JP5317561B2 - Hair dye composition - Google Patents

Description

  The present invention relates to a hair dye composition containing a dissociable azo dye.

  Various direct dyes such as acid dyes, basic dyes, and nitro dyes are used for permanent hair dyes and semi-permanent hair dyes. Since the direct dye is lost, it is prone to fading, which is noticeable in damaged hair.

  Therefore, as one of the methods for solving the problem of resistance to light, washing, sweat, friction and heat (fastness), a hair dye using a dissociable azo dye having a dissociating proton as a direct dye has been proposed ( (See Patent Documents 1 and 2). However, the speed at which the dye penetrates directly into the hair fiber is said to decrease as the size or molecular weight of the dye molecule increases (see Non-Patent Document 1). There is a demand for color matching by combining a plurality of dissociable azo dyes having similar molecular weights.

JP 2004-107343 A JP 2006-182653 A Clarence R. Robbins, Chemical and Physical Behavior of Human Hair 4th Ed., Pp238-245, Springer-Verlag, 2002

  The purpose of the present invention is to contain a dissociable azo dye that is stable against alkaline agents and oxidizing agents and does not decompose during hair dyeing, has high dyeing power, and can firmly impart a vivid color to hair. It is to provide a hair dye composition having excellent fastness to light, washing, sweat, friction and heat and less fading with time, and a hair dyeing method using the same.

  The present inventors combined a dissociable azo dye (A) represented by the following general formula (1) and a dissociable azo dye (B) represented by the general formula (2) in a hair dye composition. It has been found that the above problems can be solved.

  That is, the present invention provides a hair dye composition containing the dissociable azo dye (A) represented by the following general formula (1) and the dissociable azo dye (B) represented by the general formula (2). To do.

[Wherein, Het represents a 5-membered heteroaromatic group represented by the general formula (H) which may be the same or different, and R ¹ and R ² may be the same or different hydrogen atom, chlorine atom , Methyl group, methoxy group or carbamoyl group. ]

[Wherein, X ¹ represents S or CH, X ² represents N or CH, X ³ represents N or C—CH ₃ , X ⁴ represents N or N—CH ₃ , One of X ² and X ³ is N and the other is not N. The broken line indicates that the entire ring has two double bonds. ]

  Furthermore, this invention provides the hair dyeing method which applies said hair dye composition to hair.

  The hair dye composition of the present invention is stable against an alkaline agent or an oxidizer, does not decompose during hair dyeing, has a high dyeing power, can firmly impart a bright color to hair, It has excellent fastness to washing, sweat, friction and heat, and there is little discoloration over time.

  The hair dye composition referred to in the present invention is not only a one-component composition but also a two-part agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, which are stored separately until just before use. In addition to the first composition and the second composition, in addition to the first composition and the second composition, a multi-part composition such as a three-part composition composed of a third composition containing an oxidizing aid is included. Refers to the entire composition mixed and actually applied to the hair.

(Dissociable azo dyes (A) and (B))
The dissociable azo dye (A) represented by the general formula (1) changes the hue by dissociating the proton of the imino group located at the 4-position of the naphthalene ring with respect to the azo group under the conditions used. Is given. In addition, the dissociable azo dye (B) represented by the general formula (2), under the conditions used, dissociates protons from the hydroxyl group at the para position of the benzene ring with respect to the azo group, changes the hue, and changes the desired color. Gives hue.

  In the general formulas (1) and (2), Het includes a heteroaromatic ring group represented by any one of the formulas (H1) to (H3).

  Specific examples of the dissociable azo dye (A) include compounds represented by the following formula (1-1), but are not limited thereto.

  Examples of the dissociable azo dye (B) include the dissociable azo dye (B-1) represented by the following general formula (2a) and the dissociable azo dye (B-2) represented by the general formula (2b). Can be mentioned.

