阅读说明：本技术 液状染发剂组合物 (Liquid hair dye composition ) 是由 门田圭司 渡边雅彦 于 2019-12-24 设计创作，主要内容包括：本发明涉及一种液状染发剂组合物,其含有成分(A)、(B)及(C),且成分(A)的含量为1.5质量％以上。(A)下述式(A-1)、(A-2)及(A-3)的任一者所表示的偶氮染料；(B)选自阴离子性表面活性剂、非离子性表面活性剂及两性表面活性剂中的表面活性剂,且HLB为7以上；(C)水。(The present invention relates to a liquid hair dye composition containing components (A), (B) and (C), wherein the content of the component (A) is 1.5% by mass or more. (A) An azo dye represented by any one of the following formulae (A-1), (A-2) and (A-3);)

1. A liquid hair dye composition, wherein,

contains the following components (A), (B) and (C), wherein the content of the component (A) is more than 1.5 mass percent,

(A) 1 or 2 or more azo dyes represented by any one of the following formulae (A-1), (A-2) and (A-3);

(B) 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and having HLB of 7 or more;

(C) and (3) water.

2. The liquid hair dye composition according to claim 1, wherein,

further contains 70% by mass or less of the following component (E),

(E) 1 or more than 2 selected from monohydric alcohol and dihydric alcohol.

3. The liquid hair dye composition according to claim 1 or 2, wherein,

the content of the component (A) is 1.5 to 10 mass%.

4. The liquid hair dye composition according to any one of claims 1 to 3, wherein,

the mass ratio (A)/(B) of the component (A) to the component (B) is 0.1 to 20.

5. The liquid hair dye composition according to any one of claims 1 to 4, wherein,

the liquid hair dye composition is used by mixing with other agents to adjust the hair color.

6. The liquid hair dye composition according to claim 5, wherein,

the other preparation is 1 selected from shampoo, hair conditioner and hair dye composition.

7. The liquid hair dye composition according to claim 6, wherein,

the other preparation is a two-part hair dye composition comprising a 1 st part containing an alkaline agent and an oxidation dye precursor and a 2 nd part containing an oxidizing agent.

8. The liquid hair dye composition according to claim 7, wherein,

the liquid hair dye composition is mixed with a mixed liquid of a 1 st agent and a 2 nd agent of a two-part hair dye composition at a mass ratio of 0.01 to 0.4.

9. The method for using a liquid hair dye composition according to any one of claims 1 to 8, wherein,

after the hair color is adjusted by mixing with other preparations, it is used for dyeing hair.

Technical Field

The present invention relates to a liquid hair dye composition.

Background

Hair dyes can be classified according to the dye used or whether there is a bleaching effect on melanin. Typical examples of the hair dye include: the hair dye comprises a two-part permanent hair dye comprising a 1 st part containing an alkaline agent and an intermediate of an oxidation dye and a 2 nd part containing an oxidizing agent, or a one-part semi-permanent hair dye comprising an organic acid or an alkaline agent and at least one of direct dyes such as an acid dye, a basic dye and a nitro dye.

Permanent hair dyes have excellent properties such that they penetrate deeply into hair, dye hair uniformly from the core to the surface, are less likely to lose color, and have a lasting hair dyeing effect, but have a problem that the color tone imparted by oxidation of the dye is not sufficiently vivid. Further, in the direct dye, there is a problem that the dyed hair is remarkably faded with time, although there is a substance capable of obtaining a vivid color such as a nitro dye. Therefore, for permanent hair dyes, there has been proposed a method of obtaining a more vivid color by using a direct dye in combination with an oxidation dye (for example, patent document 1).

However, the direct dye is less stable to an alkaline agent or an oxidizing agent contained in the permanent hair dye, and may be decomposed or precipitated during storage, thereby significantly reducing the dyeing property of the direct dye. Therefore, a method has been proposed in which a direct dye is contained in a composition different from the 1 st agent containing an alkaline agent or the 2 nd agent containing an oxidizing agent, and the direct dye is mixed with the 1 st agent and the 2 nd agent immediately before use and applied to hair (patent document 2).

(patent document 1) Japanese patent application laid-open No. 2010-024158

(patent document 2) International publication No. 2018/087203 pamphlet

Disclosure of Invention

The present invention provides a liquid hair dye composition, which contains components (A), (B) and (C), wherein the content of the component (A) is more than 1.5 mass%.

(A) 1 or 2 or more azo dyes represented by any one of the following formulae (A-1), (A-2) and (A-3);

(B) 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and having HLB of 7 or more;

(C) and (3) water.

Further, the present invention provides a method for using the liquid hair dye composition, wherein the liquid hair dye composition is mixed with other agents to adjust the hair color and then used for dyeing hair.

Detailed Description

In the case of performing mixed toning in which a direct dye is mixed with other preparations to be applied to hair immediately before use, there are problems as follows: when a hair dye having a low direct dye concentration is mixed, the concentration of the dye itself in the composition after mixing tends to be low, and the color obtained as a result of dyeing is different from the intended color, and the color developed after dyeing is not easily predicted. In order to improve the predictability of the color development after dyeing when such mixed toning is performed, it is necessary to use a small amount of a hair dye having a high concentration of a direct dye, as a composition different from the above-mentioned agent 1 or agent 2, in order to be able to tone various colors or color intensities with a small amount of added color.

Further, the azo dye described in patent document 2 has a low solubility in water or various solvents, and when it is intended to formulate the azo dye in a composition at a high concentration, there is a problem of precipitation during storage, and it has been proposed to improve storage stability by using a large amount of a solvent such as a glycol for a specific direct dye. However, it is known that when a large amount of solvent is added, the dye is excessively stably dissolved in the solvent, and as a result, the dye supply into the hair is reduced, and the hair dyeing property is liable to be lowered.

On the other hand, the present inventors have found that when the hair is dyed by mixing with a permanent hair dye, the azo dye can penetrate into a specific part of the hair by applying the azo dye to the hair at a high concentration, whereby the hair can be dyed into 2-layer hues, and the unprecedented effect of changing the hue or color tone of the appearance of the hair depending on the angle at which the hair is observed can be exhibited (for example, see japanese patent application publication No. 2018-175683).

Accordingly, the present invention relates to a liquid hair dye composition which does not precipitate an azo dye during storage and can achieve excellent hair dyeing properties despite containing the azo dye at a high concentration. The present invention also relates to a liquid hair dye composition which can sufficiently exhibit an effect of changing the hue or color tone of the appearance of hair depending on the angle of observation of the hair by dyeing the hair by mixing with a permanent hair dye, and which can easily predict the hair color after dyeing when the hair is dyed by mixing with a permanent hair dye.

The present inventors have made extensive studies and as a result, have found that the solubility of the azo dye can be significantly improved by allowing 1 or more surfactants selected from anionic surfactants having a specific HLB, nonionic surfactants and amphoteric surfactants to coexist with the azo dye, thereby completing the present invention.

[ definitions ]

In the present invention, the term "Liquid" refers to a substance judged to be "Liquid" by a Solid-Liquid judgment Test based on "ASTM D4359-90 Standard Test Method for Determining surface Material a Liquid or Solid", and may include dosage forms such as paste and gel.

[ component (A): azo dyes ]

The liquid hair dye composition of the present invention contains 1 or 2 or more azo dyes represented by any one of the following formulas (A-1), (A-2) and (A-3) as a component (A).

The content of the component (a) in the liquid hair dye composition of the present invention is 1.5% by mass or more, preferably 1.6% by mass or more, more preferably 1.7% by mass or more, and even more preferably 1.8% by mass or more, from the viewpoint of improving hair dyeing properties, obtaining a hair dyeing effect in which the hue or color tone of the appearance of hair changes depending on the angle of observation of hair, and predicting ease of toning of hair after dyeing, and is preferably 10.0% by mass or less, more preferably 9.0% by mass or less, even more preferably 8.5% by mass or less, even more preferably 8.0% by mass or less, and from the viewpoint of improving solubility and storage stability of the component (a), even more preferably 7.18% by mass or less, even more preferably 7.0% by mass or less, even more preferably 6.5% by mass or less, more preferably 6.0% by mass or less, still more preferably 5.71% by mass or less, and still more preferably 5.5% by mass or less.

