JP5363701B2 - One-part hair dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair dye composition which is excellent in a hair-dyeing property, can be adjusted to a desired color, and can especially dye gray hair in a red-free black or gray color. <P>SOLUTION: This one pack type hair dye composition has pH 8 to 11 and comprises (A) one or more compounds represented by formula (1) [the broken line shows the presence or absence of a &pi;-bond; R<SP>1</SP>is OH or acetoxy; R<SP>2</SP>is H, -COOR (R is H, CH<SB>3</SB>or C<SB>2</SB>H<SB>5</SB>) or -COO<SP>-</SP>X<SP>+</SP>(X<SP>+</SP>is a cation); R<SP>3</SP>is H, acetyl, CH<SB>3</SB>or C<SB>2</SB>H<SB>5</SB>], (B) a direct dye, (C) a nonionic surfactant, and (D) a thickening polymer. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a one-component hair dye composition that is excellent in dyeability and can be adjusted to a desired color.

  Conventionally, air oxidation type hair dye compositions using melanin precursors such as indoles and indolines are known (see, for example, Patent Documents 1 to 3). However, since the color obtained by these hair dye compositions is a brownish color, it is limited to brown dyeing, and there is a problem in using it as a hair dye. In particular, there is a need for an air oxidation hair dye that can dye white hair from black to gray with little redness. In particular, men tend to prefer a slightly bluish black.

  As a hair dye that uses a melanin derivative and can be dyed black without redness, a hair dye that contains an indoline derivative and a coupling agent but does not contain a developer has been proposed (Patent Document 4).

Japanese Patent Publication No. 8-32618 Japanese Patent Laid-Open No. 2003-55175 Japanese Patent Laid-Open No. 2002-322038 Special table 2001-511436 gazette

  Therefore, the present invention does not contain a coupling agent, is excellent in dyeability, can be adjusted to a desired color, and is particularly an air oxidation type hair dye capable of dyeing gray hair from black to gray without redness. An object is to provide a composition.

  The present inventors have found that the above-mentioned problems can be solved by using a direct dye, a nonionic surfactant, and a polymer in an air oxidation hair dye composition using a melanin precursor.

  The present invention provides a one-component hair dye composition having a pH of 8 to 11 containing the following components (A) to (D).

  (A) One or more compounds represented by general formula (1)

[In the formula, the broken line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom, —COOR (R is a hydrogen atom, a methyl group or an ethyl group) or —COO ^−. X ^<+> (X ^<+> represents a cation), and R ^{< 3 >} represents a hydrogen atom, an acetyl group, a methyl or ethyl group. ]

(B) Direct dye
(C) Nonionic surfactant
(D) Thickening polymer

  The one-component hair dye composition of the present invention is excellent in dyeability and can be adjusted to a desired color, and in particular, gray hair can be dyed from black to gray without redness.

  The compound represented by the general formula (1) as the component (A) is an indole derivative or indoline derivative (melanin precursor) that is converted into a melanin pigment by being oxidized. Examples of the compound represented by the general formula (1) include 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, and 5,6-dihydroxyindoline-2-carboxylic acid. Is mentioned. These can be used alone or in combination of two or more, but by combining two or more, it is possible to adjust the dyed color. In particular, it is preferable to use 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid in combination from the viewpoint of dyeing hair in a natural color. The molar ratio in the case of using both of these is preferably in the range of 50:50 to 999: 1, particularly 80:20 to 99: 1. Here, 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid can be quantified by reverse phase HPLC.

  The total content of the component (A) compound is preferably 0.05 to 5% by weight, particularly 0.1 to 2% by weight in the hair dye composition of the present invention in terms of dyeability and economy.

  Examples of the direct dye of component (B) include acid dyes, nitro dyes, disperse dyes, basic dyes, and direct dyes described in JP-A-2003-342139. Examples of acid dyes include blue No. 1, purple No. 401, black No. 401, orange color No. 205, red No. 227, red No. 106, yellow No. 203, acidic orange 3, etc., and nitro dyes include 2-nitro Paraphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino- 3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis- (2-hydroxyethyl) -2-nitropara Examples include disperse dyes such as disperse purple 1, disperse blue 1, disperse black 9, etc., and basic dyes include basic blue 99, basic tea 16, basic tea 17, and base. Basic red 76, basic red 51, basic yellow 57, basic yellow 87, basic orange 31 and the like. Of these, acidic dyes are preferred, and black No. 401 is particularly preferred because it can be dyed black to gray with little redness.