[Wherein, Het represents the same meaning as described above, R ^1a and R ^2a represent the same or different hydrogen atom, methyl group, methoxy group or carbamoyl group, and R ^2b represents a chlorine atom or carbamoyl group. Show. However, when R ^1a and R ^2a in the general formula (2a) are a combination of a hydrogen atom and a carbamoyl group and R ^2b in the general formula (2b) is a carbamoyl group, the Het of the two compounds is not the same. ]

  Specific examples of the dissociable azo dye (B) include dissociative azo dyes (B-1), that is, the following formulas (2a-1) to (2a) corresponding to the compounds represented by the general formula (2a): -6) is a dissociative azo dye (B-2), that is, a compound represented by the general formula (2b), the following formulas (2b-1) to (2b-2) However, it is not limited to these examples.

  The dissociable azo dyes (A) and (B) can be used alone or in combination of two or more, and as the dissociable azo dye (B), a compound represented by the general formula (2a); It is preferable to use the compound represented by the general formula (2b) in combination from the viewpoint of securing a wide toning property.

As a combination of the dissociable azo dye (A) and the dissociable azo dye (B), the dissociable azo dye (A) is a heteroaromatic group in which Het is represented by the formula (H1) in the general formula (1). A dissociative azo dye (B) is a compound, wherein Het is a heteroaromatic group represented by the formula (H1) or (H3) in the general formula (2a), and R ^2a is a hydrogen atom or a methyl group And a compound in which Het is a heteroaromatic ring group represented by the formula (H2) in the general formula (2b) is preferable.

  The total content of the dissociable azo dyes (A) and (B) is preferably 0.0001 to 25% by mass in the total composition, more preferably 0.001 to 20% by mass, still more preferably 0.05 to 15% by mass, and more preferably 0.1 to 10% by mass is more preferable.

  Further, the mass ratio (A) :( B) of the dissociable azo dye (A) and the dissociable azo dye (B) is preferably 1: 1000 to 10,000: 1 from the viewpoint of securing a wide color-adjusting property. : 1000 to 1000: 1 is more preferable, and 1: 100 to 100: 1 is more preferable.

  When the dissociable azo dye (B-1) and the dissociable azo dye (B-2) are used in combination as the dissociable azo dye (B), their mass ratio (B-1) :( B- 2) is preferably from 1: 1000 to 1000: 1, more preferably from 1: 500 to 500: 1, and still more preferably from 1: 100 to 100: 1, from the viewpoint of ensuring a wide range of toning properties.

[Other dyes]
The hair dye composition of the present invention can be mixed with other direct dyes or oxidation dyes to change the color tone.

  As other direct dyes, known direct dyes such as acid dyes, basic dyes, nitro dyes, disperse dyes, and cationic dyes can be used. Examples of direct dyes include blue No. 1, purple No. 401, black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203, yellow No. 403 (1), acidic orange 3, 2- Nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitro-o-phenylenediamine, 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-nitro-p-phenylenediamine, dispersed purple 1, dispersed blue 1, dispersed black 9, basic blue 99, basic brown 16, basic brown 17, basic red 76, basic yellow 76, basic yellow 57 , Basic orange 31, basic red 51, and a methine-type cationic dye having a cyanine structure represented by the following formula.

  Also, for example, JP 2002-275040 A, JP 2003-107222 A, JP 2003-107223 A, JP 2003-113055 A, JP 2003-342139 A, JP 2004-107343 A, etc. Direct dyes described in JP-A-2004-155746 and JP-A-2006-182653 can also be added.

  When other direct dyes are used in combination, the total content of the dissociable azo dyes (A) and (B) and other direct dyes is preferably 0.0001 to 25% by mass, preferably 0.001 to 20% by mass in the total composition Is more preferable, 0.05 to 15% by mass is still more preferable, and 0.1 to 10% by mass is even more preferable.

  In the hair dye composition of the present invention, an oxidative dye can be used in combination with the dissociable azo dyes (A) and (B). Such a combination enables extremely clear and strong dyeing that cannot be obtained with an oxidation dye alone. As the oxidation dye, a known precursor and a known coupler which are usually used for an oxidation type hair dye are used.

