Hair dye composition comprising blue DYES, urea and a cationic surfactant

Abstract

To provide a hair dye composition that has a gray hair hiding effect, provides favorable finger combing when rinsed off, and is resistant to pH reduction even when stored at a relatively high temperature. A hair dye composition, comprising: (A) at least one dye selected from the group consisting of HC blue 2 and HC blue 12; (B) urea; and (C) a cationic surfactant, wherein the mass ratio (A / B) of the (A) to (B) is less than 2.

Description

HAIR DYE COMPOSITION COMPRISING BLUE DYES, UREA AND A CATIONIC SURFACTANT

[0001] The present invention relates to a hair dye composition.

[0002] Oxidative hair dyes, which dye hair through an oxidation reaction under the coexistence of an alkaline agent and an oxidizing agent, are widely used for dyeing hair. However, while these oxidative hair dyes have an excellent dyeing effect and can dye hair to a desired color, these hair dyes may cause damage to the hair and scalp. In contrast, hair dyes using basic or HC dyes are known as treatment agents that cause less damage to the hair and scalp. Among hair dyes using such basic and HC dyes, color treatments are known as hair dyes that can dye hair while simultaneously performing treatment, have excellent convenience, and provide excellent uniformity of dyeing. As an example of a color treatment, Patent Document 1 discloses a hair dye composition containing: (A): at least one dye selected from Basic Blue 75 and the like; (B): at least one dye selected from Basic Brown 16 and the like; (C): at least one dye selected from N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine and the like; (D): at least one dye selected from HC Blue No. 2 and the like; and (E) at least one dye selected from HC Yellow No. 4 and the like.PRIOR ART DOCUMENTS

[0003] Patent Documents Patent Document 1: JP 2019-64959 ASUMMARY OF THE INVENTION

[0004] PROBLEM TO BE SOLVED BY THE INVENTION

[0005] Color treatments for gray hair often contain HC blue 2 or HC blue 12 to increase the dyeability of gray hair. However, if color treatments containing HC blue 2 or HC blue 12 are stored at relatively high temperatures (e.g., 30oC or higher, and particularly 40oC or higher), the pH of the color treatment may decrease. Therefore, there is a need for color treatments that are less prone to pH reduction even when stored at relatively high temperatures. Furthermore, finger combing when rinsing off must be favorable in color treatments.

[0006] Therefore, an object of the present invention is to provide a hair dye composition that has a gray hair hiding effect, provides favorable finger combing when rinsed off, and is resistant to pH reduction even when stored at a relatively high temperature.MEANS FOR SOLVING THE PROBLEM

[0007] The present inventors arrived at the present invention as a result of extensive studies to solve the problem above. In other words, the present invention provides the following preferred aspects. 1. A hair dye composition, containing: (A) at least one dye selected from the group consisting of HC blue 2 and HC blue 12; (B) urea; and (C) a cationic surfactant, wherein the mass ratio (A / B) of the (A) to (B) is less than 2, preferably 0.1 or more and less than 2, even more preferably 0.15 to 1.5, yet even more preferably 0.18 to 1, particularly preferably 0.18 to 0.8, and more particularly preferably 0.2 to 0.6. 2. The hair dye composition according to 1, wherein, based on the total amount of the hair dye composition, the amount of (A) is 0.05 to 1.0 mass%, preferably 0.05 to 0.5 mass%, more preferably 0.08 to 0.3 mass%, and even more preferably 0.1 to 0.2 mass%, the amount of (B) is 0.01 to 10.0 mass%, preferably 0.05 to 5 mass%, and more preferably 0.1 to 2 mass%, and the amount of (C) is 0.01 to 5.0 mass%, preferably 0.1 to 5.0 mass%, more preferably 0.5 to 4.0 mass%, and even more preferably 1.0 to 3.0 mass%. 3. The hair dye composition according to 1 or 2, further containing (D) HC blue 16, wherein the amount of (D) is 0.1 to 1.0 mass%, more preferably 0.15 to 0.8 mass%, even more preferably 0.2 to 0.6 mass%, and particularly preferably 0.25 to 0.5 mass%, based on the total amount of the hair dye composition. 4. The hair dye composition according to any one of claims 1 to 3, further containing (E) at least one dye selected from the group consisting of basic red 76, basic yellow 57, basic red 51, basic yellow 87, basic orange 31 and basic brown 17, wherein the amount of (E) is preferably 0.01 to 0.8 mass%, more preferably 0.05 to 0.6 mass%, even more preferably 0.1 to 0.5 mass%, and particularly preferably 0.15 to 0.3 mass%, based on the total amount of the hair dye composition. 5. The hair dye composition according to 1 to 4, wherein the total amount of HC yellow 2, HC yellow 4, HC yellow 13, HC red 3, HC red 7, HC red 10, HC red 11, HC red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, hydroxyethyl-2-nitro-p-toluidine, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, and 2-amino-6-chloro-4-nitrophenol is 0.01 mass% or less, preferably 0 to 0.01 mass%, more preferably 0 to 0.005 mass%, even more preferably 0 to 0.001 mass%, and particularly preferably, these dyes are not included. 6. The hair dye composition according to any one of 1 to 5, wherein (A) is HC blue 12. 7. The hair dye composition according to 1 to 6, wherein the mass ratio (A / B) of (A) to (B) is 0.1 to 1. 8. The hair dye composition according to any one of 1 to 7, wherein the pH is 4 to 8, preferably 4.5 to 8.0, and more preferably 5.0 to 7.5. 9. The hair dye composition according to any one of 1 to 8, which is a color treatment.EFFECT OF THE INVENTION

[0008] The present invention can provide a hair dye composition that has a gray hair hiding effect, provides favorable finger combing when rinsed off, and is resistant to pH reduction even when stored at a relatively high temperature.EMBODIMENTS OF THE INVENTION

[0009] <<Hair Dye Composition>> The hair dye composition of the present invention contains: at least one dye selected from the group consisting of HC blue 2 and HC blue 12 (component A), urea (component B), and a cationic surfactant (component C), wherein the mass ratio (A / B) of component A to component B is less than 2.