[ component (B): surfactant having HLB of 7 or more ]

Component (B) is 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and has HLB of 7 or more.

Among these surfactants, 1 or 2 or more selected from anionic surfactants and nonionic surfactants and having an HLB of 7 or more are preferable from the viewpoints of improving the solubility of the component (a) and improving the storage stability, obtaining an effect of changing the hue or color tone of the appearance of hair depending on the angle of observation of the hair, and predicting ease of toning of the hair after dyeing.

The HLB of the component (B) is 7 or more, preferably 7 or more and 50 or less, and more preferably 7 or more and 40 or less, from the viewpoints of improving the solubility of the component (a) and improving the storage stability, obtaining an effect of changing the hue or color tone of the appearance of hair depending on the angle of observation of the hair, and predicting ease of toning of the hair color after dyeing. In the present invention, HLB refers to a value calculated by the Davis method (for example, refer to Suzuki sensitivity, color material, 77[10], 564-469 (2004)) based on the number of groups defined for each functional group and in accordance with the formula shown below.

HLB ═ 7+ Σ (number of hydrophilic groups) + Σ (number of lipophilic groups)

Examples of the anionic surfactant include: sulfate, sulfonate, carboxylate, and phosphate type anionic surfactants. More specifically, from the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair-dyeing properties, it is preferable to use 1 or 2 or more selected from alkyl sulfates or alkenyl sulfates, alkyl ether sulfates or alkenyl ether sulfates, alkyl ether carboxylates or alkenyl ether carboxylates, and N-acylamino acid salts, more preferably 1 or 2 or more selected from alkyl ether sulfates or alkenyl ether sulfates, and N-acylamino acid salts, and still more preferably 1 or 2 or more selected from N-acylamino acid salts.

The alkyl or alkenyl group of the alkyl sulfate or alkenyl sulfate is preferably a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, more preferably a linear or branched alkyl or alkenyl group having 10 to 18 carbon atoms, and still more preferably a linear alkyl group having 12 to 14 carbon atoms, from the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair-dyeing properties. These can be used alone in 1 kind, also can be combined with more than 2 kinds. Among them, from the above aspect, it preferably contains 1 or 2 or more selected from lauryl sulfate, myristyl sulfate, cetyl sulfate, stearyl sulfate and oleyl sulfate, more preferably 1 or 2 or more selected from lauryl sulfate and myristyl sulfate, and still more preferably contains lauryl sulfate.

The alkyl group of the alkyl ether sulfate or alkenyl ether sulfate is preferably a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, more preferably a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, and still more preferably a linear alkyl group having 12 to 14 carbon atoms, from the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair-dyeing properties.

The alkyl ether sulfate or alkenyl ether sulfate is preferably polyoxyethylene alkyl ether sulfate or polyoxyethylene alkenyl ether sulfate, and from the above viewpoint, the average number of moles of polyoxyethylene added is preferably 0.5 to 10, more preferably 0.5 to 5, even more preferably 0.5 to 4, and even more preferably 0.5 to 2. These can be used alone in 1 kind, also can be combined with more than 2 kinds. Among these, from the above viewpoint, 1 or 2 or more selected from among polyoxyethylene (1) lauryl ether sulfate, polyoxyethylene (1) myristyl ether sulfate, polyoxyethylene (2) lauryl ether sulfate, polyoxyethylene (2) myristyl ether sulfate, polyoxyethylene (3) lauryl ether sulfate, and polyoxyethylene (3) myristyl ether sulfate are preferable, 1 or 2 or more selected from among polyoxyethylene (1) myristyl ether sulfate, polyoxyethylene (2) lauryl ether sulfate, and polyoxyethylene (3) lauryl ether sulfate are more preferable, and polyoxyethylene (2) lauryl ether sulfate is more preferable.

From the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair-dyeing properties, the alkyl group or alkenyl group of the alkyl ether carboxylate or alkenyl ether carboxylate is preferably a linear or branched alkyl group or alkenyl group having 12 to 16 carbon atoms, more preferably a linear or branched alkyl group having 12 to 14 carbon atoms, and still more preferably a linear alkyl group having 12 to 14 carbon atoms. The alkyl ether carboxylate or alkenyl ether carboxylate is preferably a polyoxyethylene alkyl ether carboxylate or polyoxyethylene alkenyl ether carboxylate, and the average number of moles of polyoxyethylene added is preferably 1 to 10, more preferably 2 to 5, from the same viewpoint as described above. These can be used alone in 1 kind, also can be combined with more than 2 kinds. Among them, from the above viewpoint, it is preferable to contain 1 or 2 or more selected from polyoxyethylene lauryl ether carboxylate, polyoxyethylene myristyl ether carboxylate, and polyoxyethylene palmitol ether carboxylate, preferably 1 or 2 selected from polyoxyethylene lauryl ether carboxylate and polyoxyethylene myristyl ether carboxylate, and more preferably polyoxyethylene lauryl ether carboxylate.

From the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair-dyeing properties, the acyl group of the N-acylamino acid salt is preferably an acyl group derived from a saturated or unsaturated, linear or branched fatty acid having 10 to 18 carbon atoms, more preferably an acyl group derived from a saturated or unsaturated, linear or branched fatty acid having 12 to 16 carbon atoms, and still more preferably an acyl group derived from a saturated or unsaturated, linear or branched fatty acid having 12 to 14 carbon atoms. Among these fatty acids, from the same viewpoint as described above, 1 or more selected from lauric acid, myristic acid, palmitic acid, and oleic acid is preferable, and lauric acid is more preferable. The acyl group of the N-acylamino acid may be an acyl group derived from a mixed fatty acid of the above-mentioned fatty acids, and may be, for example, an acyl group obtained from coconut oil, palm kernel oil, or the like as a raw material. Among these, preferred are acyl groups obtained from coconut oil fatty acid or palm kernel fatty acid, and more preferred are acyl groups obtained from coconut oil fatty acid.

From the viewpoint of improving the solubility and storage stability of the component (a) and obtaining good hair dyeing properties, the amino acid moiety of the N-acylamino acid salt is preferably a neutral amino acid selected from glycine and alanine, or an acidic amino acid selected from glutamic acid and aspartic acid, more preferably an acidic amino acid, and still more preferably glutamic acid. The amino acid moiety may be any of the D-form, the L-form, or a mixture of the D-form and the L-form, and the L-form is preferred.

The N-acylamino acid salts can be used alone in 1 kind, or can be used in combination in 2 or more kinds. Among these, from the above viewpoint, it is preferable to include 1 or more selected from N-lauroyl glutamate, N-myristoyl glutamate, N-cocoyl glutamate, and N-lauroyl aspartate, more preferably 1 or more selected from N-lauroyl glutamate, N-myristoyl glutamate, and N-cocoyl glutamate, and still more preferably N-cocoyl glutamate.

As salts constituting these preferable anionic surfactants, there can be mentioned: alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium; salts composed of organic ammonium derived from monoethanolamine, diethanolamine, triethanolamine, etc. Among these, alkali metal salts and ammonium salts are preferable from the viewpoint of commercial availability.

Examples of the nonionic surfactant include: an alkyl polyglucoside or alkenyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms and 1 to 5 glucoside units; sorbitan esters such as polyethylene glycol sorbitan stearate, palmitic acid, myristic acid, and lauric acid esters; fatty acid polyglycol esters; a polycondensate of ethylene oxide and propylene oxide commercially available under the trade name "Pluronic (registered trademark)"; polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers.

Among the nonionic surfactants, polyoxyethylene alkyl ethers or polyoxyethylene alkenyl ethers are preferable from the viewpoint of improving stability under alkaline conditions and solubility of the component (a). The alkyl group or alkenyl group of the polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether is preferably a linear or branched alkyl group or alkenyl group having 10 to 22 carbon atoms, more preferably a linear or branched alkyl group or alkenyl group having 12 to 20 carbon atoms, and still more preferably a branched alkyl group having 12 to 20 carbon atoms and a linear alkenyl group having 12 to 20 carbon atoms.