  Examples of the precursor include paraphenylenediamine, toluene-2,5-diamine, orthochloroparaphenylenediamine, N-phenylparaphenylenediamine, N, N-bis (hydroxyethyl) paraphenylenediamine, and 3-methyl-4- Examples include aminophenol, 2-hydroxyethyl paraphenylenediamine, paraaminophenol, paramethylaminophenol, 4-amino-methcresol, orthoaminophenol, and salts thereof.

  Examples of couplers include resorcin, 2-methylresorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, metaphenylenediamine, metaaminophenol, 2,4-diaminophenoxyethanol, 2,6-diamino. Examples thereof include pyridine, 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine, and salts thereof.

  Two or more types of precursors and couplers may be used in combination, and their content is preferably 0.0005 to 20% by mass, more preferably 0.001 to 15% by mass, and more preferably 0.5 to 10% by mass in the total composition. Is more preferable.

  To the hair dye composition of the present invention, an auto-oxidation dye represented by indoles, indolines and the like can be further added.

  The total content of the dissociable azo dyes (A) and (B), other direct dyes, oxidation dyes and auto-oxidation dyes is preferably 0.001 to 25% by mass, more preferably 0.01 to 20% by mass in the total composition. 0.1 to 15% by mass is more preferable, and 0.5 to 10% by mass is more preferable.

[Alkaline agent]
When the hair dye composition of the present invention is a two-part or three-part type, the first agent contains an alkaline agent. Alkaline agents such as ammonia and salts thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and salts thereof; alkanediamines such as 1,3-propanediamine and the like Salts: carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.

  Of the above alkaline agents, ammonia, alkanolamines and salts thereof are preferred. As the ammonium salt, ammonium carbonate and ammonium hydrogen carbonate are preferable, and as the alkanolamine and its salt, monoethanolamine and its salt are preferable. Furthermore, the content of these is most preferably in the following range. The sum of the content (X) when ammonia and its salt in all compositions are converted as ammonia and the content (Y) when monoethanolamine and its salt are converted as monoethanolamine is sufficient. From the point of hair / bleaching effect, and from the point of reduction of hair damage and scalp stimulation, olfactory stimulation, it is preferably 0.05 to 15% by mass in the total composition, more preferably 0.1 to 10% by mass, More preferably, it is 0.2-5 mass%. The mass ratio of X / Y is preferably 0.01: 1 to 2: 1, more preferably 0.02: 1 to 1: 1, and further preferably 0.05: 1 to 0.5: 1. .

〔Oxidant〕
The dissociable azo dyes (A) and (B) are very stable against oxidants and can be applied to the hair after mixing with the oxidants. In other words, the hair dye composition of the present invention is of a two-component type comprising a first agent containing dissociable azo dyes (A) and (B) and a second agent containing an oxidizing agent. Can do. In this case, dyeing and decoloring are performed simultaneously, and a more vivid dyeing is obtained.

  Examples of the oxidizing agent include hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; perborates such as sodium perborate; percarbonates such as sodium percarbonate; sodium bromate; And bromates such as potassium bromate. Among these, hydrogen peroxide is preferable from the viewpoint of decolorization to hair and the stability and effectiveness of the oxidizing agent itself. In addition to hydrogen peroxide, other oxidizing agents can be used in combination as an oxidizing aid. Of these, it is preferable to use a combination of hydrogen peroxide and persulfate.

  When using an oxidizing agent, an oxidizing agent can be used individually or in combination of 2 or more types, The content is 0.5-30 mass% in the whole composition, Furthermore, 1-20 mass% is preferable. When hydrogen peroxide and persulfate are used in combination, the hydrogen peroxide content is 0.5-10% by mass in the total composition, and the persulfate content is 0.5-25% in the total composition. %, And the total content of both is preferably 1 to 30% by mass.

