JP4688149B2 - Hair dye composition - Google Patents

Description

  The present invention relates to a hair dye composition that is applied to hair and dyes the hair.

  Conventionally, as this type of hair dye composition, a two-component hair dye composition comprising a first agent containing an alkaline agent and an oxidation dye and a second agent containing an oxidant such as hydrogen peroxide. And a three-component hair dye comprising a first agent containing an alkaline agent, a second agent containing an oxidizing agent such as hydrogen peroxide, and a third agent containing a direct dye is known ( For example, see Patent Document 1).

By the way, in the above-mentioned two-component hair dye, when the first agent and the second agent are mixed after long-term storage and applied to the hair, the hair dyeing effect changes due to the first agent. There is a problem that there is.
JP 2001-316231 A

  In order to avoid such a problem, by separating the dye and the alkaline agent into the first agent and the third agent, respectively, as in the above-mentioned three-component hair dye, the first agent can be directly stored. It is conceivable to eliminate the influence of the alkaline agent on the dye. However, when a coupler is used as a dye, the following problems arise. That is, when the first agent containing a coupler is prepared, if the coupler is mixed with a base, the solubility of the coupler in the base decreases. This is considered to be due to the absence of an alkaline agent in the first agent that promotes the dissolution of the coupler in the base. As a result, there was a high possibility that the coupler would not be sufficiently dissolved in the base and precipitated during the preparation of the first agent.

  The present invention has been made in view of such conventional circumstances, and the object thereof is a hair dye composition capable of enhancing the solubility of a coupler in a base while suppressing a change in dyeing effect over time. Is to provide.

In order to achieve the above object, the hair dye composition of the invention according to claim 1 is at least one selected from resorcin and 5- (2-hydroxyethylamino) -2-methylphenol as (A) coupler. And (B) a first agent containing a base, (C) a second agent containing an oxidizing agent, and (D) a third agent containing an alkaline agent, and mixed and prepared at the time of use. In the hair dye composition, the base (B) includes (b1) a surfactant, a polyhydric alcohol, a lower alcohol (4 or less carbon atoms), a polyhydric alcohol alkyl (4 or less carbon atoms) ether, and an aromatic. And (b1) a surfactant, a polyhydric alcohol, a lower alcohol (having 4 or less carbon atoms), a polyhydric alcohol alkyl (having 4 or less carbon atoms) ether, and an aromatic Octanol / water partition coefficient of the alcohol [log (P _OW)] is summarized in that in the range of ± 3 of octanol / water partition coefficient of the (A) coupler.

The hair dye composition of the invention described in claim 2 is characterized in that, in the invention described in claim 1, the pH of the first agent is 8.5 or less .

  According to the hair dye composition of the present invention, the solubility of the coupler in the base can be enhanced while suppressing the change in the dyeing effect over time.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The hair dye composition of the present embodiment has a so-called three-part form composed of a first agent, a second agent, and a third agent. The first agent contains (A) a coupler and (B) a base. (B) The base is at least one selected from (b1) a surfactant, a polyhydric alcohol, a lower alcohol (carbon number 4 or less), a polyhydric alcohol alkyl (carbon number 4 or less) ether, and an aromatic alcohol. It contains. The second agent contains (C) an oxidizing agent. The third agent contains (D) an alkali agent. The first agent, the second agent and the third agent are mixed and prepared at the time of use, and the hair is dyed by applying the mixture to the hair.
[First agent]
The first agent contains (A) a coupler and (B) a base.

