JP7485323B2 - Hair dye composition - Google Patents

Description

The present invention relates to a hair dye composition for dyeing hair, etc. More specifically, the present invention relates to a hair dye composition containing 2,2'-[(4-aminophenyl)imino]bisethanol (hereinafter referred to as "4APE") and/or a salt thereof, which has excellent dye uniformity.

Two-component hair dye compositions, consisting of a first component containing an oxidation dye consisting of a dye intermediate and a coupler, and a second component containing an oxidizing agent, have been widely used as hair dyes. These hair dye compositions allow a low molecular weight oxidation dye to penetrate into the hair, and the oxidation dye is oxidatively polymerized within the hair to produce a pigment, which then dyes the hair. These hair dye compositions can dye hair in a variety of colors according to the customer's needs, and also have excellent hair dyeing power.

Among various dye intermediates, 4APE and its salts are known as oxidation dyes that impart shine to hair and produce a natural, smooth dyed finish. For example, Patent Documents 1 to 3 disclose hair dye compositions that contain 4APE and that reduce scalp staining, and have excellent weather resistance, deep color properties, and dyed finish.

On the other hand, when 4APE and/or its salts are used as dye intermediates, there is a drawback in that the dye cannot be dyed evenly, resulting in uneven dyeing. For this reason, hair dye compositions containing 4APE and/or its salts have been developed with the aim of improving dyeing uniformity. For example, Patent Document 4 discloses a method of improving dyeing uniformity by adding a cationic polymer to a hair dye composition containing 4APE.

Japanese Patent Application Laid-Open No. 7-267831 Japanese Patent Application Laid-Open No. 7-267833 Japanese Patent Application Laid-Open No. 7-267835 Japanese Patent Application Laid-Open No. 7-267832

The object of the present invention is to provide a new means for improving the evenness of dyeing of a hair dye composition containing 4APE and/or a salt thereof, with the aim of further improving the evenness of dyeing of a hair dye composition containing 4APE and/or a salt thereof.

As a result of intensive research into the above-mentioned problems, the inventors have found that in a hair dye composition containing 4APE and/or a salt thereof, the inclusion of an oily component having a specific octanol/water partition coefficient and polyethylene glycol improves dyeing uniformity, and have completed the present invention.
That is, the present invention relates to the following hair dye composition.

The hair dye composition of the present invention is characterized in that it contains (a) 4APE and/or a salt thereof, (b) one or more oily components selected from hydrocarbons, waxes, esters and fats and oils, each having an octanol/water partition coefficient of 14.0 or more at 25° C., and (c) polyethylene glycol having an octanol/water partition coefficient of −10.0 to −3.0 at 25° C.
According to the hair dye composition of the present invention, a hair dye composition having excellent dye uniformity can be provided.

Furthermore, one embodiment of the hair dye composition of the present invention is characterized in that the ratio of the content of (c) to the content of (b) (c/b) is 0.06 to 1.0.
According to this feature, the effect of the present invention of excellent level dyeing property can be more effectively exhibited.

Furthermore, one embodiment of the hair dye composition of the present invention is characterized in that the ratio (b/a) of the content of (b) to the content of (a) is 0.25 to 100.
When the content of the (b) component is increased, in addition to improving the dyeing uniformity, the effect of preventing background staining, the ease of application, and the stability of the formulation tend to improve. On the other hand, when the (b) component is added in excess, the dyeing power tends to decrease. Therefore, by setting the ratio of the content of the (b) to the (a) (b/a) to 0.25 to 100, the dyeing uniformity is improved, and the dyeing power, the stability of the formulation, and the ease of application are improved in a well-balanced manner.

Furthermore, one embodiment of the hair dye composition of the present invention is characterized in that the ratio (c/a) of the content of (c) to the content of (a) is 0.0025 to 100.
Increasing the content of the (c) component increases the effect of preventing background staining in addition to improving dyeing uniformity. On the other hand, excessive addition of the (c) component tends to decrease the dyeing power. Therefore, by setting the content ratio of the (c) to the (a) (c/a) to 0.0025 to 100, the effects of preventing background staining and improving dyeing power can be exhibited in a well-balanced manner in addition to improving dyeing uniformity.

Furthermore, one embodiment of the hair dye composition of the present invention is characterized by containing (d) p-aminophenol.
This feature has the effect of preventing background staining in addition to further improving the uniformity of dyeing.

The present invention provides a new means for improving dye uniformity in hair dye compositions containing 4APE and/or its salts.

Next, the present invention will be described including the best mode for carrying out the present invention.
[Hair dye composition]
The hair dye composition of the present invention is characterized in that it contains (a) 4APE and/or a salt thereof, (b) one or more oily components selected from hydrocarbons, waxes, esters, and fats and oils, each having an octanol/water partition coefficient (hereinafter referred to as "Log Kow") at 25°C of 14.0 or more, and (c) polyethylene glycol having a Log Kow of -10.0 to -3.0.

In hair dye compositions, the oxidation dye and the oxidizing agent are distributed separately, and the oxidation dye is oxidized by the oxidizing agent to develop color. A typical hair dye composition is a two-component type consisting of a first component containing an oxidation dye and a second component containing an oxidizing agent, but it may also be a multi-component type consisting of three or more components.

