators include iodine compounds, iron compounds, copper compounds and other transition metals. In addition to iodine (I), iodide compounds that are associated with relative ions that are freed in the solubilizer, compounds that are freed when iodine is used, etc. Specific examples of iodides include alkali metal salts of iodides such as potassium iodide, sodium iodide, and lithium iodide, or ammonium iodide, hydrogen iodide, cesium iodide, and silver iodide. In addition, natural materials containing iodine can also be used, such as iodized garlic extract and other extracts containing iodide. Specific examples of iron compounds include iron chloride, iron oxide, sodium iron chlorophyllin, etc. Specific examples of copper compounds include copper sulfate, sodium copper chlorophyllin, etc. Among them, potassium iodide is preferred from the perspective of excellent hair dyeing effect. One (D) component can be used alone, or two or more (D) components can be used in combination.

The lower limit of the content of the component (D) in the mixture can be appropriately set, preferably 0.001 mass % or more, more preferably 0.01 mass % or more, further preferably 0.02 mass % or more, and most preferably 0.05 mass % or more. When the content of the component (D) is 0.001 mass % or more, the hair dyeing power can be further improved.

The upper limit of the content of the component (D) in the mixture can be appropriately set, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. When the content of the component (D) is 5% by mass or less, the skin cleansing property can be further improved, and the hair dyeing power can be further improved. The range may also be any combination of the above upper and lower limits.

(Others) The hair dye composition may further contain ingredients other than the above-mentioned ingredients, such as oily ingredients, surfactants, polyols, solubilizers, water-soluble polymers, pH adjusters other than the above-mentioned, preservatives, stabilizers, plant extracts, herbal extracts, vitamins, fragrances, antioxidants, chelating agents, ultraviolet absorbers, etc., as appropriate.

Examples of the oily component include fats, waxes, higher alcohols, hydrocarbons, higher fatty acids, alkyl glyceryl ethers, esters, silicones, etc. The oily component may be an animal oil or a vegetable oil. One oily component may be used alone or in combination of two or more oily components.

Examples of the polyol include glycol and glycerol. One type of polyol may be used alone, or two or more types of polyols may be used in combination.

Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. One surfactant may be used alone, or two or more surfactants may be used in combination.

When the dosage form is formulated into a liquid form, a solubilizer is added. Examples of the solubilizer used include water and an organic solvent (solvent). One solubilizer may be used alone, or two or more solubilizers may be used in combination. Among them, water is preferably used in terms of its superior ability to dissolve other components in the first agent. When water is used as a solvent, the lower limit of the water content in the mixture (content when used) can be appropriately set, preferably 40% by mass or more, and more preferably 50% by mass or more.

The water-soluble polymer can give the hair dye composition an appropriate viscosity. Therefore, the hair dye composition may also contain a water-soluble polymer within the scope that does not hinder the effect of the present invention. Examples of water-soluble polymers include natural polymers, semi-synthetic polymers, synthetic polymers, and inorganic polymers. One water-soluble polymer may be used alone, or two or more water-soluble polymers may be used in combination.

The hair dye composition (mixture) may also contain a pH adjuster in order to adjust the pH. The pH adjuster can be appropriately selected from the known components other than the components listed in the above items. Examples of pH adjusters include inorganic acids, organic acids, salts thereof, hydroxides of alkali metals or alkali earth metals, etc. Specific examples of pH adjusters include hydrochloric acid, sodium hydroxide, etc. The above other components may be used alone or in combination of two or more.

The dosage form of the first agent is not particularly limited. As a specific example, the dosage form at 25°C can be liquid, gel, foam, cream, solid, etc., such as aqueous solution or emulsion. In addition, when it is a solid dosage form, a dispersant can also be formulated. In addition, it can also be made into an aerosol, a non-aerosol, etc. When it is a non-aerosol, it can be further made into various forms such as extrusion foaming type and pump foaming type. In addition, when it is an aerosol, known sprays and foaming agents can be applied. Specific examples of sprays or foaming agents can be listed, such as liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen, carbon dioxide, etc.

(Second agent of a two-agent hair dye composition) (Oxidizing agent) In addition to the oxidizing agent, the above-mentioned solubilizing agent and the like may be added to the second agent. The oxidizing agent further increases the decolorization of the melanin contained in the hair. Therefore, an inorganic oxidizing agent may be used. Specific examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, potassium persulfate, sodium persulfate, sodium peroxide, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, strontium peroxide, hydrogen peroxide adducts of sulfates, hydrogen peroxide adducts of phosphates, hydrogen peroxide adducts of pyrophosphates, and the like. Among them, hydrogen peroxide and percarbonate are preferred, and hydrogen peroxide is more preferred. One oxidizing agent can be used alone, or two or more oxidizing agents can be used in combination. The lower limit of the content of the oxidizing agent in the second agent can be appropriately set, preferably at least 0.1 mass%, more preferably at least 1.0 mass%, and further preferably at least 2.0 mass%. When the content of the oxidizing agent is at least 0.1 mass%, the decolorization of melanin can be further improved. In addition, the upper limit of the content of the oxidizing agent in the second agent can be appropriately set, preferably at least 15.0 mass%, more preferably at least 9.0 mass%, and further preferably at least 6.0 mass%. When the content of the oxidant is 15.0 mass % or less, it can further suppress the damage to the hair. It can also be a range of any combination of the above upper and lower limits.

