JP2002012535A - Composition for bleaching melamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a melamine-bleaching composition which can be used for bleaching pigments in hair and skin and for bleaching pigments in molds. SOLUTION: This composition for bleaching the melamine, comprising (1) 0.0005 to 1 wt.% of a peroxidaze and/or laccase, (2) 0.0005 to 5 wt.% of a mediator compound (the mediator compound is ABTS (2,2'-azobis(3- ethylbenzothiazoline-6-sulfonic acid), HST (1-hydroxybenzotriazole), syringaldehyde, veratryl alcohol, sodium-phenolsulfonate, p-hydroxybenzylalcohol, p-hydroxybenzoic acid, p-hydroxycinnamic acid, p-acetamidophenol, o- acetamidophenol, p-iodophenol, 10-methylphenothiazine, 3,3',5,5'- tetramethylbenzidine or p-fumaric acid), and, if necessary, a specific surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a melanin bleaching composition having improved melanin bleaching action, which can be used for bleaching pigments on hair and skin and for bleaching mold pigments.

[0002]

2. Description of the Related Art Melanin is widely distributed not only in animals and plants, but also in microorganisms such as molds, such as skin and hair, and in nature. Melanin is converted from tyrosine to dopa and further to dopaquinone by the action of tyrosinase and further to indole-5,6-dihydroquinone,
Finally, these are brown or black dye compounds synthesized by non-enzymatic oxidative polymerization. Melanin, which is an oxidized polymer, is a hardly decomposable polymer compound that is insoluble or hardly soluble in water or an organic solvent and soluble in warm concentrated sulfuric acid or alkali. Therefore, a strong oxidizing agent or an alkaline agent is generally used for a hair bleaching agent for decolorizing melanin, a mold removing agent for a house, and the like.

[0003] The hair bleaching agent is mainly of a two-part type, in which one part containing an alkaline agent and two parts containing hydrogen peroxide are mixed immediately before use.
A high bleach for lightening hair further comprises an alkali agent and an oxidizing agent mixed with a persulfate as an oxidation promoter, and this type of bleaching power is very strong. However, since such a hair bleaching agent has a strong oxidizing effect, there is a problem that the hair is damaged. In recent years, measures such as compounding compounds that suppress or reduce such damage have been taken.

[0004] As a mold remover, those containing a chlorine-based or oxygen-based bleach as a main component have been used. However, those containing a chlorine-based bleach such as sodium hypochlorite as a main component have excellent bleaching power of mold dyes and excellent mold removal performance, but have a great risk of damaging eyes and skin, and chlorine. When using a strong odor, it is necessary to pay attention to sufficient ventilation, and there is a drawback that harmful chlorine gas may be generated when mixed with acidic products.

On the other hand, those containing an oxygen-based bleaching agent represented by hydrogen peroxide as a main component do not have a drawback of generating chlorine gas, but have a low decolorizing power against mold dye alone,
There is a problem that a satisfactory effect cannot be obtained. From this point of view, attempts have been made to develop a melanin decolorization method that is safe for the environment and the human body and mild for the living body, and several studies focused on microorganisms and enzyme reactions that proceed under mild conditions. Have been. Examples of such a method include a method using a microorganism exhibiting decolorizing and decomposing properties against melanin pigment (JP-A-6-199933, JP-A-7-19933).
No.-213294,), a combination of hydrogen peroxide and peroxidase (JP-A-7-157409, JP-A-7-165553), an oxidase that generates hydrogen peroxide, a substrate containing the oxidase and a peroxidase (JP-A-7-97597), those containing laccase (polyphenol oxidase) as a melanin decolorizing enzyme (JP-A-8-217659, JP-A-7-165)
553) and the like are known. However, since melanin is a hardly decomposable polymer compound, the reactivity of the enzyme itself to melanin is weak, and as a result, no satisfactory melanin decolorizing agent has been available.

[0006]

An object of the present invention is to provide a composition having a safe melanin decolorizing effect.

