Hair dye composition

Abstract

To provide novel means for improving leveling in a hair dye composition containing 2,2'-[(4-aminophenyl) imino] bisethanol or a salt thereof.SOLUTION: In order to solve the subject, (a) in the hair dye composition containing 2,2'-[(4-aminophenyl)imino]bisethanol or a salt thereof, provided is a hair dye composition characterized by containing (b) one or more oil components selected from hydrocarbon, waxes, esters, and oils and fats, and having the octanol / water partition coefficient at 25°C of 14.0 or more, and (c) polyethylene glycol having the octanol / water partition coefficient at 25°C of -10.0 to -3.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] 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 leveling ability. [Background technology]

[0002] Conventionally, two-component hair dye compositions have been widely used, comprising a first component containing an oxidation dye consisting of a dye intermediate and a coupler, and a second component containing an oxidizing agent. These hair dye compositions penetrate a low-molecular-weight oxidation dye into the hair, where it undergoes oxidative polymerization to produce a pigment and dye the hair. These hair dye compositions can dye hair in a variety of colors as desired and also have excellent hair dyeing power.

[0003] Among various dye intermediates, 4APE and its salts are known as oxidation dyes that impart gloss to hair and produce natural, smooth dyed results. For example, Patent Documents 1 to 3 disclose hair dye compositions containing 4APE that reduce scalp staining, have excellent weather resistance, deep color properties, and produce excellent dyed results.

[0004] On the other hand, when 4APE and / or its salts are used as dye intermediates, there is a drawback in that the hair cannot be dyed uniformly, resulting in uneven dyeing. Therefore, hair dye compositions containing 4APE and / or its salts have been developed with the aim of improving dye levelness. For example, Patent Document 4 discloses a method of improving dye levelness by adding a cationic polymer to a hair dye composition containing 4APE. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-267831 [Patent Document 2] Japanese Patent Application Publication No. 7-267833 [Patent Document 3] Japanese Patent Application Publication No. 7-267835 [Patent Document 4] Japanese Patent Application Publication No. 7-267832 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a new means for improving the dyeing levelness of a hair dye composition containing 4APE and / or a salt thereof, with the aim of further improving the dyeing levelness of a hair dye composition containing 4APE and / or a salt thereof. [Means for solving the problem]

[0007] 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 dye levelness, and have completed the present invention. That is, the present invention relates to the following hair dye composition.

[0008] The hair dye composition of the present invention is characterized by containing (a) a hair dye composition containing 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 at 25°C of 14.0 or more, and (c) polyethylene glycol having an octanol / water partition coefficient at 25°C of -10.0 to -3.0. According to the hair dye composition of the present invention, a hair dye composition having excellent dyeing uniformity can be provided.

[0009] 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 levelness can be more effectively exhibited.

[0010] 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. As the content of component (b) increases, it is observed that in addition to improving dye levelness, the effect of preventing background staining, ease of application, and formulation stability also tend to improve. On the other hand, if component (b) is added in excess, it is observed that the hair dyeing power tends to decrease. Therefore, by setting the content ratio of (b) to (a) (b / a) to 0.25 to 100, it is possible to achieve not only improved dye levelness but also a balanced improvement in hair dyeing power, formulation stability, and ease of application.

[0011] Furthermore, one embodiment of the hair dye composition of the present invention is characterized in that the ratio (c / a) of the content of the (c) to the content of the (a) is 0.0025 to 100. Increasing the content of component (c) not only improves dyeing levelness but also enhances the effect of preventing background staining. On the other hand, excessive addition of component (c) tends to reduce dyeing power. Therefore, by setting the content ratio of (c) to (a) (c / a) to 0.0025 to 100, it is possible to achieve a balanced effect of improving dyeing levelness, preventing background staining, and improving dyeing power.

[0012] Furthermore, one embodiment of the hair dye composition of the present invention is characterized by containing (d) p-aminophenol. This feature not only further improves the levelness of dyeing, but also has the effect of preventing background staining. [Effects of the Invention]

[0013] According to the present invention, a new means for improving dye levelness in a hair dye composition containing 4APE and / or a salt thereof can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0014] Next, the present invention will be described, including the best mode for carrying out the invention. [Hair dye composition] The hair dye composition of the present invention is characterized by containing (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.

