JP2010013386A - Hair dye, hair dyeing method and its method for manufacturing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye which excels in hair dyeability and hair dyeing reproducibility, has high fastness of a hair-dyed state to shampooing, rinsing, light or the like, and moreover does not damage the hair. <P>SOLUTION: The hair dye includes two types of a hair dye component A containing at least one leuco compound and/or salt of an indigo compound and a hair dye component B containing at least one water-soluble silver salt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hair dye, and more specifically, a hair dye component A containing a leuco body of an indigo compound and / or a salt thereof, and a hair dye component B containing at least one water-soluble silver salt. It relates to a hair dye composed of seeds. The present invention relates to a hair dye that has excellent hair dyeing properties and fastness to hair and has little damage to hair.

  Conventionally, hair dyes using oxidative dyes are widely known. This hair dye comprises a first liquid containing an oxidation dye intermediate such as paraphenylenediamine or 2,5-diaminotoluene and an alkali such as ammonia, and a second liquid containing an oxidizing agent such as hydrogen peroxide. . Hair dyes using oxidative dyes have high hair dyeing power because the oxidative dye intermediate penetrates into the hair and dyes the hair by oxidative polymerization, and is excellent in fastness of the dyed state, shampoo and rinse, Or it is known that there is little fading by light. Further, by using hydrogen peroxide water in combination, decolorization and hair dyeing can be performed simultaneously, and there is a feature that hair can be dyed in various colors.

  However, hair dyes using oxidative dyes have the problem that hair is damaged by alkalis such as ammonia and oxidants used in hair dyeing treatments, and the damage causes poor gloss and moisture, resulting in unnatural touch. There was a problem of becoming hair. When ammonia is used as the alkali, there is also a problem that an unpleasant odor is produced during hair dyeing. Further, paraphenylenediamine, 2,5-diaminotoluene and the like are usually used as the oxidation dye, and it has been pointed out that these have skin irritation. Furthermore, although hair dyes using oxidative dyes can be dyed in various colors, their colors are not vivid.

  Direct dyes have been proposed as hair dyes for dyeing hair in vivid colors. Although direct dyes have the characteristic that hair can be dyed vividly, they generally have low color fastness to shampoos and rinses or light, and have problems such as discoloration and dullness. In addition, in hair dyes using direct dyes, it is necessary to use an alkali such as ammonia in order to increase the penetration of the dye into the hair. There is a problem that occurs. Furthermore, as in the case of using an oxidative dye, there is a problem that the glossiness, moisture and touch of the hair after dyeing become unnatural.

  On the other hand, hair dyes using leucoin digo are known (Patent Documents 1 and 2). This hair dye utilizes the property of coloring when leucoin digo is oxidized by air. In this case, the hair after dyeing was dyed light blue, and the hair dyeing concentration was not high. In addition, since leuco indigo is obtained directly from natural indigo “sukumo”, “precipitated indigo”, and “indigo indigo leaves”, a hair dye of a certain quality is not always obtained.

  On the other hand, hair dyes using silver salts are also known (Patent Documents 1 to 6). This hair dye uses the silver salt photosensitivity, and after applying the silver salt to the hair, the hair is dyed by reducing the silver salt with natural light or artificial light to cause color development. There is a problem that the color density is low. Moreover, the hair dye which uses a silver salt and a reducing agent is also known (patent documents 7-10). Although this hair dye develops color rapidly, there are problems such as low color density and low reproducibility of the hair density. Furthermore, when alkali such as ammonia is used to increase the penetration of silver ions into hair, there is a problem that unpleasant odor during hair dyeing or hair damage due to hair dyeing treatment occurs, and hair after hair dyeing There was also a problem that the glossiness, moisture, and feel of the skin became unnatural.

Japanese Patent No. 3542107 JP 2004-2475 A JP 2005-60354 A JP 2005-53889 A JP 2004-99502 A JP 2002-348221 A German patent DE 2714753 International Publication WO2006 / 011228 Pamphlet Japanese Examined Patent Publication No. 7-11016 JP-A-4-187625 JP-A 46-5006 German patent DE 2806603 specification

  The subject of this invention is providing the hair dye which solved said problem. More specifically, it provides a hair dye that is excellent in hair dyeability and hair color reproducibility, has high fastness to a hair dyeing state against shampoo, rinse, or light, and has little damage to hair. It is to be.

  As a result of intensive studies to solve the above problems, the present inventors have combined the leuco body of an indigo compound and / or a salt thereof with a water-soluble silver salt, so that the hair dyeing property is excellent, It has been found that it is possible to provide a hair dye having high fastness and little damage to hair. That is, by combining a hair dye component containing a leuco body of an indigo compound and / or a salt thereof and a hair dye component containing a water soluble silver salt, the water soluble silver salt becomes a leuco body of an indigo compound and / or its As the salt oxidizing agent, the leuco form of the indigo compound and / or its salt function as a reducing agent for the water-soluble silver salt, and by mixing the two, an indigo compound and metallic silver are produced, respectively, and the color developability. Has found that high hair dyeing is achieved. In this case, the hair dyeing speed is higher and the hair dyeing speed is higher than when the hair dye containing the leuco body of the indigo compound and / or its salt is used alone, or when the hair dye containing the water-soluble silver salt is used alone. A concentration is obtained.

（式中、ＸはＮＨまたはイオウ原子を表し、二つのＸは互いに同一でも異なっていてもよい。Ｒは置換基を表し、ｍは０〜４の整数を表す。ｍが２以上の整数の場合、複数のＲは同一でも異なっていてもよい。）
［３］前記一般式（Ｉ）におけるＲが、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アミノ基、及びスルホ基からなる群から選ばれる少なくとも１つの置換基を表す、［２］項に記載の染毛剤。 The problems of the present invention have been solved by the following means.
[1] A hair dye comprising a hair dye component A containing at least one leuco body of an indigo compound and / or a salt thereof, and a hair dye component B containing at least one water-soluble silver salt.
[2] The hair dye according to item [1], wherein the leuco body of the indigo compound of the hair dye component A is a compound represented by the following general formula (I) and / or a salt thereof.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)
[3] In the item [2], R in the general formula (I) represents at least one substituent selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a sulfo group. The described hair dye.

[4] The water-soluble silver salt of the hair dye component B is at least one silver salt selected from the group consisting of silver carboxylate, silver sulfonate, silver ammine complex, silver nitrate, and silver sulfate. ] The hair dye of any one of [3].
[5] The water-soluble silver salt of the hair dye component B is selected from the group consisting of a carboxylic acid silver salt represented by the following general formula (II) and a sulfonic acid silver salt represented by the following general formula (III). The hair dye according to any one of [1] to [4], which is at least one selected silver salt.
Formula (II)
R ^1- (COOAg) _n1
(Wherein, ^{R 1} represents a _{n 1} monovalent organic group, _{n 1} is an integer of 1-3.)
Formula (III)
R ² — (SO ₃ Ag) _n2
(Wherein, ^{R 2} represents a _{n 2} divalent organic group, _{n 2} is an integer of 1-3.)
[6] The water-soluble silver salt of the hair dye component B is at least one silver salt selected from the group consisting of silver acetate, silver lactate, and silver methanesulfonate, [1] to [5] The hair dye of any one of Claims.