[0007]

The present inventors have made intensive studies to achieve the above object, and have found that (1) peroxidase and / or laccase, (2) a mediator compound, and if necessary, a specific surfactant. The present inventors have found that the melanin decolorizing effect can be significantly improved by combining the agents as compared with the case where the enzyme is used alone, and the present invention has been accomplished.

[0008]

BACKGROUND OF THE INVENTION The melanin decolorizer of the present invention comprises:
(1) peroxidase and / or laccase, (2)
A composition containing a mediator compound and, if necessary, a specific surfactant, and can be used in the field of decoloring or reducing melanin pigments. For example, hair pigments such as hair bleaching agents (hair bleaching agents), skin care fields such as whitening agents for skin spots, freckles, sunburn, etc., and mold pigments adhering and depositing in dwellings such as bathrooms and kitchens It can be used for house care such as decolorization.

[0009] The peroxidase of the component (1) used in the present invention is E. coli. C. It is an enzyme classified into 1.11.1.7. Although this enzyme is contained in many plant tissues, especially in horseradish and fig liquor trees, leukocytes,
Abundant in milk. It is also present in certain microorganisms, each with different properties. Generally, it is an enzyme that catalyzes the following reaction. In the present invention, it can be used regardless of its origin. H ₂ O ₂ + AH ₂ → 2H ₂ O + A Laccase is also available from E. coli. C. It is an enzyme classified into 1.10.3.2. As a typical reaction example, it is known that urushiol is oxidized by laccase in lacquer sap to form lacquer. Laccase is an enzyme that widely exists in many plants and microorganisms other than lacquer and catalyzes the oxidation reaction of aromatic compounds. In the present invention, it can be used regardless of its origin.

The amount of the peroxidase and laccase used in the present invention in the preparation depends on the form of the preparation, the frequency of use, the treatment time and the potency of the enzyme preparation, but is usually 0.0005 to 1% by mass ( %), Preferably 0.001 to 0.5%. 0.00
If it is less than 05%, a sufficient effect cannot be obtained, and even if it exceeds 1%, the effect corresponding to the increase in the added amount does not increase.

The mediator compound (2) used in the present invention must be a substance capable of oxidizing peroxidase or laccase, and the oxidized compound must be a compound capable of effectively oxidatively decomposing melanin. Specific examples of such compounds include ABTS
(2,2'-azobis (3-ethylbenzothiazoline-
6-sulfonic acid)), HBT (1-hydroxybenzotriazole), syringaldehyde, veratryl alcohol, sodium phenolsulfonate, p-hydroxybenzyl alcohol, p-hydroxybenzoic acid, p-
Hydroxycinnamic acid, p-acetamidophenol, o-
Acetamidophenol, p-iodophenol, 10
-Methylphenothiazine, 3,3 ', 5,5'-tetramethylbenzidine, p-coumaric acid, etc., preferably, ABTS, HBT, syringaldehyde, 10-methylphenothiazine, more preferably HBT, syringaldehyde Is good. Further, one of the above mediator compounds may be used alone or as a mixture of two or more. The compounding amount of the mediator compound of the present invention is preferably 0.0005 to 5% by mass, particularly preferably 0.001 to 0.5% by mass based on the total amount of the composition.

Surfactants used as necessary include nonionic, especially polyoxyethylene alkyl ether, fatty acid alkylolamide, or cationic or carboxylic acid type anions which do not adversely affect the enzyme activity. It is preferable to use one type of surfactant or a combination of two or more types. Specifically, polyoxyethylene stearyl or polyoxyethylene hydrogenated castor oil as an example of polyoxyethylene alkyl ether, coconut oil diethanolamide as an example of fatty acid alkylolamide, and stearyl methyl ammonium chloride as an example of cation type And distearyl dimethyl ammonium chloride.