When the second agent is combined with hydrogen peroxide as an oxidizing agent, in order to improve the stability of hydrogen peroxide, the second agent preferably contains a stabilizer, such as sodium stannate, ethylene glycol phenyl ether (phenoxyethanol), hydroxyethane diphosphonic acid and its salts. Examples of hydroxyethane diphosphonic acid salts include tetrasodium hydroxyethane diphosphonic acid and disodium hydroxyethane diphosphonic acid. The second agent may also contain components that are usually contained in the hair dye composition and do not hinder the effects of the above-mentioned components. For example, the components contained in the first agent may also be appropriately contained within the range that does not hinder the effects of the present invention.

(Others) The dosage form of the second agent is not particularly limited. As a specific example, the dosage form at 25°C can be liquid, gel, foam, cream, solid, etc., such as aqueous solution or emulsion. In addition, it can also be made into an aerosol, non-aerosol, etc. When it is a non-aerosol, it can be made into various forms such as extrusion foaming type and pump foaming type. In addition, when it is an aerosol, a known spray and foaming agent can be applied. In addition, when it is a solid dosage form, a dispersant can also be formulated.

The mixing ratio of the first agent and the second agent of the two-agent hair dye composition can be appropriately set in consideration of the concentration of each component in the mixture, the miscibility, the application method, etc. When the mass of the second agent is set to 1, the lower limit of the mass of the first agent is preferably 0.1 or more, and more preferably 0.5 or more. When the mass of the second agent is set to 1, the upper limit of the mass of the first agent is preferably 10 or less, and more preferably 2 or less. The range may also be any combination of the above upper and lower limits. The dosage form of the mixture is not particularly limited as long as it can be applied to hair. As a specific example, the dosage form at 25°C can be liquid such as an aqueous solution or emulsion, gel, foam, cream, etc. From the viewpoint of making the brush easier to pick up or improving the extension and adhesion to the hair, and giving excellent coating operability, it is preferably made into a cream or paste. In addition, the hair dye composition can also be further made into a foam or mist. When the foam is made into the above foam, it can also be formed by self-foaming by mixing the hair dye composition in a mixing container and a mixing device, or the hair dye composition can be filled in a vibration container and vibrated to form foam, and a known foaming device such as a non-aerosol generator and an aerosol generator can also be used.

The hair dye composition can be applied to the hair using an application tool such as a comb, a brush, bristles, a sprayer, etc. Alternatively, the hair dye composition can be applied to the hair using a hand wearing a glove.

The effects of the hair dye composition according to this embodiment will be described.

(1-1) The hair dye composition of this embodiment comprises (A) 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof, and a predetermined (B) oxidation dye. Therefore, it is possible to improve skin cleansing properties while maintaining hair dyeing properties. When a reducing agent is further contained, the stability of the dye can be improved.

(1-2) When (B) oxidative dye is 1-hydroxyethyl-4,5-diaminopyrazole or its salt, the hair dyeing power and the hot water fading inhibition effect can be improved. In addition, by setting the pH at the time of use to 10.5 or less, the chroma can be significantly reduced, the red color can be suppressed, and the color tone can be expressed in purple to blue-black.

(1-3) In addition, when (B) oxidative dyes are used in combination with 1-hydroxyethyl-4,5-diaminopyrazole or a salt thereof and 2,6-dihydroxy-3,4-dimethylpyridine or a salt thereof, red color can be suppressed and yellow color can be exhibited.

In addition, when (B) the oxidation dye is used in combination with 1-hydroxyethyl-4,5-diaminopyrazole or its salt, 2,4,5,6-tetraaminopyrimidine, 2,7-naphthalene diol, or their salts, the red color can be suppressed and a yellow color can be displayed.

(1-4) In addition, the content of the oxidation dye (C) in the hair dye composition of the present embodiment is specified within a predetermined range. Therefore, the composition can be configured to substantially not contain dye intermediates such as p-phenylenediamine and toluene-2,5-diamine or to reduce their content. Therefore, for example, it can be used by subjects who are allergic to specific dyes.

The reason why these dye intermediates improve hair dyeing properties is presumed to be as follows: when the amine and hydroxyl groups with high electron donation properties present para/ortho orientations, the reactivity is higher. In other words, when the amine/hydroxyl groups present the above orientations, they can impart high dyeing properties to hair by reacting with other oxidative dyes. However, on the other hand, they also improve the dyeing properties to the skin by reacting with the skin, worsening skin pollution. The present invention has found that by using (A) oxidative dyes and (B) oxidative dyes as colorants and selecting the oxidative dyes used, it is possible to have excellent skin cleansing properties while maintaining hair dyeing properties.

(1-5) In addition, the hair dye composition of this embodiment can be bleached and thus has improved re-dyeing properties.

The above-mentioned implementation method can be modified and implemented as follows. The above-mentioned implementation method and the following modification examples can be combined and implemented with each other within the scope of technical non-contradiction.

・With regard to dyes other than the above-mentioned oxidation dyes, the hair dye composition of the above-mentioned embodiment may also appropriately contain, for example, direct dyes listed in the "Quadridrug Ingredients Standards" (published in June 2006, Yakuji Nichipō Sha) within the range not hindering the effects of the present invention.

・The hair dye composition of the above embodiment is a multi-agent hair dye composition having a first agent containing (A) an oxidation dye and the like and a second agent containing an oxidizing agent and the like.

