JP5415930B2 - Hair dye composition - Google Patents

Description

  The present invention relates to a hair dye composition.

  In hair dyes, the most common technique is to dye hair by oxidative coupling reaction of an oxidative dye intermediate (precursor and coupler) with an oxidant in the presence of an alkaline agent. However, it has been known that an oxidizing agent is liable to cause hair damage, and as a result, a feeling of touching is worse when touched. In particular, this feeling of exacerbation is noticeable in thick hair peculiar to Asians including Japanese.

Therefore, the following method has been proposed as a technique for achieving both improvement in feeling deterioration caused by damage by an oxidizing agent and dyeability.
(1) A method for reducing surface friction by adsorbing silicone or the like added to a hair dye on the hair surface (Patent Document 1)
(2) A method using a cationic surfactant having a long-chain alkyl group (Patent Document 2)
(3) A method using a quaternary ammonium derivative peptide having a long-chain alkyl group (Patent Document 3)

  All of these techniques reduce the frictional resistance between the hairs by adsorbing the conditioning component on the surface of the hair, and give a soft feel when touching the hair. However, these components are easily removed from the hair by washing with a shampoo after hair dyeing treatment, so that the desired effect is difficult to be exerted, especially for thick and hard Asian human hair. It was not satisfactory enough.

  On the other hand, an aromatic sulfone compound and glycylglycine or glycylglycylglycine are used for the purpose of improving the dyeing (or decoloring) power of damaged hair or naturally thin and soft hair, and giving the hair firmness, elasticity and volume. It has been proposed to use them together (Patent Document 4).

JP-A-4-59721 JP 2002-193773 A JP-A-5-2171040 JP 2009-108052 A

  The present invention softens by reducing the elasticity of each hair, and can improve the deterioration of touch caused by hair dyeing behavior even on thick and hard Asian human hair. It is an object of the present invention to provide a hair dye composition and a hair dyeing method that do not deteriorate hair color.

  This inventor discovered that the said subject can be solved by using together an aromatic sulfone compound and a carnitine in a hair dye composition.

  The present invention provides a hair dye composition containing the following components (a), (b) and (c) and having a pH of 2 to 12 at 25 ° C.

  (a) Aromatic sulfone compound represented by general formula (1) 0.1 to 20% by mass

[Wherein, Rs are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, or two adjacent Rs together form a saturated or unsaturated divalent hydrocarbon group. X represents an oxygen atom or a nitrogen atom, Y represents a hydrogen atom when X is an oxygen atom, and Y represents a carbonyl group bonded to X when X is a nitrogen atom. Z ⁺ represents a monovalent cation. ]
(b) Carnitine or a salt thereof 0.01 to 5% by mass as the amount of carnitine
(c) Oxidizing agent 0.1-10% by mass

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

  According to the present invention, the elasticity of each hair can be reduced and softened, and even the thick and hard Asian human hair can be improved against the feeling of deterioration caused by the hair dyeing behavior, There is no deterioration in dyeability.

  The hair dye composition of the present invention is a concept including both “one-drug type” and “multi-drug type”. Here, in the present invention, “one-component type” means a dosage form in which the hair dye composition is composed of a single agent containing an oxidizing agent. On the other hand, “multi-drug type” means a dosage form in which the hair dye composition is composed of two or more agents. For example, a first agent containing an alkaline agent and a second agent containing an oxidizing agent. A three-component hair dye composition comprising a first agent containing an alkaline agent, a second agent containing an oxidizing agent, and a third agent containing an oxidizing aid. Agent composition.

  In the present invention, when any of the above-mentioned dosage forms is combined with an independent agent (hereinafter referred to as “booster agent”) that does not correspond to any of the above-mentioned respective agents, it is also included in the dosage form. To do. That is, a hair dye composition obtained by further combining a one-pack hair dye composition with a booster agent is a one-pack hair dye composition, and contains a first agent containing an alkaline agent and an oxidizing agent. The hair dye composition in which the booster agent is further combined with the second agent is a two-component hair dye composition, and also includes a first agent containing an alkaline agent, a second agent containing an oxidizing agent, and an oxidation agent. The hair dye composition in which the booster agent is further combined with the third agent containing the auxiliary agent is a three-component hair dye composition.