The carboxylic acid type anion type includes C
In addition to saturated and unsaturated fatty acids of 12 to C18, potassium salts, sodium salts, tris, coconut oil fatty acids, hardened coconut oil fatty acids, palm oil fatty acids, hardened palm oil fatty acids, tallow fatty acids, hardened tallow fatty acids, etc. Fatty acid soaps such as ethanolamine salts and ammonium salts, alkyl ether carboxylates, N-acyl sarcosine salts, N
-Acyl β-alanine salt, N-acyl glutamate and the like. Of these, N-acylglutamic acid salts are preferred, and specific examples thereof include N-acylglutamic acid types such as N-coconut fatty acid acyl-L-glutamic acid triethanolamine, lauroyl-L-glutamic acid triethanolamine, and N-acylglutamic acid triethanolamine. Coconut oil fatty acid acyl-sodium L-glutamate, N-lauroyl-L
-Sodium glutamate, sodium N-myristoyl-L-glutamate, N-coconut fatty acid / hardened tallow fatty acid acyl-sodium L-glutamate, N-coconut fatty acid acyl-potassium L-glutamate and the like.

The concentration of the surfactant in the composition of the present invention is usually 0.05 to 5.0%, preferably 0.1 to 2.0%. It is usually liquid at the time of preparation, and may be used in the form of a foam by firing when used. In this case, a known method is employed as a means for foaming the composition. For example, a method in which the composition is foamed by passing the composition through a mesh in a container, or a general propellant, carbon dioxide, LPG In addition, a method of filling a pressure-resistant container into a foamed preparation, and the like can be employed.

When the melanin decolorizing composition of the present invention is used as a hair color decolorizing agent (hair bleaching agent),
It is preferable to incorporate a penetration enhancer in order to allow the active ingredient to penetrate inside the hair. N-alkylpyrrolidone such as N-methylpyrrolidone, which is conventionally known,
Aromatic alcohols such as benzyl alcohol and benzyloxyethanol, and lower alkylene carbonates are first mentioned. Otherwise, an alkyl glyceryl ether represented by the following general formula (1) can be used.

General formula (1)

Wherein R is (a) a hydrogen atom,
(B) a linear, branched or cyclic alkyl group, alkenyl group, allyl group having 1 to 10 carbon atoms, (c) aryl group, or (d) aryl group, hydroxyl group, ether group,
An amide group, a carbonyl group, and a straight-chain, branched or cyclic alkyl or alkenyl group having 1 to 10 carbon atoms having at least one substituent selected from the group consisting of a carboxyl group in a main chain or a side chain. is there.

Here, specific examples of the above R include, for example,
Isopropyl, allyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl, myristyl, pentadecyl, palmityl, stearyl, behenyl, isobutyl, t-
Butyl group, 1-methylheptyl group, 2-ethylhexyl group, hexenyl group, heptenyl group, octynyl group, nonenyl group, decenyl group, undecenyl group, dodenisel group,
Myristenyl group, pentadenisel group, palmitenyl group,
Oleyl group, linole group, rylenyl group, arachidyl group,
Examples thereof include a 2-ethylhexenyl group, a phenyl group, a 4-methylphenyl group, a benzyl group and a p-methoxybenzyl group. Among them, isopropyl group, allyl group, ethyl group, propyl group, methyl group and the like are particularly preferable. Is preferred. Specific examples of such compounds include compounds represented by the following structural formulas (1-1) to (1-4).

[0019]

Further, 1, represented by the following general formula (2):
It is also possible to use 3-dioxolan-2-one derivatives.

General formula (2)

However, in the above formula, R ₁ is a hydrogen atom or a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22, particularly 1 to 5 carbon atoms, or the above hydrocarbon group. Or a group in which an aromatic ring, a heterocyclic ring or a substituent thereof is bonded to a group represented by the formula: -Ra- (ORa) _n- ORb,-(RaO) _n- CO
Rb is a group represented by Rb, wherein Ra is the same or different alkylene group having 2 to 4 carbon atoms, and Rb is a saturated or unsaturated linear group having 1 to 22 carbon atoms, particularly 1 to 5 carbon atoms. , A branched chain, a cyclic hydrocarbon group, or a group in which an aromatic ring, a heterocyclic ring or a substituent thereof is bonded to the hydrocarbon group,
N representing the average number of moles of the alkylene oxide group is 0 to
It is an integer of 30, especially 0-20. R _{2 to} R ₆ are each a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic hydrocarbon group having 1 to 22, particularly 1 to 5 carbon atoms.

