JP2022171545A - oxidative hair dye - Google Patents

Abstract

To provide an oxidative hair dye with which it is possible to improve destaining performance while maintaining hair dyeing performance, as well as improve a densely dyeing effect.SOLUTION: Provided is an oxidative hair dye containing (A) a coupler and comprising a first agent and a second agent. In the oxidative hair dye, the mass ratio (B/A) of (B) a dye intermediate to the (A) coupler is 0.4 or less, and the content of the (A) coupler is 0.3 mass% or more. The first agent and the second agent are applied to the hair separately.SELECTED DRAWING: None

Description

The present invention relates to oxidative hair dyes containing couplers.

Oxidative hair dyes are known which consist of a first part containing, for example, an alkaline agent and an oxidation dye, and a second part containing an oxidizing agent, such as hydrogen peroxide. The alkaline agent promotes the action of the oxidizing agent contained in the second agent, and also swells the hair to improve the penetration of the dye into the hair. The oxidizing agent decomposes the melanin pigment in the hair and forms an oxidation dye polymer inside the hair. After the alkaline agent is removed, the hair cuticle is closed and the oxidation dye polymer is enclosed inside the hair.

Since the oxidation dye polymer inside the hair does not decompose easily, the decolorization performance is low. It was necessary to destain using an agent. Furthermore, in some cases, a single destaining treatment cannot be sufficiently destained.

Conventionally, oxidative hair dyes are known that are used to re-dye (recolor) hair to a clear, bright tone by decomposing the dark-toned oxidation dye polymer inside the hair without destaining with a de-staining agent. It is For example, the oxidative hair dye disclosed in Patent Document 1 improves the recoloring performance by containing a diamine-based dye intermediate or the like as a main component of the dye.

WO2009/057228

An object of the present invention is to provide an oxidative hair dye that can improve the destaining performance and the deep dyeing property while maintaining the hair dyeing performance.

As a result of intensive studies on the above problems, the present inventors have found that, in an oxidative hair dye comprising a first agent and a second agent, the content of dye intermediates relative to the content of couplers is not more than a predetermined ratio, The present invention was completed by discovering that by separately applying the first agent and the second agent to the hair, it is possible to improve the destaining performance while maintaining the hair dyeing performance, and to further improve the deep dyeing property. let me

That is, the present invention provides (A) a coupler-containing oxidation hair dye comprising a first agent and a second agent, wherein the mass of the content of the dye intermediate (B) with respect to the content of the coupler (A) The ratio (B/A) is 0.4 or less, the content of the (A) coupler is 0.3% by mass or more, and the first agent and the second agent are separately applied to the hair. It is an oxidative hair dye characterized by:
According to this feature, the oxidative hair dye of the present invention can improve the destaining performance while maintaining the hair dyeing performance, and can further improve the deep dyeing property (the ability to deepen the color).

Furthermore, the oxidative hair dye of the present invention is an oxidative hair dye characterized by containing (C) a polymerization accelerator.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.

Further, the oxidative hair dye of the present invention is an oxidative hair dye characterized in that the coupler (A) contains (A-1) 2,4-diaminophenoxyethanol and/or a salt thereof.
According to this feature, the oxidative hair dye of the present invention can further improve the hair dyeing power.

In the hair dyeing method of the present invention, the content of (B) dye intermediate with respect to the content of (A) coupler in the oxidation hair dye comprising (A) a coupler and having a first agent and a second agent The mass ratio (B/A) of is 0.4 or less, the content of the (A) coupler is 0.3% by mass or more, and the first agent and the second agent are separately applied to the hair A hair dyeing method characterized by using an oxidative hair dye.
According to this feature, the hair dyeing method of the present invention can dye the hair darkly while maintaining the destaining performance.

According to the present invention, it is an object of the present invention to provide an oxidative hair dye that can improve the destaining performance and the deep dyeing property while maintaining the hair dyeing performance.

The present invention will be described including the best mode for carrying it out.
[Oxidative hair dye]
The oxidative hair dye of the present invention contains (A) a coupler and comprises a first agent and a second agent, wherein the content of (B) dye intermediate relative to the content of (A) coupler The mass ratio (B/A) of the amount is 0.4 or less, the content of the (A) coupler is 0.3% by mass or more, and the first agent and the second agent are separately applied to the hair It is an oxidative hair dye characterized by

Hair dyes are classified into temporary hair dyes, semi-permanent hair dyes, and permanent hair dyes based on the durability of the hair dyeing effect, ie, fastness. The oxidative hair dye of the present invention is a hair dye containing an oxidative dye and is classified as a permanent hair dye. The oxidative hair dye is a substance in which an oxidizing agent and an oxidative dye are distributed as separate agents, and the oxidative dye develops color inside the hair. The oxidation hair dye of the present invention comprises a first agent containing an oxidation dye and a second agent containing an oxidizing agent, and these agents are used separately. Here, "separately used" means applying the first agent to the hair and then applying the second agent to the hair, or applying the second agent to the hair and then applying the first agent to the hair. However, before applying to the hair, mix the first and second agents before use, and take the first and second agents on a comb or the like and comb on the hair. It does not include mixing and using the first agent and the second agent using, etc.

As described above, the oxidative hair dye is typically a two-agent type consisting of a first agent and a second agent, but is not limited to this, and each of the first agent and the second agent contains A part of the ingredients may be configured as a separate agent, and may be a multi-agent type consisting of three or more agents. For example, the first agent of a two-agent type is divided into two agents, one containing a coupler and an optional alkaline agent, and the other having a composition other than that, to constitute a three-agent oxidative hair dye. good too. In this case, emulsion stability is further improved. As means for applying the oxidative hair dye to the hair, it may be applied to the hair using an applicator such as a comb, brush, brush, or applicator. The oxidative hair dye may also be applied to the hair with gloved hands.

