JPH0243722B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a novel oxidative coloring dye (hereinafter referred to as
oxidative dyes). In order to dye hair beautifully and firmly using a simple and economical method, a pigment intermediate (hereinafter referred to as the main intermediate) that develops color through oxidation is normally used. For example, paraphenylenediamine and paratolylenediamine are used. For staining with them,
A method is used in which a mixed solution obtained by mixing an oxidizing agent with a neutral or alkaline aqueous solution of the main intermediate immediately before dyeing is applied or impregnated onto the hair.
As a result, the liquid mixture penetrates into the hair fibers, where the main intermediate is oxidized and polymerized to become a water-insoluble pigment that dyes the hair. Furthermore, when dyeing using the main intermediate, a compound called a modifying intermediate is also used in addition to the main intermediate in order to change the color tone of the dyed hair. Although the modifying intermediate is generally oxidized, it does not have the ability to dye hair by itself, and moreover, it condenses with the main intermediate in the oxidation site to create color tone and fastness that cannot be created by the main intermediate alone. Refers to dye intermediates capable of producing dyes, which are characterized by the fact that their cores are aromatic compounds having electron-donating substituents (e.g., amino groups, hydroxyl groups, etc.) It is. In order to dye hair black and fast using oxidative dyes that do not contain metal compounds, 2,4-diaminoanisole, metatolylenediamine, metaphenylenediamine, etc. are usually used as modifying intermediates. There is. For example, when the main intermediates paraphenylenediamine and paratoluylenediamine are oxidized alone, only dark purple and brown pigments are produced, respectively, but the above-mentioned modified intermediates are added to these main intermediates. When properly added and blended and oxidized, a robust and beautiful black pigment can be produced. As mentioned above, modifying intermediates are essential auxiliary materials when dyeing hair, but some of these compounds have the property of inducing mutations in living cells (hereinafter referred to as mutagens). There are some substances that have certain cancers, and their correlation with carcinogenicity has become a problem. In particular, the commonly used 2,4-diaminoanisole, metatolylenediamine and metaphenylenediamine have significant mutagenicity. In addition, some of the compounds used as main intermediates are unfavorable from a safety and health perspective, and in particular, the paraphenylenediamine and paratolylenediamine have proinflammatory properties that cause severe dermatitis in people with allergies. , special care must be taken when using it. Therefore, in the hair dyeing industry, where hair must be dyed to a strong and beautiful black color in a hygienic and safe manner, the dyeing industry does not use modifying intermediates or main intermediates, which have safety and health problems such as those mentioned above. There is a strong need for the development of a non-mutagenic and non-inflammatory oxidative dye for black color. As one proposal to solve this purpose, US Pat. No. 4,171,952 proposes that 1,
The use of 5-dihydroxynaphthalene is disclosed. However, since 1,5-dihydroxynaphthalene is a fused polycyclic compound, it has a larger molecular weight than the monocyclic compounds commonly used as modification intermediates, and therefore has a relatively high penetration into the dense hair fibers. It is difficult to dye, and since it has two hydroxyl groups in its molecule, it has high solubility in alkaline water, so when it is dyed using an alkaline aqueous medium, a relatively large amount remains in the aqueous medium. The adsorption rate to hair is relatively poor. Therefore, the dyeing power of a black oxidation dye using this compound as a modifying intermediate is relatively weak. Another method is to dye hair black using oxidative dyes that contain metal compounds, but these oxidative dyes are inferior in dyeing power to black oxidative dyes that do not contain metal compounds, and require a long time to dye. Undesirable. As a result of intensive research to create a practical black oxidation dye that is non-mutagenic, non-inflammatory, and rich in fastness and dyeing power, the present inventor discovered that the main intermediate is inflammatory At least one member selected from the group consisting of a known diphenylamine type compound with relatively low toxicity, a known non-mutagenic 2,6-diaminopyridine as a first modification intermediate, a salt thereof, and 1-naphthol. When using an oxidative dye containing a mixture of an electron-donating group-containing compound and a known non-mutagenic phenolic compound in a specific proportion as a second modifying intermediate to dye hair black, The present invention was completed based on the discovery of a new fact that the above object can be easily achieved. That is, the present invention provides: (A) at least one diphenylamine type compound selected from the group consisting of 4-aminodiphenylamine, 4,4'-diaminodiphenylamine and salts thereof; (B) 2,6- Diaminopyridine, its salts and 1