[0010] However, upon examination of the pH stability of a hair dye composition containing HC blue 2 and / or HC blue 12, the present inventors discovered that combining urea (component B) with the HC blue 2 and / or HC blue 12 (component A) improves the pH stability of the hair dye composition, and the pH of the hair dye composition does not easily decrease even when stored at relatively high temperatures, specifically 30oC or higher, and particularly 40oC or higher, for example. Upon further examination on the combination of component A and component B, the present inventors discovered that when the mass ratio (A / B) of component A to component B is less than 2, a hair dye composition can be obtained, which is less prone to pH reduction even when stored at a relatively high temperature of 30oC or higher, and particularly 40oC or higher, as compared to before storage or storage at a lower temperature of approximately 5oC. Although it is not clear why the combination of component A and component B at a specific ratio makes reduction in the pH of the hair dye composition less likely to occur, the following reasons are presumed. One possible reason for the decrease in the pH decrease of the hair dye composition containing component A when stored at a relatively high temperature is that the chemical structure of the dye in component A changes over time and acts in the direction of reducing the pH of the hair dye composition. On the other hand, when the hair dye composition containing component B is stored at a relatively high temperature, component B can act in the direction of increasing the pH of the hair dye composition. Therefore, it is considered that by combining, at a specific ratio, component A, which decreases the pH of the hair dye composition over time, with component B, which increases the pH of the hair dye composition over time, the pH of the hair dye composition is less likely to decrease even when stored at a relatively high temperature. Hereinafter, in the present specification, "high pH stability when storing at a relatively high temperature" or simply "high pH stability" may be used to describe that a reduction in the pH is less likely to occur even when the product is stored at relatively high temperatures.

[0011] On the other hand, if the mass ratio (A / B) of component A to component B is 2 or more, the gray hair hiding effect and pH stability during high temperature storage are likely to decrease.

[0012] In one embodiment of the present invention, the mass ratio (A / B) of component A to component B is preferably 1.5 or less, more preferably 1 or less, even more preferably 0.8 or less, and particularly preferably 0.6 or less. Furthermore, the mass ratio (A / B) of component A and component B is preferably 0.1 or more, more preferably 0.15 or more, even more preferably 0.18 or more, and particularly preferably 0.2 or more. When the mass ratio (A / B) is less than or equal to the upper limit above, the pH stability during high temperature storage is likely to be improved. Furthermore, when the mass ratio (A / B) is more than or equal to the lower limit above, the stability of the formulation during high temperature storage is likely to be improved.

[0013] In one embodiment of the present invention, the mass ratio (A / B) of component A to component B is preferably 0.1 or more and less than 2, even more preferably 0.15 to 1.5, yet even more preferably 0.18 to 1, particularly preferably 0.18 to 0.8, and more particularly preferably 0.2 to 0.6. When the mass ratio (A / B) is within the range above, the pH stability and stability of the formulation during high temperature storage are likely to be improved.

[0014] <Component A> Component A is at least one dye selected from the group consisting of HC blue 2 and HC blue 12. For component B, only one of HC Blue 2 and HC Blue 12 may be used, or both HC Blue 2 and HC Blue 12 may be used. HC blue 2 is a compound denoted by the INCI Name (International Cosmetic Ingredient Dictionary and Handbook, 15th Edition, Volume 1, 2014, p. 1449): HC BLUE NO. 2, and HC blue 12 is a compound denoted by the INCI Name: HC Blue No. 12. By including component A, the color saturation does not overly increase and the gray hair hiding effect is easily increased.

[0015] In one embodiment of the present invention, the amount of component A is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.08 mass% or more, and particularly preferably 0.1 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component A is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.3 mass% or less, and particularly preferably 0.2 mass% or less, based on the total amount of the hair dye composition. When the amount of component A is more than or equal to the lower limit above, the dyeability and gray hair hiding effect on hair are easily improved. Furthermore, when the amount of component A is less than or equal to the upper limit above, the pH stability and dye stability are easily improved, and color transfer to a towel, clothing, and the like due to dye dissolved in water after rinsing is easily suppressed.

[0016] In one embodiment of the present invention, the amount of component A is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 1 mass%, even more preferably 0.05 to 0.5 mass%, yet even more preferably 0.08 to 0.3 mass%, and particularly preferably 0.1 to 0.2 mass%. When the amount of component A is within the range above, the dyeability of hair, gray hair hiding effect, dye stability, and pH stability are easily improved, and color transfer to a towel, clothing, and the like due to dye dissolved in water after rinsing is easily suppressed.

[0017] <Component B> The hair dye composition of the present invention contains urea as component B. As described above, the hair dye composition of the present invention contains component B, which prevents a reduction in the pH even when stored at a relatively high temperature. Furthermore, by including component B, the squeaky feel during rinsing can be reduced and finger combing can be improved.

[0018] In one embodiment of the present invention, the amount of component B (urea) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.1 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component B is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 2 mass% or less, based on the total amount of the hair dye composition. When the amount of component B is more than or equal to the lower limit above, the pH stability and finger combing during rinsing are easily improved. Furthermore, when the amount of component B is less than or equal to the upper limit above, the stability of the hair dye composition is easily improved.

