JP6403443B2 - Hair dye composition - Google Patents

Description

  The present invention relates to a hair dye composition and a hair dyeing method using the same.

  Hair dyes are classified according to the dye used or whether they have a melanin decolorization effect. As a typical one, a two-component permanent hair dye comprising a first agent containing an alkaline agent, an oxidative dye and, if necessary, a direct dye such as a nitro dye, and a second agent containing an oxidant; There are one-part semi-permanent hair dyes containing organic acids or alkali agents and direct dyes such as acid dyes, basic dyes, and nitro dyes.

  In Patent Document 1, an azo dye containing a dissociable proton is proposed as a direct dye suitable for use in hair dye applications, and is said to exhibit hair dyeing properties in an anionic state in which the dissociable proton is dissociated.

Japanese Patent Laid-Open No. 2003-342139

  On the other hand, it is known that a specific cationic polymer is contained in the hair dye composition to suppress dripping during hair dyeing and at the same time give a good texture to the hair. When a specific cationic polymer technique is applied to a hair dye composition containing an azo dye, there is a problem that a salt of the azo dye and the cationic polymer is formed, and the hair dyeing property is remarkably lowered.

  Therefore, it is conceivable to increase the amount of dye used in order to recover the reduced hair dyeing property, but increasing the amount of dye may adversely affect the stability of the formulation, so there is a limit to increasing the amount of dye. there were.

  Therefore, in the present invention, the cationic polymer and the dissociable azo dye are stably contained without forming a salt, excellent in hair dyeing operability, good hair dyeing properties, and hair after hair dyeing. The present invention relates to a hair dye composition that can give an excellent feel to the hair.

  The present inventors use a specific cationic polymer in combination with a dissociable azo dye having a specific structure and coexist with an alkali metal salt, so that the dissociable azo dye and the specific cationic polymer can be obtained even if they are alkaline. Contained stably without salt formation, less dripping, excellent hair dyeing operability, vivid hair dyeing effect, and excellent feel to hair after hair dyeing (especially excellent feel when rinsing) And found that there is an effect of imparting.

The present invention provides a hair dye composition containing the following components (A), (B) and (C) and having a pH (25 ° C.) of 7.5 or more and 12 or less.
(A): One or more azo dyes selected from the group consisting of (A-1), (A-2) and (A-3) below

(B): a cationic polymer having a nitrogen content of 0.3 to 9.0% by mass of 0.01 to 10% by mass
(C): at least one alkali metal salt of an acid selected from the group consisting of hydrochloric acid, carbonic acid and sulfuric acid 0.1% by mass to 8% by mass

  Furthermore, the present invention provides a hair dyeing method in which the above hair dye composition is applied to hair, left for 1 to 60 minutes, and then washed away.

  The hair dye composition of the present invention contains a dissociable azo dye having a specific structure and a specific cationic polymer stably without forming a salt, has little dripping, has excellent hair dyeing operability, and is vividly dyed. Along with the hair effect, it is possible to impart an excellent feel to the hair (particularly, an excellent feel during rinsing).

[Component (A): Azo dye]
The hair dye composition of the present invention comprises, as component (A), one or more azo dyes selected from the group consisting of the following (A-1), (A-2) and (A-3) Containing.

  The pKa of the azo dyes (A-1), (A-2), and (A-3) are 6.0, 6.0, and 7.5, respectively. Therefore, in the hair dye composition of the present invention having a pH (25 ° C.) of 7.5 to 12, almost 80% or more of these azo dyes exist in an anionic state in which protons are dissociated. When protons are dissociated, (A-1) is red, (A-2) is blue, and (A-3) is yellow.

  The total content of the azo dye in the total composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and further preferably 0.1% by mass, from the viewpoint of the stability of the formulation. % Or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2.5% by mass or less, still more preferably 1.5% by mass or less, and further preferably 1% by mass or less. The hair dye composition of the present invention may be used in combination with a dye other than the azo dyes (A-1), (A-2) and (A-3). However, the total content of the azo dyes (A-1), (A-2) and (A-3) is 1% by mass or more in the total dyes from the viewpoint of not affecting the dyeability of the component (A). It is preferably 100% by mass or less, more preferably 5% by mass or more and 100% by mass or less, further 10% by mass or more and 100% by mass or less, and further preferably 20% by mass or more and 100% by mass or less.

[Oxidative dye]
When the hair dye composition of the present invention is a two-part or three-part type, the first agent may contain an oxidative dye in addition to the azo dye. As an oxidation dye suitable for the hair dye composition of the present invention, known precursors and couplers that are usually used in hair dyes can be used.

