JP2007320923A - Hair dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye composition which contains a dye, is used by mixing the first agent with the second agent, has an excellent dyeing property, and can uniformly dye hair, when the hair is dyed. <P>SOLUTION: This hair dye composition prepared by mixing the first agent containing a dye with the second agent containing an oxidizing agent, when used, is characterized by containing a divalent metal salt and/or a divalent metal hydroxide and an amino carboxylic acid and/or its derivative. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hair dye composition. More specifically, the present invention relates to a hair dye composition having excellent dyeing properties for hair.

  The hair dye composition is provided as a two-part type comprising a first agent containing an oxidative dye and a second agent containing an oxidant, and is prepared by mixing the first and second agents at the time of use. Then, it is applied to the hair and dyed.

  Conventionally, two-component oxidative hair dyes comprising a first agent containing an oxidative dye such as paraphenylenediamine and a second agent containing an oxidant such as hydrogen peroxide have been widely used as hair dyes. In this hair dye, an oxidative dye penetrates into hair and oxidative polymerization is carried out in the hair to produce a dye, thereby dyeing the hair. Sufficient dyeing effect cannot be obtained as it is, and hair damage can be achieved by increasing the blending amount of the alkaline agent blended with the first agent and the oxidizing agent blended with the second agent in order to increase the dyeing power. Has the disadvantage of becoming larger.

  Various compounding agents have been studied to remedy such drawbacks, but the improvement of exhibiting excellent dyeing properties as a hair dye by sufficiently preventing hair damage and suppressing irritation to the scalp Is desired.

Therefore, as a means for suppressing hair damage and irritation to the scalp and improving the dyeability of the hair, means for containing one or more alkaline earth metal peroxides in the hair dye (JP-A-10-226630), Means (JP-A-10-114635) in which the first agent containing a dye and / or the second agent containing an oxidizing agent contains a powder of a metal oxide or a silicate mineral, an aminocarboxylic acid and Means containing the derivative (Japanese Patent Laid-Open No. 2003-171248) and means containing the hydrolyzate of marine collagen and / or a derivative thereof (Japanese Patent Laid-Open No. 2005-343826) are disclosed. However, these methods have not been able to fully exhibit the dyeability of hair.
JP-A-10-226630 JP-A-10-114635 JP2003-171248 JP-A-2005-343826

  The present invention has attracted attention as a problem existing in the prior art as described above, and an object thereof is to provide a hair dye composition having excellent dyeing properties.

  Therefore, the present inventor has prepared a divalent metal salt and / or divalent in a hair dye composition prepared by mixing a first agent containing a dye and a second agent containing an oxidizing agent at the time of use. It has been found that a hair dye composition having a sufficient dyeing effect on hair can be obtained by containing a metal hydroxide and aminocarboxylic acid and / or a derivative thereof, and the present invention has been completed. .

  According to the present invention, a hair dye composition excellent in dyeability can be provided.

  The component (A) of the present invention is a divalent metal salt and / or a divalent metal hydroxide. Specific examples of the component (A) include barium sulfate, calcium sulfate, calcium hydroxide, lead bromide, lead chloride, calcium carbonate, calcium chromate, barium hydroxide, barium nitrate, copper sulfate, iron sulfate, magnesium carbonate, Magnesium sulfate, barium bromide, magnesium hydroxide, magnesium chromate, iron nitrate, iron chloride, iron bromide, magnesium bromide, copper chloride, barium iodide, copper bromide, magnesium chloride, zinc nitrate, calcium iodide, Examples include calcium chloride, calcium bromide, copper nitrate, calcium nitrate, zinc iodide, zinc bromide, and zinc chloride. These divalent metal salts and / or divalent hydroxides may be blended singly or in combination of two or more. Among these, magnesium sulfate and calcium hydroxide are particularly preferable.

  The content of the component (A) in the hair dye composition of the present invention is 0.01 to 10 weight percent, preferably 0.1 to 3 weight percent. If it is 0.01% by weight or less, color development on the hair cannot be promoted and the dyeing effect becomes weak. On the other hand, if it exceeds 10% by weight, the dyeing effect becomes weak and the irritation to the scalp becomes high during use.

  The component (B) of the present invention is an aminocarboxylic acid and / or a derivative thereof. As the component (B), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid, ethylenediamine disuccinic acid (EDDS), ethylenediamine diglutamic acid (EGDA), 2-hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N- N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDS), 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), ethylenediaminetetraacetic acid (EDTA), hydroxy Ethylethylenediaminetriacetic acid (HEDTA), dihydroxyethylethylenediaminediacetic acid (DHEDDA), 1,3-propanediaminetetraacetic acid (1.3PDTA), triethylenetetraminehexaacetic acid (TTHA) and their sodium, potassium and Ammonium salts. These aminocarboxylic acids and / or derivatives thereof may be blended alone or in combination of two or more. Among these, sodium salts of diethylenetriaminepentaacetic acid (DTPA) and ethylenediaminetetraacetic acid (EDTA) are particularly preferable.