  The content of the component (B) is preferably 0.001 to 5% by weight, particularly 0.01 to 3% by weight in the hair dye composition of the present invention.

  Nonionic surfactants of component (C) include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, higher fatty acid sucrose esters, polyglycerin fatty acid esters, higher fatty acid monoethanolamides or diethanolamides, polyoxyethylene cured castor Examples thereof include oils, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amide amine oxides. Of these, the following general formula (2)

[Wherein, m and n represent a total number of 7 to 25, preferably 7 to 20, particularly 9 to 11, and x is a number of 6 to 16, preferably 6 to 12, particularly 8 to 10 in terms of weight average. Indicates. ]
A polyethoxylate of a secondary alcohol represented by the formula is preferred, and polyoxyethylene tridecyl ether (Nippon Shokubai Co., Ltd .: Softanol 90, m + n = 9 to 11, x = 9 in the general formula (2)) is particularly preferred.

  The nonionic surfactant of a component (C) can be used individually or in combination of 2 or more types. The content of the component (C) is preferably 0.1 to 5% by weight, particularly 0.5 to 3% by weight in the hair dye composition of the present invention from the viewpoints of usability and coating properties.

  The thickening polymer of component (D) may be either nonionic or ionic. Nonionic thickening polymers include hydroxyethyl cellulose (for example, Daicel Chemical Industries: SE-850, Nagase Sangyo: Serosize HECQP52000H), sodium carboxymethyl cellulose (for example, Daicel Chemical Industries: CMC Daicel 1220), hydroxyethyl cellulose hydroxy Sodium propylstearyl ether hydroxypropylsulfonate (for example, the compound described in Production Example 1 of JP-A-11-12139), hydroxypropylmethylcellulose (for example, Shin-Etsu Chemical Co., Ltd .: Metrose 60SH-10000), guar gum (for example, Sumitomo Dainippon) Pharmaceuticals: Fiberlon S), pullulan (for example, Hayashibara Corporation: pullulan PI-20), hydroxypropyl chitosan (for example, Ichimaru Falcos: Chitofilmer HV-10), chitosan dl-pyrrolidone carboxylate (for example, Uni On Carbide: Kitemer PC), Polyvinylpyrrolidone (BASF: Luviskol K-12, K-30, PVP K-120), Polyvinyl alcohol (Nippon Gosei Co., Ltd .: Gohsenol EG-40), Vinyl alcohol / vinyl amine copolymer (Air product company: VA-120-HCl), high polymerization degree polyethylene glycol (Nippon Union Carbide Corporation: Polyox WSRN-60K) and the like.

  Anionic thickening polymers include polyacrylic acid (Noveon: Carbopol 941, 981), acrylic acid / alkyl methacrylate copolymer (Noveon: Carbopol ETD2020), lower alkyl vinyl ether / maleic anhydride Hydrolyzate of partially crosslinked polymer by terminal unsaturated diene compound of acid copolymer or monoalkyl ester thereof (ISP: Stabilise 06, Stabilize QM), carrageenan (for example, Mitsubishi Rayon: Soagina LX22, ML210), xanthan gum ( For example, Dainippon Sumitomo Pharma Co., Ltd .: Echo Gum T), Welan gum (eg, Sanki Co., Ltd .: K1C376, K1A96), hydroxypropylxanthan gum (eg, Dainippon Sumitomo Pharma Co., Ltd .: Labor gum EX), and the like.

  Examples of the cationic thickening polymer include an aqueous solution containing an amino group or an ammonium group in the side chain of the polymer chain or a diallyl quaternary ammonium salt as a structural unit, such as a cationized cellulose derivative (for example, Lion Corporation: Leo Guard G, GP, Union Carbide: Polymer JR-125, JR-400, JR-30M, LR-400, LR-30M, National Starch and Chemical: Cellcoat H-100, L-200 ), Cationized guar gum derivatives (for example, Rhodia: Jaguar C-13S, C-17, Dainippon Sumitomo Pharma: Labor gum CG-M, CG-M7, CG-M8M), diallyl quaternary ammonium salt Polymers or copolymers (Calgon: Marquat 100, 280, 295, 550), quaternized polyvinylpyrrolidone derivatives (IPS Japan: Guffcoat 734, 755, 755N), etc. That.

