JP6045325B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic.

  In order to dye white hair, it is common to use a hair dye such as a two-component hair color, a one-component hair manicure, etc. The location is limited due to necessity and consideration of surrounding stains, the treatment method is complicated, unnaturalness immediately after dyeing due to abrupt changes in hair color and color steps with the growing white hair There was a problem.

  On the other hand, by covering the hair surface with melanin polymer by hair care behavior such as daily styling, it can easily make gray hair inconspicuous, and as a hair cosmetic that can dye hair by continuous use, A non-washing-out type hair cosmetic containing a 6-dihydroxyindole derivative and a film-forming polymer has been proposed (see Patent Document 1).

  On the other hand, the treatment with a composition containing a transition metal ion and the treatment with a composition containing 5,6-dihydroxyindole-2-carboxylic acid are continuously performed, thereby the 5,6-dihydroxyindole. A method for promoting the conversion of a derivative into a melanin-like pigment is known (see Patent Document 2).

JP 2007-326805 Japanese Unexamined Patent Publication No. 01-319413

  Although the hair cosmetic described in Patent Document 1 can easily make gray hair inconspicuous by daily hair care behavior, the hair coloring property is not sufficiently satisfactory. In addition, the method described in Patent Document 2 is complicated in operation and requires advanced processing technology. In addition, for example, in a one-component hair manicure, it is possible to use simply because there is no need to mix two agents like a two-component hair color, but in addition to the above problems, a hair dye Has been transferred to clothes.

  It is an object of the present invention to easily make gray hair inconspicuous by covering the hair surface with a melanin polymer by daily hair care behavior such as styling, and it is possible to dye the hair to a sufficient level by continuous use. The object is to provide a hair cosmetic. Furthermore, it is providing the hair cosmetics which can suppress the dye transfer by the contact with the hair by which the hair-styling process of this invention was performed, clothes, etc.

  The present inventor (i) improves the hair dyeing property of single use or multiple uses by coexisting a specific ratio of an indole derivative or indoline derivative that is a melanin precursor and a divalent iron ion. It has been found that (ii) by using an anionic film-forming polymer in combination, the hair dyeability can be further improved, and iron ions can be stably blended into the hair cosmetic.

The present invention comprises components (a), (b) and (c), has a pH of from 7.5 to 12 at 25 ° C., and a molar ratio of component (b) to component (a) (b) / (a ) Is a hair cosmetic composition of 0.01 to 0.45.
(a) Melanin precursor represented by the general formula (1)

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

  Furthermore, the present invention provides a hair styling method comprising the steps of (i) applying the above-described hair cosmetic material to hair, and (ii) styling hair to which the hair cosmetic material is applied.

  Furthermore, the present invention provides a method for dyeing gray hair by repeatedly performing (i) a step of applying the above-described hair cosmetic material to hair, and (ii) a step of styling hair to which the hair cosmetic material is applied.

  The hair cosmetic composition of the present invention can easily dye white hair by daily styling, and can be easily and gradually made inconspicuous without any inconvenience in the place and method of use. In particular, by using an anionic film-forming polymer in combination, it is possible to produce a hair cosmetic that is excellent in hair dyeability and stability and that can suppress the discharge of foreign matter even after high-temperature storage. When hair cosmetics are used as a styling agent, transfer of melanin polymer to clothing or the like becomes a problem, but the hair cosmetic of the present invention can suppress this transfer.

(Ingredient (a))
The hair cosmetic composition of the present invention contains an indole derivative or indoline derivative (hereinafter sometimes referred to as melanin precursor (1)) represented by the general formula (1) as the component (a). In the present invention, the melanin precursors represented by the general formula (1) can be used in combination of two or more, and thereby the dyed color can be adjusted.

  The melanin precursor represented by the general formula (1) includes 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2- A carboxylic acid etc. are mentioned. Among these, 5,6-dihydroxyindole alone or a combination of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid is more preferable from the viewpoint of dyeing hair in a natural color. When this 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid are used in combination, the molar ratio is preferably 50/50 or more, more preferably 60/40 or more, and still more preferably 70/30. More preferably, it is 80/20 or more, preferably 999/1 or less, more preferably 99/1 or less, further preferably 98/2 or less, and further preferably 95/5 or less. Here, the melanin precursor (1) represented by the general formula (1) can be quantified by reverse phase HPLC.