  The content of the component (B) in the hair dye composition of the present invention is 0.01 to 10 weight percent, preferably 0.1 to 3 weight percent. If it is 0.01% by weight or less, color development on the hair cannot be promoted and the dyeing effect becomes weak. On the other hand, if it exceeds 10% by weight, the dyeing effect becomes weak and the irritation to the scalp becomes high during use.

  The hair dye composition of the present invention further exhibits color development on the hair when the solubility of the divalent metal salt and / or divalent metal hydroxide in water at 25 ° C. is 4.0 mol / kg or less. It is preferable because it promotes and dyeing property is improved.

  As a thing whose solubility with respect to the water in 25 degreeC of the bivalent metal salt and / or divalent metal hydroxide is 4.0 mol / kg or less, magnesium sulfate (solubility; 3.02 mol / kg), hydroxylation Magnesium (solubility; 0.0045 mol / kg), calcium hydroxide (solubility; 0.0229 mol / kg), barium sulfate (solubility; 0.00015 mol / kg), barium hydroxide (solubility; 0.2640 mol / kg), sulfuric acid Copper (solubility; 1.39 mol / kg), iron sulfate (solubility; 1.94 mol / kg), lead chloride (solubility; 0.039 mol / Kg) and the like can be mentioned. These may be blended singly or in combination of two or more. Among these, magnesium sulfate (3.02 mol / kg) and calcium hydroxide (0.0229 mol / kg) are particularly preferable.

  It is preferable that the hair dye composition of the present invention further contains an alkali metal salt of an α-hydroxy acid because color development on the hair is promoted and dyeing property is improved.

  Examples of the alkali metal salt of α-hydroxy acid include malic acid, glycolic acid, lactic acid, tartaric acid, citric acid, succinic acid, glyceric acid, salicylic acid, and sodium and potassium salts thereof. These alkali metal salts of α-hydroxy acid may be blended singly or in combination of two or more. Among these, sodium malate is particularly preferable.

  The content of the alkali metal salt of α-hydroxy acid in the hair dye composition of the present invention is 0.01 to 10 weight percent, preferably 0.1 to 3 weight percent. If it is 0.01% by weight or less, color development on the hair cannot be promoted and the dyeing effect becomes weak. On the other hand, if it exceeds 10% by weight, the dyeing effect becomes weak and the irritation to the scalp becomes high during use.

  In addition, the hair dye composition of the present invention may be configured such that a predetermined component that does not contain a fragrance and that stimulates olfaction is not more than a certain concentration when measured with a detector tube.

  For example, when 1 gram of a hair dye composition is left in a 3 liter desiccator for 3 hours at a constant temperature (20 ° C.) and then a predetermined component that stimulates odor is detected using a detector tube, ammonia 1 ppm or less, amine The present invention is also applied to a hair dye composition that is configured to be 0.75 ppm or less, hydrogen sulfide 0.05 ppm or less, and mercaptan 0.15 ppm or less.

  These components are representative as odor components that can be contained in the hair dye composition, particularly as odor components that cause discomfort to the user. Since these components give an unpleasant feeling to the user even if the content ratio is in the order of ppm, a detection tube was used for the detection.

The detector tube contains a substance that changes its hue in response to only a specific component, and its typical form is shown in FIG. The detection tube 150 has a detectable substance and its concentration range for each tube type. The odor to be measured and the type of detector tube are as follows.
・ Ammonia; manufactured by Gastec Co., Ltd., 3 L ammonia detector tube measurement range, 0.5 to 78 ppm
Detection limit, 0.2ppm
Number of suctions: 2 times, suction volume: 100 ml / time, suction time: 60 seconds, discoloration, pink → yellow, amines: GASTEC, 180L amine detector tube measurement range, 0.5-10 ppm
Detection limit, 0.1ppm
Suction frequency: 1 time, suction volume: 100 ml / suction time, 60 seconds discoloration, pink → yellow to light yellow orange, hydrogen sulfide; manufactured by Gastec, 4LT hydrogen sulfide detector tube measurement range, 0.1 to 4 ppm
Detection limit, 0.05ppm
Number of aspirations: 2 times, aspiration volume: 100 ml / aspiration time: 60 seconds, discoloration, pale yellow → reddish brown, mercaptans; Gastec, 70L mercaptans detector tube measurement range, 0.1-8 ppm
Detection limit, 0.05ppm
The number of times of suction is 4, the amount of suction is 100 ml / time of suction time 90 seconds, the color changes from yellow to red, and the concentration of the substance can be specified by reading the area where the color has changed after the passage of time.

(FIG. 1) It is explanatory drawing which shows the external appearance of a typical detection tube.