[7] The content of the water-soluble silver salt in the hair dye component B is 0.01% by mass to 10% by mass with respect to the total mass of the hair dye component B, as the mass of silver. ] The hair dye of any one of [6].
[8] The content of the leuco and / or salt of the indigo compound in the hair dye component A is 0.1% by mass to 10% by mass with respect to the total mass of the hair dye component A. [ The hair dye according to any one of 1] to [7].
[9] The hair dye according to any one of [1] to [8], wherein the hair dye component A and / or the hair dye component B has a pH of 7 or less.
[10] A hair dyeing method comprising a step of applying the hair dye according to any one of [1] to [9] to hair.
[11] The hair dyeing method according to item [10], including a step of applying the hair dye component B to the hair after the hair dye component A is applied to the hair.

（式中、ＸはＮＨまたはイオウ原子を表し、二つのＸは互いに同一でも異なっていてもよい。Ｒは置換基を表し、ｍは０〜４の整数を表す。ｍが２以上の整数の場合、複数のＲは同一でも異なっていてもよい。）
［１３］インジゴ化合物のロイコ体および／またはその塩を少なくとも１種含有する染毛剤成分Ａと、水溶性銀塩の少なくとも１種を含有する染毛剤成分Ｂとのキットからなる染毛剤。 [12] The compound represented by the following general formula (IV) is treated with a reducing agent to obtain the compound represented by the general formula (I) of the hair dye component A, of [1] to [9] The manufacturing method of the hair dye of any one.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)
[13] A hair dye comprising a kit of a hair dye component A containing at least one leuco body of an indigo compound and / or a salt thereof, and a hair dye component B containing at least one water-soluble silver salt. .

  As a preferred embodiment of the hair dye, a hair dye comprising a combination of a hair dye component A containing at least one leuco body of an indigo compound and / or a salt thereof and a hair dye component B containing a water-soluble silver salt. As a more preferred embodiment, a hair dye in the form of a kit including a container filled with the hair dye component A and a container filled with the hair dye component B is provided. According to a further preferred embodiment, the content of the leuco body of an indigo compound and / or a salt thereof in the hair dye or hair dye component A, preferably a compound represented by the general formula (I) or a salt thereof, The hair dye that is 0.1% by mass to 10% by mass with respect to the total mass of the hair dye component A; the water-soluble silver salt content in the hair dye component B is the silver mass, A hair dye that is 0.01% by mass to 10% by mass with respect to the total mass of the hair dye component B; a hair dye in which the pH of the hair dye component A and / or the hair dye solution is 7 or less is provided. Is done.

  From still another aspect, according to the present invention, the hair dye component A containing the leuco body of the indigo compound and / or a salt thereof and the hair dye component B containing the water-soluble silver salt are combined. A hair dyeing method comprising the step of applying to hair (preferably human hair) is provided. According to a preferred embodiment of the present invention, the hair dye component A containing the leuco body of the indigo compound and / or a salt thereof and the hair dye component B containing the water-soluble silver salt are mixed at the time of use. A method comprising a step of applying to the hair; after applying the hair dye component A containing the leuco body of the indigo compound and / or a salt thereof to the hair, the hair dye component containing the water-soluble silver salt A method comprising the step of applying B; and a method comprising the step of applying the hair dye component A after applying the hair dye component B to hair.

  The hair dye of the present invention is excellent in hair dyeability and hair color reproducibility, has high fastness in the hair dyeing state against shampoo, rinse, light, etc., and has little damage to the hair. In addition, the hair dye of the present invention has a leuco body of an indigo compound and / or a hair dye containing a salt thereof alone or a hair dye containing a water-soluble silver salt alone. The hair dyeing speed is fast and a high hair dyeing concentration is obtained.

Hereinafter, the present invention will be described in detail.
The hair dye of the present invention comprises two kinds of hair dye component A containing at least one leuco body of indigo compound and / or a salt thereof, and hair dye component B containing at least one water-soluble silver salt. Consists of.

(Hair dye component A)
The hair dye component A in the present invention contains at least one leuco body and / or salt thereof of an indigo compound.
The “leuco body of an indigo compound and / or a salt thereof” used in the present invention means a compound that forms an indigo compound by being oxidized. In the present invention, the leuco form of the indigo compound and / or salt thereof may be any leuco form of the indigo compound and / or salt thereof as long as it can reduce the water-soluble silver salt.
The “leuco form of an indigo compound” in the present invention means a leucoin digo compound, a dihydroindigo compound, a leuco thioindigo compound, and a dihydrothioindigo compound. These are obtained by reducing indigo compounds. Examples of the reducing agent for the indigo compound include sodium hydrosulfite, glucose, hydrogen and the like.

  The leuco form of the indigo compound that can be used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt, or a potassium salt, or a salt such as ammonium.

  In the present invention, the compound represented by the following general formula (I) and / or a salt thereof can be preferably used as the leuco form of the indigo compound.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)

