JP5469489B2 - Hair dye composition - Google Patents

Description

In the present invention, Basic Blue 75, Basic Violet 10 and Basic Brown 16 are blended as hair dyes, and other hair dyes are mixed if necessary, and especially keratin fibers contained in human hair and livestock hair are mixed. The present invention relates to a hair dye composition that is dyed black-brown to black and has little color change even after shampoo treatment.

The general classification of hair dyeing is as follows: (1) The melanin pigment in hair is decolorized and oxidatively colored by mixing it with an oxidation dye such as paraphenylenediamine and hydrogen peroxide water at the time of use. Chemical reaction type (hair dye) that reacts with keratin fibers contained in hair and (2) direct dyes such as acid dyes and basic dyes are physically adsorbed on keratin fibers having positive or negative charges, thereby dyes It can be broadly classified into a physical adsorption type (hair dye) in which molecules penetrate and dye hair.

Most of the hair dyeing is a dyeing method using an oxidative dye, which gives a colorless precursor to hair and oxidatively polymerizes this precursor to form a giant colored substance. This makes it possible to maintain long and stable hair dyeing, but some diamine-based oxidation dyes may cause dermatological hazards, such as rarely causing a skin allergic reaction (fogging) depending on the constitution. Moreover, since it contains alkaline agents, such as ammonia, as another component, there exists a fault which hurts hair.

On the other hand, hair nail polish and color rinse are typical products for temporarily coloring hair. The main dye for hair manicure and color rinse is an acid dye used in cosmetics, and has the advantage that it can be used even by people who cause fogging with a hair dye because it has lower allergic reactivity than the previous oxidation dyes. In addition, since no alkaline agent is used, there is little damage to the hair. However, there are drawbacks such as fading easily when washing hair as compared with chemically reactive oxidation dyes.
Furthermore, acid dyes can be mixed together and dyed to black hair, but the acid dyes used in hair colors have few good blue colors, so the disadvantage of changing to a reddish hair color after repeated washing with shampoo treatments There is.

In addition to acidic dyes, basic dyes are used as colorants such as hair manicures for temporarily coloring the hair, but the fastness of hair dyeing by these dyes is moderate. In particular, among basic dyes, it is said that light fastness and shampoo fastness of hair dyed by a cationic dye are low.
Furthermore, although basic dyes can be mixed together and dyed to black hair, the basic dyes used in hair colors have few good red colors, so the excellent blue hair dyes described in Japanese Patent Application No. 2007-249854 When using Basic Blue 75, there is a problem that the hair color changes to green after repeated washing with shampoo treatment.

By mixing the three primary colors (yellow, red, and blue) of the dye in an appropriate combination, the color can be adjusted to any color, but in the case of reactive hair dyes, mixing with an oxidizing agent for each color number In order to change the ratio, the color at the time of hair dyeing is often different from the color number. On the other hand, in the case of hair dyes such as hair nail polish, since each colored dye is blended and used, there is an advantage that it is easy to prepare a target color number.

As a method for rapidly dyeing human hair or livestock hair with the above direct dyes, a method using an arylmethane dye, a cationic azo dye, a methine dye, an azomethine dye, etc. in a solvent suitable for dyeing (for example, Patent Document 1) and keratin-containing fibers, particularly literature relating to a method for dyeing human hair with a cationic dye (for example, see Patent Document 2).
In particular, cationic dyes are suitable for dyeing human hair and livestock hair because they have high dyeability and good water solubility, but the light fastness and shampoo fastness of the dye are still not sufficient. .
JP 2004-285048 A JP-T 8-507545

The present invention makes use of the high dyeability and good water-solubility characteristics of cationic dyes, and is excellent in dyeing properties for keratin fibers contained in human hair, livestock and other hair, and changes in color tone even after shampooing. An object of the present invention is to provide a black-brown to black-based hair dye composition which is small and excellent in shampoo fastness.