  The content of the melanin precursor of component (a) is preferably 0.01% by mass or more, more preferably 0.02% by mass in the hair cosmetic composition of the present invention, from the viewpoint of improving hair dyeing properties and preventing color transfer. % Or more, more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.2% by mass or less.

(Component (b))
The hair cosmetic composition of the present invention contains divalent iron ions (Fe ²⁺ ) as the component (b). To blend divalent iron ions into hair cosmetics, ferrous sulfate, ferrous ammonium sulfate, ferrous chloride and other inorganic iron (II) compounds; ferrous gluconate, ferrous citrate What is necessary is just to mix | blend as bivalent iron compounds, such as organic iron (II) compounds, such as an iron salt.

  The content of the divalent iron ion is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more in the hair cosmetic composition of the present invention, from the viewpoint of improving hair dyeing properties and preventing color transfer. More preferably, it is 0.0009 mass% or more, Preferably it is 0.1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.04 mass% or less.

  The molar ratio (b) / (a) of the component (b) to the component (a) is 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, from the viewpoint of improving hair dyeing properties at the time of single use. Preferably it is 0.04 or more, More preferably, it is 0.06 or more. In addition, the molar ratio is 0.45 or less, preferably 0.4 or less, more preferably 0.35 or less, and further preferably 0.3 or less, from the viewpoint of improving the hair dyeability after being used multiple times and from the viewpoint of preventing color transfer. In addition, the molar ratio (b) / (a) is 0.01 to 0.45, preferably 0.02 to 0.4, more preferably 0.03 to 0.35, still more preferably 0.04 to 0.3, and still more preferably 0.06 to 0.3 from the above viewpoint. .

(Ingredient (c))
The hair cosmetic composition of the present invention contains an anionic film-forming polymer as component (c). The film-forming polymer of the present invention exhibits a hair setting property by forming a film on the hair surface.

  Specific examples of the anionic film-forming polymer include methyl vinyl ether / maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, SP-215 (above, GAF); Resin 28-1310 ( National Starch Co., Ltd.), Ruby Set CA (BASF Corp.) and other vinyl acetate / crotonic acid copolymers; Resin 28-2930 (National Starch Co., Ltd.) vinyl acetate / crotonic acid / neodecanoic acid vinyl copolymers; Ruby Set CAP (BASF Vinyl acetate / crotonic acid / vinyl propionate copolymer, etc .; vinyl acetate / maleic acid monobutyl ester / isobornyl acrylate copolymer, such as ADVANTAGE CP (ISP); Diahold (Mitsubishi Chemical Corporation), etc. (Meth) acrylic acid / (meth) acrylic acid ester copolymer; plus size L-53P, L-75CB, L-9540B, L-6466, L-3200B (Keio Chemical Industry Co., Ltd.) (Alkyl acrylate / diacetone acrylamide) copolymer AMP; acrylic acid / acrylic acid alkyl ester / alkyl acrylamide such as Ultrahold 8, Ultrahold Strong (above, BASF), Anformer V-42 (National Starch) Copolymers: Polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymers such as Rubyflex VBM35 (BASF), and the like.

  As the anionic film-forming polymer of component (c), a polymer or copolymer containing a structural unit represented by the general formula (2) can be suitably used.

[Wherein, R ⁴ represents a hydrogen atom or a carboxy group, and R ⁵ represents a hydrogen atom or a methyl group. ]

  As a copolymer containing the structural unit represented by the above general formula (2), a (meth) acrylic acid / (meth) acrylic acid ester copolymer such as Diahold (Mitsubishi Chemical); plus size L-53P (Alkyl acrylate / diacetone acrylamide) copolymer AMP such as L-75CB, L-9540B, L-6466, and L-3200B (reciprocal chemical industry); Ultrahold 8, Ultrahold Strong (above, BASF) , Anformer V-42 (National Starch) and other acrylic acid / alkyl acrylate / alkyl acrylamide copolymers; Rubiflex VBM35 (BASF) and other polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymers Etc. can be used suitably.

  The weight average molecular weight of the anionic film-forming polymer (according to gel filtration chromatography (in terms of polyethylene glycol)) can be controlled to 1,000 to 1,000,000 if the polymerization conditions are selected. In the present invention, preferably 10,000 or more, more preferably It is 20,000 or more, preferably 500,000 or less, more preferably 200,000 or less.