The coupler (A) is a kind of oxidation dye, and (C) is a compound that can develop color by oxidative polymerization with an oxidizing agent.
Specific examples of the component (A) include resorcin, 5- (2-hydroxyethylamino) -2-methylphenol, pyrogallol, catechol, m-aminophenol, metaphenylenediamine, 2,4-diaminophenol, 1,2 , 4-benzenetriol, toluene-3,4-diamine, toluene-2,4-diamine, hydroquinone, α-naphthol, 2,6-diaminopyridine, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, paramethyl Examples include aminophenol, 2,4-diaminophenoxyethanol, gallic acid, tannic acid, ethyl gallate, methyl gallate, propyl gallate, pentaploid, and salts thereof. In addition, ingredients listed in "Quasi-drug raw material standards" (issued June 1991, Yakuji Nippo) are also included. These components (A) may be blended singly or in combination of two or more.

  In the present embodiment, among these components (A), at least one selected from aromatic compounds and salts thereof that are considered to have a particularly great influence on the change in hair color tone is preferable. As this aromatic compound, one in which at least two substituents selected from the group consisting of the group represented by the following general formula (1) and the —OR group are substituted at the meta position is known.

ただし、一般式（１）中のＲ^１及びＲ^２は、水素、炭素数２以下の炭化水素、及び炭素数２以下の脂肪族アルコールから任意に選択される１種であり、互いに同一であっても異なってもよい。−ＯＲ基のＲは水素、炭素数２以下の炭化水素、及び炭素数２以下の脂肪族アルコールから選択される１種である。また、前記「少なくとも２つの置換基」は互いに同一であっても異なってもよい。

However, R ¹ and R ² in the general formula (1) are one kind arbitrarily selected from hydrogen, hydrocarbons having 2 or less carbon atoms, and aliphatic alcohols having 2 or less carbon atoms, and are identical to each other. Or different. R in the —OR group is one selected from hydrogen, hydrocarbons having 2 or less carbon atoms, and aliphatic alcohols having 2 or less carbon atoms. The “at least two substituents” may be the same as or different from each other.

  Among the aromatic compounds of this type, the more preferable component is at least one selected from resorcin, 5- (2-hydroxyethylamino) -2-methylphenol, m-aminophenol, 5-aminoorthocresol and salts thereof. Is mentioned.

  The content of the component (A) in the first agent is preferably 0.001 to 50% by weight, more preferably 0.01 to 20% by weight. If this content is less than 0.001% by weight, there is a high possibility that sufficient hair dyeing power cannot be obtained. On the other hand, when it mix | blends exceeding 50 weight%, there exists a high possibility that (A) component will precipitate, without fully melt | dissolving with respect to (B) base at the time of preparation of a 1st agent.

The octanol / water partition coefficient [log (P _OW )] of this type of component (A) is −2 to 3. The octanol / water partition coefficient [log (P _OW )] is a measure for partitioning a substance (for example, a coupler) between an aqueous phase and an organic phase (octanol phase), and is represented by the following formula (1): Defined in The octanol / water partition coefficient of this embodiment is determined by the Organization for Economic Co-operation and Development (OECD) Test Guidelines (OECD Board of Directors Decision “C (81) 30 Final Attachment (1)”) 107 or Japanese Industrial Standard Z7260-107 (2000). “Measurement of distribution coefficient (1-octanol / water) —flask immersion method” and a value measured by a method defined in OECD test guideline 117.
log (P _OW ) = log ([P _O ] / [P _W ]) (1)
[P _O ]: Number of moles of substance in octanol phase [P _W ]: Number of moles of substance in aqueous phase For example, the higher the log (P _OW ) value, the more hydrophobic the substance becomes. For example, a substance with a log (P _OW ) value of 1 is 10 times better in the organic phase than the aqueous phase, and a substance with a log (P _OW ) value of 2 is 100 times better in the organic phase than the aqueous phase. Melt.

  Moreover, in this embodiment, you may use a main intermediate together with the said (A) component as an oxidation dye. Specific examples of this main intermediate include paraphenylene diamine, paraaminophenol, hydroxyethyl paraphenylene diamine, 2,2 ′-[(4-aminophenyl) imino] bisethanol, toluene-2,5-diamine, and their Examples include salts. Examples of the salt include hydrochloride, sulfate, acetate and the like. These main intermediates may be blended alone or in combination.

