JP6636243B2 - Oxidative hair dye - Google Patents

Description

  The present invention can sufficiently dye hair, especially gray hair, suppress dripping of the oxidized hair dye during application to the hair, and oxidize the hair dye from the hair even during the standing time The present invention relates to an oxidative hair dye which can also suppress dripping and has excellent storage stability.

  As a hair coloring agent for hair, a hair coloring agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, and using a mixture of the two immediately before use, a so-called two-part hair coloring agent is used. (Patent Documents 1 to 4). In such a two-part hair dye, in order to sufficiently dye hair, particularly gray hair, it is necessary to increase the amount of the oxidation dye in the first part. This allows the hair to be sufficiently dyed, but the interaction between the oxidation dye and additives such as surfactants and polymers due to the presence of a large amount of oxidation dye in the hair dye. May occur. Due to this interaction, the viscosity of the hair dye increases over time, and a precipitate is formed, which causes problems such as a decrease in storage stability and an increase in temperature when the hair dye is used.

JP 2010-006804 A JP 2011-132213 A JP 2011-132228 A JP 2012-072128 A

  When the oxidation dye is blended with the hair dye at a high concentration, as described above, an interaction occurs between the oxidation dye and an additive such as a surfactant or a polymer, and the viscosity of the hair dye decreases over time and the sedimentation occurs. In some cases. As a result, storage stability, which is a performance required as an oxidative hair dye, may be reduced. There is also a need for a hair dye that remains on the hair during application to the hair and does not sag.

  Therefore, an object of the present invention is to provide a storage agent which is stable over time even when a high concentration of an oxidation dye is blended with the first agent, and has excellent storage stability. It is an object of the present invention to provide a hair dye capable of suppressing dripping from the hair and sufficiently dyeing hair, especially gray hair.

The present inventors have conducted detailed studies on oxidative hair dyes in order to solve the above problems, and have completed the present invention.
That is, the present invention includes the following preferred embodiments.
[1] An oxidative hair dye used by mixing a first agent containing an alkali agent and a second agent containing an oxidizing agent,
The first agent contains 1 to 20% by mass of an oxidation dye based on the total mass of the first agent;
The first agent comprises at least one anionic surfactant, at least one amphoteric surfactant, and at least one alkyl glucoside-type nonionic surfactant;
An oxidative hair dye, wherein the oxidative hair dye is a gel or an emulsion.
[2] The oxidative hair dye according to the above [1], wherein the viscosity of the oxidative hair dye is 100 to 2000 mPa · s at 25 ° C.
[3] The oxidative hair dye according to [1] or [2], wherein the mass ratio of the anionic surfactant and the amphoteric surfactant is 1: 3 to 3: 1.
[4] The oxidation hair dye according to any one of [1] to [3], wherein the oxidation dye contains an oxidation dye in a salt form.

  According to the oxidative hair dye of the present invention, hair, particularly gray hair, can be sufficiently dyed, dripping of the oxidative hair dye at the time of application to hair can be suppressed, and even during standing time The dripping of the oxidative hair dye from the hair can be suppressed. In the present invention, since the first agent is stable over time, the oxidative hair dye of the present invention has excellent storage stability.

  The oxidative hair dye of the present invention includes a first agent containing an alkaline agent and a second agent containing an oxidizing agent. The oxidative hair dye of the present invention is a multi-part oxidative hair dye, and is used by mixing at least a first agent and a second agent. The first agent further contains an oxidation dye in addition to the alkali agent. Further, the first agent further includes at least one anionic surfactant, at least one amphoteric surfactant, and at least one alkylglucoside-type nonionic surfactant.

  Oxidation dyes are classified into dye intermediates and couplers. The oxidation dye preferably comprises a dye intermediate. As the oxidation dye, only one kind may be used alone, or two or more kinds may be used in combination.

  Examples of the dye intermediate include p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, 4,4′-diaminodiphenylamine, p-aminophenol, o-aminophenol, and p-phenylenediamine. Methylaminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylenediamine, 4-amino-m-cresol, 2- Amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol, and salts thereof. Examples of the salts include hydrochloride and sulfate. As these dye intermediates, only one kind may be contained alone, or two or more kinds may be contained in combination.