In order to capture the measurement object into the detection tube 150, as shown in FIG.
(1). One gram of a measurement object is taken as a sample SMP (hereinafter referred to as SMP) on a petri dish 110 having a diameter of 30 mm and a depth of 15 mm, and its surface is arranged as flat as possible.
(2). This petri dish 110 is installed in a glass screw port desiccator 100 having an internal volume of 3 liters, sealed,
(3). In this state, the detection target is uniformly dispersed in the desiccator 100 having a constant temperature (20 ° C.) for 3 hours, and then the detection tube type gas measuring device 120 having the detection tube 150 connected to the desiccator screw port 105 is connected. Then, the handle 130 is operated to suck the measurement gas.

(FIG. 2) It is explanatory drawing which shows the measuring method of the odor in embodiment.

  (Explanation of symbols)

DESCRIPTION OF SYMBOLS 100 ... Desiccator 105 ... Screw port 110 ... Petri dish 120 ... Detector tube type gas measuring device 130 ... Handle 150 ... Detector tube

  For the detector tube, manufacturers other than those manufactured by GASTECH, for example, manufactured by Komyo Chemical Co., Ltd. (Kitakawa gas detector) can be used.

  The first agent of the hair dye composition of the present invention contains an oxidation dye as a dye.

  Examples of the oxidation dye include paraphenylenediamine, 5-aminoorthocresol, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, N, N-bis (2- Hydroxyethyl) -paraphenylenediamine, 2- (2-hydroxyethyl) -paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 4,4'-diaminodiphenylamine, 1,3-bis (N- (2- Hydroxyethyl) -N- (4-aminophenyl) amino) -2-propanol, PEG-3,3,2'-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4-aminophenol, 2 -Aminomethyl-4-aminophenol, 2- (2-hydroxy Ethylaminomethyl) -4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino-1-hydroxyethylpyrazole, metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole, 2,4-diamino-5-methylphenetole, 2, 4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-dimethoxy-1,3 Diaminobenzene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis (2,4-diaminophenoxy) propane, metaaminophenol, 2-methyl -5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4 -Chloro-5-aminophenol, N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5- (2-hydroxyethylamino) phenol, 2-methyl-4-fluoro-5-aminophenol, resorcin, 2-methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5-dihydroxyna Talen, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1- (2-hydroxyethyl) amino-3,4-methylenedioxybenzene 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxy Pyridine, 2-amino-3-hydroxypyridine, 2,6- Examples include diaminopyridine and salts thereof. In addition, those listed in "Quasi-drug raw material standards" (issued in June 1991, Yakuji Nippo) can be used as appropriate. These dyes may be blended singly or in combination of two or more.

Furthermore, you may mix | blend a direct dye with the 1st agent as dyes other than an oxidation dye. Examples of the direct dye include 4-nitro-m-phenylenediamine, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, picramic acid, 1-amino-4-methylanthraquinone, 1,4 -Diaminoanthraquinone, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol and their salts, and "Ministerial ordinance for determining tar dyes that can be used for pharmaceuticals, etc." (Ministry of Health and Welfare announcement in 1966) And acidic dyes and basic dyes defined by the above. The acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 201, Red No. 227, and Red 230. No. (1), Red No. 230 (2), Red No. 231, Red No. 232, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Yellow No. 4, Yellow No. 5, Yellow 202 (1), Yellow 202 (2), Yellow 203, Yellow 402, Yellow 403 (1), Yellow 406, Yellow 407, Orange 402, Orange 205, Green 3 No., Green No. 204, Green No. 205, Green No. 401, Green No. 402, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Black No. 401 Etc. Examples of the basic dye include dyes having an ammonium group, a carbenium group, and the like. More specifically, 9- (dimethylamino) -benzo [a] phenoxadi-7-ium chloride (CI 51175; basic) Blue No. 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI42595; basic blue No. 7), 3,7-di (dimethylamino) phenothiazine- 5-ium chloride (CI 52015; Basic Blue No. 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44445; Basic Blue No. 26), 2 -[(4- (Ethyl (2-hydroxyethyl) a B) phenyl) azo] -6-methoxy-3-methyl-benzothiazolium-methyl sulfate (CI11154; basic blue No. 41), 8-amino-2-bromo-5-hydroxy-4-imino-6 -[(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalinone-chloride (CI56059; Basic Blue No. 99), bis [4- (dimethylamino) -phenyl] [4- (methyl Amino) phenyl] carbenium chloride (CI42535; basic violet No. 1), tris (4-amino-3-methylphenyl) -carbenium chloride (CI42520; basic violet No.2), tris [4- (dimethyl) Amino) phenyl] carbenium chloride (CI4) 555; Basic Violet No. 3), 2- [3,6- (Diethylamino) dibenzopyranium-9-yl] -benzoic acid-chloride (CI45170; Basic Violet No. 10), Di (4-aminophenyl) ) (4-amino-3-methylphenyl) carbenium chloride (CI42510; basic violet No. 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21010; Basic Brown No. 4), 1-[(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol-chloride (CI 12250; Basic Brown No. 16), 1- [ (4-Amino-3-nitrophenyl) azo] -7- (trimethylammo Nio) -2-naphthol chloride (CI12251; basic brown no. 17) 3,7-Diamino-2,8-dimethyl-5-phenyl-phenazinium-chloride (CI 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4- (dimethylamino) phenyl ) Azo] -1,2,4-triazolium chloride (CI11055; Basic Red No. 22), 2-hydroxy-1-[(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene- Chloride (CI12245; Basic Red No. 76), 2- [2 ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indole-1-ium-chloride (CI48055; Basic Yellow No. 11), 3-methyl-1-phenyl-4-[(3- (trimethyl) Ammonio) phenyl) azo] -pyrazol-5-one-chloride (CI12719; basic yellow No. 57), bis [4- (diethylamino) phenyl] phenylcarbenium-hydrogen sulfate (1: 1) (CI41040; basic -Green No. 1) etc. are mentioned.
These direct dyes may be blended singly or in combination of two or more.