[0023] Here, specific examples of the example isopropyl groups of R _1, allyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Undecyl group,
Dodecyl, myristyl, pentadecyl, palmityl, stearyl, behenyl, isobutyl, t-
Butyl group, 1-methylheptyl group, 2-ethylhexyl group, hexenyl group, heptenyl group, octynyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group,
Myristenyl group, pentadecenyl group, palmitenyl group,
Oleyl group, linole group, linolenyl group, arachidyl group, 2-ethylhexenyl group, phenyl group, 4-methylphenyl group, benzyl group, p-methoxybenzyl group and the like, among which isopropyl group, Allyl, ethyl, propyl and the like are preferred.

Specific examples of Rb and R _{2 to} R ₆ include the same groups as those of R ₁ . Such compounds include 4-alkyloxymethyl-
Examples thereof include 1,3-dioxolan-2-one, and specifically, 4-allyloxymethyl-1,3-dioxolan-2.
-One, 4-propyloxymethyl-1,3-dioxolan-2-one and the like. The penetration enhancer is 1
These can be used alone or in combination of two or more. The amount of the penetration enhancer in the melanin decolorizing composition of the present invention is not particularly limited,
0.1 to 50%, preferably 3 to 3%, based on the whole composition
0%, more preferably 5 to 20%. If less than 0.1%, the effect of promoting penetration may not be sufficiently obtained,
If it is more than 50%, the odor may be too strong.

When used as a decolorizing agent for hair coloring (hair bleaching agent), a water-soluble polymer may be further added. The water-soluble polymer used here can be arbitrarily used as long as it is a component used in ordinary cosmetics, but is preferably cationized cellulose, hydroxypropylmethylcellulose, an amphoteric resin (Yukaformer), or vinyl ethyl ether maleate. It is preferable to use one or a combination of two or more components selected from a polymer, polyvinylpyrrolidone, an acrylic resin alkanolamine and the like. The concentration of the water-soluble polymer used in the present invention in the composition is usually 0.01 to 10.0.
%, Preferably 0.05 to 5.0%.
In the composition of the present invention, in addition to the above components, oil, lower alcohol, antioxidant, chelating agent, pH adjuster, preservative,
Raw materials such as fragrances can also be blended.

In the present invention, when laccase is used as an enzyme, the composition is prepared so that the oxygen concentration of the composition is 0.00015% by mass or less and the increase in the oxygen concentration during the storage period until use is suppressed. In addition, long-term stabilization of the composition is possible. As a means for preparing such a composition, a known method is employed. For example, as a method of lowering the oxygen concentration, a method of removing a dissolved gas in the composition by degassing or a method of passing an inert gas such as a nitrogen gas or an argon gas is used. By filling with such an inert gas, the oxygen concentration can be reduced. As a method of suppressing an increase in the oxygen concentration during the storage period until use, a method of filling and sealing a container made of a material having low oxygen permeability is used. Examples of the material having low oxygen permeability include glass, aluminum, acetal resin, polyethylene terephthalate resin, and vinyl chloride resin.

Further, by adding an antioxidant to the composition of the present invention, laccase can be further stored for a long period of time. Specific examples include ascorbic acid, tocopherol and derivatives thereof first. Other examples include plant extracts containing tannin, such as rosemary extract and ginkgo extract. The amount of these components added to the preparation is preferably 0.01 to 5%. More preferably, it is 0.005 to 0.2%. 0.
When the content is less than 01%, the effect of addition on stabilization is not seen and 5%
% Or more inhibits the action of laccase.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples.