[0019] In one embodiment of the present invention, the amount of component B is preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass%, and even more preferably 0.1 to 2 mass%, based on the total amount of the hair dye composition, from the perspective of increasing the pH stability.

[0020] <Component C> Component C is a cationic surfactant. By including a cationic surfactant, the stability of the hair dye composition can be improved, the squeaky feel during rinsing due to the hair dye composition can be reduced, and finger combing can be increased.

[0021] The cationic surfactant is not particularly limited, and examples thereof include monoalkyl quaternary ammonium salt, dialkyl quaternary ammonium salt, trialkyl quaternary ammonium salt, monoalkyl ether type quaternary ammonium salt, alkylamines, fatty acid amidoamine, and the like. These cationic surfactants can be used alone or in combination of two or more. Of these cationic surfactants, monoalkyl quaternary ammonium salt, dialkyl quaternary ammonium salt, and fatty acid amidoamines are preferable from the perspective of treatment effect, and the monoalkyl quaternary ammonium salt and fatty acid amidoamine are more preferable.

[0022] Examples of monoalkyl quaternary ammonium salt include lauryl trimethylammonium chloride, myristyl trimethylammonium chloride, cetyl trimethylammonium chloride, stearyl trimethylammonium chloride, behenyl trimethylammonium chloride, alkyl (16,18) trimethylammonium chloride, alkyl (20-22) trimethylammonium chloride, stearyl dimethylbenzylammonium chloride, myristyl dimethylbenzylammonium chloride, tri(polyoxyethylene)stearylammonium chloride, di(polyoxyethylene)oleylmethylammonium chloride, and the like. Of these, stearyl trimethylammonium chloride, behenyl trimethylammonium chloride, alkyl (16,18) trimethylammonium chloride, and alkyl (20-22) trimethylammonium chloride are preferable, and behenyl trimethylammonium chloride is more preferable.

[0023] Examples of the fatty acid amidoamine include dimethylaminoethylamide myristate, dimethylaminopropylamide myristate, diethylaminoethylamide myristate, diethylaminopropylamide myristate, dimethylaminoethylamide palmitate, dimethylaminopropylamide palmitate, diethylaminoethylamide palmitate, diethylaminopropylamide palmitate, dimethylaminoethylamide stearate, dimethylaminopropylamide stearate, diethylaminoethylamide stearate, diethylaminopropylamide stearate, dipropylaminoethylamide stearate, dipropylaminopropylamide stearate, dimethylaminoethylamide behenate, dimethylaminopropylamide behenate, diethylaminoethylamide behenate, diethylaminopropylamide behenate, and the like. Of these, dimethylaminopropylamide stearate is preferable.

[0024] A fatty acid amidoamine is preferably used as a salt using an organic acid and / or inorganic acid. Examples of the organic acid include lactic acid, malic acid, citric acid, tartaric acid, acetic acid, and the like. Furthermore, examples of the inorganic acids include phosphoric acid, hydrochloric acid, sulfuric acid, and the like. Of these, lactic acid is preferable. The amount of the organic acid and inorganic acid is not particularly limited so long as the amount is sufficient to neutralize the fatty acid amidoamine to be added.

[0025] In one embodiment of the present invention, the amount of component C is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, and particularly preferably 1.0 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component C is preferably 5.0 mass% or less, more preferably 4.0 mass% or less, and even more preferably 3.0 mass% or less, based on the total amount of the hair dye composition. When the amount of component C is more than or equal to the lower limit above, finger combing during rinsing is easily improved.

[0026] In one embodiment of the present invention, the amount of component C is preferably 0.01 to 5.0 mass%, more preferably 0.1 to 5.0 mass%, even more preferably 0.5 to 4.0 mass%, and particularly preferably 1.0 to 3.0 mass%, based on the total amount of the hair dye composition, from the perspective of easily improving finger combing during rinsing.

[0027] <Component D> In one embodiment of the present invention, the hair dye composition of the invention preferably further contains HC blue 16 as component D. Component D is HC blue 16, which is a compound denoted by the INCI Name: HC BLUE NO. 16. The color tone of component D is highly saturated, and therefore, by including component D in addition to component A as a blue dye, the dyeability and gray hair hiding effect of hair tend to be improved. A commercial product can be used for component D. An example of a commercial product for component D includes the product name “HC Blue No. 16” manufactured by Artec Chemical.

[0028] According to the present inventors, including component D further provides the following additional effects. When the hair dye composition of the present invention further contains component D, changes in color tone due to continuous use can be suppressed. Therefore, when the hair dye composition of the present invention is a color treatment for dyeing gray hair, in addition to making gray hair less noticeable with continuous use two or three times a week, the hair can be dyed with the same color tone upon continuous or consecutive use. In general, HC dyes and basic dyes are prone to changes in chemical structure and hair dye color results over time. When the hair dye composition is stored at a low temperature of approximately 5oC, little change in the dye occurs before and after storage, but when the hair dye composition is stored at a relatively high temperature (e.g., 30oC or higher, and particularly 40oC or higher), the HC dyes and basic dyes in the hair dye composition tend to change over time. Therefore, there may be a difference in dyeing results between using a hair dye composition before storage or a hair dye composition stored at a low temperature and using a hair dye composition stored at a relatively high temperature, and the desired dyeing results may not be achieved. Surprisingly, however, the present inventors discovered that by including the dye component D in addition to the dye component A, the changes in the color of dyed hair can be suppressed even when the hair dye composition is stored at a relatively high temperature. Therefore, when the hair dye composition of the present invention further contains component D, differences in dyeing results when stored at relatively high and low temperatures can be reduced. In other words, when component D is further included, the hair dye composition of the present invention has high dye stability even when stored at a relatively high temperature. Hereinafter, in the present specification, a small difference in dyeing results between storage at relatively high and low temperatures may be described as "high dyeing stability in high temperature storage" or simply "high dyeing stability". Note that in the present specification, dyeing results refer to the color and color tone of dyed hair. Therefore, a small difference in dyeing results indicates a small difference in color and color tone of dyed hair. Furthermore, in the present specification, suppressed color tone change due to continuous use means that the same dyeing results are easily achieved each time during continuous use.