  The first agent of the hair dye composition of the present invention contains an alkaline agent.

  Examples of the alkali agent include ammonia, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl -1,3-propanediol, etc.), organic amines (morpholine, guanidine, etc.), inorganic alkalis (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, etc.), basic amino acids (Arginine, lysine, etc.) and their salts. These alkaline agents may be blended singly or in combination of two or more.

  The second agent of the hair dye composition of the present invention contains an oxidizing agent.

  Examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, sodium peroxide, potassium peroxide, and peroxide. Magnesium, barium peroxide, calcium peroxide, strontium peroxide, peroxide hydrogen peroxide adduct, phosphate hydrogen peroxide adduct, pyrophosphate hydrogen peroxide adduct, sodium bromate, etc. Of these, hydrogen peroxide is particularly preferred. These oxidizing agents may be blended singly or in combination of two or more.

  In the hair dye composition of the present invention, a surfactant, an oil component, a solvent, a thickener and the like can be blended. Specific examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Specific examples of the anionic surfactant include sodium lauryl sulfate, polyoxyethylene (hereinafter referred to as POE) sodium lauryl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, POE lauryl ether. Examples thereof include phosphoric acid and salts thereof.

  Specific examples of the cationic surfactant include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, odor Stearyltrimethylammonium chloride, dicetyldimethylammonium chloride, dicocoyldimethylammonium chloride, dodecyldimethylethylammonium chloride, polyoxypropylenemethyldiethylammonium chloride, benzalkonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, cetyltrimethylammonium saccharin , Stearyltrimethylammonium saccharin, etc. It is.

  Specific examples of nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE polyoxypropylene (hereinafter referred to as POP) alkyl ethers, POE fatty acids, POE sorbitan fatty acid esters, POE castor oil , POE hydrogenated castor oil, POE sorbitol tetrafatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside, N-alkyldimethylamine oxide, POE propylene glycol fatty acid ester, etc. . Among these, POE alkyl ethers, POE alkyl phenyl ethers, POE / POP alkyl ethers, POE sorbitan fatty acid esters and the like are preferable because of their resistance to acids and alkali agents, and POE alkyl ethers are particularly preferable. Specific examples of the POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether and POE oleyl ether.

  Specific examples of amphoteric surfactants include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxydi Examples thereof include sodium salt, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, cocoamidopropyl betaine, lauryldimethylaminoacetic acid betaane, and lauramidopropyl betaine.

  These surfactants may be blended singly or in combination of two or more.

  Specific examples of the oil component include hydrocarbons, fats and oils, waxes, higher alcohols, higher fatty acids, esters, and silicones.

  Specific examples of the hydrocarbon include α-olefin oligomer, liquid paraffin, light isoparaffin, light liquid isoparaffin, liquid isoparaffin, petrolatum, polyethylene powder, ozokerite, polybutene, ceresin and the like.

  Specific examples of fats and oils include palm oil, palm oil, olive oil, avocado oil, castor oil, sesame oil, rosehip oil, meadowweed oil, evening primrose oil, macadamia nut oil, peppermint oil, corn oil, rapeseed oil, rice bran oil, shea Vegetable oils and fats such as fat and jojoba oil; animal fats and oils such as beef tallow, milk fat, horse fat, mink oil, and lanolin.

  Specific examples of the waxes include beeswax, candelilla wax, rice bran wax, shellac, carnauba wax and the like.

  Specific examples of higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, oleyl alcohol, linoleyl. Alcohol, linolenyl alcohol, lanolin alcohol, etc. are mentioned.

  Specific examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid.

  Specific examples of esters include diisopropyl adipate, diisobutyl adipate, dioctyl adipate, 2-hexyldecyl adipate, diisostearyl adipate, isopropyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, Isodecyl isononanoate, isotridecyl isononanoate, diisopropyl sebacate, octyldodecyl myristate, isopropyl palmitate, stearyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, triisodecyl myristate, isoristyl myristate Stearyl, 2-ethylhexyl palmitate, lauryl lactate, myristyl lactate, cetyl lactate, octyldodecyl lactate, lanoli acetate , Isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, cetyl caprate, glyceryl tricaprylate, neopentyl glycol dicaprate, diisosodium malate Stearyl etc. are mentioned.