  Examples of the precursor include paraphenylenediamine, toluene-2,5-diamine, 2-chloroparaphenylenediamine, paraaminophenol, paramethylaminophenol, orthoaminophenol, 2,4-diaminophenol, and N-phenylparaphenylenediamine. These salts are mentioned.

  Examples of couplers include metaphenylenediamine, 2,4-diaminophenoxyethanol, metaaminophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, resorcin, 1- Examples thereof include naphthol, 1,5-dihydroxynaphthalene, hydroquinone and their salts.

  You may use a precursor and a coupler individually or in combination of 2 or more types, respectively. The total content in the total composition is preferably a content that does not affect the dyeability of the azo dye, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5 mass% or less, More preferably, 3 mass%, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.

[Direct dyes other than component (A)]
The hair dye composition of the present invention may further contain a direct dye other than the azo dyes (A-1), (A-2), and (A-3). When the hair dye composition of the present invention is a two-component hair dye, a direct dye other than the azo dyes (A-1), (A-2), and (A-3) in the first agent Can further be contained. As this direct dye, known acid dyes, basic dyes, disperse dyes and the like that can be used in hair dyes can be used.

  Examples of the acid dye include Blue No. 1, Purple No. 401, Black No. 401, Orange No. 205, Red No. 227, Red No. 106, Yellow No. 203, and Acid Orange 3. Examples of the basic dye include basic blue 99, basic brown 16, basic brown 17, basic red 76, basic yellow 57, and the like.

  Examples of direct dyes other than acid dyes and basic dyes include 2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, and 4-nitro. -o-phenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol, N, N-bis (2-hydroxyethyl) -2-nitro-p-phenylenediamine, dispersed purple 1 , Dispersion blue 1, dispersion black 9, HC blue 2, HC orange 1, HC red 1, HC red 3, HC yellow 2, HC yellow 4, HC yellow 5, and the like.

  Direct dyes other than these azo dyes (A-1), (A-2), and (A-3) can be used alone or in combination of two or more, and the content in the total composition is , Preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass or less, More preferably, it is 0.5 mass% or less.

[Component (B): Cationic polymer]
The hair dye composition of the present invention contains 0.01 to 10% by mass of a cationic polymer having a nitrogen content of 0.3 to 9.0% by mass. Here, the cationic polymer refers to a water-soluble 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.

  The nitrogen content of component (B) is measured by neutralization titration as follows. An arbitrary sample amount (0.5 to 10 g) of component (B) is dissolved in about 10 times the amount of a mixed solution of isopropyl alcohol and toluene (1: 1 [volume ratio]). Tetrabromophenolphthalein ethyl ester potassium is added as an indicator, and neutralization titration is performed with an aqueous perchloric acid solution. The content of nitrogen atom in 1 g of component (B) is calculated from the sample amount collected, the normality of the aqueous perchloric acid solution and the consumption.

  The nitrogen content of these cationic polymers is preferably 0.8% by mass or more, more preferably 1.4% by mass or more, still more preferably 2.4% by mass or more, from the viewpoint of suppressing dripping and improving the feel during agent rinsing. More preferably, it is 3.0 mass% or more, More preferably, it is 4.0 mass% or more, More preferably, it is 5.0 mass% or more, Preferably it is 8.8 mass% or less.

  Examples of the cationic polymer used in the present invention include cationic derivatives such as cationized cellulose derivatives, cationized guar gums, quaternized polyvinylpyrrolidone derivatives, diallyl quaternized ammonium salt polymer derivatives, and the like. For example, hydroxyethylcellulose / dimethyldiallylammonium chloride copolymer, hydroxyethylcellulose hydroxypropyltrimethylammonium chloride, cationized vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer, homopolymer of dimethyldiallylammonium chloride, dimethyldiallylammonium chloride / acrylamide Copolymer, dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylic / Acrylamide polymers and the like.