The form of each agent forming the hair dye composition of the present invention may be any form, for example, liquid such as an aqueous solution or emulsion, cream, gel, etc. In addition, the hair dye composition after mixing of each agent may be in a form having applicability such as liquid, cream, gel, etc. In addition, it may be in the form of a foam or mist when used. When it is in the form of a foam, an aerosol foamer container using a known propellant or foaming agent, a non-aerosol foamer container such as a squeeze foamer type or pump foamer type, a shaking container, etc. may be used. Specific examples of the propellant or foaming agent include liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen gas, carbon dioxide gas, etc. When it is in the form of a mist, a sprayer may be used.

The first agent containing the oxidation dye and the second agent containing the oxidizing agent are mixed at the time of use to prepare the hair dye composition. The mixing operation may be performed before or after application to the hair. For example, they may be mixed just before application to the hair, or the first agent and the second agent may be taken on a comb or the like and mixed on the hair using the comb or the like.

Next, each component used in the hair dye composition of the present invention will be described in detail. Note that the content of each component indicates the content in the hair dye composition in which each component is mixed, unless otherwise specified.

<Oxidation dyes>
Oxidation dyes are components contained in the first agent, and are dyes that develop color through oxidative polymerization in the presence of an oxidizing agent. Oxidation dyes include dye intermediates and couplers. Dye intermediates are substances that develop color through their own oxidation, and couplers are substances that can be combined with dye intermediates to produce various colors.

[Dye intermediates]
The hair dye composition of the present invention contains (a) 4APE and/or a salt thereof as a dye intermediate.
4APE is a compound represented by the following chemical formula (1): Examples of the salt include salts of organic acids or salts of inorganic acids, such as sulfates, hydrochlorides, phosphates, acetates, propionates, lactates, and citrates.

The content of 4APE and/or its salt in the hair dye composition is not particularly limited, but is preferably 0.01 to 4.0% by mass. In this case, the effect of 4APE, which imparts shine to hair and gives a natural, smooth dyed finish, can be fully exerted. The lower limit is more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. The upper limit is more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.

[Other dye intermediates]
The hair dye composition may contain dye intermediates other than 4APE and its salts. The dye intermediates are dye precursors, which are mainly o- or p-phenylenediamines or aminophenols.
Specific examples include p-phenylenediamine, p-toluylenediamine, 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, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof. Of these specific examples of dye intermediates, only one type may be contained, or two or more types may be contained in combination.

Furthermore, the hair dye composition of the present invention preferably contains (d) p-aminophenol. By containing p-aminophenol, not only can the effect of the present invention of improving dye uniformity be further enhanced, but also the effect of preventing background staining is improved. Furthermore, by using 4APE in combination with p-aminophenol, beautiful warm color tones can be achieved.

The content of (d) p-aminophenol in the hair dye composition is not particularly limited, but is preferably 0.001 to 3% by mass. The lower limit is more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more. The upper limit is more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

The ratio (d/a) of the content of (d) p-aminophenol to (a) 4APE and/or its salt is not particularly limited, but is preferably 0.001 to 50. In this case, the effect of preventing background staining can be more effectively exhibited. The lower limit is more preferably 0.01 or more, even more preferably 0.1 or more, and particularly preferably 0.3 or more. The upper limit is more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less.

One or more types of dye intermediates can be selected and used depending on the desired hair color tone. The total content of the dye intermediates containing 4APE and/or its salt is not particularly limited, but is, for example, 0.01 to 10% by mass in the hair dye composition. The lower limit is more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit is more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

〔coupler〕
The coupler mainly includes m-diamines, aminophenols, or diphenols. Specific examples thereof include m-aminophenol, resorcin, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, α-naphthol, 2,6-diaminopyridine, diphenylamine, 3,3′-iminodiphenyl, 1,5-dihydroxynaphthalene, tannic acid and salts thereof, 1-hydroxyethyl-4,5-diaminopyrazole sulfate, N,N-diethyl-m-aminophenol, and phenylmethylpyrazolone.

One or more types of couplers can be selected and used depending on the desired hair color tone. The content of the coupler is not particularly limited, but is, for example, 0.01 to 5% by mass in the hair dye composition. The lower limit is more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

<(b) One or more oily components selected from hydrocarbons, waxes, esters, and fats and oils, having a Log Kow of 14.0 or more>
The hair dye composition of the present invention contains, as an oil component, (b) one or more oil components selected from hydrocarbons, waxes, esters, and fats and oils, each having a Log Kow of 14.0 or more (hereinafter referred to as "(b) oil component").

Log Kow is a measure for the distribution of a substance between the aqueous phase and the organic phase (octanol phase) and is defined as follows:
LogKow=log([Mo]/[Mw]) ... Number (1)
[Mo]: number of moles of substance in octanol phase [Mw]: number of moles of substance in aqueous phase

In the present invention, Log Kow is measured and calculated using the program "KowWIN32" from Syracuse Research Corporation.
When the calculation cannot be performed using the program, the measurement is performed according to Japanese Industrial Standards Z7260-107:2000 "Measurement of partition coefficient (1-octanol/water) - flask shaking method".