  Specific examples of silicones include methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, polyether-modified silicone, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, etc. Is mentioned.

  These oil components may be blended singly or in combination of two or more.

  Specific examples of the solvent include water, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, dipropylene glycol, 3-methyl-1,3 -Butanediol, hexylene glycol, diglycerin, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone, propylene carbonate, ethylene carbonate, polyethylene glycol, polypropylene glycol and the like can be mentioned. These solvents may be blended singly or in combination of two or more.

  Specific examples of the thickener include carboxymethyl cellulose, carboxy vinyl polymer, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, xanthan gum, carrageenan, alginate, pectin, ferrersen, gum arabic, gatch gum, caraya gum, tragacanth gum, agate powder, bentonite And thickeners such as crosslinkable polyalkyl acid salts. These thickeners may be blended singly or in combination of two or more.

  Further, as other additional components, hydrolyzates obtained by hydrolyzing proteins such as collagen, keratin, elastin, fibroin, conchiolin, soy protein, casein, gelatin, etc. with acid, alkali, enzyme, etc., and these were quaternized. Polypeptides such as cation-modified proteins; moisturizers such as sodium pyrrolidone carboxylate and hyaluronic acid; preservatives such as parabens; pH adjusters such as phosphoric acid, citric acid, sulfuric acid, acetic acid, lactic acid, and tartaric acid; thioglycolic acid, sulfurous acid Antioxidants such as salt, ascorbic acid and dibutylhydroxytoluene; propellants such as liquefied petroleum gas, dimethyl ether, nitrogen and carbon dioxide; amino acids, plant extracts, herbal extracts, vitamins, dyes, fragrances, pigments, You may mix | blend at least 1 type chosen from a ultraviolet absorber etc.

  The hair dye composition of the present invention is provided as a two-component type comprising a first agent containing an oxidative dye and a second agent containing an oxidizer, as is the case with hair dyes that are currently widely used. These dosage forms of the first agent and the second agent can be, for example, liquid, emulsion, cream, gel, powder, paste, wax, foam, etc. You can also.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples. All amounts are in weight percent.

  (Examples 1 to 21 and Comparative Examples 1 to 8) In Examples 1 to 21 and Comparative Examples 1 to 8 as two-component hair dye compositions for creams of the first agent and the second agent, Tables 1 to 1 First agent and second agent were prepared as shown in FIG.

  About the hair dye composition of each row | line | column of Tables 1-3, after mixing a 1st agent and a 2nd agent by weight ratio 1: 1, after a hair bundle (Burax Co., Ltd. Yak hair 100%, product number; BM- YK, hair bundle: mixture of first agent and second agent = weight ratio 1: 1). The hair bundle was allowed to stand for 15 minutes, washed thoroughly with a shampoo, wiped with a towel, and then dried with a dryer. In this hair dyeing treatment, the dyeing properties after the treatment of the hair dye composition were evaluated by 20 panelists as shown below. The results are shown in Tables 1-3.

<Dyeing properties>
Dyeed uniformly and firmly (5 points), Dyed uniformly (4 points), Dyed (3 points), Slightly uneven, Slightly unstained (2 points), Unevenly, Slightly unstained ( (1 point). An average score is calculated for each paneler's scoring results, and an average value of 4.6 or higher is “uniformly dyed: 5”, 3.6 to 4.5 points is “uniformly dyed: 4 ”2.6 to 3.5 points are“ dyed: 3 ”, 1.6 to 2.5“ slightly uneven, not very dyed: 2 ”, 1 point to 1.5 points The following was set as “Evaluation results” with “unevenness and almost no staining: 1”.

  As shown to Tables 1-3, in Examples 1-21, the favorable result is obtained about dyeing property. In Examples 3 to 5, since the content of the divalent metal salt is appropriate, the result is excellent in dyeability. In Examples 10 to 12, since the content of the divalent metal hydroxide is suitable, the result is excellent in dyeability. In Examples 17-19, since content of aminocarboxylic acid and / or its derivative (s) was suitable, it was the result excellent in dyeing property.

  On the other hand, in Comparative Examples 1 and 2, since it is a monovalent or trivalent metal salt, sufficient results with respect to dyeing properties are not obtained. In Comparative Examples 3 and 4, since it is a monovalent or trivalent metal hydroxide, sufficient results for dyeability are not obtained. In Comparative Examples 5 and 6, an aminocarboxylic acid and / or a derivative thereof is not contained, and thus sufficient results regarding dyeing properties are not obtained. In Comparative Example 7, since a divalent metal salt and / or a divalent metal hydroxide is not contained, sufficient results with respect to dyeing properties are not obtained. Furthermore, since Comparative Example 8 does not contain an aminocarboxylic acid and / or derivative thereof and a divalent metal salt and / or a divalent metal hydroxide, sufficient results regarding dyeing properties are obtained. It is not done.