The form of each agent forming the oxidative hair dye of the present invention may be any form, and the dosage form at 25° C. is, for example, a liquid such as an aqueous solution or milky lotion, a gel, a foam, or a cream. , solid form, and the like. It can also be in the form of an aerosol or non-aerosol, and in the case of non-aerosol, various forms such as a squeeze foamer type and a pump foamer type can be used. For aerosols, known propellants and foaming agents can be applied. In the case of a solid dosage form, a dispersant may be blended.

Although the viscosity of the first agent is not particularly limited, it is preferably 10 to 100000 mPa·s. Although the viscosity of the second agent is not particularly limited, it is preferably 10 to 100000 mPa·s. The viscosity of the first agent and the second agent can be measured using a B-type viscometer such as a TVB-10 type viscometer, and a rotor suitable for each viscosity under the conditions of 25 ° C. and 1 minute can be measured using
The viscosity of the oxidative hair dye of the present invention is not particularly limited, but the viscosity at 25° C. is, for example, 1000 to 100000 mPa·s. From the viewpoint of suppressing dripping, the lower limit is preferably 2000 mPa·s or more, more preferably 5000 mPa·s or more, and still more preferably 10000 mPa·s or more. The upper limit is preferably 50,000 mPa·s or less, more preferably 40,000 mPa·s or less, and still more preferably 30,000 mPa·s or less, from the viewpoint of operability when applied to hair. The viscosity of the oxidative hair dye can be adjusted by adding an anionic surfactant, a cationic surfactant, or a thickening agent such as a water-soluble polymer. The mixed viscosity of the oxidative hair dye can be measured using a B-type viscometer such as a TVB-10 type viscometer, and measured at 25° C. for 1 minute using a rotor suitable for each viscosity. can be done.

Even if the oxidative hair dye is a composition of three or more formulations or a composition containing powdery agents, it is still included in the present invention as long as the effects of the present invention are exhibited.

Next, each component in the oxidative hair dye of the present invention will be described in detail. Unless otherwise specified, the content of each component is the content in the oxidative hair dye combined with each agent.

<(A) Coupler>
A coupler is a kind of oxidation dye. Oxidation dyes are classified as (A) couplers and (B) dye intermediates.

Couplers mainly include m-diamines, aminophenols and diphenols, and specific examples include resorcin, 5-amino-o-cresol, m-aminophenol, α-naphthol (1-naphthol). , 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N,N-diethyl -m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 3,3'-iminodiphenyl, tannic acid and salts thereof. Specific examples of salts include hydrochlorides, sulfates, and the like.

As couplers (A), 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5-(2-hydroxyethylamino)-2-ethylphenol and salts thereof are preferably used, and particularly preferably , from the viewpoint of hair dyeing power, (A-1) 2,4-diaminophenoxyethanol and/or a salt thereof.

One or more couplers can be selected and used depending on the desired hair color tone. The content thereof is 0.3% by mass or more as the total content of (A) coupler. The lower limit thereof is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more. is. (A) When the coupler content is 0.3% by mass or more, the hair dyeing power can be improved.

The upper limit of the content of coupler (A) is appropriately set, but the total content of coupler (A) is preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably It is 5% by mass or less, and more preferably 3.5% by mass or less. When the content of (A) coupler is 10% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (A) coupler is a salt, the content of the (A) coupler is the value in the desalted form.

<(A-1) 2,4-diaminophenoxyethanol and/or salts thereof>
(A-1) 2,4-diaminophenoxyethanol and/or its salt is a kind of coupler capable of developing color due to oxidative polymerization with an oxidizing agent.

The content of (A-1) 2,4-diaminophenoxyethanol and/or its salt is not particularly limited, but is, for example, 0.1% by mass to 5% by mass. The lower limit of the content is preferably 0.15% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.25% by mass or more. The upper limit of the content is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. When the content of (A-1) 2,4-diaminophenoxyethanol and/or its salt is 0.1% by mass or more, hair dyeing power can be improved. When (A-1) 2,4-diaminophenoxyethanol and/or its salt is a salt, its content is the value in its desalted form.

<(B) Dye Intermediate>
(B) The dye intermediate is a dye classified as an oxidation dye.

Dye intermediates are dye precursors, primarily o- or p-phenylenediamines or aminophenols, which are themselves usually colorless or weakly colored compounds. Specifically, p-phenylenediamine, o-phenylenediamine, N-phenyl-p-phenylenediamine, 4,4′-diaminodiphenylamine, p-aminophenol, o-aminophenol, p-methylaminophenol, 2- Hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylenediamine, 4-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol, p-toluylenediamine (toluene -2,5-diamine), 4,4′-diaminodiphenylamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine and salts thereof. Specific examples of salts include hydrochlorides, sulfates, and the like. One dye intermediate may be used alone, or two or more dye intermediates may be used in combination. The oxidative hair dye of the present invention, as dyes other than the specific examples of (A) couplers and (B) dye intermediates, is described in, for example, "Standards for Quasi-drug Ingredients" (published in June 2006, Yakuji Nippo Co., Ltd.). The listed oxidation dyes may be included as appropriate.

The mass ratio (B/A) of the content of the dye intermediate (B) to the content of the coupler (A) is 0.4 or less. It is more preferably 0.2 or less, still more preferably 0.15 or less, and even more preferably 0.1 or less. When the mass ratio (B/A) is 0.4 or less, destaining performance can be improved. When (A) the coupler and (B) the dye intermediate are salts, the content used for calculating the above mass ratio is the value of the desalted form of both (A) and (B).