Such booster agents are, for example,
i) A one-component hair dye composition or a multi-component hair dye composition is applied to the hair in advance before applying the mixed solution of the multi-component hair dye composition to the hair. Or a hair dyeing pretreatment agent that is mixed with the liquid mixture and is not washed away,
ii) A one-component hair dye composition or a mixed solution of a multi-component hair dye composition is applied to the hair, and then applied to the hair without being washed away. A hair dyeing post-treatment agent to be mixed with the composition or the mixed solution,
iii) It may be in the form of an additive or the like that is additionally mixed when preparing a mixed solution of a one-component hair dye composition or a multi-component hair dye composition. That is, the agent mixed with the one-component hair dye composition or the above mixed solution at the time of applying the hair is included in the “booster agent”, and mixed with the one agent type hair dye composition or the above mixed solution at the time of applying the hair. Agents that are not included are not included in “booster agents”.

  In the present invention, the term “hair dye” is a concept including a hair bleaching agent not containing a dye in addition to a hair dyeing agent containing a dye. “Dyeing” means not only dyeing hair with a hair dye containing a dye, but also decoloring and dyeing hair, and decolorizing hair with a decolorizing agent containing no dye. In the present invention, the “total composition” refers to the entire composition used for the hair dyeing treatment until it is washed away, specifically, a mixture after mixing each agent constituting the hair dye composition, or It means a mixture of the mixture and a booster agent.

<Component (a): Aromatic sulfone compound>
The aromatic sulfone compound of component (a) is a compound represented by the general formula (1).

[Wherein, Rs are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, or two adjacent Rs together form a saturated or unsaturated divalent hydrocarbon group. X represents an oxygen atom or a nitrogen atom, Y represents a hydrogen atom when X is an oxygen atom, and Y represents a carbonyl group bonded to X when X is a nitrogen atom. Z ⁺ represents a monovalent cation. ]

  Examples of the monovalent hydrocarbon group in R include an alkyl group, an aryl group, and an aralkyl group, an alkyl group having 1 to 8 (preferably 1 to 4) carbon atoms, and 6 to 10 (preferably 6 to 6) carbon atoms. The aryl group or aralkyl group of 8) is preferred, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a phenyl group, and a benzyl group.

  Examples of the saturated or unsaturated divalent hydrocarbon group formed by combining two adjacent Rs together include an alkylene group and an alkylidene group, and an alkylene having 2 to 6 (preferably 2 to 4) carbon atoms. Group or alkylidene group is preferable, for example, ethylene group, ethylidene group, vinylene group, trimethylene group, isopropylidene group, 1-propenylene group, tetramethylene group, 2-methyltrimethylene group, 1-methyltrimethylene group, 2- Examples include propenylene group, 2-butenylene group, buta-1,3-diene-1,4-diyl and the like. Specifically, when two adjacent R's together form buta-1,3-diene-1,4-diyl, tetramethylene group, 1-propenylene group, 2-propenylene group, trimethylene group, As the aromatic sulfone compound, naphthalene sulfonic acid, tetrahydronaphthalene sulfonic acid, indene sulfonic acid, and indane sulfonic acid are formed, respectively. Among them, naphthalene sulfonic acid is preferable.

  When X is an oxygen atom, Y represents a hydrogen atom, but R is preferably an alkyl group or two adjacent Rs together form an alkylidene group. On the other hand, when X is a nitrogen atom, Y represents a carbonyl group bonded to X, but R is preferably a hydrogen atom.

The aromatic sulfone compound of component (a) can have any monovalent cation Z ⁺ as a counter cation, where Z ⁺ can be a proton, an alkali metal ion (for example, sodium ion, potassium ion), ammonium Ions are preferred.

