JP2013216615A - Two-part foamy hair dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaerosol-type two-part foamy hair dye suppressed in irritating ammonia odor while having sufficient decoloring and dyeing power, and enabling hair dyeing to as-set hue without color unevenness even if using a solution mixed therewith with time elapsed from its mixing.SOLUTION: The two-part foamy hair dye comprises: a first agent containing an alkali agent; a second agent containing hydrogen peroxide; and a nonaerosol foamer vessel; wherein, the components (A) to (C) described below are included in a mixed solution of the first and second agents, and the molar ratio of the component A to total coupler is 0.2-1; and the molar ratio C/B is 0.6-0.9. (A) at least one selected from resorcinol, 2-methylresorcinol and 4-chlororesorcinol; (B) at least one selected from ammonia and ammonium ion, and (C) at least one selected from carbonate ion and bicarbonate ion.

Description

  The present invention relates to a two-component foam hair dye.

  Conventionally, as two-component hair bleaching agents and hair dyes, liquid or cream-like ones have been widely used for a long time. However, it is difficult for those who are not accustomed to apply these to the hair evenly. The viscosity of the mixture applied to the hair is adjusted to be as high as 1000 to 10,000 mPa · s to prevent sagging when left standing, and it is difficult to spread the agent uniformly, and the agent is fully applied to the root of the hair. This is because it is difficult to spread. Furthermore, skills such as blocking and a matching mirror are required for application to the root and back of the hair, and much time is required.

  On the other hand, what discharges the liquid mixture of a two-component hair decoloring agent or a two-component hair dye from a non-aerosol-type former container in the foam form is known (patent documents 1-6). This hair bleaching agent or hair coloring agent can be applied to hair easily and evenly even by unskilled people by discharging the mixture of the first and second agents in a foam form from a non-aerosol-type former container. It is possible to produce color unevenness in the finish. Since it can be applied easily, skills such as blocking and mirroring are not required, and the time required for hair dyeing is much shorter than before. In this way, it has far superior performance as compared with the conventional one, so it is being supported by a wide range of customers regardless of gender and age group. For this reason, various products have been developed to meet the needs of many customers.

  However, in the two-component foam hair dye, the liquid mixture of the first agent and the second agent is discharged in the form of foam, and the surface area of the liquid mixture becomes large, so that ammonia mixed as an alkali agent is likely to volatilize. . Therefore, when a relatively large amount of ammonia is blended in consideration of the decolorizing power and the like, the problem of irritating odor becomes larger than that of other dosage forms, and countermeasures are required. For this reason, in two-component foam hair dyes, in order to suppress volatilization of ammonia, a considerable amount of carbonate ions (including hydrogen carbonate ions) are blended to adjust the pH of the system to a low level.

JP 2004-339216 A JP 2006-124279 A JP 2007-291015 A JP 2007-291016 JP JP 2007-314524 JP 2007-314523 JP

  However, when the amount of carbonate ion is increased to further suppress the volatilization of ammonia, in the mixed solution of non-aerosol type two-component foam hair dye, which is a low-viscosity form, the oxidation dye is absorbed by carbonate ion. The reaction is promoted excessively, increasing the proportion of dye that becomes polymerized before it penetrates into the hair and cannot penetrate into the hair. As a result, compared to the liquid mixture immediately after mixing the first agent and the second agent, the hair colorability of the liquid mixture that has elapsed from the mixing is lowered, and the hair colorability of the hair becomes insufficient. In this case, the color unevenness may occur, and the merit of the non-aerosol type two-component foam hair dye was not sufficiently exhibited.

  Therefore, the present invention suppresses the pungent odor of ammonia while having sufficient decoloring power and dyeing power, and even when using a liquid mixture that has passed time after mixing, it can be dyed without unevenness in color as set. It is an object of the present invention to provide a non-aerosol type two-component foamy hair dye capable of hair.

  The inventors of the present invention can solve the above problems by setting the carbonate ion amount relative to the ammonia amount to a specific ratio and by setting the ratio of the coupler compound having a specific structure in all the couplers to a certain value or more. I found.

The present invention includes a first agent containing an alkali agent, a second agent containing hydrogen peroxide, and a non-aerosol foamer container for discharging a mixture of the first agent and the second agent in the form of foam. A foam-type hair dye,
In the mixture, the following components (A), (B) and (C)
(A) at least one selected from the group consisting of resorcin, 2-methylresorcin and 4-chlororesorcin
(B) At least one selected from the group consisting of ammonia and ammonium ions
(C) containing at least one selected from the group consisting of carbonate ions and bicarbonate ions,
The molar ratio of component (A) to all couplers [(A) / all couplers] is 0.2 to 1,
The molar ratio of the component (C) to the component (B) [(C) / (B)] is 0.6 to 0.9,
A two-component foamy hair dye is provided.

  Furthermore, the present invention uses the above-mentioned two-component foam hair dye, discharges a mixed solution of the first agent and the second agent from the non-aerosol foamer container in a foam form, and uses the foam for the hair. The present invention provides a hair coloring method for hair.