  The content of the anionic film-forming polymer of component (c) is preferably 0.001% by mass or more, more preferably in the hair cosmetic composition of the present invention, from the viewpoint of improving hair dyeing properties and preventing color transfer. Is 0.005% by mass or more, more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, Preferably it is 10 mass% or less.

  The mass ratio (b) / (c) of the component (b) to the component (c) is based on the viewpoint of improving the hair dyeing property after single use and the hair dyeing property after multiple use, and the blending stability of hair cosmetics. From the viewpoint of improving the quality and preventing the occurrence of foreign matter after high-temperature storage, preferably 0.00001 or more, more preferably 0.00005 or more, more preferably 0.0001 or more, more preferably 0.0003 or more, and preferably 0.01 or less, More preferably, it is 0.005 or less, More preferably, it is 0.003 or less, More preferably, it is 0.002 or less, More preferably, it is 0.0015 or less.

(Ingredient (d))
The hair cosmetic composition of the present invention can further contain a surfactant. Such surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acids. Salts, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, sulfosuccinic acid esters and the like; imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series , Amphoteric surfactants such as hydroxysulfobetaine or amidosulfobetaine amphoteric surfactants; polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, higher fatty acid sucrose esters, polyglycerin fatty acid esters, Nonionic surface activity such as grade fatty acid monoethanolamide or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, alkyl saccharide surfactant, alkylamine oxide, alkylamidoamine oxide Agents: Cationic surfactants such as imidazoline ring-opening quaternary ammonium salts, mono-long-chain alkyl quaternary ammonium salts, and di-long-chain alkyl quaternary ammonium salts. As counter ions of the anionic residues of these surfactants, alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, alkanol groups having 2 or 3 carbon atoms, Examples thereof include three alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine. Examples of the counter ion of the cationic residue include halogen ions such as chlorine, bromine and iodine, and methosulfate and saccharinate ions.

  These surfactants can be used alone or in combination of two or more, and as the combination, it is preferable to use a nonionic surfactant and a cationic surfactant in combination. The content of the component (d) surfactant is preferably 0.01 or more, more preferably a mass ratio (d) / (c) to the component (c) from the viewpoint of improving hair dyeability, stability and coatability. Is 0.02 or more, more preferably 0.03 or more, preferably 1.5 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

(Ingredient (e))
The hair cosmetic composition of the present invention can contain an organic polymer thickener. Organic polymer thickeners include carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, xanthan gum, hydroxypropylxanthan gum Cationic guar gum, cationized cellulose and the like can be used. The mass ratio of the organic polymer thickener to the component (c) is preferably 0.001 or more, more preferably 0.002 or more, more preferably 0.003 or more, from the viewpoint of improving hair dyeability and coatability. Preferably it is 0.05 or less, More preferably, it is 0.03 or less, More preferably, it is 0.01 or less.

  Of these organic polymer thickeners, it is preferable to use anionic thickeners such as carboxyvinyl polymer and acrylic acid / alkyl methacrylate copolymers, and anionic thickeners together with anionic thickeners. Can be used in combination with other polymer thickeners, but the content of other polymer thickeners should be lower than that of anionic thickeners to improve hair dyeing and stability. From the viewpoint of

(Ingredient (f))
The hair cosmetic composition of the present invention can contain at least one selected from the group consisting of sulfurous acid, ascorbic acid and salts thereof. The content of the hair cosmetic composition of the present invention is as sulfite and ascorbic acid (that is, as the amount of free acid in the case of a salt) because it is dyed black with no redness suitable for hiding Oriental white hair. The content is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less.

[Additional dye component]
In addition to the component (a), the hair cosmetic composition of the present invention may contain melanin produced by oxidative polymerization from the melanin precursor represented by the general formula (1) as an additional dye component. The melanin is preferably an oxidation polymer composed of at least one of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid having a molecular weight of 1,000 to 10,000. In order to contain this melanin in the hair dye composition of the present invention, a polymer is prepared in advance from the melanin precursor (1) and then blended in the hair cosmetic composition of the present invention. ) May be mixed with the air to produce melanin. Since this melanin product has the effect of concealing gray hair as a black to brown solid, the function as a temporary dyeing of the hair cosmetic composition of the present invention can be complemented. Therefore, the content of the hair cosmetic composition of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 25% by mass or less, more preferably Is 20% by mass or less, more preferably 10% by mass or less.