However, the hair dye composition is not limited to the two-ingredient formula, and a part of each component contained in the first and second agents can be used as other agents to form a three-ingredient formula or more. For example, the first agent of the two-ingredient formula can also be divided into two types, namely, an agent containing a dye and an alkaline reagent of an arbitrary component, and an agent having a composition other than the above, to form a three-ingredient hair dye composition. In this case, it will have better formulation stability. In addition, for example, dyes, alkaline reagents, and oxidants can also be combined with other agents. In addition, within the scope of the effect of the present invention, dyes, alkaline reagents, and oxidants can also be combined.

In addition, a powdered dye and a powdered oxidant may be prepared, thereby storing the dye and the oxidant in the same agent. When a powdered agent is used, it must be dissolved in the above-mentioned solvent when used.

Even when the hair dye composition is made into a composition of three or more formulations or a composition containing a powdered formulation, it is still included in the present invention as long as the effects of the present invention can be exerted.

(Second embodiment) The second embodiment of the hair dye composition embodied in the present invention is described below.

The hair dye composition of the second embodiment differs from the hair dye composition of the first embodiment in that the hair dye composition does not contain an oxidizing agent. The following description will focus on the differences from the hair dye composition of the first embodiment.

The hair dye composition of the second embodiment is composed of a single-dose hair dye composition, which contains the above-mentioned (A) oxidation dye and (B) oxidation dye, etc. In addition to the above-mentioned oxidation dye, the single-dose hair dye composition may also preferably contain an alkaline reagent, (D) polymerization accelerator, etc. It may also selectively contain the above-mentioned (C) oxidation dye.

In the second embodiment, it is preferred that the (B) oxidation dye is composed of at least one of 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, isatin, 1,5-naphthalene diol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, 5-amino-6-chloro-o-cresol, and salts thereof. In this way, even without using an oxidizing agent, a better hair dyeing ability can be obtained. The (B) oxidation dyes may be used alone or in combination of two or more.

Among them, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and salts thereof are preferred from the viewpoints of hair dyeing power, cumulative effect of continuous use, suppression of hot water fading, and superior red suppression.

The hair dye composition of the second embodiment may further contain components other than the above components, for example, the components contained in the hair dye composition described in the column of the first embodiment, as appropriate.

In addition, the second embodiment can appropriately adopt the modified examples described in the first embodiment within the scope of technical inconsistency. Among them, when the hair dye composition of the second embodiment is composed of one dosage form, the content and content ratio of each component in the mixture of the first embodiment means the content and content ratio in one dosage form.

The effects of the hair dye composition of the second embodiment are described. In the second embodiment, in addition to the effects of the first embodiment, the following effects are also achieved.

(2-1) In the second embodiment, the above-mentioned (A) oxidation dye and (B) oxidation dye are blended without using an oxidizing agent. Therefore, excellent hair dyeing ability can be obtained even without using an oxidizing agent. In addition, since the color is developed by oxidation in the air, damage to the hair can be reduced.

The second embodiment can be modified and implemented as follows. The second embodiment and the following modifications can be implemented in combination with each other within the scope of technical non-contradiction.

・The dosage form of the hair dye composition of the second embodiment is not particularly limited. For example, when the dosage form of the hair dye composition is a foam, the effect of suppressing hair stains can be further improved compared to a cream-like dosage form. When the dosage form of the hair dye composition is a cream, the hair dyeing power can be further improved compared to a foam-like dosage form.

・The second embodiment is a hair dye composition of one formulation, which contains (A) an oxidation dye, etc. However, the hair dye composition is not limited to one formulation, and may be composed of two or more formulations by using a part of each component as another formulation. For example, a hair dye composition of two formulations may be composed of a formulation containing an alkaline reagent as an arbitrary component and a formulation having a composition other than the above. In this case, the formulation stability will be better.

Embodiment

Next, embodiments and comparative examples are listed to provide a more detailed description of the above embodiments. However, the present invention is not limited to the configuration described in the embodiment column.

<Test Example 1: Two-component hair dye composition> The first component in the form of a cream containing the components shown in Tables 1 to 3 and the second component in the form of an emulsion containing the components shown in Table 4 were prepared as hair dye compositions. Hydrochloric acid and sodium hydroxide were used as pH adjusters. The numerical values in the columns representing each component in each table represent the content of the component in that column, and the unit is mass %. The symbols A to D in the "Component" column in each table represent the compounds corresponding to the components listed in the claim item of this case.

The mass ratio of the content of (A) oxidation dye to the content of (C) oxidation dye is shown in the "Component A/Component C" column of the table.

The content of (A) oxidation dye in the mixture is shown in the "Component A (1:1 mixture)" column in the table.

The content of (B) oxidation dye in the mixture is shown in the "B component (when mixed in a 1:1 ratio)" column in the table.

The content of (C) oxidation dye in the mixture is shown in the "C component (when mixed in a 1:1 ratio)" column in the table.

The content of alkaline reagent in the mixture is shown in the "Alkaline reagent (1:1 mixture)" column in the table.

The total of the content of (A) oxidation dye and the content of (B) oxidation dye in the mixture is shown in the "Component A + Component B (1:1 mixed)" column in the table.

The mass ratio of the content of the alkaline reagent to the content of (A) the oxidation dye is shown in the "Alkaline reagent/component A" column in the table.

The mass ratio of the content of the (B) oxidation dye to the content of the (A) oxidation dye is shown in the "B component/A component" column of the table.