  (Examples 22 to 31) In Examples 22 to 31 as the two-component hair dye composition of cream for both the first agent and the second agent, the first agent and the second agent are prepared as shown in Table 4. did.

  About the hair dye composition of each row | line | column of Table 4, after mixing 1st agent and 2nd agent by weight ratio 1: 1, after a hair bundle (Burax Co., Ltd. Yak hair 100%, product number; BM-YK, The hair bundle was applied to a mixture of the first agent and the second agent = weight ratio 1: 1). The hair bundle was allowed to stand for 15 minutes, washed thoroughly with a shampoo, wiped with a towel, and then dried with a dryer. In this hair dyeing treatment, the dyeing properties after the treatment of the hair dye composition were evaluated by 20 panelists as shown below. The results are shown in Table 4.

<Dyeing properties>
Dyeed uniformly and firmly (5 points), Dyed uniformly (4 points), Dyed (3 points), Slightly uneven, Slightly unstained (2 points), Unevenly, Slightly unstained ( (1 point). An average score is calculated for each paneler's scoring results, and an average value of 4.6 or higher is “uniformly dyed: 5”, 3.6 to 4.5 points is “uniformly dyed: 4 ”2.6 to 3.5 points are“ dyed: 3 ”, 1.6 to 2.5“ slightly uneven, not very dyed: 2 ”, 1 point to 1.5 points The following was set as “Evaluation results” with “unevenness and almost no staining: 1”.

  As shown in Table 4, in Examples 22 to 31, good results were obtained for dyeing properties. In Examples 22 to 27, the solubility of the divalent metal salt and / or the hydroxide of the divalent metal in water at 25 ° C. is 4.0 mol / kg or less, which results in excellent dyeing properties. Yes.

Further, the embodiment can be modified as follows.
The hair dye composition of the above embodiment is the same as the above example, even if the composition having no fragrance and the predetermined component that stimulates the sense of smell is measured with a detector tube is below a certain concentration. Has good dyeing properties.

  (Examples 32 and 33) In Examples 32 and 33 as hair dye compositions containing no ammonia in order to reduce the irritating odor during use, the first agent and the second agent are both in a two-part form of cream. The first agent and the second agent were prepared as shown in Table 5.

  About the hair dye composition of each row | line | column of Table 5, after mixing a 1st agent and a 2nd agent by weight ratio 1: 1, after a hair bundle (Burax Co., Ltd. Yak hair 100%, product number; BM-YK, The hair bundle was applied to a mixture of the first agent and the second agent = weight ratio 1: 1). The hair bundle was allowed to stand for 15 minutes, washed thoroughly with a shampoo, wiped with a towel, and then dried with a dryer. In this hair dyeing treatment, the dyeing properties after the treatment of the hair dye composition were evaluated by 20 panelists as shown below. In addition, ammonia, amines, hydrogen sulfide, and mercaptans were detected using a detector tube. Furthermore, the odor felt by each paneler before use (when the first agent and second agent were mixed), during use, and after use was evaluated as shown below. The results are shown in Table 5.

<Dyeing properties>
It is dyed uniformly and firmly (5 points), it is dyed uniformly (4 points), it can be dyed (3 points), there is a little unevenness, it is not dyed very much (2 points), there is unevenness, and it is hardly dyed ( (1 point). An average score is calculated for each paneler's scoring results, and an average value of 4.6 or higher is “uniformly dyed: 5”, 3.6 to 4.5 points is “uniformly dyed: 4 ”2.6 to 3.5 points are“ dyed: 3 ”, 1.6 to 2.5“ slightly uneven, not very dyed: 2 ”, 1 point to 1.5 points The following was set as “Evaluation results” with “unevenness and almost no staining: 1”.

<Odor>
◎… No odor at all ○… No odor at all △… Slightly irritating odor or base odor ×… I feel strong irritating odor or base odor

  As shown in Table 5, in Examples 32 and 33, good results were obtained with respect to dyeing properties. In Example 33, in order to reduce the irritating odor at the time of use, a favorable result was obtained about dyeing property similarly in the hair dye composition which does not contain ammonia.

Further, as shown in Table 5, in Example 32, ammonia is 30 ppm or more (amount exceeding the upper limit for detection of the used detector tube), and amines are 100 ppm or more (exceeds the upper limit for detection of the used detector tube). Amount), 4 ppm or more of mercaptan is detected.
On the other hand, in Example 33, ammonia, amines, hydrogen sulfide, and mercaptans are hardly detected or are extremely small amounts.