  More preferred examples of the aromatic sulfone compound of component (a) include benzenesulfonic acid or a salt thereof, paratoluenesulfonic acid or a salt thereof, 2,4-dimethylbenzenesulfonic acid or a salt thereof, and 2,5-dimethylbenzenesulfone. Examples thereof include acid or a salt thereof, naphthalenesulfonic acid or a salt thereof, saccharin or a salt thereof. Of these, p-toluenesulfonic acid or a salt thereof, 2,4-dimethylbenzenesulfonic acid or a salt thereof, naphthalenesulfonic acid or a salt thereof, or saccharin or a salt thereof is more preferable. These can be used alone or in combination of two or more.

  Component (a) may be blended in any one or more of the first agent, the second agent and the third agent, or may be blended in a booster agent.

  The content of the component (a) is 0.1 to 20% by mass in the total composition, preferably 0.5 to 10% by mass, from the viewpoint of the feel received from the composition during the treatment and the storage stability of the composition. -7 mass% is more preferable.

<Component (b): Carnitine or a salt thereof>
The component (b) is a component generally called carnitine, but may be any of L-carnitine, D-carnitine, and DL-carnitine. Moreover, the salt of an inorganic acid or an organic acid may be sufficient. Examples of the salt include carnitine hydrochloride and carnitine tartrate.

  Component (b) may be blended in any one or more of the first agent, the second agent and the third agent, or may be blended in a booster agent.

  The content of the component (b) is 0.01 to 5% by mass in the total composition, preferably 0.05 to 3% by mass, preferably 0.1 to 2% by mass as the amount of carnitine from the point of touch received from the composition during the treatment. % Is more preferable.

  In addition, the mass ratio (a) / (b) of the component (a) and the component (b) is preferably 1 to 20 from the viewpoint of suppressing color change and more reliably imparting flexibility to the hair. 2-15 are more preferable, and 2-12 are still more preferable.

  Further, the total content of the component (a) and the component (b) is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, and still more preferably 3 to 8% by mass, from the same viewpoint as described above.

<Component (c): Oxidizing agent>
The hair dye composition of the present invention contains an oxidizing agent as component (c), but in the case of a multi-component hair dye composition, the oxidizing agent is contained in the second agent. Examples of the oxidizing agent include hydrogen peroxide, hydrogen peroxide, or urea peroxide that is a generator of oxygen, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, potassium percarbonate, and the like. Hydrogen oxide is more preferred.

  An oxidizing agent can be used individually or in combination of 2 or more types. The content of the oxidizing agent is preferably 0.1 to 12% by mass, more preferably 0.5 to 9% by mass in the total composition, from the viewpoint of sufficient hair dyeing / bleaching effect and reduction of hair damage and scalp irritation. -6 mass% is still more preferable.

<Alkaline agent>
The hair dye composition of the present invention can contain an alkaline agent. In the case of a multi-component hair dye composition, the alkaline agent is contained in the first 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 these, ammonia, alkanolamines and salts thereof are more preferable.

  Two or more of these alkali agents may be used in combination. In addition, the content of the alkaline agent is preferably 0.05 to 15% by mass, preferably 0.1 to 10% by mass in the total composition from the viewpoint of sufficient dyeability and depigmentation, and reduction of hair damage and scalp irritation. More preferably, 0.2-5 mass% is still more preferable.

<Oxidizing aid>
The multi-component hair dye composition of the present invention can contain an oxidation aid in the third agent. As the oxidation aid, an oxidizing agent other than the above-described oxidizing agents can be used, and examples thereof include persulfate. Specific examples include ammonium persulfate, potassium persulfate, sodium persulfate, and the like, and these are preferably used in the form of a powder such as a granulated product.

  The oxidation aids can be used alone or in combination of two or more. The content of the oxidation aid is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and 3 to 25% by mass in the total composition from the viewpoint of sufficient decolorization effect and reduction of hair damage and scalp irritation. Is more preferable.