  Further, the hair cosmetic composition of the present invention may further contain a direct dye that is usually used in hair dyes.

  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 acid dyes include blue No. 1, purple No. 401, black No. 401, orange color No. 205, red No. 227, red No. 106, yellow No. 203, acidic orange 3, etc., and nitro dyes include 2-nitro Paraphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino- 3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis- (2-hydroxyethyl) -2-nitropara Examples include disperse dyes such as disperse purple 1, disperse blue 1, disperse black 9, etc., and basic dyes include basic blue 99, basic tea 16, basic tea 17, and base. Basic red 76, basic red 51, basic yellow 57, basic yellow 87, basic orange 31 and the like.

  When the hair cosmetic of the present invention directly contains a dye, the content thereof is preferably 0.001% by mass or less, more preferably 0.01% by mass or less, and preferably 5% by mass in the hair cosmetic of the present invention. % Or less, more preferably 3% by mass or less.

  In addition to component (b), the hair cosmetic composition of the present invention can contain a divalent ion of a metal selected from the group consisting of silver, calcium, copper, zinc and manganese. The content thereof is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, further preferably 0.001% by mass or more, and preferably 0.001% by mass or more, preferably from the viewpoint of improving hair dyeing properties. It is 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.

[Additional film-forming polymer]
In addition to component (c), the hair cosmetic composition of the present invention can contain a film-forming polymer selected from the group consisting of nonionic polymers, cationic polymers, and amphoteric polymers. The mass ratio of these film-forming polymers to component (c) is preferably 0.001 or more, more preferably 0.002 or more, more preferably 0.003 or more, and preferably from the viewpoint of improving hairdressing properties and touch. 0.8 or less, more preferably 0.5 or less, and still more preferably 0.1 or less.

  Nonionic polymers include, for example, polyvinylpyrrolidone such as Rubiscol K12, 17, 30, 60, 80, 90 (above BASF), PVP K15, 30, 60, 90 (above GAF); Lubiscol VA28, 37 , 55, 64, 73, VA37E (above, BASF), PVP / VA E-735, E-635, E-535, E-335, S-630, W-735 (above, GAF) etc. Pyrrolidone / vinyl acetate copolymer; Polyvinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer such as Rubiscol VAP343 (BASF); Vinyl acetate / N-vinyl-5- such as Dowtex (Dow Chemical) And methyl-2-oxazoline copolymer.

  Examples of the cationic polymer include vinyl imidazolium chloride / vinyl pyrrolidone copolymers such as Rubycut FC370, FC550, FC905, HM552, MonoCP (above, BASF); Cellcut H-100 (viscosity 1000 cps), L-200 (viscosity) 100 cps) (above, National Starch Co., Ltd.) hydroxyethyl cellulose / dimethyl diallylammonium chloride, such as Guffcut 734, 755N, 755 (above, GAF Co.), vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, etc .; BASF), copolymers 845, 937, 958 (above, GAF) and other polyvinylpyrrolidone / alkylaminoacrylate copolymers; polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymers such as copolymer VC-713 (GAF) ; Vinylpyrrolidone / medium such as Guffcut HS-100 (ISP) Tacrylamidopropyl trimethylammonium chloride copolymer; alkyl acrylamide / acrylate / alkyl aminoalkyl acrylamide / polyethylene glycol methacrylate copolymer such as water-soluble polymer compound described in JP-A-2-180911, N-propionyl polyethyleneimine / Methylpolysiloxane copolymer, acrylic acid amide / acrylic acid / alkyl methacrylic acid / methoxypolyethylene glycol copolymer, acrylic acid amide / acrylic acid ester copolymer, and the like.

  Examples of amphoteric polymers include N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymers such as Yuka Former M-75 and SM (Mitsubishi Chemical); Yuka Former AM -75, AM75S / SM (above, Mitsubishi Chemical Corporation) dialkylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer monochloroacetic acid amphoteric product; Anformer 28-4910, LV-71 (above, National Starch Co., Ltd.) Such as hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer.

