JP6940942B2 - Hair dyeing method using the first agent for oxidative hair dye and oxidative hair dye - Google Patents

Description

The present invention relates to a first agent for an oxidative hair dye for dyeing hair, and a hair dyeing method using an oxidative hair dye.

The oxidative hair dye used to color the hair is based on the hair dyeing principle in which the oxidative dye permeated into the hair is dyed by oxidative polymerization, and is compared with other hair coloring agents such as acidic hair dyes. And realize long-term persistence of hair color.
It is known that the color development differs depending on the selection and combination of the oxidation dyes, and according to the combination of the dye intermediate toluene-2,5-diamine and the coupler 2,4-diaminophenoxyethanol, It develops a blue color. An oxidative hair dye containing the combination of oxidative dyes is described in, for example, Patent Document 1 below.

Japanese Unexamined Patent Publication No. 2008-291024

However, with the conventional oxidative hair dye, the color development in the hair may be insufficient, and it is required to further enhance the color development. Above all, further improvement is desired for deepening the blue tint.
The present invention has been made in view of the above points, and the present invention uses a first agent for an oxidative hair dye capable of enhancing the deep dyeing property of blue in hair, and an oxidative hair dye. The purpose is to provide a hair dyeing method.

As a result of diligent studies by the present inventors on a first agent for an oxidative hair dye containing (A) toluene-2,5-diamine and (B) 2,4-diaminophenoxyethanol, the above (A) While setting the ratio [(A) / (B)] of the content to the content of (B) to 0.25 or more, (C1) dialkyl phosphate, polyoxyethylene alkyl ether phosphoric acid, and (C2). It has been found that the hair can be deeply dyed blue by containing one or more selected from (C3) mono-long-chain alkyltrimethylammonium salt and (C3) mono-long-chain alkyldimethylammonium salt.

The first agent for oxidative hair dyeing of (1) is one selected from (A) toluene-2,5-diamine, (B) 2,4-diaminophenoxyethanol, and (C) the following (C1) to (C3). As described above, (C1) dialkyl phosphate, polyoxyethylene alkyl ether phosphoric acid, (C2) di-long-chain alkyldimethylammonium salt, and (C3) mono-long-chain alkyltrimethylammonium salt are contained in the above (A). The ratio [(A) / (B)] of the content to the content of (B) is 0.25 or more.

The first agent for oxidative hair dyeing of (2) is the first agent for oxidative hair dyeing of (1), and the ratio [(A) / (B)] is 0.35 or more and 3.5 or less. ..
By setting the ratio [(A) / (B)] to 0.35 or more and 3.5 or less, the hair can be dyed with a color including an excellent deep blue color.

The first agent for oxidative hair dyeing of (3) is the first agent for oxidative hair dyeing of (1) or (2), and the above (C) is (C1) dialkyl phosphate and polyoxyethylene alkyl. It is ether phosphoric acid.
When (C1) dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid are blended as the component (C), the deep dyeing property of blue can be particularly enhanced.

The first agent for oxidative hair dyeing of (4) is the first agent for oxidative hair dyeing according to any one of (1) to (3), and further contains (D) ethylenediamine hydroxyethyl triacetate.
When the first agent for oxidative hair dyeing contains (D) ethylenediamine hydroxyethyl triacetate, it is possible to enhance the deep dyeing property of blue and accelerate the color development.

The hair dyeing method (5) is oxidative dyeing in which the first agent for oxidative hair dyeing according to any one of (1) to (4) and the second agent for oxidative hair dyeing containing an oxidative agent are mixed. This is a method of dyeing hair using a hair agent.

According to the first agent for an oxidative hair dye and the hair dyeing method using the oxidative hair dye according to the present invention, it is possible to enhance the deep dyeing property of blue in the hair.

The graph which shows the relationship between the length of dyeing time and the value of ΔL *.

Hereinafter, embodiments of the present invention will be described with reference to examples.

(First agent for oxidative hair dye)
The first agent for an oxidative hair dye of the present embodiment (hereinafter, may be simply referred to as "first agent") contains an oxidative dye (typical as the first agent of the present embodiment). The one has a water content of 70% by mass or more). Further, a known first agent raw material may be blended with the first agent according to the present embodiment as an optional raw material.