[0029] In one embodiment of the present invention, the amount of component D is preferably 0.1 mass% or more, more preferably 0.15 mass% or more, even more preferably 0.2 mass% or more, and particularly preferably 0.25 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component D is preferably 1.0 mass% or less, more preferably 0.8 mass% or less, even more preferably 0.6 mass% or less, and particularly preferably 0.5 mass% or less, based on the total amount of the hair dye composition. When the amount of component D is more than or equal to the lower limit above, the dyeability of hair, particularly for dyeing gray hair, is easily improved, dyeing stability during high temperature storage is easily increased, and color tone changes due to continuous use is easily suppressed. When the amount of component D is less than or equal to the upper limit above, the effect of suppressing skin staining is easily improved, and color transfer to a towel, clothing, and the like due to dye dissolved in water after rinsing is easily suppressed.

[0030] In one embodiment of the present invention, the amount of component D is preferably 0.1 to 1.0 mass%, more preferably 0.15 to 0.8 mass%, even more preferably 0.2 to 0.6 mass%, and particularly preferably 0.25 to 0.5 mass%, based on the total amount of the hair dye composition. When the amount of component D is within the range above, the gray hair hiding effect, dye stability, and effect of suppressing skin staining are easily improved, and color tone change due to continuous use and color transfer to a towel, clothing, and the like due to dye dissolved in water after rinsing are easily suppressed.

[0031] In one embodiment of the present invention, the mass ratio (D / A) of component D to component A is preferably 0.8 or more, more preferably 1 or more, even more preferably more than 1, yet even more preferably 1.2 or more, particularly preferably 1.5 or more, more particularly preferably 1.8 or more, and even more particularly preferably 2 or more, and preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or less. When the aforementioned mass ratio (D / A) of component D to component A is more than or equal to the lower limit above, the dyeability, gray hair hiding effect, pH stability, and dye stability are easily improved, and color tone changes due to continuous use are easily suppressed. When the mass ratio (D / A) above is more than or equal to the lower limit above, component D is a dye with higher dyeability than component A. Therefore, a hair dye composition with higher dyeability and gray hair hiding effect can be obtained. Although the reason is not clear for why the color tone change due to continuous use can be suppressed, it is considered to be because the overall color balance is easy to maintain by keeping the amount of component A, which tends to lighten in dyeability over time, at or below a specific ratio to component D, which has a relatively small change in dyeability. Although the reason that the dye stability can be increased is not clear, it is considered to be because component D is a dye that does not easily change in chemical structure or hair dye color over time, even when stored at a relatively high temperature, as compared to component A.

[0032] In one embodiment of the present invention, the mass ratio (D / A) of component D to component A is preferably 0.8 to 20, more preferably 1 to 20, even more preferably more than 1 and 20 or less, yet even more preferably from 1.2 to 20, particularly preferably 1.5 to 10, more particularly preferably 1.8 to 5, and even more particularly preferably 2 to 3. When the aforementioned mass ratio (D / A) is within the range above, dyeability, gray hair hiding effect, pH stability, and dye stability are easily improved, and color tone changes due to continuous use are easily suppressed.

[0033] In one embodiment of the present invention, the total amount of component A and component B may be, for example, 0.11 to 2.0 mass% based on the total amount of the hair dye composition, and from the perspective of efficiently achieving a gray hair dyeing effect, is preferably 1.0 mass% or less, more preferably 0.9 mass% or less, even more preferably 0.8 mass% or less, yet even more preferably less than 0.6 mass%, and particularly preferably 0.55 mass% or less. In one embodiment of the present invention, the total amount of component A and component D may preferably be 0.11 to 1.0 mass%, more preferably 0.15 to 0.9 mass%, even more preferably 0.15 to 0.8 mass%, yet even more preferably 0.2 mass% or more and less than 0.6 mass%, and particularly preferably 0.2 to 0.55 mass%, based on the total amount of the hair dye composition.

[0034] <Component E> In one embodiment of the present invention, the hair dye composition preferably further contains at least one dye selected from the group consisting of basic red 76, basic yellow 57, basic red 51, basic yellow 87, basic orange 31, and basic brown 17 as component E, from the perspective of making achieving a color tone in which the gray hair hiding effect is increased.

[0035] Basic red 76 is a compound denoted by the INCI Name: Basic Red 76. Basic yellow 57 is a compound denoted by Basic Yellow 57. Basic red 51 is a compound denoted by Basic Red 51. Basic yellow 87 is a compound denoted by Basic Yellow 87. Basic orange 31 is a compound denoted by Basic Orange 31. Basic brown 17 is a compound denoted by Basic Brown 17.

[0036] In one embodiment of the present invention, the amount of component E is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and particularly preferably 0.15 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component E is preferably 0.8 mass% or less, more preferably 0.6 mass% or less, even more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, based on the total amount of the hair dye composition. When the amount of component E is more than or equal to the lower limit above, the color fastness is easily improved. Furthermore, when the amount of component E is less than or equal to the upper limit above, skin staining is easily suppressed, color tone changes after storage is suppressed, and dyeing stability is easily increased.