  Of these, the polysaccharide type polymer is basically a thickener that increases the viscosity, and a natural polymer having a cellulose skeleton or a xanthan gum skeleton is particularly preferable. The polymer of a component (D) can be used individually or in combination of 2 or more types. The content of the component (D) is preferably 0.05 to 10% by weight, particularly 0.1 to 3% by weight in the hair dye composition of the present invention, from the viewpoints of coatability and difficulty of dripping. In addition, from the viewpoint of applicability and resistance to dripping, the viscosity of the aerosol stock solution is preferably 100 to 80000 mPa · s, particularly 300 to 50000 mPa · s. Here, the viscosity is a value after rotating for 1 minute at 6 rpm with a B-type rotational viscometer at 25 ° C.

  In order to further improve the dyeability, the hair dye composition of the present invention preferably further contains an aromatic alcohol. Aromatic alcohols include benzyloxyethanol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamon alcohol, anise alcohol, p-methylbenzyl alcohol, α, α-dimethylphenethyl alcohol, α-phenylethanol, phenoxyethanol and the like. Can be mentioned. Of these, benzyloxyethanol and benzyl alcohol are particularly preferable.

  The aromatic alcohol can be used alone or in combination of two or more thereof, and the content thereof is the hair dye composition of the present invention from the viewpoint of improving dyeability, improving usability, and controlling foam quality. The content is preferably 0.1 to 10% by weight, particularly 0.5 to 5% by weight.

  The hair dye composition of the present invention may contain a surfactant other than the component (C).

  Such surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acids. Salts, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, sulfosuccinic acid esters and the like; imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series , Hydroxysulfobetaine or amidosulfobetaine amphoteric surfactants; imidazoline ring-opening quaternary ammonium salts, mono-long-chain alkyl quaternary ammonium salts, di-long-chain alkyl quaternary ammonium Cationic surfactant such as salt Etc., and the like. As counter ions of the anionic residues of these surfactants, alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, alkanol groups having 2 or 3 carbon atoms, Examples thereof include three alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine. Examples of the counter ion of the cationic residue include halogen ions such as chlorine, bromine and iodine, and methosulfate and saccharinate ions.

  Surfactants other than these components (C) can be used alone or in combination of two or more, and the content thereof is 0.1 to 15% by weight in the hair dye composition of the present invention, particularly 0.5 to 10% by weight is preferred.

  The hair dye composition of the present invention can contain an alkali agent used in ordinary hair dyes. For example, ammonia water; alkanolamines such as mono-, di- or triethanolamine; alkyl or aralkylamines such as butylamine and benzylamine; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate Among them, monoethanolamine is preferable from the viewpoint of dyeing power.

  The alkaline agent can be used alone or in combination of two or more, and the content thereof is dyed in black with no redness suitable for concealing oriental white hair. 0.01 to 20% by weight, particularly 0.1 to 10% by weight in the agent composition is preferred.

  The hair dye composition of the present invention may contain an antioxidant used for a normal hair dye. For example, sulfurous acid, ascorbic acid, thioglycolic acid, L-cysteine, N-acetyl-L-cysteine and salts thereof are preferred, and in particular, ascorbic acid and salts thereof contribute to the stabilization of component (A). In addition to improving the dyeing power, it is preferable.

  Antioxidants can be used singly or in combination of two or more, and the content thereof is dyed in the present invention from the viewpoint of dyeing reddish black suitable for hiding Oriental white hair. 0.01 to 2% by weight, particularly 0.05 to 1% by weight in the hair composition is preferred.

  Furthermore, the hair dye composition of the present invention can contain silicones from the viewpoints of foam texture, foam slipperiness, reduction of creaking during washing, and smoothness during drying. Examples of such silicones include those shown below.

(1) Dimethylpolysiloxane Examples include those represented by the following general formula.
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] _b —Si (CH ₃ ) ₃
[Wherein b represents a number of 3 to 20000. ]

(2) Amino-modified silicone Various amino-modified silicones can be used, but in particular, the average molecular weight of about 3000 to 100,000 is Amodimethicone, Aminoethylaminopropyl Dimethicone, or Aminopropyl Dimethicone. ) And those described in the 10th edition of the CTFA Dictionary (US, International Cosmetic Ingredient Dictionary and Handbook) are preferred. This amino-modified silicone is preferably used as an aqueous emulsion, and examples of commercially available products include SM 8704C (Toray Dow Corning), DC 929 (Dow Corning), KT 1989 (GE Toshiba).

(3) Other silicones Other than the above, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone, etc. It is done.

  Two or more kinds of silicones may be used in combination, and the content thereof is preferably 0.01 to 10% by weight, more preferably 0.05 to 6% by weight, particularly 0.3 to 3% by weight in the hair dye composition of the present invention. % Is preferred.