Hydrocarbons are compounds made of carbon and hydrogen. Examples of hydrocarbons with a Log Kow of 14.0 or more include those with 28 or more carbon atoms, such as paraffin wax (14.09), petrolatum (15.2), microcrystalline wax (22.44), ozokerite (20.48), ceresin (16.06), α-olefin oligomer (17.09), synthetic squalane (14.63), squalene (14.12), and squalane (14.63). The numbers in parentheses indicate Log Kow (same below).

Waxes contain esters of higher fatty acids and higher alcohols as their main components, and examples include beeswax (21.98), candelilla wax (15.57), lanolin (15.6), and jojoba oil (18.54).

Esters are compounds obtained by the dehydration reaction of fatty acids with alcohols. Examples include octyldodecyl oleate (17.27), ethylene glycol distearate (16.12), octyldodecyl myristate (15.52), isostearyl palmitate (15.60), cetyl palmitate (14.62), 2-hexyldecyl stearate (15.52), cholesteryl stearate (17.60), hexyldecyl isostearate (15.45), oleyl oleate (16.15), phytosteryl isostearate (18.26), stearyl stearate (16.58), and pentaerythritol fatty acid esters (30.81).

Fats and oils are triglycerides, i.e. triesters of fatty acids and glycerin. Examples include olive oil (23.07), sunflower oil (22.86), grape seed oil (21.96), avocado oil (22.04), coconut oil (22.95), shea butter (23.48), macadamia nut oil (23.29), safflower oil (22.65), cocoa butter (22.74), corn oil (23.08), peanut oil (23.08), castor oil (18.75), and linseed oil (22.22).

(b) The Log Kow of the oil component is preferably 24.0 or less, more preferably 20.0 or less, and even more preferably 18.0 or less. Specifically, preferred are microcrystalline wax (22.44), olive oil (23.07), sunflower oil (22.86), grape seed oil (21.96), avocado oil (22.04), coconut oil (22.95), shea butter (23.48), macadamia nut oil (23.29), safflower oil (22.65), cocoa butter (22.74), corn oil (23.08), peanut oil (23.08), linseed oil (22.22), beeswax (21.98), ozokerite (20.48), more preferred are jojoba oil (18.54), phytosteryl isostearate (18.26), castor oil (18.75), and even more preferred are paraffin wax (14.09), petrolatum (15.2), celery wax (15.2), and oleic acid wax (15.2). Synthetic squalane (16.06), α-olefin oligomer (17.09), synthetic squalane (14.63), squalene (14.12), squalane (14.63), candelilla wax (15.57), lanolin (15.6), octyldodecyl oleate (17.27), ethylene glycol distearate (16.12), octyldodecyl myristate (15.52), isostearyl palmitate (15.60), cetyl palmitate (14.62), 2-hexyldecyl stearate (15.52), cholesteryl stearate (17.60), hexyldecyl isostearate (15.45), oleyl oleate (16.15), stearyl stearate (16.58).

Furthermore, in one embodiment of the hair dye composition of the present invention, the oil component (b) has a melting point of 40°C or higher. This characteristic allows the effects of the present invention to be more pronounced.

The content of the oil component (b) in the hair dye composition is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, and particularly preferably 10% by mass or less. In the case of a two-component hair dye, the oil component (b) may be blended into either the first or second agent, or into both the first and second agents. In the case of a multi-component hair dye of three or more agents, it may be blended into an agent other than the first and second agents.

The ratio (b/a) of the content of (b) oily component to (a) 4APE and/or its salt is not particularly limited, but is preferably 0.25 to 1000. The lower limit is more preferably 0.3 or more, and particularly preferably 0.4 or more. The upper limit is more preferably 500 or less, and particularly preferably 100 or less. When b/a is 0.25 or more, the application operability, the effect of preventing background staining, and the formulation stability are improved. On the other hand, when b/a is 1000 or less, the hair dyeing power is improved.

<(c) Polyethylene glycol having Log Kow of -10.0 to -3.0>
The hair dye composition of the present invention contains (c) polyethylene glycol (hereinafter referred to as "(c) PEG") having a Log Kow of -10.0 to -3.0. (c) PEG is a PEG having an average molecular weight of 400 to 1600, and specific examples thereof include PEG 400 (-3.12), PEG 600 (-4.22), PEG 1000 (-6.41), and PEG 1540 (-9.98). The numbers in parentheses indicate Log Kow. The method for measuring Log Kow is the same as that for the (b) oil component. The average molecular weights of the PEGs are PEG 400 (average molecular weight 360 to 440), PEG 600 (average molecular weight 560 to 640), PEG 1000 (average molecular weight 950 to 1050), and 1540 (average molecular weight 1290 to 1650). The Log Kow of (c) PEG is preferably −7.0 or more, and more preferably −4.5 or more. Specifically, (c) PEG is preferably PEG 1000, and more preferably PEG 600 or PEG 400.

The content of (c) PEG in the hair dye composition of the present invention is preferably 0.001 to 30% by mass. The lower limit is more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more. The upper limit is more preferably 20% by mass or less, and particularly preferably 10% by mass or less. In the case of a two-component hair dye, (c) PEG may be blended in either the first or second agent, or in both the first and second agents. In the case of a multi-component hair dye of three or more agents, it may be blended in an agent other than the first and second agents.