  The two-component foam hair dye of the present invention has a sufficient decoloring power and dyeing power, while suppressing the irritating odor of ammonia, and even using a mixed solution that has passed time after mixing, as set. Can be dyed without uneven color.

[(A): Coupler]
The two-component foam hair dye of the present invention contains at least one coupler selected from the group consisting of resorcin, 2-methylresorcin and 4-chlororesorcin as component (A). Component (A) is preferably contained in the first agent from the viewpoint of storage stability.

  In addition to the component (A) coupler, the two-component foam hair dye of the present invention may further use a coupler other than the component (A) (hereinafter also referred to as component (A ′)).

  Examples of the coupler of component (A ′) include N- (3-dimethylaminophenyl) urea, 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl) amino] anisole, 2,4 -Diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1- (2-hydroxyethoxy) -5-methylbenzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-aminomethoxy- 2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1- ( 2-hydroxyethoxy) benzene, 1,3-diamino-4- (2,3-dihydroxypropoxy) benzene, 2,4-diamino-1,5-di (2-hydroxyethoxy) benzene, 1- (2-amino Toxi) -2,4-diaminobenzene, 2-amino-1- (2-hydroxyethoxy) -4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3- [di (2-hydroxyethyl) amino] aniline 4-amino-2-di [(2-hydroxyethyl) amino] -1-ethoxybenzene, 5-methyl-2- (1-methylethyl) phenol, 3-[(2-hydroxyethyl) amino] aniline, 3-[(2-aminoethyl) amino] aniline, 1,3-di (2,4-diaminophenoxy) propane, di (2,4-diaminophenoxy) methane, 1,3-diamino-2,4-dimethoxy Benzene, 2,6-bis (2-hydroxyethyl) aminotoluene, 4-hydroxy-indole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro- 2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol Nord, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol , 3-amino-2,6-dimethylphenol, 2-methyl-5- (β-hydroxyethylamino) phenol, 5-amino-2-ethylphenol, 2-[(3-hydroxyphenyl) amino] acetamide, 5 -[(2-hydroxyethyl) amino] -4-methoxy-2-methylphenol, 5-[(2-hydroxyethyl) amino] -2-methylphenol, 3- [2-hydroxyethyl) amino] phenol, 3 -[(2-methoxyethyl) amino] phenol, 5-amino-2-ethylphenol, 5-amino-2-methoxyphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5-[(3- Hydroxypropyl) amino] -2-methylphenol, 3-[(2,3-dihydroxypropyl) amino] -2- Tylphenol, 3-[(2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 2-methyl- 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-acetic acid naphthol, 1-chloro-2,4-dihydroxy Benzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2 -Methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl) amino] -1,3-benzodioxole, 6-bromo-1-hydroxy -3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6- Droxy-1,4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1,4 (2H) -benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 2,3-indolinedione, 2,4-diaminophenoxyethanol, and salts thereof.

  In the two-component foam hair dye of the present invention, the component (A) and the component (A ′) in the mixed solution of the first agent and the second agent from the viewpoint of hair dyeing properties when time has elapsed since mixing. The molar ratio of the component (A) to the total coupler (component (A) / total coupler) is 0.2 or more, 0.4 or more, further 0.6 or more, further 0.65 or more, and further 0.7 or more. Further, it is preferably 0.75 or more. From the same viewpoint as described above, the molar ratio of component (A) / total coupler is 1 or less, 0.98 or less, further 0.96 or less, further 0.94 or less, further 0.92 or less, further 0.9 or less. Preferably there is. That is, the molar ratio of component (A) / total coupler is 0.2 to 1, preferably 0.4 to 0.98, more preferably 0.6 to 0.96, further 0.65 to 0.94, further 0.7 to 0.92, and further 0.75. It is preferably ˜0.90.

  Component (A) contains 0.001-5 mass% in the liquid mixture of the 1st agent and the 2nd agent from a viewpoint of favorable hair dyeing property, Furthermore, 0.01-3 mass%, Furthermore, 0.02-2 mass% is contained. Is preferred. In addition, the component (A) is preferably contained in the first agent in an amount of 0.001 to 10% by mass, more preferably 0.01 to 6% by mass, and further preferably 0.02 to 4% by mass, from the viewpoint of hair dyeability and stability.

  Component (A) contains 0.0001 to 0.5 mmol / g, further 0.0005 to 0.3 mmol / g, and further 0.001 to 0.2 mmol / g in the mixed solution of the first agent and the second agent from the same viewpoint as described above. It is preferable. Moreover, it is preferable that component (A) contains 0.0001-1 mmol / g in a 1st agent from the viewpoint similar to the above, Furthermore, 0.001-0.5 mmol / g, Furthermore, 0.002-0.4 mmol / g is contained.

  In order to make the molar ratio of component (A) / all couplers within the above range, the content of component (A ′) can be adjusted. From the viewpoint of good hair dyeing properties, component (A ′) It is preferable to contain 0.001-5 mass% in the liquid mixture of a 1st agent and a 2nd agent, Furthermore, 0.01-3 mass%, Furthermore, 0.02-2 mass% is contained. In addition, the component (A ′) is preferably contained in the first agent in an amount of 0.001 to 10% by mass, further 0.01 to 6% by mass, and more preferably 0.02 to 4% by mass, from the viewpoint of hair dyeability and stability.