  The coupler develops a color when combined with a dye intermediate. Examples of the coupler include resorcin, 5-amino-o-cresol, m-aminophenol, 5- (2-hydroxyethylamino) -2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, and toluene- 3,4-Diamine, 2,6-diaminopyridine, diphenylamine, N, N-diethyl-m-aminophenol, phenylmethylpyrazolone, and salts thereof. Examples of the salts include hydrochloride and sulfate. As these couplers, only one kind may be contained alone, or two or more kinds may be contained in combination.

  The content of the oxidation dye in the first agent is 1 to 20% by mass, preferably 2 to 15% by mass, more preferably 3 to 10% by mass, based on the total mass of the first agent. When the content of the oxidation dye in the first agent is equal to or more than the above lower limit, hair dyeability is further improved. In addition, when the content of the oxidation dye in the first agent is equal to or less than the upper limit, the agent can be a stable agent.

  Further, in the present invention, the oxidation dye may contain an oxidation dye in the form of a salt. It is said that the oxidation dye in the form of a salt tends to cause problems such as a decrease in storage stability. However, according to the present invention, even if the first agent contains the oxidation dye in the form of a salt, Oxidative hair dyes can exhibit good storage stability.

  In order to adjust the color tone, the first agent may further include a direct dye. Examples of direct dyes include nitro dyes, acid dyes, disperse dyes, HC dyes, and basic dyes. Examples of the nitro dye include paranitro orthophenylenediamine, nitroparaphenylenediamine, paranitrometaphenylenediamine sulfate, 2-amino-5-nitrophenol, and picramic acid. Examples of the acid dye include Blue No. 1 and Acid Orange 7 and the like. Examples of the disperse dye include Disperse Violet 1, Disperse Blue 1 and Disperse Black 9. Examples of the HC dye include HC Red 1 and HC Yellow 2. Examples of the basic dye include Basic Blue 99, Basic Brown 16 and Basic Yellow 87.

  The first agent includes at least one anionic surfactant, at least one amphoteric surfactant, and at least one alkyl glucoside-type nonionic surfactant. Examples of the anionic surfactant include higher fatty acid salts, alkyl sulfate salts, alkyl phosphate ester salts, alkyl ether sulfate salts, alkyl ether phosphate salts, alkyl ether carboxylate salts, and N-acylmethyltaurine salts. , Alkylsulfosuccinic acid, acyl lactate, N-acylsarcosine, N-acylglutamate and N-acylmethylalanine. Among them, from the viewpoint of foaming properties, alkyl sulfate salts and alkyl ether sulfate salts are preferred. The alkyl sulfate salt is not particularly limited, but preferably has an alkyl group having 10 to 22 carbon atoms, more preferably 10 to 16 carbon atoms. The alkyl ether sulfate is not particularly limited, but is preferably an alkyl group based on a linear primary alcohol, a linear secondary alcohol or a branched alcohol having 10 to 20 carbon atoms, more preferably 12 to 14 carbon atoms. And the average number of moles of the alkylene oxide group added is preferably 0.5 to 5, more preferably 0.5 to 4, and still more preferably 1 to 3. Examples of the alkylene oxide include ethylene oxide and propylene oxide. As the salt, an alkali metal salt is preferable, and examples thereof include a sodium salt and a potassium salt. Use of the above-mentioned anionic surfactant is preferable from the viewpoint of foaming property and stability of the preparation. As these anionic surfactants, only one kind may be used alone, or two or more kinds may be used in combination. The content of the anionic surfactant in the first agent is preferably from 0.1 to 50% by mass, and more preferably from 1 to 20% by mass, based on the total mass of the first agent, from the viewpoint of foaming properties and stability of the preparation. % Is more preferred.