<Dye>
The hair dye composition of the present invention can contain a direct dye or an oxidation dye intermediate. In the multi-component hair dye composition, the first agent can contain a direct dye or an oxidation dye intermediate.

Examples of the direct dye include acid dyes, nitro dyes, disperse dyes, basic dyes, and direct dyes described in JP-A-2003-342139.
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.
Nitro dyes include 2-nitroparaphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3-nitro Phenol, 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-nitroparaphenylenediamine and the like.
Examples of the disperse dye include disperse purple 1, disperse blue 1, and disperse black 9.
Examples of the basic dye include basic blue 99, basic brown 16, basic brown 17, basic red 76, basic red 51, basic yellow 57, basic yellow 87, basic orange 31 and the like.

  Two or more direct dyes may be used in combination, or may be used in combination with an oxidation dye intermediate. The content of the direct dye is preferably 0.001 to 5% by mass and more preferably 0.01 to 3% by mass in the total composition.

  As the oxidation dye intermediate, known precursors and couplers that are usually used in hair dyes can be 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-hydroxyethylparaphenylenediamine, paraaminophenol, paramethylaminophenol, 4-aminometacresol, 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 -Diaminopyridine, 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine and salts thereof.

  Two or more precursors and couplers may be used in combination, and the content thereof is preferably 0.01 to 5% by mass, and more preferably 0.1 to 4% by mass in the total composition.

<Other ingredients>
-Surfactant The hair dye composition of this invention can contain 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, for example, a mono long chain alkyl quaternary ammonium salt is preferable, and specifically, cetrimonium chloride, steartrimonium chloride, behentrimonium chloride, stearalkonium chloride, benzalkonium chloride and the like. And steartrimonium chloride and behentrimonium chloride are more preferable.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hardened castor Examples thereof include oil, polyoxyethylene sorbitan fatty acid ester series, polyoxyethylene sorbite fatty acid ester series, alkyl saccharide series, alkylamine oxide series, and alkylamidoamine oxide series. Of these, polyoxyalkylene alkyl ethers and polyoxyethylene hydrogenated castor oil are preferred, and polyoxyethylene alkyl (C12-14) ethers are more preferred.

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

  Anionic surfactants include, for example, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, Examples include alkyl or alkenyl ether carboxylate series, α-sulfone fatty acid salt series, N-acyl amino acid series, phosphate mono- or diester series, and sulfosuccinate series. Examples of alkyl ether sulfates include polyoxyethylene alkyl ether sulfates. Examples of the counter ion 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; Examples include alkanolamines having 1 to 3 alkanol groups (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  The content of the surfactant is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass, based on the emulsifying performance.

-Cationic polymer The hair dye composition of this invention can contain a 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, examples of the cationic polymer include water-soluble ones 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. Derivatives, cationic starch, cationized guar gum derivatives, polymers or copolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives, and the like. Among these, diallyl quaternary ammonium salt is included as a structural unit in terms of softness during shampooing, smoothness and ease of fingering, ease of consolidation during drying and moisturizing effect, and stability of the agent. Polymers, quaternized polyvinylpyrrolidone derivatives, and cationized cellulose derivatives are preferred, and polymers or copolymers of diallyl quaternary ammonium salts and cationized cellulose derivatives are more preferred.

  Specific examples of the cationic polymer include dimethyldiallylammonium chloride polymer (Polyquaternium-6, such as Marquat 100; Nalco Japan), dimethyldiallylammonium chloride / acrylic acid copolymer (Polyquaternium-22, such as Marquat 280, Marquat 295, etc. Nalco Japan), dimethyldiallylammonium chloride / acrylamide copolymer (polyquaternium-7, such as Marquat 550; Nalco Japan), quaternized polyvinylpyrrolidone derivatives (Guffcoat 734, Guffcoat 755, Guffcoat 755N; ASP Japan) ), Cationized cellulose derivatives (polyquaternium-10, such as Leogard G, GP; Lion, polymer JR-125, polymer JR-30M, polymer LR-400, polymer LR-30M; above, Dow Chemical Japan ), And the like.