  The base as the component (B) is selected from (b1) a surfactant, a polyhydric alcohol, a lower alcohol (carbon number 4 or less), a polyhydric alcohol alkyl (carbon number 4 or less) ether, and an aromatic alcohol. It contains at least one kind. (B1) Surfactant, polyhydric alcohol, lower alcohol (4 or less carbon atoms), polyhydric alcohol alkyl (4 or less carbon atoms) ether, and aromatic alcohol are soluble in component (A) with respect to component (B) It is blended to promote. Examples of the surfactant among the component (b1) include nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

  Specific examples of nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) alkyl ethers, POE alkylphenyl ethers, POE / polyoxypropylene (hereinafter referred to as POP) alkyl ethers, and POE sorbitan fatty acid esters. And POE propylene glycol fatty acid ester. For example, specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, and the like.

  Specific examples of the cationic surfactant include cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, ethyl Examples include lanolin sulfate fatty acid aminopropylethyldimethylammonium, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin and the like.

  Specific examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate, POE alkyl sulfates such as POE sodium lauryl ether sulfate, alkyl sulfate esters such as lauryl sulfate triethanolamine, stearoylmethyl taurine sodium, dodecyl Examples include benzene sulfonic acid triethanolamine, sodium tetradecene sulfonate, POE lauryl ether phosphoric acid and salts thereof.

  Specific examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, cocoamidopropyl betaine, lauryldimethylaminoacetic acid betaine and the like.

  In this embodiment, among these surfactants, the solubility of the component (A) with respect to the component (B) can be improved, so that the octanol / water partition coefficient is the octanol / water partition of the component (A). Nonionic surfactants that are within a range of ± 3 of the coefficient are used.

  Specific examples of this type of nonionic surfactant include POE (15) lauryl ether (partition coefficient: 0.65), POE (20) stearyl ether (partition coefficient: 2.23), POE (15) oleyl. Ether (partition coefficient: 3.39), POE (15) isocetyl ether (partition coefficient: 2.54), POE (15) cetyl ether (partition coefficient: 2.62), POE (15) isostearyl ether (partition) Coefficient: 3.53), POE (20) octyldodecyl ether (partition coefficient: 3.14), and the like. The numerical value accompanying POE indicates the number of added moles. These nonionic surfactants may be blended singly or in combination of two or more.

  Specific examples of the polyhydric alcohol in the component (b1) include propylene glycol (hereinafter referred to as PG), polyethylene glycol (hereinafter referred to as PEG) 400, PEG200, glycerin, 1,3-butylene glycol, ethylene glycol. , Diethylene glycol, dipropylene glycol, 1,3-butanediol, hexylene glycol, sorbitol, maltitol and the like.

  In this embodiment, among these polyhydric alcohols, the solubility of the component (A) with respect to the component (B) can be improved, so that the octanol / water partition coefficient is the octanol / water partition of the component (A). A polyhydric alcohol having a coefficient within ± 3 is used.

  Specific examples of this type of polyhydric alcohol include PG (partition coefficient: -0.78), PEG400 (partition coefficient: -3.12), glycerin (partition coefficient: -2.2), ethylene glycol (partition coefficient). : -1.4), diethylene glycol (partition coefficient: -1.3), 1,3-butanediol (partition coefficient: -1.4), hexylene glycol (partition coefficient: -0.7), and the like. . These polyhydric alcohols may be blended singly or in combination of two or more.

  Specific examples of the lower alcohol (having 4 or less carbon atoms) in the component (b1) include 2-propanol, ethanol, propanol and the like. In the present embodiment, among these lower alcohols, since the solubility of the component (A) with respect to the component (B) can be improved, the octanol / water partition coefficient is the octanol / water partition coefficient of the component (A). A lower alcohol that is within the range of ± 3 is used. Specific examples of this type of lower alcohol include 2-propanol (partition coefficient: 0.28), ethanol (partition coefficient: -0.14), and the like. These lower alcohols may be blended singly or in combination of two or more.