[Examples 1 to 5, Comparative Examples 1 to 6] The melanin decolorizing effect of one of the products of the present invention peroxidase was examined. Peroxidase requires hydrogen peroxide to decolorize. During storage of the composition of the present invention, an aqueous solution of hydrogen peroxide was stored in a separate container, and when used, an equal amount of 1: 1 was mixed to obtain 1.0 mL. Uniform dispersion treatment of melanin (Sigma) solution with ultrasonic wave (10
(Second), 0.1 mL of the solution after the addition was added and mixed to start the reaction. 550 n of the solution after standing at 30 ° C. for 30 minutes
The absorbance at m was measured. The melanin decolorization rate (%) was calculated according to the following equation. Table 1 shows the results.

Formula: Melanin decolorization rate (%) = (1−absorbance after reaction with evaluation sample solution / absorbance after reaction with solution consisting of buffer only) × 100

[0030]

[Table 1]

As is evident from Table 1, the composition of the present invention can improve the melanin decolorizing effect by combining a mediator compound and peroxidase.

Examples 6-9, Comparative Examples 7-11 The melanin decolorizing effect of one laccase of the present invention was examined.
1.0 mL of the melanin decolorizing composition of the present invention shown in Table 2
Then, 0.1 mL of a solution prepared by subjecting a 0.1% synthetic melanin (Sigma) solution, which was a specimen, which had been prepared in advance, to an ultrasonic treatment (for 10 seconds) was added thereto, and the reaction was started. 30
After standing at 12 ° C. for 12 hours, the absorbance at 550 nm of the solution was measured. The melanin decolorization rate (%) was calculated from the relative value to the absorbance after the reaction with the solution consisting of the buffer alone. Table 2 shows the results.

[0033]

[Table 2]

As is clear from Table 2, it can be seen that the composition of the present invention can improve the melanin decolorizing effect by combining a mediator compound and laccase.

Examples 10 to 13 and Comparative Examples 12 to 15
The decolorizing effect of the product of the present invention on melanin granules contained in hair was examined. 200 mg of human hair was treated with 10 mL of the test hair treatment agent at 37 ° C. for 12 hours. The solution after the reaction was filtered with a cloth to remove the residue. Centrifuge the mouth liquid (1
(000 × 20 minutes, 4 ° C.), and the resulting precipitate was used as melanin granules. The melanin granules obtained by washing three times with distilled water were suspended in 30 mL of distilled water, and the suspension was used for evaluation of decolorization and decomposition. 1.0 mL of each composition shown in Table 3
To the mixture was added 0.1 mL of a melanin granule suspension to start a reaction. The reaction was carried out at 30 ° C. for 1 hour, the absorbance at 550 nm was measured, and the decolorization rate (%) of the melanin granules was calculated from the relative value to the absorbance after the reaction with a solution consisting of a buffer alone. Here, when peroxidase is used as the enzyme (Examples 10 and 11, Comparative Examples 12 to 1)
For 4), 0.02% aqueous hydrogen peroxide housed in a separate container was mixed and used in a 1: 1 equivalent. Table 3 shows the results.

[0036]

[0037]

[Table 3]

As is evident from Table 3, the use of the composition of the present invention can improve the decolorizing effect on melanin granules contained in hair.

Examples 14 to 17, Comparative Examples 16 to 21
The decolorizing effect of the product of the present invention on the mold dye was examined. Black mold (Cladosporium clados)
poroides) were cultured and applied to adjust the surface of the unglazed tile (2.5 × 2.5 cm). 0.5 mL (0.5 mg) of each composition shown in Table 4 was dropped on this tile, left for 1 hour, washed with water, dried at 30 ° C. for 2 hours, and decolorization was determined according to the following criteria. . Here, when peroxidase is used as an enzyme (Examples 14, 15 and Comparative Examples 16, 17, and 20), 0.02% hydrogen peroxide solution stored in a separate container is equivalent to 1: 1. And used as a mixture. Table 4 shows the results. Criteria for bleaching

[0040]

[Table 4]

As is clear from Table 4, the use of the composition of the present invention can exert a decolorizing effect on mold dyes.