From the above viewpoint, the average number of moles of polyoxyethylene added to the polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether is preferably 15 to 200, more preferably 18 to 150, and still more preferably 20 to 60. More specifically, it is preferably 1 or 2 or more selected from the group consisting of laureth-23, ceteth-25, isocetyl-20, ceteth-40, octyldodecaneth-25, oleyl-50, behenyl polyether-30 and ceteth-150, more preferably 1 or 2 or more selected from the group consisting of laureth-23, ceteth-25, isocetyl-20, ceteth-40, octyldodecaneth-25 and oleyl polyether-50, and still more preferably 1 or 2 or more selected from the group consisting of isocetyl-20, octyldodecaneth-25 and oleyl polyether-50.

The amphoteric surfactant is preferably a variety of publicly known betaines such as alkyl betaine, fatty acid amide alkyl betaine, and sulfobetaine such as lauryl hydroxysulfobetaine, long-chain alkyl amino acids such as cocamidoacetate, cocamidopropionate, sodium cocoamphopropionate, and sodium cocoamphoacetate.

Among the amphoteric surfactants, fatty acid amide alkylbetaines are preferable from the viewpoint of improving stability under alkaline conditions, solubility of the component (a), and hair dyeing properties. The fatty acid group of the fatty acid amidoalkylbetaine preferably has 8 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, and still more preferably 10 to 14 carbon atoms. The alkyl group of the fatty acid amide alkyl betaine preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. Specifically, lauramidopropyl betaine is preferable.

The content of the component (B) in the liquid hair dye composition of the present invention is preferably 3 mass% or more, more preferably 4 mass% or more, further preferably 5 mass% or more, further preferably 7 mass% or more, and further preferably 20 mass% or less, more preferably 18 mass% or less, further preferably 15 mass% or less, and further more preferably 13 mass% or less, from the viewpoint of stably dissolving the component (a), improving storage stability, and improving hair dyeing properties, and from the viewpoint of maintaining the preparation in a liquid state.

From the viewpoint of stably dissolving the component (a) and improving storage stability, and from the viewpoint of efficiently supplying the component (a) into hair and improving hair dyeing properties, the mass ratio [ (a)/(B) ] of the component (a) to the component (B) in the liquid hair dye composition of the present invention is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, further preferably 2 or more, and further preferably 20 or less, more preferably 15 or less, further preferably 10 or less, further preferably 8 or less.

[ component (C): water ]

The liquid hair dye composition of the present invention contains water as a medium as component (C). The content of the component (C) in the liquid hair dye composition of the present invention is preferably more than 2 mass%, more preferably 10 mass% or more, further preferably 39 mass% or more, further preferably 95.5 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, from the viewpoint of enhancing the solubility and storage stability of the component (a), from the viewpoint of obtaining an effect of changing the hue or color tone of the appearance of hair depending on the angle of observation of the hair, and from the viewpoint of predicting ease of toning of the hair color after dyeing.

From the viewpoint of stably dissolving the component (a) and improving storage stability, and from the viewpoint of maintaining the preparation in a liquid state, the mass ratio [ (B)/(C) ] of the component (B) to the component (C) in the liquid hair dye composition of the present invention is preferably 0.02 or more, more preferably 0.05 or more, further preferably 0.08 or more, and further preferably 1.0 or less, more preferably 0.5 or less, and further preferably 0.2 or less.

[ component (D): alkaline agent

In order to achieve both good storage stability and high hair dyeing properties, the liquid hair dye composition of the present invention preferably further contains an alkaline agent as component (D). As the alkaline agent, there may be mentioned: ammonia and salts thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, diethanolamine, triethanolamine, monoethanolmethylamine, monoethanoldimethylamine, diethanol methylamine, monoethanolethylamine, monoethanoldiethylamine, diethanol ethylamine, monoethanolpropylamine, monoethanoldipropylamine, diethopropylamine, monoethanolbutylamine, and diethoxybutylamine, and salts thereof; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkyldiamines such as 1, 3-propanediamine and salts thereof; carbonates such as sodium carbonate, potassium carbonate, and guanidine carbonate; and bicarbonates such as sodium bicarbonate and potassium bicarbonate. Among these, from the viewpoint of improving storage stability and high hair dyeing properties, alkanolamines and salts thereof are preferable, ammonia, monoethanolamine, isopropanolamine, and 2-amino-2-methylpropanol are more preferable, and 2-amino-2-methylpropanol is particularly preferable. These components (D) may be used alone or in combination of 2 or more.

The content of the component (D) in the liquid hair dye composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.25% by mass or more, even more preferably 0.5% by mass or more, from the viewpoint of obtaining good storage stability, and is preferably 15% by mass or less, more preferably 12.5% by mass or less, even more preferably 10% by mass or less, even more preferably 9.0% by mass or less, from the viewpoint of suppressing skin irritation.

[ component (E): monohydric alcohol or dihydric alcohol ]

From the viewpoint of further improving the storage stability, the liquid hair dye composition of the present invention may contain a monohydric alcohol or a dihydric alcohol as the component (E). Examples of the monohydric alcohol include: lower alkanol, aromatic alcohol, alkoxy alcohol, and as the dihydric alcohol, there may be mentioned: alkylene glycol, dialkylene glycol, polyethylene glycol. More specifically, the monohydric alcohol is preferably ethanol, 1-propanol or 2-propanol which is a lower monohydric alcohol having 2 or 3 carbon atoms; monocyclic aromatic monohydric alcohols such as benzyl alcohol and 2-benzyloxyethanol; the dihydric alcohol is preferably a C2-6 dihydric alcohol such as propylene glycol, 1, 3-butylene glycol, diethylene glycol, or the like. From the viewpoint of improving the storage stability and leveling property of the component (a), the component (E) preferably contains 1 or 2 or more selected from a lower monohydric alcohol having 2 or 3 carbon atoms, a monocyclic aromatic monohydric alcohol, and a dihydric alcohol having 2 to 6 carbon atoms, more preferably contains 1 or 2 or more selected from a lower monohydric alcohol having 2 or 3 carbon atoms and a dihydric alcohol having 2 to 6 carbon atoms, still more preferably contains 1 or 2 or more selected from ethanol, 1-propanol, 2-propanol, propylene glycol, 1, 3-butanediol, and diethylene glycol, and still more preferably contains 1 or 2 selected from 2-propanol and propylene glycol.

The content of the component (E) in the liquid hair dye composition of the present invention is preferably 70% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and further preferably 0.1% by mass or more, from the viewpoint of obtaining an effect of changing the hue or color tone of the appearance of hair depending on the angle of observation of the hair, and from the viewpoint of predicting ease of toning of the hair color after dyeing.

[ direct dyes other than the component (A) ]

In the liquid hair dye composition of the present invention, a direct dye other than the component (a) may be used in combination for the purpose of adjusting the dyed color. However, from the viewpoint of not affecting the hair dyeing properties obtained by the component (a), the content of the component (a) is preferably 1 mass% or more and 100 mass% or less, more preferably 5 mass% or more and 100 mass% or less, still more preferably 10 mass% or more and 100 mass% or less, further preferably 20 mass% or more and 100 mass% or less, still further preferably 50 mass% or more and 100 mass% or less, and still further preferably 80 mass% or more and 100 mass% or less of the total direct dye.