  In the general formula (I), examples of the substituent represented by R include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, and an arylsulfonyl group. Group, amino group, acyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, aminocarbonyloxy group, carbamoyl group, cyano group, nitro group, carboxyl group and sulfo group are preferred. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly preferably a fluorine atom or a chlorine atom. The alkyl group may be cyclic or chain-like, and may further have a substituent. The chain alkyl group may have a branch. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 to 4. Examples of this alkyl group include methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, cyclohexyl, 2-ethylhexyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxyethyl, carboxymethyl, 2- Carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, vinyl, allyl, 2-buten-1-yl, 3-methyl-2-buten-1-yl, propargyl, benzyl, phenethyl and furfuryl are preferred, methyl, ethyl Isopropyl is particularly preferred. The aryl group may have a substituent, and the number of carbon atoms is preferably 6 to 18, and most preferably 6 to 10. Examples of aryl groups include phenyl, naphthyl, 4-methylphenyl, 4-carboxyphenyl, 4-acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl 4-methanesulfonamidophenyl and 4-butanesulfonamidophenyl. Phenyl is preferred. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring, or may have a substituent. Examples of heterocyclic rings (including fused rings) include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, imidazole ring, pyrazole ring, thiazole ring, pyrrolidine ring, piperidine ring, morpholine ring, piperazine ring, Pyridine ring, quinoline ring, indole ring, carbazole ring, phenothiazine ring, phenoxazine ring, indoline ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring are included. The alkoxy group preferably has 1 to 12 carbon atoms, particularly preferably 1 to 4 carbon atoms. For example, methoxy group, ethoxy group, normal propyloxy group, isopropyloxy group, normal butyloxy group, tertiary butyloxy group, 3-pentyloxy group, normal hexyloxy group, normal octyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, normal decyloxy group, normal dodecyloxy group, cyclohexyloxy group, benzyloxy group, allyloxy group, methallyloxy group, prenyloxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group Group, 2-phenoxyethoxy group, 2- (2,5-di-tertiary amylphenoxy) ethoxy group, 2-benzoyloxyethoxy group, methoxycarbonylmethyloxy group, methoxycarbonylethyloxy group, butoxyca Isobornyl ethyl group, 2-isopropyloxyethyl group are preferable. Methoxy and ethoxy are particularly preferable. The aryloxy group may further have a substituent or may be unsubstituted. As the substituent, for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, or a cyano group is preferable. An aryloxy group having 6 to 20 carbon atoms in total is preferred. For example, phenoxy, 4-methylphenoxy, 2-methylphenoxy and 2-chlorophenoxy are preferable. Phenoxy is particularly preferred. As the alkylthio group, an alkylthio group having 1 to 12 carbon atoms is preferable, and an alkylthio group having 1 to 4 carbon atoms is particularly preferable. Methylthio, ethylthio, normal butylthio, normal hexylthio, 2-ethylhexylthio and cyclohexylthio are preferred, and methylthio and ethylthio are particularly preferred. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms, preferably phenylthio, 2-methylthio, 4-methylthio, 2-chlorothio, 4-chlorothio, 4-acetamidothio, 4-methoxythio, phenylthio, 4-methylthio, 4-chlorothio is particularly preferred. The alkylsulfonyl group preferably has 1 to 10 carbon atoms. Examples of alkylsulfonyl groups are mesyl and ethanesulfonyl. The arylsulfonyl group preferably has 6 to 10 carbon atoms. Examples of arylsulfonyl groups are tosyl and benzenesulfonyl. The amino group may be an amino group having a substituent, a monoalkylamino group, a dialkylamino group, an alkylarylamino group, a monoarylamino group, a diarylamino group, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group. A sulfonylamino group. Examples of preferred amino groups are unsubstituted amino group, dimethylamino, diethylamino, N-methyl-N-phenylamino, diphenylamino group, acetamide, methoxycarbonylamino, ethoxycarbonylamino, carbamoylamino, pyrrolidinocarbonylamino, methanesulfone Amides and toluenesulfonamides are preferred. The acyl group preferably has 2 to 10 carbon atoms. Examples of acyl groups are preferably acetyl, propionyl and benzoyl. The alkoxycarbonyl group may have a substituent or may be unsubstituted. As the substituent, for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, or a cyano group is preferable. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and particularly preferably an alkoxycarbonyl group having 2 to 4 carbon atoms. Methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl are preferred. The alkoxycarbonyloxy group may have a substituent or may be unsubstituted. As the substituent, for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, or a cyano group is preferable. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 12 carbon atoms, and particularly preferably an alkoxycarbonyloxy group having 2 to 4 carbon atoms. Methoxycarbonyloxy, ethoxycarbonyloxy and butoxycarbonyloxy are preferred. The aminocarbonyloxy group may have a substituent or may be unsubstituted. As the substituent, for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, or a cyano group is preferable. The aminocarbonyloxy group is preferably an aminocarbonyloxy group having 2 to 12 carbon atoms, and particularly preferably an aminocarbonyloxy group having 2 to 4 carbon atoms. Methylaminocarbonyloxy, ethylaminocarbonyloxy and dimethylaminocarbonyloxy are preferred. The carbamoyl group is preferably a carbamoyl group having 1 to 12 carbon atoms, and unsubstituted carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-butylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, pyrrolidin And carbonyl and hexamethyleneiminocarbonyl are preferred. Carboxyl and sulfo may be free acids or may form salts with cations. As a cation in this case, a lithium cation, a sodium cation, a potassium cation, an ammonium cation, and a triethylammonium cation are preferable.

  In the general formula (I), the substitution position of R is preferably at least one of 3, 3 ', 4, 4'.

  In the general formula (I), m represents an integer of 0 to 4, preferably 0 to 2, and particularly preferably 0 to 1.

  Although the specific example of the leuco body of the indigo compound contained in the hair dye component A is shown below, this invention is not limited to these. Among the following specific examples, exemplary compounds L-1 to L-10 are leucoin digo compounds, and exemplary compounds L-11 to L-18 are leuco thioindigo compounds. In the present specification, Me represents a methyl group, and Et represents an ethyl group.

  In addition, the compound represented by the said general formula (I) may exist as a keto-enol tautomer.

  For the hair dye component A, the above exemplified compounds and / or salts thereof are preferably used, and leucoin digo (exemplary compound L-1) and leucothioindigo (exemplary compound L-11) are particularly preferably used.

  The compound represented by the general formula (I) can be obtained by treating a compound represented by the following general formula (IV) with a reducing agent. Any reducing agent can be used.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)

  X, R and m in the general formula (IV) have the same meanings as X, R and m in the general formula (I), and preferred ranges thereof are also the same.

  The compound represented by the general formula (IV) is a method described in Synthetic Communications, 2001, 31 (23), 3721, Journal of Chemical Education, 1991, 68 (10), A242, etc. Can be obtained.

  The content of the leuco body of the indigo compound and / or salt thereof in the hair dye component A is not particularly limited, but when preparing the hair dye component A in the form of a solution containing the leuco body of the indigo compound and / or salt thereof. Is preferably contained in an amount of about 0.05% by mass to 20% by mass, and particularly preferably 0.1% by mass to 10% by mass, based on the total mass of the hair dye component A. In the hair dye of this invention, the color tone after dyeing can be changed by changing the density | concentration of the leuco body of the indigo compound of the hair dye component A, and / or its salt.

The hair dye component A may contain a reducing agent other than the leuco body of the indigo compound and / or a salt thereof. For example, reductones (specifically ascorbic acid, sodium ascorbate), paraphenylenediamines (specifically paraphenylenediamine, 2,5-diaminotoluene, 4,4′-diaminodiphenylamine, 2-chloro-para) Phenylenediamine, N-phenylparaphenylenediamine and salts thereof), orthophenylenediamines (specifically orthophenylenediamine and salts thereof), paraaminophenols (specifically paraaminophenol and salts thereof), Orthoaminophenols (specifically orthoaminophenol, 2,4-diaminophenol and their salts), hydroquinones (specifically hydroquinone, 2-sulfohydroquinone and their salts), catechols (specifically In the category Cole, pyrogallol, gallic acid, methyl gallate, 1,2,4-benzenetriol, and salts thereof), reducing sugars (such as glucose), sodium hydrosulfite, sodium sulfite, and sodium bisulfite. Two or more reducing agents other than the leuco form of the indigo compound and / or a salt thereof may be used in combination. Of these, ascorbic acid, paraphenylenediamine, 2,5-diaminotoluene, paraaminophenol, orthoaminophenol, 4,4′-diaminodiphenylamine, and sodium hydrosulfite are preferable.
The other components that can be contained in the hair dye component A will be described later.