[0037] In one embodiment of the present invention, the amount of component E is preferably 0.01 to 0.8 mass%, more preferably 0.05 to 0.6 mass%, even more preferably 0.1 to 0.5 mass%, and particularly preferably 0.15 to 0.3 mass%, based on the total amount of the hair dye composition. When the amount of component E is within the range above, color fastness is easily improved, skin staining is easily suppressed, color tone changes after storage is suppressed, and dyeing stability is easily increased.

[0038] In one embodiment of the present invention, the mass ratio (A / E) of component A to component E is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and particularly preferably 0.4 or more. Furthermore, the aforementioned mass ratio (A / E) is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and particularly preferably 0.6 or less.

[0039] In one embodiment of the present invention, the mass ratio (A / E) of component A to component E is preferably 0.1 to 1, more preferably 0.2 to 0.9, even more preferably 0.3 to 0.8, and particularly preferably 0.4 to 0.6.

[0040] In one embodiment of the present invention, the mass ratio (D / E) of component D to component E is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, and particularly preferably 1.2 or more. Furthermore, the aforementioned mass ratio (D / E) is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and particularly preferably 2 or less.

[0041] In one embodiment of the present invention, the mass ratio (D / E) of component D to component E is preferably 0.5 to 5, more preferably 0.8 to 4, even more preferably 1 to 3, and particularly preferably 1.2 to 2.

[0042] In one embodiment of the present invention, the mass ratio [(A+D) / E] of the total amount of component A and component D to component E is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, and particularly preferably 1.1 or more. Furthermore, the aforementioned mass ratio [(A+D) / E] is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and particularly preferably 2 or less from the perspective of increasing the gray hair hiding effect.

[0043] In one embodiment of the present invention, the mass ratio [(A+D) / E] of the total amount of component A and component D to component E is preferably 0.5 to 5, more preferably 0.8 to 4, even more preferably 1 to 3, and particularly preferably 1.1 to 2, from the perspective of increasing the gray hair hiding effect.

[0044] In one embodiment of the present invention, the mass ratio (B / [A+D+E]) of component B to the total amount of component A, component D, and component E is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, from the perspective of increasing pH stability. Furthermore, the mass ratio (B / [A+D+E]) is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less, from the perspective of further improving pH stability.

[0045] In one embodiment of the present invention, the mass ratio (B / [A+D+E]) of component B to the total amount of component A, component D, and component E is preferably 0.1 to 2, more preferably 0.2 to 1.5, and even more preferably 0.3 to 1, from the perspective of increasing pH stability.

[0046] In one embodiment of the present invention, component E preferably contains at least two dyes, and more preferably contains at least three dyes, from the perspective of increasing the gray hair hiding effect. Furthermore, in one embodiment of the present invention, component E preferably contains at least one dye selected from the group consisting of basic red 76, basic yellow 57, basic red 51, and basic yellow 87, and more preferably contains at least two dyes selected from the group consisting of basic red 76, basic yellow 57, basic red 51, and basic yellow 87.

[0047] In one embodiment of the present invention, component E preferably includes at least one dye (component E1) selected from the group consisting of basic red 76 and basic yellow 57 and at least one dye (component E2) selected from the group consisting of basic red 51, basic yellow 87, basic orange 31, and basic brown 17, from the perspective of further increasing the dyeability of hair and the gray hair hiding effect. In other words, in one embodiment of the present invention, the hair dye composition of the present invention preferably further contains component E1 and component E2. Furthermore, as a result of examining red dyes and yellow dyes to be combined with component A and, in some cases, the blue dye of component D, the present inventors also discovered that combining component E1 and component E2 selected from a specific group improves the dye stability during high temperature storage, and easily suppresses color tone changes due to continuous use. Therefore, in one embodiment of the present invention, the hair dye composition of the present invention can have a sufficient dyeing effect, gray hair hiding effect, and high dyeing stability, and can suppress color tone changes due to continuous use.

[0048] In one embodiment of the present invention, component E1, which is at least one dye selected from the group consisting of basic red 76 and basic yellow 57, preferably contains at least basic yellow 57, from the perspective of increasing the gray hair hiding effect. Furthermore, component C1 preferably contain two dyes, in other words, both basic red 76 and basic yellow 57, from the perspective of further increasing the gray hair hiding effect.

[0049] In one embodiment of the present invention, component E2 preferably contains at least two dyes from the perspective of increasing the gray hair hiding effect. Furthermore, in one embodiment of the present invention, component E2, which is at least one dye selected from the group consisting of basic red 51, basic yellow 87, basic orange 31, and basic brown 17, is preferably at least one dye selected from the group consisting of basic red 51 and basic yellow 87, from the perspective of further increasing the gray hair hiding effect.

[0050] In one embodiment of the present invention, when the hair dye composition contains component E1 and component E2, at least one of component E1 and component E2 preferably contains at least two dyes, and both components C1 and C2 more preferably contain at least two dyes.

[0051] In one embodiment of the present invention, the amount of component E1 is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.1 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component E1 is preferably 1.0 mass% or less, more preferably 0.8 mass% or less, and even more preferably 0.5 mass% or less, based on the total amount of the hair dye composition. In one embodiment of the present invention, the amount of component E2 is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.02 mass% or more, based on the total amount of the hair dye composition. Furthermore, the amount of component E2 is preferably 0.3 mass% or less, more preferably 0.2 mass% or less, and even more preferably 0.15 mass% or less, based on the total amount of the hair dye composition. Note that the total amount of component E1 and component E2 corresponds to the amount of component E above.

