JP2002255758A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair dye composition having excellent development of activity of an idoreductase and excellent dyeing property of the hair. SOLUTION: This hair dye composition contains 0.01-10 U, based on 1 g of the hair dye composition, of the enzyme capable of oxidizing 2,5- diaminotoluene and an oxidation dye intermediate in an amount to give a concentration in use of <100 mM.

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 having excellent oxidoreductase activity during hair dyeing.

[0002]

2. Description of the Related Art 2-4% by weight in the presence of an alkaline substance
(Hereinafter simply referred to as%) with hydrogen peroxide, paraphenylenediamine, 2,5-diaminotoluene, 1,3,3
Oxidizing an oxidation dye intermediate such as 5-triaminobenzene,
Hair dyeing is performed to dye the hair using the generated pigment.However, treatment with an alkaline substance or hydrogen peroxide causes damage to the hair, worsens the feel of the dyed hair, and causes split ends and cut hair. It may be. As a hair dyeing method that does not easily cause such damage to hair, a hair dyeing method using an oxidoreductase has been proposed. For example, a method of contacting an oxidase enzyme such as laccase, lactate oxidase, or aldehyde oxidase with an aromatic compound as a primary oxidation dye precursor to dye hair (JP-A-47-9933), a two-electron reduction using the enzyme as an acceptor Type oxidase, a donor for the oxidase different from the oxidation dye precursor, a hair dye containing an oxidation dye and a peroxidase (Japanese Patent Application Laid-Open No. 11-21215), and a hair dyeing composition containing a laccase (Japanese Patent Application Laid-Open No. 11-60454) Gazette).

[0003]

However, in these hair dyeing methods, the activity of the oxidoreductase used is not sufficiently exhibited, and the hair dyeability is insufficient. An object of the present invention is to provide a hair dye composition which is excellent in expressing the enzyme activity of oxidoreductase when dyeing hair and has good hair dyeability.

[0004]

Means for Solving the Problems In dyeing hair, the present inventors use an oxidoreductase having a specific enzymatic activity for a specific amount of an oxidation dye intermediate to thereby express the enzyme activity. And good hair dyeability were obtained. That is, the present invention provides an enzyme capable of oxidizing 2,5-diaminotoluene by using a hair dye composition 1
The present invention provides a hair dye composition containing 0.01 to 10 U per g, and an oxidation dye intermediate such that the concentration at the time of use is less than 100 mM, and a method for dyeing hair using the composition. is there.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of oxidoreductases that oxidize oxidation dye intermediates for dyeing hair include laccase, peroxidase, uricase, glucose oxidase, diaphorase, and NADH oxidase. The oxidoreductase used in the present invention includes 2,5-
An enzyme capable of sufficiently oxidizing diaminotoluene, which effectively oxidizes and polymerizes 2,5-diaminotoluene to increase hair dyeing. The activity of oxidoreductase can be measured by the following method. .

Method for measuring enzyme activity 1 mM 2,5-diaminotoluene and 1 mM resorcinol, 2 mM
3 mL of a reaction solution containing 5 mM phosphate-sodium buffer (pH 7) and an appropriate amount of oxidoreductase was prepared, and the increase in absorbance (506 nm) in the formation reaction of the dye was measured with a spectrophotometer using a 1 cm thick cell. Measure at 25 ° C. for 30 minutes (preferably 5 minutes). The enzyme activity (U) is calculated from the change in absorbance (Abs) at 506 nm for 5 minutes according to the following equation. (Formula) Enzyme activity (U) = ((Abs × 3) /0.915) / 5

In the case of oxidoreductases other than laccase, 0.1% of hydrogen peroxide is added to an appropriate substrate of the oxidoreductase, for example, peroxidase. Uricase,
In the case of glucose oxidase or the like, uric acid and glucose are added at 1 to 10 mM, respectively. Also, if necessary, N
An appropriate amount of a mediator (a compound that mediates a redox reaction) such as AD (H), NADP (H), phenazine methosulfate, and dichlorophenol indophenol can also be added.

In this method, an oxidoreductase 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 oxidoreductases 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 oxidoreductase is laccase, and the amount of the enzyme is 0.1.
It is 1 to 8 U / g, more preferably 0.4 to 6 U / g from the viewpoint of the effect and economy of the oxidoreductase.