- at least one electron-donating group-containing compound selected from the group consisting of naphthol, and (C) meta-aminophenol and its salt, 4-amino-2-hydroxytoluene and its salt,
resorcinol, pyrogallol, pyrocatechol,
Fluoroglucin, gallic acid, salicylic acid, 4
- contains as an active ingredient at least one phenolic compound selected from the group consisting of chlorresorcinol and hydroquinone (provided that component (A) is 4-
aminodiphenylamine or a salt thereof, component (B) is 2,6-diaminopyridine or a salt thereof, and (C)
(A) and (B), (B) and (C), and (A) and (B), (B) and (C), and
The molar ratio of (A) and (C) is (A):(B) = 96.1 to 72.8:
3.9 ~ 27.2, (B): (C) = 30.8 ~ 0.1: 69.2 ~ 99.9 and
(A):(C)=58.8~0.9:41.2~99.1 [However, (A)≦(B)
+(C) (mol)]. More preferred compositions of the present invention include (A) and (B), (B) and (C), and (A)
and (C) are respectively (A):(B)=96~73:4~27, (B):(C)
=30~4:70~96 and (A):(C)=58~35:42~65
[However, (A)≦(B)+(C) (mol)]. In the present invention, component (A) which is the main intermediate is at least one diphenylamine type compound selected from the group consisting of 4-aminodiphenylamine, 4,4'-diaminodiphenylamine and salts thereof. Among them, 4-aminodiphenylamine and its salts tend to shift the dyed hair color to a relatively pale color (remaining color on the short wavelength side), so it is used when a pale black color is required. Also, since 4,4'-diaminodiphenylamine and its salts tend to shift the dyed hair color to a relatively deep color (remaining color on the long wavelength side), a deep black color is required. Good to use when traveling. As component (B), which is the first modification intermediate, at least one member selected from the group consisting of 2,6-diaminopyridine, its salt, and 1-naphthol, which are known as modification intermediates, is used. . Component (C), which is the second modification intermediate, includes meta-aminophenol and its salt, 4-amino-2-hydroxytoluene and its salt, resorcinol, pyrogallol, pyrocatechol, which are known as modification intermediates. At least one phenolic compound selected from the group consisting of fluoroglucin, gallic acid, salicylic acid, 4-chlorresorcin, and hydroquinone is used. Furthermore, in order to produce an even safer black tone, if desired, in addition to component A, non-mutagenic and low inflammatory 2,5-diaminopyridine and/or component (A) can be added. The salt may be used as the main intermediate. Among the intermediates used in the present invention, those having an amino group include salts with inorganic acids or organic acids,
For example, it can be used in the form of hydrochloride, sulfate, phosphate, acetate, propionate, lactate, citrate, and the like. Generally, when preparing oxidation dyes, unlike when preparing other dyes or pigments, it is almost impossible to create an intermediate color by simply mixing two types of ready-made dyes. . This is because, as mentioned above, oxidative dyes produce a unique color tone by oxidation, polymerization, or condensation of each pigment intermediate within the hair fiber. When two types of two-component ready-made oxidation dyes are prepared, four types of dye intermediates are condensed or polymerized with each other, generally producing seven or more types of dyes, and these seven or more types of dyes exhibit the mixed color. It is from. Therefore, in order to obtain the desired color tone by mixing oxidation dyes, it is necessary to carefully study the correlation between the mutual reactivity and reaction rate of each dye intermediate, and then decide on the mixing ratio of each dye intermediate. Must be.
