JP2002255765A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair dye composition having no hair damage such as split hair, cut hair, not causing reduction in touch feeling of the hair, having excellent dyeing property. SOLUTION: This hair dye composition comprises (A) 0.01-10 U/g of an indoline compound represented by formula (1) (R<1> , R<2> , R<3> , R<4> and R<5> are each independently hydrogen or a 1-4C alkyl group) or its acid addition salt and (B) 0.01-10 U/g of an enzyme capable of oxidizing 5,6-dihydroxy indoline and 2,6-diaminotoluene in the hair dye composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye composition which has less damage to the hair such as split ends and cut hairs and has excellent dyeability without causing a reduction in the feel of the hair.

[0002]

2. Description of the Related Art Permanent hair dyes for dyeing hair include oxidative hair dyes, vegetable hair dyes, and hair dyeing methods using hair dyes. Oxidative hair dyes are superior in effect and bleach. It is also used most often because it has an effect and can be dyed in bright colors. The oxidation hair dye is used to dye an oxidation dye intermediate by oxidizing it with an oxidizing agent such as hydrogen peroxide, and uses an alkali agent in combination to improve the dyeing effect. The alkaline agent may cause damage to the hair and may cause a reduction in the feel of the hair due to generation of split ends and cut hairs. As a hair dyeing method that is unlikely to cause a reduction in the feel of hair due to the alkaline agent, a method of oxidizing and dyeing an oxidative dye intermediate using an oxidoreductase has been proposed (for example, JP-A-47-9933). JP, JP-A-6-172145, JP-A-11-21
215, JP-A-11-60454, etc.).

[0003]

However, the hair dyeing method of oxidizing and dyeing an oxidative dye intermediate with these oxidoreductases has a hair feel that is less than that of dyeing with an oxidizing agent such as hydrogen peroxide. Excellent without reduction, but hair dyeing is not sufficient. An object of the present invention is to provide a hair dye composition having an excellent dyeing effect without reducing the feel of hair.

[0004]

Means for Solving the Problems The present inventor has found that when an indoline derivative or a salt thereof and an oxidoreductase having a specific redox activity are used as an oxidation dye intermediate, an excellent dyeing effect can be obtained without reducing the feeling of hair. It has been found that a hair dye composition having the following formula is obtained. That is, the present invention
(A) General formula (1)

[0005]

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Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are
And independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms. )
Or an acid addition salt thereof represented by the formula: (B)
An object of the present invention is to provide a hair dye composition containing an enzyme capable of oxidizing 5,6-dihydroxyindoline and 2,5-diaminotoluene in the hair dye composition in an amount of 0.01 to 10 U / g.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The component (A) used in the present invention comprises:
An oxidation dye intermediate having a general formula (1)

[0008]

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And an acid addition salt thereof. Examples of the acid addition salt include hydrochloride, hydrobromide, sulfate, phosphate, acetate, propionate, lactate, citrate and the like. preferable.

The indoline represented by the general formula (1) is
5,6-dihydroxyindoline in which R ^{1 to} R ⁵ are all hydrogen, ^{1 in} which R ¹ is an alkyl group and R ^{2 to} R ⁵ are all hydrogen
-Alkyl-5,6-dihydroxyindoline is preferred.

Of these, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline hydrochloride,
6-Dihydroxyindoline hydrobromide is particularly preferred.

The component (A) in the hair dye composition of the present invention comprises:
Not less than 0.01% by weight (hereinafter simply referred to as%) and 1.0% or more
Less, preferably 0.05-0.8%, especially 0.05-
It is preferred to contain 0.5%.

The enzyme capable of oxidizing 5,6-dihydroxyindoline according to the present invention is defined as an enzyme capable of oxidizing 5,6-dihydroxyindoline using oxygen.
An enzyme having an ability to oxidatively polymerize dihydroxyindoline, wherein an increase in the amount of oxygen absorbed by oxidation of 5,6-dihydroxyindoline when the enzyme is added in an aqueous solution under the optimal conditions of the enzyme (method 1); or By measuring the increase in the amount of coloring due to oxidative polymerization of 5,6-dihydroxyindoline during the addition of the enzyme in the aqueous solution (method 2), it can be determined whether the enzyme is the target enzyme.