The ratio (c/a) of the content of (c) PEG to (a) 4APE and/or its salt is not particularly limited, but is preferably 0.0025 to 1000. The lower limit is more preferably 0.01 or more, and particularly preferably 0.1 or more. The upper limit is more preferably 500 or less, and particularly preferably 100 or less. When c/a is 0.0025 or more, the effect of preventing scalp staining is achieved. On the other hand, when c/a is 1000 or less, the hair dyeing power is improved.

In the hair dye composition of the present invention, the ratio (c/b) of the content of (c) PEG to (b) oil component is preferably 1.0 or less. When it is 1.0 or less, the effect of the present invention of improving dyeing uniformity is further improved. On the other hand, the lower limit is preferably 0.01 or more, more preferably 0.06 or more, even more preferably 0.1 or more, and particularly preferably 0.3 or more. When it is 0.01 or more, there is an effect of preventing background staining.

<Other ingredients>
The hair dye composition of the present invention may contain the following components, if necessary, in addition to the above-mentioned oxidation dye, (b) the oil component, and (c) PEG.
Examples of other components include oily components (excluding (b) oily components), polyhydric alcohols (excluding (c) PEG), oxidizing agents, alkali agents, direct dyes, surfactants, antioxidants such as ascorbic acid and anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, organic solvents such as ethanol, sugars such as sorbitol and maltose, water-soluble polymers such as hydroxyethyl cellulose and carboxyvinyl polymers, cationized water-soluble polymers such as polychlorinated dimethylmethylene piperidinium solution, diallyldimethylammonium chloride-hydroxyethyl cellulose, chelating agents such as trisodium hydroxyethylethylenediaminetriacetate dihydrate and tetrasodium hydroxyethanediphosphonate solution, inorganic salts such as sodium chloride and sodium carbonate, pH adjusters such as ammonium sulfate, ammonium nitrate, ammonium acetate, citric acid, tartaric acid, lactic acid, malic acid, succinic acid, fumaric acid, maleic acid, pyrophosphoric acid, gluconic acid, glucuronic acid, and ammonium bicarbonate, hair growth components, plant extracts, herbal extracts, amino acids and peptides, urea, vitamins, fragrances, and ultraviolet absorbers.

<Other oily ingredients>
Examples of other oily components include hydrocarbons having a Log Kow of less than 14.0, higher alcohols, higher fatty acids, silicone oils, oils and fats having a Log Kow of less than 14.0, fluorine oils, alkyl glyceryl ethers, esters having a Log Kow of less than 14.0, etc. One or more of these oily components can be selected and used.
The hair dye composition of the present invention preferably further contains a higher alcohol in addition to the oil component having a Log Kow of 14.0 or more, whereby emulsion stability can be improved.

Examples of hydrocarbons with a Log Kow of less than 14.0 include liquid paraffin (12.13), liquid isoparaffin (13.05), limonene (4.2), and turpentine (4.19).

Examples of higher alcohols include cetanol (6.73), stearyl alcohol (7.72), cetostearyl alcohol (7.32), oleyl alcohol (7.50), arachidyl alcohol (8.70), behenyl alcohol (9.68), lauryl alcohol (4.77), myristyl alcohol (5.75), 2-hexyldecanol (6.66), isostearyl alcohol (7.64), 2-octyldodecanol (8.63), decyltetradecanol (10.59), phytosterol (9.47), and cholesterol (8.74).

Examples of higher fatty acids include oleic acid (7.73), lauric acid (5.00), myristic acid (5.98), palmitic acid (6.96), stearic acid (7.94), behenic acid (9.91), isostearic acid (7.87), 12-hydroxystearic acid (6.41), and linoleic acid (7.51).

Examples of fats and oils with a Log Kow of less than 14.0 include almond oil (3.47).

Silicone oil is a synthetic polymer in which silicon with organic groups and oxygen are alternately linked through chemical bonds. Examples include dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxyl end groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, highly polymerized silicone with an average degree of polymerization of 650 to 10,000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, and fluorine-modified silicone.

Among the above, examples of amino-modified silicones include aminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: aminopropyl dimethicone), aminoethylaminopropylsiloxane-dimethylsiloxane copolymer (INCI name: amodimethicone), and aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: trimethylsilylamodimethicone).

Specific examples of alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, selachyl alcohol, and isostearyl glyceryl ether.

Esters with a Log Kow of less than 14.0 include diisopropyl adipate (2.94), isopropyl myristate (7.18), myristyl myristate (12.65), cetyl isooctanoate (10.61), isopropyl palmitate (8.16), 2-ethylhexyl palmitate (10.61), butyl stearate (9.70), and hexyl laurate (7.74).

The content of other oily components in the hair dye composition is not particularly limited, but is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

<Other polyhydric alcohols>
The polyhydric alcohol is an alcohol having two or more hydroxyl groups in the molecule, and specific examples thereof include ethylene glycol (-1.93), diethylene glycol (-1.3), triethylene glycol (-1.98), polyethylene glycols other than component (c), propylene glycol (-1.4), dipropylene glycol (-0.64), glycerin (-0.29), 1,3-butylene glycol (-0.29), and the like.