(Oil agent)
Furthermore, the hair cosmetic composition of the present invention can contain an oil as a conditioning agent. Oils include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; waxes such as beeswax, whale wax, lanolin, carnauba wax; Esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate; capric acid Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; Alcohol, stearyl alcohol, behenyl alcohol, 2-octyldodecanol, higher alcohols such as cetostearyl alcohol; Other isostearyl glyceryl ether, polyoxypropylene butyl ether. Of these, higher alcohols are preferable, and myristyl alcohol, cetyl alcohol, and stearyl alcohol are more preferable. These oil agents can be used in combination of two or more, and the content thereof is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more in the hair cosmetic composition of the present invention. In addition, it is preferably 2% by mass or less, more preferably 1.8% by mass or less, and further preferably 1.5% by mass or less.

[Other ingredients]
In the hair cosmetic of the present invention, other components used in normal hair dyes and hair cosmetics, such as humectants, ultraviolet absorbers, pH adjusters, stabilizers, buffers, fragrances, touch improvers, Chelating agents, solubilizers, preservatives, and the like can be appropriately blended depending on the purpose. The hair cosmetic composition of the present invention is produced by dissolving the above components in an aqueous medium, and examples of the aqueous medium include water and lower alcohols such as ethanol and isopropyl alcohol.

  The melanin precursor of component (a) is oxidized by oxygen in the air under basic conditions and converted to a melanin pigment. For this reason, the pH of the hair cosmetic composition of the present invention at 25 ° C. is 7.5 or more, preferably 8 or more, more preferably 8.5 or more, and 12 or less, preferably 11 or less.

  The hair cosmetic composition of the present invention is preferably used as a type of hair cosmetic composition (hairdressing composition) that does not wash away. Moreover, since the melanin precursor is mix | blended as a component (a), the hair cosmetics of this invention can be used as a hair dye (especially hair dye for white hair dyeing) simultaneously with the use as a hairdressing agent.

  As a usage form of the hair cosmetic composition of the present invention, it is convenient to use it in a form filled in a container such as pump spray or pump foam. More preferably, the hair cosmetic composition of the present invention is used as a stock solution and a propellant. At the same time, it may be used in a single agent form such as aerosol spray or aerosol foam sealed in a pressurized container. As an aerosol propellant, for example, liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, a mixture thereof or the like is preferably used. Furthermore, LPG, DME, or a mixture of LPG and DME It is preferable to use a gas. The propellant is preferably used in such a range that the mass ratio of the hair cosmetic / the propellant is (99.5 to 40) / (0.5 to 60), and further (95 to 80) / (5 to 20). Further, the hair cosmetic / propellant may be used as a hair spray containing a large amount of propellant at a ratio of (5-70) / (95-30), and further (20-60) / (80-40). .

[Hairdressing method, gray hair dyeing method]
When the hair cosmetic composition of the present invention is used as a hair styling agent, the hair styling is performed by performing the steps of (i) applying the hair cosmetic composition of the present invention to the hair, and (ii) styling the hair to which the hair cosmetic composition is applied. can do. Such hair styling method can easily make gray hair inconspicuous.

  The application step (i) can be carried out by applying an appropriate amount of the hair cosmetic directly to the hair, or taking it out to a tool such as a brush or directly into the hand and then applying it to the hair. Hair cosmetics may be applied to dry hair as well as wet hair such as after towel drying.

  The hair styling step (ii) can be performed using a tool such as a brush or a direct hand. From the viewpoint of improving the hair dyeing property and preventing migration, it is preferable to use a hair dryer such as a hair dryer in combination for hair shaping.

  By repeating steps (i) and (ii), the gray hair can be gradually made inconspicuous and dyed to a sufficient level. In this case, after step (ii), (iii) from hair to hair cosmetics A step of removing can also be included.

  The removal step of (iii) is performed 30 minutes to 72 hours after hair styling in step (ii), more preferably 1 hour to 48 hours, from the viewpoint of improving hair dyeing properties, preventing migration, and maintaining cleanliness. The hair cosmetic is preferably removed after 3 to 24 hours, more preferably 6 to 18 hours. The removing step can be performed using a commercially available shampoo.