  Component (A ′) contains 0.0001 to 0.5 mmol / g, more preferably 0.0005 to 0.3 mmol / g, and more preferably 0.001 to 0.2 mmol / g in the mixture of the first and second agents from the same viewpoint as above. It is preferable to do. Moreover, it is preferable that component (A ') contains 0.0001-1 mmol / g in a 1st agent from the viewpoint similar to the above, Furthermore, 0.001-0.5 mmol / g, Furthermore, 0.002-0.4 mmol / g is contained.

<Dye precursor>
The two-component foam hair dye of the present invention can contain a dye precursor in the first agent. Examples of the dye precursor include 1,4-diaminobenzene (also called p-phenylenediamine), 1,4-diamino-2-methylbenzene (also called toluene-2,5-diamine, p-toluenediamine), 1, 4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2 -Chloro-1,4-diaminobenzene, 1,4-diamino-2- (thiophen-2-yl) benzene, 1,4-diamino-2- (thiophen-3-yl) benzene, 1,4-diamino- 2- (pyridin-3-yl) benzene, 2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene, 1,4-diamino-2- Hydroxymethylbenzene, 1,4-diamino-2- (2-hydroxyethoxy) benzene, 2- (2- (acetylamino) ethoxy) -1,4-diaminobenzene, 4-phenylamino Niline, 4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline, 4- [ethyl (2-hydroxyethyl) amino] aniline, 4- [di (2-hydroxyethyl) amino] aniline, 4- [Di (2-hydroxyethyl) amino] -2-methylaniline, 4-[(2-methoxyethyl) amino] aniline, 4-[(3-hydroxypropyl) amino] aniline, 4-[(2,3- Dihydroxypropyl) amino] aniline, 1,4-diamino-2- (2-hydroxyethyl) benzene, 1,4-diamino-2- (1-methylethyl) benzene, 1,3-bis-[(4-aminophenyl) ) (2-hydroxyethyl) amino] -2-propanol, 1,4-bis-[(4-aminophenyl) amino] butane, 1,8-bis- (2,5-diaminophenoxy) -3,6- Dioxaoctane, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3- (hydroxymethyl) phenol, 4-amino-3- Fluorophenol, 4-methylaminophenol, 4-amino-2- (aminomethyl) phenol, 4-amino-2- (hydroxymethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2- [ (2-hydroxyethyl) amino] methylphenol, 4-amino-2-methylphenol, 4-amino-2- (methoxymethyl) phenol, 4-amino-2- (2-hydroxyethyl) phenol, 5-aminosalicylic acid 2,5-diaminopyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4- (1H) -pyrimidone, 4,5-diamino-1- (2-hydroxyethyl) ) -1H-pyrazole, 4,5-diamino-1- (1-methylethyl) -1H-pyrazole, 4,5-diamino-1-[(4-methylphenyl) methyl] -1H-pyrazole, 1- [ (4-Chlorophenyl) methyl] -4,5-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol Nord, 2-amino-5-methylphenol, 2-chloro-1,4-benzenediamine, 4,4' Iminojianirin, and salts thereof.

  The dye precursor may be contained in a mixed solution of the first agent and the second agent in an amount of 0.001 to 5% by mass, further 0.01 to 3% by mass, and further 0.02 to 2% by mass, from the viewpoint of good hair dyeability. preferable. In addition, the dye precursor is preferably contained in the first agent in an amount of 0.001 to 10% by mass, further 0.01 to 6% by mass, and more preferably 0.02 to 4% by mass, from the viewpoint of hair dyeability and stability.

<Direct dye>
The two-component foam hair dye of the present invention can contain a direct dye. The direct dye can be contained in the first agent or the second agent or both, but is preferably contained in the first agent from the viewpoint of storage stability.

  Direct dyes include paranitroorthophenylenediamine, paranitrometaphenylenediamine, nitroparaphenylenediamine, basic yellow 87, basic orange 31, basic red 12, basic red 51, basic blue 99, acid orange 7, and salts thereof. Is mentioned.

  The direct dye is preferably contained in the mixed solution of the first agent and the second agent in an amount of 0.001 to 5% by mass, further 0.01 to 2% by mass, and more preferably 0.02 to 1% by mass, from the viewpoint of good hair dyeability. . Moreover, it is preferable that a direct dye contains 0.001-5 mass% in a 1st agent from the viewpoint of hair dyeing property and stability, Furthermore, 0.01-2 mass%, Furthermore, 0.02-1 mass% is contained.

  The two-component foam hair dye of the present invention is 0.001 to 10 in the mixed solution of the first agent and the second agent as a whole dye (coupler, dye precursor, direct dye) from the viewpoint of good hair dyeability. It is preferable to contain it by mass%, Furthermore 0.01-5 mass%, Furthermore, 0.02-3 mass% is contained.

[(B): ammonia and / or ammonium ion]
The two-component foam hair dye of the present invention contains at least one selected from the group consisting of ammonia and ammonium ions as component (B). Component (B) is preferably contained in the first agent from the viewpoint of storage stability.