Among them, the dyes using acid salts in the following table, such as 6-methoxy-2-methylamino-3-aminopyridine 2 hydrochloride, are obtained by neutralizing 1 mol of 6-methoxy-2-methylamino-3-aminopyridine hydrochloride as a raw material with 2 mol of hydrochloric acid generated by adding an alkaline reagent or NaOH as a pH adjuster. That is, the dyes using acid salts in the reagents listed in the table, such as 6-methoxy-2-methylamino-3-aminopyridine 2 hydrochloride, are contained in the form of free 6-methoxy-2-methylamino-3-aminopyridine.

In each of the Examples and Comparative Examples, the first agent and the second agent were mixed at a mass ratio of 1:1 to prepare a mixture of the hair dye composition of each example. 2 g of the obtained mixture was applied to 1 g of a hair bundle sample (manufactured by Beaulax) (hereinafter referred to as the hair bundle) of 10 cm in length using a brush. 30 minutes after the mixture was applied to the hair bundle, the mixture attached to the hair bundle was washed off with water, and shampoo (conditioning shampoo manufactured by Hoyu Co., Ltd.) was applied twice and conditioner (conditioning conditioner manufactured by Hoyu Co., Ltd.) was applied once to the hair bundle. The hair bundle was then dried with warm air to obtain a dyed hair bundle of each example.

The hair bundles of each example that had been subjected to the hair dyeing treatment were evaluated for hair dyeing ability, skin washability, hot water fading inhibition, and redness inhibition according to the following methods on the day after the hair dyeing treatment.

(Evaluation method of hair dyeing power) For each of the dyed hair bundles obtained above, 10 panelists visually observed the dyeing density under a standard light source and judged using the following criteria. The panelists scored using a 6-level method: Very good (6 points), Excellent (5 points), Good (4 points), Fair (3 points), Slightly poor (2 points), and Poor (1 point). The average value was calculated from the scoring results of each panelist. Then, the average value of 5.6 points or more was rated as "very good: 6", the average value of 4.6 points or more but less than 5.6 points was rated as "excellent: 5", the average value of 3.6 points or more but less than 4.6 points was rated as "good: 4", the average value of 2.6 points or more but less than 3.6 points was rated as "fair: 3", the average value of 1.6 points or more but less than 2.6 points was rated as "slightly poor: 2", and the average value of less than 1.6 points was rated as "poor: 1" as the evaluation results. The results are shown in the "hair dyeing power" column of each table.

(Evaluation method for skin cleansing properties) Twenty panelists applied the hair dye composition of each case to the upper arm and left it there for 30 minutes. The hair dye composition was then washed off and the upper arm was gently rubbed with soap. At this time, the skin cleansing properties of each case were evaluated using the following 6-step method based on the number of panelists who judged that the hair dye composition (skin contamination) attached to the upper arm had decreased or had been washed off.

17 or more people rated 6 points, 14 to 16 people rated 5 points, 11 to 13 people rated 4 points, 8 to 10 people rated 3 points, 5 to 7 people rated 2 points, and 4 or less people rated 1 point. The results are shown in the "Skin Cleansing" column of each table.

(Evaluation method for red suppression) For each of the dyed hair bundles obtained above, 10 panelists visually observed the red color of the dyed hair under a standard light source and evaluated it using the following criteria. The panelists scored the hair using a 6-step method: no redness (6 points), almost no redness (5 points), slight redness (4 points), slight redness (3 points), redness (2 points), and obvious redness (1 point). The average value was calculated from the scoring results of each panelist. Those with an average of 5.6 points or more were rated as "no red feeling: 6", those with an average of 4.6 points or more but less than 5.6 points were rated as "almost no red feeling: 5", those with an average of 3.6 points or more but less than 4.6 points were rated as "faint red: 4", those with an average of 2.6 points or more but less than 3.6 points were rated as "feeling a little red: 3", those with an average of 1.6 points or more but less than 2.6 points were rated as "feeling red: 2", and those with an average of less than 1.6 points were rated as "feeling obvious red: 1". This result applies to the "Red Suppression" column of each table.

(Evaluation method for hot water fading inhibition) The dyed hair bundles of each example obtained above were immersed in a 1% sodium lauryl sulfate aqueous solution heated to 50°C for 15 minutes. The 1% sodium lauryl sulfate aqueous solution was then washed off with water, and then a conditioning conditioner manufactured by Hoyu was applied and rinsed with water. The hair bundles were then dried with a towel and finally dried with a hair dryer. The obtained hair bundles (hereinafter referred to as "faded hair bundles") were used as a model system for the faded state. The faded hair bundles were compared with the hair bundles of each example that had undergone the fading treatment, and 20 specialized sensory reviewers evaluated visually. The evaluation criteria are: 17 or more panelists rated the hair bundles as not easy to fade due to fading treatment and having excellent color retention as 6 points, 14-16th rated as 5 points, 11-13th rated as 4 points, 8-10th rated as 3 points, 5-7th rated as 2 points, and 4th rated as 1 point. The results are shown in the "Hot Water Fading Inhibition" column of each table.