(B) The upper limit of the content of the dye intermediate is appropriately set within the range of the mass ratio (B/A) of the above content, preferably 1% by mass or less, more preferably 0.5% by mass or less , more preferably 0.2% by mass or less. (B) When the content of the dye intermediate is 1% by mass or less, the destaining performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (B) dye intermediate is a salt, the content of the (B) dye intermediate is the value in the desalted form.

A polymer of dye intermediates, or a polymer of a dye intermediate and a coupler, has the characteristic that it is difficult to decompose with an alkaline agent or an oxidizing agent, so there was a problem that the hair could not be dyed with a bright color tone after the next time. . The oxidative hair dye of the present invention contains (B) a dye intermediate in a predetermined ratio or less with respect to (A) a coupler, thereby forming a polymer that is easily decomposed by an alkaline agent. It is excellent, and the influence on the hair color after the next time is reduced. As a result, various hair colors can be enjoyed without considering the next hair color.

Since the oxidative hair dye of the present invention contains a very small amount of dye intermediates, there is a possibility that it can be used by subjects who are allergic to specific dye intermediates, for example.

The oxidative hair dye of the present invention is applied to hair separately as a first agent and a second agent. "Separately" means applying the first agent and the second agent separately to the hair. Specifically, after applying the first agent to the hair, it is allowed to stand for a predetermined time, and then the second agent is applied to the hair. The order in which the first agent and the second agent are applied is not particularly limited, but it is preferable to first apply the first agent containing the alkaline agent to the hair. Since the hair expands due to the alkaline agent, the penetration of the dye and the oxidizing agent into the hair is promoted, and the color can be made darker (excellent deep dyeing property), thereby improving the hair dyeing power and fading. It can exhibit excellent effect in suppression.

The means for applying the first agent or the second agent to the hair is not particularly limited. can. Alternatively, the first agent or second agent may be attached or applied to the hair with a gloved hand. In addition, the first agent and the second agent in the oxidative hair dye of the present invention are used for the dyed part of the hair that has been dyed once and a certain period of time has passed, and the newly grown hair after the previous hair dyeing treatment. It may be applied without separately painting the part, or may be applied after separately painting the dyed part and the nascent part of the hair.

A period of time may or may not be provided between the treatments of the first agent and the second agent, but it is preferable to provide a period of time. The time between the application of the first agent and the application of the second agent is for allowing the alkaline agent to act on the hair to swell the hair. The time for leaving is appropriately designed according to the concentration of the alkaline agent and the like, but is preferably 1 to 60 minutes. The lower limit is more preferably 3 minutes or longer, and particularly preferably 5 minutes or longer. The upper limit is more preferably 45 minutes or less, particularly preferably 30 minutes or less.

Moreover, after applying the second agent to the hair, a treatment may be provided in which the hair is left for a predetermined period of time. This standing time is for oxidizing the oxidation dye to develop color. The time for leaving is appropriately designed according to the type of oxidation dye, the concentration of the oxidizing agent, etc., but is preferably 1 to 60 minutes. The lower limit is more preferably 3 minutes or longer, and particularly preferably 5 minutes or longer. The upper limit is more preferably 45 minutes or less, particularly preferably 30 minutes or less.

In the case of a multi-agent type consisting of three or more agents, it is preferable to provide a treatment for applying an agent such as a thickener to the hair, before applying the first agent to the hair or applying the first agent to the hair. It may be applied between the treatment of applying the second agent and the treatment of leaving it for a predetermined time after applying the second agent, and after the application, a treatment of leaving it for a predetermined time may be provided. Alternatively, the first agent and the agent such as the thickener may be mixed and applied to the hair, and then the second agent may be applied to the hair.

After applying the second agent to the hair and leaving it for a predetermined period of time, the oxidative hair dye may be rinsed off, or the hair may be treated with a treatment, conditioner, or the like.

<(C) Polymerization accelerator>
The oxidative hair dye of the present invention can contain (C) a polymerization accelerator. The oxidative hair dye contains an oxidative dye, and the oxidative dye is a dye that develops color by oxidative polymerization with an oxidizing agent. Therefore, it is possible to deepen the color (it is excellent in deep dyeing), which leads to an improvement in hair dyeing power. (C) Polymerization accelerators include, for example, iodine compounds and carbonates. (C) The polymerization accelerator is usually contained in the first part of the oxidative hair dye.

The lower limit of the content of the polymerization accelerator (C) in the oxidative hair dye of the present invention is set appropriately, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more. more preferably 0.01% by mass or more, still more preferably 0.015% by mass or more, and particularly preferably 0.02% by mass or more. (C) When the content of the polymerization accelerator is 0.001% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the polymerization accelerator (C) in the oxidative hair dye of the present invention is appropriately set, but is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably. is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. (C) When the content of the polymerization accelerator is 20% by mass or less, the destaining performance can be further improved.

In the oxidative hair dye of the present invention, the lower limit of the mass ratio (C/A) of the content of (C) the polymerization accelerator to the content of (A) the coupler is appropriately set, but is preferably 0.5. 001 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. When the mass ratio (C/A) is 0.001 or more, the hair dyeing power can be improved. The upper limit of the mass ratio (C/A) of the content of the (C) polymerization accelerator to the content of the (A) coupler is appropriately set, but is preferably 15 or less, more preferably 12.5 or less. and more preferably 10 or less. When the mass ratio (C/A) is 15 or less, the destaining performance can be improved. When the weights of (A) coupler and (C) polymerization accelerator are salts, the content used for calculating the above mass ratio is the value in the desalted form.