(Hair dye component B)
The hair dye component B in the present invention contains at least one water-soluble silver salt.
The kind of water-soluble silver salt is not particularly limited, and any water-soluble silver salt may be used as long as it has sufficient solubility in water. Since silver halides such as silver chloride and silver bromide are not substantially water-soluble, it is not desirable to use them as components of the hair dye component B in the present invention. Moreover, since these contain halogen ions, they may affect the environment and are not preferable.

  The hair dye component B in the present invention is preferably at least one silver salt selected from the group consisting of silver carboxylate, silver sulfonate, silver ammine complex, silver nitrate, and silver sulfate, but is not limited thereto. It will never be done. Among these, silver carboxylate, silver sulfonate, silver nitrate, or silver sulfate is more preferable, and silver carboxylate represented by the following general formula (II) or silver sulfonate represented by the following general formula (III) Particularly preferred.

Formula (II)
R ^1- (COOAg) _n1
(Wherein, ^{R 1} represents a _{n 1} monovalent organic group, _{n 1} is an integer of 1 to 3)

Formula (III)
R ² — (SO ₃ Ag) _n2
(Wherein, ^{R 2} represents a _{n 2} divalent organic group, _{n 2} is an integer of 1 to 3)

In the general formula (II), n ₁ monovalent organic group represented by R ^1, total carbon number is 1-20 organic group are preferred, more preferably a total carbon number of 1 to 6 An organic group is preferable, and an organic group having 2 to 4 total carbon atoms can be used particularly preferably. n ₁ is preferably ₁ to 3, and n ₁ is particularly preferably 1 or 2. N ₁ monovalent organic group represented by R ¹ may be either an aliphatic organic group or an aromatic organic group, it can be preferably used aliphatic organic radical.
N ₁ monovalent organic group represented by R ¹ may have one or more substituents. Examples of the substituent include a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an amino group, an amide group, a carbamoyl group, and a carbamoyl group. An amino group, an alkoxycarbonylamino group, a carbamoyloxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonamide group, a sulfamoyl group, or a sulfo group can be mentioned, and particularly preferred substituents are Examples include a hydroxyl group, an alkoxy group, an alkyl group, a carboxy group, an amino group, an amide group, a carbamoyl group, an alkylsulfanyl group, an alkylsulfonyl group, and a sulfo group.

Examples of the aliphatic carboxylic acid constituting the silver carboxylate represented by the general formula (II) include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, trifluoroacetic acid, behenic acid, lactic acid, glycolic acid, and levulin. Acid, fumaric acid, maleic acid, succinic acid, glycine, α-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, tyrosine, aspartic acid, glutamic acid, arginine, lysine, histidine, tryptophan, Examples include cysteine, cystine, methionine, tartaric acid, malic acid, citric acid, mandelic acid, and nicotinic acid. Among these, acetic acid, propionic acid, or lactic acid is particularly preferable.
Examples of the aromatic carboxylic acid constituting the silver carboxylate represented by the general formula (II) include benzoic acid, salicylic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, anthranilic acid, 4-amino- 2-hydroxybenzoic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2,6-naphthalenedicarboxylic acid, or orthosulfobenzoic acid is preferred.

In the general formula (III), _{n 2} divalent organic group represented by ^{R 2,} the total number of carbon atoms of preferably 1-20 organic group, more preferably a total carbon number of 1 to 7 amino organic Group is preferable, and an organic group having 1 to 4 carbon atoms is particularly preferable. n ₂ is preferably 1 to 3, and n is particularly preferably 1 or 2. N ₂ divalent organic group represented by R ² may be either an aliphatic organic group or an aromatic organic group, it can be preferably used aliphatic organic radical.
N ₂ divalent organic groups represented by R ² may have one or more substituents. Examples of the substituent include a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an amino group, an amide group, a carbamoyl group, and a carbamoyl group. An amino group, an alkoxycarbonylamino group, a carbamoyloxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonamide group, a sulfamoyl group, or a sulfo group can be mentioned, and particularly preferred substituents are Examples include a hydroxyl group, an alkoxy group, an alkyl group, a carboxy group, an amino group, an amide group, a carbamoyl group, an alkylsulfanyl group, an alkylsulfonyl group, and a sulfo group.

Examples of the aliphatic sulfonic acid constituting the silver sulfonate represented by the general formula (III) include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, hexanesulfonic acid, taurine, and hydroxyethanesulfonic acid. , Trifluoromethanesulfonic acid or 1,4-butanedisulfonic acid is preferred, and methanesulfonic acid, ethanesulfonic acid or taurine is particularly preferred.
Examples of the aromatic sulfonic acid constituting the silver sulfonate represented by the general formula (III) include, for example, benzenesulfonic acid, 4-toluenesulfonic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and alternic acid. , Metanilic acid, sulfanilic acid, orthosulfobenzoic acid, 1,5-naphthalenedisulfonic acid and the like are preferable.

The water-soluble silver salt in hair dye component B is more preferably at least one silver salt selected from the group consisting of silver acetate, silver lactate, and silver methanesulfonate. Two or more water-soluble silver salts may be used in combination.
Components that can be contained in the hair dye component B in addition to the water-soluble silver salt will be described later.

  The water-soluble silver salt in the hair dye component B is preferably a silver salt having a solubility in water as silver of 0.03% by mass or more, particularly preferably 0.3% by mass or more. The content of the water-soluble silver salt in the hair dye component B is not particularly limited, but is preferably 0.01% by mass to 20% by mass with respect to the total mass of the hair dye component B as the mass of silver. It is particularly preferable that the content is 0.01 mass% to 10 mass%. In the hair dye of the present invention, the color tone of the hair after hair dyeing can be changed by changing the concentration of the water-soluble silver salt of the hair dye component B.

(Optional component)
In addition to the leuco body of the indigo compound in the hair dye component A and / or its salt, and the water-soluble silver salt in the hair dye component B, the hair dye of the present invention includes a surfactant, an oil component, alcohol, Arbitrary components, such as a high molecular compound, a thickener, dye, a fragrance | flavor, and an ultraviolet absorber, can be contained. These optional components may be contained in the hair dye component A and / or B, or may be contained in the hair dye of the present invention as another component other than the hair dye components A and B.

  A surfactant can be blended in the hair dye of the present invention. Specific examples of the surfactant include, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. These surfactants are used in combination of two or more. May be.

Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate, alkylbenzene sulfonates such as dodecylbenzene sulfonic acid, alkyl naphthalenes sulfonates, and alkyl sulfonates such as sodium tetradecene sulfonate.
Cationic surfactants include cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl trimethyl ammonium bromide, dibromide dichloride. And quaternary ammonium salts such as stearyldimethylammonium and cetylpyridinium bromide.
Nonionic surfactants include polyethylene oxides, polyethylene oxide monoalkyl ethers, polyethylene oxide diethers, polyethylene oxide monoalkenyl ethers, polyethylene oxide monophenyl ethers, polypropylene oxides, polypropylene oxide monoalkyl ethers. , Polypropylene oxide dialkyl ethers, polyethylene oxide fatty acid esters, glycerin fatty acid esters, glycerin monoethers (monostearyl glyceryl ether, monocetyl glyceryl ether, monooleyl glyceryl ether, isostearyl glyceryl ether, etc.), sorbitan fatty acid esters Can be mentioned. Among these, polyethylene oxides, polyethylene oxide monoalkyl ethers, polyethylene oxide diethers, polyethylene oxide monoalkenyl ethers, polyethylene oxide monophenyl ethers, polypropylene oxides, polypropylene oxide monoalkyl ethers, polypropylene oxide dialkyl ethers Polyethylene oxides, polyethylene oxide monoalkyl ethers, polyethylene oxide diethers, polyethylene oxide monoalkenyl ethers, polypropylene oxides, and polypropylene oxide monoalkyl ethers are particularly preferred.
Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, cetyldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine.