Table 1-1 Element Embodiment 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 A 6-Methoxy-2-methylamino-3-aminopyridine 2-hydrochloride 1 2 2 1 1 1 1 1 B 1-Hydroxyethyl-4,5-diaminopyrazole sulfate 3 3 3 3 3 3 3 3 2,6-Dihydroxy-3,4-dimethylpyridine 2 - 2 - - - - - 2,4,5,6-Tetraaminopyrimidine sulfate - 3 - - - - - - 2,7-Naphthalenediol - 1 - - - - - - C p-Phenylenediamine Sulfate - - - - - - - - Toluene-2,5-diamine Sulfate - - - - - - - - Alkaline reagent 70 mass% monoethanolamine 6 6 6 6 6 6 6 6 pH Adjuster Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Polyoxyethylene (30) cetyl wax ether 2 2 2 2 2 2 2 2 Polyoxyethylene (5) cetyl wax ether 1 1 1 1 1 1 1 1 Stearyl trimethicone chloride 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Cetearyl Alcohol 4 4 4 4 4 4 4 4 Ascorbic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Pure water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 10% dilution pH when mixed 9.5 9.5 9.5 9.5 7.0 7.5 8.0 8.5 Ingredient A/Ingredient C - - - - - - - - Component A (when mixed in a ratio of 1:1) 0.50 1.00 1.00 0.50 0.50 0.50 0.50 0.50 Component B (when mixed in a 1:1 ratio) 2.50 3.50 2.50 1.50 1.50 1.50 1.50 1.50 Component C (when mixed in a 1:1 ratio) - - - - - - - - Alkaline reagent (1:1 mixed) 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 Component A + Component B (1:1 mixed) 3.00 4.50 3.50 2.00 2.00 2.00 2.00 2.00 Alkaline reagent/component A 4.20 2.10 2.10 4.20 4.20 4.20 4.20 4.20 Ingredient B/Ingredient A 5 3.5 2.5 3 3 3 3 3 Hair Dyeing Power 6 6 6 6 3 4 5 6 Skin cleansing properties 6 6 6 5 5 5 5 6 Red Suppression 6 6 6 5 6 6 6 6 Hot water fading inhibition 6 6 6 6 6 6 6 6

Table 1-2 Element Embodiment 1-9 1-10 1-11 1-12 1-13 1-14 1-15 1-16 1-17 A 6-Methoxy-2-methylamino-3-aminopyridine 2-hydrochloride 1 1 1 1 1 1 1 1.5 2 B 1-Hydroxyethyl-4,5-diaminopyrazole sulfate 3 3 3 3 3 3 3 3 3 2,6-Dihydroxy-3,4-dimethylpyridine - - - - - - - - - 2,4,5,6-Tetraaminopyrimidine sulfate - - - - - - - - - 2,7-Naphthalenediol - - - - - - - - - C p-Phenylenediamine Sulfate - - 1.1 0.6 0.45 - - 1 1 Toluene-2,5-diamine Sulfate - - - - - 1.1 0.45 - - Alkaline reagent 70 mass% monoethanolamine 6 6 6 6 6 6 6 6 6 pH Adjuster Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Polyoxyethylene (30) cetyl wax ether 2 2 2 2 2 2 2 2 2 Polyoxyethylene (5) cetyl wax ether 1 1 1 1 1 1 1 1 1 Stearyl trimethicone chloride 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Cetearyl Alcohol 4 4 4 4 4 4 4 4 4 Ascorbic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Pure water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 100 10% dilution pH when mixed 10.0 10.6 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Ingredient A/Ingredient C - - 0.91 1.67 2.22 0.91 2.22 1.50 2.00 Component A (when mixed in a ratio of 1:1) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.75 1.00 Component B (when mixed in a 1:1 ratio) 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 Component C (when mixed in a 1:1 ratio) - - 0.55 0.30 0.225 0.55 0.225 0.50 0.50 Alkaline reagent (1:1 mixed) 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 Component A + Component B (1:1 mixed) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.25 2.50 Alkaline reagent/component A 4.20 4.20 4.20 4.20 4.20 4.20 4.20 2.80 2.10 Ingredient B/Ingredient A 3 3 3 3 3 3 3 2 1.5 Hair Dyeing Power 6 4 6 6 6 6 6 6 6 Skin cleansing properties 5 4 3 4 4 3 4 4 4 Red Suppression 4 3 3 4 5 3 5 4 5 Hot water fading inhibition 6 5 6 6 6 6 6 6 6

Table 2 Element Embodiment Comparison Example 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-29 1-1 1-2 1-3 A 6-Methoxy-2-methylamino-3-aminopyridine 2-hydrochloride 1 1 1 1 0.5 1.5 1 1 1 1 1 1 - 1 - B 1-Hydroxyethyl-4,5-diaminopyrazole sulfate 0.2 1.7 9 11 3 3 3 3 3 3 3 3 3 - 3 C p-Phenylenediamine Sulfate - - - - - - - - - - - - - - 0.5 Alkaline reagent 70 mass% monoethanolamine 6 6 6 6 6 6 18 12 8 - 1 - 6 6 6 28 mass% ammonia water - - - - - - - - - 6 - 1 - - - pH Adjuster Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Polyoxyethylene (30) cetyl wax ether 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polyoxyethylene (5) cetyl wax ether 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Stearyl trimethicone chloride 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Cetearyl Alcohol 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Ascorbic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Pure water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 10% dilution pH when mixed 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Ingredient A/Ingredient C - - - - - - - - - - - - - - - Component A (when mixed in a ratio of 1:1) 0.50 0.50 0.50 0.50 0.25 0.75 0.50 0.50 0.50 0.50 0.50 0.50 - 0.50 - Component B (when mixed in a 1:1 ratio) 0.10 0.85 4.50 5.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 - 1.50 Component C (when mixed in a 1:1 ratio) - - - - - - - - - - - - - - 0.25 Alkaline reagent (1:1 mixed) 2.10 2.10 2.10 2.10 2.10 2.10 6.30 4.20 2.80 0.84 0.35 0.14 2.10 2.10 2.10 Component A + Component B (1:1 mixed) 0.60 1.35 5.00 6.00 1.75 2.25 2.00 2.00 2.00 2.00 2.00 2.00 1.50 0.50 1.50 Alkaline reagent/component A 4.20 4.20 4.20 4.20 8.40 2.80 12.60 8.40 5.60 1.68 0.70 0.28 - 4.20 - Ingredient B/Ingredient A 0.2 1.7 9 11 6 2 3 3 3 3 3 3 - - - Hair Dyeing Power 4 5 6 6 5 6 4 4 6 6 4 4 2 2 2 Skin cleansing properties 3 4 4 3 4 5 4 4 5 5 4 4 1 2 1 Red Suppression 5 5 4 3 4 5 3 4 5 5 4 3 4 4 2 Hot water fading inhibition 4 5 6 6 6 6 4 5 6 6 5 4 2 2 2