Preferred laccases for the present invention include laccases other than those derived from plants, and include microorganisms (bacteria, fungi,
Laccases derived from yeast, fungi, etc.) are preferred in view of their oxidoreductase properties (affinity for a substrate (so-called Km value), reaction rate), productivity, economy and the like. Specific examples include Biochim. Biophys. Acta. 205, 35-47.
Or laccase as described in the same journal, Vol. 1292, pages 303-311. For example, Polyporus pinsitus, Rhizoctonia solani, Myceliophthora thermophila, Scytalidium thermohiram
m). These may be used as crude enzymes or purified, or may be products produced by genetic engineering techniques.

The enzyme capable of oxidizing 2,5-diaminotoluene used in the present invention has a Michaelis constant of Km
Is preferably 1 mM or less, preferably 0.1 μM to 1 mM, more preferably 1 μM to 0.8 mM, particularly preferably 1 μM to 0.5 mM. Here, Km is a reaction rate constant, which can be determined, for example, by the method described in “Tokyo Kagaku Dojin, Lecture on Biochemistry, 5 Enzyme Research Method (above)”.

The activity of the oxidative dye intermediate used in the present invention, which is used together with the enzyme capable of oxidizing 2,5-diaminotoluene to oxidize and polymerize to form a dye for dyeing hair, is measured by the following method. .

Activity of oxidation dye intermediate (1) : 30 mL of a reaction solution containing 10 mM of a test oxidation dye intermediate, 25 mM of sodium phosphate-pH 7 buffer and an oxidoreductase (eg, laccase) was prepared, and a dissolved oxygen meter was prepared. The dissolved oxygen concentration (DO (ppm)) in the solution is measured using (for example, Model F102-5, manufactured by Iijima Electric Industry Co., Ltd.), and the decrease is measured. The rate of decrease in DO before the addition of oxidoreductase was taken as a blank, and the enzyme activity (ppm /
Minute). In this method, an oxidation dye intermediate which consumes 0.3 ppm or more, preferably 1 ppm or more of oxygen per minute when an appropriate amount of oxidoreductase is added is preferable.

Activity of oxidation dye intermediate (2) : 1 mM test oxidation dye intermediate, 25 mM sodium phosphate-pH 7 buffer, and ability to oxidize 2,5-diaminotoluene used in combination with hair dyeing When 3 mL of the reaction solution containing the enzyme U is placed in a 1-cm thick cell, and the oxidative polymerization reaction of the oxidative dye intermediate is performed, 350 to 800 nm of the produced dye is obtained.
The change in the absorbance at the optimum wavelength in is measured based on the absorbance before adding the oxidoreductase. Where 2,5
If the enzyme capable of oxidizing diaminotoluene cannot directly oxidize the test oxidation dye intermediate, a substrate for the oxidoreductase, for example, hydrogen peroxide for peroxidase, urea for uricase; In the case of glucose oxidase, glucose and the like are added at 1 to 100 mM for measurement. In this method, an oxidation dye intermediate having a change in absorbance at an optimum wavelength of 0.1 or more, preferably 0.3 or more, particularly 0.5 or more in a reaction for 5 minutes is preferred.

The oxidation dye intermediate used in the present invention is:
In addition to 2,5-diaminotoluene, as the oxidation dye intermediate, one or more of phenylenediamines, aminophenols, diaminopyridines and the like, which are usually used, and salts thereof can be mentioned. The salts include hydrochloride, sulfate, acetate and the like. Among these, paraphenylenediamine, N, N-bis (2-hydroxyethyl)
-Paraphenylenediamine, N-phenyl-paraphenylenediamine, 4,4'-diaminodiphenylamine,
2-chloroparaphenylenediamine, N, N-dimethylparaphenylenediamine, paraaminophenol, 2,
6-Dichloroparaphenylenediamine, paraaminophenylsulfamic acid and salts thereof can also be used. In addition, phenol derivatives such as cresol and thymol, catechol derivatives such as catechol, guaiacol, vanillin, caffeic acid, indoline derivatives, indole derivatives, hydroquinone derivatives, resorcinol derivatives, triphenol derivatives such as pyrogallol and esters thereof, naphthalene Among naphthalene derivatives such as diols, any compound can be used as long as it is an enzyme capable of oxidizing 2,5-diaminotoluene used in the present invention as described above.

The oxidation dye intermediate used in the hair dye composition of the present invention is prepared for a usual desired time, ie, 5 to 60 hours.
The concentration at the time of use is less than 100 mM in terms of the hair dyeability within a minute, but is preferably 0.1 to 50 mM, more preferably 1 to 3
It is preferable that the hair dye composition is contained in the hair dye composition so as to be 0 mM. Here, the “concentration at the time of use” refers to the concentration in the agent in the case of a single agent, and the concentration after mixing two agents in the case of the two agent.