  Specific examples of the polyhydric alcohol alkyl (with 4 or less carbon atoms) ether among the components (b1) include ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether. , Etc. In this embodiment, among these polyhydric alcohol alkyl ethers, the solubility of the component (A) with respect to the component (B) can be improved, so that the octanol / water partition coefficient is octanol / water of the component (A). Polyhydric alcohol alkyl ethers having a water partition coefficient within ± 3 are used. Specific examples of this type of polyhydric alcohol alkyl ether include ethylene glycol monoethyl ether (partition coefficient: -0.42), ethylene glycol monomethyl ether (partition coefficient: -0.91), and the like. These polyhydric alcohol alkyl ethers may be blended singly or in combination of two or more.

  Specific examples of the aromatic alcohol among the components (b1) include benzyl alcohol, benzyloxyethanol, nonylphenoxyethanol, octylphenoxyethanol, γ-phenylpropyl alcohol, cinnamon alcohol, anise alcohol, p-methylbenzyl alcohol, α-dimethyl. Examples include phenethyl alcohol, α-phenylethanol, phenoxyethanol and the like. In this embodiment, among these aromatic alcohols, the solubility of the component (A) with respect to the component (B) can be improved, so that the octanol / water partition coefficient is the octanol / water partition of the component (A). An aromatic alcohol having a coefficient within ± 3 is used.

  Specific examples of this type of aromatic alcohol include benzyl alcohol (partition coefficient: 1.08), benzyloxyethanol (partition coefficient: 1.2), α-phenylethanol (partition coefficient: 1.2), and the like. It is done. These aromatic alcohols may be blended singly or in combination of two or more.

  The content of the component (b1) in the first agent is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight. When the content is less than 0.01% by weight, the solubility of the component (A) with respect to the component (B) decreases, and the base stability of the first agent may not be sufficiently maintained. . On the other hand, even if it exceeds 50% by weight, there is a high possibility that no further effect will be obtained regarding the solubility of the component (A) with respect to the component (B).

The component (B) preferably contains a higher alcohol, water, a pH adjuster, an oily component, etc. as other components.
Higher alcohols are blended to improve the viscosity stability of the first agent, and those having 14 or more carbon atoms are preferred from this viewpoint. However, the higher alcohol of this embodiment means what excludes the said aromatic alcohol. Specific examples of this higher alcohol include stearyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, 2-octyldodecanol, and oleyl alcohol. These higher alcohols may be blended singly or in combination of two or more.

Water is blended in an appropriate amount to make the first agent as a solution, dispersion or emulsion as a solvent or dispersion medium for each component.
The pH adjuster is blended in order to set the pH of the first agent in a desired range. Specific examples of the pH adjuster include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, lactic acid, tartaric acid, and salts thereof. The blending amount of the pH adjusting agent in the first agent is preferably set to an amount that makes the pH of the first agent within a desired range.

The oil component is blended in order to improve the finished feeling. Examples of the oil component include fats and oils, waxes, hydrocarbons, esters, and silicones.
Specific examples of fats and oils include jojoba oil and glyceride of olive oil, specific examples of waxes include beeswax and lanolin, and specific examples of hydrocarbons include petrolatum, liquid paraffin, solid paraffin, isoparaffin, squalane, etc. Is mentioned. Specific examples of esters include isopropyl myristate and octyldodecyl myristate. Specific examples of silicones include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, highly polymerized silicone, and amino-modified silicone. It is done.