  The content of ammonia and ammonium ions is 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further 0.1 to 2% by mass in the mixed solution of the first agent and the second agent from the viewpoint of good decoloring power. preferable. From the same viewpoint, the content of ammonia and ammonium ions is preferably 0.005 to 6 mmol / g, more preferably 0.02 to 3 mmol / g, and even more preferably 0.05 to 2 mmol / g in the mixed solution of the first agent and the second agent. .

  In addition, what is derived from the supply source of the component (C) mentioned later is contained in the ammonium ion here.

[(C): carbonate ion and / or bicarbonate ion]
The two-component foam hair dye of the present invention contains at least one selected from the group consisting of carbonate ions and bicarbonate ions as component (C).

  Examples of the supply source of carbonate ions and hydrogen carbonate ions include ammonium carbonate, sodium carbonate, potassium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, guanidine carbonate, and the like. Among them, ammonium carbonate and ammonium hydrogen carbonate are preferable. .

  Component (C) carbonate ion or hydrogen carbonate ion content (ion equivalent amount assuming that the source is 100% dissociated) suppresses the reaction rate of the oxidation dye when mixing the first agent and the second agent From the point of preventing the liquid temperature rise and color unevenness of the mixed solution, 0.01 to 7.5% by mass, further 0.5 to 5% by mass, and further 1 to 3% by mass in the mixed solution of the first agent and the second agent. preferable. In addition, from the same viewpoint, the content of the carbonate ion or hydrogen carbonate ion of the component (C) is 0.002 to 1.5 mmol / g, more preferably 0.05 to 1 mmol / g in the mixed solution of the first agent and the second agent, Is preferably 0.1 to 0.5 mmol / g.

  The molar ratio (C) / (B) of the content of the carbonate ion or hydrogen carbonate ion of the component (C) to the content of ammonia or ammonium ion of the component (B) is sufficient for both sufficient decolorization performance and suppression of ammonia volatilization amount. From the viewpoint of preventing color unevenness, it is preferably 0.6 or more, 0.63 or more, and more preferably 0.65 or more. From the same viewpoint as described above, the molar ratio (C) / (B) is 0.9 or less, preferably 0.85 or less, more preferably 0.8 or less, and further preferably 0.75 or less. That is, the molar ratio (C) / (B) is 0.6 to 0.9, more preferably 0.6 to 0.85, and further preferably 0.65 to 0.75.

[(D): Alkanolamine]
From the viewpoint of preventing the volatilization of the component (B) while solving the problems of the present invention, the first agent of the two-component foam hair dye of the present invention is an alkaline agent other than the component (B). An alkanolamine can be contained as the component (D). Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and the like, and monoethanolamine is preferable from the viewpoint of dyeability.

  The alkanolamine of component (D) can be used in combination of two or more, and the content thereof is 0.01 to 5% by mass, further 0.1 to 4% by mass in the mixed solution of the first agent and the second agent, Is preferably 1 to 3% by mass.

  The pH (25 ° C.) of the first agent in the two-component foam hair dye of the present invention is preferably 8 to 12, and more preferably 9 to 11 from the viewpoint of hair dyeability.

  The pH (25 ° C.) of the mixed solution of the first agent and the second agent in the two-component foam hair dye of the present invention is 8.8 to 12, more preferably 8.9 to 12, further 9 to 11.5, and further 9.2 to 11 is preferred, but the total amount used as the alkaline agent including the components (B) and (D) is appropriately adjusted so that the pH of the mixed solution falls within the above range.

  The pH here is that the first and second agents are equilibrated to 25 ° C and then mixed thoroughly at a predetermined mixing ratio into a pH meter (HORIBA F-51 type). The value after 1 minute from the start of measurement.

〔hydrogen peroxide〕
The content of hydrogen peroxide in the second agent is preferably 1 to 9% by mass, more preferably 3 to 6% by mass. The content of hydrogen peroxide in the mixed solution of the first agent and the second agent is preferably 1 to 6% by mass, and more preferably 2 to 5% by mass. The pH of the second agent (25 ° C.) is preferably 2 to 6, and more preferably 2.5 to 4 in order to suppress decomposition of hydrogen peroxide during storage.

[Surfactant]
In order to make the foam easily formed by mixing the air and the hair cosmetic by the foam discharge means of the former container and to stabilize the foam, either the first agent or the second agent, or Both contain a surfactant. Examples of surfactants include anionic surfactants, amphoteric surfactants, nonionic surfactants, and cationic surfactants, which provide good foaming that is easy to apply to hair even when the liquid temperature is low or close to room temperature. In order to implement | achieve, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant are preferable.