  These surfactants may be used alone or in combination of two or more. The content of the surfactant in the hair dye of the present invention is preferably 0.5 to 55% by mass, more preferably 2 to 50% by mass with respect to the total mass when the hair dye is used.

  An oil component can also be mix | blended with the hair dye of this invention (preferably hair dye of a liquid form). The type of the oil component is not limited as long as it can be dissolved or dispersed in the hair dye without reducing the performance of the hair dye. By blending the oil component, it is possible to suppress damage to hair after hair dyeing and to give glossiness and moisture. Examples of the oil component include silicones, hydrocarbons, oils and fats, waxes, and higher fatty acids.

Examples of silicone derivatives include dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, highly polymerized silicone, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, and mercapto-modified. Examples thereof include silicone, carboxy-modified silicone, fluorine-modified silicone, and polyglycerin-modified silicone (for example, those described in JP-A Nos. 10-316540 and 2006-69893).
Examples of the hydrocarbon include squalanes, α-olefin oligomers, paraffins, isoparaffins, petrolatum, and the like.
Examples of the fat include olive oil, camellia oil, tea seed oil, safflower oil, sunflower oil, soybean oil, cotton seed oil, sesame oil, cocoa butter, corn oil, peanut oil, and rapeseed oil.
Examples of waxes include beeswax, carnauba wax, jojoba oil, or lanolin.
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, stearic acid, hydroxystearic acid, and linoleic acid.

  These oil components may be used alone or in combination of two or more. Although content of the oil-based component in the hair dye of this invention is not specifically limited, Preferably it is 0.005-10 mass% with respect to the total mass at the time of use of a hair dye, More preferably, it is 0.01-5 mass%. More preferably, it is 0.05-2 mass%.

Alcohol can be added to the hair dye of the present invention (preferably in a liquid form). The type of alcohol is not particularly limited as long as it can be dissolved or dispersed in the hair dye without reducing the performance of the hair dye. Specific examples include cetanol, oleyl alcohol, stearyl alcohol, hexadecanol and the like.
These alcohols may be used alone or in combination of two or more. Although content of alcohol in the hair dye of this invention is not specifically limited, Preferably it is 0.005-10 mass% with respect to the total mass at the time of use of a hair dye, More preferably, 0.01-5 mass%, More preferably, it is 0.05-2 mass%.

  A polymer compound can be added to the hair dye of the present invention. The kind of the polymer compound is not particularly limited as long as it can be dissolved or dispersed in the hair dye without reducing the performance of the hair dye. Examples of the polymer compound include a cationic polymer compound, an amphoteric polymer compound, an anionic polymer compound, and a nonionic polymer compound.

Examples of the cationic polymer compound include cationized cellulose (for example, O- [2-hydroxy-3- (trimethylammonio) propyl] chloroethyl chloride, O- [2-hydroxy-3- (lauryldimethylammonio chloride). ) Propyl) hydroxyethylcellulose), cationic starch, cationized guar gum derivatives (for example, derivatives described in JP-B-58-35640, JP-B-60-46158, JP-A-58-53996), polydimethyl Examples include diallylammonium salts.
Examples of the anionic polymer compound include copolymer polymers of acrylic acid or methacrylic acid and other vinyl monomers, or carboxymethyl cellulose.
Nonionic polymer compounds include, for example, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, guar gum, hydroxypropyl xanthan gum, agar, starch, polyacrylic acid ester, polymethacrylic acid ester. Acid esters, polyacrylamides, polymethacrylamides, polyethylene glycols, or polypropylene glycols.
Other useful polymer compounds include, for example, gum arabic, carrageenan, galactan, quince seed gum, locust bean gum, tragacanth gum, pectin, mannan, xanthan gum, dextran, curdlan, gellan gum, succinoglucan, gelatin, tamarind gum, Examples include natural polymer compounds such as casein.

  These polymer compounds may be used alone or in combination of two or more. Although content of the high molecular compound in the hair dye of this invention is not specifically limited, Preferably it is 0.01 mass%-10 mass% with respect to the total mass at the time of use of a hair dye, More preferably, it is 0.1 mass. % To 5% by mass.

  A thickener can be mix | blended with the hair dye of this invention. Examples of the thickener include sodium alginate, carrageenan, gum arabic, cross-linked acrylic acid polymer, cellulose derivative, xanthan gum, or bentonite. These thickeners may be used alone or in combination of two or more. Although content of the thickener in the hair dye of this invention is not specifically limited, Preferably it is 0.1 mass%-5 mass% with respect to the total mass at the time of use of a hair dye, More preferably, it is 0.2 mass. % To 3% by mass.

A known direct dye can be added to the hair dye of the present invention for the purpose of adjusting the color tone. Known direct dyes include, for example, black 401, blue 1, blue 2, blue 201, blue 202, blue 203, blue 204, blue 205, blue 403, blue 404, purple 201 No., purple 401, red 102, red 106, red 201, red 202, red 203, red 204, red 205, red 206, red 207, red 208, red 213, Red 214, Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Orange 201, Orange 203, Orange 205 No., orange 206, orange 207, orange 401, orange 402, orange 403, yellow 201, yellow 203, yellow 204, yellow 205, yellow 206, Color No. 207, Yellow No. 401, Yellow 402 No., or yellow No. 403, etc. known direct dye such as nitro dye or disperse dyes.
In addition, to the hair dye component A in the hair dye of the present invention, an auto-oxidizing dye typified by indoles and indolines can also be added.

  In addition to the substances described above, other substances can be added to the hair dye of the present invention. The other substances are not particularly limited as long as they can be dissolved or dispersed in the hair dye without deteriorating the performance of the hair dye. Examples of other substances include collagen, keratin, elastin, fibroin, conchiolin, sodium pyrrolidone carboxylate, sodium lactate, sorbitol, hyaluronic acid, benzyl alcohol, phenethyl alcohol, benzyloxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, Examples thereof include ethylene carbonate, propylene carbonate, paraben, and an ultraviolet absorber.