  Further, as other components, fatty acids such as lauric acid, myristic acid and linolenic acid, sugars such as sorbitol and maltose, alkyl glyceryl ethers such as batyl alcohol and chimyl alcohol, gum arabic, karaya gum, tragacanth gum, sodium alginate, xanthan gum and cellulose Derivatives, cross-linked polyacrylic acid, water-soluble polymer compounds such as polydimethylmethylenepiperidinium chloride, ascorbic acids, reducing agents such as sodium sulfite, antiseptics such as parabens, chelating agents such as EDTA, phenacetin, 8-hydroxyquinoline, Stabilizers such as acetanilide, sodium pyrophosphate, barbituric acid, uric acid and tannic acid, plant extracts, herbal extracts, ultraviolet absorbers, direct dyes, fragrances and the like can be mentioned. Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

The pH of the first agent is 8.5 or less, preferably less than 7. If the pH of the first agent exceeds 8.5, there is a high possibility that the hair dyeing effect will change during long-term storage.
Examples of the dosage form of the first agent include aqueous solutions, dispersions, emulsions, gels, foams, and creams. This first agent is filled in various containers such as a tube container and an aerosol container and stored until use.
[Second agent]
The second agent contains (C) an oxidizing agent. The oxidizing agent as the component (C) is blended to oxidize and polymerize an oxidative dye to develop a color and decolorize melanin contained in the hair. Specific examples of the component (C) include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium peroxide, potassium peroxide, peroxide. Examples thereof include magnesium, barium peroxide, calcium peroxide, strontium peroxide, sulfate hydrogen peroxide adduct, phosphate hydrogen peroxide adduct, pyrophosphate hydrogen peroxide adduct, and the like. These components (C) may be blended singly or in combination of two or more. In the present embodiment, among these components (C), it is preferable to use hydrogen peroxide because it has excellent melanin decoloring power.

  The content of the component (C) in the mixture of the first agent, the second agent and the third agent (hereinafter simply referred to as the mixture) is preferably 0.1 to 10% by weight, more preferably 1 to 6% by weight. It is. If the content is less than 0.1% by weight, it may be difficult to sufficiently oxidatively polymerize the oxidation dye. On the other hand, if it exceeds 10% by weight, hair damage may not be reduced.

  The second agent contains water, oily components, surfactants and the like described in the first agent as other components. Further, when hydrogen peroxide is contained as the component (C), it is preferable to contain a stabilizer in order to improve the storage stability of hydrogen peroxide. Examples of hydrogen peroxide stabilizers include urea, phenacetin, sodium stannate, ethylene glycol phenyl ether, 8-oxyquinoline, phosphoric acid, 1-hydroxyethane-1,1-diphosphonic acid and its salts, dibutylhydroxytoluene, etc. Is mentioned. Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

Examples of the dosage form of the second agent include aqueous solutions, dispersions, emulsions, gels, foams, and creams.
[Third agent]
The third agent contains (D) an alkali agent. (D) The alkali agent as a component is mix | blended in order to provide the lightness to hair by promoting the effect | action of (C) component.

  Specific examples of the component (D) include alkanolamine, ammonia, organic amines (2-amino-2-methyl-1,3-propanediol, guanidine, etc.), inorganic alkali (sodium hydroxide, potassium hydroxide, carbonic acid) Sodium, potassium carbonate, etc.) and basic amino acids (arginine, lysine, etc.). Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2- Examples include amino-2-methyl-1-propanol and 2-amino-2-hydroxymethyl-1,3-propanediol.

  These (D) components may be blended singly or in combination of two or more. Moreover, you may mix | blend combining the salt of (D) component. In the present embodiment, among these components (D), the lightness of the hair is improved and the hair dyeing power can be sufficiently exerted. Therefore, at least one selected from at least monoethanolamine and ammonia in the third agent. It is preferable to contain.

  The content of the component (D) in the mixture is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight. If the content is less than 0.1% by weight, sufficient brightness may not be obtained. On the other hand, if it exceeds 20% by weight, it may be difficult to obtain a good feel in the finished hair.

  In addition, the third agent contains water, an oily component, a surfactant and the like described in the first agent as other components. Furthermore, you may mix | blend at least 1 type chosen from what is listed in "Quasi-drug raw material specification" (June 1991 issue, Yakuji Nippo).