<Method 1> 30 mL of a reaction solution containing 10 mM 5,6-dihydroxyindoline, 25 mM sodium phosphate-pH 7 buffer and an enzyme was prepared, and a dissolved enzyme meter (for example, F102-5, manufactured by Iijima Electronics Co., Ltd.) ), The dissolved oxygen concentration (DO (ppm)) in the solution is measured, and the decrease is measured. The rate of decrease in DO before addition of the enzyme was used as a blank, and the enzyme activity (ppm /
Min or μmoel enzyme / min = U). At this time, if necessary, a suitable amount of a mediator such as NAD, NADP, or phenazine methosulfate can be added. In this method 1, an enzyme that consumes 0.5 ppm or more, preferably 2 ppm or more of oxygen per minute when an appropriate amount of enzyme is added can be used in the present invention. Such examples include oxygen reductases, especially laccase, tyrosinase and the like.

<Method 2> 3 mL of a reaction solution containing 1 to 5 mM 5,6-dihydroxyindoline, 25 mM sodium phosphate-pH 7 buffer and an appropriate amount of enzyme was prepared, and a 1 cm thick cell was used to form a dye. Absorbance at 350 nm
The increase in the optimum wavelength selected from 800 nm) is measured using a spectrophotometer. The rate of increase in absorbance before the addition of the enzyme is used as a blank, and the absorbance / minute is calculated from the difference from the rate after the addition of the enzyme. Furthermore, in the case of enzymes other than laccase and tyrosinase, an appropriate substrate other than dihydroxyindoline, such as hydrogen peroxide (e.g.
Uricase, glucose oxidase, and the like, uric acid and glucose can be added in appropriate amounts, respectively. In addition, if necessary, other oxidoreductases include NAD, NA
Mediators such as DP, phenazine methosulfate can be added. In this method, an enzyme that changes the absorbance at the optimum wavelength by 0.1 or more, preferably 0.3 or more at 5 minutes when an appropriate amount of enzyme is added can be used in the present invention. Examples of such enzymes include laccase, tyrosinase, peroxidase, uricase, glucose oxidase, diaphorase and the like.

As such enzymes, laccase and tyrosinase are particularly preferred.

Measurement of enzyme activity 3 mL of a reaction solution containing 10 mM 2,5-diaminotoluene, 25 mM sodium phosphate buffer (pH 7), 20% ethanol and an appropriate amount of enzyme was prepared, and a dye was formed using a 1 cm thick cell. The increase in absorbance (485 nm) in the reaction was measured using a spectrophotometer for 1 to 30 minutes (preferably 5 minutes) for 25 minutes.
Measure in ° C. The enzyme activity (U) is calculated from the change in absorbance at 485 nm (Abs) for 5 minutes according to the following equation. (Formula) Enzyme activity (U) = ((Abs × 3) /0.3) / 5

In the case of oxygen reductase other than laccase, 0.1% of hydrogen peroxide is added to an appropriate substrate of the enzyme, for example, peroxidase. In uricase, glucose oxidase and the like, uric acid and glucose
Add 〜１０10 mM. In addition, if necessary,
An appropriate amount of a mediator (a compound that mediates a redox reaction) such as (H), NADP (H), phenazine methosulfate, and dichlorophenolindophenol can also be added.

In this method, an enzyme having an activity of 0.1 U or more, preferably 0.3 U or more, more preferably 1 U or more per mg of the pure enzyme protein can be used in the present invention. Examples of such enzymes include laccase, peroxidase, uricase, glucose oxidase, diaphorase and the like.

In the present invention, the hair dye of the present invention is contained in the hair dye of the present invention in an amount of 0.01 to 10 U / g when used, based on the amount of the enzyme defined by the above method. Preferably, the enzyme is laccase and the amount of enzyme is 0.1-8 U
/ G, more preferably from the viewpoint of enzyme effect and economic efficiency.
It is 4-6 U / g.

Preferred laccases for the present invention are laccases derived from microorganisms (bacteria, molds, yeasts, fungi, etc.).
Its enzymatic activity (affinity for substrate (so-called Km
Value), reaction rate), productivity, economy and the like. As a specific example, Biochim. Biophys. Acta. 205
Vol. 35-47, or the same magazine, Vol. 1292, 303
Laccases as described on page -311 can be used. For example, Polyporus pins
itus), Rhizoctonia solan
i), Myceliophthora thora
ermophila), Citalidium thermohiram (Scytali)
Produced from microorganisms such as dium thermophilum). These may be used as crude enzymes or purified, or may be products produced by genetic engineering techniques.

The hair dye composition of the present invention comprises the indoline represented by the general formula (1) of the component (A) or an acid addition salt thereof and the 5,6-dihydroxyindoline and the 2,5- In addition to the essential component of an enzyme capable of oxidizing diaminotoluene, a compound (coupler) that changes the color tone of 5,6-dihydroxyindoline as a developing compound
May be contained.