Examples 18 to 21 and Comparative Examples 22 to 27
The decolorizing effect of the product of the present invention on black hair was examined. That is, after each composition shown in Table 5 was prepared, it was packed in a container having a mesh therein, and the foamed preparation 1 was prepared by passing through the mesh.
g is applied to human hair having a weight of 0.5 g and a length of 10 cm,
It was left at 30 ° C. for 1 hour. The black hair treated after standing was taken out, washed with water, shampooed and air-dried, and the bleaching property of the black hair was determined according to the following criteria. Here, when peroxidase is used as the enzyme (Examples 18, 1
9, Comparative Examples 22, 23, and 26) used a 0.02% aqueous hydrogen peroxide solution contained in a separate container in an equal amount of 1: 1. Table 5 shows the results. Judgment standard of bleaching ability ：: High bleaching effect was recognized △: Slight bleaching effect was recognized ×: No change

[0043]

[Table 5]

As is clear from Table 5, it is understood that the use of the composition of the present invention can exert a decolorizing effect on black hair.

Examples 22 and 23, Comparative Examples 28 and 29
In order to determine whether the melanin decolorizing effect was maintained when the product of the present invention using laccase as an enzyme was stored under deoxygenation conditions, the melanin decolorizing effect after storage was examined. That is, a composition excluding laccase is prepared, and the oxygen concentration in the composition is reduced to 0.00 by passing nitrogen gas.
015% or less. After laccase was further added to a predetermined concentration, the mixture was placed in a glass container and sealed with an aluminum cap. Liquefied petroleum gas (raw liquid: liquefied petroleum gas = 9.
5: 0.5), the internal gas was replaced, and stored at 40 ° C. for one month. 1 g of the foamed preparation after storage was applied to human black hair having a weight of 0.5 g and a length of 10 cm and left at 30 ° C. for 1 hour. The black hair treated after standing was taken out, washed with water, shampooed and air-dried, and the bleaching property of the black hair was determined according to the following criteria. Judgment standard of bleaching ability ：: High bleaching effect was recognized △: Slight bleaching effect was recognized ×: No change

[0046]

[Table 6]

As is clear from Table 6, the composition of the present invention using laccase as an enzyme can exert a melanin decolorizing effect even after storage at 40 ° C. for one month by deoxygenation. I understand.

[0048]

According to the present invention, there is provided a composition for decolorizing melanin, which comprises (1) a peroxidase and / or a laccase, and (2) a median compound, whereby the melanin can be effectively decolorized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/48 A61K 7/48 F term (Reference) 4C083 AB282 AC102 AC171 AC172 AC182 AC211 AC212 AC292 AC392 AC432 AC471 AC481 AC551 AC641 AC662 AC791 AC811 AC842 AC851 AC852 AC861 AD471 AD472 AD642 AD662 CC02 CC35 DD23 EE16 EE27

Claims (2)

[Claims] 1. A melanin decolorizing composition comprising (1) a peroxidase and / or a laccase, and (2) a mediator compound. 2. The method according to claim 1, wherein the mediator compound is ABTS (2,
2'-azobis (3-ethylbenzothiazoline-6-sulfonic acid)), HBT (1-hydroxybenzotriazole), syringaldehyde, veratryl alcohol,
Sodium phenolsulfonate, p-hydroxybenzyl alcohol, p-hydroxybenzoic acid, p-hydroxycinnamic acid, p-acetamidophenol, o-acetamidophenol, p-iodophenol, 10-methylphenothiazine, 3,3 ', 5 The melanin decolorizing composition according to claim 1, which is one or a mixture of two or more of 5'-tetramethylbenzidine and p-coumaric acid.