In the iodine compound, iodine constituting the iodine compound decomposes hydrogen peroxide to promote polymerization of the oxidation dye, thereby improving the hair dyeing power. The effect of the iodine compound on improving the hair dyeing power is exhibited more strongly when the blending amount of the dye intermediate (B) is small or when it is not blended. The iodine compound is usually contained in the first agent of the oxidation hair dye. Examples of iodine compounds include iodine (I), iodides with counter ions that are released in solubilizers, and compounds that release iodine during use. Specific examples of iodides include alkali metal salts of iodides such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide and silver iodide. In addition, a natural material containing iodine, for example, an extract containing iodide such as iodinated garlic extract may be applied. One iodine compound may be used alone, or two or more iodine compounds may be used in combination.

The lower limit of the content of the iodine compound in the oxidation hair dye of the present invention is appropriately set, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further It is preferably 0.01% by mass or more, still more preferably 0.015% by mass or more, and particularly preferably 0.02% by mass or more. When the content of the iodine compound is 0.001% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the iodine compound in the oxidative hair dye of the present invention is appropriately set, but is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass. %, more preferably 0.75% by mass or less, and particularly preferably 0.5% by mass or less. When the content of the iodine compound is 3% by mass or less, the destaining performance can be further improved.

Carbonates are compounds containing carbonate ions. Carbonates include, for example, sodium carbonate, ammonium carbonate, magnesium carbonate and the like. Ammonium carbonate is preferred. Carbonates also include carbamate ions, carbonate ions, hydrogen carbonate ions, and the like.

The lower limit of the carbonate content in the oxidative hair dye of the present invention is appropriately set, but is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and further It is preferably 0.5% by mass or more, still more preferably 0.75% by mass or more, and particularly preferably 1% by mass or more. When the carbonate content is 0.1% by mass or more, the hair dyeing power can be further improved.

The upper limit of the carbonate content in the oxidative hair dye of the present invention is appropriately set, but is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass. % or less, more preferably 5 mass % or less, and particularly preferably 3 mass % or less. When the carbonate content is 20% by mass or less, the destaining performance can be further improved. The content used for the carbonate is the value for the desalted form.

Carbamate, carbonate, bicarbonate ions may be added to the first part in the form of carbamates, carbonates, and bicarbonates with counterions liberated in the solubilizer. Specific examples of the carbamate include ammonium carbamate and the like, and specific examples of the hydrogencarbonate include sodium hydrogencarbonate and ammonium hydrogencarbonate.

The lower limit of the content of carbamate ions, carbonate ions or hydrogen carbonate ions in the oxidative hair dye of the present invention is appropriately set, but is preferably 0.1% by mass or more, more preferably 0.1% by mass or more. It is 25% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.75% by mass or more, and particularly preferably 1% by mass or more. When the content is 0.1% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of carbamate ions, carbonate ions, or bicarbonate ions in the oxidation hair dye of the present invention is appropriately set, but is preferably 20% by mass or less, more preferably 15% by mass or less. , more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the content is 20% by mass or less, the destaining performance can be further improved. In addition, content here shows the value in carbamate, ammonium carbonate, or ammonium hydrogencarbonate conversion.

When two or more kinds of carbamate ions, carbonate ions or hydrogen carbonate ions are contained in the oxidation hair dye of the present invention, the lower limit of the total content is appropriately set, but preferably 0.1 mass. % or more, more preferably 0.25% by mass or more, still more preferably 0.5% by mass or more, even more preferably 0.75% by mass or more, and particularly preferably 1% by mass or more be. When the total content is 0.1% by mass or more, the hair dyeing power can be further improved. On the other hand, the upper limit of the total content of them is set as appropriate, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more It is preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the total content is 20% by mass or less, the destaining performance can be further improved. In addition, content here shows the value in carbamate, ammonium carbonate, or ammonium hydrogencarbonate conversion.

[Other ingredients]
The oxidative hair dye of the present invention may contain the following components, if necessary, in addition to the above components.
Other components include, for example, oxidizing agents, alkaline agents, direct dyes, oily components, surfactants, polyhydric alcohols, ascorbic acid, antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, Sugars such as sorbitol and maltose, water-soluble polymers such as hydroxyethyl cellulose and carboxyvinyl polymer, polydimethyldimethylenepiperidinium chloride liquid (polydimethyldimethylenepyrrolidinium chloride liquid), diallyldimethylammonium chloride, hydroxyethylcellulose, etc. cationized water-soluble polymers, polyhydric alcohols such as polyethylene glycol and dipropylene glycol, chelating agents such as ethylenediaminehydroxyethyltriacetic acid trisodium dihydrate, hydroxyethanediphosphonate tetrasodium solution, inorganic salts such as sodium chloride, Ammonium sulfate, ammonium nitrate, ammonium acetate, citric acid, tartaric acid, lactic acid, malic acid, succinic acid, fumaric acid, maleic acid, pyrophosphate, gluconic acid, glucuronic acid, pH adjuster, hair growth ingredients, plant extract, crude drug extract, Amino acids/peptides, urea, vitamins, fragrances, ultraviolet absorbers, solubilizers, stabilizers, and the like.

<Oxidizing agent>
The oxidizing agent is a component contained in the second agent, and may be any substance having oxidizing power. The oxidizing agent has the action of oxidizing the oxidation dye to develop color and the action of decomposing melanin inside the hair. Specifically, for example, hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, potassium persulfate, sodium persulfate, peroxide Sodium, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, strontium peroxide, sulfate hydrogen peroxide adduct, phosphate hydrogen peroxide adduct, pyrophosphate hydrogen peroxide adduct , persulfates such as potassium persulfate and sodium persulfate, peracetic acid and its salts, performic acid and its salts, permanganates, bromate salts and the like. Among these, hydrogen peroxide is preferred. In addition, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate may be contained as oxidation aids.