Examples of direct dyes other than component (a) include: anionic dyes, cationic dyes, neutral dyes. Examples of anionic dyes include: acid black No. 1, acid blue No. 3, food blue No. 2, food blue No. 5, acid blue 7, acid blue 9, acid blue 74, acid orange 3, acid orange 6, acid orange 7, acid orange 10, acid red 1, acid red 14, acid red 18, acid red 27, acid red 50, acid red 52, acid red 73, acid red 87, acid red 88, acid red 92, acid red 155, acid red 180, acid violet 9, acid violet 43, acid violet 49, acid yellow 1, acid yellow 23, acid yellow 3, food yellow No. 8, acid orange 24, acid green 25, solvent green 7, solvent red 73, acid red 95, solvent red 43, solvent red 48, acid red 33, solvent violet 13, acid yellow 73, food red No. 17, food red No. 1, food yellow No. 3, food blue No. 2, food black No. 1, food black No. 2, disperse black No. 9, disperse black 9, acid orange 7, acid red 95, acid red 6, acid orange 7, acid red 33, acid red, acid yellow 13, acid yellow 73, acid red 1, acid red 14, acid violet 43, acid violet 49, acid yellow 1, acid yellow 8, food red No. 1, food yellow No. 3, food red No. 3, food yellow No. 3, and dispersion black, Disperse violet 1, and alkali metal salts (sodium salt or potassium salt) thereof. Examples of cationic dyes include: basic blue 6, basic blue 7, basic blue 9, basic blue 26, basic blue 41, basic blue 99, basic Brown 4, basic Brown 16, basic Brown 17, Natural Brown (Natural Brown)7, basic green 1, basic red 2, basic red 12, basic red 22, basic red 76, basic violet 1, basic violet 2, basic violet 3, basic violet 10, basic violet 14, basic yellow 57, basic red 51, basic yellow 87, basic blue 17, basic orange 31, and the like. As neutral dyes comprising nitro dyes, mention may be made of: HC blue 2, HC blue 4, HC blue 5, HC blue 6, HC blue 7, HC blue 8, HC blue 9, HC blue 10, HC blue 11, HC blue 12, HC blue 13, HC brown 1, HC brown 2, HC green 1, HC orange 2, HC orange 3, HC orange 5, HC Red BN, HC Red 1, HC Red 3, HC Red 7, HC Red 8, HC Red 9, HC Red 10, HC Red 11, HC Red 13, HC Red 54, HC Red 14, HC Violet BS, HC Violet 1, HC Violet 2, HC yellow 4, HC yellow 5, HC yellow 6, HC yellow 7, HC yellow 8, HC yellow 9, HC yellow 10, HC yellow 11, HC yellow 12, HC yellow 13, HC yellow 14, HC yellow 15, 2-amino-6-chloro-4-nitrophenol, picloram, 1, 2-diamino-4-nitrobenzene, 1, 4-diamino-2-nitrobenzene, 3-amino-4-nitrophenol, 1-hydroxy-2-amino-3-nitrobenzene, 2-hydroxyethylpicloram, 3-nitro-p-hydroxyethylaminophenol, 4-hydroxypropylamino-3-nitrophenol, N-bis (2-hydroxyethyl) -2' -nitro-p-phenylenediamine, and the like.

[ other solvents, surfactants ]

The liquid hair dye composition of the present invention may further contain a solvent other than the components (C) and (E) for the purpose of adjusting the viscosity and feel of the preparation. Examples of the solvent other than the components (C) and (E) include: a 3-or more-membered polyhydric alcohol such as glycerin; n-alkylpyrrolidinones such as N-methylpyrrolidone and N-ethylpyrrolidinone; alkylene carbonates such as propylene carbonate, and lactones such as γ -valerolactone and γ -caprolactone. In addition, when a solvent other than the components (C) and (E) is contained, from the viewpoint of maintaining the leveling property, efficiently supplying the component (a) into the hair and improving the hair dyeing property, the content of water is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and the balance is preferably water as the component (C) in the liquid hair dye composition.

From the viewpoint of maintaining the solubility of the component (a) to be good, it is preferable that the liquid hair dye composition of the present invention contains substantially no cationic surfactant, and the content of the cationic surfactant in the liquid hair dye composition is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.001% by mass or less.

[ Hair-caring ingredients ]

The liquid hair dye composition of the present invention may contain a hair care ingredient suitable for application to hair, and examples of the hair care ingredient include: cationic polymers, silicones, higher alcohols, organic hair care oils, and the like.

[pH]

The pH of the liquid hair dye composition of the present invention is preferably 7.5 or more, more preferably 8.0 or more, further preferably 8.5 or more, and further preferably 9.0 or more from the viewpoint of enhancing hair dyeing properties, and is preferably 12.0 or less, more preferably 11.5 or less, and further preferably 11.0 or less from the viewpoint of suppressing skin irritation. In the present invention, the pH of the liquid hair dye composition is a value at 25 ℃ when diluted 10 times by mass with water using a pH meter (F-51, manufactured by horiba Ltd.).

Examples of the pH adjuster for adjusting the pH of the composition include: inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid and lactic acid, hydrochlorides such as ammonium chloride and monoethanolamine hydrochloride, and phosphates such as potassium dihydrogen phosphate and disodium hydrogen phosphate.

[ other optional ingredients ]

The liquid hair dye composition of the present invention may further contain other components generally used as cosmetic materials, as long as the stable liquid form and the function as a hair dye are not impaired. As such arbitrary components, there can be mentioned: a penetration enhancer, a pearlizing agent, a preservative, a metal blocking agent, a stabilizer, an antioxidant, an ultraviolet absorber, a humectant, an aromatizing agent, and the like, and specific arbitrary components include: protein hydrolysate, protein derivatives, amino acids, plant extract, vitamins, perfume, etc.

[ method of use ]

The liquid hair dye composition of the present invention can also be used alone as a hair dye composition. Further, since the component (a) as a direct dye is contained at a high concentration, even when mixed for color matching, the color development after hair dyeing can be easily predicted, and the composition can be applied to hair and used for hair dyeing after being mixed with other preparations before use. Here, examples of the "other preparation" include, in addition to a diluting liquid such as an aqueous solution containing water or an alkaline agent: shampoo, hair conditioner, and hair dye composition. The formulation of the other preparation is preferably liquid from the viewpoint of satisfactory mixing with the liquid hair dye composition of the present invention. Examples of the hair dye composition include: one-pack hair dye compositions containing a direct dye, two-pack hair dye compositions comprising a 1 st pack containing an alkaline agent and an oxidative dye precursor, and a 2 nd pack containing an oxidizing agent, and the like.

When the liquid hair dye composition of the present invention is used by mixing it with the 1 st and 2 nd agents of the two-part hair dye composition, the mixture is applied to the hair, whereby the central part of the cross section of the hair is dyed with the oxidation dye and the peripheral part of the cross section of the hair is dyed with the component (a), and as a result, the hair can be dyed into 2-layer colors. Such hair dyed with 2-layer hue has an unprecedented hair dyeing effect in which the hue or color tone of the appearance of the hair changes depending on the angle at which the hair is observed.

As a method for dyeing hair by mixing the liquid hair dye composition of the present invention with the 1 st and 2 nd agents of the two-part hair dye composition, a dyeing method having the following steps (I) and (II) can be exemplified.

A step (I): mixing a 1 st agent containing an alkaline agent and an oxidation dye precursor, a 2 nd agent containing an oxidizing agent, and the liquid hair dye composition of the present invention as a 3 rd agent;

step (II): applying the liquid mixture prepared in step (I) to hair.

[ Process (I) ]

The step (I) is a step of mixing the agent 1 containing an alkaline agent and an oxidation dye precursor, the agent 2 containing an oxidizing agent, and the liquid hair dye composition of the present invention as the agent 3. The alkaline agent and oxidation dye precursor used in the agent 1 and the oxidizing agent used in the agent 2 are not particularly limited, and those commonly used in two-part oxidation hair dyes can be used.

From the viewpoint of sufficiently swelling hair to obtain a hair dyeing effect, the content of the alkaline agent in the liquid mixture prepared in step (I) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and further preferably 7% by mass or less, more preferably 6% by mass or less, further preferably 4% by mass or less.

The oxidation dye precursor used in the two-part hair dye composition can be used without limitation as long as it is a substance used in a general hair dye.