[0015] In hair dye compositions, the oxidation dye and the oxidizing agent are separated and distributed, 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 the oxidation dye and a second component containing the oxidizing agent, but it may also be a multi-component type consisting of three or more components.

[0016] The individual components constituting the hair dye composition of the present invention may be in any form, including, for example, liquid forms such as aqueous solutions and emulsions, creams, gels, etc. Furthermore, the hair dye composition after mixing the individual components may be in a dosage form that allows application in liquid, cream, gel, etc. Furthermore, the composition may be in the form of a foam or mist upon use. To form a foam, an aerosol foamer container containing a known propellant or foaming agent, a non-aerosol foamer container such as a squeeze foamer or pump foamer, or a shaking container may be used. Specific examples of propellants or foaming agents include liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen gas, carbon dioxide gas, etc. To form a mist, a sprayer may be used.

[0017] 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 up in a comb or the like and mixed on the hair using the comb or the like.

[0018] Next, each component used in the hair dye composition of the present invention will be described in detail. The content of each component refers to the content in the hair dye composition in which each component is mixed, unless otherwise specified.

[0019] <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.

[0020] [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 salts include salts of organic acids or inorganic acids, such as sulfates, hydrochlorides, phosphates, acetates, propionates, lactates, and citrates. [ka]

[0021] The content of 4APE and / or a salt thereof 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 gloss 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.

[0022] [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 may be contained, or two or more may be contained in combination.

[0023] 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 levelness be further enhanced, but also the effect of preventing background staining is improved. Furthermore, by using 4APE and p-aminophenol in combination, beautiful warm color tones can be achieved.

[0024] 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.

[0025] 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.

[0026] One or more types of dye intermediates can be selected and used depending on the desired hair color tone. The total content of dye intermediates containing 4APE and / or a salt thereof 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.

[0027] 〔coupler〕 Examples of couplers include mainly m-diamines, aminophenols, and diphenols. Specific examples include m-aminophenol, resorcinol, catechol, pyrogallol, phloroglucinol, 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.

[0028] One or more 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.

[0029] <(b) one or more oily components selected from hydrocarbons, waxes, esters, and fats and oils, each having a Log Kow of 14.0 or more> The hair dye composition of the present invention contains, as an oily component, (b) one or more oily 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) oily component").

[0030] Log Kow is a measure of the distribution of a substance between the aqueous phase and the organic (octanol) phase, and is defined by the following mathematical formula (1): LogKow = log([Mo] / [Mw]) (1) [Mo]: number of moles of substance in the octanol phase [Mw]: number of moles of substance in the aqueous phase

[0031] In the present invention, LogKow is measured and calculated using the program "KowWIN32" from Syracuse Research Corporation. If the calculation cannot be performed using the program, the measurement shall be performed according to the Japanese Industrial Standard Z7260-107:2000 "Measurement of partition coefficient (1-octanol / water) - Shake flask method."

[0032] Hydrocarbons are compounds composed of carbon and hydrogen. Examples of hydrocarbons with a LogKow of 14.0 or higher include hydrocarbons 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 values ​​in parentheses indicate LogKow (the same applies below).

[0033] 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).

[0034] 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).

[0035] Fats and oils are triglycerides, i.e. triesters of fatty acids and glycerin, such as olive oil (23.07), sunflower oil (22.86), grape seed oil (21.96), avocado oil (22.04), palm 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).

[0036] (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 (15.4), and cereals such as cereals containing hydroxypropyl methylcellulose (15.4). 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).

[0037] 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 effectively exhibited.

[0038] The content of (b) oily component 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, (b) oily component may be blended into either the first or second component, or may be blended into both the first and second components. In the case of a multi-component hair dye composition having three or more components, it may be blended into a component separate from the first and second components.

[0039] Furthermore, 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 effects of improving application operability, the effect of preventing background staining, and the formulation stability are achieved. On the other hand, when b / a is 1000 or less, the hair dyeing power is improved.

