JPS6155885B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel oxidative color-forming dye (hereinafter referred to as "oxidative dye"). More specifically, at least one compound selected from (A) para-amino diphenylamine or a salt thereof, (B) 2,6-diaminopyridine or a salt thereof, and (C) meta-aminophenol or a salt thereof, or resorcinol. This invention relates to an oxidative dye for keratin fibers. To dye keratin fibers (particularly hair or fur) in a beautiful and fast manner by a simple and economical method, dye intermediates which develop color upon oxidation are usually used. In other words, if a neutral or alkaline aqueous solution of this dye intermediate mixed with an oxidizing agent is applied or impregnated on keratin fibers immediately before dyeing,
This penetrates into the keratin fibers and is oxidized there to become a water-insoluble pigment, which dyes the keratin fibers, and the above intermediate is called the main intermediate. When dyeing keratin fibers with the main intermediate, a compound called a different type of modifying intermediate is often added together with the main intermediate in order to vary the dyeing. Even if this modification intermediate is oxidized alone, it does not have the ability to dye keratin fibers, but it undergoes a condensation reaction with the main intermediate during oxidation, producing a color tone and solid pigment that cannot be produced by the main intermediate alone. It refers to a dye intermediate that produces . Now, in order to dye keratin fibers (especially hair or fur) black and fast with oxidation dyes that do not contain metal compounds, 2.4
-Diaminoanisole, metatolylenediamine, metaphenylenediamine, etc. are used. These modifying intermediates are usually added to the main intermediate such as para-phenylene diamine, para-tolylene diamine, para-aminodiphenylamine, etc., thereby producing color tones and high fastness that cannot be produced with the main intermediate alone. Produces pigment. For example, when paraphenylenediamine, paratoluylenediamine, and paraaminodiphenylamine are oxidized alone, they only produce dark purple, brown, and dark brown pigments, respectively, but these main intermediates are combined with the above-mentioned modifying intermediates. It is possible to produce a beautiful and robust black pigment by adding and oxidizing the appropriate amount of pigment. In other words, these modifying intermediates are essential materials for the black dyeing of keratin fibers, but these substances have the property of inducing mutations in living cells (hereinafter referred to as ``mutagenicity''). Because this property is correlated with carcinogenicity, the use of these modifying intermediates in the dyeing of keratin fibers is being regulated in developed countries where milled rice is used. Therefore, in the hair and fur dyeing industry, where safe and robust black dyeing of keratin fibers is required, dyeing products that do not contain the above-mentioned modifying intermediates and are non-mutagenic to living organisms are required. It is hoped that a black oxidation dye will appear. Currently, there are many black oxidation dyes that do not contain the mutagenic modification intermediates mentioned above, such as 5,5'-diamino-bis(2-
Some of the black oxidation dyes whose main intermediates are pyridyl)amine, 4-amino-2,6-dihydroxypyridine, 2,4,6-triaminopyridine, or 2,5-diaminopyridine are mutagenic. Some do not contain any modified intermediates. However, each of these things has its drawbacks. That is, 5,5'-diamino-bis(2-
Pyridyl) amine itself is mutagenic, and black oxidation dyes that use 4-amino-2,6-dihydroxypyridine and 2,4,6-triaminopyridine as main intermediates are synthesized from these intermediates. It is not preferred for various reasons, such as low yield and high cost, and black oxidation dyes containing 2,5-diaminopyridine as the main intermediate have low sunlight fastness. There is also a method of dyeing hair black using oxidation dyes containing metal compounds, but these dyes have weak dyeing power and require a long time to dye compared to black oxidation dyes that do not contain metal compounds. Undesirable. In view of these circumstances, the present inventor conducted intensive research to obtain a non-mutagenic, robust and practical black oxidation dye, and as a result, (A) para-aminodiphenylamine or its salt was used as the main intermediate. As a body, (B)2.6
- The black oxidation dye, which uses as a modification intermediate one or more compounds selected from diaminopyridine or its salt, (C) meta-aminophenol or its salt, or resorcinol, is non-mutagenic to living organisms, and its fastness is also high. They discovered that it is excellent, has a strong dyeing power, and is highly economical, leading to the completion of the present invention. It is a known fact that para-aminodiphenylamine, 2,6-diaminopyridine, meta-aminophenol or resorcinol used in the present invention is used as a pigment intermediate for oxidative dyes. That is, when oxidatively dyeing keratin fibers, if a small amount of a mixture of para-aminodiphenylamine and meta-aminophenol in an equimolar ratio is used, the color will be gray, and if a large amount is used, it will be dyed blue-black. It is known that if a mixture of phenylenediamine and 2,6-diaminopyridine in an equimolar ratio is used, dyeing will be brown or blue, respectively. However, the oxidative dyes of the present invention, such as (A) para-amino diphenylamine, (B)