Example 34
<First agent (cream)> Weight percent Barium nitrate ²¹⁾ 2.0
(Solubility: 0.39 mol / kg)
Ethylenediaminetetraacetic acid tetrasodium 1.0
Sodium malate 3.0
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
Cetanol 2.0
Stearyl alcohol 0.5
Polyoxyethylene stearyl ether 4.0
Stearyltrimethylammonium chloride (70%) 1.0
L-ascorbic acid 0.5
Glycerin 5.0
Ammonia water (25%) 3.0
Monoethanolamine 5.0
Make to 100 with purified water.
<Second agent (milky liquid)>
Cetanol 1.0
Polyoxyethylene cetyl ether 0.5
Stearyltrimethylammonium chloride (70%) 0.5
Hydroxyethanediphosphonic acid 0.2
Propylene glycol 10.0
Hydroxyethane diphosphonic acid 0.1
Phosphoric acid, sodium monohydrogen phosphate Appropriate amount (pH 3.3)
Hydrogen peroxide (35%) 16.6
Make to 100 with purified water.
21) Special reagent grade 99% barium nitrate (manufactured by Sigma Aldrich Japan Co., Ltd.)
In the composition, the first agent is creamy and the second agent is liquid, and the mixing ratio of 1 agent: 2 agent is mixed at a ratio of 1: 1. As for the obtained emulsion hair dye composition, the result with favorable dyeing property is obtained similarly to the Example.

Example 35
<First Agent (Liquid)> Weight percent Magnesium sulfate ²²⁾ 1.0
(Solubility: 3.02 mol / kg)
Sodium citrate 0.1
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
N-methylpyrrolidone 10.0
Polyoxyethylene oleyl ether 29.0
Polyoxyethylene lauryl ether 8.0
Oleyl alcohol 0.5
Palm oil fatty acid diethanolamide 5.0
Cetyltrimethylammonium chloride (50%) 1.0
L-ascorbic acid 0.5
Glycerin 5.0
Monoethanolamine 5.0
Ammonia (25%) 3.0
Ethanol 20.0
Make 100 with purified water <Second Agent (Emulsion)> Weight percent Cetanol 1.5
Cetyl sulfate 0.5
Propylene glycol 10.0
Diethylenetriaminepentaacetic acid pentasodium 2.0
Phosphoric acid, sodium monohydrogen phosphate Appropriate amount (pH 3.4)
Hydrogen peroxide (35%) 16.6
Make to 100 with purified water.
22) 99.99% magnesium sulfate (manufactured by Sigma Aldrich Japan Co., Ltd.)
The composition is composed of the first agent in liquid form and the second agent in emulsion, and the mixture ratio of 1 agent: 2 agent is mixed at a ratio of 1: 1. The gel-like hair dye composition thus obtained has good results in dyeability as in the examples.

Example 36
<First Agent (Gel)> Weight percent Magnesium hydroxide ²³⁾ 2.0
(Solubility: 0.0045 mol / kg)
Sodium malate 1.0
Diethylenetriaminepentaacetic acid pentasodium 2.0
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
Polyoxyethylene lauryl ether 5.0
Polyoxyethylene oleyl ether 20.0
Oleyl alcohol 5.0
Propylene glycol 5.0
Cetyltrimethylammonium chloride (50%) 0.5
Lauryldimethylamine oxide solution (30%) 5.0
L-ascorbic acid 0.5
Ethanol 10.0
Monoethanolamine 5.0
Ammonia (25%) 3.0
Make 100 with purified water <Second Agent (Liquid)> Weight percent Phosphoric acid, Sodium monohydrogen phosphate Appropriate amount (amount to be pH 2.9)
Hydroxyethanediphosphonic acid 0.2
Hydrogen peroxide (35%) 16.6
Make to 100 with purified water.
23) First grade reagent 95% magnesium hydroxide (Sigma Aldrich Japan Co., Ltd.)
In the composition, the first agent is in the form of gel and the second agent is in liquid form, and the mixing ratio of 1 agent: 2 agent is mixed at a ratio of 1: 1. The gel-like hair dye composition thus obtained has good results in dyeability as in the examples.

Example 37
<First Agent (Cream)> Weight percent Magnesium sulfate ²⁴⁾ 0.5
(Solubility: 3.02 mol / kg)
Calcium hydroxide ²⁵⁾ 0.5
(Solubility: 0.0229 mol / kg)
Diethylenetriaminepentaacetic acid pentasodium 1.0
Ethylenediaminetetraacetic acid tetrasodium 1.0
Sodium malate 0.5
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
Sodium citrate 0.5
Cetanol 5.0
Stearyl alcohol 3.0
Liquid paraffin 10.0
Polyoxyethylene cetyl ether 4.0
Stearyltrimethylammonium chloride (70%) 2.0
Glycerin 5.0
L-ascorbic acid 0.5
Ammonia water (25%) 3.0
Monoethanolamine 5.0
Make to 100 with purified water.
<Second Agent (Wax)> Weight percent Cetanol 12.0
Stearyl alcohol 4.0
Polyoxyethylene cetyl ether 8.0
Liquid paraffin 6.0
Polyethylene glycol 2.0
Phosphoric acid, sodium monohydrogen phosphate Appropriate amount (pH 2.9)
Hydroxyethanediphosphonic acid 0.2
Hydrogen peroxide (35%) 16.6
Make to 100 with purified water.
24) 99.99% magnesium sulfate (manufactured by Sigma Aldrich Japan Co., Ltd.)
25) 99.995% calcium hydroxide (manufactured by Sigma Aldrich Japan Co., Ltd.)
In the composition, the first agent is in the form of cream and the second agent is in the form of wax, and the mixing ratio of 1 agent: 2 agent is mixed at a ratio of 1: 1. The obtained waxy hair dye composition has good results in dyeability as in the examples.

