JPH03246217A - Oxidation hair-dyeing agent - Google Patents

Abstract

PURPOSE:To obtain a safe oxidation dyeing agent containing a plant extract containing a zeolite and pyrogallol tannin having a transition metal carried thereon as the second liquid and reduced in damage of hair and irritation of hair and free from mutagenic property. CONSTITUTION:The aimed dyeing agent containing a diamine based oxidation dyestuff as the first liquid and one or more kinds of plant extract containing zeolite and pyrogallol tannin on which a transition metal is carried as the second liquid. Optimum pH of reaction liquid of mixed solution of the first liquid and second liquid is 8.5-10.5. The zeolite consists essentially of aluminosilicate of alkali or alkaline earth metal. The transition metal-carried zeolite can be used as an oxidizing agent concerned in hydrogen peroxide in polymerization reaction of diamine-based oxidation dye.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an oxidizing hair dye that uses a solid acid catalyst as an oxidizing agent instead of hydrogen peroxide, unlike ordinary hair dyes.
It is an object of the present invention to provide a hair dye that causes less hair damage and skin irritation and is not mutagenic.

<Conventional technology> There are the types of hair dyes conventionally used as shown in Table 1 (Fragrance Journal (24) 16-23 (
1979) > Among these several types of hair dyes, the one with the best dyeing properties is a permanent hair dye.

Most permanent hair dyes use a diamine oxidation dye such as phenylene diamine as the first agent and hydrogen peroxide as the second agent.

<Problems to be Solved by the Invention> Regarding diamine-based oxidative dyes used in permanent hair dyes, primary irritation and sensitization to the skin have become a problem.

Additionally, it has been reported that mutagenicity is enhanced when diamine-based oxidation dyes are used together with hydrogen peroxide (
B, N, A+*es et at,; Proc.

1bt1. Acad, Sei, 72 2423-
2427 (1975)).

In particular, it has been suggested that Bandrowski base, which is a trimer produced when paraphenylenediamine is treated with hydrogen peroxide, is involved.

Furthermore, hydrogen peroxide, which is used as an oxidizing agent in permanent hair dyes, is known to cause hair damage such as split ends, hair breakage, and elution of hair keratin (Fragrance Journal (24)). 52-57.64
(1977)).

As mentioned above, hydrogen peroxide, which is conventionally used as an oxidizing agent in hair dyes, not only damages hair, but also
It has the effect of expressing the mutagenicity of diamine oxidation dyes. On the other hand, although diamine-based oxidation dyes have problems such as skin sensitization, they have excellent dyeability and it is difficult to find dyes that can replace them.

Therefore, we attempted to develop a hair dye that can dye hair without using hydrogen peroxide as an oxidizing agent. We also investigated a hair dye that could reduce the amount of diamine oxidation dye used as much as possible and dye hair efficiently in a short time.

As a result, we have found that the above problems can be solved by using a solid acid catalyst in which transition metal ions are supported on zeolite. Zeolite is
It is mainly composed of aluminosilicates of alkali or alkaline earth metals, and has a methane-type structure of SiO4 tetrahedra and AI.
It forms a three-dimensional skeletal structure with large, regular cavities in which O, tetrahedra share one oxygen atom with each other. There are types such as A type, X type, and Y type depending on the crystal structure. Zeolite exchanged with transition metal ions has H2,
CO, C2H4, NH.

It shows high activity in the oxidation of compounds such as, and is being applied as a solid acid catalyst. We investigated the catalytic activity of transition metal-supported zeolite in the polymerization reaction of diamine oxidation dyes.

Table 2 shows the redox potentials of various metals in aqueous solutions.
Hair samples were prepared by washing hair bundles made using Kamoji with methanol, washing with water, and air-drying them. In addition, the catalytic activity of the polymerization reaction of diamine-based oxidation dyes was determined by using a plant extract containing pyrogallol tannin, such as Hamamelis, as a coupler.
The study was conducted by evaluating the degree of hair dyeing of hair samples using the basic formulation shown in Table 3.

2H+ Fe(CN) i-co MnO’″’″ p　e　s　+ A g+ pb’+ +e = H2 +e = Fe(CN)s'- +e 72MnO2- +e:　　Fe” +e　e＋++　Ag +e Nigo P b2+ 0.00 0.36 0.60 0.77 0.80 1.80 isoproper tool NH,0H 10,0 0,5 Staining was performed.

The results are shown in Table 4. No hair dyeing was observed with zeolite alone as a carrier, while zeolite supporting a transition metal with an oxidation-reduction potential of 0°60 (V) or higher showed a fair to good degree of hair dyeing. Ta.

However, no hair dyeing was observed with silver ions or iron ions alone, and only the transition metal ions present in the zeolite crystal lattice showed effective catalytic activity. Therefore, it was shown that transition metal-supported zeolite can be used as a useful oxidizing agent in place of hydrogen peroxide in the polymerization reaction of diamine-based oxidation dyes.

Fairly good Fairly good Fairly good Good Good No dyeing No staining Drop effect> Next, we investigated the formulation of a hair dye using transition metal-supported zeolite as an oxidizing agent.