  Examples of the amphoteric surfactant include a carbobetaine-based, an amidobetaine-based, a sulfobetaine-based, a hydroxysulfobetaine-based, an amidosulfobetaine-based, and a phosphobetaine-based having an alkyl group, an alkenyl group, or an acyl group having 8 to 24 carbon atoms. And imidazolinium-based surfactants. Among them, carbobetaine surfactants and sulfobetaine surfactants are preferable from the viewpoint of viscosity. Preferred amphoteric surfactants include amide laurate betaine, coconut oil fatty acid amidopropyl betaine, betaine lauryl dimethylaminoacetate, lauryl hydroxysulfobetaine, and the like. As these amphoteric surfactants, only one type may be used alone, or two or more types may be used in combination. In the present invention, the content of the amphoteric surfactant in the first agent is preferably from 0.1 to 50% by mass, more preferably from 1 to 20% by mass, based on the total mass of the first agent, in order to obtain an appropriate viscosity. Is more preferred.

Examples of the alkyl glucoside nonionic surfactant include octyl glucoside, nonyl glucoside, decyl glucoside, octyl thioglucoside, lauryl glucoside, and coconut oil alkyl glucoside. The nonionic surfactant of the alkyl glucoside type is preferably C ₆ -C ₂₀ alkyl-, more preferably C ₆ -C ₁₅ alkyl-, and even more preferably C ₆ -C ₁₂ alkyl-glucoside. Use of these alkylglucoside-type nonionic surfactants is preferable from the viewpoint of foaming properties. As these alkylglucoside-type nonionic surfactants, only one kind may be used alone, or two or more kinds may be used in combination. In the present invention, the content of the alkylglucoside-type nonionic surfactant is preferably from 0.1 to 10% by mass, preferably from 0.5 to 5%, based on the total mass of the first agent, from the viewpoint of the stability of the preparation. % Is more preferred.

  In the oxidative hair dye of the present invention, the first agent contains at least one anionic surfactant, at least one amphoteric surfactant, and at least one alkyl glucoside nonionic surfactant. After the oxidative hair dye containing the first and second agents is applied to the hair, the oxidative hair dye can be foamed by foaming. By lathering like shampooing, the oxidized hair dye can be uniformly attached to the hair. For this reason, it is possible to make the dyed hair less likely to have uneven dyeing.

  The total content of the surfactant in the first agent is preferably 5.0 to 50% by mass, and more preferably 10 to 30% by mass, based on the total mass of the first agent in consideration of dripping and foaming. Is more preferable.

  The mass ratio of the anionic surfactant and the amphoteric surfactant in the first agent is preferably from 1: 3 to 3: 1, more preferably from 1: 2 to 2: 1. When the mass ratio of the anionic surfactant and the amphoteric surfactant in the first agent is within the above range, it is particularly excellent in hair dyeing properties, and a viscosity that can be easily applied can be obtained.

  In the present invention, the first agent contains an alkaline agent. In the present invention, the alkali agent is not particularly limited. As the alkali agent, a conventionally known alkali agent can be used. The alkali agent may be an inorganic alkali agent or an organic alkali agent. As the alkali agent, only one kind may be used alone, or two or more kinds may be used in combination.

  Examples of the alkaline agent include ammonia, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium carbonate, isopropanolamine, monoethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1- And propanol.

  In the present invention, the content of the alkaline agent in the first agent is not particularly limited, but can be appropriately adjusted in consideration of desired dyeing properties and the like. The content of the alkali agent in the first agent is preferably 0.01 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 10% by mass, based on the total mass of the first agent. is there. When the content of the alkali agent is equal to or more than the above lower limit, the dyeability is particularly increased. When the content of the alkaline agent is equal to or less than the above upper limit, skin irritation is reduced.

  In the present invention, the first agent preferably further contains a reducing agent in addition to the alkali agent and the oxidation dye. By adding the reducing agent, the color development of the oxidation dye can be suppressed when the first agent is exposed to the atmosphere. Examples of the reducing agent include N-acetyl-L-cysteine, L-ascorbic acid, sodium sulfite, sodium pyrosulfite, thioglycolic acid, and the like, and salts thereof. As the reducing agent, only one type may be used alone, or two or more types may be used in combination. The content of the reducing agent in the first agent is preferably 0 to 2% by mass, more preferably 0.01 to 1% by mass, based on the total mass of the first agent, from the viewpoint of improving storage stability.