The first agent for an oxidative hair dye of the present embodiment contains (A) toluene-2,5-diamine and (B) 2,4-diaminophenoxyethanol as essential oxidative dyes. With these oxidation dyes, it is possible to realize a color tone including a bluish tint.

<(A) Toluene-2,5-diamine>
The toluene-2,5-diamine (A) to be blended in the first agent for the oxidative hair dye of the present embodiment is a toluene-2,5-diamine salt (toluene hydrochloride-2,5-diamine (molecular weight: 195). .09), toluene-2.5-diamine sulfate (molecular weight: 220.25), etc.), and toluene-2.5-diamine (molecular weight: 122.17) may be used. can.

The blending amount of (A) toluene-2,5-diamine in the first agent for oxidative hair dye of the present embodiment is toluene-2,5-diamine (toluene-) from the viewpoint of obtaining a color including deep blue. When a 2,5-diamine salt is used, the amount of toluene-2,5-diamine containing no salt) is preferably 0.0005% by weight or more and 1.7% by weight or less, preferably 0.005% by weight or more. 1.11% by weight or less is more preferable, and 0.02% by weight or more and 0.9% by weight or less is further preferable.

<(B) 2,4-diaminophenoxyethanol>
The 2,4-diaminophenoxyethanol (B) to be blended in the first agent for the oxidative hair dye of the present embodiment is 2,4-diaminophenoxyethanol salt (hydrochloric acid 2,4-diaminophenoxyethanol (molecular weight: 241.11)). , Sulfuric acid 2,4-diaminophenoxyethanol (molecular weight: 266.27), etc.), and 2,4-diaminophenoxyethanol (molecular weight: 168.19).

The blending amount of (B) 2,4-diaminophenoxyethanol in the first agent for oxidative hair dye of the present embodiment is 2,4-diaminophenoxyethanol (2,4-) from the viewpoint of obtaining a color including deep blue. When a diaminophenoxyethanol salt is used, the amount of 2,4-diaminophenoxyethanol containing no salt) is preferably 0.001% by weight or more and 0.35% by weight or less, and 0.0035% by weight or more and 0.25% by weight. % Or less is more preferable.

The ratio (A) / (B) calculated by ((A) toluene-2,5-diamine content / (B) 2,4-diaminophenoxyethanol content) in the first agent for oxidative hair dye of the present embodiment. ) Is 0.25 or more. By setting (A) / (B) to 0.25 or more, the dyed hair tends to have a deep blue tint. Further, from the viewpoint of obtaining an excellent color including deep blue, it is more preferable that (A) / (B) is 0.35 or more and 3.5 or less, and more preferably 0.45 or more and 2.5 or less. It is preferable, and it is particularly preferable that it is 0.6 or more and 2.0 or less.

In the first agent for oxidative hair dye of the present embodiment, the total amount of (A) toluene-2,5-diamine content and (B) 2,4-diaminophenoxyethanol content [(A) + (B)]. Is, for example, 0.05% by mass or more and 1.5% by mass or less.

The first agent for an oxidative hair dye of the present embodiment contains one or more of oxidative dyes other than (A) toluene-2,5-diamine and (B) 2,4-diaminophenoxyethanol. Is also good. With this composition, it becomes possible to dye various tones including a bluish tint.

(A) When a dye intermediate other than toluene-2,5-diamine is further blended with the first agent for oxidative hair dye of the present embodiment, the dye intermediates include para-phenylenediamine and toluene-3,4. -Diamine, 2,2'-[(4-aminophenyl) imino] phenylenediamine derivatives such as bisethanol; phenol derivatives such as paramethylaminophenol, orthoaminophenol, paraaminophenol; and the like.

Further, when a coupler other than (B) 2,4-diaminophenoxyethanol is further added to the first agent for oxidative hair dye of the present embodiment, the coupler includes a phenylenediamine derivative such as meta-phenylenediamine; 5-amino. Aminophenol derivatives such as orthocresol, 5- (2-hydroxyethylamino) -2-methylphenol, and metaaminophenol; resorcin; α-naphthol; and the like can be mentioned.

The blending concentration of the oxidative dye in the first agent for the oxidative hair dye of the present embodiment is, for example, 0.05% by mass or more and 2.5% by mass or less.