Examples of the dosage form of the third agent include aqueous solutions, dispersions, emulsions, gels, foams, and creams.
[blend]
The mixture is obtained by mixing and preparing the first agent, the second agent, and the third agent at a predetermined ratio. The content of the component (A) in the mixture is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. When this content is less than 0.001% by weight, it is difficult to obtain sufficient hair dyeing power. On the other hand, if it exceeds 10% by weight, there is a high possibility that no more remarkable effect can be obtained with respect to the hair dyeing power, which is not economical.

  Further, the content of the component (b1) in the mixture is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight. When the content is less than 0.1% by weight, the solubility of the component (A) with respect to the component (B) decreases, and there is a high possibility that sufficient hair dyeing power cannot be obtained. On the other hand, even if it exceeds 50% by weight, there is a possibility that no further effect can be obtained with respect to the solubility of the component (A) with respect to the component (B), and no further effect can be obtained with respect to the hair dyeing power. Is expensive.

  The pH of the mixture at the time of mixing preparation is preferably 8 to 12, more preferably 9 to 11. If this pH is less than 8, there is a high possibility that the action of the component (C) cannot be sufficiently promoted. On the other hand, when the pH exceeds 12, when the hair is decolorized, there is a high possibility that problems such as damage will occur in the hair.

Examples of the dosage form of this mixture include aqueous solutions, dispersions, emulsions, gels, foams, and creams.
Now, to prepare the first agent, the component (A) is added to the component (B), and this is stirred and mixed. And the 1st agent with which various containers were filled is preserve | saved until use. Here, in this embodiment, by excluding the component (D) in the first agent, even when the first agent is stored for a long period of time, changes in the hair dyeing effect are suppressed.

  Further, by using the component (b1) having an octanol / water partition coefficient that is within a range of ± 3 with respect to the octanol / water partition coefficient of the component (A), the component (A) cooperates with the component (b1). It becomes easy to dissolve in the component (B) by the action. For this reason, in this embodiment, the solubility of (A) component with respect to (B) component does not decrease by excluding (D) component in the first agent, and (A) component with respect to (B) component Good solubility is ensured. Therefore, according to this embodiment, while the change of the hair dyeing effect with time is suppressed, the solubility of (A) component with respect to (B) component is improved at the time of preparation of the 1st agent.

  Next, a mixture is prepared by mixing the first agent, the second agent, and the third agent in a predetermined mixing ratio, and a necessary amount of the mixture is attached to a comb or a brush and applied to the hair. In this mixture, the component (A) is colored by the oxidative polymerization of the component (A) by the component (C). Thereby, hair is dyed.

The effects exhibited by the above embodiment will be described below.
-In this embodiment, (A) component and (D) component are each isolate | separated into the 1st agent and the 3rd agent, and (D) component with respect to (A) component at the time of the preservation | save of 1st agent The effect of is avoided. That is, in this embodiment, by excluding the component (D) in the first agent, even when the first agent is stored for a long period of time, changes in the hair dyeing effect are suppressed. As a result, a hair dye composition having a sufficiently stable hair dyeing power is obtained.

-The pH of the first agent is 8.5 or less. Thereby, since the influence of (D) component with respect to (A) component is suppressed, the change of the hair dyeing effect with time can be suppressed suitably.
The octanol / water partition coefficient of the component (b1) is set within a range of ± 3 with respect to the octanol / water partition coefficient of the component (A). Thereby, (A) component becomes easy to melt | dissolve in (B) component by the cooperation effect | action with (b1) component. For this reason, the favorable solubility of (A) component with respect to (B) component is securable.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-5 and Comparative Examples 1-5: Dyeability test)
Each component shown in Table 1 was mixed, and in Examples 1 to 5, the first agent to the third agent were prepared, and in Comparative Examples 1 to 5, the first agent and the second agent were prepared. After storing for 1 month, the hair dye composition of each example was obtained. And the hair dye composition of each example was apply | coated to the hair | bristle bundle. Next, the hair bundle to which the hair dye composition was applied was allowed to stand for 30 minutes, and then a plain rinse was applied to complete the hair dyeing treatment of the hair bundle. The following items were evaluated for the hair bundle that was subjected to the hair dyeing treatment.