Particularly in systems with three or more components as in the present invention, it is very difficult to predict the relationship between them, and it is even more difficult to predict whether the resulting dye can solve health and safety problems. . According to the research of the present inventor, the dye produced by the condensation of component (A) and component (B) is a deep color (extra color of long wavelength color) type pigment, and component (A) and (C) A pigment in which the components are condensed is a hypsochromic pigment (an extra color of a short wavelength color), while component (D) produces a hypsochromic pigment when it is condensed with component (B) or component (C), and self-polymerizes. However, if there is a large amount of the (B) component, it will be a deep color, if there is a lot of the (C) component, it will be a hypochromic color, and if you add the (D) component, it will be a hypochromic pigment. There is a tendency for the dyed hair color to shift to the sides. Further, the present inventors have discovered by conducting hair dyeing tests that there is the following tendency regarding the reaction rate of oxidation, polymerization, or condensation of each coloring intermediate of the present invention. (1) The self-polymerization rate of component (A) is lower than the reaction rate of condensation of component (A) with component (B) or component (C). (2) The reaction rate at which component (A) condenses with component (B) is greater than the reaction rate at which component (A) condenses with component (C). (3) The reaction rate at which component (D) condenses with components (B) and (C) is lower than the reaction rate at which component (A) condenses with components (C) and (C). (4) The reaction rate of condensation of component (D) with component (A) is much lower than the various reaction rates mentioned above. (5) The self-polymerization rate of component (D) is the lowest among all the reaction rates mentioned above. Furthermore, the self-polymerized product of component (A) has slight mutagenicity and slight inflammatory properties. Based on these facts, the number of moles of the three-component mixture containing components (A), (B), and (C) as active ingredients in the present invention must satisfy (A)≦(B)+(C) from the viewpoint of safety and health. In addition, in order to obtain a mixed pigment that can dye hair black, the molar ratios of (A) and (B), (B) and (C), and (A) and (C) are respectively (A). :(B)=96.1~72.8:3.9~27.2,(B):(C)=
30.8 ~ 0.1: 69.2 ~ 99.9 and (A): (C) = 58.8 ~ 0.9:
41.2~99.1, preferably (A):(B)=96~73:4~
27, (B):(C)=30~4:70~96 and (A):(C)=58~
35:42-65 is required. In the case of (A)>(B)+(C), excess component (A) self-polymerizes in the oxidation field, resulting in self-polymerization of component (A) that exhibits slight mutagenicity and slight inflammatory properties. It is undesirable because it causes problems. In addition, as mentioned above, component (B) has a high condensation reaction rate with component (A), so if component (B) is in excess of the molar ratio shown in the above formula, or component (C) is If the molar ratio is less than the molar ratio shown in , the deep-colored pigment produced by both components (B) and (A) will be produced in excess of what is necessary, and this pigment will dye the hair blue or green. Undesirable. Furthermore, in order to obtain a black oxidation dye that is safer than the oxidation dye containing the three-component mixture of (A), (B), and (C) as an active ingredient,
Component (D) may be added to components (A), (B), and (C). Component (D) is a main intermediate like component (A), but
Unlike component (A), its self-polymer does not exhibit mutagenicity, and the inflammation caused by the polymer is weaker than that shown by the polymer of component (A), so it is safer than component (A). It is the main intermediate. However, as mentioned above, component (D) only condenses with component (B) or (C), or self-polymerizes with component (D) alone to produce a hypsochromic pigment (A).
Unlike component (B), it does not have the ability to condense with component (B) to produce a deep color pigment. Therefore, when adding component (D) to a three-component mixture consisting of (A), (B), and (C), the amount of component (B) should be increased because the dyed hair color will shift to the lighter color side as described above. Unless it is neutralized by returning it to the deep color side, it will not be possible to obtain an oxidation dye that can dye hair black. Therefore, when component (D) is added to a three-component mixture consisting of (A), (B) and (C), (A) is 4-aminodiphenylamine or a salt thereof, and (B) is 2,6- When aminopyridine or its salt, (C) is meta-aminophenol or its salt, and (D) is 2,5-diaminopyridine or its salt, the amount of component (D) is 2.098 mol relative to component (A). (A) is 4,4'-diaminodiphenylamine or its salt, (B) is 1-naphthol, (C) is meta-aminophenol or its salt, ( D) is 2,5-
In the case of diaminopyridine or a salt thereof, it is necessary to add component (D) in an amount of 3.635 moles or less relative to component (A). In those cases, the molar ratios of (A) and (B), (B) and (C), and (A) and (C) are
In the former case, (A): (B) = 90.8 to 32.3:
9.2~67.7, (B):(C)=99.9~10.10.1~:89.9 and
(A): (C) = 99.8 ~ 40.0: 0.2 ~ 60.0, in the latter case (A): (B) = 89.7 ~ 17.6: 10.3 ~ 82.4, (B): (C) = 99.9
~11.2:0.1~88.8 and (A):(C)=99.6~52.4:0.4
-47.6, an oxidative dye capable of dyeing hair black can be obtained. (D) If the component is the former (A)
