TW202404564A - Air oxidation hair dye - Google Patents

Abstract

The present invention provides a plural-agent-type air oxidation hair dye with which polymerization of a melanin precursor before use is prevented, and through simultaneous application of constituent agents, a sufficient hair-dyeing power is obtained. This air oxidation hair dye is a plural-agent-type air oxidation hair dye that contains an acidic agent containing a melanin precursor and serving as component (A) and an alkaline agent containing an alkaline compound and serving as component (B), the two agents being simultaneously applied to hair, and the total alkalinity when the two agents are mixed being 3.0 ml/g or below.

Description

Air oxidation hair dye

The present invention relates to an air oxidation type hair dye, which uses the precursor of melanin, a hair pigment, as an oxidative dye, and polymerizes and develops color through air oxidation. More specifically, the invention relates to a multi-dose hair dye. An air oxidation hair dye, in which a mixture of each agent is coated on the hair at the same time.

5,6-Dihydroxyindoline, 5,6-dihydroxyindoline, etc. are called melanin precursors, and they polymerize and develop color through air oxidation to become melanin. Utilizing this point, it is possible to provide an air-oxidative hair dye that does not require the addition of an oxidizing agent.

Patent Document 1 discloses a one-pack air oxidation hair dye composition, which contains an indoline derivative represented by a specific general formula or a salt thereof and an amine or a salt thereof as essential components. Patent Document 1 can provide a one-dose hair dye composition that can dye hair into a black color that is not reddish with excellent hair dyeing power by adjusting the pH of the composition to a range of 8.5 to 11.

Patent document 2 discloses an air oxidation type two-part hair dye, which includes an agent with a pH of 3 to 8 containing 5,6-dihydroxyindole or its salts and ascorbic acid or its salts, and an alkaline agent with a pH of 8 to 11's b dose. This 2-part hair dye uses a "two-time coating" method. First, apply Part A to the hair and leave it temporarily, then wipe it off and then apply Part B to the hair.

As suggested by Patent Documents 1 and 2, the oxidative polymerization reaction of the melanin precursor depends on a certain pH, and generally a range of about pH 8 to 11 is preferred.

Patent Document 3 discloses a one-dose air oxidation hair dye composition, in addition to melanin precursors such as 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid represented by a specific general formula In addition to materials, it uses specific reducing agents and metal salts as essential components. According to Patent Document 3, it is possible to change the dyed color without using a color-developing agent by using a melanin precursor and the above-mentioned reducing agent or metal salt.

Prior technical literature patent documents Patent Document 1: Japanese Patent Application Publication No. 2002-322037 Patent Document 2: Japanese Patent Application Publication No. 2018-52833 Patent Document 3: Japanese Patent Application Publication No. 2007-326810

Invent the problem to be solved Since the air oxidation type hair dye described in Patent Document 1 is a one-package formula, the operation during use is relatively simple. However, since the melanin precursor is pre-contained in the alkaline agent, even if a reducing agent such as ascorbic acid is mixed with the agent, the melanin precursor will still undergo oxidative polymerization to a certain extent during storage (before use), so there is a high risk. Molecular concerns. The polymerized melanin does not penetrate into the hair and is easily removed from the hair by washing with water after hair dyeing, so the hair dyeing power is not good.

On the other hand, for example, the air oxidation type hair dye described in Patent Document 2 has a two-pack formula. As long as the melanin precursor is contained in the acidic agent, the polymerization reaction of the melanin precursor (polymer) before use can be avoided. change). In addition, when using, as long as the acidic agent is applied to the hair for treatment, the acidic agent is wiped off from the surface of the hair, and then a separately prepared alkaline agent is applied to the hair, it will cause the oxidative polymerization reaction of the melanin precursor.

However, the two-part air oxidation hair dye described in Patent Document 2 uses "two coatings" of coating → wiping → coating, which imposes a heavy burden on the user both in terms of procedures and the time required. The reason why the troublesome secondary coating method is necessary is speculated below.

Specifically, if agents a and b described in Patent Document 2 are mixed in advance and then applied to the hair at the same time, the polymerization caused by the oxidative polymerization reaction of the melanin precursor will occur before the melanin precursor fully penetrates into the hair. In the process, melanin cannot be formed when the melanin precursor has been fully penetrated into the hair. Therefore, hair dyeing power will be insufficient. Even if Agent A and Agent B are not mixed in advance but are applied sequentially to the hair and mixed on the hair, the result is that Agent A and Agent B are applied at the same time, so the same result as above will still occur.

In other words, although the two-part air oxidation hair dye described in Patent Document 2 can avoid the shortcoming of "the polymerization of the melanin precursor before use" in the one-part hair dye described in Patent Document 1, it has the opposite effect. It is said that in order to obtain sufficient hair dyeing power, it is necessary to apply it twice inconveniently.

In this regard, the problem to be solved by the present invention is to constitute a multi-dose air oxidation hair dye that can prevent the polymerization of the melanin precursor before use, and at the same time, even if the various agents are applied to the hair at the same time, the Achieve satisfactory hair coloring power. In addition, an additional subject of the present invention is to suppress hair damage after hair dyeing, which meets the general needs of hair dyes, and to further improve the hair dyeing power of air oxidation-type hair dyes by blending appropriate additional ingredients. In addition, another subject of the present invention is to enrich the color changes in the air oxidation hair dye.

means to solve problems

(Structure of the first invention) The first invention of this case to solve the above-mentioned problems is an air oxidation type hair dye, which is a multi-agent hair dye in which each agent is applied to the hair at the same time. It is composed of acidic agent and alkaline agent, The above-mentioned acidic agent contains the following component (A), The above-mentioned alkaline agent contains the following component (B), When mixing each agent, the total alkalinity is below 3.0ml/g. (A) Ingredient: Melanin precursor (B) Ingredients: Alkaline compounds.

The so-called "total alkalinity" in the above-mentioned first invention is a parameter that refers to the amount of acid-consuming components in the sample or the amount of free [OH-] derived from alkali in the sample. Specifically, it is when neutralized with 0.1N hydrochloric acid. The amount of hydrochloric acid in mL units required to titrate 1 g of a mixed solution of each agent as a sample. Among them, the mixture of each agent may have multiple neutralization points depending on the type of alkaline compound or the combination of two or more alkaline compounds. In this case, the total alkalinity refers to the total alkalinity consumed up to the final neutralization point. The amount of the above hydrochloric acid in mL units. In addition, the so-called "simultaneous coating" refers to the state in which the acidic agent and the alkaline agent are applied to the hair together. Therefore, the two agents can be mixed in advance and then applied to the hair, or the two agents can be applied sequentially without mixing them first. On the hair. The basic difference between the present invention and the invention described in Patent Document 2 is that the present invention does not require wiping off the acidic agent (agent) before applying the alkaline agent (b agent).

In addition, "multi-dose hair dye" can be a two-dose hair dye, or a multi-dose hair dye. The two-dose hair dye is composed of an acidic agent containing component (A) and a component containing (A). B) component is composed of an alkaline agent; a multi-part hair dye includes one or more other agents that are mixed with the above two-part hair dye when applied to the hair at the same time. When applied to hair, unnecessary additional agents applied simultaneously with the above-mentioned acidic agent or alkaline agent may or may not be regarded as constituent elements of the hair dye of the first invention. The melanin precursor of component (A) also includes, in addition to 5,6-dihydroxyindole, 5,6-dihydroxyindoline or these -2-carboxylic acid derivatives listed in the second invention below. Various derivatives or salts thereof, which retain the property of being oxidized by air to cause oxidative polymerization and thus color development.

(Structure of the second invention) The second invention of the present invention is intended to solve the above-mentioned problems. In the above-mentioned first invention, the pH of the air-oxidative hair dye is in the range of 8 to 11 when the ingredients are mixed.

(Structure of the third invention) The third invention of the present invention is used to solve the above-mentioned problems. In the first invention or the second invention, at least one of the air oxidation hair dyes contains the following component (C), (C) Component: Polymer with cationic group.

Specifically, the air oxidation hair dye can be a two-part hair dye, or a multi-part hair dye, in which one or more of the two-part hair dyes contains component (C); multi-part hair dye The hair dye of the formula includes one or more other agents that are mixed with the above two-part hair dye when applied to the hair at the same time, and they may or may not contain the component (C).

(Structure of the 4th invention) The fourth invention of the present invention is used to solve the above-mentioned problems. In any one of the above-mentioned first to third inventions, the component (A) is selected from 5,6-dihydroxyindole and 5,6-dihydroxyindole-2. -Carboxylic acid, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and one or more of these salts.

(Structure of the fifth invention) In the fifth invention of the present invention to solve the above-mentioned problems, in any one of the above-mentioned first to fourth inventions, the component (B) contains carbonate and/or bicarbonate.

Invention effect According to the present invention, it is possible to prevent the polymerization of the melanin precursor before use and to obtain sufficient hair dyeing power by applying the respective agents simultaneously.