  In the present invention, the first agent may further contain, if necessary, other components which can be usually added to a hair dye. For example, other components that can be added include cationized cellulose and its derivatives, cationic starch, cationized guar gum and its derivatives, diallyl quaternary ammonium salt / acrylamide copolymer, vinyl imidazolium trichloride / vinyl pyrrolidone copolymer. Polymer, hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate copolymer, polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer Water-soluble cationic polymers such as vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer; isopropyl palmitate; Esters such as isopropyl listate, octyl dodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, and tridecyl isononanoate; beeswax, spermaceti, lanolin , Wax such as carnauba wax; ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carb Alcohols such as tall, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and glycerin; dimethylpolysilo Silicones such as xane and amino-modified silicone; anti-dandruff agents such as zinc pyrithione and benzalkonium chloride; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; humectants such as panthenol; Coloring agent: protein or hydrolyzate thereof obtained from silk, protein-containing extract obtained from seeds of legumes, Panax ginseng extract, rice germ extract, hibamata extract, camellia extract, aloe extract, moon peach leaf Extracts such as extracts and chlorella extracts; pearl powders such as titanium mica; fragrances; pigments; ultraviolet absorbers;

  In the present invention, the second agent contains an oxidizing agent. In the present invention, the oxidizing agent is not particularly limited, and a conventionally known oxidizing agent can be used. As the oxidizing agent, only one type may be used alone, or two or more types may be used in combination. The oxidizing agent is not particularly limited, but includes, for example, hydrogen peroxide, urea peroxide, persulfate, perborate, percarbonate, bromate and periodate. From the viewpoint of further improving the dyeability, the oxidizing agent is preferably hydrogen peroxide. In the present invention, the content of the oxidizing agent in the second agent can be appropriately adjusted. The content of the oxidizing agent in the second agent is preferably 0.01 to 12% by mass, more preferably 0.1 to 6% by mass, based on the total mass of the second agent, from the viewpoint of improving the dyeability. .

  The second agent may include an anionic polymer as the thickening polymer. When the second agent contains the anionic polymer, the oxidative hair dye of the present invention has a more preferable viscosity when mixed with the first agent, and it is more difficult for sagging from the hair to occur. Examples of the anionic polymer include alkyl acrylate / alkyl methacrylate / polyoxyethylene stearyl ether copolymer, alkyl acrylate / polyoxyethylene polypropylene ether copolymer, alkyl acrylate / polyoxyitaconate Examples include an ethylene cetyl ether copolymer and an alkyl acrylate / polyoxyethylene stearyl ether crosspolymer. The content of the anionic polymer in the second agent can be appropriately adjusted in consideration of the viscosity and properties of the oxidative hair dye. The content of the anionic polymer in the second agent is preferably 0 to 7% by mass, more preferably 0.3 to 5.0% by mass, based on the total mass of the second agent. When the content of the anionic polymer in the second agent is not less than the lower limit, dripping hardly occurs during application and during the standing time. When the content of the anionic polymer in the second agent is equal to or less than the above upper limit, it is easy to apply to the entire hair and uneven dyeing is unlikely to occur.

  The second agent has a pH at 25 ° C. of preferably 2 to 5, more preferably 2 to 4. When the pH of the second agent is within the above range, the hair dyeability of the oxidative hair dye used by mixing with the first agent is good.

  In the oxidative hair dye of the present invention, the mass ratio between the first agent and the second agent is not particularly limited. The mass ratio (first agent: second agent) of the first agent to the second agent in the oxidative hair dye of the present invention is preferably 1:10 to 10: 1, and more preferably from the viewpoint of hair dyeability. The ratio is 1: 5 to 5: 1, still more preferably 1: 4 to 3: 1, particularly preferably 1: 3 to 2: 1.