If more than 2.098 moles of component (A) is added, or in the latter case 3.635 moles of component (A),
Only oxidative dyes that dye dark brown can be obtained. However, even when adding component (D) to a three-component mixture consisting of (A), (B), and (C), the molar relationship of (A)≦(B)+(C) is essential for safety and health reasons. . Combinations of components (A), (B) and (C), or even component (D) that can be used in the above composition range include, for example, (A) 4-aminodiphenylamine, (B) ) A mixture consisting of 2,6-diaminopyridine and (C) pyrogallol, (A) a mixture consisting of 4-aminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) pyrocatechol, (A) 4
-A mixture consisting of aminodiphenylamine, (B) 2,6-diaminopyridine and (C) fluoroglucine, (A) 4-aminodiphenylamine, (B) 2,6-
A mixture consisting of diaminopyridine and (C) gallic acid, (A) 4-aminodiphenylamine, (B) 2,6-
A mixture consisting of diaminopyridine and (C) 4-chlorresorcin, (A) 4-aminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) hydroquinone, (A) 4-aminodiphenyl Amine, (B) 2,6-diaminopyridine and (C)
A mixture consisting of 4-amino-2-hydroxytoluene, (A) 4,4'-diaminodiphenylamine, (B)
A mixture consisting of 2,6-diaminopyridine and (C) meta-aminophenol, (A) a mixture consisting of 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine and (C) resorcin, (A) ) 4,4'-diminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) pyrogallol, (A)
4,4'-diaminodiphenylamine, (B)2,6-
A mixture consisting of diaminopyridine and (C) pyrocatechol, (A) 4,4'-diaminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) fluoroglucin, (A) 4,4' -diaminopyridine, (B) 2,6-diaminopyridine and (C)
A mixture consisting of gallic acid, (A) 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine and (C) 4-chlorresorcin, (A)
4,4'-diaminodiphenylamine, (B)2,6-
A mixture consisting of diaminopyridine and (C) hydroquinone, (A) 4,4'-diaminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) 4-amino-2-hydroxytoluene,
(A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 2,6-diaminopyridine and (C) meta-aminophenol, (A) a mixture of 4-aminodiphenylamine, enylamine and 4,
4′-diaminodiphenylamine mixture, (B)2,
A mixture consisting of 6-diaminopyridine and (C) resorcinol, (A) 4-aminodiphenylamine and 4,
4′-diaminodiphenylamine mixture, (B)2,
A mixture of 6-diaminopyridine and (C) pyrogallol, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
A mixture consisting of 2,6-diaminopyridine and (C) pyrocatechol, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine and ( C) a mixture consisting of fluoroglucin, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine and (C)
A mixture consisting of gallic acid, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine, and (C) 4
-A mixture consisting of chlorresorcin, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) hydroquinone, (A) )4-
A mixture of aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 2,6-diaminopyridine and (C) 4-amino-2-hydroxytoluene, (A) 4-aminodiphenylamine. enylamine, (B) a mixture consisting of 1-naphthol and (C) meta-aminophenol, (A) a mixture consisting of 4-aminodiphenylamine, (B) 1-naphthol and (C) resorcin, (A) 4- Aminodiphenylamine, (B)
A mixture consisting of 1-naphthol and (C) pyrogallol, (A) 4-aminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) pyrocatechol, (A) 4-aminodiphenylamine, (B) ) a mixture consisting of 1-naphthol and (C) fluoroglucine,
A mixture consisting of (A) 4-aminodiphenylamine, (B) 1-naphthol and (C) gallic acid, (A) 4-aminodiphenylamine, (B) 1-naphthol and (C)
A mixture consisting of 4-chlorresorcin, (A) 4-aminodiphenylamine, (B) 1-naphthol and
(C) A mixture consisting of hydroquinone, (A) 4-aminodiphenylamine, (B) 1-naphthol and (C) 4
-A mixture consisting of amino-2-hydroxytoluene, (A) 4-aminodiphenylamine, (B) 1-naphthol and (C) a mixture consisting of 4-amino-2-hydroxytoluene, (A) 4,4' -diaminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) meta-aminophenol, (A) 4,4'-diaminodiphenylamine, (B) 1-naphthol and (C)
A mixture consisting of resorcinol, (A) 4,4'-diaminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) pyrogallol, (A) 4,4'-diaminodiphenylamine, (B) 1 - a mixture consisting of naphthol and (C) pyrocatechol, (A) 4,4'-diaminodiphenylamine, (B) 1-naphthol and (C)
A mixture consisting of fluoroglucin, (A) 4,4'-diaminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) gallic acid, (A) 4,4'-diaminodiphenylamine, (B) 1-Naphthol and (C)
A mixture consisting of 4-chlorresorcin, (A)4,
A mixture consisting of 4'-diaminodiphenylamine, (B) 1-naphthol and (C) hydroquinone, (A)
4,4'-diaminodiphenylamine, (B) a mixture of 1-naphthol and (C) 4-amino-2-hydroxytoluene, (A) 4-aminodiphenylamine and 4,4'-diaminodiphenyl A mixture of amines, (B) a mixture of 1-naphthol and (C) meta-aminophenol, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1- A mixture consisting of naphthol and (C) resorcinol, (A) 4-aminodiphenylamine and 4,