(1st Embodiment) The following describes embodiments of the present invention (including the best embodiments thereof). The technical scope of the present invention is not limited to the following embodiments.

[Air oxidation hair dye] The air-oxidative hair dye of the present invention uses the precursor of melanin, a hair pigment, and polymerizes and develops color through air oxidation. The hair dye is a multi-dose formula consisting of two or more formulations, and contains at least an acidic agent and an alkaline agent. The acidic agent contains the melanin precursor of component (A), and the alkaline agent contains the alkaline component of (B). compound. The acidic agent containing at least the melanin precursor of component (A) and the alkaline agent containing the basic compound of component (B) are applied to the hair after being mixed in a "simultaneous coating" manner, or they are applied sequentially without mixing. On the hair.

Furthermore, it is particularly preferred that one or more agents in the air oxidation hair dye contain a polymer having a cationic group as the component (C).

Hair dye is usually a two-part formula, but may also be a multi-part formula such as a three-part formula in which a third agent is added as an optional component. The third agent contains components that are not present in (A) and (B). ) appropriate composition of any of the ingredients. The mixing ratio of the alkaline agent and the acidic agent in the two-part hair dye can be set appropriately. For example, it can be set arbitrarily in the range of alkaline agent:acidic agent = 1:5 to 5:1, but the premise is that When each agent is mixed, the total alkalinity is 3.0 ml/g or less, and the pH is preferably in the range of 8 to 11. Specifically, for example, the mixing ratio can be 1:1, 1:1.5, 1.5:1, etc. .

The dosage form of each agent is not limited, but a liquid dosage form using water as a base is preferred. Part of each agent may be in the form of powder or granules. The liquid dosage form is not limited, and examples include soluble form (solution form), emulsion form, gel form, cream form, etc. The best ones are in the form of emulsions or creams. It can also be used by aerosol spraying into cream form or spraying together with propellant into bubble form.

When used as an aerosol-type air oxidation hair dye, the aerosol container is preferably one that can have a filling container for an acidic agent and a filling container for an alkaline agent, and can spray the acidic agent and the alkaline agent simultaneously.

Examples of the ejection mechanism of the aerosol container include a pair of aerosols that can be filled with a propellant such as dimethyl ether, liquefied petroleum gas, or nitrogen, and the contents (acidic agent, alkaline agent) can be ejected from the center by the pressure of the propellant. can, a member connecting the aerosol cans, an operating member for simultaneously squeezing the centers of a pair of aerosol cans from the outside, and a discharging member for discharging the contents discharged from the center to the outside. In addition, there is also a dual-structure aerosol container with separate filling and the same pressurization type, which is configured such that two inner bags filled with acidic agent and alkaline agent are housed in one aerosol container with a center filled with propellant. Inside the sol tank, the inner bags will be fixed to receive the same ejection pressure.

[pH and total alkalinity] The air oxidation type hair dye of the present invention is preferably in the range of pH 8 to 11, more preferably in the range of pH 9 to 10 when the ingredients are mixed (when used). The pH of the air-oxidative hair dye of the present invention when each agent is mixed is a value measured immediately after diluting the mixture of each agent to 10% with water. The measurement method can be measured using a pH meter such as pH-METER F-22 manufactured by HORIBA. If the pH during mixing is in the range of 8 to 11, it is less likely to cause the hair dyeing performance of the air-oxidative hair dye to be reduced due to too low a pH or to damage the hair due to too high a pH. From the viewpoint of the storage stability of the melanin precursor contained, the acidic agent preferably has a pH of about 3 to 7, more preferably a pH of about 3 to 5. The alkaline agent is preferably adjustable so that the pH of the hair dye falls within the range of 8 to 11 when each agent is mixed.

From the viewpoint of achieving high hair dyeing power, the total alkalinity of the hair dye when mixing each agent must be 3.0 ml/g or less, more preferably 2.5 ml/g or less, particularly preferably 2.0 ml/g or less. On the other hand, the lower limit of the total alkalinity is not limited, but it is preferably 0.4 ml/g or more, more preferably 0.8 ml/g or more, and particularly preferably 1.2 ml/g or more. As an effective means to maintain the pH in the range of 8 to 11 when mixing each agent and the total alkalinity of 3.0 ml/g or less, the carbonate and/or bicarbonate described below can be used as the basic compound of the component (B). .

[Important component of air oxidation hair dye]

[Ingredients inherent in acidic agents] The acidic agent contains the melanin precursor of component (A). The type of melanin precursor is not limited, and is preferably selected from 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, 5,6 - Dihydroxyindoline-2-carboxylic acid and one or more of these salts, preferably selected from the group consisting of 5,6-dihydroxyindoline-2-carboxylic acid and 5,6-dihydroxyindoline-2-carboxylic acid. More than one of these salts.

Examples of the above-mentioned salt include hydrochloride, hydrobromide, phosphate, sulfate, acetate, lactate, citrate, etc., among which hydrobromide, hydrochloride, phosphate, sulfate or lactic acid are preferred. salt.

The content of component (A) in the acidic agent is not limited, but when each agent is mixed, it is preferably 0.001 mass% or more, more preferably 0.01 mass% or more. In addition, the content of component (A) when each agent is mixed is preferably 2.0 mass% or less, more preferably 1.5 mass% or less. If the content of component (A) is 0.001% by mass or more when mixing each agent, the hair dyeing power will be excellent. If it is 2.0% by mass or less, the proportion of component (A) polymerizing outside the hair will be reduced, so it is easy to obtain a product corresponding to component (A). Hair dyeing effect based on the amount.

The acidic agent may contain a pH adjuster to adjust the pH to about 3 to 7, or may contain a reducing agent to improve the storage stability of component (A).

Various acids such as hydrochloric acid, orthophosphoric acid, phosphoric acid, tartaric acid, citric acid, and lactic acid can be used as the pH adjuster. In addition, bases such as sodium hydroxide, ammonia, and alkyl amines can also be used appropriately.

Examples of the reducing agent include ascorbic acid, sulfurous acid, L-cysteine, thioglycolic acid, and salts thereof. The content of the reducing agent in the acidic agent is not limited, but is preferably 0.001 mass% or more, particularly preferably 0.01 mass% or more. In addition, the content of the reducing agent in the acidic agent is preferably 1% by mass or less, particularly preferably 0.5% by mass or less.

The acidic agent of the hair dye of the present invention does not contain oxidizing agents such as hydrogen peroxide, sodium percarbonate, potassium perborate, ammonium persulfate, sodium peroxide, hydrogen peroxide adducts of sulfates, and ammonium persulfate. Even if an oxidizing agent is contained, its content in the acidic agent is 1% by mass or less, preferably 0.5% by mass or less.

[Ingredients inherent in alkaline agents] The alkaline agent contains the alkaline compound of component (B). The type of the alkaline compound is not limited. In addition to ammonia, carbonate and bicarbonate (bicarbonate) which are electrolyte alkaline compounds are preferably used. In addition, the hair dyeing power of these electrolyte alkaline compounds varies with the type of counter ion. From the perspective of hair dyeing power, metal salts are better than ammonium salts. Among them, the metal salts are preferably sodium salts, potassium salts, calcium salts, and magnesium salts. Salt, particularly preferably sodium salt and potassium salt.

When an alkaline compound, for example, ammonia is used together with carbonate and/or bicarbonate, it is possible to obtain particularly excellent hair dyeing power and hair damage prevention effects as described in the "Effects of the Fifth Invention" column below. And the effect of inhibiting ammonia odor. At this time, the total content of carbonate and/or bicarbonate is preferably 0.001 mass% or more, particularly preferably 0.01 mass% or more when each agent is mixed. On the other hand, the total content of carbonates and/or bicarbonates is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.8% by mass or less.

Preferred embodiments of the alkaline compound include the combined use of ammonia such as 28% ammonia water and sodium carbonate, the combined use of ammonia, sodium carbonate, and sodium bicarbonate (baking soda), the combined use of ammonia and ammonium bicarbonate, and the combined use of sodium carbonate and bicarbonate. Concomitant use of sodium. The content of the basic compound is not limited, but from the viewpoint of ensuring polymerization of the melanin precursor, it is preferably 0.01 mass% or more during agent mixing, more preferably 0.1 mass% or more, and particularly preferably 0.5 mass% or more. On the other hand, from the viewpoint of reducing hair damage during hair dyeing, the content of the basic compound is preferably 2.5 mass% or less when the agent is mixed, more preferably 2.0 mass% or less, and particularly preferably 1.8 mass% or less.

Examples of basic compounds other than ammonia, carbonate, and hydrogen carbonate include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine. Examples of the basic compound include silicate salts such as sodium silicate and potassium silicate. Examples of basic compounds include various metasilicates, phosphates, basic amino acids, hydroxides, and the like.

The alkaline agent may further contain direct dyes to enhance the hair dyeing effect. The types of direct dyes are not limited, and examples include acid dyes, nitro dyes, disperse dyes, basic dyes, and the like.