A ternary mixture of 2,6-diaminopyridine and (C) meta-aminophenol, or (A) para-aminodiphenylamine, (B) 2,6-diaminopyridine, and
(C) The ternary mixture of resorcinol is not mutagenic and
The fact that it can be used as an intermediate for oxidation dyes that can dye keratin fibers in a robust and economical black color is a new discovery made by the present inventor, and no one could have predicted this before. It is something that In other words, in the case of known oxidation dyes that use a binary mixture of para-aminodiphenylamine and meta-aminophenol as a dye intermediate, keratin fibers can only be dyed gray if a small amount is used, and bluish black even if a large amount is used. In contrast, the oxidative dye of the present invention, which uses a three-component mixture, can dye keratin fibers (especially hair) black or slightly reddish black using only a small amount of pigment intermediate. However, when oxidatively dyeing keratin fibers, especially hair, dyes that can dye hair black or slightly reddish black are used, using as small a quantity of pigment intermediates as possible in order to prevent the dye from harming the human body. Since the oxidation dye of the present invention satisfies this requirement, the present invention is extremely significant industrially. Regarding the mixing ratio of the dye intermediate used in the present invention, if the ratio of (A) para-amino diphenylamine or its salt is increased, the color becomes brownish black, and (B)
If the ratio of 2,6-diaminopyridine or its salt is increased, the color tone will be slightly biased to greenish-blue black, and if the ratio of (C) meta-aminophenol or resorcinol is increased, the color tone will be slightly biased to reddish black. Deflection can be prevented by increasing the total amount of dye intermediates used in the oxidative dyeing of keratin fibers. In order to dye hair black or slightly reddish black using as little amount of the dye intermediate as possible, the mixing ratio (molar ratio) of the dye intermediate of the present invention should be (A) para-amino diphenylamine or is a salt thereof: (B) 2,6-diaminopyridine or a salt thereof: (C) at least one compound selected from the group consisting of meta-aminophenol, a salt thereof, and resorcinol = 1.0 to 3.0: 0.1 to
0.3: 0.9 to 0.7 is preferable. That is, the oxidation dye of the present invention consisting of the dye intermediate in the above mixing ratio is applied to white hair.
When gray hair is dyed using 1.2% by weight and a bath ratio of 2.5 according to the dyeing method shown in Example 1 below, the gray hair is dyed black or slightly reddish black. Furthermore, (A):(B):(C)=1.0:0.1~0.3:0.9
The oxidation dye consisting of ~0.7 can dye keratin fibers black with little polarization under the above-mentioned dyeing conditions. on the other hand,
In the above-mentioned dyeing method, even if a known oxidation dye, that is, a mixed dye intermediate composition of para-aminodiphenylamine and meta-aminophenol in an equimolar ratio, is used at the above concentration (1.2%), gray hair is simply dyed gray. It cannot be dyed black. As described above, the oxidative dye of the present invention is an oxidative dye that can dye hair black or slightly reddish black using as small a quantity of dye intermediates as possible, that is, an oxidative dye known as a black oxidative dye with strong dyeing power. Better than dye. Among the oxidation dye intermediates of the present invention, those having an amino group can be used as is or as a salt with an inorganic or organic acid, such as hydrochloride, sulfate, phosphate, acetate, propionate, lactate. It can be used in the form of , citrate, etc. The present invention will be specifically explained below with reference to Examples and Reference Examples, but the present invention is not limited to these Examples unless it departs from the gist thereof. for example,
In the hair dyeing examples below, only a method using a mixture of an aqueous solution of a dye intermediate and an aqueous oxidizing agent solution is described, but when the oxidative dye of the present invention is actually used, it may be combined with a method known in the hair dyeing industry. Adhesives (starch, synthetic thickeners, gum arabic, higher alcohols, etc.), wetting agents (triethanolamine, etc.), hair nourishing agents (lanolin emulsion, etc.), fragrances (diasmin, etc.),
A propellant (such as 1,1-difluoroethane) is added and can be used for hair dyeing in various forms such as solid, aqueous solution, suspension, and aerosol. In addition, in the following fur dyeing examples, only a dyeing method using chromium mordant is described, but when the oxidized dye of the present invention is actually used, iron mordant and copper mordant known in the fur dyeing industry are used. and chromium/copper,
It is also possible to use a dyeing method using a mixed mordant method such as copper/iron or chromium/iron. Example 1 Para-aminodiphenylamine hydrochloride
2.0g (9.062 mmol) 2,6-diaminopyridine
0.2 g (1.833 mmol) meta-aminophenol 0.8 g (7.331 mmol) was suspended in 524 c.c. of water, and 1.0 g of hydrochloric acid with a concentration of 35% was added to this.
cc to make these dye intermediates into a homogeneous aqueous solution, and to this add about 20 c.c. of ammonia water to make the solution.