Mixture of 4'-diaminodiphenylamine, (B)1-
A mixture consisting of naphthol and (C) pyrogallol, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) pyrocatechol, ( A)
A mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 1-naphthol and (C) fluoroglucine, (A) 4-
A mixture of aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol and
(C) a mixture consisting of gallic acid, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture consisting of 1-naphthol and (C) 4 chlorresorcin, ( A) A mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) A mixture of 1-naphthol and (C) hydroquinone, (A) A mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine. '-Diamino diphenylamine mixture, (B) 1-naphthol and (C) 4-amino-2-
A mixture consisting of hydroxytoluene, (A) 4-aminodiphenylamine, (B) 2,6-diaminopyridine and (C) salicylic acid, (A) 4,
4'-diaminodiphenylamine, (B) a mixture consisting of 2,6-diaminopyridine and (C) salicylic acid, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, ( B) a mixture consisting of 2,6-diaminopyridine and (C) salicylic acid, (A) a mixture consisting of 4-aminodiphenylamine, (B) 1-naphthol and (C) salicylic acid, (A)
A mixture consisting of 4,4'-diaminodiphenylamine, (B) 1-naphthol and (C) salicylic acid, (A) 4
-aminodiphenylamine, (B) 2,6-diaminopyridine, (C) meta-aminophenol and (D) 2,
A mixture consisting of 5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 2,6-diaminopyridine, (C) a mixture consisting of resorcinol and (D) 2,5-diaminopyridine, (A) 4 -aminodiphenylamine, (B) 2,6-diaminopyridine, (C) pyrogallol and (D) 2,5-diaminopyridine mixture, (A) 4-aminodiphenylamine, (B)
2,6-diaminopyridine, (C) a mixture consisting of pyrocatechol and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 2,6-
Diaminopyridine, (C) fluoroglucine and (D)
A mixture consisting of 2,5-diaminopyridine, (A)4
-aminodiphenylamine, (B) 2,6-diaminopyridine, (C) a mixture consisting of gallic acid and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 2, 6-diaminopyridine, (C)4-
A mixture consisting of chlorresorcin and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 2,6-diaminopyridine, (C) hydroquinone and (D) 2,5-diaminopyridine a mixture consisting of (A) 4-aminodiphenylamine, (B)
2,6-diaminopyridine, (C)4-amino-2-
A mixture consisting of hydroxytoluene and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine, (C)
A mixture consisting of meta-aminophenol and (D) 2,5-diaminopyridine, (A) 4,4-diaminodiphenylamine, (B) 2,6-diaminopyridine,
(C) a mixture consisting of resorcinol and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine, (C) pyrogallol and (D) 2 , 5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine, (C) pyrocatechol and (D) 2,5-diaminopyridine. , (A) 4,4′-diaminodiphenylamine,
(B) 2,6-diaminopyridine, (C) a mixture consisting of fluoroglucine and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B)
2,6-diaminopyridine, (C) gallic acid and (D)
A mixture consisting of 2,5-diaminopyridine (A)
4,4'-diaminodiphenylamine, (B)2,6-
A mixture consisting of diaminopyridine, (C) 4-chlorresorcin and (D) 2,5-diaminopyridine,
(A) 4,4′-diaminodiphenylamine, (B) 2,6
-diaminopyridine, (C) hydroquinone and (D)
A mixture consisting of 2,5-diaminopyridine (A)
4,4'-diaminodiphenylamine, (B)2,6-
Diaminopyridine, (C) a mixture of 4-amino-2-hydroxytoluene and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine ,(B)
A mixture of 2,6-diaminopyridine, (C) meta-aminophenol and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine and 4,
4′-diaminodiphenylamine mixture, (B)2,
6-diaminopyridine, (C) resorcinol and (D)
A mixture consisting of 2,5-diaminopyridine, (A)4
-A mixture of aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 2,6-diaminopyridine, (C) pyrogallol and (D) 2,5-diaminopyridine, (A) A mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, a mixture consisting of (B) 2,6-diaminopyridine, (C) pyrocatechol and (D) 2,5-diaminopyridine, ( A) mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
2,6-diaminopyridine, (C) a mixture of fluoroglucine and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 2,6-diaminopyridine, (C) gallic acid and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine (B) 2,6-diaminopyridine, (C)
A mixture of 4-chlorresorcin and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 2,6-diaminopyridine , (C) a mixture of hydroquinone and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
2,6-diaminopyridine, (C)4-amino-2-
A mixture consisting of hydroxytoluene and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 1-naphthol, (C) meta-aminophenol and (D) 2,5-diaminopyridine (A) 4-aminodiphenylamine, (B) 1-