Examples of acid dyes include Black No. 401, Orange No. 205, Red No. 227, Red No. 106, Yellow No. 203, Blue No. 1, Purple No. 401, Acid Orange 3, etc. Examples of nitro dyes include 2-nitroterephthalene. Amine, 2-amino-6-chloro-4-nitrophenol, 4-nitro-o-phenylenediamine, HC cyan 2, HC orange 1, HC red 13, HC yellow 4, HC yellow 2, etc. Disperse dyes can Examples of the basic dye include Disperse Violet 1, Disperse Cyan 1, Disperse Black 9, etc. Examples of basic dyes include Alkaline Tea 16, Alkaline Tea 17, Basic Red 76, Basic Red 51, Basic Yellow 57, Basic Yellow 87, etc. Among them, from the viewpoint of hair dyeing power, it is preferable to contain one or more types selected from acid dyes and/or nitro dyes, and particularly preferred to contain one or more types selected from the group consisting of HC Red 13, HC Yellow 4, and HC Yellow 2. .

[Unlimited important ingredients contained in the medicine] The polymer containing the component (C) and having a cationic group is particularly preferably one or more of an acidic agent, an alkaline agent, or other agents mixed with these agents when used. Examples of the polymer having a cationic group include cationic polymers and amphoteric polymers.

Cationic polymers improve the feel of your hair. On the other hand, when combined with an amphoteric polymer such as Merquat 3330 (Polyquaternium-39), the effect of improving the touch feel is not as good as that of a cationic polymer such as Merquat 100 (Polyquaternium-6), but it improves hair dyeing power. The effect is excellent. When aiming to simultaneously improve hair dyeing power, the molecular weight of the cationic polymer is not limited, but is preferably 10,000 or more, more preferably 100,000 or more, and particularly preferably 140,000 or more. In addition, the cation density (meq/g) of the cationic polymer is not limited, but is preferably 25 or less, more preferably 15 or less, and particularly preferably 8 or less.

The reason why hair dyeing power can be improved by blending a cationic polymer with a molecular weight of 10,000 or more is presumed to be that when the polymer has a high degree of polymerization, it interferes with the polymerization of the melanin precursor, resulting in a bluish tint. Melanin has a low degree of polymerization, so it looks darker.

The reason why hair dyeing power can be improved by blending a cationic polymer with a cation density (meq/g) of 25 or less is presumed to be because theoretically, the lower the cationic charge density, the less likely it is to cause hair dyeing obstruction caused by ionic complexes.

From the viewpoint of hair dyeing power, the content ratio (A)/(C) between (C) the polymer having a cationic group and (A) the melanin precursor when mixing the air-oxidative hair dye of the present invention is preferable It is 0.001 or more, more preferably 0.1 or more, particularly preferably 5 or more. On the other hand, from the viewpoint of tactility, the content ratio (A)/(C) is preferably 25 or less, more preferably 20 or less, and particularly preferably 15 or less.

Examples of the cationic polymer include cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, diallyl quaternary ammonium salt/acrylamide copolymer, and quaternary polyvinylpyrrolidone derivatives. Polymers such as diallyldimethylammonium chloride, polydimethylmethylenepiperidinium chloride, etc. can be specifically mentioned.

The content of the polymer having a cationic group (C) when mixing the air oxidation hair dye is not limited, but it is preferably in the range of 0.01 to 5 mass %, and more preferably 0.05 to 2 mass % when each agent is mixed. within the range.

[Any component of air-oxidizing hair dye] The acidic agent, alkaline agent, or other agent constituting the air oxidation type hair dye may optionally contain the following higher alcohols, surfactants, oily components, water-soluble solvents, etc., respectively.

Examples of higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, cetearyl alcohol, oleyl alcohol, arachidyl alcohol, behenyl alcohol, octyldodecanol, and the like.

Examples of surfactants include cationic surfactants, nonionic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of cationic surfactants include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride (cetrimonium chloride), stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, and distearyldimethylammonium chloride. , cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, methyl chloride Acrylyloxyethyltrimethylammonium, and behenyltrimethylammonium methylsulfate.

Examples of the nonionic surfactant include polyoxyethylene (hereinafter referred to as "POE") cetyl ether, POE stearyl ether, POE sorbitol monooleate, POE methyl glucoside, etc., and examples of the cationic surfactant include alkanes. trimethylammonium or its salts, dialkyl dimethyl ammonium or its salts, ethyl sulfate lanolin fatty acid aminopropyl ethyl dimethyl ammonium, etc. Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates Salts, alkyl ether sulfate ester salts, etc. Examples of amphoteric surfactants include laurylamide propyl betaine, coconut oil fatty acid amide propyl betaine, and the like.

Among nonionic surfactants, POE addition-type nonionic surfactants with shorter ethylene oxide chains will improve the hair dyeing power of the hair dye of the present invention. Specifically, the molar number of addition of ethylene oxide is preferably 100 or less, more preferably 50 or less.

Examples of oily components include waxes, hydrocarbons, vegetable oils, animal oils, ester oils, fatty acids, and silicones.

Examples of waxes include beeswax, lanolin, candelilla wax, and carnauba wax. Examples of the hydrocarbon include paraffin, microcrystalline wax, petroleum jelly, light flowing isoparaffin, and flowing paraffin. Examples of vegetable oils include avocado oil, olive oil, sunflower oil, safflower oil, camellia oil, soybean oil, macadamia nut oil, and castor oil. Examples of animal oil include mink oil, sardine oil, cod liver oil, mutton fat, beef tallow, lard, egg yolk oil, etc.

Examples of the ester oil include diisopropyl adipate, isopropyl myristate, myristyl myristate, and cetyl caprylate. Examples of fatty acids include lauric acid, myristic acid, 12-hydroxystearic acid, and oleic acid. Examples of silicones include dimethyl polysiloxane (INCI name: dimethicone), dimethyl polysiloxane with a hydroxyl end group (INCI name: dimethiconol), methylphenyl polysiloxane, and modified polyether Silicone, amine modified silicone, etc.

Examples of water-soluble solvents include polyols, lower alcohols, and the like. Polyhydric alcohols and lower alcohols will enhance the dyeing power of air-oxidative hair dyes. Preferred polyols are propylene glycol, polyethylene glycol, and ethoxydiethylene glycol. Preferred lower alcohols are ethanol, and polyethylene glycol is particularly preferred.

In addition to any of the above ingredients, the air-oxidative hair dye of the present invention may also optionally contain preservatives such as sodium benzoate, organic solvents, sugars such as sorbitol and maltose, hydroxyethyl cellulose, carboxyvinyl polymers, etc. Water-soluble polymers, chelating agents such as tetrasodium hydroxyethane diphosphonate, inorganic salts such as sodium chloride, hair nourishing ingredients, plant extracts, crude drug extracts, amino acids, peptides, urea, vitamins, spices, and UV absorbers, etc.

The effect of the hair dye composition of this embodiment is demonstrated.

(1-1) (Effects of the first invention) According to the first invention, the air oxidation type hair dye is configured as a multi-pack type. Since the acidic agent contains the melanin precursor of the component (A), the melanin precursor does not undergo oxidative polymerization before use (during storage) and becomes a polymer. to improve the storage stability of melanin precursors. Therefore, there is no doubt that the dyeing power of the hair dye will be reduced.

Next, when using the hair dye, the acidic agent and the alkaline agent are applied simultaneously, thereby satisfying the conditions for initiating the oxidative polymerization reaction of the melanin precursor. In addition, if the total alkalinity when mixing each agent is 3.0 ml/g or less, the problem described in Patent Document 2 that "the oxidative polymerization reaction proceeds before the low molecular weight melanin precursor fully penetrates into the hair" will not occur. Because it is polymerized, it cannot be directly linked to hair dyeing power."

Specifically, for example, if ammonia is appropriately used together with carbonate or bicarbonate as an alkaline compound used as an alkaline agent, the pH and total alkalinity during mixing can be additionally adjusted. Through the trial implementation of these examples, the inventor of the present case found that: first, the oxidative polymerization reaction of the melanin precursor (the hair dyeing effect) basically depends on the total alkalinity (the amount of free [OH-] from the alkali) when the agents are mixed ) rather than depending on pH. The inventor of this case also found that: secondly, if the total alkalinity when mixing each agent is adjusted to less than 3.0ml/g, the oxidative polymerization reaction of the melanin precursor can be effectively delayed until the melanin precursor penetrates into the hair. happen.

The above-mentioned hair dyeing effect brought about by the air-oxidative hair dye of the present invention is not affected by the one-part air-oxidative hair dye of Patent Document 1 or the two-part formula of the first agent (acidic agent) and the second agent (alkali agent). The air oxidation type hair dye disclosed or suggested in Patent Document 2 uses "secondary coating" without mixing.

(1-2) (Effects of the second invention) According to the second invention, the pH in the range of 8 to 11 when mixing each agent is not a determining factor of the effect of the present invention on the hair dyeing power, but it is an effective condition for further improving the hair dyeing power and inhibiting hair damage after hair dyeing.