The content of the other polyhydric alcohol in the hair dye composition of the present invention is not particularly limited, but is preferably less than 3% by mass, more preferably less than 2.5% by mass, and particularly preferably less than 1.5% by mass. When other polyhydric alcohols are added, the effect of dye uniformity tends to decrease, so by making the content of other polyhydric alcohols less than 3% by mass, the effect of the present invention can be further exerted.

<Oxidizing Agent>
The oxidizing agent is a component contained in the second agent, and is a substance having oxidizing power. The oxidizing agent has the function of oxidizing the oxidizing dye to develop color, and the function 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, and other persulfates, sodium peroxide, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, strontium peroxide, hydrogen peroxide adducts of sulfates, hydrogen peroxide adducts of phosphates, hydrogen peroxide adducts of pyrophosphates, peracetic acid and its salts, performic acid and its salts, permanganates, and bromates. Among these, hydrogen peroxide is preferred. Of these specific examples of the oxidizing agent, only one may be contained alone, or two or more may be contained in combination. In addition, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate may be contained as an oxidation assistant.

The content of the oxidizing agent in the hair dye composition is not particularly limited, but is, for example, 0.1 to 15% by mass. The lower limit is more preferably 1% by mass or more, and the upper limit is more preferably 9% by mass or less. When hydrogen peroxide is contained as the oxidizing agent, it is preferable to add a stabilizer such as sodium stannate, ethylene glycol phenyl ether (phenoxyethanol), hydroxyethane diphosphonic acid, phosphoric acid, citric acid, or a salt thereof, to improve its stability.

<Alkaline agent>
The alkaline agent has the effect of swelling the hair and promoting the penetration of the dye or oxidizing agent. Examples of the alkaline agent include ammonia, alkanolamines, silicates, carbonates, hydrogencarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, and hydroxides of alkali metals or alkaline earth metals. Specifically, examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, isopropylamine, etc.; examples of silicates include sodium silicate, potassium silicate, etc.; examples of carbonates include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, etc.; examples of hydrogen carbonates include sodium hydrogen carbonate, ammonium hydrogen carbonate, etc.; examples of metasilicates include sodium metasilicate, potassium metasilicate, etc.; examples of phosphates include ammonium monophosphate, ammonium diphosphate, disodium monohydrogen phosphate, trisodium phosphate, etc.; examples of sulfates include ammonium sulfate, etc.; examples of chlorides include ammonium chloride; examples of organic amines include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, and guanidine; examples of basic amino acids include arginine, lysine, and salts thereof, etc.; examples of hydroxides of alkali metals or alkaline earth metals include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among these, it is preferable to contain ammonia and alkanolamine.

The content of the alkaline agent in the hair dye composition is not particularly limited, but is preferably 0.01 to 20% by mass. The lower limit is more preferably 0.1% by mass or more, and the upper limit is more preferably 15% by mass or less.

The hair dye composition of the present invention preferably contains (e) ammonia. By containing ammonia, the effect of the present invention of improving dye uniformity can be further achieved. Furthermore, the effect of improving the brightness and color development of hair in the hair dyeing process is also achieved. If it is desired to achieve both the effect of ammonia and the suppression of unpleasant odors during hair dyeing, ammonia may be used in combination with other alkaline agents, but the greater the ammonia content, the more the effect of ammonia can be exerted. Therefore, it is particularly preferable to use only ammonia as the alkaline agent.

The ratio (e/a) of the content of (e) ammonia to (a) 4APE and/or its salt is not particularly limited, but is preferably 0.01 to 100. The lower limit is more preferably 0.2 or more, and particularly preferably 1 or more. The upper limit is more preferably 50 or less, even more preferably 20 or less, and particularly preferably 10 or less. When e/a is 0.01 or more, the effect of improving dyeing uniformity can be further exerted, and when it is 100 or less, the unpleasant odor of ammonia can be suppressed.

<Direct dyes>
Direct dyes are compounds that have color and dye hair by adhering to or penetrating the hair. Examples of direct dyes include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, disperse dyes, etc. These direct dyes may be used alone or in combination.

Examples of the above 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, etc.

Examples of the 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.

Examples of the above natural dyes include gardenia dye, turmeric dye, annatto dye, sodium copper chlorophyllin, paprika dye, lac dye, henna, etc.

Examples of the nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and salts thereof.

Examples of the above 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, and HC Yellow No.15.

Examples of 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, etc.

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

<Surfactant>
The surfactant may, for example, be a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant.
In the following description, POE denotes a polyoxyethylene chain, POP denotes a polyoxypropylene chain, and the numbers in parentheses following each indicate the number of moles added. The number in parentheses following the alkyl group indicates the number of carbon atoms in the fatty acid chain.

Examples of nonionic surfactants include POE alkyl ethers, POE alkyl phenyl ethers, POE-POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, polyglycerin fatty acid esters, monoglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkyl polyglucosides, etc. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, POE phytosterol, etc.