The content of the oxidizing agent in the oxidative hair dye of the present invention is not particularly limited, but is, for example, 0.1 to 15% by mass, more preferably 1 to 9% by mass. When hydrogen peroxide is contained as an oxidizing agent, ethylene glycol phenyl ether (phenoxyethanol), hydroxyethane diphosphonic acid, phosphoric acid, citric acid, or a salt thereof, etc., should be blended as stabilizers to improve its stability. is preferred.

<Alkaline agent>
The alkaline agent has the effect of expanding the hair and promoting the penetration of dyes and oxidizing agents. Examples of alkaline agents include ammonia, alkanolamines, silicates, metasilicates, phosphates, sulfates, basic amino acids, chlorides, organic amines and hydroxides. Specifically, examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine, and examples of silicate include sodium silicate, potassium silicate, and the like. Examples of metasilicates include sodium metasilicate and potassium metasilicate. Phosphates include primary ammonium phosphate, secondary ammonium phosphate, disodium monohydrogen phosphate, trisodium phosphate, and diphosphate. Examples include ammonium hydrogen and diammonium hydrogen phosphate, examples of sulfates include ammonium sulfate, examples of basic amino acids include arginine, lysine and salts thereof, and examples of chlorides include ammonium chloride. Examples of organic amines include 2-amino-2-methyl-1-propanol (AMP) and 2-amino-2-methyl-1,3-propanediol, and hydroxides include calcium hydroxide, Magnesium hydroxide etc. are illustrated. Among these, ammonia and alkanolamine are preferred. The alkaline agent is usually contained in the first agent.

The content of the alkaline agent in the oxidative hair dye is not particularly limited, but the lower limit is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, and still more preferably 1% by mass. That's it. The upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.
The content of the alkaline agent in the first agent is not particularly limited, but the lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more. be. The upper limit is preferably 20% by mass or less, more preferably 14% by mass or less, and even more preferably 10% by mass or less.

<Direct dye>
Direct dyes are compounds that have a color and are dyes that adhere to or penetrate the hair to color it. Examples include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, and disperse dyes. These direct dyes may be blended singly or in combination.

Examples of the acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, Red No. 230 (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3, Green No. 204 , Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, Black No. 401, and the like.

The above basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17 , Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc. can be exemplified.

Examples of the natural dyes include gardenia pigments, turmeric pigments, annatto pigments, sodium copper chlorophyllin, paprika pigments, lac pigments, and henna.

Examples of the nitro dye include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and and the like can be exemplified.

The HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No.12, HC Blue No.13, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No. 11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No.15 and the like can be exemplified.

The disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and the like can be exemplified.

The content of the direct dye in the oxidative hair dye is not particularly limited, but is preferably 0.001 to 10% by mass. As a lower limit, it is more preferably 0.01% by mass or more. The upper limit is more preferably 5% by mass or less, and still more preferably 3% by mass or less.

<Oil component>
Examples of oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, and fluorine oils. One or two or more of these oily components can be selected and used. Hair dyeability can be improved by containing an oily component.

Examples of higher alcohols include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol, and isostearyl alcohol. alcohol, 2-octyldodecanol, decyltetradecanol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, ergosterol and the like. Among these, cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, arachyl alcohol, and behenyl alcohol are preferred from the viewpoint of emulsion stability and operability.

Fats and oils are triglycerides, triesters of fatty acids and glycerin. For example, olive oil, rosehip oil, camellia oil, shea butter, macadamia nut oil, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef tallow, cocoa butter, corn oil, peanut oil. oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, castor oil, linseed oil, coconut oil, mink oil, egg yolk oil and the like.

Waxes are esters of higher fatty acids and higher alcohols. Examples include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, wart wax, kapok wax, and shellac wax.

Hydrocarbons are compounds consisting of carbon and hydrogen. Examples include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, α-olefin oligomer, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, and turpentine oil. Among these, liquid paraffin and petrolatum are preferred from the viewpoint of emulsion stability and operability.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid. is mentioned.

Esters are compounds obtained by a dehydration reaction between fatty acids and alcohols. For example, diisopropyl adipate, 2-hexyldecyl adipate, isopropyl myristate, myristyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, diisopropyl sebacate, isopropyl palmitate, 2-ethylhexyl palmitate, Cetyl ethylhexanoate (cetyl 2-ethylhexanoate), butyl stearate, isocetyl isostearate, hexyl laurate, decyl oleate, fatty acid (C10-30) (cholesteryl/lanosteryl), lauryl lactate, octyldodecyl lactate, lanolin acetate , dipentaerythritol fatty acid esters, N-alkyl glycol monoisostearate, lanolin derivatives and the like.

Silicone oil is a synthetic polymer in which silicon and oxygen with organic groups are alternately linked by chemical bonds. For example, dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxy end groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, average Highly polymerized silicone having a degree of polymerization of 650 to 10000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like can be mentioned.

Among the above, amino-modified silicones include, for example, aminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane/dimethylsiloxane copolymer (INCI name: amodimethicone), Aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone) and the like.

The content of the oil component in the oxidative hair dye is not particularly limited, but is preferably 0.1 to 20% by mass. The lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit is more preferably 17% by mass or less, still more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less.

<Surfactant>
Surfactants include nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.
In the following description, POE indicates a polyoxyethylene chain, POP indicates a polyoxypropylene chain, and the numbers in parentheses following these indicate the number of added moles. Also, the numbers in parentheses following alkyl indicate the number of carbon atoms in the fatty acid chain.

Examples of nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE/POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, and polyglycerin fatty acid esters. monoglycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylpolyglucosides, and the like. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, and POE phytosterol.
The number of repeating units of POE and POP is, for example, 2 to 100, and any one can be used as long as it exhibits surface activity.