(1-3) (Effects of the third invention) According to the third invention, at least one agent in the air-oxidative hair dye of the first invention contains a polymer having a cationic group (for example, a cationic polymer or an amphoteric polymer) as the component (C), thereby further improving hair dyeing. The dyeing power of the agent. The reason for this is considered to be that the polymer having a cationic group has the property of being adsorbed on the surface of the anionic hair, so the melanin precursor or melanin is not easily detached from the hair. Among them, even if it is a polymer with a cationic group, amine-modified silicone has not been confirmed to have such an effect of improving hair dyeing power.

(1-4) (Effects of the 4th invention) Preferred examples of the melanin precursor include the four types of melanin precursors defined in the fourth invention or salts thereof. Among them, in relation to the effect of the first invention, one selected from the group consisting of 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and salts thereof is more preferred. above.

(1-5) (Effects of the fifth invention) The alkaline compound of component (B) preferably contains carbonate and/or bicarbonate. Carbonates such as sodium carbonate have the effect of increasing the total alkalinity and pH of the reaction system, and bicarbonates such as sodium bicarbonate have the effect of increasing the total alkalinity and lowering the pH of the reaction system. Therefore, carbonate and/or bicarbonate, for example, used together with ammonia, can easily adjust the pH and total alkalinity when mixing each agent, and ultimately can also achieve the effect of suppressing ammonia odor.

(Second Embodiment) The embodiments of the present invention will be described below, including the best embodiments. The technical scope of the present invention is not limited to the following embodiments.

[Air oxidation hair dye] The air-oxidative hair dye of the present invention uses the precursor of melanin, a hair pigment, and polymerizes and develops color through air oxidation. The hair dye is a multi-dose formula consisting of two or more components, and it contains at least an acidic agent and an alkaline agent. The acidic agent contains the melanin precursor of component (A) and the reducing agent of component (D). The alkaline agent Alkaline compound containing component (B). In addition, any one or more agents constituting the hair dye contain the direct dye of component (E). At least the above-mentioned acidic agent and alkaline agent and the agent containing component (E) are applied to the hair after being mixed in a "simultaneous coating" manner, or applied to the hair sequentially without mixing.

Hair dye is usually a two-part formula, but may also be a multi-part formula such as a three-part formula in which a third agent is added as an optional component. The third agent is not included in (A) or (B). , an appropriate composition of any one of the components (D) and (E). The mixing ratio of the alkaline agent and the acidic agent in the two-part hair dye can be set appropriately. For example, it can be set arbitrarily in the range of alkaline agent:acidic agent = 1:5 to 5:1, but the premise is that When each agent is mixed, the total alkalinity is 3.0 ml/g or less, and the pH is preferably in the range of 8 to 11. Specifically, for example, the mixing ratio can be 1:1, 1:1.5, 1.5:1, etc. .

The dosage form of each agent is not limited, but a liquid dosage form using water as a base is preferred. Part of each agent may be in the form of powder or granules. The liquid dosage form is not limited, and examples include soluble form (solution form), emulsion form, gel form, cream form, etc. The best ones are in the form of emulsions or creams. It can also be used by aerosol spraying into cream form or spraying together with propellant into bubble form.

When used as an aerosol-type air oxidation hair dye, the aerosol container is preferably one that can have a filling container for an acidic agent and a filling container for an alkaline agent, and can spray the acidic agent and the alkaline agent simultaneously. The discharge mechanism of the aerosol container is the same as that described in the first embodiment column.

[pH and total alkalinity] The air oxidation type hair dye of the present invention has a total alkalinity of 3.0 ml/g or less when each agent is mixed (when used). When each agent is mixed, it is preferably in the range of pH 8 to 11, more preferably in the range of pH 9 to 10. The pH of the air-oxidative hair dye of the present invention when each agent is mixed is a value measured immediately after diluting the mixture of each agent to 10% with water. The measurement method can be measured using a pH meter such as pH-METER F-22 manufactured by HORIBA. If the pH during mixing is in the range of 8 to 11, it is less likely to cause a decrease in the hair dyeing performance of the air-oxidative hair dye due to an excessively low pH or a decrease in the solubility of component (E) due to an excessively high pH, and further When the air-oxidative hair dye is stored or used in an aerosol form, component (E) is unlikely to precipitate when the air-oxidative hair dye is filled into an aerosol container.

From the viewpoint of the storage stability of the melanin precursor contained, the acidic agent preferably has a pH of about 3 to 7, more preferably about 3 to 5. The alkaline agent is preferably adjustable so that the pH of the hair dye falls within the range of 8 to 11 when each agent is mixed.

From the viewpoint of achieving high hair dyeing power, the total alkalinity of the hair dye when mixing each agent must be 3.0 ml/g or less, more preferably 2.5 ml/g or less, particularly preferably 2.0 ml/g or less. On the other hand, the lower limit of the total alkalinity is not limited, but when each agent is mixed, it is preferably 0.4 ml/g or more, more preferably 0.8 ml/g or more, and particularly preferably 1.2 ml/g or more.

As an effective means to maintain the pH in the range of 8 to 11 when mixing each agent and the total alkalinity of 3.0 ml/g or less, the carbonate and/or bicarbonate described below can be used as the basic compound of the component (B). .

[Ingredients inherent in acidic agents]

((A) ingredient) The acidic agent contains the melanin precursor of component (A) and the reducing agent of component (D). The type of melanin precursor is not limited, and is preferably selected from 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, 5,6 - Dihydroxyindoline-2-carboxylic acid and one or more of these salts, preferably selected from the group consisting of 5,6-dihydroxyindoline-2-carboxylic acid and 5,6-dihydroxyindoline-2-carboxylic acid. More than one of these salts.

Examples of the above-mentioned salt include hydrochloride, hydrobromide, phosphate, sulfate, acetate, lactate, citrate, etc., among which hydrochloride, hydrobromide, phosphate, sulfate or lactic acid are preferred. salt.

The content of component (A) is not limited, but when each agent is mixed, it is preferably 0.001 mass% or more, more preferably 0.01 mass% or more. In addition, when each agent is mixed, the content of component (A) is preferably 2.0 mass% or less, more preferably 1.5 mass% or less. If the content of component (A) is 0.001% by mass or more when mixing each agent, the hair dyeing power will be excellent. If it is 2.0% by mass or less, the proportion of component (A) polymerizing outside the hair will be reduced, so it is easy to obtain a product corresponding to component (A). Hair dyeing effect based on the amount.

((D) ingredient) In order to improve the storage stability of component (A), the acidic agent contains (D) reducing agent. Examples of the reducing agent include ascorbic acid, sulfurous acid, L-cysteine, thioglycolic acid, and salts thereof. The content of the reducing agent in the acidic agent is not limited, but is preferably 0.001 mass% or more, particularly preferably 0.01 mass% or more. In addition, the content of the reducing agent in the acidic agent is preferably 1% by mass or less, particularly preferably 0.5% by mass or less.

(Other ingredients in acidic agents) The acidic agent may contain a pH adjuster for adjusting the pH to about 3 to 7. Various acids such as hydrochloric acid, orthophosphoric acid, phosphoric acid, tartaric acid, citric acid, and lactic acid can be used as the pH adjuster. Other alkalis such as sodium hydroxide, ammonia, and alkyl amines can also be used appropriately.

The acidic agent of the hair dye of the present invention does not contain oxidizing agents such as hydrogen peroxide, sodium percarbonate, potassium perborate, ammonium persulfate, sodium peroxide, hydrogen peroxide adducts of sulfates, and ammonium persulfate. Even if an oxidizing agent is contained, its content in the acidic agent is 1% by mass or less, preferably 0.5% by mass or less.

[Ingredients inherent in alkaline agents]

((B)Component) The alkaline agent contains the alkaline compound of component (B). The type of alkaline compound is not limited. In addition to ammonia, carbonates such as sodium carbonate, ammonium carbonate, magnesium carbonate, and guanidine carbonate are preferably used, and hydrogen carbonates such as sodium bicarbonate (baking soda) are more preferably used. In addition, the hair dyeing power of these electrolyte alkaline compounds varies with the type of counter ion. From the perspective of hair dyeing power, metal salts are better than ammonium salts. Among them, the metal salts are preferably sodium salts, potassium salts, calcium salts, and magnesium salts. Salt, particularly preferably sodium salt and potassium salt.

The content of component (B) is not limited, but from the viewpoint of ensuring the polymerization of the melanin precursor, it is preferably 0.01 mass% or more when the agent is mixed, more preferably 0.1 mass% or more, and particularly preferably 0.5 mass% or more. . On the other hand, from the viewpoint of reducing hair damage during hair dyeing, the content of component (B) is preferably 2.5 mass% or less when the agent is mixed, more preferably 2.0 mass% or less, and particularly preferably 1.8 mass% or less. .