  In Examples 1 to 5, the first agent to the third agent are mixed in a weight ratio of 1: 2: 1. In Comparative Examples 1 to 5, the first agent and the second agent are mixed at a ratio of 1: 1. Moreover, the unit of the numerical value which shows the mixing | blending of each component in Table 1 shows weight%.

<Presence or absence of change in hair dyeing effect due to long-term storage>
After preparing the first agent to the third agent in Examples 1 to 5 and preparing the first agent and the second agent in Comparative Examples 1 to 5, they were dyed at the same mixing ratio as above without storing them. An agent composition was prepared and used as a standard sample for each example. Next, after applying the standard sample of each example to the hair bundle, the hair dyeing process of the hair bundle was completed by performing the same operation as described above. And the color tone (hair color tone) of the hair bundles when the hair bundles were dyed using the hair dye composition of each example and the standard sample, and whether there was any change in the color tone of the hair bundles An expert panel evaluated the following criteria. The results are shown in Table 1.

○: There is no change in the color tone of the hair bundle with respect to the standard sample. ×: The color tone of the hair bundle changes with respect to the standard sample.

表１より明らかなように、実施例１〜５では、第１剤と第３剤とにそれぞれ（Ａ）成分と（Ｄ）成分とが分離されていることから、第１剤〜第３剤を長期に亘って保存した後に染毛剤組成物を調製したとしても、標準サンプルに対する染毛色調の変化が無く、染毛効果の変化が抑制された。これに対し、比較例１〜５では、第１剤中に（Ａ）成分と（Ｄ）成分とが共存しているため、第１剤及び第２剤を長期に亘って保存した後に染毛剤組成物を調製した際には、標準サンプルに対する染毛色調の変化が認められ、染毛効果の変化（低下）が確認された。これは、長期の保存に際し第１剤中で、（Ｄ）成分による（Ａ）成分への影響が生じ、（Ａ）成分の作用効果が弱められたものと推測される。

As apparent from Table 1, in Examples 1 to 5, since the (A) component and the (D) component are separated into the first agent and the third agent, respectively, the first agent to the third agent. Even if the hair dye composition was prepared after storing for a long time, there was no change in the color of the hair dye relative to the standard sample, and the change in the hair dyeing effect was suppressed. On the other hand, in Comparative Examples 1 to 5, since the component (A) and the component (D) coexist in the first agent, the hair is dyed after storing the first agent and the second agent over a long period of time. When the agent composition was prepared, a change in the color of the hair dye relative to the standard sample was observed, and a change (decrease) in the hair dyeing effect was confirmed. This is presumed that the (D) component has an influence on the (A) component in the first agent during long-term storage, and the action effect of the (A) component has been weakened.

(Examples 6 to 11 and Comparative Examples 6 to 9: solubility test)
Here, each component shown in Table 2 was mixed to prepare the first agent. And regarding the 1st agent of each example obtained here, the solubility of (A) component with respect to (B) component was evaluated visually according to the following references | standards. The results are shown in Table 2. In addition, regarding the first agent (Examples 9 to 11 and Comparative Example 9) using 5- (2-hydroxyethylamino) -2-methylphenol (hereinafter referred to as 5HM) as the component (A), the first agent Means that 5HM is sufficiently dissolved in the base (B) as the color becomes lighter. Moreover, the unit of the numerical value which shows content of each component in a table | surface is weight%, and the numerical value accompanying each component is an octanol / water partition coefficient.
(Examples 6-8 and Comparative Examples 6-8)
○: Resorcinin remaining in the first agent is not observed ×: Resorcinin remaining in the first agent is observed (Examples 9 to 11 and Comparative Example 9)
○: Lightening of the first agent is recognized ×: Lightening of the first agent is not recognized