[0040] <(c) Polyethylene glycol with a 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 LogKow of -10.0 to -3.0. The (c)PEG has an average molecular weight of 400 to 1600, and specific examples include PEG400 (-3.12), PEG600 (-4.22), PEG1000 (-6.41), and PEG1540 (-9.98). The values ​​in parentheses indicate LogKow. The method for measuring LogKow is the same as that for the (b) oily component. The average molecular weights of the PEGs are PEG400 (average molecular weight 360 to 440), PEG600 (average molecular weight 560 to 640), PEG1000 (average molecular weight 950 to 1050), and PEG1540 (average molecular weight 1290 to 1650). The LogKow of the (c)PEG is preferably -7.0 or higher, and more preferably -4.5 or higher. Specifically, (c) PEG is preferably PEG1000, and more preferably PEG600 or PEG400.

[0041] 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 component, or in both the first and second components. In the case of a multi-component hair dye composition of three or more components, it may be blended in a component separate from the first and second components.

[0042] Furthermore, the ratio (c / a) of the content of (c) PEG to (a) 4APE and / or a salt thereof 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.

[0043] In the hair dye composition of the present invention, the ratio (c / b) of the content of (c) PEG to (b) oily component is preferably 1.0 or less. When it is 1.0 or less, the effect of the present invention of improving dye levelness is further enhanced. 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.

[0044] <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) oily component, and (c) PEG. Other ingredients include, for example, oily ingredients (excluding (b) oily ingredients), polyhydric alcohols (excluding (c) PEG), oxidizing agents, alkaline 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 polymer, polydimethylmethylene piperidinium chloride solution, diallyldimethylammonium chloride, hydroxyethyl cellulose, etc. cationized water-soluble polymers, chelating agents such as hydroxyethylethylenediaminetriacetate trisodium dihydrate and hydroxyethanediphosphonic acid tetrasodium 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 ingredients, plant extracts, herbal extracts, amino acids and peptides, urea, vitamins, fragrances, and UV absorbers.

[0045] <Other oily ingredients> Examples of other oily components include hydrocarbons with a Log Kow of less than 14.0, higher alcohols, higher fatty acids, silicone oils, fats and oils with a Log Kow of less than 14.0, fluorinated oils, alkyl glyceryl ethers, esters with 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 an oily component having a Log Kow of 14.0 or more, thereby improving emulsion stability.

[0046] 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).

[0047] Examples of higher alcohols include cetanol (6.73), stearyl alcohol (7.72), cetostearyl alcohol (7.32), oleyl alcohol (7.50), arachyl 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).

[0048] 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).

[0049] Examples of fats and oils with a LogKow of less than 14.0 include almond oil (3.47).

[0050] Silicone oils are synthetic polymers in which silicon and oxygen atoms with organic groups are alternately linked by chemical bonds. Examples include dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxyl terminal 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.

[0051] Of 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).

[0052] Specific examples of alkyl glyceryl ethers include batyl alcohol, chimyl alcohol, selachyl alcohol, and isostearyl glyceryl ether.

[0053] Esters with a LogKow 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).

[0054] 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.

[0055] <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), etc.

[0056] 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 the other polyhydric alcohol is added, the effect of level dyeing tends to decrease, so by making the content of the other polyhydric alcohol less than 3% by mass, the effects of the present invention can be further exhibited.

[0057] <Oxidizing agent> The oxidizing agent is a component contained in the second agent and is a substance with oxidizing power. The oxidizing agent has the effect of oxidizing the oxidation dye to develop color and decomposing melanin inside the hair. Specific examples include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, persulfates such as potassium persulfate and sodium persulfate, 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 oxidizing agents, only one may be contained alone, or two or more may be contained in combination. Furthermore, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate may be contained as an oxidizing aid.

[0058] 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 to improve its stability, such as sodium stannate, ethylene glycol phenyl ether (phenoxyethanol), hydroxyethanediphosphonic acid, phosphoric acid, citric acid, or a salt thereof.