table 3 Element Embodiment Comparison Example 1-30 1-31 1-32 1-33 1-34 1-35 1-36 1-37 1-38 1-39 1-40 1-41 1-42 1-43 1-4 A 6-Methoxy-2-methylamino-3-aminopyridine 2-hydrochloride 1 1 1 1 1 1 1 1 1 1 1 1 1 1 - B(1) 1-Hydroxyethyl-4,5-diaminopyrazole sulfate - - - - - - - - - - - - 3 - - B(4),(6) 2-Methyl-5-hydroxyethylaminophenol 3 - - - - - - - - - - - - 3 3 B(2) Resorcinol - 3 - - - - - - - - - - - - - B(1) 2,6-Dihydroxy-3,4-dimethylpyridine - - 3 - - - - - - - - - - - - B(1) 2,4,5,6-Tetraaminopyrimidine sulfate - - - 3 - - - - - - - - - - - B(2) 2,7-Naphthalenediol - - - - 3 - - - - - - - - - - B(3),(4) Phenylmethylpyrazole - - - - - 3 - - - - - - - - - B(3),(4) Hydroxyethyl-3,4-methylenedioxyaniline - - - - - - 3 - - - - - - - - B(4),(6) 2,6-Hydroxyethylaminotoluene - - - - - - - 3 - - - - - - - B(5),(6) 4,6-Bis-(2-hydroxyethoxy)-m-phenylenediamine - - - - - - - - 3 - - - - - - B(6) 2,4-Diaminophenoxyethanol - - - - - - - - - 3 - - - - - B(6) m-Aminophenol - - - - - - - - - - 3 - - - - B(6) 4-Amino-2-hydroxy-toluene - - - - - - - - - - - 3 - - - C p-Phenylenediamine Sulfate - - - - - - - - - - - - - - 0.5 D Potassium iodide - - - - - - - - - - - - 0.2 0.2 - 70 mass% monoethanolamine 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 pH Adjuster Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Polyoxyethylene (30) cetyl wax ether 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polyoxyethylene (5) cetyl wax ether 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Stearyl trimethicone chloride 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Cetearyl Alcohol 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Ascorbic acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Pure water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 10% dilution pH when mixed 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Component A (when mixed in a ratio of 1:1) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 - Component B (when mixed in a 1:1 ratio) 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 Alkaline reagent (1:1 mixed) 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 2.10 Component A + Component B (1:1 mixed) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.50 Alkaline reagent/component A 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 4.20 - Ingredient B/Ingredient A 3 3 3 3 3 3 3 3 3 3 3 3 3 3 - Hair Dyeing Power 6 6 6 6 6 3 5 5 5 6 6 6 6 6 6 Skin cleansing properties 5 5 5 5 5 5 5 4 4 3 3 3 6 6 1 Hot water fading inhibition 4 4 4 4 4 4 4 4 4 4 4 4 5 3 5

Table 4 Second dose (ingredient name) Prescription 1 Prescription 2 Cetearyl alcohol 4 4 Polyoxyethylene stearyl ether 0.5 0.5 Polyoxyethylene cetyl wax ether 0.5 0.5 Stearyl trimethicone chloride 0.1 0.1 Hydroxyethanediphosphonic acid 0.1 0.1 Tetrasodium Hydroxyethanediphosphonate 0.1 0.1 Phenoxyethanol 0.1 0.1 Flowing wax - 30 35 mass% hydrogen peroxide 16.5 16.5 Pure water Remaining amount Remaining amount 2nd dose 100 100

As shown in Tables 1 to 3, it can be confirmed that the hair dyeing ability and skin cleansing ability of each example are both acceptable results.

Among them, in the second dose listed in Table 4, the case where prescription 2 was applied also obtained the same test results as the case where prescription 1 was applied.

In addition, the first agent of Example 1-4 and the first agent of Example 1-4 without ascorbic acid were prepared and stored at room temperature for 1 month. The hair dyeing ability was evaluated in the same manner as in Example 1-4. The results showed that the hair dyeing ability of the first agent without ascorbic acid was inferior to that of the first agent of Example 1-4.

Furthermore, it was confirmed that in each of the above examples, when an equal amount of an iron compound or a copper compound was used instead of potassium iodide as a polymerization accelerator, the same evaluation was obtained.

<Test Example 2: Single-dose hair dye composition without using an oxidizing agent> Single-dose hair dye compositions containing the components shown in Table 5 were prepared respectively.

The content of (A) oxidation dye in 1 dose is shown in the "Component A" column in the table.