  More specifically, dimethyldiallylammonium chloride polymer (polyquaternium-6; for example, Marquat 100 (nitrogen content 8.7% by mass, Nippon Lubrizol)), dimethyldiallylammonium chloride / acrylic acid copolymer (polyquaternium-22; for example, Marquat 280 (nitrogen content 7.0% by mass, Nihon Lubrizol), Marquat 295 (nitrogen content 8.3% by mass, Nihon Lubrizol)), dimethyldiallylammonium chloride / acrylamide copolymer (polyquaternium-7; for example, Marquat 550 (nitrogen) Content 4.5% by mass, Nippon Lubrizol Co.)), dimethyldiallylammonium chloride / acrylic acid / acrylamide polymer (Polyquaternium-39; for example, Marquat 3331PR (nitrogen content 3.8% by mass, Nihon Lubrizol)), vinylpyrrolidone / N, N- Methylaminoethyl methacrylic acid copolymer diethyl sulfate solution (polyquaternium-11; for example, Guffcut 734 (nitrogen content 0.3 to 0.4 mass%, IS Japan), Guffcut 755N (nitrogen content 0.4 to 0.6 mass%, ISPE Japan))), O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-10; for example, Ucare polymer JR-400 (nitrogen content 1.5-2.2 mass%, Dow Chemical Company), Poise C-60H (nitrogen content 2.0 mass%, Kao), Poise C-150L (nitrogen content 1.0-1.2 mass%, Kao), Cachisero M-80 (nitrogen content 1.5 mass%, Kao)) It is done. Among these, dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride / acrylic acid copolymer, and dimethyldiallylammonium chloride / acrylamide copolymer are preferable from the viewpoint of suppressing dripping and improving the feel when rinsing the agent. .

  Two or more of these cationic polymers may be used in combination, and the content in the total composition is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably from the viewpoint of conditioning effect and hair dyeing operability. 0.5 mass% or more, more preferably 1 mass% or more, and 10 mass% or less, preferably 6 mass% or less, more preferably 5 mass% or less, still more preferably 4 mass% or less, still more preferably 3 mass%. % Or less.

[Component (C): Alkali metal salt of hydrochloric acid, carbonic acid or sulfuric acid]
The hair dye composition of the present invention is selected from the group consisting of hydrochloric acid, carbonic acid, and sulfuric acid as the component (C) from the viewpoint of providing stability of the formulation, vivid hair dyeing effect, and a good feel during use. At least one alkali metal salt of an acid is contained in an amount of 0.1% by mass to 8 % by mass.

  The alkali metal salt of hydrochloric acid, carbonic acid or sulfuric acid of component (C) is a compound in which part or all of the hydrogen atoms of hydrochloric acid, carbonic acid or sulfuric acid are substituted with an alkali metal. A potassium salt and a sodium salt are preferable from the viewpoint of touch when the hair is dried after the hair dyeing treatment. Specific examples include sodium chloride, potassium chloride, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium sulfate, and potassium sulfate.

  These components (C) can be used in combination of two or more, the content in the total composition is a viewpoint of stably containing the components (A) and (B) without forming a hardly soluble salt From 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.6% by mass or more, and from the viewpoint of remaining on the hair after hair dyeing, 8% by mass. % Or less, preferably 7% by mass or less, more preferably 6% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and further preferably 2% by mass or less.

  The mass ratio (B) / [(A) + (C)] of the component (B) to the sum of the components (A) and (C) in the total composition is from the viewpoint of improving dyeability and agent stability. Preferably it is 0.01 or more, more preferably 0.05 or more, preferably 0.08 or more, more preferably 0.2 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably Is 1 or less, more preferably 0.9 or less.

(Component (D): Anionic surfactant or nonionic surfactant)
The hair dye composition of the present invention may further contain an anionic surfactant or a nonionic surfactant as component (D).

  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 acids, phosphoric acid mono- or diesters, and sulfosuccinic acid esters. Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate. Counter ions of the anionic group of these anionic surfactants include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamines having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  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 saccharides, alkylamine oxides, and alkylamidoamine oxides. Of these, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, and alkyl saccharide are preferred, and polyoxyethylene alkyl (12-14) ether and alkyl polyglucoside are more preferred.

  Of these anionic surfactants and nonionic surfactants, alkyl sulfates, polyoxyalkylene alkyl sulfates, fatty acid salts, alkyl ether carboxylates, alkyl glyceryl ethers and alkyl polyglucosides are preferred.

  Two or more components (D) can be used in combination, and the content of component (D) in the total composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of foaming properties of the formulation. Moreover, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[Surfactants other than component (D)]
The hair dye composition of the present invention may contain a surfactant other than component (D). As the other surfactant, either a cationic surfactant or an amphoteric surfactant can be used.

  As the cationic surfactant, monoalkyltrimethylammonium chloride, dialkyldimethylammonium chloride and monoalkyltrimethylammonium bromide are preferable from the viewpoint of imparting an excellent feel to the hair after dyeing, and stearyltrimethylammonium chloride is particularly preferable. (Steartrimonium chloride), cetyltrimethylammonium chloride (cetrimonium chloride), and lauryltrimethylammonium chloride (lauryltrimonium chloride) are more preferable, and it is also preferable to mix two or more.

  Examples of amphoteric surfactants include imidazoline, carbobetaine, amide betaine, sulfobetaine, hydroxysulfobetaine, amide sulfobetaine, and the like, and betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are more preferable. Fatty acid amidopropyl betaine is more preferred.