[0052] In one embodiment of the present invention, the amount of component E1 is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.8 mass%, and even more preferably 0.1 to 0.5 mass%, based on the total amount of the hair dye composition.

[0053] In one embodiment of the present invention, the amount of component E2 is preferably 0.005 to 0.3 mass%, more preferably 0.01 to 0.2 mass%, and even more preferably 0.02 to 0.15 mass%, based on the total amount of the hair dye composition.

[0054] In one embodiment of the present invention, the mass ratio (E1 / E2) of component E1 to component E2 is preferably 1 or more, more preferably 1.2 or more, even more preferably 2 or more, and particularly preferably 3 or more, from the perspective of suppressing overly high saturation and increasing the gray hair hiding effect. The aforementioned mass ratio (E1 / E2) of component E1 to component E2 is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 6 or less from the perspective of increasing the gray hair hiding effect.

[0055] In one embodiment of the present invention, the mass ratio (E1 / E2) of component E1 to component E2 is preferably 1 to 20, more preferably 1.2 to 15, even more preferably 2 to 10, and particularly preferably 3 to 6, from the perspective of increasing the gray hair hiding effect.

[0056] <Other Dyes> In one embodiment of the present invention, the hair dye composition of the present invention may contain another dye other than the aforementioned component A, component D, and component E, such as other HC dyes and basic dyes. Examples of other dyes include basic blue 124, basic blue 75, basic brown 16, and the like. The amount of the other dye can be selected, as appropriate, to the extent that does not impair the effect of the present invention. When the other dye is included, the total amount is preferably 1 mass% or less, more preferably 0.8 mass% or less, and even more preferably 0.5 mass% or less, and preferably 0.01 mass% or more, based on the total amount of the hair dye composition.

[0057] The present inventors discovered that when the hair dye composition contains, in addition to the aforementioned component A, component D, and component E, a certain dye selected from the group consisting of 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, and 2-amino-6-chloro-4-nitrophenol, a decrease in pH is more likely to occur. Therefore, in one embodiment of the present invention, from the perspective of improving pH stability, the total amount of 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, and 2-amino-6-chloro-4-nitrophenol in the hair dye composition of the present invention is preferably 0.01 mass% or less, more preferably 0 to 0.01 mass%, even more preferably 0 to 0.005 mass%, yet even more preferably 0 to 0.001 mass%, and particularly preferably, these dyes not being including, based on the total amount of the hair dye composition.

[0058] The present inventors discovered that if the hair dye composition contains, in addition to the aforementioned component A, component D, and component E, a certain dye, HC yellow 2, HC yellow 4, HC yellow 13, HC red 3, HC red 7, HC red 10, HC red 11, HC red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine and hydroxyethyl-2-nitro-p-toluidine, color tone changes due to continuous use easily occur, and the stability of the hair dye composition, particularly dyeing stability, tends to decrease. Therefore, in one embodiment of the present invention, from the perspective of suppressing color tone changes due to continuous use and from the perspective of dye stability, the total amount of HC yellow 2, HC yellow 4, HC yellow 13, HC red 3, HC red 7, HC red 10, HC red 11, HC red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, and hydroxyethyl-2-nitro-p-toluidine in the hair dye composition of the present invention is preferably 0.01 mass% or less, more preferably 0 to 0.01 mass%, even more preferably 0 to 0.005 mass%, yet even more preferably 0 to 0.001 mass%, and particularly preferably, these dyes are not included.

[0059] In one embodiment of the present invention, from the perspective of suppressing color tone changes due to continuous use and from the perspective of improving dye stability and pH stability, the total amount of HC yellow 2, HC yellow 4, HC yellow 13, HC red 3, HC red 7, HC red 10, HC red 11, HC red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, hydroxyethyl-2-nitro-p-toluidine, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, and 2-amino-6-chloro-4-nitrophenol in the hair dye composition of the present invention is preferably 0.01 mass% or less, more preferably 0 to 0.01 mass%, even more preferably 0 to 0.005 mass%, yet even more preferably 0 to 0.001 mass%, and particularly preferably, these dyes are not included.

[0060] <Other Components> In addition to the aforementioned component A to component E and the other dye, the hair dye composition of the present invention may contain another component, if necessary. Examples of other components include: anionic surfactants; amphoteric surfactants; nonionic surfactants; polyhydric alcohols; higher alcohols; lower alcohols; fatty acid amides; hydrocarbon oils; ester oils; pH adjusters; algefacients such as l-menthol, 1,8 cineole, camphor, and the like; preservatives such as phenoxyethanol and the like; vegetable oils such as olive oil, macadamia nut oil, argan oil, and the like; silicones; moisture absorbents such as silica and the like; hyaluronic acid or derivatives thereof, collagen or derivatives thereof; amino acids or derivatives thereof; antioxidants; sequestering agents; vitamins; extracts from plants and animals; pearling agents; coloring agents; fragrances; and the like. These can be used alone or in combination of two or more. The total amount of the other component is not particularly limited so long as the effect of the present invention is not impaired, but may be, for example, 0.1 to 10 mass%, based on the total amount of the hair dye composition.

[0061] In one embodiment of the present invention, the hair dye composition of the invention preferably contains a higher alcohol. Examples of higher alcohols include alcohols having 16 to 22 carbon atoms such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol, isostearyl alcohol, 2-octyldodecanol, oleyl alcohol, behenyl alcohol. These higher alcohols can be used alone or in combination of two or more. The amount of the higher alcohol is not particularly limited, but from the perspective of pH stability and dye stability, the amount is preferably 1.0 to 10.0 mass%, and more preferably 3.0 to 8.0 mass%, based on the total amount of the hair dye composition.