The present inventor is superior in dyeing property of keratin fibers contained in human hair etc. among hair dye compositions using the mixed black cationic dye, and is dyed with a conventional black cationic dye. As a result of intensive studies, the inventors have found a black hair dye composition with improved shampoo fastness, which is a weak point of the hair composition, and less change in color tone.

That is, the present invention contains an oxazine hair dye represented by the general formula (I), a xanthene hair dye represented by the general formula (II), and other hair dyes that can be used for hair dyeing. The dye (a) component for hair dye, the auxiliary agent (b) component includes a wetting agent, a swelling agent, a penetrating agent, a pH adjuster, a surfactant, a fragrance and the like, and a water (c) component, The content of the hair dye (a) component is 0.001 to 5% by mass with respect to the total hair dye composition, and the auxiliary (b) component is at least an anionic surfactant, a cationic surfactant or a nonion. It is a black-brown to black-based hair dye composition excellent in dyeability and shampoo fastness, characterized by containing a surfactant.

In the formula, R1 and R2 are each independently a hydrogen atom or a linear or branched alkyl group (having 1 to 5 carbon atoms), and the anion An is a chlorine ion, bromine ion, sulfate ion, phosphate ion, organic anion. Represents an ion or complex anion.

（ＩＩ）

(II)

In the formula, An ⁻ represents a chlorine ion or an R—COO ion. R represents an alkyl group having 1 to 18 carbon atoms.

The surfactant as the auxiliary component (b) is at least an anionic surfactant, a cationic surfactant, or a nonionic surfactant such as polyoxyethylene sorbitan monooleate.

Furthermore, the hair dye composition of the present invention has a pH value of 3 to 8, excellent in dyeing property, little change in color tone even after washing with shampoo, excellent in shampoo fastness, black brown to black It is a hair dye composition.

Further, the complex salt anion in the general formula (I) is an anion represented by the general formula (III).

Furthermore, the dye represented by formula (I) is a dye represented by formula (IV) C.I. I. It is characterized as Basic Blue 75.

（ＩＶ）

(IV)

The anion An represents a chlorine ion, a bromine ion, a sulfate ion, a phosphate ion, an iodine ion, other inorganic anions, an organic anion, or a complex salt anion.

Further, the dye represented by the general formula (II) is a dye Basic Violet 10 represented by the general formula (V).

（Ｖ）

(V)

Further, according to the present invention, the hair dye (a) is an oxazine blue dye Basic Blue 75 represented by the general formula (IV), a xanthene red dye Basic Violet 10 represented by the general formula (V), and brown. A black-brown to black-based hair dye composition excellent in dyeability and shampoo fastness, characterized in that it is the dye Basic Brown 16.

Furthermore, the present invention is characterized in that the hair dye (a) contains Basic Blue 75, Basic Violet 10, Basic Brown 16, and other hair dyes that can be used for hair dyeing. A black-brown to black-based hair dye composition excellent in dyeing property and fastness to shampoo.

As is clear from the evaluation test results of the examples, the combination of dyes used in the present invention is easy to be mixed in black, excellent in dyeability, and a combination example of a cationic dye which is a conventional dye for hair dyeing. In comparison, it has excellent shampoo fastness and can suppress unnatural color at the time of fading.

Moreover, the said hair dye composition can be used in the wide range whose pH value is 3-8.

The blue cationic dye Basic Blue 75 has the advantage of being dyed in a dark color, but it is too strong to be dyed to the hair, and when mixed with other cationic dyes to make it blackish brown to black, it can be repeatedly used in shampoo treatments. When the hair is washed, the blue color remains strongly, so that there is a problem that the hair color after washing is changed to green.

The hair dye composition of the present invention has excellent shampoo fastness by using red Basic Violet 10 and brown Basic Brown 16 in combination, and has little change in color tone from black to light black after washing. However, for example, when Basic Red 76 or Basic Red 51, which is a red cationic dye that can be used for hair dyeing, is used instead of Basic Violet 10, the bluish color is strong after the shampoo treatment test. Later hair becomes green.