  Two or more surfactants other than component (D) can be used in combination, and the content in the total composition is preferably 0.1% by mass or more, more preferably 0.2%, from the viewpoint of good touch and emulsification performance. It is at least mass%, more preferably at least 0.5 mass%, preferably at most 20 mass%, more preferably at most 10 mass%, still more preferably at most 5 mass%.

[Component (E): Alkaline agent]
The hair dye composition of the present invention may further contain an alkali agent. When the hair dye composition of the present invention is a two-part or three-part type, the alkaline agent is contained in the first agent. Alkaline agents include ammonia and salts thereof, sodium hydroxide, potassium hydroxide, monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol and other alkanolamines and salts thereof, 1,3- Examples include alkanediamines such as propanediamine and salts thereof, and carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and guanidine carbonate.

  Two or more alkali agents may be used in combination, and the content in the total composition is 0.01% by mass or more, further 0.05% by mass or more, and further 0.1% by mass or more from the viewpoint of sufficient hair dyeing effect. Furthermore, 0.2% by mass or more is preferable, and from the viewpoint of reducing hair damage and scalp irritation, 20% by mass or less, further 10% by mass or less, further 5% by mass or less, and further 4% by mass or less are preferable. .

(PH adjuster)
The hair dye composition of the present invention may further contain a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid and phosphoric acid, and organic acids such as citric acid, glycolic acid, and lactic acid, in addition to the above alkaline agents.

〔Oxidant〕
When the hair dye composition of the present invention is a two-part or three-part type, the second agent contains an oxidizing agent. In this case, dyeing and decoloring are performed simultaneously, and a more vivid dyeing is obtained. The azo dye used in the present invention is extremely stable against an oxidizing agent.

  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 the oxidizing agent is used, the oxidizing agent can be used alone or in combination of two or more, and the content in the whole composition is 0.1% by mass or more, further 0.5% by mass or more from the viewpoint of sufficient hair dyeing effect. Further, it is preferably 1.0% by mass or more, and from the viewpoint of reducing hair damage and scalp irritation, it is preferably 12.0% by mass or less, more preferably 9.0% by mass or less, and further preferably 6.0% by mass or less.

  When hydrogen peroxide and persulfate are used in combination, the hydrogen peroxide content is 0.5% by mass or more and 10% by mass or less in the total composition, and the persulfate content is in the total composition. It is preferably 0.5% by mass or more and 25% by mass or less, and the total content of both is preferably 1% by mass or more and 30% by mass or less.

[Conditioning ingredients]
The hair dye composition of the present invention may contain a conditioning component suitable for application to hair other than the cationic polymer of component (B). The conditioning component is a polymer or oil that can be dissolved or dispersed in the hair dye composition, and adheres to the hair when the hair dye composition is washed away or diluted with water or shampoo.

  Suitable conditioning components for use in the hair dye composition of the present invention include silicone (eg, silicone oil, cationic silicone, silicone gum, silicone resin), organic conditioning oil (eg, hydrocarbon oil, polyolefin, fatty acid ester). ), Aliphatic amides, polyalkylene glycols and the like.

  These conditioning components can be used alone or in combination of two or more, and the content in the total composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.5%. It is at least 20% by mass, preferably at most 20% by mass, more preferably at most 15% by mass, still more preferably at most 5% by mass.

〔Organic solvent〕
The hair dye composition of the present invention may contain an organic solvent. Examples of organic solvents include lower alkanols such as ethanol, 1-propanol and 2-propanol, aromatic alcohols such as benzyl alcohol, 2-benzyloxyethanol and phenoxyethanol, propylene glycol, 1,3-butanediol, diethylene glycol and glycerin. Polyols, ether alcohols such as ethoxyethanol, ethoxydiglycol and methoxyethanol, N-alkylpyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; alkylene carbonates such as propylene carbonate; lactones such as γ-valerolactone and γ-caprolactone Is mentioned.

  These organic solvents can be used alone or in combination of two or more, and the content in the total composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2%. It is not less than 35% by mass, preferably not more than 35% by mass, more preferably not more than 30% by mass, and further preferably 25% by mass.

<Medium>
In the hair dye composition of the present invention, water is used as a medium. The content of water in the hair dye composition is preferably 10% by mass or more, more preferably 20% by mass or more, further 30% by mass or more, further 40% by mass or more, and further preferably 50% by mass or more. It is preferably not more than mass%, more preferably not more than 90 mass%, and further preferably not more than 85 mass%.

