JP5043368B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic that can easily make gray hair inconspicuous by covering the hair surface with a melanin polymer by daily hair care behavior.

  In order to dye or conceal gray hair, it is common to use hair coloring agents such as hair colors and hair manicures. However, there are problems such as unnaturalness immediately after hair dyeing due to abrupt changes in the color of the hair and color steps with the growing white hair.

  Moreover, the present inventors have proposed the hair cosmetics using an enzyme and a melanin precursor (refer patent document 1). The advantage of using the enzyme is that the oxidation rate of the melanin precursor is increased, and melanin is easily generated on the hair surface in a short time after application. However, the disadvantages of using an enzyme are not necessarily sufficient, such as the need to study the preparation of the enzyme and its stability. Moreover, the polymer by the enzyme of each melanin precursor single is fundamentally only black, Therefore Color control was not possible and the color tone was also monotonous. Moreover, in the hair cosmetics containing a melanin precursor, it was necessary to wait for the time to polymerize on the hair.

  Some temporary hair dyes using melanin have also been proposed (see, for example, Patent Documents 2 to 4), but there is no discussion of the color tone, and in fact, only those with a monotonous color such as black to gray. Met.

JP 2002-47144 A JP-A-6-128129 JP-A-6-128138 Japanese National Publication No. 6-507424

  The object of the present invention is to make gray hair stand out easily with natural hair color without any inconvenience in use place and method by covering the hair surface with melanin polymer in a single hair care action such as daily styling. An object of the present invention is to provide a hair cosmetic that can be eliminated, can be adjusted in color, and has excellent stability and safety.

  This inventor discovered that the said subject could be solved by using together the melanin which superposed | polymerized 2 or more types of melanin, and a film forming polymer.

  The present invention provides a non-washing-type hair cosmetic containing the following components (A) and (B).

  (A) Melanin having a molecular weight of 1000 or more obtained by polymerizing two or more compounds 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) Film-forming polymer

  The hair cosmetic composition of the present invention can easily make gray hair inconspicuous by daily styling, without the trouble of using place and method. In particular, by producing melanin obtained by polymerizing two or more kinds of melanin precursors without using an enzyme, the natural color is excellent, and the adjustment thereof is possible, and the stability and safety are also excellent.

  The compound represented by the general formula (1) is an indole derivative or an indoline derivative (melanin precursor) that is converted into a melanin pigment by being oxidized. Polymerized melanin is used. Examples of the compound represented by the general formula (1) include 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, and 5,6-dihydroxyindoline-2-carboxylic acid. The color can be adjusted by polymerizing these two or more combinations. In particular, from the viewpoint of dyeing hair in a natural color, a combination using 5,6-dihydroxyindole is preferable, and a polymer of a combination of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid is used. Most preferred. The molar ratio in the case of using both of these is preferably in the range of 50:50 to 999: 1, particularly 80:20 to 99: 1. Here, 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid before polymerization can be quantified by reverse phase HPLC.

  The oxidative polymerization of the melanin precursor (1) can easily proceed with an oxidizing agent such as oxygen, left in the air, aerated against the melanin precursor solution, or an appropriate amount of oxidizing agent such as hydrogen peroxide. Melanin can be prepared by addition. The formed polymer has various molecular weights, structures, and the like, but in the present invention, melanin having a molar average molecular weight of 1000 or more is excellent in terms of stability and gray hair concealing properties, and particularly preferably has a molar average molecular weight of 2000 or more ( Molecular weight measurement method: Shimadzu Corporation MALDI-TOF-MASS). In addition, since the formed melanin partially preserves the functional group derived from the melanin precursor (1), 5,6-dihydroxyindole-2-carboxylic acid or 5,6-dihydroxyindoline-2-carboxylic acid is added. When used, it becomes a melanin having a carboxy group and water solubility is increased. Moreover, although a detailed reason is not clear, this inventor uses the melanin precursor of 2 types at the time of this superposition | polymerization, and monotonous colors, such as black-gray in the temporary hair dye using the melanin until now, are used. It was found that the color tone changed from brown to gray to bluish gray, unlike the taste.

  The content of component (A) melanin is preferably 0.01 to 10% by weight, more preferably 0.02 to 5.0% by weight, particularly 0.05 to 2.0% by weight in the hair cosmetic composition of the present invention, from the viewpoint of the concealing effect of white hair. preferable.