  Two or more of these cationic polymers may be used in combination. The content of the cationic polymer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.05 to 5% by mass in the total composition from the viewpoints of the touch improvement effect and the stability of the composition. preferable.

-Silicone It is preferable that the hair dye composition of this invention contains silicone in order to provide the outstanding usability.
Examples of silicone include polysiloxane, modified silicone (for example, amino-modified silicone, fluorine-modified silicone, alcohol-modified silicone, polyether-modified silicone, epoxy-modified silicone, alkyl-modified silicone, etc.), and cyclic polysiloxane. Siloxane, polyether-modified silicone, and amino-modified silicone are preferred. For example, BY11-026, BY22-19, FZ-3125, SH200-1,000,000cs (Toray Dow Corning), TSF451-100MA (Momentive Performance Materials (Japan)) [above polysiloxane], TSF4440 (Momentive Performance Materials Japan), KF-6005, KF-6011 (Shin-Etsu Chemical Co., Ltd.) [above polyether-modified silicone], SF8451C, SF8452C, SF8457C, SM8704C , SM8904 (Toray Dow Corning And KF-867 (Shin-Etsu Chemical Co., Ltd.) [above amino-modified silicone].

  The content of the silicone is preferably 0.02 to 40% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 15% by mass in the total composition from the viewpoint of sufficient effects and suppression of stickiness.

Higher alcohol The hair dye composition of the present invention preferably contains a higher alcohol from the viewpoint of improving the feel of the hair and the stability of the composition. Thereby, while forming a structure with a surfactant to prevent separation of the hair dye composition, it is possible to improve 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 cetanol, stearyl alcohol, behenyl alcohol, and the like, and mixtures thereof.
Two or more 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.

-Medium Water and, if necessary, an organic solvent are used as a medium in the hair dye composition of the present invention.
Examples of organic solvents include lower alkanols such as ethanol and 2-propanol; aromatic alcohols such as benzyl alcohol and benzyloxyethanol; polyols such as propylene glycol, 1,3-butanediol, diethylene glycol and glycerin; ethyl cellosolve and butyl cellosolve Cellosolve; carbitols such as ethyl carbitol and butyl carbitol.

Others 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. Such optional components include hydrocarbons, animal and vegetable oils and fats, higher fatty acids, natural or synthetic polymer ethers, preservatives, chelating agents, stabilizers, antioxidants, plant extracts, herbal extracts, vitamins, A fragrance | flavor, a ultraviolet absorber, etc. are mentioned.

<PH, dosage form, viscosity>
The hair dye composition of the present invention has a pH of 2 to 12 at 25 ° C. at the time of use (mixing), but the pH is 3 to 11 in terms of hair dyeing / bleaching effect and skin irritation. 8 to 11 are more preferable.
In addition to the alkali agents described above, hydroxides such as sodium hydroxide and potassium hydroxide; inorganic acids such as hydrochloric acid and phosphoric acid; organic acids such as citric acid, glycolic acid and lactic acid; monoethanolamine hydrochloride And the like; and phosphates such as monopotassium dihydrogen phosphate and disodium monohydrogen phosphate can be used. The pH of the first agent before mixing is preferably 8 to 12, and the pH of the second agent before mixing is preferably 2 to 5.

  The dosage form of each agent constituting the hair dye composition of the present invention can be, for example, liquid, emulsion, cream, gel, paste, mousse or aerosol.

  In addition, the hair dye composition of the present invention preferably has a viscosity that does not easily spill when the components constituting the composition are mixed and applied to the hair. For example, a B-type rotational viscosity with a helical stand at 25 ° C. It is preferable that the viscosity of all compositions measured with a meter (B8R viscometer, TOKIMEC) is 2000 to 100,000 mPa · s. Here, the viscosity is a value after rotating at 10 rpm for 1 minute using the rotor T-C.