[0062] In one embodiment of the present invention, the hair dye composition may contain a nonionic surfactant from the perspective of pH stability and dye stability. Examples of the nonionic surfactant include polyoxyethylene fatty acid, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyglycerin alkyl ether, polyoxyethylene (hardened) castor oil, fatty acid alkylolamide, and the like. The amount of the nonionic surfactant is not particularly limited, but from the perspective of pH stability and dye stability, the amount is preferably 0.5 to 10.0 mass%, and more preferably 1.0 to 5.0 mass%, based on the total amount of the hair dye composition.

[0063] The hair dye composition of the present invention contains water. The water is not particularly limited but purified water is preferable. The amount of water can be adjusted according to the amount of components other than the water, and is preferably 50.0 to 90.0 mass%, and more preferably 60.0 to 80.0 mass%, based on the total amount of the hair dye composition.

[0064] <Hair Dye Composition> The hair dye composition of the present invention contains component A, component B, and component C, and the mass ratio (A / B) of component A to component B is less than 2. Therefore, the composition has sufficient dyeability and gray hair hiding effect, favorable finger combing during rinsing, and high pH stability. The hair dye composition of the present invention suppresses reductions in the pH. Therefore, it is possible to suppress decomposition and transformation of the dye contained in the hair dye composition, and to suppress effects on the stability of the formulation system itself, for example, on usability and on the feel, finger combing, and the like of the hair after use. Furthermore, particularly in one embodiment that further includes component D, and particularly in an embodiment that includes component D with a large mass ratio (D / A) between component D and component A, the hair dye composition of the present invention has high dye stability and can suppress color tone changes due to continuous use.

[0065] In one embodiment of the present invention, the pH of the hair dye composition is preferably 4.0 or more, more preferably 4.5 or more, and even more preferably 5.0 or more, from the perspective of dyeability. Furthermore, the pH of the hair dye composition is preferably 8.0 or less, and more preferably 7.5 or less, from the perspective of stability. The pH of the hair dye composition is preferably 4.0 to 8.0, more preferably 4.5 to 8.0, and even more preferably 5.0 to 7.5. The aforementioned pH of the hair dye composition is the pH at 25°C and can be measured with a pH meter, for example, by a method described in the Examples.

[0066] The dosage form of the hair dye composition of the present invention is not particularly limited, and examples include liquid, viscous liquid, gel, emulsion, cream, and the like. Of these, a cream form is preferable from the perspective of dyeability and texture.

[0067] The hair dye composition of the present invention can dye hair ash, black, brown, green, blue-purple, or the like, and preferably ash, black, or brown. Therefore, the hair dye composition of the present invention can be used as a hair dye composition for gray hair dyeing, fashionable hair dyeing, or the like. In particular, the hair dye composition of the present invention can be used as a hair dye composition for gray hair dyeing from the perspective of color tone.

[0068] The hair dye composition of the present invention is preferably a color treatment. Color treatments are hair treatment agents that are generally used at the time of hair washing and applied to the hair after washing and then rinsed off. After washing hair with shampoo, the color treatment is used by a method in which the color treatment is applied to the hair, allowed to blend into the hair immediately after application or for approximately 3 to 10 minutes, and then rinsed off. Note that the color treatment may be used before washing hair. In such cases, the color treatment is used by a method in which the color treatment is applied to wet hair, and then allowed to blend into the hair immediately after application or for approximately 3 to 10 minutes before rinsing.

[0069] <<Method for Manufacturing Hair Dye Composition>> The method for manufacturing the hair dye composition of the present invention is not particularly limited and can be manufactured by a known method. The hair dye composition of the present invention may be manufactured, for example, by a method of stirring each component included in the hair dye composition using a paddle mixer or the like to homogeneity, or by a method of preparing an oil phase and an aqueous phase in advance and then adding the aqueous phase to the oil phase and emulsifying. In the method of adding the aqueous phase to the oil phase for emulsification, manufacture is specifically possible by the following method. For example, an aqueous phase heated to 70 to 90°C is gradually added to an oil phase that has been sufficiently dissolved by heating to 70 to 90°C, and then the mixture is thoroughly stirred for 5 minutes to perform emulsification. After emulsification, cooling to 20 to 40°C is performed, thorough and uniform stirring is performed, then additives such as urea previously dissolved in water, a pH adjuster, or the like is added, and then thorough and uniform stirring is performed to obtain a cream-like hair dye composition. EXAMPLES

[0070] The following examples further describe the present invention in detail, but the present invention is not limited by the examples.

[0071] <Example 1> A hair dye composition was prepared by blending each component in the proportions shown in Table 1. Specifically, an aqueous phase in which dyes and the like are heated to 80oC and dissolved is added to an oil phase in which an oil phase component is heated uniformly to 80oC, and the mixture is uniformly emulsified and cooled to 40oC. The additives were then added to obtain a cream-like hair dye composition. Sodium hydroxide was added in an amount such that the pH of the hair dye composition was 6.8 at 25oC.

[0072] <Examples 2 to 10 and Comparative Examples 1 to 3> Hair dye compositions were prepared in the same manner as in Example 1 in accordance with the compositions shown in Tables 1 and 2.