The content of (B) oxidation dye in 1 dose is shown in the "B component" column in the table.

The content of (C) oxidation dye in 1 dose is shown in the "C component" column in the table.

The amount of alkaline reagent in one dose is shown in the "Alkaline reagent" column in the table.

The total of the content of (A) oxidation dye and the content of (B) oxidation dye in one dose is shown in the "Component A + Component B" column in the table.

About 2 g of the prepared hair dye composition is placed on a plate and applied to 1 g of a 10 cm long white hair bundle sample with a brush. The hair bundle sample coated with the hair dye composition is placed in a 30°C constant temperature bath for 10 minutes and then washed with water. The washed hair bundle sample is then dried with warm air to obtain a hair bundle sample for evaluation after one dyeing. In addition, this series of steps is repeated 3 times to prepare three hair bundle samples for evaluation after dyeing. At this time, after the second time, there is an additional step of washing the hair bundle sample with "conditioning shampoo" (manufactured by Hoyu Co., Ltd.) and drying it with a towel before applying the hair dye composition.

The hair bundles of each example after the hair dyeing treatment were evaluated for hair dyeing ability, skin cleansing property, redness suppression, and hot water fading suppression in the same manner as in Test Example 1. The cumulative effect of continuous use was evaluated in the following manner.

The hair tress samples after the first dyeing and the hair tress samples after the third dyeing were visually observed by 5 specialized panelists, and the hair tress samples after the third dyeing were evaluated to see whether the hair was dyed darker than the hair tress samples after the first dyeing. In addition, the hair tress samples after the third dyeing were visually observed by the same panelists and compared with the hair dyeing performed once in the same manner using the oxidative hair dyes "Cielo Hair Color EX Cream No. 4" and "Cielo Hair Color EX Cream No. 5" (both manufactured by Hoyu Co., Ltd.). In addition, each panelist gave a score using the following 5-step scale.

5 points: Very high cumulative effect after continuous use (the hair sample after three times of dyeing was darker than the hair sample after one time of dyeing, and the color intensity was equivalent to that of "Cielo Hair Color EX Cream No. 5").

4 points: High cumulative effect after continuous use (the hair sample after three times of dyeing was darker than the hair sample after one time of dyeing, and the color concentration was equivalent to that of "Cielo Hair Color EX Cream No. 4").

3 points: Low cumulative effect after continuous use (the hair sample after three times of dyeing was darker than the hair sample after one time of dyeing, but the color density did not reach the same as "Cielo Hair Color EX Cream No. 4").

2 points: Very low cumulative effect after continuous use (the hair sample after three dyeings was only slightly darker than the hair sample after one dyeing).

1 point: No cumulative effect after consecutive use (the hair tress sample after three dyeings did not become darker than the hair tress sample after one dyeing).

The average score was calculated from the ratings of the five sensory reviewers, and the average score of 4.6 or above was rated as "excellent: 5", 3.6 or above but less than 4.6 was rated as "good: 4", 2.6 or above but less than 3.6 was rated as "fair: 3", 1.6 or above but less than 2.6 was rated as "slightly poor: 2", and less than 1.6 was rated as "poor: 1". The results are shown in the "cumulative" column of each table.

table 5 Element Embodiment Comparison Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11 2-12 2-1 2-2 A 6-Methoxy-2-methylamino-3-aminopyridine 2-hydrochloride 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - 0.5 B 5,6-Dihydroxyindole - 1.5 - - - - - - - - - - - - 5,6-Dihydroxyindoline 0.75 - 1.5 1.5 - - - - - 1.5 1.5 1.5 0.75 - 2,4,5,6-Tetraaminopyrimidine sulfate 0.75 - - - 1.5 - - - - - - - 0.75 - 2,7-Naphthalenediol - - - - - 1.5 - - - - - - - - 2-Methylresorcinol - - - - - - 1.5 - - - - - - - 3-Amino-2,4-dichlorophenol - - - - - - - 1.5 - - - - - - 5-Amino-6-chloro-o-cresol - - - - - - - - 1.5 - - - - - C p-Phenylenediamine Sulfate - - - - - - - - - 0.45 - - - - Alkaline reagent 70 mass% monoethanolamine 3 3 3 - 3 3 3 3 3 3 6 1 3 3 28 mass% ammonia water - - - 3 - - - - - - - - - - pH Adjuster Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Moderate Polyoxyethylene (30) cetyl wax ether 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polyoxyethylene (5) cetyl wax ether 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Stearyl trimethicone chloride 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Cetearyl Alcohol 4 4 4 4 4 4 4 4 4 4 4 4 4 0.5 Ascorbic acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Liquefied Petroleum Gas (LPG) - - - - - - - - - - - - - 7 Pure water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 10% dilution pH when mixed 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Ingredient A/Ingredient C - - - - - - - - - 1.11 - - - - Ingredient A 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 - 0.50 B ingredient 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 - C ingredient - - - - - - - - - 0.45 - - - - Alkaline reagent 2.10 2.10 2.10 0.84 2.10 2.10 2.10 2.10 2.10 2.10 4.20 0.70 2.10 2.10 Ingredient A + Ingredient B 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.50 0.50 Alkaline reagent/component A 4.20 4.20 4.20 1.68 4.20 4.20 4.20 4.20 4.20 4.20 8.40 1.40 - 4.20 Ingredient B/Ingredient A 3 3 3 3 3 3 3 3 3 3 3 3 - - Hair Dyeing Power 6 6 6 6 5 4 6 4 3 6 6 4 2 1 Cumulative 5 5 5 5 4 4 5 5 4 5 5 4 3 2 Skin cleansing properties 6 6 6 6 5 5 5 5 5 3 5 3 2 2 Red Suppression 6 6 6 6 4 4 3 5 5 5 5 5 6 6 Hot water fading inhibition 6 6 6 6 6 6 6 6 4 6 6 5 4 2

As shown in Table 5, it can be confirmed that the hair dye composition containing no oxidizing agent also has excellent hair dyeing ability. In particular, the hair dyeing ability of Example 2-1 was rated 6, and the hair was dyed beautifully without dyeing spots.