<Hair treatment method>
The hair dye composition of the present invention is applied to hair, for example, by mixing each agent (including the booster agent described above) constituting the hair dye composition at the time of use. After applying to hair, a method of leaving it for a predetermined time, washing and drying is adopted. The application temperature to the hair is preferably 15 to 45 ° C, and the application time is preferably 1 to 60 minutes. In this case, the hair dye composition may be lightly washed with water, then washed with a shampoo containing an anionic surfactant, and then washed with water. In the case where the hair dye composition contains a cationic polymer and silicone, the cationic polymer flows out moderately and silicone remains in the hair moderately, so that a good conditioning effect can be imparted. As the shampoo, a general aqueous shampoo containing about 5 to 20% by mass of an anionic surfactant such as sodium lauryl sulfate, sodium laureth-1 sulfate, sodium laureth-2 sulfate, or sodium laureth-3 sulfate is suitable.

Examples 1-2 and Comparative Examples 1-3 (two-component hair dye composition)
First agents X _{1 to} X ₂ and x _{1 to} x ₃ shown in Table 1 were prepared. And these first agent, Table 2 shows the second agent Y ₁ and a mass ratio of 9: 1 mixture, respectively Examples 1-2 was a hair dye composition of Comparative Example 1-3.

[Bend elastic modulus ratio]
Using the hair dye compositions of Examples 1 and 2 and Comparative Examples 1 to 3, the ratio of flexural modulus was measured according to the following procedure.

[1] Measurement of flexural modulus (before treatment)
Ten Japanese hairs that had not been chemically treated were cut to a length of 6 cm and immersed in ion-exchanged water for 3 hours. Next, 10 pieces were linearly shaped and then left to dry for 24 hours in a constant temperature and humidity room at a room temperature of 20 ° C. and a relative humidity of 65%. After shaping, one of 10 pieces was taken out in the same constant temperature and humidity room, and the bending elastic modulus of one hair was measured using a bending tester FB2-SH manufactured by Kato Tech Co., Ltd. Similarly, the flexural modulus was measured for the remaining nine and the average value D of ten was determined.

[2] Hair dyeing process Ten hairs whose D was measured in the above [1] were fixed to a 1 g Japanese hair bundle prepared separately. 1 g of the hair dye composition of each Example / Comparative Example was applied to 1 g of a hair bundle having 10 hairs fixed thereto. After leaving at 30 ° C. for 20 minutes, it was rinsed with about 40 ° C. water, washed with an evaluation shampoo shown in Table 3, and washed with water.

[3] Measurement of flexural modulus (after processing)
Ten hairs for which D was measured in [1] were taken out from the hair bundle subjected to the above treatment [2]. Next, 10 pieces were bundled into a bundle and formed into a linear shape, and then allowed to dry for 24 hours in a constant temperature and humidity room at a room temperature of 20 ° C. and a relative humidity of 65%. After shaping, one of 10 pieces was taken out in the same constant temperature and humidity room, and the bending elastic modulus of one hair was measured using a bending tester FB2-SH manufactured by Kato Tech Co., Ltd. Similarly, the flexural modulus was measured for the remaining nine pieces, and the average value D ′ of ten pieces was obtained.

[4] Ratio calculation of flexural modulus Using the values of flexural modulus obtained in [1] and [3] above, the ratio of flexural modulus was calculated from the following formula. The results are shown in Table 4. The smaller the value of D ′ / D, the softer the hair after treatment.

                  (Bend elastic modulus ratio) = D '/ D

  From the results in Table 4, it can be seen that the hair dye composition of the present invention reduces the bending elasticity of each hair.

Example 3, Comparative Example 4 (Two-pack hair dye composition (booster booster combined use))
Booster agents Z ₀ and Z ₁ shown in Table 5, the first agent X ₃ shown in Table 6, and the second agent Y ₂ shown in Table 7 were prepared.