The content of the nonionic surfactant in the oxidative hair dye is not particularly limited, but is preferably 0.001 to 30% by mass. The lower limit is more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. is. The upper limit is more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

Examples of cationic surfactants include monoalkyl-type quaternary ammonium salts, dialkyl-type quaternary ammonium salts, trialkyl-type quaternary ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts. Alkyl quaternary ammonium salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, amine salts such as Arcobel-type tertiary amine salts, cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts salts, benzethonium chloride and the like.

From the viewpoint of formulation stability, alkyl quaternary ammonium salts are preferred, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts are more preferred, and monoalkyl quaternary ammonium salts are particularly preferred. be.

Monoalkyl-type quaternary ammonium salts include, for example, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharine chloride, Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl (28) trimethylammonium chloride, di-POE (2) oleylmethylammonium chloride, di-POE stearylmethylammonium chloride, POE (1) chloride POP(25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and the like. Particularly preferred are stearyltrimethylammonium chloride, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride and behenyltrimethylammonium chloride.

Examples of dialkyl-type quaternary ammonium salts include dialkyl(12-15) dimethylammonium chloride, dialkyl(12-18) dimethylammonium chloride, dialkyl(14-18) dimethylammonium chloride, dicocoyldimethylammonium chloride, and dicetyl chloride. dimethylammonium, distearyldimethylammonium chloride, isostearyllauryldimethylammonium chloride and the like.

The content of the cationic surfactant in the oxidative hair dye is not particularly limited, but is preferably 0.01 to 10% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 5% by mass or less, and still more preferably 3% by mass or less.

Examples of anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefinsulfonates, alkanesulfonates, and saturated or unsaturated fatty acid salts. , alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphoric acid mono- or diester type surfactants, and sulfosuccinates. Counter ions for the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.

More specifically, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, POE sodium lauryl ether sulfate, POE lauryl ether sulfate triethanolamine, POE Ammonium lauryl ether sulfate, POE sodium stearyl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecene sulfonate, sodium lauryl phosphate, POE lauryl ether - telluric acid and its salts, N-lauroyl glutamates (lauroyl sodium glutamate, etc.), N-lauroylmethyl-β-alanine salts, N-acylglycine salts, N-acylglutamate salts, higher fatty acids such as lauric acid, myristic acid and salts of these higher fatty acids, 1 or 2 More than one species can be used.

The content of the anionic surfactant in the oxidative hair dye is not particularly limited, but is preferably 0.01 to 5% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 3% by mass or less, and still more preferably 1.5% by mass or less.

Amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
Specific examples of amino acid type amphoteric surfactants include, for example, N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethyl Imidazolinium Betaine, Undecyl Hydroxyethylimidazolinium Betaine Sodium, Alkyldiaminoethylglycine Hydrochloride, N-Cocoate Acyl-N'-Carboxyethyl-N'-Hydroxyethylethylenediamine Sodium, N-Cocoate Acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, sodium lauryldiaminoethylglycinate, palm oil fatty acid acyl-N - glycine-type amphoteric surfactants such as sodium carboxyethyl-N-hydroxyethylethylenediamine; aminopropionic acid-type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, triethanolamine laurylaminopropionate; etc.
Specific examples of betaine-type amphoteric surfactants include, for example, coconut oil alkylbetaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm aminoacetate betaine type amphoteric surfactants such as oil fatty acid amidopropyl betaine, lauramidopropyl betaine, ricinoleic acid amidopropyl betaine, stearyldihydroxyethyl betaine; and sulfobetaine type amphoteric surfactants such as lauryl hydroxysulfobetaine. .

The content of the amphoteric surfactant in the oxidative hair dye is not particularly limited, but is preferably 0.001 to 5% by mass. The lower limit is more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more. The upper limit is more preferably 3% by mass or less, and still more preferably 2.5% by mass or less.

The total content of all surfactants in the oxidative hair dye is not particularly limited, but is preferably 0.01 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is more preferably 40% by mass or less, and even more preferably 30% by mass or less.

<Polyhydric alcohol>
The oxidative hair dye of the present invention may further contain a polyhydric alcohol. When containing a polyhydric alcohol, formulation stability can be improved. Polyhydric alcohols include, for example, glycol and glycerin. Glycols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, high polymer polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, 1,3-butylene glycol and the like. Glycerin includes, for example, glycerin, diglycerin, polyglycerin and the like. A single polyhydric alcohol may be used alone, or two or more polyhydric alcohols may be used in combination. From the viewpoint of formulation stability, polyethylene glycol is particularly preferred.

<Solubilizer>
A solubilizer is added, for example, when the dosage form is liquid. Examples of solubilizers used include, for example, water and organic solvents (solvents). Specific examples of organic solvents include ethanol, n-propanol, isopropanol, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anise alcohol, p-methylbenzyl alcohol, α-dimethylphenethyl alcohol, α-phenylethanol, ethylene glycol phenyl ether (phenoxyethanol), phenoxyisopropanol, 2-benzyloxyethanol, N-alkylpyrrolidone, alkylene carbonate, alkyl ether and the like. A single solubilizer may be used alone, or two or more solubilizers may be used in combination. Among these, water is preferably applied because of its excellent ability to dissolve other components in the first agent. When water is used as the solvent, the content of water in the mixture (content at the time of use) is preferably 40% by mass or more, more preferably 50% by mass or more.

<Water-soluble polymer>
The water-soluble polymer imparts moderate viscosity to the oxidative hair dye. Therefore, the oxidative hair dye may contain a water-soluble polymer within a range that does not impair the effects of the present invention. Examples of water-soluble polymers include natural polymers, semi-synthetic polymers, synthetic polymers, and inorganic polymers. Specific examples of natural polymers include guar gum, locust bean gum, quince seed, carrageenan, galactan, gum arabic, tragacanth gum, pectin, mannan, xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, dextrin, triglucopolysaccharide (pullulan) and the like.