The content of the nonionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 40% by mass. The lower limit is more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit is more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The hair dye composition of the present invention preferably contains a nonionic surfactant having an HLB of 12.0 or less. This makes it possible to more effectively prevent background staining. Examples of nonionic surfactants having an HLB of 12.0 or less include POE(2) oleyl ether and POE(2) stearyl ether.
The HLB value may be measured according to "20.3.1 Actual measurement of HLB value by emulsification method" (pp. 854-855) described in "Handbook-Cosmetics and Pharmaceutical Raw Materials-Revised Edition (published February 1, 1977, Nikko Chemicals Co., Ltd.)."

The content of the nonionic surfactant having an HLB of 12.0 or less in the hair dye composition is not particularly limited, but is preferably 0.1 to 5.0% by mass. The lower limit is more preferably 0.5% by mass, and particularly preferably 1.0% by mass or more. The upper limit is more preferably 4.5% by mass or less, and particularly preferably 4.0% by mass or less. When it is 0.1% by mass, the effect of the present invention of improving dye uniformity is further enhanced. On the other hand, when it is 5.0% by mass or less, the effect of preventing background staining is enhanced.

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

Preferably, alkyl quaternary ammonium salts are used, more preferably, monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts, and particularly preferably, monoalkyl quaternary ammonium salts.

Examples of monoalkyl quaternary ammonium salts include lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, alkyl (16,18) trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium saccharin, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, stearyl trimethyl ammonium saccharin, alkyl (28) trimethyl ammonium chloride, diPOE (2) oleyl methyl ammonium chloride, diPOE stearyl methyl ammonium chloride, POE (1) POP (25) diethyl methyl ammonium chloride, POP methyl diethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, behenyl trimethyl ammonium methyl sulfate, etc. Particularly preferred are stearyl trimethyl ammonium chloride, alkyl (16,18) trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride.

Examples of dialkyl-type quaternary ammonium salts include dialkyl (12-15) dimethyl ammonium chloride, dialkyl (12-18) dimethyl ammonium chloride, dialkyl (14-18) dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, isostearyl lauryl dimethyl ammonium chloride, etc.

The content of the cationic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. The lower limit is more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit is more preferably 5% by mass or less, and particularly 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, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid surfactants, mono- or diester phosphate surfactants, sulfosuccinates, N-alkyloylmethyl taurine salts, and derivatives thereof. The counter ion of the anionic group of these surfactants may be, for example, any of sodium ions, potassium ions, and triethanolamine.

More specifically, examples include sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium POE lauryl ether sulfate, triethanolamine POE lauryl ether sulfate, ammonium POE lauryl ether sulfate, sodium POE stearyl ether sulfate, sodium stearoyl methyl taurine, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, sodium lauryl phosphate, POE lauryl ether phosphate and its salts, N-lauroyl glutamate salts (sodium lauroyl glutamate, etc.), N-lauroyl methyl-β-alanine salt, N-acyl glycine salt, N-acyl glutamate salt, sodium N-stearoyl-N-methyl taurine, higher fatty acids such as lauric acid and myristic acid, and salts of these higher fatty acids. One or more of these may be used.

The content of the anionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. The lower limit is more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit is more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

Examples of the amphoteric surfactant include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
Specific examples of the amino acid type amphoteric surfactant include glycine type amphoteric surfactants such as sodium N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium undecylhydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, sodium N-coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine, sodium N-coconut oil fatty acid acyl-N'-carboxyethoxyethyl-N'-carboxyethylethylenediamine, disodium N-coconut oil fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine, sodium lauryldiaminoethylglycine, and sodium palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine; and aminopropionic acid type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, and triethanolamine laurylaminopropionate.
Specific examples of betaine-type amphoteric surfactants include aminoacetic acid betaine-type amphoteric surfactants such as coconut oil alkyl betaine, lauryl dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, sodium stearyl dimethyl betaine, coconut oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, ricinoleic acid amidopropyl betaine, and stearyl dihydroxyethyl betaine; and sulfobetaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine.

The content of the amphoteric surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. The lower limit is more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The upper limit is more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

The total content of all surfactants in the hair dye composition 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 particularly preferably 0.1% by mass or more. The upper limit is more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[Method of using the hair dye composition]
The method of using the hair dye composition of the present invention is characterized by applying the hair dye composition to hair. According to the method of using the hair dye composition, it is possible to provide a hair dyeing method that reduces unevenness in the dyed result and has excellent dyeing uniformity. The hair dye composition of the present invention can be suitably used on both healthy hair and damaged hair that has been treated with a hair treatment agent such as a hair dyeing treatment, a bleaching treatment, a decoloring treatment, or a perm treatment, and has the effect of excellent dyeing uniformity. Furthermore, since color unevenness due to hair dyeing treatment is likely to occur in damaged hair, the effect of the present invention of excellent dyeing uniformity can be further exhibited. Furthermore, since color unevenness is more likely to occur in hair that has both healthy hair and damaged hair, the hair dye composition of the present invention can be more suitably used.