A mixture consisting of naphthol, (C) resorcinol and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 1-naphthol, (C) pyrogallol and (D) 2,5-diamino A mixture consisting of pyridine, (A) 4-aminodiphenylamine, (B) 1-naphthol, (C) a mixture consisting of pyrocatechol and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine , (B) a mixture consisting of 1-naphthol, (C) fluoroglucine and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B)
A mixture consisting of 1-naphthol, (C) gallic acid and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 1-naphthol, (C) 4-chlorresorcin and (D ) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 1-naphthol, (C) 4-amino-2-hydroxytoluene and (D) 2,5-diaminopyridine. A mixture consisting of (A) 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) meta-aminophenol and (D) 2,5-diaminopyridine, (A) 4,4' -diaminodiphenylamine, (B) 1-naphthol, (C) resorcinol and (D)
A mixture consisting of 2,5-diaminopyridine (A)
A mixture consisting of 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) pyrogallol and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) ) 1-naphthol, (C) a mixture of pyrocatechol and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) fluoroglucine and (D) a mixture consisting of 2,5-diaminopyridine,
(A) 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) a mixture consisting of gallic acid and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenyl A mixture consisting of amine, (B) 1-naphthol, (C) 4-chlorresorcin and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) A mixture consisting of hydroquinone and (D) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 1
-naphthol, (C) a mixture consisting of 4-amino-2-hydroxytoluene and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine and 4,
Mixture of 4'-diaminodiphenylamine, (B)1-
naphthol, (C) meta-aminophenol and (D)
A mixture consisting of 2,5-diaminopyridine, (A)4
-Mixture of aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C)
A mixture of resorcinol and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
1-naphthol, (C) pyrogallol and (D) 2,5
-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C) pyrocatechol and (D) 2,5- A mixture consisting of diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
1-naphthol, (C) fluoroglucine and (D)
A mixture consisting of 2,5-diaminopyridine, (A)4
-Mixture of aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C)
A mixture of gallic acid and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B)
1-naphthol, (C)4-chlorresorcin and
(D) A mixture consisting of 2,5-diaminopyridine, (A)
Mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol,
(C) a mixture consisting of hydroquinone and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol, (C ) 4-amino-2-hydroxytoluene and (D) 2,5-diaminopyridine, (A) 4-aminodiphenylamine, (B) 2,6-diaminopyridine, (C) salicylic acid and (D ) 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B)
2,6-diaminopyridine, (C) salicylic acid and
(D) A mixture consisting of 2,5-diaminopyridine, (A)
A mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) a mixture of 2,6-diaminopyridine, (C) salicylic acid and (D) 2,5-diaminopyridine, (A) ) 4-aminodiphenylamine, (B) 1-naphthol, (C) salicylic acid and (D) a mixture consisting of 2,5-diaminopyridine, (A) 4,4'-diaminodiphenylamine, (B) 1
- naphthol, (C) a mixture of salicylic acid and (D) 2,5-diaminopyridine, (A) a mixture of 4-aminodiphenylamine and 4,4'-diaminodiphenylamine, (B) 1-naphthol , (C) salicylic acid and (D) 2,5-diaminopyridine. Components (A), (B), and (C), which are the active ingredients of the oxidation dye of the present invention, or component (D) may pose safety problems when used alone or in combination. It is not possible to obtain the beautiful black color tone that can be obtained with certain paraphenylene diamines, paratolylene diamines, 2,4-diaminoanisole, metatolylene diamines, etc., and it is difficult to obtain the beautiful black color tone that can be obtained with certain paraphenylene diamines, paratolylene diamines, 2,4-diaminoanisole, metatolylene diamines, etc. Only by doing this can you obtain a beautiful and durable black hair color. Moreover, the oxidative dye of the present invention is much safer than conventional dyes. As a method for mixing or blending the oxidation dye of the present invention, conventional methods can be used without any particular limitations. To dye hair, an oxidative dye may be made into an aqueous solution, a PH regulator and an oxidizing agent may be added and mixed thereto, and the solution may be applied or impregnated onto the hair. For example, hydrogen peroxide solution, solid hydrogen peroxide, etc. are used as the oxidizing agent.
Examples of pH regulators include aqueous ammonia and ammonium carbonate. Normally, the oxidation dye solution is treated with a pH regulator before being mixed with the oxidizing agent.