  When the hair dye composition of the present invention is a two-component type, the mixing ratio of the first agent containing the dissociable azo dyes (A) and (B) and the second agent containing the oxidizing agent is a volume ratio. And preferably in the range of 2: 1 to 1: 3.

[Conditioning ingredients]
The hair dye composition of the present invention can contain a conditioning component suitable for application to hair. Conditioning ingredients are polymers or oils that can be dissolved or dispersed in the hair dye composition and adhere to the hair when rinsed or diluted with water or shampoo.

  When using a conditioning component, the compounding quantity is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.1 to 10% by mass in the total composition.

  Suitable conditioning components for use in the hair dye composition of the present invention generally include cationic polymers, silicones, higher alcohols, and organic conditioning oils (eg, hydrocarbon oils, polyolefins, fatty acid esters). .

Cationic polymer The cationic polymer refers to a polymer having a cationic group or a group that can be ionized into a cationic group, and includes an amphoteric polymer that becomes cationic as a whole. That is, as the cationic polymer, those containing an amino group or an ammonium group in the side chain of the polymer chain or containing a diallyl quaternary ammonium salt as a structural unit, such as cationized cellulose, cationic starch, cationized guar gum, diallyl A quaternary ammonium salt polymer or copolymer, quaternized polyvinylpyrrolidone and the like can be mentioned. Among these, a polymer containing diallyl quaternary ammonium salt as a structural unit in terms of softness during shampooing, smoothness and ease of fingering, ease of packing during drying and moisturizing effect, and stability of the agent. Quaternized polyvinylpyrrolidone and cationized cellulose are preferable, and a diallyl quaternary ammonium salt polymer or copolymer and cationized cellulose are more preferable.

  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 / acrylic acid amide copolymer (polyquaternium-7, for example, Marquat 550; Nalco), and the like.

  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. (Above, IPS Japan 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 (above, Lion)), polymer JR- 125, same JR-400, same JR-30M, same LR-400, same LR-30M (above, Amerchol)), hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer (polyquaternium-4, for example, Cellcoat H-100, And L-200 (National Starch and Chemical Co., Ltd.)).

  Two or more cationic polymers may be used in combination. The effect of the cationic polymer increases as the content increases. However, when the content is too large, the stability is poor, and the viscosity of the agent alone or at the time of mixing is reduced. From these points and the point of improving touch, the content of the cationic polymer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.05 to 5% by mass in the total composition.

-Silicones It is preferable that the hair dye composition of this invention contains silicones in order to provide the outstanding usability. Examples of silicones include dimethylpolysiloxanes and modified silicones (for example, amino-modified silicone, fluorine-modified silicone, alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, and alkyl-modified silicone). Of these, polyether-modified silicones and amino-modified silicones are preferred.

  The dimethylpolysiloxane may be a cyclic or acyclic dimethylsiloxane polymer, for example, SH200 series, BY22-019, BY22-020, BY11-026, BY22-029, BY22-034, BY22-050A, BY22-055, BY22-060, BY22-083, FZ-4188 (above, Toray Dow Corning) KF-9008, KM-900 series, MK-15H, MK-88 (above, Shin-Etsu Chemical) Can be mentioned.

  The polyether-modified silicone may be any silicone having a polyoxyalkylene group, and examples of the group constituting the polyoxyalkylene group include an oxyethylene group and an oxypropylene group. More specifically, for example, KF-6015, KF-945A, KF-6005, KF-6009, KF-6013, KF-6019, KF-6029, KF-6017, KF-6043, KF-353A, KF- 354A, KF-355A (Shin-Etsu Chemical Co., Ltd.), FZ-2404, SS-2805, FZ-2411, FZ-2412, SH3771M, SH3772M, SH3773M, SH3775M, SH3749, SS-280X series, BY22-008M, BY11- 030, BY25-337 (above, Toray Dow Corning).