<One or more selected from (C) (C1), (C2), (C3)>
The first agent for the oxidative hair dye of the present embodiment includes (C1) dialkyl phosphate, polyoxyethylene alkyl ether phosphoric acid, (C2) di-long-chain alkyldimethylammonium salt, and (C3) mono-long-chain alkyl. one or more selected from trimethylammonium salt is compounded.
By blending one or more of the above (C1) to (C3) with the first agent for an oxidative hair dye containing (A) toluene-2,5-diamine and (B) 2,4-diaminophenoxyethanol, For dyed hair, it is possible to deepen the color including blue color (make it excellent in deep dyeing property). Further, by blending one or more of the above (C1) to (C3), the dispersibility of the oxidation dye can be improved.

<(C1) Dialkyl Phosphate and Polyoxyethylene Alkyl Ether Phosphoric Acid>
When dialkyl phosphate (C1) and polyoxyethylene alkyl ether phosphoric acid are blended in the first agent for oxidative hair dye of the present embodiment, dialkyl phosphate represented by the following general formula (Ia) , Polyoxyethylene alkyl ether phosphoric acid represented by the following general formula (Ib) is used.

上記一般式（Ｉａ）において、Ｒ¹及びＲ²は二重結合を有していても良い直鎖の炭素
数１２〜２２（好ましくは１４〜２０、より好ましくは１６〜１８）のアルキル基を表す。また、Ｒ¹及びＲ²は同じでも良く、異なっていても良い。

In the above general formula (Ia), R ¹ and R ² are linear alkyl groups having 12 to 22 carbon atoms (preferably 14 to 20, more preferably 16 to 18) which may have a double bond. show. Further, R ¹ and R ² may be the same or different.

上記一般式（Ｉｂ）において、Ｒ³は二重結合を有していても良い直鎖の炭素数１２〜
２２（好ましくは１４〜２０、より好ましくは１６〜１８）のアルキル基を表わし、ｎは１以上５０以下（好ましくは３〜４０、より好ましくは５〜２５）を表す。

In the above general formula (Ib), R ³ may have a double bond and has a linear carbon number of 12 to 12 to
It represents 22 (preferably 14 to 20, more preferably 16 to 18) alkyl groups, and n represents 1 or more and 50 or less (preferably 3 to 40, more preferably 5 to 25).

Examples of the dialkyl phosphate represented by the general formula (Ia) include disetyl phosphate.
Examples include dioleyl phosphate.
Examples of the polyoxyethylene alkyl ether phosphoric acid represented by the above general formula (Ib) include polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene cetyl ether phosphoric acid, polyoxyethylene oleyl ether phosphoric acid, and polyoxy. Examples thereof include ethylene stearyl ether phosphoric acid.

The total amount of (C1) dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid in the first agent for oxidative hair dye of the present embodiment is 1% by weight or more from the viewpoint of deepening the color including blue. 7.5% by weight or less is preferable, 1.5% by weight or more and 6% by weight or less is more preferable, and 2% by weight or more and 4.5% by weight or less is further preferable.
The blending ratio of dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid in the first agent for oxidative hair dye of the present embodiment is preferably 1: 3 to 3: 1.

<(C2) Di-long chain alkyldimethylammonium salt>
When the (C2) di-long-chain alkyldimethylammonium salt is blended in the first agent for the oxidative hair dye of the present embodiment, the di-long-chain alkyldimethylammonium salt represented by the following general formula (II) is used. Be done.

上記一般式（ＩＩ）において、Ｒ⁴及びＲ⁵は炭素数１２〜２２（好ましくは１４〜２０
、より好ましくは１６〜１８）のアルキル基を表わし、Ｘはハロゲン原子（例えば、塩素、臭素、ヨウ素など）またはメトサルフェート（ＣＨ₃ＳＯ₄）を表す。

In the above general formula (II), R ⁴ and R ⁵ have 12 to 22 carbon atoms (preferably 14 to 20).
, More preferably 16-18), where X represents a halogen atom (eg, chlorine, bromine, iodine, etc.) or metosulfate (CH ₃ SO ₄ ).

Examples of the dilong-chain alkyldimethylammonium salt represented by the general formula (II) include dilauryldimethylammonium, dimyristyldimethylammonium, disetyldimethylammonium, distearyldimethylammonium, dibehenyldimethylammonium and the like. ..