As the dye precursor, there may be mentioned: 1,2, 4-trihydroxybenzene, 1, 3-bis (2, 4-diaminophenoxy) -propane, 1, 5-naphthalenediol, 1-naphthol, 1-hydroxyethyl-4, 5-diaminopyrazole, 1-hexyl-1H-pyrazole-4, 5-diaminopyrazole, 2'- [ (4-aminophenyl) imino ] diethanol, 2' -methylenebis-4-aminophenol, 2, 3-indolinedione, 2,4,5, 6-tetraaminopyrimidine, 2, 4-diaminophenol, 2, 4-diaminophenoxyethanol, 2,5, 6-triamino-4-pyrimidineol, 2, 6-diaminopyridine, 2, 6-dihydroxy-3, 4-lutidine, 2, 6-dihydroxyethylaminotoluene, 2, 6-dimethoxy-3, 5-pyridinediamine, 2, 7-naphthalenediol, 2-amino-3-hydroxypyridine, 2-amino-4-hydroxyethylaminoanisole, 2-amino-5-ethylphenol, 2-chloro-p-phenylenediamine, 2-methyl-1-naphthol, 2-methyl-5-hydroxyethylaminophenol, 2-methylresorcinol, 2-methoxy-methyl-p-phenylenediamine, 3' -diiminophenol, 3-amino-2, 6-dimethylphenol, 4-amino-2-hydroxytoluene, 4-amino-m-cresol, 2-hydroxy-3-aminom-cresol, 2-hydroxy-3-ethylaminotoluene, 2-amino-4-hydroxyethylaminotoluene, 2-hydroxy-p-phenylenediamine, 2-hydroxy-2-methyl-2-hydroxy-ethyl-phenyl-methyl-2-hydroxy-2-methyl-2-hydroxy-2-hydroxy-phenol, 3-imino-2-hydroxy-2-methyl-hydroxy-2-hydroxy-phenol, 4-chlororesorcinol, 4-formyl-1-methylquinolinium p-toluenesulfonic acid, 5- (2-hydroxyethylamino) -2-methylphenol, 5-amino-4-chloro-o-cresol, 5-amino-6-chloro-o-cresol, 6-amino-m-cresol, 6-hydroxyindole, 6-methoxy-2-methylamino-3-aminopyridine, m-aminophenol, N-bis (2-hydroxyethyl) p-phenylenediamine, N '-bis (4-aminophenyl) -2, 5-diamino-1, 4-quinonediimine, N-phenyl-p-phenylenediamine, p-aminophenol, p-phenylenediamine, p-methylaminophenol, acetoxy-2-methoxynaphthalene, p-toluenesulphonic acid, methyl-2-hydroxyquinoline, methyl-2-carboxylic acid, methyl-2-hydroxy-amino-3-amino-pyridine, methyl-2-amino-phenol, methyl-2-amino-p-aminophenol, N' -bis (2-hydroxy-ethyl-2-hydroxy-o-p-phenylenediamine, N, S, P, S, ortho-aminophenol, catechol, dihydroxyindoline, diphenylamine, tannic acid, toluene-2, 5-diamine, toluene-3, 4-diamine, hydroxyethyl-3, 4-methylenedioxyaniline, hydroxyethyl-p-phenylenediamine, hydroxyethylaminopyrazolopyridine, hydroxypropyl bis (N-hydroxyethyl-p-phenylenediamine), hydroxybenzomorph-ine, hydroquinone, pyrogallol, phenylmethylpyrazolone, phloroglucinol, m-phenylenediamine, methylimidazolium propyl-p-phenylenediamine, resorcinol, gallic acid and the like and salts thereof.

From the viewpoint of obtaining sufficient hair-dyeing properties, the content of the oxidation dye precursor in the mixed solution is preferably 0.001 mass% or more, more preferably 0.002 mass% or more, even more preferably 0.004 mass% or more, further preferably 0.01 mass% or more, and further preferably 8 mass% or less, more preferably 6 mass% or less, even more preferably 4 mass% or less, further preferably 2 mass% or less.

From the viewpoint of hair-bleaching and hair-dyeing properties, the content of the oxidizing agent in the liquid mixture is preferably 0.06% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, still further preferably 1% by mass or more, and further preferably 17% by mass or less, more preferably 12.5% by mass or less, still more preferably 11% by mass or less, and further preferably 9% by mass or less.

The content of the dye (a) in the mixed solution is preferably 0.02 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.08 mass% or more, and even more preferably 0.10 mass% or more, and is preferably 5 mass% or less, more preferably 2 mass% or less, even more preferably 1.0 mass% or less, and even more preferably 0.5 mass% or less, from the viewpoint of obtaining a hair dyeing effect in which the appearance hue or color tone of the hair changes depending on the angle of observation of the hair by dyeing the hair into 2 layers, and from the viewpoint of predicting ease of toning of the hair after dyeing, and is dissolved in the mixed solution to obtain uniform dyeing.

From the viewpoint of maintaining the solubility of the component (a) to be good, it is preferable that the liquid mixture of the liquid hair dye composition of the present invention and the two-part hair dye composition does not substantially contain a cationic surfactant, and the content of the cationic surfactant in the liquid hair dye composition is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, and still more preferably 0.001% by mass or less.

In the step (I), the hair is dyed in 2 layers, and the hue or hue of the appearance of the hair changes depending on the angle of observation of the hair, and the ease of toning of the color after dyeing is predicted, the mixing is performed so that the mass ratio of the dye (a) to the oxidation dye precursor (dye (a)/oxidation dye precursor) in the mixed solution is preferably 0.005 or more, more preferably 0.015 or more, more preferably 0.03 or more, further preferably 0.1 or more, further preferably 0.2 or more, further preferably 0.3 or more, and preferably 5000 or less, more preferably 500 or less, more preferably 100 or less, further preferably 50 or less, further preferably 10 or less, and further preferably 8 or less.

[ mixing ratio ]

From the viewpoint of obtaining sufficient hair-dyeing properties, the mixing mass ratio of the 1 st agent and the 2 nd agent (2 nd agent/1 st agent) is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.5 or more, and further preferably 5 or less, more preferably 3 or less, further preferably 2 or less. From the viewpoint of a high coloring effect in which the hair is colored in 2 layers and the hue or color tone of the appearance of the hair changes depending on the angle of observation of the hair, and from the viewpoint of predicting ease of toning of the colored hair after coloring, the mass ratio of the 3 rd agent to the total mass of the 1 st agent and the 2 nd agent (the 3 rd agent/(the 1 st agent + the 2 nd agent)) is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.03 or more, further preferably 0.4 or less, more preferably 0.3 or less, and further preferably 0.2 or less.

[ Process (II) ]

Step (II) is a step of applying the liquid mixture prepared in step (I) to hair. When the liquid mixture is applied to hair, the bath ratio, that is, the ratio of the mass of the applied liquid mixture to the mass of hair (mass of the applied liquid mixture)/(mass of hair), the standing time after the liquid mixture is applied to hair until shampooing, and the standing temperature greatly affect the manageability.

The bath ratio (mass of the applied liquid mixture)/(mass of hair) is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.4 or more from the viewpoint of enhancing the hair dyeing property and preventing color unevenness, and is preferably 2 or less, more preferably 1.75 or less, and even more preferably 1.5 or less from the viewpoint of economy and reducing the risk of dripping.

The standing time after the liquid mixture is applied to the hair until the hair is washed is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 10 minutes or more, and from the viewpoint of suppressing skin irritation, preferably 60 minutes or less, more preferably 45 minutes or less, and further preferably 40 minutes or less, from the viewpoint of enhancing hair-dyeing property.

The temperature during which the liquid mixture is applied to hair and left to stand is preferably 5 ℃ or higher, more preferably 10 ℃ or higher, and still more preferably 20 ℃ or higher from the viewpoint of enhancing hair-dyeing properties, and is preferably 60 ℃ or lower, more preferably 50 ℃ or lower, and still more preferably 40 ℃ or lower from the viewpoint of suppressing skin irritation.

[ Process (III) ]

After step (II), the hair may be rinsed or washed. The rinsing may be carried out using any aqueous medium known in the art, preferably using water, more preferably using tap water, and the rinsing may be carried out using any detergent composition known in the art, preferably using a shampoo composition. The root portion, the terminal portion and the portions therebetween of the hair may be rinsed or washed simultaneously or separately.

[ Process (IV) ]

Any hair care composition known in the art may also be applied to the hair after step (III), or before step (III), or in place of step (III).

[ Process (V) ]

The hair may be dried after step (II), (III) or (IV). Drying of the hair may be carried out using a drying appliance, for example an electric drying appliance such as a towel or a hair dryer, and drying may be carried out partially or completely.

Preferred aspects of the present invention are further disclosed below with respect to the above-described embodiments.