When an alkaline compound is used together with carbonate and/or bicarbonate, for example, ammonia can obtain particularly excellent hair dyeing power, hair damage prevention effects, and Suppresses ammonia odor.

Preferable embodiments of the alkaline compound include the combined use of ammonia such as 28% ammonia water and sodium carbonate, the combined use of ammonia, sodium carbonate, and sodium bicarbonate (baking soda), the combined use of ammonia and ammonium bicarbonate, and the combined use of sodium carbonate and sodium bicarbonate. The combined use, etc. The content of carbonate and bicarbonate is not limited, but when each agent is mixed, it is preferably 0.001 mass% or more, particularly preferably 0.01 mass% or more. On the other hand, the content of carbonate and bicarbonate is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.8% by mass or less.

Examples of basic compounds other than ammonia, carbonate, and bicarbonate (bicarbonate) include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine. Examples of the basic compound include silicate salts such as sodium silicate and potassium silicate. Examples of basic compounds include various metasilicates, phosphates, basic amino acids, hydroxides, and the like.

〔Other important ingredients〕

((E)INGREDIENT) Multi-pack air oxidation hair dye contains nonionic or anionic direct dye as component (E). Since cationic direct dyes may form ionic complexes with the indoline of (A) melanin precursor, they are not recommended, but they can still be used.

Nonionic nitro dyes or HC dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino- 5-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, picric acid, picric acid, and their salts, HC Blue No.2, HC Blue No.4, HC Blue No.5 , HC Blue No.6, HC Blue No.8, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No.12, HC Blue No.13, HC Blue No.14, HC Brown No.1, HC Brown No.2, HC Green No.1, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Orange No.5, HC Red No.1, HC Red No .3, HC Red No.7, HC Red No.8, HC Red No.9, 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.7, HC Yellow No.8, 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, etc.

In addition, nonionic 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, etc.

Anionic 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. 201, Red No. 227, Red No. 230 (1), red No. 230 (2), red No. 231, red No. 232, red No. 401, red No. 502, red No. 503, red No. 504, red No. 506, yellow No. 4, yellow No. 5, yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Yellow No. 402, Yellow No. 403 (1), Yellow No. 406, Yellow No. 407, Orange No. 205, Orange No. 207, Orange No. 402 , Green No. 3, Green No. 204, Green No. 205, Green No. 401, Green No. 402, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Black No. 401, Acid Blue No. 1, Acid Blue No. 3, Acid Blue No. 62, Acid Black No. 52, Acid Brown No. 13, Acid Green No. 50, Acid Orange No. 6, Acid Red No. 14, Acid Red No. 35, Acid Red No. 73, Acid Red No. 184, Melanin No. 1, etc.

From the viewpoint of stability, it is generally preferable that component (E) is contained in an acidic agent. However, in the present invention, since the acidic agent contains both (A) melanin precursor and (D) reducing agent, there is a concern that component (E) may be destabilized. This means that component (E) is preferably contained in an alkaline agent.

Therefore, for example, when the content of the reducing agent (D) in the acidic agent is relatively small, the component (E) can still be preferably contained in the acidic agent. Examples of the component (E) in this case include HC Blue 15, HC Blue 16, 2-Amino-6-Chloro-4-Nitrophenol, HC Yellow 4, HC Yellow 2, HC Red 13, N, N, which have excellent reducing agent resistance. '-Bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, HC Blue 2, HC Blue 11, etc., among which the best ones are HC Blue 15, HC Yellow 4, HC Yellow 2, HC Red 13 , 3-nitro-p-hydroxyethylaminophenol.

On the other hand, when there is a concern that the reducing agent may destabilize the component (E), it is preferable that the component (E) is contained in an alkaline agent. Examples of the component (E) in this case include HC Red 13, HC Yellow 4, HC Yellow 2, 2-Amino-6-Chloro-4-Nitrophenol, HC Blue 15, HC Blue 16, and HC Blue, which are excellent in resistance to alkaline compounds. 2. HC Blue 11, N, N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, red No. 106, red No. 27, orange No. 205, etc., among which the best one is HC Red 13. HC Yellow 4, HC Yellow 2, HC Blue 16, HC Blue 2, 3-nitro-p-hydroxyethylaminophenol.

The content of component (E) in the air oxidation hair dye is not limited as long as it is appropriately determined, but it is preferably 0.001 mass % or more when each agent is mixed, and more preferably 0.01 mass % or more. On the other hand, the content of component (E) in the air oxidation hair dye is preferably 0.5 mass% or less, more preferably 0.4 mass% or less.

When the content of component (E) is too high, precipitation of component (E) may occur during storage of air-oxidized hair dyes or when filling aerosol containers of air-oxidized hair dyes used in aerosols. . If component (E) precipitates, it may cause unexpected hair coloring or clogging of the internal structure of the aerosol container. On the other hand, the precipitation of component (E) can be suppressed by blending component (E), which increases solubility under alkaline conditions, into an alkaline agent. Such component (E) is preferably 3-nitro-p-hydroxyethylaminophenol.

((F)Component) The air oxidation hair dye can further contain an appropriate amount of component (F), which is one or more selected from the group consisting of methyl carbitol, ethyl carbitol, butyl carbitol or their salts, and/or octanol/ A solvent whose water partition coefficient (Log Pow) is smaller than water.

The octanol/water partition coefficient (Log Pow) is known as the formula Log[PO]/[PW] (where [PO] represents the molar number of the solvent in the octanol phase, and [PW] represents the molar number of the solvent in the water phase. (number of ears), which means the distribution coefficient of the sample molecules relative to the octanol phase and the aqueous phase. Solvents with an octanol/water partition coefficient (Log Pow) smaller than water include diethylene glycol, polyethylene glycol (PEG100, PEG200, PEG400, PEG600, PEG1000, PEG1540, etc.), glycerol, diglycerol, polyglycerol, etc.

If the air oxidation hair dye contains component (F), it can inhibit the precipitation of the nonionic or anionic direct dye of component (E). If the component (F) and the component (E) are contained in the same agent, the effect of inhibiting the desorption of the component (E) during storage of the air-oxidized hair dye can be obtained. In addition, it can suppress the precipitation of component (E) when filling the aerosol container of air-oxidized hair dye used in aerosol form. The Log Pow of this solvent is preferably in the range of -1.5 to -6.0, and most preferably in the range of -1.5 to -3.2. Specific examples of such solvents include glycerin (Log Pow=-1.65) and PEG 400 (Log Pow=-3.12).

The content of component (F) in the air-oxidative hair dye is not limited, but it is preferably 0.5% by mass or more in the agent containing component (E) or when the components of the air-oxidative hair dye are mixed, and more preferably 3 mass % or more, particularly preferably 5 mass % or more. On the other hand, the content of component (F) in the agent containing component (E) or when the components of the air oxidation hair dye are mixed is preferably 20 mass % or less, more preferably 17 mass % or less, and is particularly preferred. 15% by mass or less. If the content of component (F) is 0.5% by mass or more, precipitation of component (E) can be effectively suppressed.

[Any component of air-oxidizing hair dye] The acidic agent, alkaline agent, or other agent constituting the air oxidation type hair dye of the present invention may optionally contain solvents other than component (F), higher alcohols, surfactants, oily components, and the like.

Examples of solvents other than the component (F) include ethylene glycol, propylene glycol, polypropylene glycol, ethanol, n-propanol, isopropyl alcohol, methylcelusal, benzyl alcohol, phenethyl alcohol, and the like.

Specific examples of higher alcohols are the same as those listed in the first embodiment column.

Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Among them, the cationic surfactant is not suitable because it may form an ionic complex with the indoline of (A) the melanin precursor.

Specific examples of each surfactant are the same as those listed in the first embodiment column.

Among the nonionic surfactants, the POE addition type nonionic surfactant will improve the hair dyeing power of the hair dye of the present invention. The added mole number of ethylene oxide is preferably 100 or less, more preferably 50 or less.

Specific examples of the oily component are the same as those listed in the first embodiment column.

In addition to any of the above-mentioned components, the air-oxidative hair dye of the present invention may also optionally contain preservatives such as sodium benzoate, organic solvents such as ethanol, sugars such as sorbitol and maltose, hydroxyethyl cellulose, and carboxyvinyl polymer. Water-soluble polymers such as polydimethylmethylene piperidinium chloride, diallyldimethylammonium chloride, hydroxyethylcellulose and other cationized water-soluble polymers, hydroxyethane diphosphonic acid Tetrasodium and other chelating agents, sodium chloride and other inorganic salts, hair nourishing ingredients, plant extracts, herbal medicine extracts, amino acids, peptides, urea, vitamins, spices, UV absorbers, etc.

The effect of the hair dye composition of the second embodiment will be described.

(2-1) (Effects of Appendix 1) According to Appendix 1, the air oxidation hair dye is composed of a multi-pack formula. Since the acidic agent contains the melanin precursor of component (A), the melanin precursor will not undergo oxidative polymerization and polymerization before use (during storage). doubts, thereby improving the storage stability of melanin precursors. Therefore, there is no doubt that the dyeing power of the hair dye will be reduced.