[Other optional ingredients]
In addition to the above components, other components that are usually used as cosmetic raw materials can be added to the hair dye composition of the present invention.

  Examples of the purpose of blending such optional ingredients include viscosity adjustment, pearlization, antiseptic, metal sequestration, stabilization, antioxidant, ultraviolet absorption, moisture retention, product coloring, fragrance, and the like. Examples thereof include animal and vegetable oils and fats, higher fatty acids, protein hydrolysates, protein derivatives, amino acids, plant extracts, vitamins, pigments, and fragrances.

[Drug type]
The hair dye composition of the present invention can be used as various one-part, two-part, or three-part hair dyes. The one-pack hair dye composition comprises a single agent containing component (A). The two-component hair dye composition preferably comprises a first agent containing component (A) and an alkaline agent, and a second agent containing hydrogen peroxide. The three-component hair dye composition comprises a first agent containing a direct dye and an alkali agent other than an oxidation dye and / or component (A), a second agent containing hydrogen peroxide, and component (A). It is preferably composed of a third agent containing, or a first agent containing a component (A) and an alkaline agent, a second agent containing hydrogen peroxide, and a third agent containing other components. . As the third agent containing the above-mentioned other components, a powdery oxidizer made of a granulated material such as persulfate (ammonium persulfate, potassium persulfate, sodium persulfate, etc.) may be used to improve decolorization power. preferable.
In the present invention, the “total composition” refers to the entire composition at the time of use of the hair dyeing treatment. In the above-mentioned two-component hair dye, after mixing the first agent and the second agent In the case of a three-part hair dye, it means a mixture after mixing the first agent, the second agent and the third agent.

  The hair dye composition of the present invention can be used, for example, in the form of liquid, emulsion, cream, gel, paste, mousse, etc., and can also be in the form of an aerosol. It is desirable to adjust the viscosity of the entire composition in these cases so that it does not easily drip when applied to the hair. The viscosity (25 ° C.) of this whole composition was rotated at 10 rpm for 1 minute using a rotor TC by a B-type rotational viscometer with a helical stand (model; digital viscometer TVB-10, Toki Sangyo Co., Ltd.). The subsequent measured value is preferably 2,000 to 200,000 mPa · s, more preferably 4,000 to 150,000 mPa · s, still more preferably 6,000 to 100,000 mPa · s, and further preferably 8,000 to 80,000 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

  The hair dye composition of the present invention can also be used in the form of foam by being discharged from a non-aerosol foamer container when applied to hair, or by shaking in a cup and foaming. In this case, the viscosity of the entire composition before foaming is also preferably adjusted so that it does not easily drip when applied to the hair as a foam. The viscosity (25 ° C.) of all the compositions was rotated for 1 minute at 60 rpm using a rotor No. 1 with a B-type rotational viscometer (model: Digital Viscometer TV-10, Toki Sangyo Co., Ltd.). The measured value (however, when the viscosity exceeds 160 mPa · s, the measured value after rotating for 1 minute at 12 rpm) is preferably 1 to 800 mPa · s, more preferably 1 to 600 mPa · s, still more preferably 1 to 500 mPa · s, more preferably 1 to 300 mPa · s. In addition, in the case of a two-part type or a three-part type, the measurement shall be made after 3 minutes have elapsed since the mixing of each agent.

[PH]
The pH (25 ° C.) of the hair dye composition of the present invention is 7.5 or more at the time of use (during mixing in the case of two-part or three-part type) from the viewpoint of good hair dyeing effect and suppression of skin irritation. Preferably it is 8 or more, more preferably 8.5 or more, still more preferably 9 or more, and 12 or less, preferably 11.5 or less, more preferably 11 or less. When the hair dye composition of the present invention is a two-component hair dye, the pH of the first agent (25 ° C.) is 8 or more and 12 or less, and the pH of the second agent (25 ° C.) is 2 or more and 5 or less. Is preferred. In the present specification, the pH of the hair dye composition is a value measured at room temperature (25 ° C.) using a pH meter F-22 manufactured by Horiba, Ltd.

[Method for producing hair dye composition]
When the hair dye composition of the present invention is a one-pack type, from the viewpoint of the stability of the hair dye composition, after mixing component (B) and component (C), the resulting mixture and component (A) It is preferable to prepare by mixing the components (A) and (C), and then mixing the resulting mixture and the component (B). Further, when the hair dye composition of the present invention is a two-part or three-part type and contains all of the components (A) to (C) in the first agent, the first agent is also a hair dye. From the viewpoint of the stability of the agent composition, after mixing component (B) and component (C), the resulting mixture and component (A) are mixed, or component (A) and component (C) are mixed. After mixing, it is preferable to prepare by mixing the resulting mixture and component (B).
[Hair dyeing method]
For hair dyeing treatment using the hair dye composition of the present invention, for example, the hair dye composition of the present invention (first agent and second agent in the case of two agents, first in the case of three agents). After mixing the agent, the second agent, and the third agent immediately before use), the mixture is applied to the hair, left standing for a predetermined time, rinsed and dried. The hair dye composition of the present invention is applied in an amount of 0.1 to 10 times the hair mass, the application temperature to the hair is 15 to 45 ° C., the application time is 1 to 60 minutes, and further 3 to 45 minutes. Furthermore, 5 to 30 minutes are preferable.