  The hair dye compositions of Example 3 and Comparative Example 4 were prepared at the blending ratios shown in Table 8, and the flexural moduli D and D ′ were respectively determined according to the procedure described in [Ratio of flexural modulus]. The ratio of bending elastic modulus = D ′ / D was determined. Table 8 also shows the results.

(Dyeability evaluation)
The hue of 1 g of a goat hair bundle manufactured by Beaulux Co., Ltd. was measured with a CIE color system using a color difference meter (color difference meter CR-400 manufactured by Konica Minolta Sensing) (L ^* ₁ , a ^* _1). , b ^* ₁ ). 4 g of the hair dye composition of Example 3 was applied to 4 sets of the hair bundles (4 g in total). After standing at 30 ° C. for 20 minutes, it was rinsed with about 40 ° C. water, washed with the evaluation shampoo shown in Table 3, and washed with water. Next, using the above color difference meter, the color of the hair bundle after the hair dyeing treatment was again measured for each 1 g of the hair bundle using the CIE color system (L ^* ₂ , a ^* ₂ , b ^* ₂ ). ΔE ^* was calculated for each 1 g of hair bundles according to the following formula, and the average value for four sets was obtained. Higher ΔE ^* means better dyeability. ΔE ^* was similarly determined for Comparative Example 4. The results of dyeability evaluation are also shown in Table 8.

[Feel evaluation]
A hair bundle of 5 g was prepared using Japanese hair that was not chemically treated with a length of 20 cm, and 5 g of the hair dye composition of Example 3 was applied. After standing at 30 ° C. for 20 minutes, it was rinsed with about 40 ° C. water, washed with the evaluation shampoo shown in Table 3, and washed with water. Next, towel drying was performed, the upper end of the hair bundle was fixed, and the hair was naturally dried. Regarding the softness of the hair after drying the hair, five professional panelists conducted a sensory test according to the following criteria. Similarly, Comparative Example 4 was evaluated for feel. The results are ranked according to the average score of five people and are shown in Table 8.

<Softness of hair>
4: Very soft 3: Soft 2: Can't say either 1: There is a tension 0: There is a very tension

<Evaluation>
◎: Average evaluation score is 3.5 or more ○: Average evaluation score is 2.5 or more and less than 3.5 △: Average evaluation score is 1.5 or more and less than 2.5 ×: Average evaluation score is less than 1.5

  The hair dye composition of the present invention is one that reduces the elasticity of each hair and softens without deteriorating the dyeability, and improves the feeling of touch associated with dyeing.

Formulation Example 1
After mixing 1 part by mass of the second agent Y ₂ shown in Table 7 with 1 part by mass of the first agent X ₄ shown in Table 9, it can be applied to the hair.

Claims (5)

A hair dye composition containing the following components (a), (b) and (c), and having a pH of 2 to 12 at 25 ° C.
(a) Aromatic sulfone compound represented by general formula (1) 0.1 to 20% by mass

[Wherein, Rs are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, or two adjacent Rs together form a saturated or unsaturated divalent hydrocarbon group. X represents an oxygen atom or a nitrogen atom, Y represents a hydrogen atom when X is an oxygen atom, and Y represents a carbonyl group bonded to X when X is a nitrogen atom. Z ⁺ represents a monovalent cation. ]
(b) Carnitine or a salt thereof 0.01 to 5% by mass as the amount of carnitine
(c) Oxidizing agent 0.1-10% by mass   The hair dye composition according to claim 1, wherein the mass ratio (a) / (b) of the components (a) and (b) is 1 to 20.   The hair dye composition according to claim 1 or 2, wherein the total content of components (a) and (b) is 1 to 10% by mass.   The component (a) is at least one selected from p-toluenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, naphthalenesulfonic acid, saccharin, and salts thereof. Hair dye composition.   A hair dyeing method wherein the hair dye composition according to any one of claims 1 to 4 is applied to hair and left for 1 to 60 minutes, and then washed away.