Claims (11)

A hair dye composition, characterized in that: It comprises (A) an oxidation dye and (B) an oxidation dye, (A) the oxidation dye comprises 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof, (B) the oxidation dye comprises any one or more of (1) to (6): (1) an oxidation dye without a benzene ring, (2) an oxidation dye without an amine group, (3) an oxidation dye with a benzene ring and a heterocyclic ring, wherein the benzene ring and the heterocyclic ring are directly bonded, bonded by one covalent bond, or bonded by two or three consecutive covalent bonds, (4) an oxidation dye with a benzene ring and an amine group, wherein all the amine groups are diamines or tertiary amines and are substituted by carbon chains having two or more carbon atoms, (5) Oxidative dyes having a benzene ring and a primary amine group, wherein all primary amine groups have the following functional groups: Functional groups bonded to carbons located on both sides of the carbon to which the primary amine group is bonded, or functional groups bonded to carbons adjacent to the carbon to which the primary amine group is bonded and having two or more consecutive covalent bonds, (6) Oxidative dyes having a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes the meta position. The hair dye composition as described in claim 1, wherein the above-mentioned (B) oxidation dye comprises any one or more of the following oxidation dyes: an oxidation dye satisfying the above-mentioned requirement (1), an oxidation dye satisfying the above-mentioned requirement (2), and an oxidation dye satisfying any two or more of the above-mentioned requirements (3) to (6). The hair dye composition as described in claim 1, wherein The above-mentioned (B) oxidation dyes include 4-chlororesorcinol, 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, 2-amino-4-hydroxyethylaminoanisole, hydroxyethyl-3,4-methylenedioxyaniline, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-pyridinediamine, 2-amino-3-hydroxypyridine, 2,5,6-triamino-4-pyrimidinol, 1-hydroxyethyl-4,5-diaminopyrazole, resorcinol, 1,5-naphthalene diol, 1-naphthol, 2-methyl-5-hydroxyethylaminophenol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and any one or more of the salts thereof. The hair dye composition as described in claim 1, wherein the above-mentioned (B) oxidation dye contains at least 1-hydroxyethyl-4,5-diaminopyrazole or its salt. A hair dye composition as described in claim 4, wherein the pH during use is below 10.5. A hair dye composition as described in any one of claims 1 to 5, further comprising (D) a polymerization accelerator. A hair dye composition, characterized in that: It does not contain an oxidizing agent, It comprises (A) an oxidation dye and (B) an oxidation dye, (A) the oxidation dye comprises 6-methoxy-2-methylamino-3-aminopyridine or a salt thereof, (B) the oxidation dye comprises any one or more of (1) to (6): (1) an oxidation dye without a benzene ring, (2) an oxidation dye without an amine group, (3) an oxidation dye with a benzene ring and a heterocyclic ring, wherein the benzene ring and the heterocyclic ring are directly bonded, bonded by one covalent bond, or bonded by two or three consecutive covalent bonds, (4) an oxidation dye with a benzene ring and an amine group, wherein all the amine groups are diamines or tertiary amines and are substituted by carbon chains having two or more carbon atoms, (5) Oxidative dyes having a benzene ring and a primary amine group, wherein all primary amine groups have the following functional groups: Functional groups bonded to carbons located on both sides of the carbon to which the primary amine group is bonded, or functional groups bonded to carbons adjacent to the carbon to which the primary amine group is bonded and having two or more consecutive covalent bonds, (6) Oxidative dyes having a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes the meta position. The hair dye composition as described in claim 7, wherein the above-mentioned (B) oxidation dye comprises 2,7-naphthalene diol, 3-amino-2,4-dichlorophenol, 2-methylresorcinol, 2,4,5,6-tetraaminopyrimidine, isatin, 1,5-naphthalene diol, 5,6-dihydroxyindoline, 5,6-dihydroxyindole, 5-amino-6-chloro-o-cresol, and any one or more of the salts thereof. The hair dye composition as described in claim 7, wherein the above-mentioned (B) oxidation dye comprises one or more of 5,6-dihydroxyindoline, 5,6-dihydroxyindole, and salts thereof. A hair dye composition as described in any one of claims 1 to 5 and 7 to 9, wherein when further selectively comprising (C) oxidation dye, the mass ratio (A/C) of the content of (A) oxidation dye relative to the total content of the above-mentioned (C) oxidation dye is 1 or more, the (C) oxidation dye (excluding the above-mentioned (B) oxidation dye) has a benzene ring and an amine group, wherein the positional relationship between the amine groups or the positional relationship between the amine group and the hydroxyl group includes ortho-position or para-position. A hair dye composition as described in any one of claims 1 to 5 and 7 to 9, wherein the mass ratio of the content of the alkaline reagent to the content of the above-mentioned (A) oxidation dye (alkaline reagent/A) is 0.1 or more.