  From the viewpoint of making gray hair less noticeable, it is preferable to repeat steps (i) to (iii) a plurality of times. These steps (i) to (iii) are performed once every 1 to 4 days, further once every 1 to 3 days, further once every 1 to 2 days, and more preferably from the viewpoint of making gray hair less noticeable. It is preferable to repeat the cycle once a day. These steps (i) to (iii) are preferably repeated 1 to 8 times, 2 to 7 times, and 3 to 7 times a week from the viewpoint of making gray hair less noticeable. The time from step (iii) to the next step (i) is preferably 3 to 96 hours, more preferably 4 to 84 hours, and even more preferably 6 to 72 hours from the viewpoint of making gray hair less noticeable. .

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

<1>
It contains components (a), (b) and (c), has a pH at 25 ° C. of 7.5 or more and 12 or less, and a molar ratio (b) / (a) of component (b) to component (a) is 0.01 or more Hair cosmetics that are 0.45 or less.
(a) Melanin precursor represented by the general formula (1)

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

<2>
The content of component (a) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, The hair cosmetic according to <1>, more preferably 0.2% by mass or less.

<3>
The content of component (b) is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, more preferably 0.0009% by mass or more, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, The hair cosmetic according to <1> or <2>, more preferably 0.04% by mass or less.

<4>
The molar ratio (b) / (a) of the component (b) to the component (a) is preferably 0.02 or more, more preferably 0.03 or more, further preferably 0.04 or more, more preferably 0.06 or more <1> to < The hair cosmetic composition according to any one of 3>.

<5>
The molar ratio (b) / (a) of component (b) to component (a) is preferably 0.4 or less, more preferably 0.35 or less, and even more preferably 0.3 or less, according to any one of <1> to <4> The hair cosmetic composition described.

<6>
The molar ratio (b) / (a) of component (b) to component (a) is preferably 0.02 or more, more preferably 0.03 or more, more preferably 0.04 or more, more preferably 0.06 or more, and preferably 0.4 Hereinafter, the hair cosmetic composition according to any one of <1> to <5>, more preferably 0.35 or less, and still more preferably 0.3 or less.

<7>
Component (c) is represented by the following general formula (2)

[Wherein, R ⁴ represents a hydrogen atom or a carboxy group, and R ⁵ represents a hydrogen atom or a methyl group. ]
The hair cosmetic according to any one of <1> to <6>, which is a polymer or copolymer containing a structural unit represented by formula (1).

<9>
The weight average molecular weight of component (c) is preferably 10,000 or more, more preferably 20,000 or more, preferably 500,000 or less, more preferably 200,000 or less, according to any one of <1> to <8>. Hair cosmetics.

<10>
The mass ratio (b) / (c) of component (b) to component (c) is preferably 0.00001 or more, more preferably 0.00005 or more, more preferably 0.0001 or more, more preferably 0.0003 or more, and preferably The hair cosmetic composition according to any one of <1> to <9>, which is 0.01 or less, more preferably 0.005 or less, more preferably 0.003 or less, more preferably 0.002 or less, and still more preferably 0.0015 or less.

<11>
The mass ratio of the film-forming polymer selected from the group consisting of nonionic polymer, cationic polymer and amphoteric polymer to component (c) is preferably 0.001 or more, more preferably 0.002 or more, more preferably 0.003 or more, The hair cosmetic according to any one of <1> to <10>, preferably 0.8 or less, more preferably 0.5 or less, and still more preferably 0.1 or less.

<12>
Preferably, the hair cosmetic composition according to any one of <1> to <11>, further comprising (d) a surfactant.

<13>
The mass ratio (d) / (c) of component (d) to component (c) is preferably 0.01 or more, more preferably 0.02 or more, more preferably 0.03 or more, and preferably 1.5 or less, more preferably The hair cosmetic composition according to <12>, which is 1.2 or less, more preferably 1.0 or less.

<14>
Preferably, the hair cosmetic composition according to any one of <1> to <13>, further comprising (e) an organic polymer thickener.

<15>
The hair cosmetic composition according to <14>, which preferably contains an anionic thickener as the component (e).
<16>
The mass ratio of component (e) to component (c) is preferably 0.001 or more, more preferably 0.002 or more, more preferably 0.003 or more, preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.01. <14> or <15> hair cosmetics according to the following.

<17>
<14> to <16>, wherein the content of the organic polymer thickener other than the anionic thickener in the component (e) is preferably less than the content of the anionic thickener Hair cosmetics.