[0059] <Alkaline agent> Alkaline agents have the effect of swelling hair and promoting the penetration of dyes and oxidizing agents. Examples of alkaline agents include ammonia, alkanolamines, silicates, carbonates, bicarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, and hydroxides of alkali metals or alkaline earth metals. Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine. Examples of silicates include sodium silicate and potassium silicate. Examples of carbonates include sodium carbonate, ammonium carbonate, magnesium carbonate, and guanidine carbonate. Examples of bicarbonates include sodium bicarbonate and ammonium bicarbonate. Examples of metasilicates include sodium metasilicate and potassium metasilicate. Examples of phosphates include ammonium monophosphate. Examples of the basic amino acid include arginine, lysine, and salts thereof, and examples of the alkali metal or alkaline earth metal hydroxide include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among these, it is preferable to contain ammonia and alkanolamine.

[0060] 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.

[0061] The hair dye composition of the present invention preferably contains (e) ammonia. By containing ammonia, the effect of the present invention, that is, improved dyeing uniformity, can be further exhibited. Furthermore, the effect of improving the brightness and color development of hair in a hair dyeing process is also exhibited. When it is desired to simultaneously achieve the effect of ammonia and suppress 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 exhibited. Therefore, it is particularly preferable to use ammonia alone as the alkaline agent.

[0062] The ratio (e / a) of the content of (e) ammonia to (a) 4APE and / or a salt thereof 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 levelness of dyeing can be further exerted, and when it is 100 or less, the unpleasant odor of ammonia can be suppressed.

[0063] <Direct dye> Direct dyes are colored compounds that adhere to or penetrate hair to color it. Examples include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, disperse dyes, etc. These direct dyes may be used alone or in combination.

[0064] Examples of the acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, Red No. 230 (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3, Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, Black No. 401, etc.

[0065] The above basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange. 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet11:1, Basic Examples include Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, and Basic Yellow 87.

[0066] Examples of the natural dyes include gardenia dye, turmeric dye, annatto dye, copper chlorophyllin sodium, paprika dye, lac dye, and henna.

[0067] Examples of the nitro dye include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and salts thereof.

[0068] 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. Examples include 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.

[0069] Examples of the disperse dye 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, and Disperse Violet 15.

[0070] 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.

[0071] <Surfactant> The surfactant may be a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant. In the following description, POE represents a polyoxyethylene chain, POP represents a polyoxypropylene chain, and the number in parentheses following each represents the number of moles added. The number in parentheses following alkyl represents the number of carbon atoms in the fatty acid chain.

[0072] Examples of nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE·POP alkyl ethers, POE sorbitan fatty acid esters, POE monofatty 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, and POE phytosterol.

[0073] 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.

[0074] The hair dye composition of the present invention preferably contains a nonionic surfactant having an HLB of 12.0 or less. This further enhances the effect of preventing scalp 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 can be measured according to "20·3·1 Measurement of HLB value by emulsification method" (pp. 854-855) in the "Handbook - Cosmetics and Pharmaceutical Raw Materials - Revised Edition (published February 1, 1977, Nikko Chemicals Co., Ltd.)."

[0075] 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 the content is 0.1% by mass, the effect of the present invention of improving dye levelness is further enhanced. On the other hand, when the content is 5.0% by mass or less, the effect of preventing background staining is enhanced.

[0076] 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 Arcobel tertiary amine salts; cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts; and benzethonium chloride.

[0077] Preferred are alkyl quaternary ammonium salts, more preferred are monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts, and particularly preferred are monoalkyl quaternary ammonium salts.

[0078] Examples of monoalkyl quaternary ammonium salts include lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl(28)trimethylammonium chloride, diPOE(2)oleylmethylammonium chloride, diPOEstearylmethylammonium chloride, POE(1)POP(25)diethylmethylammonium chloride, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate, etc. Particularly preferred are stearyltrimethylammonium chloride, alkyl(16,18)trimethylammonium chloride, and cetyltrimethylammonium chloride.

[0079] Examples of dialkyl quaternary ammonium salts include dialkyl(12-15)dimethylammonium chloride, dialkyl(12-18)dimethylammonium chloride, dialkyl(14-18)dimethylammonium chloride, dicocoyldimethylammonium chloride, dicetyldimethylammonium chloride, distearyldimethylammonium chloride, and isostearyllauryldimethylammonium chloride.

[0080] 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.