< 1 > a liquid hair dye composition which comprises the following components (A), (B) and (C) and contains the component (A) in an amount of 1.5% by mass or more.

(A) 1 or 2 or more azo dyes represented by any one of the following formulae (A-1), (A-2) and (A-3);

(B) 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and having HLB of 7 or more;

(C) and (3) water.

< 2 > a liquid hair dye composition which comprises the following components (A), (B) and (C) and in which the content of component (A) is 1.5 to 5.5 mass%.

(A) 1 or 2 or more azo dyes represented by any one of the following formulae (A-1), (A-2) and (A-3);

(B) 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and having HLB of 7 to 50 inclusive;

(C) and (3) water.

< 3 > a liquid hair dye composition comprising the following components (A), (B) and (C), wherein the content of the component (A) is 1.5 to 5.5 mass%.

(A) 1 or 2 or more azo dyes represented by any one of the following formulae (A-1), (A-2) and (A-3);

(B) 1 or 2 or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, and having HLB of 7 to 40;

(C) and (3) water.

[ 4] the liquid hair dye composition according to any one of [ 1] to [ 3], wherein the component (B) is 1 or 2 or more selected from anionic surfactants and nonionic surfactants.

< 5 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from the group consisting of alkyl sulfate or alkenyl sulfate, alkyl ether sulfate or alkenyl ether sulfate, alkyl ether carboxylic acid or alkenyl ether carboxylic acid or salt thereof, and N-acyl amino acid salt.

< 6 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from the group consisting of alkyl ether sulfates, alkenyl ether sulfates and N-acyl amino acid salts.

The liquid hair dye composition according to any one of < 7 > to < 1 > -4 > wherein the component (B) is 1 or 2 or more selected from N-acylamino acid salts.

The liquid hair dye composition according to any one of < 8 > to < 1 > -to < 4 >, wherein the component (B) contains a polyoxyethylene alkyl ether or a polyoxyethylene alkenyl ether.

< 9 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is a fatty acid amide alkyl betaine having a fatty acid group with 10 to 14 carbon atoms and an alkyl group with 2 to 4 carbon atoms.

< 10 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from alkyl ether sulfates or alkenyl ether sulfates having a linear alkyl group or alkenyl group having 12 to 14 carbon atoms and an average addition mole number of polyoxyethylene of 0.5 to 4.

< 11 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from the group consisting of polyoxyethylene (1) lauryl ether sulfate, polyoxyethylene (1) myristyl ether sulfate, polyoxyethylene (2) lauryl ether sulfate, polyoxyethylene (2) myristyl ether sulfate, polyoxyethylene (3) lauryl ether sulfate and polyoxyethylene (3) myristyl ether sulfate.

< 12 > the liquid hair dye composition according to any one of < 1 > -4 > wherein the component (B) is 1 or 2 or more selected from N-acylamino acid salts, the acyl group of the N-acylamino acid salt is an acyl group derived from a saturated or unsaturated, linear or branched fatty acid having 10 to 18 carbon atoms, the amino acid moiety is 1 selected from glutamic acid and aspartic acid, and the amino acid moiety is an L-form.

< 13 > the liquid hair dye composition according to any one of < 1 > -4 > wherein the component (B) is 1 or 2 or more selected from the group consisting of N-lauroyl glutamate, N-myristoyl glutamate and N-cocoyl glutamate.

[ 14] the liquid hair dye composition according to any one of [ 1] to [ 4], wherein the component (B) is a polyoxyalkyl ether or a polyoxyalkenyl ether having an alkyl group or an alkenyl group having 12 to 20 carbon atoms and having an average molar number of addition of polyoxyethylene of 20 to 60.

< 15 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from the group consisting of laureth-23, ceteth-25, isocetylpolyether-20, ceteth-40, octyldodecyl polyether-25 and oleyl polyether-50.

< 16 > the liquid hair dye composition according to any one of < 1 > to < 4 >, wherein the component (B) is 1 or 2 or more selected from lauramidopropyl betaine, polyoxyethylene (2) lauryl ether sulfate, sodium cocoyl glutamate, isocetyl polyether-20, octyldodecyl polyether-25 and oleyl polyether-50.

The liquid hair dye composition according to any one of < 17 > to < 16 >, wherein the content of the component (B) in the liquid hair dye composition is 3 to 20 mass%.

[ 18] the liquid hair dye composition according to any one of [ 1] to [ 16], wherein the content of the component (B) in the liquid hair dye composition is 4 to 18 mass%.

The liquid hair dye composition according to any one of < 19 > to < 1 > -16 >, wherein the content of the component (B) in the liquid hair dye composition is 5 to 15 mass%.

The liquid hair dye composition according to any one of < 20 > to < 1 > -16 >, wherein the content of the component (B) in the liquid hair dye composition is 7 to 13 mass%.

< 21 > such as < 1 > to < 20 >, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) in the liquid hair dye composition is 0.1 to 20.

< 22 > the liquid hair dye composition according to any one of < 1 > to < 20 >, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) in the liquid hair dye composition is 0.5 to 15.

< 23 > the liquid hair dye composition according to any one of < 1 > to < 20 >, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) in the liquid hair dye composition is 1 or more and 10 or less.

< 24 > the liquid hair dye composition according to any one of < 1 > to < 20 >, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) in the liquid hair dye composition is 2 or more and 8 or less.

The liquid hair dye composition according to any one of < 25 > to < 1 > -to < 24 >, wherein the content of the component (C) in the liquid hair dye composition is more than 2 mass% and 95.5 mass% or less.

The liquid hair dye composition according to any one of < 26 > to < 24 >, wherein the content of the component (C) in the liquid hair dye composition is 10 mass% or more and 95 mass% or less.

The liquid hair dye composition according to any one of < 27 > to < 24 >, wherein the content of the component (C) in the liquid hair dye composition is 39 to 90 mass%.

< 28 > the liquid hair dye composition according to any one of < 1 > to < 27 >, wherein the mass ratio [ (B)/(C) ] of the component (B) to the component (C) in the liquid hair dye composition is 0.02 to 1.0.

< 29 > the liquid hair dye composition according to any one of < 1 > to < 27 >, wherein a mass ratio [ (B)/(C) ] of the component (B) to the component (C) in the liquid hair dye composition is 0.05 or more and 0.5 or less.

< 30 > the liquid hair dye composition according to any one of < 1 > to < 27 >, wherein the mass ratio [ (B)/(C) ] of the component (B) to the component (C) in the liquid hair dye composition is 0.08 or more and 0.2 or less.

The liquid hair dye composition according to any one of < 31 > to < 1 > to < 30 >, which further comprises an alkaline agent as component (D).

< 32 > and < 31 > wherein the component (D) contains 1 or 2 or more selected from the group consisting of ammonia, monoethanolamine, isopropanolamine and 2-amino-2-methylpropanol.

< 33 > such as < 31 >, wherein the component (D) contains 1 or 2 or more selected from ammonia and 2-amino-2-methylpropanol.

The liquid hair dye composition according to any one of < 34 > to < 31 > to < 33 >, wherein the content of the component (D) in the liquid hair dye composition is 0.1 mass% or more and 15 mass% or less.

The liquid hair dye composition according to any one of < 35 > to < 31 > to < 33 >, wherein the content of the component (D) in the liquid hair dye composition is 0.2 mass% or more and 12.5 mass% or less.

The liquid hair dye composition according to any one of < 36 > to < 31 > -33 >, wherein the content of the component (D) in the liquid hair dye composition is 0.25 mass% or more and 10 mass% or less.

The liquid hair dye composition according to any one of < 37 > to < 31 > to < 33 >, wherein the content of the component (D) in the liquid hair dye composition is 0.5 mass% or more and 9.0 mass% or less.

The liquid hair dye composition according to any one of < 38 > to < 1 > -37 >, which further comprises 70 mass% or less of the following component (E).

(E) 1 or more than 2 selected from monohydric alcohol and dihydric alcohol.

< 39 > such as < 38 >, wherein the content of the component (E) in the liquid hair dye composition is 0.1 to 40% by mass.

The liquid hair dye composition according to < 40 > or < 38 >, wherein the content of the component (E) in the liquid hair dye composition is 0.1 to 20% by mass.