The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited to these examples.
[Preparing the hair bundle]
Hair bundle samples (same human hair, hair diameter: 75-95 micrometers) were treated with "Promaster EX LT" (a bleaching agent manufactured by Hoyu Corporation) at 30°C for 30 minutes, then rinsed with water, shampooed and dried with a hair dryer (bleaching treatment). Next, the hair was permed in the usual manner with a perm agent ("Lutea TG" manufactured by Hoyu Corporation), then rinsed with water, shampooed and dried with a hair dryer (perm treatment).
In this way, hair bundles were prepared by carrying out the above-mentioned bleaching treatment and then carrying out the above-mentioned continuous perm treatment once (damaged hair bundles), and hair bundles were prepared by carrying out only one water wash, shampoo and dryer treatment (healthy hair bundles).
[Preparation of hair dye composition]
Two-part hair dye compositions were prepared, each consisting of a first part and a second part, with the compositions shown in the following Tables 1 to 3. The first and second parts were mixed in a 1:1 ratio.
Next, the hair dye compositions were evaluated for "even dyeing,""hair dyeing power,""staining on the background," and "ease of application." Additionally, the first agent was evaluated for "formulation stability." The evaluation methods are described below. The evaluation results are shown in the lower part of each table.

[Evaluation method]
In the evaluation of the hair dye composition, damaged hair strands and healthy hair strands were dyed using the hair dye composition of each example. The hair dyeing method was as follows.
(Hair dyeing method)
3 g of the hair dye composition of each example was applied to 1 g of hair bundle using a brush and left to stand at 25° C. for 20 minutes. The hair bundle was then rinsed to wash away the oxidative hair dye, and further washed twice with shampoo (Promaster Color Care Stylish Shampoo, manufactured by Hoyu Co., Ltd.) to wash away the hair dye composition. Next, a treatment (Promaster Color Care Stylish Hair Treatment, manufactured by Hoyu Co., Ltd.) was applied to the hair bundle. After rinsing the hair bundle to wash away the treatment, the moisture of the hair bundle was wiped off with a towel, and finally dried with a hair dryer.

＜Even dyeing＞
The lightness of the damaged hair bundles and healthy hair bundles dyed as described above was measured using a colorimeter (CM-508D, manufactured by Minolta Co., Ltd.).
Then, the difference (L1-L2) between the lightness (L1 value) of the damaged hair bundle (sample that was bleached and then permed once) and the lightness (L2 value) of the healthy hair bundle (sample that was not bleached or permed) was given a rating of "5" if it was less than 0.6, a rating of "4" if it was 0.6 or more and less than 1.0, a rating of "3" if it was 1.0 or more and less than 1.4, a rating of "2" if it was 1.4 or more and less than 1.8, and a rating of "1" if it was 1.8 or more. In this measurement, the smaller the difference in lightness (L1-L2), the better the dyeing uniformity.
The evaluation results are shown in the item "Evenness of Dyeing" in the column "Evaluation" of Tables 1 to 4.

<Hair dyeing power>
Ten panelists visually evaluated the dyeing power of healthy hair bundles dyed as described above, based on Example 1, which was superior to all of Comparative Examples 1 to 3. The evaluation method was to give the dyeing power of the hair dye composition 2 points for "superior to Example 1," 1 point for "same as Example 1," and 0 point for "inferior to Example 1," and to rank them by the total score. The average score of the scores given by each panelist was then calculated.
5: Average score is 1.9 or more 4: Average score is 1.4 or more but less than 1.9 3: Average score is 0.9 or more but less than 1.4 2: Average score is 1.4 or more but less than 0.9 1: Average score is less than 0.4

＜Prevents scalp stains＞
The hair dye composition of each example was applied to the upper arms of 20 panelists and left for 30 minutes. After that, the hair dye was washed off, and the upper arms were lightly scrubbed with soap. Based on the number of panelists who judged that the hair dye (skin stain) attached to the upper arms was easily removed, the skin stain prevention effect of each hair dye example was evaluated on the following 5-point scale.
5: 20-17 people 4: 16-13 people 3: 12-9 people 2: 8-5 people 1: 4-0 people

<Coating operability>
The hair dye composition of each example was applied to human hair using a brush, and the application operability of each hair dye composition was evaluated by 10 panelists. The evaluation method was as follows: for each of the items of "ease of application with a brush,""spread when applied to hair," and "adhesion to hair,""verygood" was given 2 points, "good" was given 1 point, and "insufficient" was given 0 points, and the total score was calculated. Next, the average score of each panelist's scores was calculated.
5: Average score is 5.0 or more 4: Average score is 4.0 or more but less than 5.0 3: Average score is 3.0 or more but less than 4.0 2: Average score is 2.0 or more but less than 3.0 1: Average score is less than 2.0

<Formulation stability>
The first agent of each example was filled into a transparent No. 4 standard bottle (about 37 mL capacity) to about 80% and sealed. This was left to stand in a thermostatic chamber at 25°C, and the emulsified state after 24 hours was visually evaluated by 10 panelists. The evaluation criteria were 4 points for no separation at all, 3 points for slight separation, 2 points for considerable separation, and 1 point for complete separation. The average score was calculated from the results of the evaluation by each panelist.
5: Average score is 4.0 or more 4: Average score is 3.5 or more but less than 4.0 3: Average score is 3.0 or more but less than 3.5 2: Average score is 2.5 or more but less than 3.0 1: Average score is less than 2.5

In Table 1, comparing Examples 1 to 6 and Comparative Example 1, improvement in level dyeing property was recognized by containing (b) oil component and (c) PEG. Moreover, as shown in Comparative Examples 2 and 3, addition of an oil component having a Log Kow of less than 14.0 or PEG having a Log Kow of more than -3.0 did not improve level dyeing property.
In addition, comparing Example 1 with Examples 5 and 6, it was found that when the ratio (c/b) of the content of (c) PEG to the content of (b) oily component was 1.0 or less and 0.06 or more, the effect of further improving the uniformity of dyeing was observed.