  The first agent and the second agent are preferably in a liquid or gel form, respectively. When the first agent and the second agent are in a liquid or gel state, uneven mixing can be suppressed when these agents are mixed.

  The oxidative hair dye of the present invention, which is used by mixing the first and second agents, is in the form of a gel or an emulsion. Since the oxidative hair dye of the present invention has an appropriate viscosity, the oxidative hair dye hardly drips when applied to hair and is easily applied to the whole. The oxidative hair dye of the present invention is preferably spread over the entire hair while lathering. By bubbling the oxidized hair dye applied to the hair on the hair, the oxidized hair dye can be evenly spread over the hair. When the oxidized hair dye is foamed, the oxidized hair dye can be sufficiently blended into the hair by whisking in the manner of shampooing. According to the present invention, the foamed oxidative hair dye is less likely to hang during the standing time. Further, according to the present invention, hair can be dyed with a small amount of use, and hair can be dyed economically.

  The oxidative hair dye of the present invention used by mixing the first agent and the second agent is preferably 100 to 2000 mPa · s at 25 ° C., more preferably 200 to 1000 mPa · s, and still more preferably 350 to 1000 mPa. Has a viscosity of s. When the viscosity of the oxidized hair dye is equal to or more than the above lower limit, dripping hardly occurs during application and during the standing time. When the viscosity of the oxidized hair dye is not more than the above upper limit, it is easier to apply the oxidized hair dye to the hair, and the oxidized hair dye can be evenly spread on the hair.

  The oxidative hair dye of the present invention, which is used by mixing the first agent and the second agent, has a pH at 25 ° C. of preferably 7 to 12, more preferably 8 to 11. When the pH of the oxidative hair dye is within the above range, the hair dyeability is good.

  The oxidative hair dye of the present invention may be applied to dry hair or towel-dried hair after washing with water after mixing the first and second agents, and may be left as it is for a predetermined time, or may be left on the hair. It may be left for a predetermined time after foaming. After a lapse of a predetermined time, the oxidized hair dye is washed off with water and dried.

  The time from application of the oxidative hair dye to the hair to bubbling is preferably 10 minutes or less, more preferably 5 minutes or less, and still more preferably 3 minutes or less, from the viewpoint of preventing dripping. The standing time for dyeing the hair after bubbling the oxidized hair dye is preferably 5 minutes or more, more preferably 10 minutes or more, preferably 60 minutes or less, more preferably 40 minutes or less, from the viewpoint of the hair dyeing effect. Minutes or less. After the hair has been sufficiently dyed, the oxidative hair dye is removed by washing it away from the hair.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

  In each of the examples and comparative examples, an oxidative hair dye containing the first agent and the second agent having the composition shown in Table 1 was prepared.

  The viscosity of these oxidative hair dyes was measured by the following method. The viscosity of the mixture of the first agent and the second agent is such that the first agent and the second agent are mixed in a 1: 1 mixing ratio of 50 g in a cylindrical glass sample tube having a diameter of 35 mm and a height of 78 mm. The mixture was weighed, the lid was closed, and the mixture was used until the first agent and the second agent were mixed. After being immersed in a constant temperature phase at 25 ° C. for 30 minutes, the sample was taken out of the constant temperature phase, and the viscosity at 25 ° C. was measured with a B-type viscometer (TVB-10M manufactured by Toki Sangyo Co., Ltd.) using a No. 3 rotor for 1 minute at 30 rotations. When the measured value was 400 mPa · s or less, the measurement was performed with a No. 2 rotor for 1 minute at 30 rotations, and the result was shown as a numerical value. The measurement was performed three times, and the average value was adopted.

The oxidation hair dyes prepared in each of the examples and comparative examples were evaluated as follows. The evaluation was performed by five specialized panelists and was determined according to the following criteria. In addition, when the evaluation of five specialized panelists was divided into two, the evaluation with the larger number was adopted, and when the evaluation was divided into three or more, the test and evaluation were performed again.
Table 1 shows the results.