The blending amount of the (C2) di-long-chain alkyldimethylammonium salt in the first agent for an oxidative hair dye of the present embodiment is 0.1% by weight or more and 5% by weight or less from the viewpoint of deepening the color including blue. Is preferable, and 1.5% by weight or more and 3.5% by weight or less is more preferable.

<(C3) Monolong-chain alkyltrimethylammonium salt>
When the (C3) mono-long-chain alkyltrimethylammonium salt is blended in the first agent for the oxidative hair dye of the present embodiment, the mono-long-chain alkyltrimethylammonium salt represented by the following general formula (III) is used. Be done.

上記一般式（ＩＩＩ）において、Ｒ⁶は炭素数１２〜２２（好ましくは１４〜２０、より好
ましくは１６〜１８）のアルキル基を表し、Ｘはハロゲン原子（例えば、塩素、臭素、ヨウ素など）またはメトサルフェート（ＣＨ₃ＳＯ₄）を表す。

In the above general formula (III), R ⁶ represents an alkyl group having 12 to 22 carbon atoms (preferably 14 to 20, more preferably 16 to 18), and X represents a halogen atom (for example, chlorine, bromine, iodine, etc.). Or it represents metosulfate (CH ₃ SO _4).

Examples of the monolong-chain alkyltrimethylammonium salt represented by the general formula (III) include lauryltrimethylammonium, myristyltrimethylammonium, cetyltrimethylammonium, stearyltrimethylammonium, and behenyltrimethylammonium.

The blending amount of the (C3) mono-long-chain alkyltrimethylammonium salt in the first agent for an oxidative hair dye of the present embodiment is 0.1% by weight or more and 5% by weight or less from the viewpoint of deepening the color including blue. Is preferable, and 0.5% by weight or more and 3.5% by weight or less is more preferable.

<(D) Ethylenediamine hydroxyethyl triacetate>
The first agent for an oxidative hair dye of the present embodiment may contain (D) ethylenediamine hydroxyethyl triacetate. When ethylenediamine hydroxyethyl triacetate is added, the blue color is deeply developed and the color development speed is excellent (the time required for the dyeing process can be shortened to obtain the same level of color development).
Examples of the ethylenediamine hydroxyethyl triacetate include ethylenediamine hydroxyethyl trisodium triacetate or a hydrate thereof.

The blending amount of (D) ethylenediamine hydroxyethyl triacetate in the first agent for oxidative hair dye of the present embodiment is 0.01% by weight or more from the viewpoint of deep blue color development and excellent color development speed. 8% by weight or less is preferable, and 0.05% by weight or more and 0.5% by weight or less is more preferable.

The above (A) toluene-2,5-diamine, (B) 2,4-diaminophenoxyethanol, (C1) dialkyl phosphate, and polyoxyethylene alkyl ether phosphoric acid, (C2) di-long chain alkyldimethyl. ammonium salts, (C3) material optionally blended in the first agent for oxidation hair dye of the present embodiment in addition to the essential components at least one selected from mono-long chain alkyl trimethylammonium salts, known oxidizing hair dye It is the same as the raw material for the first agent. Examples of the raw materials to be optionally blended include alkaline agents, higher alcohols, nonionic surfactants, polyhydric alcohols, hydrocarbons, fats and oils, antioxidants, and direct dyes.

The alkaline agent as the raw material for the first agent for the oxidative hair dye promotes the action of the oxidant contained in the oxidative hair dye and swells the hair to improve the penetration of the dye into the hair. Therefore, the dyeability is improved. Examples of the alkaline agent include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; metal phosphates such as sodium phosphate; ammonia; ammonium such as ammonium carbonate and ammonium sulfate. Salts; alkanolamines such as monoethanolamine, triethanolamine, isopropanolamine; and the like.

When blending an alkaline agent, it is preferable to blend one or more kinds of alkaline agents, and the blending amount of the alkaline agent in the first agent for oxidative hair dye of the present embodiment is 1 to 15% by mass. preferable.

Examples of the higher alcohol as the raw material for the first agent for the oxidative hair dye include cetanol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol and the like. It is preferable to add one or more kinds of higher alcohols to the first agent for oxidative hair dyes, and the concentration of higher alcohols in the first agent for oxidative hair dyes is appropriately set, but for example, 2 mass. % Or more and 20% by mass or less.