  With respect to the embodiments described above, preferred aspects of the present invention will be further disclosed below.

<1> A hair dye composition comprising the following components (A), (B) and (C), and having a pH (25 ° C.) of 7.5 or more and 12 or less when used.
(A): One or more azo dyes selected from the group consisting of (A-1), (A-2) and (A-3) below

(B): a cationic polymer having a nitrogen content of 0.3 to 9.0% by mass of 0.01 to 10% by mass
(C): at least one alkali metal salt of an acid selected from the group consisting of hydrochloric acid, carbonic acid and sulfuric acid 0.1% by mass to 8% by mass

<2> The total content of component (A) in the total composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The dye according to <1>, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2.5% by mass or less, further preferably 1.5% by mass or less, and further preferably 1% by mass or less. Hair composition.

<3> Component (B) is preferably dimethyldiallylammonium chloride polymer, dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylamide copolymer, dimethyldiallylammonium chloride / acrylic acid / acrylamide polymer , Vinylpyrrolidone / N, N-dimethylaminoethyl methacrylate copolymer diethyl sulfate solution, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride, and hydroxyethylcellulose / dimethyldiallylammonium chloride The hair dye composition according to <1> or <2>, which is one or more selected from the group consisting of polymers.

<4> The nitrogen content of the component (B) is preferably 0.8% by mass or more, more preferably 1.4% by mass or more, further preferably 2.4% by mass or more, further preferably 3.0% by mass or more, and further preferably 4.0% by mass. As described above, the hair dye composition according to any one of <1> to <3>, which is more preferably 5.0% by mass or more, and preferably 8.8% by mass or less.

<5> The content of component (B) in the entire composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 6% by mass or less. The hair dye composition according to any one of <1> to <4>, more preferably 5% by mass or less, further preferably 4% by mass or less, and further preferably 3% by mass or less.

<6> The component (C) is preferably one or two selected from the group consisting of sodium chloride, potassium chloride, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium sulfate, and potassium sulfate The hair dye composition according to any one of <1> to <5>, which is described above.

<7> The content of component (C) in the total composition is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.6% by mass or more, and preferably 7% by mass or less. The dye according to any one of <1> to <6>, more preferably 6% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less. Hair composition.

<8> The mass ratio (B) / [(A) + (C)] of component (B) to the sum of component (A) and component (C) in the total composition is preferably 0.01 or more, more preferably 0.05 or more, preferably 0.08 or more, more preferably 0.2 or more, and preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less, still more preferably 0.9. The hair dye composition according to any one of <1> to <7>, which is the following.

<9> Preferably, the hair dye composition as described in any one of <1>-<8> which contains an anionic surfactant or a nonionic surfactant further as a component (D).

<10> The anionic surfactant of component (D) is alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl Or it is 1 type (s) or 2 or more types selected from the group which consists of alkenyl ether carboxylate, alpha-sulfo fatty acid salt, N-acyl amino acid, phosphoric acid mono- or diester, and sulfosuccinic acid ester, <9> Hair dye composition.

<11> The nonionic surfactant of component (D) is polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor The dye according to <9>, which is one or more selected from the group consisting of oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, alkyl saccharide, alkyl amine oxide, and alkyl amido amine oxide. Hair composition.

<12> Component (D) is one or more selected from the group consisting of alkyl sulfates, polyoxyalkylene alkyl sulfates, fatty acid salts, alkyl ether carboxylates, alkyl glyceryl ethers and alkyl polyglucosides The hair dye composition according to <9>.

<13> The content of the component (D) in the total composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and preferably 20% by mass or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, The hair dye composition as described in any one of <9>-<12>.

<14> Preferably, the hair dye composition according to any one of <1> to <13>, further containing an alkali agent as the component (E).

<15> The content of the component (E) in the total composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and preferably The hair dye composition according to <14>, wherein is 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 4% by mass or less.

<16> The hair dye composition according to any one of <1> to <15>, wherein the hair dye composition is a two-part or three-part type, and preferably contains an oxidizing agent in the second part.