In addition, since the acidic agent also contains (D) the reducing agent, the storage stability of the melanin precursor can be further improved. In addition, since one or more agents constituting the hair dye contain the direct dye of component (E), the color changes in the hair dye can be enriched. In addition, since component (E) is a nonionic or anionic direct dye, it will not become unstable even if it coexists with a reducing agent or an alkaline compound during storage or when each agent is mixed.

Next, when the hair dye is used, other agents such as acidic agents and alkaline agents are applied simultaneously, and if the total alkalinity is set to 3.0 ml/g or less, the "low molecular weight problem" described in Patent Document 2 will not occur. "The melanin precursor will undergo polymerization due to oxidative polymerization before it fully penetrates into the hair, so it cannot be directly linked to hair dyeing power."

Specifically, for example, if ammonia is appropriately used together with carbonate or bicarbonate as an alkaline compound used as an alkaline agent, the pH and total alkalinity during mixing can be additionally adjusted. Through the trial of these examples, the inventor of the present case found that: first, the oxidative polymerization reaction of the melanin precursor (hair dyeing effect) basically depends on the total alkalinity (the amount of free [OH-] from the alkali) when the agents are mixed ) rather than depending on pH. The inventor of this case also found that: secondly, if the total alkalinity when mixing each agent is adjusted to less than 3.0ml/g, the oxidative polymerization reaction of the melanin precursor can be effectively delayed until the melanin precursor penetrates into the hair. happen.

The above-mentioned hair dyeing effect brought about by the air-oxidative hair dye of the present invention is not affected by the one-part air-oxidative hair dye of Patent Document 1 or the two-part formula of the first agent (acidic agent) and the second agent (alkali agent). The air oxidation type hair dye disclosed or suggested in Patent Document 2 uses "secondary coating" without mixing.

It is preferable if the pH when mixing each agent is in the range of about 8 to 11 because it can effectively suppress hair damage after hair dyeing.

(2-2) (Effects of Appendix 2) Preferably, the melanin precursors include the two types of melanin precursors defined in Appendix 2 or their salts.

(2-3) (Effects of Appendix 3) The alkaline compound of component (C) preferably contains carbonate and/or bicarbonate. Carbonates such as sodium carbonate have the effect of increasing the total alkalinity and pH of the reaction system, and bicarbonates such as sodium bicarbonate have the effect of increasing the alkalinity and lowering the pH of the reaction system. Therefore, carbonate and/or bicarbonate, for example, used together with ammonia, can easily adjust the pH and total alkalinity when mixing each agent, and ultimately can also achieve the effect of suppressing ammonia odor.

(2-4) (Effects of Appendix 4) If the air-oxidized hair dye contains component (F), it can inhibit the precipitation of component (E) during storage of the air-oxidized hair dye. In addition, the air-oxidized hair dye used in an aerosol type can be inhibited from being exposed to the aerosol container. Precipitation of component (E) before filling, after filling or during filling.

Example

Examples of the present invention and corresponding comparative examples will be described below. The technical scope of the present invention is not limited to these Examples and Comparative Examples.

(Test example 1)

[Preparation of air oxidation hair dye] All the acidic agents and alkaline agents of the two-part air oxidation hair dyes of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-2 shown in Table 1 and Table 2 were prepared according to common methods. Creamy. The "common base" indicated by the composition of the acidic agent and alkaline agent in each Example and each Comparative Example is a base with the composition shown in Table 3.

Among the components shown in Tables 1 to 2, those corresponding to the (A) component, (B) component, (C) component, and (D) component of this embodiment are marked as "A" in the left column of the component name. , "B", "C", "D". "Dihydroxyindoline HBr" in the ingredient name column indicates the hydrobromide of dihydroxyindoline. In addition, the numerical value of each component in the table indicates the content of the component in mass % units in the acidic agent or the alkaline agent.

As shown in the "Mixing Ratio" column shown in Tables 1 and 2, the acidic agent and alkaline agent of each embodiment and each comparative example are mixed in a mass ratio of 1:1 and are applied to hair. The item "A/C" shown in Tables 1 and 2 means the mass ratio of the content of component (A) to the content of component (C) when the acidic agent and alkaline agent of each example and each comparative example are mixed. Therefore, for example, A/C in Example 1 is 1.5/(0.1+0.1)=7.5.

When mixing the acidic agent and alkaline agent of each Example and Comparative Example, a part of the mixture was used to measure the total alkalinity (ml/g) and pH. These measurement results are shown in the "Total alkalinity during mixing [ml/g]" and "PH during mixing" columns of Table 1 and Table 2.

[Evaluation of air oxidation hair dye]

Evaluation of hair dyeing power The acidic agent and alkaline agent of each Example and each Comparative Example were mixed at a mass ratio of 1:1 immediately before the evaluation, and 1 g of the mixed composition was applied to a 10 cm long white hair tube made by Beaulax Co., Ltd. with a brush. Apply evenly to 1 g of sample bundle. The coated hair bundle sample was placed in a constant temperature bath at 30° C. for 10 minutes, and then washed with water. The washed hair bundle sample was dried with warm air to obtain a hair bundle sample for evaluation.

The dyeing state of the hair bundle samples for evaluation in each Example and each Comparative Example was evaluated by 10 trained specialized sensory examiners visually scoring the hair dyeing power based on the following five-step evaluation standard. Each sensory examiner refers to a sample of the dyed hair bundle sample specifically showing the five-step evaluation criteria during evaluation. For each Example and each Comparative Example, the average value of the scores of 10 sensory examiners was used, and when there was a numerical value below the decimal point, the score was determined by rounding off the value.

5: Very high hair dyeing power 4: High hair dyeing power 3: Medium hair dyeing power 2: Low hair dyeing power 1: Hair dyeing power is very low

The evaluation results of each Example and each Comparative Example are shown in the "Hair Dyeing Power" column of Tables 1 and 2.

Evaluation of the feel of hair after treatment The acidic agent and alkaline agent of each Example and each Comparative Example were mixed at a mass ratio of 1:1 immediately before the evaluation, and the above mixture with the same weight as the weight of the hair bundle was brushed on a 30cm long hair made by Beaulax Co., Ltd. White hair strand swatches are evenly coated. The coated hair bundle sample was placed in a constant temperature bath at 30° C. for 10 minutes, and then washed with water. The washed hair bundle sample was dried with warm air to obtain a hair bundle sample for evaluation.

The hair tactility of the hair bundle samples for evaluation in each Example and each Comparative Example was touched by 10 trained specialized sensory examiners, and the hair tactility was rated as "good" or "poor". method evaluation. Then, the following five levels of scoring are set based on the number of sensory examiners who judge "good".

5: There are more than 8 sensory examiners who judge "good" 4: The number of sensory examiners who judge "good" is 6 to 7 3: The number of sensory examiners who judge "good" is 4 to 5 2: The number of sensory examiners who judge "good" is 2 to 3 1: The number of sensory examiners who judge "good" is less than 1

The evaluation results of each Example and each Comparative Example are shown in the "Feel of hair after treatment" column of Tables 1 and 2.

Table 1 acidic agent Example 1-1 Example 1-2 Example 1-3 Examples 1-4 Examples 1-5 Examples 1-6 Example 1-7 Example 1-8 Example 1-9 Examples 1-10 Example 1-11 Examples 1-12 A Dihydroxyindoline HBr 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Steartrimonium Chloride 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 C Polyquaternium-6 (Merquat 100, molecular weight 150000, cation density 7.9 meq/g) 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.5 0.1 C Polydiallyldimethylammonium chloride (Merquat 106, molecular weight 15000, cation density 7.9 meq/g) 0.1 C Polyethylenimine (molecular weight 10000, cation density 23.2meq/g) 0.1 Amodimethicone 1 1 1 1 1 1 1 1 1 1 1 1 D ascorbic acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 100 100 alkaline agent B 28% ammonia 2 2 2 3.5 0.5 3.5 2 2 2 2 2 2 B sodium carbonate 0.2 0.75 1 0.2 1 0.2 0.2 0.2 0.2 0.2 B sodium bicarbonate 0.2 0.75 1 0.2 1 0.2 0.2 0.2 0.2 0.2 B ammonium carbonate 0.2 B ammonium bicarbonate 0.2 Steartrimonium Chloride 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 C Polyquaternium-6 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.5 0.1 Amodimethicone 1 1 1 1 1 1 1 1 1 1 1 1 D sodium sulfite 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 100 100 mixing ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Total alkalinity when mixed [ml/g] 1.66 2.50 2.89 2.89 1.65 2.58 1.66 1.66 1.66 1.66 1.66 1.66 pH during mixing 9.5 9.3 9.3 9.8 7.9 10.5 9.5 9.5 9.5 9.5 9.5 9.0 A/C 7.50 7.50 7.50 7.50 7.50 7.50 7.50 7.50 15.00 - 1.50 7.5 Hair dyeing power 5 5 4 4 3 4 4 4 5 4 4 4 The feeling of hair after treatment 5 5 5 4 5 3 5 5 3 4 5 5