[0073] < Dyeability > Untreated white human hair bundles (10 cm long and 1 g in weight, manufactured by Beaulax Co., Ltd.) were used as test hair bundles. The test hair bundles were washed with a commercial shampoo and then lightly drained. Thereafter, 5 g of each hair dye composition obtained in the examples and comparative examples was applied to the test hair bundle immediately after manufacture, and then blended into the entire hair bundle (hair) using a brush for one minute. Next, after leaving the hair bundles for five minutes, the hair dye composition was thoroughly rinsed from the hair bundle using lukewarm water at 40oC, towel-dried, and then dried thoroughly using a hair dryer to prepare evaluation hair bundles. The resulting evaluation hair bundles were observed and the dyeability thereof was evaluated by seven expert evaluators using the following criteria. The average values of the results of the evaluation by the seven expert evaluators are shown in Tables 1 and 2. (Dyeability Evaluation Criteria) 5: Very darkly dyed. 4: Sufficiently dyed. 3: Dyed (standard) 2: Slightly dyed 1. Lightly dyed

[0074] < Finger Combing When Rinsed Off > The same hair dyeing treatment (from washing using shampoo to drying) as described in <Dyeability> was performed, and seven expert evaluators assessed the ease of finger combing when the hair dye composition was rinsed from the hair bundle in accordance with the following criteria. The average values of the results of the evaluation by the seven expert evaluators are shown in Tables 1 and 2. (Evaluation Criteria for Easy of Finger Combing) 5: Very favorable finger combing. 4: Favorable finger combing 3: Finger combing is not very favorable 2: Inferior finger combing 1: Very inferior finger combing.

[0075] <Gray Hair Hiding Effect > A hair bundle of untreated 30% gray hair (10 cm in length and 1 g in weight, manufactured by Beaulax Co., Ltd.) was used as the test hair bundle to evaluate the gray hair hiding effect as follows. 5 g of each hair dye composition obtained in the examples and comparative examples was applied to the test hair bundle immediately after manufacture, and then blended into the entire hair bundle (hair) using a brush for one minute. Next, after leaving the hair bundles for five minutes, the hair dye composition was thoroughly rinsed from the hair bundle using lukewarm water at 40oC, towel-dried, and then dried thoroughly using a hair dryer to prepare evaluation hair bundles. The resulting evaluation hair bundles were observed and the gray hair hiding effect was visually evaluated by seven expert evaluators using the following criteria. The average values of the results of the evaluation by the seven expert evaluators are shown in Tables 1 and 2. <Evaluation Criteria of Gray Hair Hiding Effect> 5: Gray hair is not noticeable 4: Gray hair is slightly noticeable 3: Gray hair is noticeable 2: Gray hair is not dyed very well 1: Gray hair is not dyed

[0076] <Stability (pH)> 30 g of each hair dye composition obtained in the Examples and Comparative Examples was placed in a 200 mL polyethylene bottle with a cap, and stored in a thermostatic bath at 50oC for four weeks to obtain hair dye compositions that have been stored at 50oC for four weeks. Similarly, hair dye compositions that have been stored at 5oC for four weeks were obtained. The pH of the hair dye compositions stored at 50oC for four weeks and at 5oC for four weeks were measured at 25oC using a pH meter (product name "Desktop pH Meter F-71" manufactured by HORIBA Advanced Techno, Co., Ltd.). In general, 5oC is the temperature at which reductions in the pH of the hair dye composition is unlikely to occur, while 50oC is the temperature at which reductions in the pH of the hair dye composition is likely to occur. Therefore, the difference (ΔpH = [pH of hair dye composition stored at 5oC for four weeks] - [pH of hair dye composition stored at 50oC for four weeks]) between the pH of the hair dye composition stored at 5oC for four weeks and the pH of the hair dye composition stored at 50oC for four weeks was determined, and the pH stability during high temperature storage was evaluated using the following criteria. The results are shown in Tables 1 and 2. (Evaluation Criteria of pH Stability) 5：ΔpH < 0.2 4：0.2 ≦ ΔpH < 0.4 3：0.4 ≦ ΔpH < 0.6 2：0.6 ≦ ΔpH < 0.8 1：ΔpH ≧ 0.8

[0077]

[0078]

[0079] The numbers listed in each component column in the table indicate the amount of each component, and the units are in mass%. As shown in Tables 1 and 2, it was confirmed that the hair dye compositions in the examples have favorable dyeability and gray hair hiding effect, favorable finger combing when rinsed off, high pH stability, and suppressed reductions in the pH even after storage at a high temperature of 50oC.

Claims

1. A hair dye composition, comprising: (A) at least one dye selected from the group consisting of HC blue 2 and HC blue 12; (B) urea; and (C) a cationic surfactant, wherein the mass ratio (A / B) of the (A) to (B) is less than 2.

2. The hair dye composition according to claim 1, wherein, based on the total amount of the hair dye composition, the amount of (A) is 0.05 to 1.0 mass%, the amount of (B) is 0.01 to 10.0 mass%, and the amount of (C) is 0.01 to 5.0 mass%.

3. The hair dye composition according to claim 1, further comprising (D) HC blue 16.

4. The hair dye composition according to claim 1, further comprising (E) at least one dye selected from the group consisting of basic red 76, basic yellow 57, basic red 51, basic yellow 87, basic orange 31, and basic brown 17.

5. The hair dye composition according to claim 1, wherein the total amount of HC yellow 2, HC yellow 4, HC yellow 13, HC red 3, HC red 7, HC red 10, HC red 11, HC red 13, N,N'-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, hydroxyethyl-2-nitro-p-toluidine, 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, and 2-amino-6-chloro-4-nitrophenol is 0.01 mass% or less.

6. The hair dye composition according to claim 1, wherein (A) is HC blue 12.

7. The hair dye composition according to claim 1, wherein the mass ratio (A / B) of (A) to (B) is 0.1 to 1.

8. The hair dye composition according to claim 1, wherein the pH is 4 to 8.

9. The hair dye composition according to claim 1, which is a color treatment.

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