From these facts, the hair dye composition containing Basic Blue 75, Basic Violet 10 and Basic Brown 16 of the present invention is excellent in dyeing power, and even when shampoo treatment treatment is repeated at the same time as dyeing hair darkly black. It does not become reddish or greenish and fades while maintaining a blackish color, and has excellent characteristics as a hair dye composition.

Hereinafter, embodiments of the present invention will be described in detail.
The hair dye composition of the present invention comprises a plurality of dyes for hair dyeing (a), auxiliary agent (b) components (wetting agents, swelling agents, penetrating agents, pH adjusting agents, surfactants, perfumes, etc.), and It contains water (c) component.

Examples of the surfactant appropriately blended in accordance with the purpose of the present invention include an anionic surfactant, a cationic surfactant or a nonionic surfactant, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyglycerin fatty acid. Sugar alcohol ethers such as esters, sorbitol alkyl ethers, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan monooleate, etc. Can be mentioned. Preference is given to polyoxyethylene sorbitan monooleate.

Dye represented by formula (IV) C.I. I. Basic Blue 75 (CAS. No. 12221-43-1, CAS. No. 73398-25-1) and Basic Violet 10 represented by the general formula (V) are mixed with other cationic dyes such as Basic Brown 16 and the like. Can be used. The total of the compounding amounts is 0.001 to 5% by mass with respect to the total hair dye composition. When the concentration is less than 0.001% by mass, the effects of color tone maintenance and leveling cannot be obtained, and when it exceeds 5% by mass, the effect of addition cannot be expected. Preferably it is 0.01-2.5 mass%.

In the hair dye composition of the present invention, conventionally known cosmetic ingredients can be added and used within a range not impeding the effects of the present invention. Examples include higher alcohols, petrolatum, polyhydric alcohols, esters, preservatives, bactericides, silicone derivatives, thickeners, solvents, and the like. Moreover, the pH value of the hair dye composition is 3-8.

The water used in the present invention is blended in order to dissolve a plurality of the dyes for hair dyeing (a) and the auxiliary component (b), and the blending ratio is from 100% by mass to the component (a). And the balance obtained by subtracting the mass% of the component (b). In addition, water is ion exchange water, purified water, or purified water.

The dye names described in the following examples and comparative examples are abbreviated as follows.
C. I. Basic Blue 75: Blue 75
C. I. Basic Blue 99: Blue 99
C. I. Basic Violet 10: Violet 10
C. I. Basic Brown 16: Brown 16
C. I. Basic Red 76: Red 76
C. I. Basic Red 51: Red 51
C. I. Solvent Red 49 (Stearate): Red 49

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In addition, a compounding quantity represents a mass part.

Examples 1-6, Comparative Examples 1-5
[Sample preparation]
The contents of each dyeing composition solution are shown in [Table 2] and [Table 3]. Further, in order to dye human white hair with the dye composition liquid, 10 parts by weight of the black dye composition liquid is taken into a dyeing container, and 1 part by weight of 100% human white hair (BM-W manufactured by Beaulux Co., Ltd.) is added. And stained at 45 ° C. for 20 minutes. The hair was lightly washed with water, treated in 10 parts by mass of a 5% aqueous sodium lauryl sulfate solution at 45 ° C. for 5 minutes, washed with water and naturally dried to prepare a test specimen. Each of these specimens was evaluated according to the following test method and evaluation method. The results are shown in [Table 2] and [Table 3].

[Shampoo and Treat Men Test]
1 part by mass of the specimen is treated in 10 parts by mass of a 5% aqueous sodium lauryl sulfate solution at 45 ° C. for 20 minutes, washed with water and then treated in 10 parts by mass of a 5% aqueous solution of stearyltrimethylammonium chloride at 45 ° C. for 20 minutes. This operation is repeated 5 times.