<17> The content of the oxidizing agent in the total composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and preferably 12.0% by mass or less, more preferably Is 9.0 mass% or less, more preferably 6.0 mass% or less, The hair dye composition as described in <16>.

<18> In use, the pH at 25 ° C. is preferably 8 or more, more preferably 8.5 or more, still more preferably 9 or more, and preferably 11.5 or less, more preferably 11 or less, <1> Hair dye composition as described in any one of-<17>.

<19> A hair dyeing method in which the hair dye composition according to any one of <1> to <18> is applied to hair, left standing for 1 to 60 minutes, and then washed away.

Examples 1-5 and Comparative Examples 1-2
A hair dye composition (one-component hair dye) having the composition shown in Table 1 was prepared by the following method. About the obtained hair dye composition, the following methods evaluated dripping, the feel at the time of agent rinsing, dyeability, and agent stability. These results are also shown in Table 1.
[Method for preparing hair dye composition]
After mixing ammonium chloride and component (C) in water and confirming that they were dissolved, component (B) was added and stirred for a certain period of time. Subsequently, the component (D) component was added and the liquid mixture 1 was prepared. Separately, a mixed solution 2 in which ammonia and the component (A-2) were dissolved in water was prepared. And the liquid mixture 2 was mix | blended with the liquid mixture 1, and the hair dye composition was obtained by stirring for a fixed time.

[Drip evaluation]
20 g of the hair dye composition was weighed into a 200 mL oval cylindrical plastic bottle, the cap was closed, and the mixture was foamed by shaking 100 times up and down. After 10 g of foam was transferred to a 200 mL beaker and allowed to stand for 5 minutes, the waste liquid accumulated at the bottom of the beaker was taken out with a dropper, and its mass was measured. The smaller the amount of waste liquid, the less dripping of the hair dye.

[Feel when rinsing]
A hair bundle having a width of 5 cm, a length of 23 cm, and a weight of 8 g was prepared using Western hair. Apply the hair dye composition to the hair bundle at a bath ratio (agent: hair) = 1: 1, leave it at 30 ° C. for 20 minutes, and then comb the fingering property when rinsing in water at about 40 ° C. It was measured with a force measuring machine. The Coming Force measuring machine hangs the hair bundle on a hook connected to the load cell and holds the hair bundle in a state where it is sandwiched using a Denman brush (Denman brush Denman brush D-3 (total length 204mm, number of rows 7)). This is a method to read the force detected by the load cell at the time of coming and to evaluate the fingering quality quantitatively (see J. Soc. Cosmet. Chem., 37, 111-124 (May / June 1986)) . The average value of the force detected by the load cell when the hair bundle was combed 10 times was defined as the coming force measurement value. It shows that it is excellent in the feel at the time of agent rinsing, so that a coming force (g) is small.

[Dyeability]
Apply the hair dye composition to 1g of Chinese white hair at a bath ratio (agent: hair) = 1: 1, leave it at 30 ° C for 20 minutes, rinse with water at about 40 ° C, and use a commercial shampoo. Washed and washed with water. Next, after applying a commercial hair rinse, it was rinsed with water at about 40 ° C., wiped with a towel, and dried with a dryer.
The color of the resulting hair bundle immediately after dyeing is measured with a CIE color system (L ^* , a ^* , b ^* ) using a color difference meter (manufactured by Konica Minolta Sensing Co., Ltd., color difference meter CR-400), The difference from the color before dyeing was determined by the following formula and was defined as dyeability ΔE ^* . The larger ΔE ^{*, the} better the dyeability.

[In the formula, L ^* ₀ , a ^* ₀ and b ^* ₀ represent the values of L ^* , a ^* and b ^* of the hair bundle before dyeing, respectively, L ^* ₁ , a ^* ₁ and b ^* ₁ are The values of L ^* , a ^* and b ^* immediately after staining are shown, respectively. ]

[Agent stability]
Evaluation of the stability of the hair dye composition was confirmed by visual observation according to the following criteria immediately after mixing the first agent and the second agent.
3: There is no precipitate and it is transparent 2: There is no precipitate but it is cloudy 1: There is a precipitate

  As shown in Table 1, while the hair dye compositions of Examples 1 to 5 are excellent in all of the dripping, feel during dye rinsing, dyeability, and agent stability, Comparative Example 1 Compared with Examples 1-5, it was inferior in the point of the touch at the time of dripping and agent rinse, and Comparative Example 2 was inferior in the point of dyeability and agent stability compared with Examples 1-5.