  The amino-modified silicone may be any silicone having an amino group or an ammonium group, for example, an amino-modified silicone oil in which all or part of the terminal hydroxyl groups are blocked with methyl groups or the like, or amodimethicone in which the terminals are not blocked. and so on. Preferred amino-modified silicones include those represented by the following general formula (S).

[In the formula, R ′ represents a hydroxyl group, a hydrogen atom or R ^X , R ^X represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, D represents R ^X , a group R ″ — (NHCH ₂ CH ₂ ) _m NH ₂ , a group OR ^X or a hydroxyl group, R ″ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, m represents a number of 0 to 3, and p and q are The number average is 10 or more and less than 20000, preferably 20 or more and less than 3000, more preferably 30 or more and less than 1000, and still more preferably 40 or more and less than 800. ]

  Specific examples of suitable commercially available amino-modified silicones include SF8452C, SS-3551 (above, Toray Dow Corning), KF-8004, KF-867S, KF-8015 (above, Shin-Etsu Chemical Co., Ltd.), etc. Examples thereof include amino-modified silicone oils and amodimethicone emulsions such as SM8704C, SM8904, BY22-079, FZ-4671, and FZ-4672 (above, Toray Dow Corning).

  The total content of these silicones in the hair dye composition of the present invention is preferably 0.02 to 40% by mass, more preferably 0.1 to 20% by mass in the total composition, from the viewpoint of sufficient effect and suppression of stickiness. 0.2 to 15% by mass is more preferable.

  When the hair dye composition of the present invention contains silicones and a cationic polymer, the mass ratio of the cationic polymer (active amount): silicones in the total composition is preferably 100: 1 to 1:50, 50 : 1-1: 10 is more preferable.

-Higher alcohol It is preferable that the hair dye composition of this invention contains a higher alcohol in any one or more of a 1st agent, a 2nd agent, and a 3rd agent from a viewpoint of touch improvement and stability. The inclusion of the higher alcohol has the effect of forming a structure with the surfactant to prevent separation of the hair dye composition and improving the feel during rinsing.

  As the higher alcohol, those having 8 to 22 carbon atoms are preferable, and those having 16 to 22 carbon atoms are more preferable. Specific examples include cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like, and mixtures thereof.

  Two or more types of higher alcohols may be used in combination, and the content thereof is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass in the total composition.

-Organic conditioning oil It is also preferable that the hair dye composition of this invention contains organic conditioning oil in order to provide the outstanding usability. The organic conditioning oil suitably used as a conditioning component is preferably a low viscosity, water insoluble liquid, selected from hydrocarbon oils having at least 10 carbon atoms, polyolefins, fatty acid esters and mixtures thereof. The viscosity of such an organic conditioning oil is preferably 1 to 200 mPa · s, more preferably 1 to 100 mPa · s, and further preferably 2 to 50 mPa · s, as measured at 40 ° C.

  Examples of hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), and these polymers and mixtures are also included. . The linear hydrocarbon oil preferably has 12 to 19 carbon atoms. The branched hydrocarbon oil contains a hydrocarbon polymer and preferably has more than 19 carbon atoms.

  The polyolefin is a liquid polyolefin, more preferably a liquid poly-α-olefin, and most preferably a hydrogenated liquid poly-α-olefin. The polyolefin used here is prepared by polymerizing an olefin monomer having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms.

  Examples of fatty acid esters include fatty acid esters having at least 10 carbon atoms. Examples of these fatty acid esters include esters having hydrocarbon chains derived from fatty acids and alcohols (eg, monoesters, polyhydric alcohol esters, di- and tricarboxylic acid esters). The hydrocarbon groups of these fatty acid esters may have other compatible functional groups such as amide groups and alkoxy groups as substituents, and may be covalently bonded to them. More specifically, an alkyl and alkenyl ester of a fatty acid having an aliphatic chain having 10 to 22 carbon atoms, an aliphatic alcohol carvone having an aliphatic chain derived from an alkyl and / or alkenyl alcohol having 10 to 22 carbon atoms. Acid esters and mixtures thereof are preferably used. Specific examples of such preferred fatty acid esters include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl. Examples include stearate, dihexadecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetylpropionate and dioleyl adipate.