[Evaluation method]
The specimens before and after these tests were evaluated according to “Evaluation items and conditions” shown in [Table 1], and the results are shown in [Table 2] and [Table 3].

[concentration]
The reflectance R was measured with a spectrocolorimeter JS555 (manufactured by Color Techno System Co., Ltd.), and the concentration (K / S) was calculated by the following formula (Kubelka-Munk formula).
K / S is proportional to the concentration, and the larger the value, the higher the concentration.
K / S = Σ (1-R _λ ) ² / 2R _λ
R _lambda: Numerical divided by the reflectance of the wavelength lambda in 100 lambda: 400 to 700 nm of 10nm interval K / Sd: value obtained by subtracting the K / S of blank (Misomeke)

[Calculation of saturation C *, saturation difference ΔC *, and color difference ΔE *]
Using a spectrocolorimeter JS555, L * a * b * (CIE1976 color system) was measured and obtained from the following equation.

The color specification is defined by three parameters (L *, a * and b *).
L * is lightness, and a * and b * are chromaticities indicating hue and saturation.
The greater the L * value, the lower the intensity of coloring.
a * corresponds to the axis of the red / green pair. Plus is red and minus is green.
b * corresponds to the axis of the yellow / blue pair. Plus is yellow and minus is blue.

C * = {(a *) ² + (b *) ² } ^1/2
C * represents saturation, and the smaller the value, the duller color (Grayish).
ΔC * represents a saturation difference. The smaller the numerical value, the smaller the saturation difference.
If the saturation difference ΔC * is 3.0 or less, it can be said that the saturation is in a similar range.

ΔE * = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2
ΔE * represents a color difference. The smaller the numerical value, the smaller the color difference.

[Evaluation items and conditions]
Regarding the items (1) to (7) in the following [Table 1], those satisfying the conditions were marked with ◯, and those not satisfactory were marked with ×.

[Comprehensive evaluation]
Those that satisfy all the evaluation items are accepted ◎, those that are dissatisfied with two evaluation items are △,
A case where three or more evaluation items were unsatisfactory was rated as x.

As described in detail, according to the present invention, the dyeing power is excellent, the hair is darkly dyed black, and at the same time, even if the shampoo treatment is repeated, the reddish or greenish color is maintained and the color is faded while maintaining the blackish color. Therefore, a hair dye having a natural hair feeling with little color change can be provided.

Claims (4)

A dye containing an oxazine hair dye represented by the following general formula (I), a xanthene hair dye represented by the following general formula (II) and other hair dyes usable for hair dyeing, Hair dye (a) component, auxiliary (b) component, and water (c) component,
The content of the hair dye (a) component is 0.001 to 5% by mass relative to the total hair dye composition, and the auxiliary (b) component is at least an anionic surfactant or a cationic surfactant. Alternatively, a black-brown to black hair dye composition excellent in dyeability and shampoo fastness, characterized by containing a nonionic surfactant.

(I)

[Wherein R1 and R2 are each independently a hydrogen atom or a linear or branched carbon atom of 1 to
The alkyl group 5 and the anion An ⁻ represent a chlorine ion, a bromine ion, a sulfate ion, a phosphate ion, an organic anion, or a complex anion. ]

(II)

[In the formula, An ⁻ represents a chlorine ion or an R—COO ion. R represents an alkyl group having 1 to 18 carbon atoms. ]
2. The black-brown to black-based hair dye composition excellent in dyeability and shampoo fastness according to claim 1, wherein the hair dye composition has a pH value of 3 to 8. 3.
The black-brown to black-based hair dye excellent in dyeing property and shampoo fastness according to claim 1, wherein the hair dye (a) is Basic Blue 75, Basic Violet 10 and Basic Brown 16. Composition.
The dye according to claim 1, wherein the hair dye (a) contains Basic Blue 75, Basic Violet 10, Basic Brown 16, and other dyes that can be used for hair dyeing. A black-brown to black-based hair dye composition excellent in wearability and fastness to shampoo.