The nonionic surfactant as the raw material for the first agent for the oxidative hair dye is, for example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly. Examples thereof include oxyethylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, and sucrose fatty acid ester. It is preferable to add one or more kinds of nonionic surfactants to the first agent for oxidative hair dye, and the concentration of the nonionic surfactant in the first agent for oxidative hair dye is, for example, 0.1% by mass or more 15 It is less than mass%.

Examples of the polyhydric alcohol as a raw material for the first agent for an oxidative hair dye include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, and butylene glycol. One or more kinds of polyhydric alcohols may be blended in the first agent, and the blending concentration of the polyhydric alcohol in the first agent for oxidative hair dye is, for example, 0.1% by mass or more and 3% by mass or less.

Examples of the hydrocarbon as the first raw material for the oxidative hair dye include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, and microcrystalline wax. It is preferable to blend one or more kinds of hydrocarbons in the first agent, and the blending concentration of the hydrocarbons in the first agent for oxidative hair dye is, for example, 0.1% by mass or more and 10% by mass or less.

Examples of the oil and fat as the first raw material for the oxidative hair dye include hydrogenated oil, almond oil, avocado oil, olive oil, shea butter oil, evening primrose oil, camellia oil, peanut oil, and rose hip oil. It is preferable to blend one or more kinds of fats and oils in the first agent, and the blending concentration of the fats and oils in the first agent for oxidative hair dye is, for example, 0.1% by mass or more and 10% by mass or less.

Examples of the antioxidant as a raw material for the first agent for an oxidative hair dye include ascorbic acid and sulfites.

(Dosage form)
Examples of the dosage form of the first agent for oxidative hair dye according to the present embodiment include liquid, cream and gel.

(viscosity)
The viscosity of the first agent for an oxidative hair dye according to the present embodiment is, for example, a value after 60 seconds measured at 25 ° C. and 12 rpm using a B-type viscometer is 4000 mPa · s or more and 60,000 mPa · s or less. ..

(PH)
The pH of the first agent for an oxidative hair dye according to the present embodiment is preferably 7.0 or more and 11.5 or less, and more preferably 8.0 or more and 11.0 or less. As the pH, the measured value at 25 ° C. is adopted.

(Second agent for oxidative hair dye)
The second agent for the oxidative hair dye of the present embodiment contains an oxidizing agent (typically, the second agent of the present embodiment contains 70% by mass or more of water. be.). Further, a known second agent raw material for an oxidative hair dye may be blended with the second agent for an oxidative hair dye according to the present embodiment as an optional raw material.

Examples of the oxidizing agent to be blended in the second agent for oxidative hair dye include hydrogen peroxide, bromate, percarbonate, and perborate. The blending concentration of the oxidizing agent in the second agent for the oxidative hair dye is not particularly limited, but is, for example, 0.3% by mass or more and 7% by mass or less.

A cationic surfactant may be blended in the second agent for the oxidative hair dye of the present embodiment.
(C1) The first agent for oxidative hair dyeing of the present embodiment containing dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid, and the oxidative hair dyeing agent of the present embodiment containing a cationic surfactant. In the oxidative hair dye mixed with the second agent, the pungent odor such as ammonia can be reduced.

Examples of the cationic surfactant to be blended in the second agent for oxidative hair dye of the present embodiment include dilong-chain alkyldimethylammonium salts such as disetyldimethylammonium chloride, distearyldimethylammonium chloride, and dicocoyldimethylammonium chloride. Mono-long-chain alkyltrimethylammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, behenyltrimethylammonium methsulfate; Chain alkoxyalkyltrimethylammonium salts; It is preferable to combine one or more of the above cationic surfactants.
The blending concentration of the cationic surfactant in the second agent for oxidative hair dye of the present embodiment is, for example, 0.1% by mass or more and 5% by mass or less.

As a known second agent raw material for an oxidative hair dye to be optionally blended with the second agent for an oxidative hair dye of the present embodiment, a higher alcohol (blending concentration is, for example, 2% by mass or more and 15% by mass or less) and a nonionic interface. Activators (blending concentration is, for example, 0.5% by mass or more and 6% by mass or less), polyhydric alcohols, ester oils, antioxidants, chelating agents and the like.

The dosage form of the second agent for oxidative hair dye is not particularly limited, and examples thereof include liquid, cream, and gel.