[Surfactant]
The hair dye composition of the present invention can contain a surfactant. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Trimethylammonium and behenyltrimethylammonium chloride are preferred.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is more preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Anionic 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 carboxylates, Examples include α-sulfo fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Counterions of the anionic residues of these surfactants include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; alkanol groups having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  The surfactants can be used alone or in combination of two or more, and the content thereof is not limited, but for example, 0.05 to 20% by mass in the total composition is preferable, 0.1 to 18% by mass is more preferable, and 0.5 to 15 More preferred is mass%.

[Medium]
In the hair dye composition of the present invention, water and, if necessary, an organic solvent are used as a medium. Examples of organic solvents include lower aliphatic alcohols such as ethanol, propanol and isopropanol; aromatic alcohols such as benzyl alcohol and benzyloxyethanol; polyols such as propylene glycol, 1,3-butanediol, diethylene glycol and glycerin; Cellosolves such as cellosolve and butylcellosolve; and carbitols such as ethylcarbitol and butylcarbitol.

  Although content of an organic solvent is not restrict | limited, For example, 0.05-20 mass% in the whole composition is preferable, 0.1-15 mass% is more preferable, 0.5-10 mass% is still more preferable.

[Other ingredients]
In addition to the above components, other components that are normally used as cosmetic raw materials can be added to the hair dye composition of the present invention. Such optional ingredients include animal and vegetable oils and fats, higher fatty acids, natural or synthetic polymers, ethers, proteins, hydrolyzed proteins, amino acids, preservatives, chelating agents, stabilizers, antioxidants, plant properties Examples include extracts, herbal extracts, vitamins, fragrances, and UV absorbers.

[PH]
The dissociable azo dyes (A) and (B) are excellent in storage stability in a wide range of pH 2 to 14 used in ordinary hair dyes, and can be used at any pH within the above range. From the viewpoint of hair dyeing / bleaching effect and skin irritation, the pH of the whole composition at the time of use (mixing) is preferably 8 to 14 (25 ° C.), more preferably 8 to 13. Moreover, when the hair dye composition of this invention is a multi-drug type, the pH of the 1st agent before mixing has preferable pH 8-14, and the pH of the 2nd agent before mixing has preferable 2-5. As the pH adjuster, in addition to the above alkaline agents, inorganic acids such as hydrochloric acid and phosphoric acid, organic acids such as citric acid, glycolic acid and lactic acid, hydrochlorides such as monoethanolamine hydrochloride, monopotassium dihydrogen phosphate, phosphorus Phosphate such as disodium acid monohydrogen can be used.

(Drug type)
The hair dye composition of the present invention comprises: a first agent containing a dissociative azo dye (A) and (B) and an alkali agent and a second agent containing an oxidizing agent such as hydrogen peroxide. In order to improve decoloring power, the third agent is a combination of powdered oxidizers composed of granules such as persulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.) as the third agent. Preferably provided as a formula.

  The one-part formula can be, for example, liquid, emulsion, cream, gel, paste, mousse, etc., and can also be in aerosol form. In the case of the two-part type (or three-part type), the dosage form of the first agent and the second agent can be, for example, liquid, emulsion, cream, gel, paste, mousse, etc. It can also be in the form. It is desirable that the first agent and the second agent (the third agent in the case of the three-agent type) are mixed and applied to the hair so that the viscosity becomes difficult to spill, and the hair dye composition of the present invention The viscosity of all compositions measured with a B-type rotational viscometer with a helical stand at 25 ° C. (B8R type viscometer, Tokimec) in either one agent type, two agent type, or three agent type is 2000 to 10 It is preferably 10,000 mPa · s. Here, the viscosity is a value obtained by rotating the rotor T-C at 10 rpm for 1 minute.