After adjusting the pH to 10, add 80 c.c. of hydrogen peroxide solution with a concentration of 6% to this, stir well, and add about 250 c.c.
After applying it on the gray hair of g and leaving it for 20 minutes at about 37℃,
When washed and dried, gray hair was dyed a vivid black. Using a part of this hair wash, Japanese Industrial Standards (JIS)
A color change and fading test against sunlight was conducted in accordance with the L0841-1966 method, and the sunlight fastness was grade 4. Further, when a portion of this washed hair was tested for color fastness to potash soap in accordance with the Japanese Industrial Standards (JIS) L0841-1970 method, the color fastness to color fading was grade 2. Furthermore, when a portion of this dyed hair was tested for color fastness to sweat in accordance with the Japanese Industrial Standard (JIS) L0848-1965-D method, the color fastness to sweat was grade 2. Reference Example 1 In the same manner as in Example 1, a hair dye containing the following dye intermediate as a component was prepared, and when the hair was dyed, the hair was dyed black. Therefore, various fastness tests against discoloration and fading due to sunlight, potash soap, and sweat were conducted according to the method described in Example 1, and the results shown below were obtained.
However, these fastness test results were all inferior to the fastness test results for the dye of the present invention shown in Example 1. Pigment component intermediate para-aminodiphenylamine hydrochloride
…………2.0g (9.062 mmol) Metaphenylenediamine dihydrochloride
…………0.332g (1.833 mmol) meta-aminophenol
…………0.8g (7.331 mmol) Fastness Fastness to sunlight …………Color fastness to 3rd class potash soap …………Color fastness to 1st class perspiration …………1st class reference example 2 Implementation In the same manner as in Example 1, a hair dye containing the following dye intermediate as a component was prepared, and when hair was washed, gray hair was dyed gray but not black. Pigment component intermediate para-aminodiphenylamine hydrochloride
…………2.0g (9.062 mmol) meta-aminophenol
…………1.0g (9.164 mmol) Examples 2 to 6 In the same manner as in Example 1, hair dyes containing the pigment intermediates shown in Table 1 as pigment components were prepared and dyed, and the results shown in Table 1 were obtained. I got it.

[Table] Example 8 100g of para-aminodiphenylamine in 75% of water
(0.543 mol), meta-aminophenol 47.4g
(0.434 mol), 2,6-diaminopyridine 11.8 g
(0.108 mol) and 57 g of 35% hydrochloric acid were added and dissolved uniformly, and the ammonia water with a concentration of about 25% was added to the PH
8.0, and then alum tanned and chromium mordanted using the Urahata method (Dye and Medicine Vol. 8, p. 109, 1963).
2.5 kg (dry product equivalent) was added and stirred at about 30°C for 30 minutes. Furthermore, 333 c.c. of hydrogen peroxide solution with a concentration of 30% was added and stirred at 30°C for 3 hours. After that, the fur was taken out, thoroughly washed with water, and dried, and the fur was dyed a bright black color with high wet fastness. When this fur was subjected to a color fading test due to sunlight in accordance with the Japanese Industrial Standards (JIS) L-0841-1966 method, its sunlight fastness was grade 5. Example 9 Salmonella typhimurium (Ames-TA98 strain or TA100 strain), S-9 activator regulated by rat liver in which drug-metabolizing enzymes were induced with PCB,
A mutagenicity test was conducted on the oxidation dye intermediates shown in Table 2 within the dosage range (10 to 1000 μg/plate) using hydrogen peroxide and hydrogen peroxide, and the results were as shown in Table 2. The dye intermediate used in the present invention had almost no property of increasing the number of variants and was good.

[Table] As mentioned above, in the oxidative color-forming dye for keratin fibers of the present invention, by using the specific dye intermediates in combination, a non-mutagenic, vivid and robust black dye can be produced. obtained, and remarkable effects can be achieved.

Claims (1)

[Scope of Claims] 1 (A) para-aminodiphenylamine or a salt thereof, (B) 2,6-diaminopyridine or a salt thereof, and (C) at least one selected from the following compound group:
An oxidative color-forming dye for keratin fibers containing more than one type of compound. (Compound group): meta-aminophenol, meta-aminophenol salt, resorcinol, 2 (A): (B): (C) = 1.0-3.0: 0.1-0.3: 0.9-0.7
(molar ratio) The oxidative color-forming dye for keratin fibers as set forth in claim 1. 3. The oxidative color-forming dye for keratin fibers according to claim 2, wherein (A):(B):(C)=1.0:0.1 to 0.3:0.9 to 0.7 (molar ratio).