(Oxidation hair dye)
The oxidative hair dye of the present embodiment is a mixture of the first agent for the oxidative hair dye of the present embodiment and the second agent for the oxidative hair dye of the present embodiment. The mixing ratio of the first agent for oxidative hair dye and the second agent for oxidative hair dye is, for example, the first agent for oxidative hair dye: the second agent for oxidative hair dye = 1: 0.4 to It is 2.

(Target hair)
The target hair to be treated with the first agent for oxidative hair dyeing of the present embodiment is not particularly limited, and the hair having a history of hair dyeing treatment with an oxidative hair dye and the history of hair dyeing treatment with an oxidative hair dye are available. The target hair can be a non-existent hair or the like.

(Hair dyeing)
In the hair dyeing treatment in which the oxidative hair dye obtained by mixing the first agent for the oxidative hair dye of the present embodiment and the second agent for the oxidative hair dye of the present embodiment is applied to the hair, the hair is applied. It is preferable that the time left in the state (the time until the oxidative hair dye is washed away) is 5 minutes or more and 30 minutes or less. As a result, the hair can be dyed deeply in blue while suppressing damage to the hair and scalp to a small extent.

Hereinafter, the present invention will be described in detail with reference to Examples, but the description of these Examples does not limit the present invention.

(First agent for oxidative hair dyeing)
The first agent for oxidative hair dyeing of Examples and Comparative Examples shown in Tables 1 to 4 below was prepared.
In Table 1, (C1) to (C3) in Examples 1a to 1c and Comparative Example 1a,
The blending amount of (C') is different because each molar concentration is constant.

(Second agent for oxidative hair dyeing)
A second agent for oxidative hair dyeing for obtaining an oxidative hair dye by mixing with the first agent for oxidative hair dyeing was prepared by mixing the components shown in Table 5 below with water.
(Oxidation hair dye)
The first agent for oxidative hair dyeing of Examples and Comparative Examples prepared above and the second agent for oxidative hair dyeing prepared above were mixed at a mass ratio of 1: 1 to obtain an oxidative hair dyeing agent.

(Hair dyeing)
4 g of an oxidative hair dye was applied to a hair bundle (“BM-WM” manufactured by Burax Co., Ltd .: about 1 g, about 10 cm of human white hair bundle), and the hair bundle was left at room temperature for 20 minutes. Then, the oxidative hair dye was washed from the hair bundle with warm water, the hair bundle was further washed with shampoo (Milbon's shampoo "DEESSE'S NEU Willow Luxe"), and then the hair bundle was dried with warm air while combing. The above is the hair dyeing treatment.
Examples 1a to 1c and Comparative Example 1a shown in Table 1, Examples 2a to 2b and Comparative Example 2a shown in Table 2, Examples 3a to 3e shown in Table 3, and Example 4a shown in Table 4 In ~ 4b, hair bundles having different lot numbers were used.

(Deep dyeing)
The blue color of the dyed hair bundle was visually confirmed as compared with the standard hair bundle.
As the reference hair bundle, Comparative Example 1a is used as a reference in Table 1, Comparative Example 2a is used as a reference in Table 2, Example 3e is used as a reference in Table 3, and Example 4b is used as a reference in Table 4. It was used as a standard.
The evaluation criteria were as follows.
◎: The blue color is much darker than the "standard" hair bundle.
◯: The blue color is darker than the “standard” hair bundle.
―: The blue color is the same as the “standard” hair bundle.
Δ: The blue color is lighter than the “standard” hair bundle.
X: The blue color is much lighter than the "standard" hair bundle.

(Measurement of ΔL *)
For the hair bundle that has been dyed, use a spectrophotometer (CM-5, manufactured by Konica Minolta), and measure 6 times while changing the measurement site by SCE measurement (regular reflection light removal) in the measurement mode. Then, the average value of the lightness L * was calculated. Similarly, the average value of the lightness L * of the hair bundles that had not been dyed was calculated. Then, a value obtained by subtracting the L * value of the hair bundle you do not have the hair dyeing process from the L * value of the hair bundle was dyed processing, was calculated as △ L *.
It should be noted that the smaller the value of ΔL *, the lower the brightness and the deeper the dyeing.