[0081] 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, phosphate mono- or diester surfactants, sulfosuccinate esters, N-alkyloylmethyl taurine salts, and derivatives thereof. The counter ion of the anionic group of these surfactants may be, for example, any of sodium ion, potassium ion, and triethanolamine.

[0082] More specific examples include sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, 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 stearoylmethyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, sodium lauryl phosphate, POE lauryl ether phosphate and salts thereof, N-lauroyl glutamates (such as sodium lauroyl glutamate), N-lauroylmethyl-β-alanine salts, N-acylglycine salts, N-acylglutamate, sodium N-stearoyl-N-methyl taurate, higher fatty acids such as lauric acid and myristic acid, and salts of these higher fatty acids, and one or more of these may be used.

[0083] 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.

[0084] Examples of amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants. Specific examples of amino acid type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, undecylhydroxyethylimidazolinium betaine sodium, alkyldiaminoethylglycine hydrochloride, N-coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine sodium, N-coconut oil fatty acid acyl-N'-carboxyethoxyethyl-N' Glycine-type amphoteric surfactants such as N-carboxyethylethylenediamine disodium, N-cocoacyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, lauryldiaminoethylglycinate sodium, and palmacyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium; aminopropionic acid-type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, and triethanolamine laurylaminopropionate; and the like. Specific examples of betaine-type amphoteric surfactants include aminoacetic acid betaine-type amphoteric surfactants such as coconut oil alkyl betaine, lauryl dimethyl aminoacetic acid betaine, myristyl dimethyl aminoacetic acid betaine, stearyl dimethyl aminoacetic 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.

[0085] 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.

[0086] 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.

[0087] [Method of using the hair dye composition] A method for using the hair dye composition of the present invention is characterized by applying the hair dye composition to hair. This method for using the hair dye composition can provide a hair dyeing method that reduces unevenness in the finished color and provides 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, bleaching treatment, decoloring treatment, or perm treatment, and exhibits the effect of excellent dyeing uniformity. Furthermore, since damaged hair is prone to color unevenness due to hair dyeing treatment, the effect of the present invention of excellent dyeing uniformity can be further exhibited. Furthermore, since color unevenness is even more likely to occur in hair that is a combination of healthy hair and damaged hair, the hair dye composition of the present invention can be used more suitably. [Example]

[0088] The present invention will be specifically described 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" (Hoyu Co., Ltd., bleach) at 30°C for 30 minutes, then rinsed with water, shampooed, and dried with a hair dryer (bleaching treatment). Next, they were permed using a perm agent (Hoyu Co., Ltd., "Lutea TG") in the usual manner, then rinsed with water, shampooed, and dried with a hair dryer (perm treatment). In this way, hair bundles (damaged hair bundles) were created by performing the above bleaching treatment followed by the above continuous perm treatment process once, and hair bundles (healthy hair bundles) were created by performing only water washing, shampooing, and hair dryer treatment once. [Preparation of Hair Dye Composition] Two-part hair dye compositions were prepared, consisting of a first part and a second part, with the compositions shown in the following Tables 1 to 3. The first part and the second part were mixed at a mixing ratio of 1:1. Next, the hair dye compositions were evaluated for "even dyeing," "hair dyeing power," "staining on the scalp," and "ease of application." Additionally, the first pack was evaluated for "formulation stability." These evaluation methods are described below. The evaluation results are shown at the bottom of each table.

[0089] [Evaluation method] In the evaluation of the hair dye compositions, damaged hair strands and healthy hair strands were dyed using the hair dye compositions 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 strand using a brush and left to stand at 25°C for 20 minutes. The hair strand 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 strand. After rinsing the treatment, the hair strand was wiped dry with a towel and finally dried with a hair dryer.

[0090] <Level 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.). If the difference (L1 value) between the lightness of the damaged hair bundle (a sample that had been bleached and then permed once) and the lightness (L2 value) of the healthy hair bundle (a sample that had not been bleached or permed) (L1-L2) was less than 0.6, it was given a rating of "5," if it was 0.6 or more and less than 1.0 it was given a rating of "4," if it was 1.0 or more and less than 1.4 it was given a rating of "3," if it was 1.4 or more and less than 1.8 it was given a rating of "2," and if it was 1.8 or more it was given a rating of "1." 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 "Evaluation" column of Tables 1 to 4.