Examples of the anionic surfactant include a sulfuric acid anionic surfactant and a carboxylic acid anionic surfactant.
Examples of the sulfate-based anionic surfactant include alkyl sulfates and polyoxyalkylene alkyl sulfates, and those having an alkyl group having 10 to 24 carbon atoms, more preferably 12 to 18 carbon atoms, are preferred. Those in which the alkyl group is linear are preferred. In addition, polyoxyalkylene alkyl sulfates, more preferably polyoxyethylene alkyl sulfates, more preferably those having an average addition mole number of oxyethylene groups of 1 to 10, and more preferably 2 to 5, are preferred.
Examples of the carboxylic acid anionic surfactant include N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, amide type N-acyl amino acid salts, ether carboxylates, sulfosuccinic acid ester salts, fatty acid salts, and succinic acids. Examples thereof include salts of alkyl alkenyl or alkenyl succinate. Among them, N-acyl amino acid salts, N-acyl-N-alkyl amino acid salts, ether carboxylates, and sulfosuccinic acid ester salts are preferable.

  Amphoteric surfactants include carbobetaines, amidebetaines, sulfobetaines, hydroxysulfobetaines, amidesulfobetaines, phosphobetaines, imidazo having 8 to 24 carbon atoms, alkyl groups, alkenyl groups or acyl groups. Examples thereof include linium-based surfactants, and among them, carbobetaine-based surfactants and sulfobetaine-based surfactants are preferable. Preferred amphoteric surfactants include lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, lauryldimethylaminoacetic acid betaine, lauryl hydroxysulfobetaine and the like.

  Nonionic surfactants include alkyl polyglucosides, polyoxyalkylene alkyl ethers, alkyl glyceryl ethers and the like. As the alkyl polyglucoside, those in which the alkyl group has 8 to 18 carbon atoms, more preferably 8 to 14 carbon atoms, and further 9 to 11 carbon atoms are preferable, and those in which the alkyl group is linear are preferable. The average degree of polymerization of glucoside is preferably 1 to 5, and more preferably 1 to 2. As the polyoxyalkylene alkyl ether, those in which the alkyl group has 10 to 22 carbon atoms, more preferably 12 to 18 carbon atoms, are preferred, and those in which the alkyl group is linear are preferred. Further, polyoxyethylene alkyl ether is more preferable, and those having an average addition mole number of oxyethylene group of 1 to 40, and further 4 to 30 are preferable. As the alkyl glyceryl ether, those in which the alkyl group has 8 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, are preferred, and those in which the alkyl group is branched are preferred.

  Examples of the cationic surfactant include monoalkyltrimethylammonium salt and dialkyldimethylammonium salt. More specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, isostearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and behenyltrimethyl chloride. Ammonium, cocoyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl trimethyl ammonium bromide, isostearyl lauryl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, etc. Is mentioned.

  The content of the surfactant is 1 to 20% by mass, further 2 to 18% by mass, more preferably 3 to 15% by mass in the mixed solution of the first agent and the second agent, from the viewpoint of good foaming. Is preferably 4 to 10% by mass.

(Water-soluble cationic polymer)
The two-component foam hair dye of the present invention can contain a water-soluble cationic polymer in one or both of the first agent and the second agent. The water-soluble cationic polymer refers to a water-soluble polymer having a cationic group or a group that can be ionized to a cationic group, and includes an amphoteric polymer that becomes cationic as a whole. That is, the water-soluble cationic polymer includes an amino group or an ammonium group in the side chain of the polymer chain, or a water-soluble one containing a diallyl quaternary ammonium salt as a constituent unit, such as cationized cellulose, cationic starch, Examples thereof include cationized guar gum, a polymer or copolymer of diallyl quaternary ammonium salt, and quaternized polyvinyl pyrrolidone.

  Specific examples of the polymer or copolymer of diallyl quaternary ammonium salt include dimethyldiallylammonium chloride polymer (polyquaternium-6, such as Marquat 100; Nalco), dimethyldiallylammonium chloride / acrylic acid copolymer (polyquaternium- 22, for example, Marquat 280, 295; Nalco), dimethyldiallylammonium chloride / acrylamide copolymer (polyquaternium-7, eg, Marquat 550; Nalco); acrylic acid / diallyl quaternary ammonium salt / acrylamide copolymer ( Polyquaternium-39 such as Marquat Plus 3331 (Nalco).

  Specific examples of the quaternized polyvinylpyrrolidone include a quaternary ammonium salt (polyquaternium-11 such as Guffcoat 734, 755, and 755N) obtained from a copolymer of vinylpyrrolidone (VP) and dimethylaminoethyl methacrylate and diethyl sulfate. ; IS Japan Co., Ltd.).

  Specific examples of the cationized cellulose include a polymer of a quaternary ammonium salt obtained by adding glycidyltrimethylammonium chloride to hydroxyethyl cellulose (polyquaternium-10 such as Leogard G, GP; Lion Corporation, polymer JR-125, JR-400, JR-30M, LR-400, LR-30M; Amerchol), hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (polyquaternium-4, eg Cellcoat H-100, L-200; National Starch and Chemical Co.).

  Among these, polymers having a dimethyldiallylammonium salt structure as a structural unit, for example, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-39 are preferred, and polyquaternium-6, polyquaternium-7, Polyquaternium-22 and polyquaternium-39 are preferable, and polyquaternium-22 is particularly preferable.