Example 38
<First Agent (Aerosol)> Weight percent Magnesium sulfate ²⁶⁾ 0.5
Diethylenetriaminepentaacetic acid pentasodium 0.5
Sodium malate 0.5
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
Cetanol 4.0
Sodium cetyl sulfate 0.5
Polyoxyethylene cetyl ether 1.0
Propylene glycol 10.0
Isopropyl palmitate 0.5
Beeswax 0.3
L-ascorbic acid 0.5
Ammonia water (25%) 3.0
Monoethanolamine 5.0
Make to 100 with purified water.
―――――――――――――――――――――――――――――
Initial internal pressure (nitrogen gas) 0.6 MPa
Initial ejection volume 11.0 g / 5 seconds ―――――――――――――――――――――――――――――
<Second Agent (Aerosol Form)> Weight percent Cetanol 4.0
Sodium cetyl sulfate 0.5
Polyoxyethylene cetyl ether 1.0
Hydroxyethane diphosphonic acid 0.1
Phosphoric acid, sodium monohydrogen phosphate Appropriate amount (pH 3.2)
Hydroxyethanediphosphonic acid 0.2
Hydrogen peroxide 16.6
Isopropyl palmitate 0.5
Beeswax 0.4
Make to 100 with purified water.
―――――――――――――――――――――――――――――
Initial internal pressure (nitrogen gas) 0.6 MPa
Initial ejection volume 12.0 g / 5 seconds ―――――――――――――――――――――――――――――
26) 99.99% magnesium sulfate (manufactured by Sigma Aldrich Japan Co., Ltd.)
The first composition and the second agent are both in the form of an aerosol, and the composition is mixed at a 1: 1 ratio of 1 agent: 2 agent. As for the obtained creamy hair dye composition, the result with favorable dyeing property is obtained similarly to the Example.

Example 39
<First Agent (Powder)> Weight percent Magnesium sulfate ²⁷⁾ 3.0
Sodium malate 0.5
Paraphenylenediamine 0.9
Resorcin 0.4
Orthoaminophenol 0.2
Paraaminophenol 0.6
Metaaminophenol 0.1
5-Aminoorthocresol 0.1
Sodium carboxymethylcellulose 24.0
Sodium carbonate 7.0
Uric acid 14.0
Uricase 8.0
<Second Agent (Liquid)> Weight percent Phosphoric acid, sodium monohydrogen phosphate Appropriate amount (amount to be pH 2.9)
Diethylenetriaminepentaacetic acid pentasodium 3.0
Hydrogen peroxide (35%) 16.6
Make to 100 with purified water.
27) 99.99% Magnesium sulfate (Sigma Aldrich Japan Co., Ltd.)
In the composition, the first agent is powdery and the second agent is liquid, and the mixing ratio of 1 agent: 2 agent is mixed at a ratio of 1: 1. As for the obtained liquid hair dye composition, the result with favorable dyeing property was obtained similarly to the Example.

  As described above, according to the hair dye composition of the present invention, by containing a divalent metal salt and / or a divalent metal hydroxide and an aminocarboxylic acid and / or a derivative thereof, hair Can have excellent dyeing properties.

Claims (4)

In the hair dye composition prepared by mixing the first agent containing the dye and the second agent containing the oxidizing agent at the time of use, the following components (A) and (B)
(A) A hair dye composition comprising a divalent metal salt and / or a divalent metal hydroxide (B) an aminocarboxylic acid and / or a derivative thereof. The hair dye composition according to claim 1, wherein the solubility of (A) in water at 25 ° C is 4.0 mol / kg or less. The hair dye composition according to claim 1, further comprising an alkali metal salt of α-hydroxy acid. The hair dye composition does not contain a fragrant component, and after leaving 1 gram of the hair dye composition in a 3 liter desiccator at a constant temperature (20 ° C.) for 3 hours, a predetermined ingredient that stimulates olfaction The amount of ammonia is not more than 1 ppm, the amines are not more than 0.75 ppm, the hydrogen sulfide is not more than 0.05 ppm, and the mercaptan is not more than 0.15 ppm. A hair dye composition as described in 1. above.