  The pH of the hair dye of the present invention and the hair dye components A and B in the hair dye of the present invention can be adjusted appropriately. From the viewpoint of hair dyeing properties, the pH of the liquid composition after mixing the hair dye components A and B is preferably in the range of 2 to 11, and particularly preferably in the range of 2 to 8. From the viewpoint of suppressing hair damage, the pH of the liquid composition is preferably 8 or less, more preferably 7 or less, and particularly preferably in the range of 5 to 7. The pH of the hair dye of the present invention and the hair dye component A in the hair dye of the present invention is preferably 6 to 9, and particularly preferably 6 to 8, from the viewpoint of storage stability. 3-7 are preferable and, as for pH of the hair dye component B in the hair dye of this invention, the range of 5-7 is more preferable. The pH of the hair dye may be unadjusted, but it is also preferably adjusted using an appropriate pH adjuster.

  An appropriate acid can be used as a pH adjuster used for adjusting the pH. More specifically, acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, pyrrolidone carboxylic acid, levulinic acid, fumaric acid, succinic acid, butyric acid, valeric acid, oxalic acid, maleic acid, mandelic acid, aspartic acid , Organic acids such as adipic acid and nicotinic acid, and inorganic acids such as phosphoric acid, sulfuric acid and nitric acid. Of these, organic acids such as acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, fumaric acid, succinic acid, butyric acid, valeric acid, maleic acid, mandelic acid, aspartic acid, or adipic acid may be used. preferable. These acid salts (sodium salt, potassium salt, ammonium salt, etc.) may be used as a pH regulator. From the viewpoint of stability of the hair dye component A and suppression of hair damage, it is preferable to use an organic acid as a pH adjuster.

  Moreover, you may use an appropriate base as a pH regulator. More specifically, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and organic bases such as ammonia, ethanolamine, diethanolamine and guanidine. A salt of these bases (hydrochloride, sulfate, etc.) may be used as a pH regulator.

  Although content of a pH adjuster is not specifically limited, For example, 0.01 mass%-20 mass% are preferable with respect to the total mass at the time of use of a hair dye, Furthermore, 0.1 mass%-10 mass% are preferable, 0.5 mass%-5 mass% are especially preferable.

  A stabilizer may be added to the hair dye component B of the present invention in order to impart stability of the silver salt. Examples of the stabilizer include sulfur. Although the addition amount of sulfur is not specifically limited, For example, 0.01 mass%-1 mass% with respect to the total mass of the hair dye component B are preferable.

  Arbitrary fragrance | flavor can also be added to the hair dye of this invention as needed.

  The hair dye of the present invention can be used for hair coloring of human or animal hair, such as hair or body hair, animal hair, etc., preferably human hair coloring or pets such as dogs or cats It can be used for hair dyeing of human hair, particularly preferably for human hair dyeing.

(Form of hair dye)
The hair dye of the present invention can be provided, for example, in a form containing the respective components of the hair dye components A and B separately, for example, each component as a dry solid in a separate packaging form. Or it can also provide as a form containing the component of hair dye component A and B simultaneously, for example, a dry state mixture.
Thus, when providing the hair dye of the present invention as a solid in a dry state, for example, water or water, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, Hair dye components A and B, or mixtures thereof are dissolved or suspended in use in isoprene glycol, hexylene glycol, ethyl carbitol, glycerin, diglycerin, polyethylene glycol, polypropylene glycol, etc. and used as a hair dye. be able to.

  Moreover, the hair dye of this invention can be provided with a liquid form. In the present specification, the “liquid form” means a state other than solid or gas, and examples include a solution form, a suspension form, an emulsion, a cream form, a foam form, a gel form, or a paste form. Can do. The type of solvent for providing the hair dye in liquid form is not particularly limited. For example, water, methanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, isoprene glycol, Hexylene glycol, ethyl carbitol, glycerin, diglycerin, polyethylene glycol, polypropylene glycol and the like can be used. These solvents may be used alone or in combination of two or more. It is preferable to use water alone or a mixture of water and the above organic solvent. Among these forms, a solution form is preferable, and it is particularly preferable to provide hair dye component A and hair dye component B as separate solution forms in different containers. However, the hair dye of the present invention can be prepared in any form suitable for hair dyeing, for example, hair dye components A and B, or a mixture thereof together with a propellant under pressure in an aerosol container. It can also be provided in an encapsulated form.

  The hair dye of the present invention may be a composition comprising the hair dye component A and the hair dye component B, or may comprise a kit of the hair dye component A and the hair dye component B.

(Hair dyeing method)
Hair can be dyed by applying the hair dye of the present invention to hair.
When performing hair dyeing using the hair dye kit of the present invention, the hair dye component A and the hair dye component B are used in combination. When the hair dye component A and the hair dye component B are used in combination, the application order of the hair dye components A and B is not particularly limited, and can be applied in any order. For example, when performing hair dyeing using the liquid hair dye component A and the hair dye component B, the hair dye component B may be applied to the hair after the hair dye component A is applied to the hair, or The hair dye component A may be applied to the hair after the hair dye component B is applied to the hair. Alternatively, a mixture obtained by mixing the dye set A and the hair dye component B immediately before use may be applied to the hair. Among these, the method of applying the hair dye component A after applying the hair dye component B is particularly preferable.

  After applying the hair dye component B to the hair, the hair dye component A may be applied to the hair after standing for a while and then left for a while. Although the leaving time is not particularly limited, for example, 0 to 30 minutes is preferable, and 5 to 20 minutes is particularly preferable. Similarly, after applying the hair dye component A to the hair, the hair dye component B may be applied to the hair for a while and then left for a while. Although the leaving time is not particularly limited, for example, 0 to 30 minutes is preferable, and 5 to 20 minutes is particularly preferable.

The hair dyeing treatment with the hair dye of the present invention can be performed at a temperature of about 0 ° C. to 40 ° C., for example.
Although the usage-amount of the hair dye component A and the hair dye component B in the hair dye of this invention is not specifically limited, The range of 3/1-1/3 is preferable as both volume ratio. The application method of hair dye component A and / or hair dye component B, or a mixture thereof is not particularly limited, and any method such as applying the liquid to hair or immersing the hair in the liquid is used. Can be adopted. In the hair dyeing method using the hair dye of the present invention, the hair can be treated with shampoo and / or rinse after dyeing. Then, it is preferable to dry as needed.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited by the following examples.

Example 1
(Samples 101 and 102)
0.66 g of Indigo was weighed and about 2 g of deaerated ion exchange water was added and lightly mixed. 7.5 mL of 1N sodium hydroxide aqueous solution and about 10 g of degassed ion exchange water were added to this, and 1.3 g of hydrosulfite sodium was further added and mixed. Furthermore, deaerated ion exchange water was added to make 25.0 g in total. A stir bar was added and the mixture was stirred at 50 ° C. for 30 minutes to obtain a leucoin digo solution (hair dye component A-1 is a sodium salt of leuco digo compound L-1) (hair dye component A). -1 2.6% by mass as leucoin digo based on the total amount).
Weigh out 0.256 g of silver lactate 0.5 hydrate, add ion-exchanged water to make 25.0 g, stir and dissolve to obtain hair dye component B-1 (total amount of hair dye component B-1 0.54% by mass as silver).