<18>
Preferably, the hair cosmetic composition according to any one of <1> to <17>, further comprising (f) at least one selected from the group consisting of sulfurous acid, ascorbic acid, and salts thereof.

<19>
Preferably, the hair cosmetic according to any one of <1> to <18>, further comprising a divalent ion of a metal selected from the group consisting of silver, calcium, copper, zinc and manganese.

<20>
The hair cosmetic according to any one of <1> to <19>, wherein the pH at 25 ° C is preferably 8 or more, more preferably 8.5 or more, and preferably 11 or less.

<21>
The hair cosmetic according to any one of <1> to <20>, which is preferably used as a hair styling agent that does not wash away.

<22>
The hair cosmetic according to any one of <1> to <21>, which is preferably used for dyeing gray hair.

<23>
<1>-<22> Aerosol hair cosmetics comprising the hair cosmetic according to any one of <22> and a propellant.

<24>
(i) A hair styling method comprising a step of applying the hair cosmetic according to any one of <1> to <23> to hair, and (ii) a step of styling hair to which the hair cosmetic is applied.

<25>
(i) A method for dyeing white hair by repeatedly performing the step of applying the hair cosmetic composition according to any one of <1> to <23> to hair, and (ii) the step of styling hair to which the hair cosmetic composition is applied.

<26>
Preferably, after the step (ii), the hair dyeing method according to <25>, further comprising (iii) a step of removing the hair cosmetic from the hair, wherein the steps (i) to (iii) are repeated.

<27>
Steps (i) to (iii) are preferably repeated once every 1-4 days, more preferably once every 1-3 days, more preferably once every 1-2 days, and even more preferably once a day. The gray hair dyeing method according to <26>.

Examples 1-4 and Comparative Examples 1-3
An aerosol-type hair cosmetic stock solution is prepared according to the formulation shown in Table 1, and this stock solution is packed in an aerosol compatible bottle (Tokyo Polymer Co., Ltd.) and clinched, and then the stock solution: gas ratio = 90: 10 (mass ratio) Thus, an aerosol-type hair cosmetic material was obtained which was filled with LPG as a propellant and discharged in the form of foam.
The obtained hair cosmetics were evaluated as follows. The results are also shown in Table 1.

-Hair dyeing after one treatment The aerosol type hair cosmetic was applied to 1 g of Chinese white hair at a bath ratio (hair: agent) of 1: 0.2 and allowed to dry naturally for 1 hour. Before and after this treatment, L ^* , a ^* , b ^* were measured using a color difference meter CR-400 (manufactured by Konica Minolta), and the change from the initial value (untreated) (ΔE ^* _ab) ) Was calculated.

Delta] E ^* _ab = _{^{[(L * 2 -L * 1)}} 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2 ] ^0.5
[In the formula, L ^* ₁ , a ^* ₁ , and b ^* ₁ are measured values before treatment, and L ^* ₂ , a ^* ₂ , and b ^* ₂ are measured values after staining. ]

・ Hair-dyeing property after 30 treatments The above aerosol-type hair cosmetic is applied to 1 g of Chinese white hair at a bath ratio (hair: agent) of 1: 0.2, allowed to dry naturally for 1 hour, then washed and dried with a hair dryer. A series of operations was repeated 30 times. Before and after this process, L ^* , a ^* , b ^* were measured using a color difference meter CR-400 (manufactured by Konica Minolta), and the change from the initial value (unprocessed) (ΔE ^* _ab) ) Was calculated.

・ Transferability after one treatment Assuming that it is wet with rain or sweat after the treatment, apply the above-mentioned aerosol-type hair cosmetic to 1g of Chinese white hair with bath ratio (hair: agent) 1: 0.2, After natural drying for 1 hour, the bath is immersed in artificial sweat (JIS0848) so that the bath ratio is 1: 1. After leaving at 40 ° C. for 1 hour, it was put on a filter paper, placed on a 1 kg weight, and the transferability to the filter paper was evaluated in 5 stages (1: there is a significant color transfer, 2: there is a clear color transfer, 3: There is some color transfer, 4: There is slight color transfer, 5: There is almost no color transfer).

-Stability after storage at high temperature (aggregate generation experiment)
The aerosol type hair cosmetic was stored in a storage container at 45 ° C. for 1 month, and then the state of aggregation of the aggregates in the foam when the foam was discharged was evaluated in 5 stages (1: there was a large amount of contamination, 2: slightly mixed, 3: slightly mixed, 4: very slightly mixed, 5: no mixed).