Adjusted to 9.0-10.5. Furthermore, the oxidation dye of the present invention can be applied to commonly used thickeners such as starch, synthetic glue, gum arabic, and higher alcohols, leveling agents such as anionic or nonionic surfactants, sulfite agents, and thioglycol. Stabilizers such as acid salts, the above-mentioned PH regulators, or optionally water, solvents such as isopyropanol, fragrances such as diasmine oil, hair nourishing agents such as lanolin emulsion, sequestering agents such as ethylenediaminetetraacetate, 1,1- By appropriately adding a propellant such as difluoroethane, it can be used in various forms such as a solid, an aqueous solution, a suspension, and an aerosol. In order to dye hair using such a form of oxidative dye, a mixture of the oxidative dye and an oxidizing agent may be applied or impregnated onto the hair. The oxidative dye of the present invention is suitable not only for dyeing hair, but also for dyeing keratinous materials such as fur, horns and hooves, wood and bamboo materials. Next, examples of the oxidized dye of the present invention will be explained by giving experimental examples, comparative experimental examples, and test examples, but the present invention is not limited only to these examples. In addition, although Experimental Examples 1 and 7 to 12 are outside the scope of the present invention, they are listed for reference. Experimental example 1 (A) 4-aminodiphenylamine hydrochloride 2.0g
(6.06 mmol), (B) 2,6-diaminopyridine
0.2 g (1.83 mmol) and (C) meta-aminophenol 0.8 g (7.33 mmol) [molar ratio (A):(B)=
83.2: 16.8, (B): (C) = 20.0: 80.0, (A): (C) = 55.3:
44.7] in 53 ml of water, and add about ammonia water to this.
20 ml was added and the pH of the solution was adjusted to 10 to obtain an oxidized dye aqueous solution. Add 6% hydrogen peroxide solution to the obtained oxidation dye aqueous solution
After adding ml of the solution and stirring thoroughly, it was applied to about 250 g of gray hair and left at about 37°C for 20 minutes. When this was washed with water and dried, hair dyed a clear black color was obtained. Using part of the dyed hair, JISL0841−1966
A discoloration test against sunlight was conducted in accordance with the law. As a result, the sunlight fastness was grade 4. Then, using a part of the dyed hair, the color fastness to potassium soap was 90% according to JISL0841-1970 method.
As a result of testing at ℃ for 30 minutes, the color fastness to fading was grade 2. Furthermore, using a part of the dyed hair, JISL0848−1965−
Color fastness to sweat at 90℃ in accordance with D method
As a result of testing for 30 minutes, the color fastness to fading was grade 2. Comparative Experimental Example An oxidized dye aqueous solution was obtained in the same manner as in Experimental Example 1, except that 1.0 g (9.16 mmol) of meta-aminophenol was used instead of 2,6-diaminopyridine.
Then, gray hair was dyed in the same manner as in Experimental Example 1, but the gray hair was not dyed black but dark brown. Experimental Examples 2 to 6 Oxidation dye aqueous solutions were prepared in the same manner as in Experimental Example 1 using components (A), (B) and (C) as shown in Table 1 in the amounts shown in the table. Then, gray hair was dyed in the same manner as in Experimental Example 1. As a result, the dyed hair color obtained and the sunlight fastness measured in the same manner as in Experimental Example 1 are shown in Table 1.

【table】

[Table] Experimental Examples 7 to 67 An aqueous oxidation dye solution was prepared in the same manner as in Experimental Example 1 using components (A), (B), and (C) shown in Table 2 in the amounts shown in the same table. Then, gray hair was dyed in the same manner as in Experimental Example 1. The resulting hair dye colors are shown in Table 2.

【table】

【table】

【table】

【table】

【table】

[Table] Experimental example 68 (A) 4-aminodiphenylamine hydrochloride 0.964g
(4.367 mmol), (B) 2,6-diaminopyridine
0.999 g (9.154 mmol), (C) meta-aminophenol 0.001 g (0.009 mmol) and (D) 2.5-diaminopyridine 1.000 g (9.163 mmol) [mole ratio
(A):(B)=32.3:67.7,(B):(C)=99.9:0.1,(A):(C
)
= 99.8:0.2 and (A):(D) = 1.000:2.098] was used in the same manner as in Experimental Example 1 to prepare an aqueous oxidation dye solution to dye gray hair. The dyed hair obtained was a clear black color, and the color fastness to sunlight was measured in the same manner as in Experimental Example 1 using the dyed hair, and as a result, it showed grade 4. Experimental example 69 (A) 4,4'-diaminodiphenylamine hydrochloride
0.749g (2.52 mmol), (B) 1-naphthol 1.700
g (11.79 mmol), (C) meta-aminophenol
0.001 g (0.001 mmol) and (D) 1.000 g (9.16 mmol) of 2.5-diaminopyridine [molar ratio (A): (B)
=17.6:82.4, (B):(C)=99.9:0.1, (A):(C)=
99.6:0.4 and (A):(D)=1.000:3.635] was used in the same manner as in Experimental Example 1 to prepare an aqueous oxidation dye solution to dye gray hair. The dyed hair obtained was a clear black color, and the color fastness to sunlight was measured using the dyed hair, and as a result, it showed grade 4. Experimental example 70 100 g of 4-aminodiphenylamine in 75 water
(0.543 mol) and 57 g of hydrochloric acid with a concentration of 35%,
After heating to 90℃ to make a homogeneous solution, activate carbon
10 g was added and stirred for 5 minutes. The liquid obtained by heating was then cooled to 30°C, and 47.4 g (0.434 mol) of meta-aminophenol and 2,6-
Add 11.9g (0.109mol) of diaminopyridine,
After uniformly dissolving and adding aqueous ammonia with a concentration of about 25% at about 30°C until the pH reached 8.0, the Urahata method (Dye and Medicine, Vol. 8, p. 109, 1963) was added.