  Furthermore, the hair dye composition of the present invention may contain an oil agent as another conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; beeswax, whale wax, lanolin, carnauba wax, etc. Waxes: Esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; myristyl al Lumpur, cetyl alcohol, stearyl alcohol, behenyl alcohol, 2-octyldodecanol, higher alcohols such as cetostearyl alcohol; Other isostearyl glyceryl ether, polyoxypropylene butyl ether. Of these, higher alcohols are preferable, and myristyl alcohol, cetyl alcohol, and stearyl alcohol are particularly preferable. Two or more kinds of these oil agents can be used in combination, and the content thereof is preferably 0.2 to 2% by weight, more preferably 0.3 to 1.8% by weight, particularly 0.5 to 1.5% by weight in the hair dye composition of the present invention. % Is preferred.

  In addition to the above-mentioned components, the hair dye composition of the present invention includes components usually used in hair cosmetics, such as aqueous media, stabilizers, buffers, fragrances, touch improvers, chelating agents, solubilizers, antiseptics. An agent or the like can be appropriately blended depending on the purpose.

  The melanin precursor of component (A) reacts with oxygen in the air under basic conditions and is converted to a melanin pigment. For this reason, pH of the hair dye composition of this invention is adjusted to the range of 8-11, Preferably it is the range of 9-11.

  The hair dye composition of the present invention is preferably in the form of an aerosol in order to maintain dyeing power and improve dyeing power even after repeated use. In order to obtain an aerosol type form, the hair dye composition of the present invention may be filled into a pressure-resistant container (such as an aerosol can) together with a propellant as an aerosol stock solution.

  As the propellant, compressed gas, liquefied gas and the like generally used for aerosol products can be used. As compressed gas, nitrogen gas, carbon dioxide gas, argon gas and the like are used. 5 volatile hydrocarbons, dimethyl ether and the like. Of these, nitrogen gas, liquefied petroleum gas, and dimethyl ether are preferred. Two or more kinds of propellants can be used in combination, and in order to obtain an appropriate jet speed, it is preferable to contain 1 to 20% by weight, particularly 3 to 15% by weight, in the total composition consisting of the stock solution and the propellant. . Moreover, it is preferable to adjust so that the internal pressure of the aerosol can after filling may be 0.3 to 0.5 MPa (25 ° C.).

  At the time of product filling, it is preferable to deaerate simultaneously with clinching to reduce the air remaining in the container, and such deaeration operation is more effective in terms of stabilizing the contents. For example, the deaeration operation is preferably performed at a pressure of 48 kPa or less.

  The hair dye composition of the present invention can be used at room temperature, but the dyeing power can also be improved by supplying heat and oxygen with a dryer or the like.

Examples 1-2 and Comparative Example 1
According to the composition shown in Table 1, an aerosol type one-component hair dye composition stock solution (gel type) is prepared, and this stock solution is packed in an aerosol compatible bottle (Tokyo Kogyo Co., Ltd.) and clinched, and then used as a propellant. Filled with 0.5 MPa of nitrogen gas, an aerosol type one-component hair dye composition was obtained.
The obtained aerosol type one-component hair dye composition was evaluated for dyeability as shown below. The results are also shown in Table 1.

-Dyeability (ΔE):
1 g of each aerosol-type hair dye composition was applied to about 1 g of dry white hair traces of a Chinese woman, allowed to stand at room temperature for 5 minutes, shampooed, and washed with water. This dyeing operation was repeated three times, and the dyeability (ΔE, Minolta CR300) and color of gray hair were evaluated.
By the above dyeing operation, the gray hair bundle was dyed gray in Example 1, dyed brown to gray in Example 2, and dyed brown in Comparative Example 1.

Claims (5)

PH 8-11 containing the following components (A)- (E) and having a molar ratio of 5,6-dihydroxyindole to 5,6-dihydroxyindole-2-carboxylic acid of 50: 50-99: 1 One-part hair dye composition.
(A) 0.05 to 5% by weight of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid in total
(B) 0.01-5% by weight direct dye
(C) Polyethoxylate of secondary alcohol represented by general formula (2)

[In formula, m and n show the number used as a total of 7-25, and x shows the number of 6-16 in a weight average. ]
(D) Thickening polymer
(E) benzyl alcohol and / or benzyloxyethanol   The one-component hair dye composition according to claim 1, wherein component (B) is an acid dye.   The one-component hair dye composition according to claim 1, wherein the component (B) is black No. 401. The viscosity (25 ° C.) are one-part hair dyeing composition according to any one of claims 1 to 3 which is 100~80000mPa · s. The one-component hair dye composition according to any one of claims 1 to 4 , which is used for concealing gray hair.