The liquid hair dye composition according to < 41 > or < 38 >, wherein the content of the component (E) in the liquid hair dye composition is 0.1 to 10% by mass.

< 42 > such as < 38 >, wherein the content of the component (E) in the liquid hair dye composition is 0.1 to 5% by mass.

The liquid hair dye composition according to < 43 > such as < 1 > to < 42 > which is used by mixing with other agents to adjust the dyed color.

< 44 > such as < 43 >, wherein the other preparation is 1 selected from the group consisting of shampoo, conditioner and hair dye composition, preferably hair dye composition.

< 45 > and < 43 > wherein the other agent is a two-part hair dye composition comprising a 1 st agent containing an alkaline agent and an oxidation dye precursor and a 2 nd agent containing an oxidizing agent.

< 46 > such as < 45 > is mixed in a mass ratio of 0.01 to 0.4 with respect to a mixed liquid of the 1 st component and the 2 nd component of the two-component hair dye composition.

< 47 > a method for using the liquid hair dye composition as defined in any one of < 1 > -42 > for dyeing hair after adjusting the dyeing color by mixing with other agents.

< 48 > such as < 47 > wherein the other preparation is 1 selected from the group consisting of shampoo, conditioner and hair dye composition, preferably hair dye composition.

< 49 > and, as shown in < 47 >, a method for using a liquid hair dye composition, wherein the other preparation is a two-part hair dye composition comprising a 1 st part containing an alkaline agent and an oxidation dye precursor and a 2 nd part containing an oxidizing agent.

< 50 > such as < 49 >, wherein the liquid hair dye composition is mixed in a mass ratio of 0.01 to 0.4 inclusive relative to a mixed liquid of the 1 st component and the 2 nd component of the two-component hair dye composition.

Example 1

Examples 1 to 12 and comparative examples 1 to 8

The components shown in tables 1 and 2 were mixed to prepare a liquid hair dye composition, and the solubility and storage stability of the dye and the hair dyeing effect when the hair dye was mixed with the two-part hair dye composition were evaluated according to the following methods.

[ method for evaluating solubility of dye ]

The components shown in tables 1 and 2 except for the dye were uniformly dissolved to prepare a surfactant solution, and then the dye was added thereto and stirred for 20 minutes or more to prepare a liquid hair dye composition. The liquid hair dye composition was visually observed, and the solubility was evaluated according to the following criteria. For those whose evaluation was "X", no other evaluation was performed.

A: mixed uniformly, no insoluble matter was observed;

x: the mixture was not uniformly mixed, and insoluble matter was observed.

[ storage stability ]

In the method for evaluating the solubility of the dye, the liquid hair dye composition whose solubility immediately after the preparation was evaluated as "A" was visually observed to have a solubility after being stored at-5 ℃, 20 ℃ and 40 ℃ for 1 week, and was evaluated according to the following criteria.

A: no insoluble matter was confirmed;

x: insoluble matter was confirmed.

Further, the agent 1 and the agent 2 of the oxidation hair dye having the compositions shown in table 3 were prepared, and the oxidation hair dye and each of the liquid hair dye compositions shown in tables 1 and 2 were used to dye hair by the following dyeing method, and the effects of the color difference from the case of dyeing hair by using only the oxidation hair dye and the change in the hue or color tone of the appearance of hair depending on the angle at which the hair was observed were evaluated.

Hair dyeing method

A hair bundle having a length of 15cm and a weight of about 1g was prepared as evaluation hair using White hair (manufactured by IHIP).

4g of the 1 st dose, 6g of the 2 nd dose, and 1.25g of the liquid hair dye composition were weighed out and placed in a plastic beaker, and mixed 10 times with a spatula. Approximately 1g of the mixture was applied to evaluation hair with bristles and left at 30 ℃ for 30 minutes to dye the hair. Rinsing hair with warm water of 40 deg.C for more than 30 seconds, washing with shampoo, treating with hair conditioner, and drying.

[ evaluation method of changes in hue or hue of appearance of hair due to observation angle of hair ]

The dried hair after dyeing was placed under an artificial solar lighting lamp (model XC-100AP, 100W) manufactured by Seric corporation, and a bundle of hair at a distance of about 30cm was observed. The evaluator observed the change in the color of the hair by fixing one end of the evaluation hair bundle and moving the other end while changing the observation angle of the hair.

Evaluation the degree of color change was evaluated by 5 evaluators in an unlimited choice answer mode of direct judgment. That is, a straight line 10cm long was horizontally drawn, and the left end of the straight line was set to evaluate that "no color change was perceived even when the angle was changed" and the right end was set to evaluate that "completely different colors were visible depending on the angle", and it was evaluated that which position between the two was the position of the hair in the example and comparative example to draw a line answer. Then, the degree of change in hue or color tone of the appearance of the hair is indicated by drawing a line at a position several cm from the left end on the straight line. The average of 5 evaluators is shown in tables 1 and 2 as a score. A higher score indicates a greater change in hue or color tone of the appearance of the hair due to the angle at which the hair is viewed.

[ color difference ]

A color difference (. DELTA.E) was measured using a color difference meter (CR-400, manufactured by Konika Meinenda Co., Ltd.) with respect to the following case: hair dyeing was carried out in the same manner as described above except that only the oxidative hair dye (4 g of the 1 st agent, 6g of the 2 nd agent, and 1.12 mass% aqueous solution 1.25g of the 3 rd agent of ammonia) was used.

[ Table 1]

*: calculated according to the formula of Davis

[ Table 2]

*: calculation according to Davis's equation

*1: amphitol 20AB (manufactured by Kao corporation)

*2: emal E-227 (manufactured by Kao corporation)

*3: amisoft CS-22B (manufactured by Ajinomoto Co., Ltd.)

*4: emulgen 123P (manufactured by king corporation)

*5: emulgen 2025G (made by Huawang company)

*6: BC-2 (manufactured by Nikko Chemicals Co., Ltd.)

*7: quartamin 86W (manufactured by Huawang Co., Ltd.)

[ Table 3]

Formulation examples 1 to 16

The agents 1 to 6, the agents 2 to 14 and the agents 3 to 15 were prepared. In the combinations shown in tables 16 to 19, the ratios of 1: 1: the 1 st, 2 nd and 3 rd agents were mixed at a mixing ratio of 0.2 and used.

[ Table 4]

Formulation example 1 formulation examples I-A	(mass%)
		Lauramide DEA*8	10.0
Isostearyl glyceryl ether*9	10.0
		Butoxyethanol	9.0
Octyl dodecanol polyether-20*10	7.0
		Ethanol	6.0
Oleyl alcohol	5.0
		Propylene glycol	4.0
Oleic acid	2.5
		Ammonia	1.5
Monoethanolamine	2.7
		Stearamide ethyl diethylamine*11	2.5
EDTA 4Na	0.8
		Ammonium chloride	To a pH of 9.8
Sodium sulfite	0.5
		Ascorbic acid	0.5
Oxidation dye (any one of formula examples od-A-od-E)	The contents described in the respective formulation examples
		Purified water	Balance of

*8: amisol LDE-G (manufactured by Kawaken Fine Chemicals Co., Ltd.)

*9: GE-IS (U) (manufactured by Kao corporation)

*10: emulgen 2020G (King of flower company)

*11: ayacol AMINEAMIDE 50E (manufactured by CHEMIZATION CHEMICAL CORPORATION)

[ Table 5]

Formulation examples 1-B	(mass%)
		Cetostearyl alcohol	7.0
Lanolin alcohol	1.0
		Sodium laureth sulfate*2	2.8
EDTA 4Na	0.1
		Sodium sulfite	0.4
Ascorbic acid	0.3
		Ammonia	1.3
Ammonium chloride	To a pH of 9.8
		Oxidation dye (any one of formula examples od-A-od-E)	The contents described in the respective formulation examples
Purified water	Balance of

*2: emal E-227 (manufactured by Kao corporation)

[ Table 6]

Formulation examples 1-C	(mass%)
		Decyl glucoside*13	3.2
Laureth-23*4	2.0
		Propylene glycol	4.0
Polyquaternium-7*14	0.4
		Ammonia	2.4
Ammonium bicarbonate	0.1
		Ammonium chloride	To a pH of 9.8
EDTA 4Na	0.1
		Sodium sulfite	0.4
Ascorbic acid	0.3
		Oxidation dye (any one of formula examples od-A-od-E)	The contents described in the respective formulation examples
Purified water	Balance of

*13: AG-10LK (made by Huawang company)

*4: emulgen 123P (manufactured by king corporation)

*14: merquat 550 (manufactured by Japan Lubrizol Co., Ltd.)