(Speed of color development)
As shown in Table 4, the hair dyeing treatment is performed in the same manner as the above hair dyeing treatment except that the standing time at room temperature in the state where the oxidative hair dyeing agent is applied is 5, 10, 15 and 20 minutes, respectively, and the dyeing treatment is performed. After 5 minutes, 10 minutes after the dyeing treatment, 15 minutes after the dyeing treatment, and 20 minutes after the dyeing treatment, each hair bundle that had been dyed was obtained.
The evaluation of the speed of color development was carried out according to the following evaluation criteria by comparing with the standard hair bundle 10 minutes after the dyeing treatment. As the standard hair bundle in Table 4, Example 4b was used as the standard.
◯: The blue color is darker than the “standard” hair bundle.
―: The blue color is the same as the “standard” hair bundle.
X: The blue color is lighter than the "standard" hair bundle.

Further, for each hair bundle 5 minutes after the dyeing treatment, 10 minutes after the dyeing treatment, 15 minutes after the dyeing treatment, and 20 minutes after the dyeing treatment, the value of ΔL * was calculated in the same manner as in the above measurement of ΔL *. .. In FIG. 1, for Examples 4a and 4b, the relationship between the length of the staining time and the value of ΔL * is shown in a graph.

According to Table 1 above, when any of (C1), (C2), and (C3) is blended as the component (C), the condition of the component (C) is not satisfied (C') cetyl phosphate. It can be seen that the deep dyeing property of blue can be enhanced as compared with the case of blending. Among the components (C), it can be seen that when (C1) dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid are blended, the deep dyeing property of blue color can be particularly enhanced.

Further, according to Table 2 above, the value of (A) toluene-2,5-diamine content / (B) 2,4-diaminophenoxyethanol content is as small as about 0.2 (Comparative Example 2a). It can be seen that when the value is as large as about 0.8 (Example 2a), the value of ΔL * is smaller and the deep dyeing property of blue can be enhanced. Furthermore, the value of (A) toluene-2,5-diamine content / (B) 2,4-diaminophenoxyethanol content is as large as about 3.14 as compared with the case where the value is as small as about 0.2 (Comparative Example 2a). In this case (Example 2b), it can be seen that the value of ΔL * becomes smaller (the deep dyeing property of blue increases).

Further, according to Table 3 above, the values of (A) toluene-2,5-diamine content / (B) 2,4-diaminophenoxyethanol content are 0.38 (Comparative Example 3e) to 0.8 (implementation). It can be seen that as the value increases in Example 3a), the value of ΔL * becomes smaller and the deep dyeing property of blue can be enhanced.

Further, according to Table 4 above, both in Example 4b in which disodium (D') edetate was blended as a chelating agent and in Example 4a in which ethylenediaminehydroxyethyl triacetate trinatrim dihydrate was blended as a chelating agent. , It can be seen that sufficient deep blue dyeability is obtained in each case.

In particular, when comparing the case where the dyeing treatment time is the same in Example 4a containing ethylenediaminehydroxyethyl triacetic acid trinatrim dihydrate as compared with Example 4b containing (D') disodium edetate, It can be seen that the value of ΔL * is small and the deep dyeing property of blue can be enhanced. That is, when the same degree of deep blue dyeability is required, it can be seen that Example 4a can shorten the leaving time at room temperature in the state where the oxidative hair dye is applied as compared with Example 4b.

Claims (4)

(A) Toluene-2,5-diamine,
(B) 2,4-diaminophenoxyethanol,
(C) One or more selected from the following (C1) to (C3),
(C1) Dialkyl Phosphate and Polyoxyethylene Alkyl Ether Phosphoric Acid,
(C2) Di-long chain alkyldimethylammonium salt,
(C3) Mono-long chain alkyltrimethylammonium salt,
Contains,
As the (C), at least (C1) dialkyl phosphate and polyoxyethylene alkyl ether phosphoric acid are contained.
The first agent for oxidative hair dyeing, wherein the ratio [(A) / (B)] of the content of (A) to the content of (B) is 0.25 or more and 3.5 or less. The first agent for oxidative hair dyeing according to claim 1, wherein the ratio [(A) / (B)] is 0.35 or more and 3.5 or less. (D) The first agent for oxidative hair dyeing according to claim 1 or 2 , further containing ethylenediamine hydroxyethyl triacetate. Hair is treated with an oxidative hair dye that is a mixture of the first agent for oxidative hair dyeing according to any one of claims 1 to 3 and the second agent for oxidative hair dyeing containing an oxidant. Hair dyeing method.

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