[Hair dyeing method]
For the hair dyeing treatment using the composition of the present invention, for example, the first agent and the second agent of the composition of the present invention (or the third agent in the case of the three-component type) are mixed immediately before use, and then the hair. Applying to the above, after leaving for a predetermined time within 1 hour, it may be washed away and dried. The application temperature to the hair is 15 to 45 ° C., and the application time is preferably 3 to 50 minutes, more preferably 5 to 40 minutes, and even more preferably 10 to 30 minutes. In this case, first, the hair dye is lightly washed with water, then washed with a shampoo containing an anionic surfactant, and then washed with water, the cationic polymer flows out moderately, and the silicones remain in the hair moderately. And a good conditioning effect. As the shampoo, a general aqueous shampoo containing about 5 to 20% by mass of an anionic surfactant such as sodium laureth-1 sulfate, sodium laureth-2 sulfate, or sodium laureth-3 sulfate is suitable.

  The dissociable azo dyes (A) and (B) used in the hair dye composition of the present invention were prepared from so-called coupler components such as phenols and aminoaryl compounds or aminoheteroaromatic compounds (so-called diazo components). It can be synthesized by a known azo coupling reaction by azo coupling with a diazonium salt. For example, the dissociable azo dye (1-1) can be synthesized as follows.

  The dissociable azo dye (B) used in the hair dye composition of the present invention can be synthesized, for example, by a combination of a diazo component and a coupler component as shown in Table 1.

Examples 1-7
A two-component hair dye first agent shown in Table 2 and a second agent A shown in Table 3 are prepared, and the first agent: second agent: purified water is mixed at a mass ratio of 4: 7: 1. An agent composition is obtained. 1 g of each hair dye composition is applied to 1 g of goat wool at 30 ° C., left for 30 minutes, washed with water and shampooed, and dried.

Examples 9-11
The foam type one-component hair dye shown in Table 4 is prepared. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 12-15
A creamy two-component hair dye first agent shown in Table 5 and a common second agent shown in Table 6 are prepared, and the first agent: common second agent is mixed at a mass ratio of 1: 1 to obtain a hair dye. It is set as a composition. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 16-19
A two-component hair dye first agent shown in Table 7 is prepared, and the first agent: common second agent is mixed at a mass ratio of 1: 1 to obtain a hair dye composition. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 20-23
A two-component hair dye first agent and a booster solution shown in Table 8 are prepared, and the first agent: booster solution: common second agent is mixed at a mass ratio of 1: 0.1: 1 to obtain a hair dye composition. . Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Examples 24-26
According to a conventional method, the creamy three-component hair dye first agent and third agent shown in Table 9 are prepared, and the first agent: common second agent: third agent is mixed at a mass ratio of 1: 1: 0.3. A hair dye composition is obtained. Apply equal amounts of each of these hair dye compositions to 1 g of human hair bundles containing 10% gray hair, leave it for 30 minutes, wash with water and shampoo, and dry. Good dyed hair is obtained.

Claims (5)

Dissociable azo dye represented by formula (1-1) (A) , and formulas (2a-1), (2a-2), (2a-3), (2a-4), (2a-5), Hair dye composition containing at least one dissociable azo dye (B) represented by any formula selected from the group consisting of (2a-6), (2b-1) and (2b-2) .

The hair dye composition according to claim 1, wherein the total content of the dissociable azo dyes (A) and (B) is 0.0001 to 25% by mass in the total composition. The hair dye composition according to claim 1 or 2, wherein a mass ratio (A) :( B) of the dissociable azo dye (A) and the dissociable azo dye (B) is from 1: 1000 to 10,000: 1. A one-component composition, a two-component composition comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, or a third containing an oxidizing aid in addition to the first and second agents. The hair dye composition according to any one of claims 1 to 3, which is a three-part composition comprising a combination of agents.   The method of dyeing hair by applying the hair dye composition in any one of Claims 1-4 to hair.