Specific examples of semi-synthetic polymers include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxyethylcellulose dimethyldiallylammonium chloride, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, cationized cellulose, cationized guar gum, and starch phosphorus. acid esters, propylene glycol alginic acid esters, alginates, and the like.

Specific examples of synthetic polymers include polyvinylcaprolactam, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), vinylpyrrolidone-vinyl acetate (VP/VA) copolymer, polyvinyl butyral, polyvinyl methyl ether, carboxyvinyl polymer, polyvinyl Sodium acrylate, polyacrylamide, polyethylene oxide, ethylene oxide/propylene oxide block copolymer, acrylic acid/alkyl acrylate copolymer, polydimethyldimethylene pyrrolidinium chloride (polyquaternium-6) (Mercoat 100: manufactured by Merck) , a half ester of itaconic acid and polyoxyethylene (hereinafter referred to as "POE") alkyl ether, or an ester of methacrylic acid and POE alkyl ether, and at least one selected from acrylic acid, methacrylic acid and alkyl esters thereof and a copolymer consisting of a monomer. One water-soluble polymer may be used alone, or two or more water-soluble polymers may be used in combination.

The pH of the oxidative hair dye is preferably alkaline, for example, preferably 8.5 or higher, more preferably 8.75 or higher, and even more preferably 9.0 or higher. If the pH of the oxidative hair dye is 8.5 or higher, a more excellent hair dyeing effect can be exhibited.
The pH of the oxidative hair dye can be adjusted using an acid such as phosphoric acid or an alkali such as sodium hydroxide.
The pH of the oxidative hair dye of the present invention is the measured value in a 10% solution of a 1:1 mixture of the first part and the second part. As a measuring method, it can be measured using a pH meter such as pH-METER-22 manufactured by HORIBA.

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the configurations described in Examples, and the technical scope of the present invention is not limited by these Examples.

[Evaluation of oxidative hair dye]
(Preparation of oxidative hair dye)
As oxidative hair dyes, a cream-like first agent containing each component shown in Tables 1 to 5 and an emulsion-like second agent containing each component shown in Table 6 were each prepared according to a conventional method. A two-part oxidative hair dye was prepared. The numerical values in the columns indicating each component in each table below indicate the content of the component in that column, and the unit is % by mass. The notations (A) to (C) in the "Component" column in each table indicate compounds corresponding to the respective components (A) to (C) described in the claims and the specification of the present application.

The 2,4-diaminophenoxyethanol in the table below is obtained by neutralizing the raw material 2,4-diaminophenoxyethanol hydrochloride with NaOH as a pH adjuster. Since 2,4-diaminophenoxyethanol hydrochloride produces 2 mol of hydrochloric acid per 1 mol, it was neutralized by blending 2,4-diaminophenoxyethanol hydrochloride:NaOH=1:2 mol. That is, the first agent contains 2,4-diaminophenoxyethanol in a free form.

(Darkness, hair dyeing power and destaining performance)
For each example, 1.5 g of the first agent was applied to 1 g of a 10 cm-long evaluation white hair bundle sample (manufactured by Beaulux Co., Ltd.) (hereinafter simply referred to as hair bundle) using a brush. and left at 30° C. for 15 minutes. Subsequently, 1.5 g of the second agent was applied to the hair tress and allowed to stand at 30° C. for 25 minutes.
For each comparative example, the first agent and the second agent were mixed at a mass ratio of 1:1 to prepare a mixture of the oxidative hair dye of each comparative example. 3 g of the resulting mixture was applied to 1 g of hair tresses using a brush, and left at 30° C. for 40 minutes.
In each example and each comparative example, after standing, the oxidative hair dye adhering to the hair bundle was washed away with water, and the hair bundle was shampooed (Bigen Treatment Shampoo manufactured by Hoyu Co., Ltd.) twice and rinsed (Hoyu Co., Ltd.). Bigen Treatment Rinse) was applied once. Subsequently, the hair tresses were dried with warm air to obtain dyed hair tresses of each example.

The dyed hair tresses of each example were evaluated for deep dyeing and destaining performance on the day following the hair dyeing according to the methods described below.

(Evaluation method for deep dyeing)
Ten panelists visually observed the dyeing density of the dyed hair tresses of each example obtained as described above under a standard light source. In the visual evaluation, the degree of increase in dyeing density of each example was evaluated based on the corresponding comparative example according to the following evaluation criteria. The evaluation score of the oxidative hair dye used in each example was obtained by rounding off the average score of the 10 panelists. The results are shown in Tables 1 to 5 in the "Darkness" column. In the corresponding comparative example, the content of each component is the same as that of the example.
(Evaluation criteria for deep dyeing)
6: Significantly darker than the corresponding comparative example 5: Darker than the corresponding comparative example 4: Slightly darker than the corresponding comparative example 3: Equivalent to the corresponding comparative example 2: Lighter than the corresponding comparative example 1: Corresponding significantly thinner than the comparative example

(Method for evaluating hair dyeing power)
The effect of improving the hair dyeing power was evaluated. For the dyed hair tresses of Examples 1, 5, and 6 obtained as described above, 10 panelists visually observed the depth of dyeing under a standard light source, and the depth of dyeing of Comparative Example 1 was observed. was evaluated as follows. The evaluation score of the oxidative hair dye used in each example was obtained by rounding off the average score of the 10 panelists. The results are shown in the "hair dyeing power" column of Tables 1 to 5. If the result in the "Hair dyeing power" column is "-", the hair dyeing power has not been evaluated.
(Evaluation criteria for hair dyeing power)
6: Significantly darker than Comparative Example 1 5: Darker than Comparative Example 1 4: Slightly darker than Comparative Example 1 3: Equivalent to Comparative Example 1 2: Lighter than Comparative Example 1 1: Greater than Comparative Example 1 very thin

(Method for evaluating destaining performance)
The dyed hair tresses of each example obtained as described above are destained according to a conventional method using a more general decolorizing/destaining agent, "Lece Powder Bleach" (manufactured by Hoyu Co., Ltd.). A destained hair tress was obtained by carrying out.