First, the blending amount of the transition metal-supported zeolite was studied. Figure 1 shows the relationship between the ratio of the zeolite and the change in the degree of hair dyeing (ΔS) when the first liquid is 1. ΔS was determined by measuring the change in the area (S) surrounded by the spectral reflectance curve using a Murakami spectrophotometer for a dyed hair sample. ΔS is metal-supported zeolite:
The maximum is reached when the ratio of the first liquid is 0.5, and this ratio is 1.0.
In this case, the viscosity of the dyeing solution became high and it was difficult to handle it. On the other hand, the smaller this ratio is, the faster the reaction rate is, as shown in Figure 1.
Therefore, 0.2 was judged to be appropriate.

Next, we investigated couplers to be added to the first liquid.

We focused on plant extracts containing pyrogallol tannins. Table 5 shows the reaction rates when various plant extracts were used as the second liquid in the above basic formulation. The reaction rate was 10
After a few minutes, the color difference in the case where no extract solution was added to the reaction solution was measured and expressed as the difference in brightness ΔL. A reaction accelerating effect was observed in Hamamelis extract, gallic extract, and pentagram extract containing pyrogallol tannin.

On the other hand, no promoting effect was observed in Acacia japonica extract and Sumac extract containing catechol tannins.

The amount of diamine-based oxidation dye such as phenylenediamine in the first liquid is the minimum amount (0.5 to 1.0
Weight 2) showed sufficient hair dyeing.

Finally, we investigated the influence of the pH of the reaction solution. Figure 2 shows ΔL and I.
+) (Which relationship does the reaction rate ΔL show when the pH is around 10?
was maximum, and the optimum pH was 8.5 to 10.5.

<Effects> Furthermore, the effects of the present invention will be explained in detail with reference to Examples.

The formulations of Example 1 and Example 2 are shown below.

For hair dyeing, 9 parts of the first solution and 1 part of the second solution are mixed, applied to the hair, and washed off after about 30 minutes.

Example 1 (1st liquid) Paraphenylene diamine isopropanol Ammonium hydroxide Sodium sulfite 1.3-Butylene glycol Oleate Polyoxyethylene (20 mol) Sorbitan monooleate Cetyl alcohol Purified water 1.0 (Weight 2) 10.0 12.0 1.2 10.0 25.0 8.0 1.0 31.8 (2nd liquid) Silver-supported zeolite Hamamelis extract 20.0 80.0 Example 2 (1st liquid) WJLi! ! 2 Toluene-2,5-diamine metaphenylene diamine monoethanolamine Sodium sulfite propylene glycol oleic acid Polyoxyethylene (20 mol) Sorbitan monooleate Iso 10 Panol Cetyl alcohol Purified water 1.5 (Weight 2) 0.5 13.0 1.2 10.0 25.0 8.0 10.0 1.0 29.8 (Second liquid) Silver-supported zeolite 20.0 (Weight 2) Five-fold extract liquid 80.0 As a comparative example, A hair dye containing hydrogen peroxide as the second liquid was used. Both Example 1 and Example 2 showed sufficient hair dyeing effects with 30 minutes of dyeing treatment.

Next, we investigated their skin irritation and hair damage. The skin irritation properties of Example 1, Example 2, and Comparative Example were evaluated using the Draize method. Moreover, the damage to the hair caused by these was measured by measuring the friction of the hair using a surface friction meter (manufactured by Kadochik). The results are shown in Table 6.

In the examples of the present invention, the skin irritation value was significantly lower than that of the comparative example, and the coefficient of friction of hair was also significantly lower by 5%.

Furthermore, their mutagenicity was investigated. The study used the S9 addition system and the first and second liquids by the Awes method.
This was done by examining the relationship between the elapsed reaction time after mixing the liquids and the appearance of His revertant mutants. The results are shown in Figure 3.

In the comparative example, a high reverse mutation expression rate was shown immediately after mixing, and reached a maximum after 5 minutes.

However, in Examples 1 and 2, almost no reversion mutations were observed. That is, in the Examples of the present invention, no mutagenicity as seen in the Comparative Examples was observed.

As described above, the present invention reduces skin irritation and hair damage caused by the diamine oxidation dye used in the first liquid and the hydrogen peroxide used in the second liquid, and provides a safe, non-mutagenic dye. A hair dye can be provided.

[Brief explanation of drawings]

Figure 1 shows the relationship between the amount of transition metal supported zeolite and the degree of hair dyeing, Figure 2 shows the relationship between the pH of the reaction solution and the reaction rate ΔL, and Figure 3 shows the relationship between the first and second solutions. FIG. 3 is a diagram showing the relationship between the elapsed reaction time after liquid mixing and the incidence of reverse mutation.

Claims (2)

[Claims] (1) An oxidation dye characterized in that the first liquid contains a diamine-based oxidation dye, and the second liquid contains at least one of zeolite supporting a transition metal and a plant extract containing pyrogallol tannin. Hair preparation. (2) The pH of the reaction solution after mixing the first solution and the second solution is 8.
The oxidative hair dye according to claim 1, which has a molecular weight of 5 to 10.5.