The hair dye composition of the present invention comprises
The components are preferably prepared so that they are preferably mixed immediately before or at the time of use. Hair dye A containing an enzyme capable of oxidizing 2,5-diaminotoluene, hair dye B containing an oxidation dye intermediate, and a hair dye A and hair dye B mixed in advance As the base in the case of the formula, benzyl alcohol, phenethyl alcohol, aromatic alcohols such as benzyloxyethanol, N-methylpyrrolidone, alkylpyrrolidones such as N-ethylpyrrolidone, ethylene carbonate, alkylene carbonates such as propylene carbonate, An aqueous medium containing lower alcohols such as ethyl alcohol and isopropyl alcohol can be used.

Caprase, which is a compound that changes the color of a dye formed by oxidative polymerization of an oxidation dye intermediate, may be appropriately contained. As a preferable coupler, for example, 3 mL of a reaction solution containing 0.2 mM 2,5-diaminotoluene, 1 mM test coupler, 25 mM sodium phosphate-pH 7 buffer and 1 U of laccase was reacted at 30 ° C. for 1 to 24 hours. Thereafter, the absorption spectrum at 350 to 800 nm is measured with a spectrophotometer in a 1 cm thick cell. The maximum or minimum absorption wavelength is 5 based on the case where no coupler is added.
nm or a specific wavelength (for example, 470
nm) are preferred.

The coupler is selected in relation to the oxidation dye intermediate. For example, aminophenol derivatives, phenol derivatives, naphthalene derivatives, aniline derivatives, pyridine derivatives, "Standards for Quasi-Medical Products" (issued in June 1991) , Pharmaceutical Daily) etc.

The pH of the hair dye composition of the present invention is 2,5-
The pH is preferably from 4 to 9, particularly preferably from 5 to 8, at which an enzyme capable of oxidizing diaminotoluene can exhibit the enzymatic activity. This pH adjustment is performed with an alkali agent such as sodium hydroxide and monoethanolamine, a buffer such as an acid such as phosphoric acid and lactic acid, and an amino acid such as an amino acid, which are generally used in cosmetics.

The hair dye composition of the present invention is used as a one-pack type or a two-pack type filled in a container, and the hair dye A containing an enzyme capable of oxidizing 2,5-diaminotoluene is used.
It is preferable to use a hair dyeing method in which a hair dye and a hair dye B agent containing an oxidation dye intermediate are mixed and used 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.

[0022]

EXAMPLES Examples 1 to 3 Hair dyeing test : 10 mL of goat hair 10 cm in length preliminarily washed with 5 mL of a hair dye composition placed in a 7 cm square balance dish
g bundle, soaked at 30 ° C. for 30 minutes at 85 rpm, washed with water at 40 ° C. for 30 seconds, and then washed with a commercial shampoo for 15 minutes.
The substrate was washed for 30 seconds, washed with water at 40 ° C. for 30 seconds, then rinsed with a commercially available plain type rinse for 15 seconds, and dried with hot air using a dryer. L, a, b values of dyed and dried goat hair,
It is measured using a color difference meter (color difference meter CR200 manufactured by Minolta Co., Ltd.), and the average value of the difference from the L, a, b values before hair dyeing, Δ
ΔE was calculated using L, Δa, and Δb.

Table 1 shows the evaluation results based on the following dyeing evaluation criteria. Dyeing evaluation: Evaluation ΔE value ○ Less than 40 to 50 Good dyeing △ Less than 30 to 40 Slight staining × Less than 30 Less dyeing

[0024]

[Table 1]

The hair dye compositions of the present invention were all evaluated for good hair dyeing.

Example 4 Hair dyes shown in Table 2 were prepared.

[0027]

[Table 2]

In both Formulations 1 and 2, good dyeing was obtained.

[0029]

EFFECT OF THE INVENTION The expression of oxidoreductase activity is excellent, and the hair has good dyeability.

Claims (3)

[Claims] 1. An enzyme capable of oxidizing 2,5-diaminotoluene is used in an amount of 0.01 to 10 per gram of a hair dye composition.
A hair dye composition comprising U and an oxidation dye intermediate such that the concentration at the time of use is less than 100 mM. 2. The hair dye composition according to claim 1, wherein the enzyme is a laccase other than a plant-derived enzyme, and has a Km value of 1 mM or less for 2,5-diaminotoluene. 3. An enzyme capable of oxidizing 2,5-diaminotoluene is used in an amount of 0.01 to 10 per gram of the hair dye composition.
A method of dyeing hair with a hair dye composition containing U and an oxidation dye intermediate such that the concentration at the time of use is less than 100 mM.