Then, 10 panelists visually observed under a standard light source whether or not the dyeing tone of the dedyed hair tress was good by comparing it with the untreated white hair tress. did. The results of comparative observation with these hair tresses were combined to evaluate the destaining performance, and judgment was made according to the following criteria. "5 points: excellent destaining performance", "4 points: good destaining performance", "3 points: slightly good destaining performance", "2 points: slightly poor destaining performance", "1 point: Destaining performance is poor", and the average value was calculated from the scoring results of each panelist and evaluated according to the following criteria. The results are shown in the "Destaining Performance" column of Tables 1 to 5.
(Evaluation criteria for destaining performance)
6: Average value of 4.7 points or more (very excellent)
5: The average value is 4.0 or more and less than 4.7 points (excellent)
4: The average value is 3.3 points or more and less than 4.0 points (good)
3: The average score is 2.6 or more and less than 3.3 points (acceptable)
2: The average value is 1.9 points or more and less than 2.6 points (slightly poor)
1: The average value is less than 1.9 points (defective)

As shown in Tables 1 to 4, the oxidative hair dyes of the present invention according to the examples were evaluated to be 4 to 6 in dark dyeing property, showing excellent results in all the examples. In addition, the destaining performance was evaluated as 5 to 6, showing good results of "excellent" or better in all the examples. In other words, in the evaluation of deep dyeability and destaining performance, all the examples gave good results.

As shown in Tables 1 to 4, when the examples are compared with the corresponding comparative examples, the comparative examples differ from the examples in that the first agent and the second agent are applied simultaneously. It can be seen that in each example, the deep dyeing property is remarkably improved while the destaining performance is maintained.
Further, as shown in Table 5, a comparison of Comparative Examples 11-1 and 11-2 shows that the content of coupler (A) is less than 0.3% by mass in both cases, indicating that the oxidative dyeing hair of the present invention is used. The content of (A) coupler in the agent is not satisfied. In addition, in Comparative Example 11-1, the second agent was applied after applying the first agent, and in Comparative Example 11-2, the first agent and the second agent were applied at the same time. As described above, in the examples shown in Tables 1 to 3 and the corresponding comparative examples, the comparative examples in which the first agent and the second agent were applied at the same time resulted in inferior deep dyeing properties. I understand. However, it can be seen that there is no difference in deep dyeing between Comparative Examples 11-1 and 11-2. That is, in the oxidative hair dye of the present invention, when the content of (A) the coupler is 0.3% by mass or more, when the first agent and the second agent are separately applied, the first agent and the second agent are applied. It can be seen that the dyeing is better than applying at the same time.
Furthermore, a comparison of Comparative Examples 12-1 and 12-2 shows that the mass ratio (B/A) of the content of the dye intermediate (B) to the content of the coupler (A) is 0.4. and does not satisfy "(B/A) is 0.4 or less" in the oxidative hair dye of the present invention. In addition, in Comparative Example 12-1, the second agent was applied after applying the first agent, and in Comparative Example 12-2, the first agent and the second agent were applied at the same time. However, it can be seen that there is no difference in deep dyeing between Comparative Examples 12-1 and 12-2. That is, in the oxidation hair dye of the present invention, when the mass ratio (B/A) of the content of the dye intermediate (B) to the content of the coupler (A) is 0.4 or less, the first agent and the second agent It can be seen that applying the agents separately provides better dyeing than applying the first and second agents simultaneously.

When comparing Example 1, Example 5-1 and Example 6, Example 5-1 and Example 6 having (C) a polymerization accelerator are higher than Example 1 containing no (C) polymerization accelerator. It was found to be excellent in hair dyeing power.
Further, when comparing Examples 5-1, 6, 7, and 8, when the content of (C) the polymerization accelerator is increased, the degree of increase in density compared to the corresponding comparative example It can be seen that the deep dyeing property is more effective.

Comparing Examples 1, 3 and 4, Example 1 using 2,4-diaminophenoxyethanol as the (A) coupler shows a better result in deep dyeing. From this, it can be seen that 2,4-diaminophenoxyethanol and/or its salt is preferable as the (A) coupler.

When Example 5-1 and Example 5-2 are compared, Example 5-1 gives better results in terms of deep dyeing, so it is possible to apply the second agent after applying the first agent. It turns out to be preferable.

The oxidative hair dye of the present invention can be used as a hair dye for dyeing human body hair such as head hair, beard, eyebrows and shin hair. In addition, it may be used for dyeing body hair of animals such as pets.
The oxidative hair dye of the present invention can be used as a hair dye for coloring and a hair dye for self-coloring in beauty salons, barber shops, and the like.

Claims (4)

(A) In an oxidative hair dye containing a coupler and comprising a first agent and a second agent,
The mass ratio (B/A) of the content of the dye intermediate (B) to the content of the coupler (A) is 0.4 or less,
The content of the (A) coupler is 0.3% by mass or more,
An oxidative hair dye, wherein the first agent and the second agent are separately applied to the hair. 2. The oxidative hair dye according to claim 1, further comprising (C) a polymerization accelerator. 3. The oxidative hair dye according to claim 1, wherein the (A) coupler contains (A-1) 2,4-diaminophenoxyethanol and/or a salt thereof. A method of dyeing hair, comprising using the oxidative hair dye according to any one of claims 1 to 3.