3 mL of a reaction solution containing 1 to 5 mM dihydroxyindoline, 0.1 to 1 mM of the coupler test compound, 25 mM sodium phosphate-pH 7 buffer and an appropriate amount of laccase is prepared, and the mixture is prepared at 30 ° C. for an appropriate time (for example, 1 minute ~
24 hours) Keep warm. The absorption spectrum (350 nm to 800 nm) of the solution is measured using a spectrophotometer using a 1 cm thick cell. At this time, the measurement is performed using a solution to which no coupler compound is added as a blank. A compound having a difference between the sample and the blank spectrum is defined as a coupler compound. The difference between the spectra means a difference of 5 nm or more between the maximum or minimum absorption wavelength and an increase or decrease in absorbance at a specific wavelength (for example, 485 nm).

Compounds that change the color tone of 5,6-dihydroxyindoline include, for example, aminophenol derivatives, phenol derivatives, naphthalene derivatives, aniline derivatives, pyridine derivatives, “Standards for Quasi-Medical Products” (19).
Published in June 1991, Pharmaceutical Daily).

The pH of the hair dye composition of the present invention is 5,6-
PH at which an enzyme capable of oxidizing dihydroxyindoline and 2,5-diaminotoluene can exhibit enzymatic activity
The range of 4 to 9, especially 5 to 8, is preferred. This pH adjustment is generally used in cosmetics, for example, sodium hydroxide, alkaline agents such as monoethanolamine,
It is performed with an acid such as phosphoric acid and lactic acid.

The hair dye composition of the present invention is used by filling it into a container as a one-part or two-part type, and has the ability to oxidize 5,6-dihydroxyindoline and 2,5-diaminotoluene. Hair dye A containing enzyme, and 5,6-
It is preferable to use a two-part hair dyeing agent containing dihydroxyindoline and mix the two at the time of use. As a two-part system, in addition to mixing and discharging both in two containers, a method of discharging and mixing as a foam by passing through a mesh in the container, carbon dioxide gas as an injection gas,
An aerosol method using liquefied petroleum gas, dimethyl ether or the like and filling the pressure-resistant container is preferable.

[0027]

EXAMPLES Example 1 The hair dye compositions shown in Table 1 were prepared and subjected to the following hair dye test.

Hair dyeing test : 5 g of the hair dye composition was placed in a 7 cm square balance dish, and 1 g of a 10 cm long goat hair bundle, which had been preliminarily washed, was immersed in the dish at 85 ° rp at 30 ° C. for 30 minutes.
After shaking and staining with m, washing with water at 40 ° C. for 30 seconds, washing with a commercial shampoo for 15 seconds, washing with water at 40 ° C. for 30 seconds, rinsing with a commercial plain type rinse for 15 seconds, and drying with hot air using a dryer. Dyed, dried goat hair L,
The a and b values are measured using a color difference meter (Minolta Co., Ltd.
200), and ΔE was calculated using the average of the differences from the L, a, and b values before hair dyeing, ΔL, Δa, and Δb.

[0029]

[0030]

[Table 1]

The products of the present invention were all dyed, while the comparative products showed only slight dyeing.

Example 2 Laccase (from Myceliophthora thermophila) 10 U 2,5-dihydroxyindoline 0.1 g Polyoxyethylene (10) dodecyl ether 0.5 g Dipotassium phosphate 0.2 g Monosodium phosphate 0.1 g Glycerin 0 g ethanol 10.0 g xanthan gum 1.0 g organopolysiloxane 0.2 g methyl paraben 0.2 g fragrance 0.1 g purified water 100 g (adjusted to pH 7.0)

To 1 g of 10 cm long goat hair which has been pre-washed,
After applying 2 g of the hair dye composition and leaving it to stand at 40 ° C. for 30 minutes, washing, drying and the like were performed in the same manner as in Example 1. ΔE after repeating the above operation three times was 40. There was no difference in goat hair feel before and after dyeing.

[0034]

According to the present invention, it is possible to obtain a hair dye composition having excellent dyeability without causing damage to the hair such as split ends and cut hairs and without causing a decrease in the feel of the hair.

Claims (5)

[Claims] (A) General formula (1) (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms) or an acid addition salt thereof, and (B ) An enzyme capable of oxidizing 5,6-dihydroxyindoline and 2,5-diaminotoluene is used in a hair dye composition in an amount of 0.01 to 1;
A hair dye composition containing 0 U / g. 2. The hair dye composition according to claim 1, wherein R ² , R ³ , R ⁴ and R ⁵ are hydrogen. 3. The hair dye composition according to claim 1, wherein the acid of the acid addition salt is hydrochloric acid or hydrobromic acid. 4. The hair dye composition according to claim 1, wherein the component (B) is selected from laccase and tyrosinase. 5. A hair dyeing method using the hair dye composition according to claim 1.