1. Sensory evaluation of dripping at the time of application An oxidative hair dye obtained by mixing 10 g of the first agent and 10 g of the second agent until uniform was used for evaluation. The evaluation was performed manually. First, the hair was washed with a shampoo, and after sufficiently wiping off the water with a towel, the oxidized hair dye obtained in each of the examples or comparative examples was applied. About the dripping at the time of application of the oxidation hair dye, five expert panelists judged according to the following judgment criteria.
[Judgment criteria for dripping during application]
◎: No dripping at all ○: Pouring of liquid but no dripping △: Slight dripping ×: Dripping occurs and hinders application

2. Sensory evaluation of foaming (foaming property) at the time of dyeing After the above evaluation, five expert panelists each tried to foam the oxidized hair dye applied to the hair in the manner of shampooing. Five expert panelists determined the foaming (foaming property) of the oxidized hair dye according to the following criteria.
[Criteria for foaming]
◎: Sufficient foaming, foam spread throughout hair ○: Slightly less foaming, foam spread throughout hair △: Poor foaming, foam not spread throughout hair ×: No foaming

3. Sensory evaluation of dripping during standing time After the above evaluation, five specialized panelists each left to work for 30 minutes after foaming, or when no foaming occurred at all, try to foam. Five expert panelists determined the dripping of the oxidized hair dye during standing for 30 minutes according to the following criteria.
[Criteria for judging dripping during standing time]
◎: No dripping occurs during the standing time ○: Liquid pool is formed but no dripping △: Slight dripping occurs ×: Dripping is severe and cannot be left for 30 minutes

4. Sensory Evaluation of Finish After Dyeing After the above evaluation, five expert panelists each washed the oxidized hair dye left for 30 minutes with warm water, shampooed and rinsed. Next, hot air drying with a towel dryer and a dryer was performed. Five expert panelists judged the finish of the dyed hair according to the following criteria.
[Finish judgment criteria]
◎: No unevenness, dyed uniformly to the root of hair ○: Almost no unevenness, dyed uniformly to the root of hair △: Slightly uneven ×: Uniform, dyed uniformly Not

From the above results, in Examples 1 to 14 in which the first agent contains an anionic surfactant, an amphoteric surfactant, and an alkyl glucoside-type nonionic surfactant, dripping during application, foaming, and standing time In the sensory evaluation of the dripping in the inside and the finish after dyeing, all of the results were good. Further, the oxidation hair dye of the present invention had good storage stability even if it contained a large amount of oxidation dye. On the other hand, in Comparative Examples 1 to 7 in which the first agent does not contain at least one of an anionic surfactant, an amphoteric surfactant, and an alkylglucoside-type nonionic surfactant, the above sensory evaluation is insufficient. As a result, the object of the present invention could not be achieved.
Further, for example, in the case of Example 1 (417 mPa · s), Example 3 (609 mPa · s), Example 8 (388 mPa · s), Example 13 (510 mPa · s), dripping at the time of application is completely lost. Did not. On the other hand, in Comparative Examples 1, 3, and 7, the viscosity was less than 100 mPa · s, which caused sagging and hindered application.

Claims (4)

An oxidative hair dye that is used by mixing a first agent containing an alkaline agent and a second agent containing an oxidizing agent,
The first agent contains 2 to 20% by mass of an oxidation dye based on the total mass of the first agent;
Wherein the first agent comprises at least one sulfate type anionic surfactant, at least one betaine type amphoteric surfactant, and at least one alkyl glucoside type nonionic surfactant;
An oxidative hair dye, wherein the oxidative hair dye is a gel or an emulsion.   The oxidative hair dye according to claim 1, wherein the oxidative hair dye has a viscosity of 100 to 2000 mPa · s at 25 ° C.   The oxidative hair dye according to claim 1 or 2, wherein the mass ratio of the anionic surfactant and the amphoteric surfactant is 1: 3 to 3: 1.   The oxidation hair dye according to any one of claims 1 to 3, wherein the oxidation dye contains an oxidation dye in a salt form.