  After the hair dye component B-1 was applied to white goat hair, it was left at 30 ° C. for 20 minutes. The hair dye component A-1 was further applied to the goat hair, then left at 30 ° C. for 20 minutes, washed with running water at 40 ° C., and dried using a dryer. The above operation was performed twice. These were designated as samples 101 and 102, respectively.

  0.66 g of Indigo was weighed and about 2 g of deaerated ion exchange water was added and lightly mixed. 7.5 mL of 1N sodium hydroxide aqueous solution and about 10 g of degassed ion-exchanged water were added to this, and 1.4 g of glucose was further added and mixed. Furthermore, deaerated ion exchange water was added to make 25.0 g in total. A stir bar was added and the mixture was stirred at 50 ° C. for 30 minutes to obtain a leucoin digo solution (hair dye component A-2) (containing 2.6% by mass as leucoin digo based on the total amount of hair dye component A-2) ).

(Samples 103 and 104)
Moreover, after apply | coating the said hair dye component B-1 to white goat hair, it was left to stand at 30 degreeC for 20 minutes. The hair dye component A-2 was further applied to the goat hair, then left at 30 ° C. for 20 minutes, washed with running water at 40 ° C., and dried using a drier. The above operation was performed twice. These were designated as samples 103 and 104, respectively.

(Samples 105 and 106)
Moreover, after apply | coating the said hair dye component A-1 to white goat hair, it was left to stand at 30 degreeC for 20 minutes. The goat hair was washed with running water at 40 ° C. and dried using a dryer. The above operation was performed twice. These were designated as Samples 105 and 106, respectively.

(Evaluation)
About the goat hair (samples 101-106) after hair dyeing, the hair dye density | concentration (L ^* ) was measured using the color difference meter (CR-400, brand name, Konica Minolta Sensing Co., Ltd. product). Moreover, about each sample, the color taste was evaluated visually and the damage of the goat hair after hair dyeing was evaluated by touch.
The damage of goat hair was judged according to the following criteria.
○: The same touch as before dyeing.
(Triangle | delta): The touch is bad compared with before hair dyeing.
X: The touch is much worse than before hair dyeing.
The results are shown in Table 1.

  As is apparent from the results in Table 1, according to the hair dye of the present invention, a high hair dye density is obtained, the hair dye reproducibility is excellent, and it is possible to dye natural hair, It was found that there was little damage.

Example 2
(Samples 201-205)
Hair dye components A-3 to A-7 containing leucoin digo at concentrations shown in Table 2 below were prepared. The preparation procedure is the same as in Example 1. The pH of the obtained hair dye components A-3 to A-7 was about 7 as a result of measurement with a pH test paper.
Hair dye component B-1 was prepared in the same procedure as in Example 1. The pH of the obtained hair dye component B-1 was about 7 as measured with a pH test paper.

  After immersing five white goat hairs in the hair dye components A-3 to A-7 obtained above, they were left at 30 ° C. for 20 minutes. These goat hairs were further immersed in the hair dye component B-1 obtained in Example 1, respectively, left at 30 ° C. for 20 minutes, washed with running water at 40 ° C., and dried using a dryer. Each was designated as Samples 201-205.

(Samples 206-210)
Moreover, after immersing five white goat hairs in the hair dye components A-3 to A-7 obtained above, they were left at 30 ° C. for 20 minutes. The goat hair was washed with running water at 40 ° C. and dried using a dryer. Each was designated as Samples 206-210.

(Evaluation)
The goat hair after hair dyeing (samples 201 to 210) was evaluated in the same manner as in Example 1. The results are shown in Table 3.

  As is apparent from the results in Table 3, the hair dye of the present invention can change the hue after dyeing by changing the concentration of leucoin digo in the hair dye component A, and is natural. You can dye the hair. Furthermore, it turns out that there is little damage of hair.

Example 3
(Samples 301 and 302)
0.74 g of thioindigo was weighed, and about 2 g of deaerated ion exchange water was added and lightly mixed. 7.5 mL of 1N sodium hydroxide aqueous solution and about 10 g of degassed ion exchange water were added to this, and 1.3 g of hydrosulfite sodium was further added and mixed. Furthermore, deaerated ion exchange water was added to make 25.0 g in total. A stir bar was added, and the mixture was stirred at 50 ° C. for 30 minutes to obtain a leuco thioindigo solution (hair dye component A-8) (3.0% by mass as leuco thioindigo with respect to the total amount of hair dye component A-8). Containing).
Weigh out 0.258 g of silver lactate 0.5 hydrate, add ion-exchanged water to make 25.0 g, stir and dissolve to obtain hair dye component B-3 (total amount of hair dye component B-3) 0.54% by mass as silver).

  After the hair dye component B-3 was applied to white goat hair, it was left at 30 ° C. for 20 minutes. The goat hair was further coated with the hair dye component A-8, left at 30 ° C. for 20 minutes, washed with running water at 40 ° C., and dried using a drier. The above operation was performed twice. These were designated as samples 301 and 302, respectively.

(Samples 303 and 304)
The hair dye component A-8 was applied to white goat hair, and then allowed to stand at 30 ° C. for 20 minutes. The goat hair was washed with running water at 40 ° C. and dried using a dryer. The above operation was performed twice. These were designated as samples 303 and 304, respectively.

(Evaluation)
The goat hair after dyeing (samples 301 to 304) was evaluated in the same manner as in Example 1. The results are shown in Table 4.

  As is apparent from the results in Table 4, according to the hair dye of the present invention, a high hair dye density is obtained, the hair dye reproducibility is excellent, and it is possible to dye natural hair. It was found that there was little damage.

Example 4
(Sample 401)
Dye goat hair by performing the same operation as Sample 101 of Example 1 except that 0.185 g of silver acetate was used as hair dye component B instead of 0.256 g of silver lactate 0.5 hydrate. The hair was evaluated by evaluation (containing 0.54% by mass as silver based on the total amount of the hair dye component B).

(Sample 402)
The same procedure as in Sample 101 of Example 1 was performed except that 0.225 g of silver methanesulfonate was used instead of 0.256 g of silver lactate 0.5 hydrate as the hair dye component B, and goat hair And was evaluated (containing 0.54% by mass as silver with respect to the total amount of the hair dye component B).

(Sample 403)
The same procedure as in Sample 101 of Example 1 was performed except that 0.310 g of silver paratoluenesulfonate was used in place of 0.256 g of silver lactate 0.5 hydrate as the hair dye component B, and the goat The hair was dyed and evaluated (containing 0.54% by mass as silver with respect to the total amount of the hair dye component B).

(Sample 404)
Dye goat hair by performing the same operation as Sample 101 of Example 1 except that 0.188 g of silver sulfate was used instead of 0.256 g of silver lactate 0.5 hydrate as hair dye component B. The hair was evaluated by evaluation (containing 0.54% by mass as silver based on the total amount of the hair dye component B).

(Sample 405)
Except for using 0.189 g of silver nitrate instead of 0.256 g of silver lactate 0.5 hydrate as the hair dye component B, the same operation as in sample 101 of Example 1 was performed to dye goat hair. And evaluated (containing 0.54% by mass as silver with respect to the total amount of the hair dye component B).