The oxidation dyes used in the formulation of the above agent 1 are the following oxidation dye formulations od-A to od-E.

[ Table 7]

Oxidation dye formulation example od-A	(mass%)
		N-phenyl-p-phenylenediamine	0.08
P-phenylenediamine	0.08
		Toluene-2, 5-diamine	0.08
N, N-bis (2-hydroxyethyl) p-phenylenediamine	0.08
		2,4,5, 6-tetraaminopyrimidine	0.08
Dihydroxyindolines	0.08
		Hydroxy ethyl p-phenylenediamine	0.08
2, 6-dihydroxyethylaminotoluene	0.1
		1-naphthols	0.1
Resorcinol	0.1
		4-Chlororesorcinol	0.1
6-methoxy-2-methylamino-3-aminopyridine	0.1
		5-amino-4-chloro-o-cresol	0.1
Acetoxy-2-methoxynaphthalene	0.1

[ Table 8]

Oxidation dye formulation example od-B	(mass%)
		6-hydroxyindoles	0.08
2-amino-3-hydroxypyridines	0.08
		P-methylaminophenol	0.08
1, 3-bis (2, 4-diaminophenoxy) -propane	0.08
		Phenylmethylpyrazolinones	0.08
2-methyl-1-naphthol	0.1
		2, 7-naphthalenediol	0.1
Meta-aminophenol	0.1
		2, 6-dihydroxy-3, 4-dimethylpyridine	0.1
2-methyl-5-hydroxyethylaminophenol	0.1
		Hydroxy benzomorpholine	0.1
2, 6-dimethoxy-3, 5-pyridinediamine	0.1

[ Table 9]

Oxidation dye formulation example od-C	(mass%)
		Hydroxypropyl bis (N-hydroxyethyl p-phenylenediamine)	0.08
2-amino-5-ethylphenol	0.08
		P-aminophenol	0.08
1-hydroxyethyl-4, 5-diaminopyrazoles	0.08
		2,2' -methylenebis-4-aminophenol	0.08
1-hexyl-1H-pyrazole-4, 5-diaminopyrazoles	0.08
		1, 5-naphthalenediol	0.1
4-amino-2-hydroxytoluene	0.1
		2, 4-diaminophenoxyethanol	0.1
2-Methylresorcinol	0.1
		4-amino-m-cresol	0.1
2-amino-4-hydroxyethylamino-phenetidine	0.1
		Hydroxyethyl-3, 4-methylenedioxyaniline	0.1

[ Table 10]

Oxidation dye formulation example od-D	(mass%)
		2,5, 6-triamino-4-pyrimidineols	0.08
Hydroxyethylaminopyrazolopyridines	0.08
		N-phenyl-p-phenylenediamine	0.08
1,2, 4-trihydroxybenzene	0.08
		6-amino-m-cresol	0.08
2-chloro-p-phenylenediamine	0.08
		Methylimidazolium propyl p-phenylenediamine	0.08
4-formyl-1-methylquinolinium p-toluenesulfonic acid	0.1
		2, 3-indoline diones	0.1
5-amino-6-chloro-o-cresol	0.1
		2, 6-diaminopyridine	0.1
3-amino-2, 6-dimethylphenol	0.1
		2, 6-dihydroxyethylaminotoluene	0.1

[ Table 11]

Oxidation dye formulation example od-E	(mass%)
		Catechol	0.08
Hydroquinone	0.08
		Pyrogallol	0.08
Gallic acid	0.08
		2,2' - [ (4-aminophenyl) imino]Bis ethanol	0.08
Tannic acid	0.08
		2, 4-diaminophenol	0.08
M-phenylenediamine	0.1
		Diphenylamines	0.1
Phloroglucinol	0.1
		3,3' -diiminophenol	0.1
Toluene-3, 4-diamine	0.1
		Ortho-aminophenols	0.1
5- (2-hydroxyethylamino) -2-methylphenol	0.1
		N, N' -bis (4-aminophenyl) -2, 5-diamino-1, 4-quinonediimine	0.1

[ Table 12]

Formulation example 2 II-A	(mass%)
		Hydrogen peroxide	6.0
Phosphoric acid	Amount to pH3
		Etidronic acid	0.04
Salicylic acid	0.01
		Sodium lauryl sulfate*15	0.2
Cetostearyl alcohol	1.7
		Purified water	Balance of

*15: emal 10 powder (manufactured by Huawang company)

[ Table 13]

Formulation example 2 II-B	(mass%)
		Hydrogen peroxide	6.0
Phosphoric acid	Amount to pH3
		Cetostearyl alcohol	7.0
Lanolin alcohol	1.0
		Sodium laureth sulfate*2	2.8
Etidronic acid	0.04
		Purified water	Balance of

*2: emal E-227 (manufactured by Kao corporation)

[ Table 14]

Formulation example 2-C	(mass%)
		Hydrogen peroxide	6.0
Phosphoric acid	Amount to pH3
		Sodium laureth sulfate*2	1.9
Cetyl alcohol	1.5
		Etidronic acid	0.04
Purified water	Balance of

*2: emal E-227 (manufactured by Kao corporation)

[ Table 15]

Formulation example 3 III-A	(mass%)
		Sodium laureth sulfate*2	10.0
2-amino-2-methylpropanol	4.0
		HC Red 18	0.25
HC yellow 16	1.1
		HC blue 18	1.1
Purified water	Balance of

*2: emal E-227 (manufactured by Kao corporation)

[ Table 16]

Combination of	Formulation example 1	Formulation example 2	Formulation example 3	Formulation example 4
					Agent 1	Formulation examples I-A	Formulation examples I-B	Formulation examples I-B	Formulation examples I to C
Oxidation dyes	Formulation example od-A	Formulation example od-A	Formulation example od-A	Formulation example od-A
					Agent 2	Formulation example II-A	Formulation example II-A	Formulation examples II-B	Formulation examples II to C
Agent 3	Formulation example III-A	Formulation example III-A	Formulation example III-A	Formulation example III-A

[ Table 17]

Combination of	Formulation example 5	Formulation example 6	Formulation example 7	Formulation example 8
					Agent 1	Formulation examples I-A	Formulation examples I-B	Formulation examples I-B	Formulation examples I to C
Oxidation dyes	Formulation example od-B	Formulation example od-B	Formulation example od-B	Formulation example od-B
					Agent 2	Formulation example II-A	Formulation example II-A	Formulation examples II-B	Formulation examples II to C
Agent 3	Formulation example III-A	Formulation example III-A	Formulation example III-A	Formulation example III-A

[ Table 18]

Combination of	Formulation example 9	Formulation example 10	Formulation example 11	Formulation example 12
					Agent 1	Formulation examples I-A	Formulation examples I-B	Formulation examples I-B	Formulation examples I to C
Oxidation dyes	Formulation example od-C	Formulation example od-C	Formulation example od-C	Formulation example od-C
					Agent 2	Formulation example II-A	Formulation example II-A	Formulation examples II-B	Formulation examples II to C
Agent 3	Formulation example III-1	Formulation example III-1	Formulation example III-1	Formulation example III-1

[ Table 19]

Combination of	Formulation example 13	Formulation example 14	Formulation example 15	Formulation example 16
					Agent 1	Formulation examples I-A	Formulation examples I-B	Formulation examples I-B	Formulation examples I to C
Oxidation dyes	Formulation example od-D	Formulation example od-D	Formulation example od-D	Formulation example od-D
					Agent 2	Formulation example II-A	Formulation example II-A	Formulation examples II-B	Formulation examples II to C
Agent 3	Formulation example III-A	Formulation example III-A	Formulation example III-A	Formulation example III-A