  Two or more kinds of water-soluble cationic polymers can be used in combination, and the content thereof is from the first agent and the second agent in terms of good foaming, prevention of dripping, and good dischargeability from the former container. 0.01-3 mass% in the liquid mixture of an agent, Furthermore, 0.02-2 mass%, Furthermore, 0.03-1 mass% is preferable.

[Higher alcohol]
The two-component foam hair dye of the present invention can contain a higher alcohol in order to improve foaming and enhance the effect of suppressing dripping after being left on the hair. . As the higher alcohol, those having an alkyl group or alkenyl group having 10 to 30 carbon atoms, more preferably 12 to 24 carbon atoms, more preferably 14 to 22 carbon atoms are preferable, and those having an alkyl group and further a linear alkyl group are particularly preferable. preferable. Examples of the higher alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, isostearyl alcohol, oleyl alcohol and the like. Two or more of these can be used in combination.

  Two or more types of higher alcohols can be used in combination, and can be contained in one or both of the first agent and the second agent. The content of the higher alcohol in the mixed liquid of the first agent and the second agent does not inhibit the foaming property when the liquid temperature is low, and enhances the effect of suppressing dripping while standing, It is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, and further preferably 0.2 to 1.0% by mass.

[Non-volatile hydrophilic solvent]
Furthermore, it is preferable to contain a non-volatile hydrophilic solvent in the first agent or the second agent. As a result, after applying the two-component foam hair dye of the present invention to the hair and leaving it to stand, moisture evaporates from the hair dye to concentrate irritating components such as hydrogen peroxide. Can reduce irritation to the scalp. As the non-volatile hydrophilic solvent, those having no defoaming action such as polyols and lower (1 to 4 carbon atoms) alkyl ethers thereof are preferable. As the polyols, those having 2 to 6 carbon atoms are preferable, for example, glycerin, propylene glycol, dipropylene glycol, polypropylene glycol having a weight average molecular weight of 200 to 1200, 1,3-butanediol, ethylene glycol, diethylene glycol, isoprene glycol. And sorbitol. Examples of the lower alkyl ethers of the polyol include mono-lower alkyl ethers and poly-lower alkyl ethers (for example, di-lower alkyl ethers) of the above-described polyols. Of these, monomethyl ether or monoethyl ether of polyol is preferable, and specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. Two or more of these can be used in combination.

  The content of the non-volatile hydrophilic solvent in the mixture of the first agent and the second agent is 0.01 to 5 mass from the viewpoint of reducing the scalp irritation and improving the foam quality even when the liquid temperature is low. %, Preferably 0.1 to 4% by mass, and more preferably 0.2 to 3% by mass.

[Silicones]
The two-component foam hair dye of the present invention may further contain silicones. Examples of silicones include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, amino-modified silicone, oxazoline-modified silicone elastomer, and the like, and emulsions in which these are dispersed in water using a surfactant. Of these, polyether-modified silicones, amino-modified silicones, and emulsions thereof are preferable because they can be stably dispersed in water without using a thickener.

  The polyether-modified silicone includes terminal-modified and side-chain-modified types such as a pendant type (comb type), a both-end modified type, and a one-end modified type. Examples of such modified silicones include dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane / methyl (polyoxyethylene / polyoxypropylene) siloxane. A copolymer etc. are mentioned. As the polyether-modified silicone, those having HLB of 10 or more and more preferably HLB of 10 to 18 are preferable from the viewpoint of compatibility with water. Here, HLB is based on the value obtained from the cloud number (cloud number: an index correlated with HLB and applied to ether type nonionic surfactants).

  Any amino-modified silicone may be used as long as it has an amino group or an ammonium group, but amodimethicone is preferable.

  The content of the silicones in the mixed solution of the first agent and the second agent is preferably 0.01 to 10% by mass in order to smoothly blend the foam into the hair and to impart a high conditioning effect to the hair. 0.1-5 mass%, Furthermore, 0.5-3 mass% is preferable.

[Other ingredients]
In addition, the first agent and the second agent are fragrances, ultraviolet absorbers, sequestering agents such as edetic acid, bactericides, preservatives such as methyl parahydroxybenzoate, phenacetin, 1-hydroxyethane-1 , Stabilizers such as 1-diphosphonic acid and oxyquinoline sulfate, organic solvents such as ethanol, benzyl alcohol and benzyloxyethanol, water-soluble polymer compounds such as hydroxyethyl cellulose, humectants and the like. The mixed liquid of the first agent and the second agent is preferably water as a main medium.

The two-component foam hair dye of the present invention is provided as a two-component oxidative hair dye containing a first agent containing an alkaline agent and a second agent containing hydrogen peroxide. The mixing ratio of the first agent and the second agent is preferably 1: 4 to 4: 1 by mass ratio, and more preferably 1: 2 to 2: 1.
Here, the two-part formula means a three-part oxidative hair dye which is used by further mixing a third part containing a persulfate or a third part containing a conditioning component in addition to the first and second parts. Agents should also be included.