Examples 6 to 10 and Comparative Examples 3 to 4
A first agent and a second agent of a hair dye composition (two-component hair dye) having the composition shown in Table 2 were prepared by the following method. Using the hair dye composition in which the first agent and the second agent shown in Table 2 are mixed at a ratio of 1: 1, evaluation of dripping, feel during agent rinsing, dyeability, and agent stability are performed as described above. Went. The evaluation results are also shown in Table 2.
[Method for preparing first agent]
After mixing ammonium chloride and component (C) in water and confirming that they were dissolved, component (B) was added and stirred for a certain period of time. Subsequently, the component (D) was added and the liquid mixture 1 was prepared. Separately, a mixed solution 2 in which ammonia and the component (A) were dissolved in water was prepared. And the liquid mixture 2 was mix | blended with the liquid mixture 1, and the 1st agent was obtained by stirring for a fixed time.
[Method for preparing second agent]
Hydrogen peroxide and etidronic acid were mixed in water, and the second agent was obtained by stirring for a certain time.

  As shown in Table 2, while the hair dye compositions of Examples 6 to 10 are excellent in all of the dripping, feel during dye rinsing, dyeability, and agent stability, Comparative Example 3 It was inferior in terms of dripping and feel when rinsing the agent as compared with Examples 6 to 10, and Comparative Example 4 was inferior in terms of dyeability and agent stability as compared with Examples 6 to 10.

Example 11 and Comparative Example 5
A hair dye composition (one-component hair dye) having the composition shown in Table 3 was prepared by the following method. About the obtained hair dye composition, the touch at the time of dripping, agent rinse, dyeing property, and agent stability was evaluated similarly to the above. The evaluation results are also shown in Table 3.
[Method for preparing hair dye composition]
Isostearyl glyceryl and component (C) were blended in water, and after confirming that they were dissolved, component (B) was added and stirred for a certain period of time. Subsequently, the component (D) was added and the liquid mixture 1 was prepared. Separately, a mixed solution 2 in which monoethanolamine and components (A-1) to (A-3) were dissolved in water was prepared. And the liquid mixture 2 was mix | blended with the liquid mixture 1, and the hair dye composition was obtained by stirring for a fixed time.

  As shown in Table 3, the hair dye composition of Example 11 is excellent in dripping, feel at the time of agent rinsing, and dyeability, whereas Comparative Example 5 is an agent rinsing compared to Example 11. It was inferior in the feeling of time, dyeability, and agent stability.

Examples 12-16
A hair dye composition (one-component hair dye) having the composition shown in Table 4 was prepared by the following method. About the obtained hair dye composition, dyeing property and the presence or absence of the precipitation at the time of a mixing | blending were evaluated. The evaluation results are also shown in Table 4.
[Method for preparing hair dye composition]
After confirming that ammonium chloride and component (C) were blended in water and dissolved, component (B) was added and stirred for a certain period of time. Subsequently, the component (D) was added and the liquid mixture 1 was prepared. Separately, a mixed solution 2 in which ammonia and the component (A) were dissolved in water was prepared. And the liquid mixture 2 was mix | blended with the liquid mixture 1, and the hair dye composition was obtained by stirring for a fixed time.

Claims (7)

A hair dye composition comprising the following components (A), (B) and (C), and having a pH (25 ° C.) of 7.5 or more and 12 or less.
(A): One or more azo dyes selected from the group consisting of (A-1), (A-2) and (A-3) below

(B): Cationic polymer having a nitrogen content of 0.3 to 9.0% by mass 0.01 to 10% by mass
(C): at least one alkali metal salt of an acid selected from the group consisting of hydrochloric acid, carbonic acid and sulfuric acid 0.1% by mass to 8% by mass   The hair dye composition according to claim 1, further comprising an anionic surfactant or a nonionic surfactant as component (D).   The component (D) is one or more selected from the group consisting of alkyl sulfates, polyoxyalkylene alkyl sulfates, fatty acid salts, alkyl ether carboxylates, alkyl glyceryl ethers and alkyl polyglucosides. 2. A hair dye composition according to 2.   The hair dye composition according to claim 2 or 3, wherein the content of component (D) is 0.1% by mass or more and 20% by mass or less based on the total composition.   Furthermore, the hair dye composition as described in any one of Claims 1-4 which contains 0.01 mass% or more and 20 mass% or less of an alkaline agent in a whole composition as a component (E).   The mass ratio (B) / [(A) + (C)] of the component (B) to the sum of the components (A) and (C) in the total composition is 0.01 or more and 6 or less. The hair dye composition according to any one of 5.   A hair dyeing method in which the hair dye composition according to any one of claims 1 to 6 is applied to hair, left standing for 1 to 60 minutes, and then washed away.