表２より明らかなように、実施例６〜１１では、（Ａ）成分のオクタノール／水分配係数の±３の範囲内である値のオクタノール／水分配係数を有する（ｂ１）成分が添加されていることから、（Ｂ）基剤に対する（Ａ）成分の溶解性は良好なものであった。すなわち、実施例６〜８に関しては第１剤中におけるレゾルシンの残存が認められず、また、実施例９〜１１に関しては第１剤の淡色化が認められた。これは、（Ａ）成分及び（ｂ１）成分のオクタノール／水分配係数が上記の関係を満たす場合には、（Ａ）成分が（ｂ１）成分との協働作用により（Ｂ）成分に溶解されやすくなるためと思われる。これに対し、（Ａ）成分及び（ｂ１）成分のオクタノール／水分配係数が上記の関係を満たしていない比較例６〜９では、（Ｂ）成分に対する（Ａ）成分の溶解性が芳しくない結果となった。すなわち、比較例６及び７に関しては第１剤中におけるレゾルシンの残存が認められ、また、比較例８及び９に関しては第１剤の淡色化が認められなかった。

As apparent from Table 2, in Examples 6 to 11, the component (b1) having an octanol / water partition coefficient having a value within the range of ± 3 of the octanol / water partition coefficient of the component (A) was added. Therefore, the solubility of the component (A) in the base (B) was good. That is, resorcinol in the first agent was not observed in Examples 6-8, and lightening of the first agent was observed in Examples 9-11. This is because, when the octanol / water partition coefficients of the component (A) and the component (b1) satisfy the above relationship, the component (A) is dissolved in the component (B) by the cooperative action with the component (b1). It seems to be easier. On the other hand, in Comparative Examples 6 to 9 where the octanol / water partition coefficients of the component (A) and the component (b1) do not satisfy the above relationship, the solubility of the component (A) in the component (B) is not good. It became. That is, for Comparative Examples 6 and 7, resorcinin remained in the first agent, and for Comparative Examples 8 and 9, no lightening of the first agent was observed.

In addition, the said embodiment can also be changed and comprised as follows.
In this embodiment, a so-called three-component hair dye composition composed of the first agent, the second agent, and the third agent is employed. However, each component constituting the first agent, the second agent, and the third agent may be further separated to constitute four or more agents. For example, when two or more types of (A) couplers are blended, a four-component hair dye composition obtained by separating these (A) couplers into a first agent and a fourth agent can be mentioned.

Further, the technical idea that can be grasped from the embodiment will be described below.
A hair dye characterized in that the content of the (A) coupler in the mixture prepared by mixing the first agent, the second agent and the third agent is 0.001 to 10% by weight. Composition.

Claims (2)

(A) a first agent containing at least one selected from resorcin and 5- (2-hydroxyethylamino) -2-methylphenol as a coupler and (B) a base, and (C) a first agent containing an oxidizing agent. In a hair dye composition composed of two agents and (D) a third agent containing an alkali agent and mixed and prepared at the time of use,
The base (B) is at least one selected from (b1) a surfactant, a polyhydric alcohol, a lower alcohol (carbon number 4 or less), a polyhydric alcohol alkyl (carbon number 4 or less) ether, and an aromatic alcohol. Contains seeds,
(B1) Surfactant, polyhydric alcohol, lower alcohol (4 or less carbon atoms), polyhydric alcohol alkyl (4 or less carbon atoms) ether, and octanol / water partition coefficient [log (P _OW )] of aromatic alcohol Is in the range of ± 3 of the octanol / water partition coefficient of the coupler (A). The hair dye composition according to claim 1, wherein the pH of the first agent is 8.5 or less.