〔viscosity〕
The viscosity of the mixed solution of the first agent and the second agent is preferably 1 to 480 mPa · s, more preferably 1 to 400 mPa · s, further 1 to 300 mPa · s, further 2 to 200 mPa · s, Is preferably 3 to 100 mPa · s, more preferably 5 to 30 mPa · s. In addition, the viscosity here is a value after rotating for 1 minute at 30 rpm using a rotor No. 1 with a B-type rotational viscometer (model TV-10) manufactured by Tokimec Co., Ltd. at 25 ° C. However, when the viscosity exceeds 200 mPa · s, the value after rotating at 12 rpm for 1 minute is taken. Note that the measurement is performed in a constant temperature bath at 25 ° C., the measurement is performed immediately after mixing the first agent and the second agent, and the temperature change due to reaction heat is ignored.

  By adjusting the viscosity of the mixed solution of the first agent and the second agent to be in the above range, it is possible to realize a foam volume that is easy to apply, and to prevent dripping after the mixed solution is applied to the hair. In addition to being able to suppress, it becomes easy to squeeze when discharging bubbles with a squeeze foamer or the like. In order to adjust the viscosity of the mixed solution to the above-described range, a water-soluble solvent such as ethanol may be added, or the content and type of surfactants, polyols, higher alcohols, and the like may be appropriately adjusted. .

[Gas-liquid mixture ratio]
The gas / liquid mixing ratio of the air and the mixed liquid by the foam discharge means of the former container is preferably 7 to 40 mL / g, more preferably 15 to 30 mL / g from the viewpoint of ease of application of the agent to the hair and ease of application. preferable. In addition, the gas-liquid mixing ratio here is a value measured as follows.

  First, the gas-liquid mixing ratio is determined by measuring the mass and volume of bubbles discharged at 25 ° C. S1 squeeze foamer container (Daiwa Seisakusha, volume 210mL, mesh roughness (mesh) is 150 mesh mixing chamber (mesh = number of eyes per inch), tip 200 mesh), 100g of the mixed solution is put in, From the time when the remaining amount is 80 g, 20 g of foam is discharged into a 1000 mL measuring cylinder and the volume of the foam is measured 1 minute after the start of discharge. The gas-liquid mixing ratio (mL / g) is obtained by dividing the volume (mL) of the discharged foam by the mass of 20 g.

[Former container]
In the present invention, the former container is a non-aerosol type container, and is used for mixing the liquid mixture of the first agent and the second agent with air without using a propellant and ejecting it in the form of foam. . By using the former container, an effect of preventing scattering of the discharged agent can be obtained. In particular, a non-aerosol type container can manufacture a product at a lower cost than an aerosol type container and does not require a propellant for high-pressure gas, so that the product can be handled more safely in distribution.

  As the former container, a known pump former container having a foam discharge means, a squeeze foamer container, an electric frother, a pressure accumulating pump former container or the like can be used. More specifically, for example, pump former E3 type, F2 type [above, Daiwa Steel, Food and Containers (vol.35, No.10, p588-593 (1994); vol.35, No. 11, p624 to 627 (1994); vol.36, No.3, p154 to 158 (1995))], S1 squeeze foamer (Yamato Seisakusha, JP 7-215352 A), electric whisk (Matsushita) Electric industry), air spray former (air spray international company), and the like. As the former container used for the two-component foam hair dye of the present invention, a pump former container and a squeeze foamer container are preferable because they are inexpensive and easy to use.

  A pump former container or a squeeze foamer container has a foam generating part such as a net, and when the mixed liquid of the first agent and the second agent is dried and solidified, clogging occurs. It is preferable to have a thin-walled net because the solidified material can be dissolved immediately by the flow of the bubbles to eliminate clogging. In this case, the net mesh is preferably 50 to 280 mesh, more preferably 90 to 250 mesh, and more preferably 130 to 220 mesh. By using a mesh net in this range, creamy foam can be generated. Examples of the material of such a net include nylon, polyethylene, polypropylene, polyester, Teflon (registered trademark), carbon fiber, stainless steel, and the like, more preferably nylon, polyethylene, polypropylene, polyester, and more. Nylon is preferable.

  In the former container used in the two-component foam hair dye of the present invention, at least one, preferably a plurality of such nets are disposed, and the mixing chamber is particularly advantageous from the viewpoints of economy, foam stability, and the like. It is preferable to dispose one sheet at each of the two locations of the tip and the tip.

  In the former container, the parts that come into contact with the contents (the inner wall of the container, the inner wall of the foam discharge means, etc.) are made of a material that does not corrode with alkali and hydrogen peroxide and is permeable to oxygen generated by the decomposition of hydrogen peroxide. It is preferable.

  As the product form of the two-component foam hair dye of the present invention consisting of the first agent, the second agent and the former container, the first agent or the second agent is filled in a container separate from the former container, and at the time of use Both agents may be transferred to the former container and mixed, but one agent is filled in the former container, the other agent is filled in a separate container, and the other agent is placed in the former container at the time of use. You may make it move to. In this case, the second agent is a gas permeable container, particularly an oxygen permeable material (for example, polyethylene) in order to prevent the pressure in the container from rising due to oxygen generated by the decomposition of hydrogen peroxide. It is preferable to fill a former container consisting of On the other hand, in order to prevent the oxidation of the oxidation dye, the first agent needs to use a container that does not easily transmit oxygen.