As can be seen from Table 2, by using (a) 4APE and (d) p-aminophenol in combination as dye intermediates, further improvement in dye levelness was observed. In addition, the effect of preventing background staining was improved.

In Table 3, comparing Examples 1, 9 and 10, it can be seen that as the ratio (b/a) of the content of (b) oily component to (a) 4APE increases, the effect of preventing background staining, the stability of the formulation and the ease of application improve, while as the ratio (b/a) decreases, the hair dyeing power improves.
Furthermore, comparing Examples 1, 11 and 12, it can be seen that as the ratio (c/a) of the content of (c) PEG to (a) 4APE increases, the effect of preventing scalp staining increases, while as c/a decreases, the hair dyeing power improves.

Table 4 shows that components (b) and (c) have excellent dye uniformity even when contained in the second agent, just as they do when contained in the first agent.

The hair dye composition of the present invention can be used as a hair dye composition for dyeing human body hair such as head hair, beard, eyebrows, leg hair, etc. In addition, it may be used for dyeing body hair of animals such as pets.
The hair dye composition of the present invention can be used as a hair dye composition for use in a beauty salon or a barber shop, or as a hair dye composition for self-coloring.

The hair dye composition of the present invention can be suitably used on healthy hair and damaged hair that has been subjected to hair treatment such as dyeing, bleaching, decoloring, and perming, and has the effect of excellent dye uniformity. Furthermore, from the viewpoint of excellent dye uniformity, the hair dye composition of the present invention can be particularly suitably used on hair that is both healthy and damaged.

The hair dye composition of the present invention can be used for hair dyeing treatments in beauty salons, barber shops, etc., and for self-coloring.
The hair dyeing method can be suitably used for both healthy and damaged hair, and is particularly suitable for dyeing hair that is a mixture of healthy and damaged hair.

Claims (6)

(a) A hair dye composition containing 2,2'-[(4-aminophenyl)imino]bisethanol and/or a salt thereof,
(b) one or more oil components selected from hydrocarbons, waxes, esters, and fats and oils, each having an octanol/water partition coefficient of 14.0 or more at 25° C.;
(c) polyethylene glycol having an octanol/water partition coefficient at 25° C. of −10.0 to −3.0;
Contains
In the hair dye composition,
The content of (b) is 1% by mass or more,
A hair dye composition, characterized in that the content of the (c) is 0.01% by mass or more (provided that the hair dye composition contains all of the following components: resorcinol, 2,2'-[(4-aminophenyl)imino]bisethanol sulfate, 2,4-diaminophenoxyethanol hydrochloride, toluene-2,5-diamine, α-naphthol, cetyl octanoate, soft cholesteryl lanolin fatty acid, paraffin, stearyl alcohol, cetrimonium chloride, POE cetyl ether, POE behenyl ether, lipophilic glyceryl stearate, ammonium chloride, highly polymerized dimethicone-1, PEG (20), PG, aqueous ammonia, ammonium bicarbonate, ascorbic acid, sodium sulfite anhydride, trisodium ethylenediamine hydroxyethyl triacetate dihydrate, tetrasodium hydroxyethane diphosphonate solution, fragrance, and water;
As well as water, stearyl alcohol, PEG-20, ceteth-20, ethanolamine, cetanol, p-phenylenediamine, ceteth-2, ceteth-30, petrolatum, resorcin, fragrance, ascorbic acid, steartrimonium chloride, 2,4-diaminophenoxyethanol HCl , m-aminophenol, hydroxyethylethylenediaminetriacetate trisodium solution , The hair dye composition except for the hair dye composition consisting of a mixture of a first agent containing all of the components of N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate , polyquaternium-6, sodium sulfite, taurine, olive oil, p-aminophenol, pullulan, sodium hydroxide, tocopherol, and dibutylhydroxytoluene, and a second agent containing all of the components of water, hydrogen peroxide, cetanol, stearyl alcohol, PEG-4, ceteth-20, ceteth-2, isostearyl alcohol, steartrimonium chloride, phenoxyethanol, propylene glycol, and citric acid. The hair dye composition according to claim 1, characterized in that the content of (a) is 0.01 to 4% by mass. The hair dye composition according to claim 1 or 2, characterized in that the ratio (c/b) of the content of (c) to that of (b) is 0.06 to 1.0. The hair dye composition according to any one of claims 1 to 3, characterized in that the ratio (b/a) of the content of (b) to the content of (a) is 0.25 to 100. The hair dye composition according to any one of claims 1 to 4, characterized in that the ratio (c/a) of the content of (c) to that of (a) is 0.0025 to 100. The hair dye composition according to any one of claims 1 to 5, further comprising (d) p-aminophenol.