Example 5
The effect was confirmed by using the aerosol type hair cosmetic prepared in Example 3 above by the following method of use (use in actual life).

<How to use>
Every morning, the aerosol hair cosmetic was shaken well and discharged from the container, and an appropriate amount was taken out by hand. Next, the hair was applied so as to be applied to the entire hair, the hair was trimmed with hands, and dried with a hair dryer. That night, the hair was washed with a commercially available shampoo (manufactured by Kao Corporation: Ajiens (registered trademark)), towel-dried, and then dried with a hair dryer. This was used repeatedly for 5 days a week for 1 month. Depending on the day, the hair cosmetic composition may be overcoated the next day without washing it off. In addition, it was used twice a day (morning and evening) for hair.

<Effect>
After 1 month of use, gray hair became inconspicuous, and a satisfactory effect could be obtained.
Further, during the period of use, even if sweat was applied, the colored sweat did not sag, and the color did not transfer to the handkerchief when wiped with a handkerchief or the like. In other words, it was found that the hair dyeing effect without transfer, which has been considered as a problem with temporary hair dyes and hair manicures, can be obtained.

Formulation Example 1 Gel-type hair cosmetic
(Mass%; active amount)
5,6-Dihydroxyindole 0.05
Divalent iron ion (Ferrous sulfate heptahydrate) 0.002 (* 7)
(Alkyl acrylate / diacetone acrylamide) copolymer AMP
(Plus size L-6466 (manufactured by Reciprocal Chemical Industries)) 3.0
Carbomer (Carbopol 980 (Nikko Chemicals)) 1.5
Ascorbic acid 0.1
Sodium bicarbonate 0.5
Hydroxyl Na adjusted to pH 9 Water remaining
* 7: Amount of iron (II) ions

Formulation Example 2 Aerosol spray hair cosmetic (stock solution) (mass%; active amount)
5,6-Dihydroxyindole 0.05
Divalent iron ion (ferrous sulfate heptahydrate) 0.002 (* 7)
(Alkyl acrylate / diacetone acrylamide) copolymer AMP
(Plus size L-3200B (Made by Mutual Chemical Engineering)) 2.0
Ascorbic acid 0.1
Sodium bicarbonate 0.5
Ethanol 30.0
Hydroxyl Na adjusted to pH 9 Water remaining
* 7: Amount of iron (II) ions (propellant)
LPG
Stock solution / propellant (mass ratio) = 60/40

Claims (10)

It contains components (a), (b) and (c), has a pH at 25 ° C. of 7.5 or more and 12 or less, and a molar ratio (b) / (a) of component (b) to component (a) is 0.01 or more Hair cosmetics that are 0.45 or less.
(a) Melanin precursor represented by the general formula (1)

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

[Wherein, R ⁴ represents a hydrogen atom or a carboxy group, and R ⁵ represents a hydrogen atom or a methyl group. ]
An anionic film-forming polymer which is a polymer or copolymer containing a structural unit represented by   The hair cosmetic composition according to claim 1, wherein the mass ratio (b) / (c) of the component (b) to the component (c) is 0.0001 or more and 0.01 or less.   The hair cosmetic according to claim 1 or 2, further comprising (d) a surfactant.   The hair cosmetic according to any one of claims 1 to 3, further comprising (e) an organic polymer thickener.   Furthermore, the hair cosmetics in any one of Claims 1-4 containing at least 1 sort (s) chosen from the group which consists of (f) sulfurous acid, ascorbic acid, and these salts. Furthermore, the hair cosmetics in any one of Claims 1-5 containing the bivalent ion of the metal chosen from the group which consists of silver, calcium, copper, zinc, and manganese. The hair cosmetic composition according to any one of claims 1 to 6 , which is used as a hair styling agent of a type that does not wash away. The hair cosmetic composition according to any one of claims 1 to 7 , which is used for white hair dyeing. Aerosol hair cosmetic composition comprising a hair cosmetic and propellant according to any one of claims 1-8. A hair styling method comprising the steps of (i) applying the hair cosmetic composition according to any one of claims 1 to 9 to hair, and (ii) styling hair to which the hair cosmetic composition is applied.