〔how to use〕
In order to dye hair (particularly hair) using the two-component foam hair dye of the present invention, it is preferable to comb the hair in advance. This makes it difficult for the hair to be entangled during the refoaming process described later, so there is no possibility that the mixed solution will scatter. Moreover, after combing hair, it is not necessary to perform the blocking operation generally used by application of a hair dye composition, and it is preferable not to perform blocking operation. Thereby, the operation which applies the hair dye composition mentioned later to hair, and the operation which foams again become easy. Next, the first agent and the second agent are mixed in the former container of the two-component foam hair dye of the present invention. The foamy liquid mixture discharged from the container may be applied directly to the hair, or may be applied to the hair using a tool such as a hand or a brush. From the viewpoint of preventing the agent from splashing and dripping, it is more preferable to apply it to the hair after taking it once in a hand (with gloves).

  After application, leave for about 3 to 60 minutes, preferably about 5 to 45 minutes. At this time, it is preferable to foam again on the hair from the viewpoint of further preventing dripping during standing and allowing the mixed solution to sufficiently spread to the base of the hair. In order to foam again, gas may be injected, an instrument such as a vibrator or brush may be used, or a finger may be used, but it is more preferable to use a finger.

  Here, the foaming time may be after the foam has completely disappeared, during the foam disappearance, or before the applied foam changes. Or it may be in the middle of application, even after it completes application to the whole range which wants to apply foam. Foaming again may be performed once continuously or may be repeated a plurality of times intermittently.

  After these operations, the mixture is washed away. Then, after shampooing and rinsing as appropriate, the hair is washed and dried.

Examples 1-4 and Comparative Examples 1-3
The 1st agent and 2nd agent of the compounding composition (mass%) shown in Table 1 and 2 were prepared, and the following evaluation was performed. The results are also shown in Tables 1 and 2.

<Ammonia volatilization>
1 g of the mixture of the first agent and the second agent in a ratio of 1: 1.5 is weighed in a petri dish (inner diameter 2.7 cm), set in a sealed 2 L beaker, and after 2 minutes, a detector manufactured by GASTEC Was used to measure the amount of ammonia volatilization in the beaker. In the above 2 minutes, the mixture was stirred (200 rpm) with a stirrer (stirring bar length 20 mm) for the initial 5 seconds.

<Change in color of hair dye after 15 minutes of mixing>
Immediately after mixing the first agent and the second agent at a ratio of 1: 1.5, a squeeze foamer (S1 squeeze foamer made by Daiwa Steel, volume 210 mL. Mesh roughness is 150 mesh, mixing tip 200 mesh, the total opening area of the narrowest part of the air introduction path is 0.27mm ² and the inner diameter of the dip tube is φ1.7mm). (Mixed liquid / hair mass ratio) 0.7). After leaving at 30 ° C. for 30 minutes, the hair was washed and dried.
The hair dyeing operation was similarly performed on the mixed solution after 15 minutes from the mixing.
Using a colorimeter CR-400 manufactured by Konica Minolta Co., Ltd., the color difference (ΔE) in the case of using the mixed solution after 15 minutes of mixing with respect to the case of using the mixed solution immediately after mixing was measured and calculated.

Claims (9)

Two-component foam including a first agent containing an alkali agent, a second agent containing hydrogen peroxide, and a non-aerosol foamer container for discharging a mixture of the first agent and the second agent into a foam A hair dye,
In the mixture, the following components (A), (B) and (C)
(A) at least one selected from the group consisting of resorcin, 2-methylresorcin and 4-chlororesorcin
(B) At least one selected from the group consisting of ammonia and ammonium ions
(C) containing at least one selected from the group consisting of carbonate ions and bicarbonate ions,
The molar ratio of component (A) to all couplers [(A) / all couplers] is 0.2 to 1,
The molar ratio of the component (C) to the component (B) [(C) / (B)] is 0.6 to 0.9,
Two-component foam hair dye.   The two-component foamy hair dye according to claim 1, wherein the mixed solution has a pH (25 ° C) of 8.8 to 12.   The two-component foamy hair dye according to claim 1 or 2, wherein the content of the component (B) is 0.01 to 10% by mass in the mixed solution.   The two-component foam hair dye according to any one of claims 1 to 3, wherein a supply source of the component (C) is ammonium carbonate or ammonium hydrogen carbonate.   The two-component foam hair dye according to any one of claims 1 to 4, further comprising a component (D) alkanolamine.   The two-component foamy hair dye according to any one of claims 1 to 5, wherein the mixed solution has a viscosity at 25 ° C of 1 to 480 mPa · s.   Using the two-component foam hair dye according to any one of claims 1 to 6, the liquid mixture of the first agent and the second agent is discharged from the non-aerosol foamer container in a foam form, and the foam is hand-made. Hair dyeing method applied to hair using hair.   The method for dyeing hair according to claim 7, wherein the foam is applied to the hair and then foamed again on the hair using a hand.   The hair dyeing method according to claim 7 or 8, wherein the foam is applied to the hair, left for 3 to 60 minutes, and then washed away.