(Sample 406)
As hair dye component B, similar to Sample 101 of Example 1 except that 0.189 g of silver nitrate and 1.2 mL of 28% aqueous ammonia were used instead of 0.256 g of silver lactate 0.5 hydrate. The operation was performed, and evaluation was performed by dyeing goat hair (containing 0.54% by mass as silver based on the total amount of the hair dye component B). The pH of the hair dye component B was 10. Silver ammon complex was formed in the hair dye. There was an unpleasant odor when dyeing hair.

(Sample 407)
Dye goat hair by performing the same operation as Sample 101 of Example 1 except that 0.160 g of silver chloride was used instead of 0.256 g of silver lactate 0.5 hydrate as the hair dye component B. The hair was evaluated by evaluation (containing 0.54% by mass as silver based on the total amount of the hair dye component B). However, silver chloride was not completely dissolved at this time.

(Sample 408)
Except that 0.210 g of silver bromide was used as the hair dye component B instead of 0.256 g of silver lactate / 0.5 hydrate, the same operation as in sample 101 of Example 1 was performed, The hair was dyed and evaluated (containing 0.54% by mass as silver with respect to the total amount of the hair dye component B). However, silver bromide was not completely dissolved at this time.

(Sample 409)
Similar to the preparation of the hair dye component B-1 in Example 1, except that 0.188 g of silver nitrate and 1.2 mL of 28% ammonia water were used instead of 0.256 g of silver lactate 0.5 hydrate. Thus, hair dye component B-4 was obtained (containing 0.54% by mass as silver based on the total amount of hair dye component B-4). The pH of the hair dye component B-4 was 10. Silver ammon complex was formed in the hair dye component B-4.

In addition, 0.233 g of paraphenylenediamine (PPD) was weighed out, and ion-exchanged water was added to make 25.0 g.
Using the hair dye X instead of the hair dye component A-1, using the hair dye component B-4 instead of the hair dye component B-1, and performing the same operation as the sample 101 of Example 1. Evaluation was performed by dyeing goat hair. During the hair dyeing, an unpleasant odor occurred when the hair dye component B was applied.

(Evaluation)
The goat hair after dyeing (samples 401 to 409) was evaluated in the same manner as in Example 1. The results are shown in Table 5.

  As is apparent from the results in Table 5, when silver halide that is not substantially water-soluble is used, hair cannot be dyed, and when silver ammon complex is used, an unpleasant odor occurs during hair dyeing, It was found that hair damage occurred. On the other hand, it was found that the hair dye of the present invention has a high hair dyeing property with respect to the hair and has little damage to the hair.

Example 5
(Samples 501 and 502)
Using goat hair after hair dyeing obtained by the same method as Samples 101 and 105 in Example 1, the shampoo and rinse resistance was examined.

(Samples 503 and 504)
In addition, shampoo / rinse resistance was examined by using goat hair after dyeing obtained by the same method as Samples 301 and 303 of Example 3.

(Evaluation)
The goat hair after dyeing was moistened with 40 ° C. hot water, washed with shampoo, washed with running water at 40 ° C., rinsed, and washed with running water at 40 ° C. This shampoo washing-rinsing process was repeated 40 times. After drying, the concentration was measured. The difference (ΔL ^* ) between L ^* before and after shampoo / rinse was calculated. The results are shown in Table 6.

  As is apparent from the results in Table 6, the hair dyed with the hair dye of the present invention has less change in lightness due to shampoo / rinse than the hair dyed with the hair dye of the comparative example, and the shampoo / rinse resistance It turns out that the nature is high.

Example 6
(Samples 601 and 602)
Light resistance was examined using goat hair after hair dyeing obtained by the same method as Samples 101 and 105 of Example 1.

(Samples 601 and 602)
Moreover, light resistance was investigated using the goat hair after the hair dyeing obtained by the same method as the samples 301 and 303 of Example 3, respectively.

(Evaluation)
After the dyed goat hair was dried and irradiated with 170,000 lux of xenon light for 93 hours, the density was measured. The difference in L ^* (ΔL ^* ) before and after the light resistance test was calculated. The results are shown in Table 7.

As is apparent from the results in Table 7, it was found that the hair dyed with the hair dye of the present invention had a small change in brightness due to irradiation with xenon light and high light resistance.

Claims (13)

  A hair dye comprising a hair dye component A containing at least one leuco body of an indigo compound and / or a salt thereof, and a hair dye component B containing at least one water-soluble silver salt. The hair dye according to claim 1, wherein the leuco body of the indigo compound of the hair dye component A is a compound represented by the following general formula (I) and / or a salt thereof.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)   The hair dye according to claim 2, wherein R in the general formula (I) represents at least one substituent selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a sulfo group. .   The water-soluble silver salt of the hair dye component B is at least one silver salt selected from the group consisting of silver carboxylate, silver sulfonate, silver ammine complex, silver nitrate, and silver sulfate. The hair dye of any one of these. The water-soluble silver salt of the hair dye component B is at least selected from the group consisting of a carboxylic acid silver salt represented by the following general formula (II) and a sulfonic acid silver salt represented by the following general formula (III). The hair dye according to any one of claims 1 to 4, wherein the hair dye is one silver salt.
Formula (II)
R ^1- (COOAg) _n1
(Wherein, ^{R 1} represents a _{n 1} monovalent organic group, _{n 1} is an integer of 1-3.)
Formula (III)
R ² — (SO ₃ Ag) _n2
(Wherein, ^{R 2} represents a _{n 2} divalent organic group, _{n 2} is an integer of 1-3.)   The water-soluble silver salt of the hair dye component B is at least one silver salt selected from the group consisting of silver acetate, silver lactate, and silver methanesulfonate. The described hair dye.   Content of the water-soluble silver salt in the said hair dye component B is 0.01 mass%-10 mass% with respect to the said hair dye component B total mass as silver mass. The hair dye of any one of these.   Content of the leuco body of the indigo compound in the said hair dye component A and / or its salt is 0.1 mass%-10 mass% with respect to the said hair dye component A total mass, The claim 1- The hair dye according to any one of 7 above.   The hair dye according to any one of claims 1 to 8, wherein the pH of the hair dye component A and / or the hair dye component B is 7 or less.   The hair dyeing method including the process of applying the hair dye of any one of Claims 1-9 to hair.   The hair dyeing method according to claim 10, comprising a step of applying the hair dye component A to the hair after applying the hair dye component B to the hair. The compound represented by the following general formula (IV) is treated with a reducing agent to obtain the compound represented by the general formula (I) of the hair dye component A, according to any one of claims 1 to 9. The manufacturing method of the hair dye of description.

(In the formula, X represents NH or a sulfur atom, and two Xs may be the same or different from each other. R represents a substituent, m represents an integer of 0 to 4. m is an integer of 2 or more. A plurality of R may be the same or different.)   A hair dye comprising a kit of a hair dye component A containing at least one leuco body of an indigo compound and / or a salt thereof, and a hair dye component B containing at least one water-soluble silver salt.