Table 2 acidic agent Comparative example 1-1 Comparative example 1-2 A Dihydroxyindoline HBr 1.5 1.5 Steartrimonium Chloride 0.3 0.3 C Polyquaternium-6 0.1 0.1 Amodimethicone 1 1 D ascorbic acid 0.1 0.1 common base Special watch Special watch pure water Remaining Remaining total 100 100 alkaline agent B 28% ammonia 5 5 B sodium carbonate 1 0.2 B sodium bicarbonate 1 0.2 Steartrimonium Chloride 0.3 0.3 C Polyquaternium-6 0.1 0.1 Amodimethicone 1 1 D sodium sulfite 0.1 0.1 common base Special watch Special watch pure water Remaining Remaining total 100 100 mixing ratio 1:1 1:1 Total alkalinity when mixed [ml/g] 5.25 4.12 pH during mixing 9.5 11.1 A/C 7.5 7.5 Hair dyeing power 2 2 The feeling of hair after treatment 2 1

table 3 Common base parts for acidic agents and alkaline agents in Tables 1 and 2 Stearyl Alcohol 5 Cetyl Alcohol 3 Oleth-50 1 Steareth-2 2 Microcrystalline Wax 3 Cetyl Octanoate 3 PEG-8 5 Methylparaben 0.1 HEDTA-3Na 0.1

(Test example 2)

[Preparation of air oxidation hair dye] All the acidic agents and alkaline agents of the two-part air oxidation hair dyes of Examples 2-1 to 2-29 and Comparative Examples 2-1 to 2-3 shown in Tables 4 to 7 were prepared according to common methods. Creamy. The "common base" indicated in the compositions of the acidic agent and alkaline agent in each Example and each Comparative Example is a base with a composition shown in another table (that is, Table 8).

Among the components shown in Tables 4 to 7, those corresponding to the component (A), (B), (D), (E) or (F) of this embodiment are listed outside the left column of the component name. Marked as "A", "B", "D", "E" or "F". "Dihydroxyindoline HBr" in the ingredient name column indicates the hydrobromide of dihydroxyindoline. The numerical value of each component in Tables 4 to 8 represents the content of the component in mass % units in the acidic agent or the alkaline agent.

Next, as shown in the "mixing ratio" column shown in Tables 4 to 7, the acidic agent and alkaline agent of each embodiment and each comparative example are mixed in a mass ratio of 1:1 and applied to hair. When mixing the acidic agent and alkaline agent of each Example and Comparative Example, a part of the mixture was used to measure the total alkalinity (ml/g) and pH. These measurement results are shown in the columns of "Total alkalinity during mixing [ml/g]" and "pH during mixing" of Tables 4 to 7.

[Evaluation of air oxidation hair dye]

(Evaluation of hair dyeing power) The acidic agent and alkaline agent of each Example and each Comparative Example were mixed at a mass ratio of 1:1 immediately before evaluation to form a creamy hair dye composition, and each of these hair dye compositions was Use a brush to evenly apply 1g of white hair sample 10cm in length. The coated hair bundle sample was placed in a constant temperature bath at 30° C. for 10 minutes, and then washed with water. The washed hair bundle sample was dried with warm air to obtain a hair bundle sample for evaluation.

The dyeing state of the hair bundle samples for evaluation in each Example and each Comparative Example was evaluated by 10 trained specialized sensory examiners visually scoring the hair dyeing power based on the following five-step evaluation standard. Each sensory examiner refers to a sample of the dyed hair bundle sample specifically showing the five-step evaluation criteria during evaluation. For each Example and each Comparative Example, the average value of the scores of 10 sensory examiners was used, and when there was a numerical value below the decimal point, the score was determined by rounding off the value. The evaluation results of each Example and each Comparative Example are shown in the "Hair Dyeing Power" column of Tables 4 to 7.

5: Very high hair dyeing power 4: High hair dyeing power 3: Medium hair dyeing power 2: Low hair dyeing power 1: Hair dyeing power is very low

(Evaluation of hair dyeing power stability) 30 g each of the above-mentioned acidic agent and alkaline agent of each Example and Comparative Example were respectively filled into a No. 4 specification bottle and stored in a constant temperature bath at 50° C. for 2 weeks. Then, 1 g of each hair dye composition in which the acidic agent and alkaline agent of each example after storage were mixed at a mass ratio of 1:1 was used as described in the item "Evaluation of hair dyeing power" mentioned above. hair dye treatment. These hair bundle samples obtained after hair dyeing treatment are called "stability evaluation hair bundle samples".

On the other hand, the immediately prepared acidic agent and alkaline agent of each example and comparative example were mixed at a mass ratio of 1:1 to form a hair dye composition, and 1 g of each of these hair dye compositions was used. Hair dyeing treatment as described in the item "Evaluation of Hair Dyeing Power" above. The hair bundle samples obtained after hair dyeing treatment are called "base hair bundle samples".

The stability evaluation hair bundle sample and the reference hair bundle sample of each Example and each comparative example were visually compared and observed by 10 trained professional sensory examiners. The stability evaluation hair bundle sample was considered to have the same The standard hair bundle sample has the same hair dyeing effect and is evaluated as "0 (good)", and the stability evaluation hair bundle sample shows a decrease in dyeing power or changes to a different color tone compared with the standard hair bundle sample. The situation evaluation is "× (poor)". Then, the hair dye composition stability of each Example and each Comparative Example was evaluated based on the following evaluation criteria. The evaluation results of each Example and each Comparative Example are shown in the "Hair Dyeing Power Stability" column of Tables 4 to 7.

5: The number of sensory examiners who rated 0 was 9 to 10 4: There are 7 to 8 sensory examiners who rated 0 3: There are 5 to 6 sensory examiners who rated 0 2: There are 3 to 4 sensory examiners who rated 0 1: The number of sensory examiners who rated 0 is less than 2

(Evaluation of dye precipitation) Take out 1 g of each of the acidic agent and alkaline agent from each of the examples and comparative examples in the above "Evaluation of Hair Dyeing Power Stability" after storage in a constant temperature bath at 50°C for 2 weeks, and visually observe whether there is any creamy precipitate. . Then, the dye precipitation of the hair dye compositions of each Example and each Comparative Example was evaluated based on the following evaluation criteria. The evaluation results of each Example and each Comparative Example are shown in the "Dye Precipitation" column of Tables 4 to 7.

〇(Good): No precipitate is visible △ (fair): Slight precipitates are visible × (poor): Many precipitates are visible

Table 4 acidic agent Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 Example 2-7 Example 2-8 Example 2-9 Example 2-10 A Dihydroxyindoline HBr 1 1 1 1 1 1 1 1 1 1 E HC Yellow 4 - - - - - - - - - - E HC red 13 - - - - - - - - - - D ascorbic acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.1 F PEG400 (LogPow=-3.12) 8 8 8 8 8 8 8 8 8 8 common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 alkaline agent B 28% ammonia 2 2 2 3.5 0.5 3.5 2 2 2 2 B sodium carbonate 0.2 0.7 1 0.2 1 - 0.4 - 0.2 0.2 B sodium bicarbonate 0.2 0.7 1 0.2 1 - - 0.4 0.2 0.2 D sodium sulfite 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.15 E HC Yellow 4 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E HC Yellow 2 - - - - - - - - - - E HC red 13 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 E HC Green 2 - - - - - - - - - - E N, N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine - - - - - - - - - - E Red No. 102 - - - - - - - - - - F PEG400 (LogPow=-3.12) 8 8 8 8 8 8 8 8 8 8 F Glycerin (LogPow=-1.65) - - - - - - - - - - F Dipropylene glycol (LogPow=-0.64) - - - - - - - - - - F Butyl carbitol - - - - - - - - - - common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 mixing ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Total alkalinity when mixed [ml/g] 1.74 2.50 2.97 2.97 1.74 2.66 1.81 1.67 1.68 1.77 pH during mixing 9.5 9.3 9.3 9.8 7.9 10.5 9.8 9.4 9.4 9.5 Hair dyeing power 5 5 4 4 3 4 5 4 5 5 Hair color stability 5 5 5 4 5 4 5 5 5 4 Dye precipitation 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇

table 5 acidic agent Example 2-11 Example 2-12 Example 2-13 Example 2-14 Example 2-15 Example 2-16 Example 2-17 Example 2-18 Example 2-19 Example 2-20 Example 2-21 Example 2-22 Example 2-23 A Dihydroxyindoline HBr 1 1 1 1 1 1 1 1 1 1 1 1 1 E HC Yellow 4 0.2 - - - - - - - - - - - - E HC red 13 0.6 - - - - - - - - - - - - D ascorbic acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 F PEG400 (LogPow=-3.12) 8 8 8 8 8 8 8 8 8 8 - 8 8 common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 100 100 100 alkaline agent B 28% ammonia 2 2 2 2 2 2 2 2 2 2 2 2 2 B sodium carbonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 B sodium bicarbonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 D sodium sulfite 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 E HC Yellow 4 - 0.8 - - - - - 0.2 0.2 0.2 0.2 0.2 0.2 E HC Yellow 2 - - 0.8 - - - - - - - - - - E HC red 13 - - - 0.8 - - - 0.6 0.6 0.6 0.6 0.6 0.6 E HC Green 2 - - - - 0.8 - - - - - - - - E N, N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine - - - - - 0.8 - - - - - - - E Red No. 102 - - - - - - 0.8 - - - - - - F PEG400 (LogPow=-3.12) 8 8 8 8 8 8 8 - - - - 4 12 F Glycerin (LogPow=-1.65) - - - - - - - 8 - - - - - F Dipropylene glycol (LogPow=-0.64) - - - - - - - - 8 - - - - F Butyl carbitol - - - - - - - - - 8 - - - common base Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 100 100 100 100 100 100 100 mixing ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Total alkalinity when mixed [ml/g] 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 1.74 pH during mixing 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 Hair dyeing power 5 5 5 5 5 5 4 5 5 5 4 5 5 Hair color stability 5 5 5 5 5 4 3 5 4 5 3 4 5 Dye precipitation 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 △ 〇 〇

Table 6 acidic agent Example 2-24 Example 2-25 Example 2-26 Example 2-27 Example 2-28 Example 2-29 A Dihydroxyindoline HBr 1 1 1 1 1 1 D ascorbic acid 0.1 0.1 0.1 0.1 0.1 0.1 F PEG400 (LogPow=-3.12) 8 8 8 - - 8 common base Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 alkaline agent B 28% ammonia 2 2 2 2 2 3.5 B sodium carbonate 0.2 0.2 0.2 0.2 0.2 0.2 B sodium bicarbonate 0.2 0.2 0.2 0.2 0.2 0.2 D sodium sulfite 0.05 0.05 0.05 0.05 0.05 0.05 E HC Yellow 4 - - - - - - E HC red 13 - - - - - - E 3-nitro-p-hydroxyethylaminophenol 0.01 0.05 0.8 0.05 0.8 0.05 F PEG400 (LogPow=-3.12) 8 8 8 - - 8 common base Special watch Special watch Special watch Special watch Special watch Special watch pure water Remaining Remaining Remaining Remaining Remaining Remaining total 100 100 100 100 100 100 mixing ratio 1:1 1:1 1:1 1:1 1:1 1:1 Total alkalinity when mixed [ml/g] 1.74 1.74 1.74 1.74 1.74 2.97 pH during mixing 9.5 9.5 9.5 9.5 9.5 9.8 Hair dyeing power 4 5 5 4 4 5 Hair color stability 3 4 4 4 4 4 Dye precipitation 〇 〇 〇 〇 〇 〇

Table 7 acidic agent Comparative example 2-1 Comparative example 2-2 Comparative example 2-3 A Dihydroxyindoline HBr 1 1 - F PEG400 (LogPow=-3.12) 8 8 8 D ascorbic acid 0.1 0.1 0.1 common base Special watch Special watch Special watch pure water Remaining Remaining Remaining total 100 100 100 alkaline agent B 28% ammonia 5 5 2 B sodium carbonate 1 0.2 0.2 B sodium bicarbonate 1 0.2 0.2 D sodium sulfite 0.05 0.05 0.05 E HC Yellow 4 0.2 0.2 0.2 E HC red 13 0.6 0.6 0.6 F PEG400 (LogPow=-3.12) 8 8 8 common base Special watch Special watch Special watch pure water Remaining Remaining Remaining total 100 100 100 mixing ratio 1:1 1:1 1:1 Total alkalinity when mixed [ml/g] 5.25 4.12 1.66 pH during mixing 9.5 11.1 9.5 Hair dyeing power 2 2 2 Hair color stability 5 4 5 Dye precipitation 〇 〇 〇

Table 8 Common base parts of acidic agents and alkaline agents in Tables 4 to 7 Stearyl Alcohol 5 Cetyl Alcohol 3 Oleth-50 1 Steareth-2 2 Microcrystalline Wax 3 Cetyl Octanoate 3 Methylparaben 0.1 HEDTA-3Na 0.1 Steartrimonium Chloride 0.3 Polyquaternium-6 0.1 Amodimethicone 1

This disclosure also includes the following forms.

(Appendix 1) An air oxidation hair dye, which is a multi-dose hair dye in which each agent is applied to the hair at the same time. It is composed of acidic agent and alkaline agent, The above-mentioned acidic agent contains the following components (A) and (D), The above-mentioned alkaline agent contains the following component (B), Any one or more of the above air oxidation hair dyes contains the following component (E), When mixing each agent, the total alkalinity is below 3.0ml/g. (A) Ingredient: Melanin precursor (D) Ingredients: reducing agent (B) Ingredients: Alkaline compounds (E) Ingredients: nonionic or anionic direct dyes.

The so-called "total alkalinity" in Appendix 1 above is a parameter that refers to the amount of acid-consuming components in the sample or the amount of free [OH-] derived from alkali in the sample. Specifically, it is neutralized and titrated with 0.1N hydrochloric acid. The amount of hydrochloric acid in mL units required for 1 g of the mixed solution of each agent as a sample. Among them, the mixture of each agent may have multiple neutralization points depending on the type of alkaline compound or the combination of two or more alkaline compounds. In this case, the total alkalinity refers to the total alkalinity consumed up to the final neutralization point. The amount of the above hydrochloric acid in mL units. In addition, the so-called "simultaneous coating" refers to the state in which the acidic agent and the alkaline agent are applied to the hair together. Therefore, the two agents can be mixed in advance and then applied to the hair, or the two agents can be applied in different orders without mixing them first. Suitable for hair. The present invention is basically different from the invention described in Patent Document 2 in that the acidic agent (agent) is not wiped off before applying the alkaline agent (b agent).

In addition, "multi-dose hair dye" can be a two-dose hair dye, or a multi-dose hair dye. The two-dose hair dye is composed of ingredients (A) and (D). An acidic agent and an alkaline agent containing component (B), and any one or more of these agents contain component (E); a multi-part hair dye includes mixing the above two-part hair dye when it is applied to the hair at the same time 1 or 2 or more other agents, which may or may not contain ingredient (E). When applied to hair, unnecessary additional agents applied simultaneously with the above-mentioned acidic agent or alkaline agent may or may not be regarded as constituent elements of the hair dye of the first invention. In addition to the 5,6-dihydroxyindoline or 5,6-dihydroxyindoline-2-carboxylic acid listed in Appendix 2 below, the melanin precursor of the component (A) also includes, for example, 5,6-dihydroxyindoline-2-carboxylic acid. Various melanin precursors such as hydroxyindole or 5,6-dihydroxyindole-2-carboxylic acid and their derivatives or salts thereof maintain the property of oxidative polymerization by air oxidation to develop color.

(Appendix 2) Air oxidation hair dye as described in Appendix 1, wherein The above-mentioned component (A) is at least one selected from the group consisting of 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and salts thereof.

(Appendix 3) Air oxidation hair dye as described in Appendix 1 or 2, wherein The above-mentioned component (B) contains carbonate and/or bicarbonate.

(Appendix 4) The air oxidation hair dye as described in any one of Appendices 1 to 3, wherein Furthermore, it contains the following component (F): (F) Ingredients: Select one or more from methyl carbitol, ethyl carbitol, butyl carbitol or their salts, and/or a solvent with an octanol/water partition coefficient (Log Pow) smaller than water .

Industrial availability The present invention provides a multi-agent air oxidation hair dye that can prevent melanin precursors from polymerizing before use and obtain sufficient hair dyeing power by simultaneously applying each agent.

Claims (5)

An air oxidation hair dye, which is a multi-dose hair dye in which each agent is applied to the hair at the same time. It is composed of acidic agent and alkaline agent, The above-mentioned acidic agent contains the following component (A), The above-mentioned alkaline agent contains the following component (B), When mixing each agent, the total alkalinity is below 3.0ml/g. (A) Ingredient: Melanin precursor (B) Ingredients: Alkaline compounds. The air oxidation hair dye as described in claim 1, wherein The pH of each agent of the above-mentioned air oxidation hair dye is in the range of 8 to 11 when mixed. The air oxidation hair dye as described in claim 1 or 2, wherein Any one or more of the above air oxidation hair dyes contains the following component (C), (C) Component: Polymer with cationic group. The air oxidation hair dye as described in any one of claims 1 to 3, wherein The above-mentioned component (A) is selected from the group consisting of 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, and 5,6-dihydroxyindoline -More than one type of 2-carboxylic acid and its salts. The air oxidation hair dye as described in any one of claims 1 to 4, wherein The above-mentioned component (B) contains carbonate and/or bicarbonate.