[0091] <Hair dyeing power> Ten panelists visually evaluated the dyeing power of healthy hair strands dyed as described above, using Example 1, which was superior to all of Comparative Examples 1 to 3, as the standard. The evaluation method involved assigning 2 points for "better than Example 1," 1 point for "same as Example 1," and 0 point for "inferior to Example 1," and then adding up the total score to evaluate the dyeing power of the hair dye composition. The average score was then calculated from the scores of each panelist. 5: Average score is 1.9 or higher 4: Average score is 1.4 or more but less than 1.9 3: Average score is between 0.9 and 1.4 2: Average score is between 1.4 and 0.9 1: Average score is less than 0.4

[0092] <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 stains) adhering to the upper arms could be easily removed, the scalp 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

[0093] <Coating operability> Each hair dye composition 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: "Ease of application with a brush," "Spreadability when applied to hair," and "Hair adhesion." "Very good" was given 2 points, "good" was given 1 point, and "insufficient" was given 0 points, and the total score was calculated. The average score of each panelist's evaluation results was then calculated. 5: Average score is 5.0 or above 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 between 2.0 and 3.0 1: Average score is less than 2.0

[0094] <Formulation stability> The first agent of each example was filled into a transparent No. 4 standard bottle (approximately 37 mL capacity) to approximately 80% of the capacity 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: no separation observed, 4 points; slight separation observed, 3 points; significant separation observed, 2 points; and complete separation, 1 point. The average score was calculated from the scores of each panelist. 5: Average score is 4.0 or above 4: Average score is between 3.5 and 4.0 3: Average score is 3.0 or more but less than 3.5 2: Average score is between 2.5 and 3.0 1: Average score is less than 2.5

[0095] [Table 1]

[0096] In Table 1, comparing Examples 1 to 6 with Comparative Example 1, it was found that the inclusion of (b) an oily component and (c) PEG improved the level dyeing property. Moreover, as shown in Comparative Examples 2 and 3, the addition of an oily component with a LogKow of less than 14.0 or PEG with a LogKow of more than -3.0 did not improve the level dyeing property. Furthermore, 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 level dyeing property was observed.

[0097] [Table 2]

[0098] As can be seen from Table 2, the use of (a) 4APE and (d) p-aminophenol as dye intermediates in combination further improved the level dyeing property. In addition, the effect of preventing background staining was improved.

[0099] [Table 3]

[0100] Comparing Examples 1, 9, and 10 in Table 3, 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 scalp staining, formulation stability, and application operability improve, while as 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.

[0101] [Table 4]

[0102] Table 4 shows that components (b) and (c) have excellent leveling properties when contained in the second agent, just as when contained in the first agent. [Industrial Applicability]

[0103] 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 also be used to dye the 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 barber shop, or as a hair dye composition for self-coloring.

[0104] 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, dedying, perming, etc., and exhibits the effect of excellent dyeing uniformity. Furthermore, from the viewpoint of excellent dyeing uniformity, the hair dye composition of the present invention can be particularly suitably used on hair that is a mixture of healthy hair and damaged hair.

[0105] The hair dye composition of the present invention can be used for hair dyeing treatments at 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

1. (a) A hair dye composition containing 2,2'-[(4-aminophenyl)imino]bisethanol 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 at 25°C of 14.0 or more; (c) polyethylene glycol having an octanol / water partition coefficient at 25°C of -10.0 to -3.0; A hair dye composition comprising:

2. 2. The hair dye composition according to claim 1, wherein the ratio of the content of said (c) to the content of said (b) (c / b) is 0.06 to 1.

0.

3. 3. The hair dye composition according to claim 1, wherein the ratio of the content of said (b) to the content of said (a), (b / a), is 0.25 to 100.

4. The hair dye composition according to any one of claims 1 to 3, wherein the ratio (c / a) of the content of said (c) to the content of said (a) is 0.0025 to 100.

5. The hair dye composition according to any one of claims 1 to 4, comprising (d) p-aminophenol.

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