Add 2.5 kg (dry product equivalent) of alum-tanned and chromium-mordanted white rabbit fur (dry product equivalent), stir at approximately 30°C for 30 minutes, then add 333 ml of hydrogen peroxide solution with a concentration of 30% and raise the temperature to 30°C. The mixture was stirred for 3 hours.
After that, the fur was taken out, thoroughly washed with water, and dried.The fur was dyed a bright black color with high wet fastness. Using this fur, a color fading test due to sunlight was conducted in the same manner as in Experimental Example 1, and the color fastness to sunlight was grade 5. Experimental Examples 71 to 74 An aqueous oxidation dye solution was prepared in the same manner as in Experimental Example 1 using components (A), (B), (C) and (D) as shown in Table 3 in the amounts shown in the table. Next, gray hair was dyed in the same manner as in Experimental Example 1, and the results are shown in Table 3.

[Table] Test example Salmonella tyhimurium
typhimurium) (Ames-TA98 strain), an S-9 activator regulated by rat liver in which drug-metabolizing enzymes were induced with PCB, and hydrogen peroxide solution.
Mutagenicity tests were conducted on the compounds shown in Table 4 in the dosage range of 10 to 1000 μg/medium plate ●. The results are shown in Table 4. Note that meta-aminophenol, 1-naphthol, resorcinol, pyrogallol, pyrocatechol, fluoroglucine, gallic acid, salicylic acid, 4-chlorresorcinol, hydroquinone, 4-amino-2-hydroxytoluene, para-aminophenol, para-methyl used in the present invention The fact that aminophenol and ortho-aminophenol are non-mutagenic is stated in Sanitation Laboratory Report No. 94, page 28 (1976). The experiment of this test example was conducted according to the above-mentioned literature.

【table】

[Table] As is clear from Table 4, the increase in the number of mutants in the oxidative dye of the present invention is small, that is, the mutagenicity is low, and it does not cause any health and safety problems.

Claims (1)

[Claims] 1 (A) 4-aminodiphenylamine, 4,4'-
at least one diphenylamine type compound selected from the group consisting of diaminodiphenylamine and salts thereof, (B) 2,6-diaminopyridine, a salt thereof and 1
- at least one electron-donating group-containing compound selected from the group consisting of naphthol, and (C) meta-aminophenol and its salt, 4-amino-2-hydroxytoluene and its salt,
resorcinol, pyrogallol, pyrocatechol,
Fluoroglucin, gallic acid, salicylic acid, 4
- contains as an active ingredient at least one phenolic compound selected from the group consisting of chlorresorcinol and hydroquinone (provided that component (A) is 4-
aminodiphenylamine or a salt thereof, component (B) is 2,6-diaminopyridine or a salt thereof, and (C)
(A) and (B), (B) and (C), and (A) and (B), (B) and (C), and
The molar ratio of (A) and (C) is (A):(B) = 96.1 to 72.8:
3.9 ~ 27.2, (B): (C) = 30.8 ~ 0.1: 69.2 ~ 99.9 and
(A):(C)=58.8~0.9:41.2~99.1 [However, (A)≦(B)
+(C) (mole)] is an oxidative color-forming dye. 2 The molar ratios of (A) and (B), (B) and (C), and (A) and (C) are (A):(B)=96-73:4-27, (B):( C)=30~4:
70-96 and (A): (C) = 58-35: 42-65 [However,
(A)≦(B)+(C) (mol)] Claim 1
Staining agent described in Section. 3 (A) 4,4'-diaminodiphenylamine and/or its salt, (B) 1-naphthol, (C) meta-aminophenol and/or its salt, and (D) 2,5-diaminopyridine and (or)
Contains the salt as an active ingredient, and (A) and (B), (B) and (C), and (A) and (C) are respectively (A): (B) = 89.7 to 17.6: 10.3
~82.4, (B): (C) = 99.9 ~ 11.2: 0.1 ~ 88.8 and
(A):(C)=99.6~52.4:0.4~47.6 [However, (A)≦(B)
+ (C) (mol), (A) x 3.635≧(D) (mol)].