  The film-forming polymer of component (B) forms a film on the hair surface and exhibits hair setting properties. Examples of the film-forming polymer include nonionic polymers, cationic polymers, anionic polymers and amphoteric polymers, and two or more kinds may be used in combination.

  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) 100cps) (National Starch) hydroxyethyl cellulose / dimethyl diallylammonium chloride; Gaffcut 734, 755N, 755 (above, GAF) vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer; Rubyflex (BASF), polyvinyl pyrrolidone / alkylamino acrylate copolymers such as copolymers 845, 937, and 958 (above, GAF); polyvinyl pyrrolidone / alkyl amino acrylate / vinyl caprolactam copolymer such as copolymer VC-713 (GAF) Combined: Vinyl pyrrolidone such as Guffcut HS-100 (ISP) / Methramidopropyl trimethylammonium chloride copolymer; alkyl acrylamide / acrylate / alkyl aminoalkyl acrylamide / polyethylene glycol methacrylate copolymer such as water-soluble polymer compound described in JP-A-2-809911, N-propionyl polyethylene imine / Examples thereof include a methylpolysiloxane copolymer, an acrylic amide / acrylic acid / alkyl methacrylic acid / methoxypolyethylene glycol copolymer, and an acrylic amide / acrylic ester copolymer.

  Examples of the anionic 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), Vinyl acetate / crotonic acid copolymers such as Ruby Set CA (BASF); Virni acetate / crotonic acid / vinyl neodecanoate copolymers such as Resin 28-2930 (National Starch); Ruby Set CAP (BASF), etc. Vinyl acetate / crotonic acid / vinyl propionate copolymer; vinyl acetate / maleic acid monobutyl ester / isopolonyl acrylate copolymer such as ADVANTAGECP (ISP); plus size L53P, L-75CB, L-9540B (interaction) Chemical Co.), Diahold (Mitsubishi Chemical Co., Ltd.) and other (meth) acrylic acid / (meth) acrylic acid ester copolymers; Ultrahold 8, Ultraho Acrylic acid / alkyl acrylate / alkyl acrylamide copolymers such as Yold Strong (above BASF) and Unformer V-42 (National Starch); Polyvinylpyrrolidone such as Rubyflex VBM35 (BASF) / Examples thereof include acrylate / (meth) acrylic acid copolymers.

  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) and other dialkylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer monochloroacetic acid amphoteric products; Anformer 28-4910, LV-71 (above, National Starch Co., Ltd.) ) And other hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers.

  Of these film-forming polymers, (meth) acrylic polymers are preferable, and among them, N-methacryloyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer (for example, Mitsubishi Chemical Company, Yucaformer SM) is preferred.

  The content of the film-forming polymer of component (B) is preferably 0.01 to 40% by weight, particularly preferably 0.5 to 10% by weight, in the hair cosmetic composition of the present invention.

  An inorganic or organic pigment can be added as an additional component to the hair cosmetic composition of the present invention in order to complement the color tone or improve the concealment property of white hair. As inorganic or organic pigments, carbon black, titanium black, bentonite, black iron oxide, bengara, yellow iron oxide, titanium oxide, titanium mica, kaolin, mica, sericite, talc, gunjo, gunjo pink, red No. 202, Examples include red 220, red 226, blue 404, yellow 401, nylon powder, carmine-coated titanium mica, carmine-conjugate-coated mica titanium, and silicic anhydride.

  When a pigment is added, the dispersant is also added. Dispersants include soap, zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, sodium lauryl sulfate, triethanolamine lauryl sulfate, cetyl sulfate Sodium, polyoxyethylene lauryl ether sulfate triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether phosphate, polyoxyethylene lauryl ether sodium phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether sodium phosphate, Polyoxyethylene stearyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene oleate Anionic surfactants such as sodium ether phosphate, polyoxyethylene alkylphenyl ether phosphate, polyoxyethylene alkylphenyl ether triethanolamine, sodium polyoxyethylene alkylphenyl ether phosphate, sodium lauroyl sarcosine, soybean phospholipid; stearyl trimethyl ammonium chloride , Cationic surfactants such as distearyldimethylammonium chloride, benzalkonium chloride, benzethonium chloride, stearyldimethylbenzylammonium chloride, cetylpyridinium chloride, alkylisoquinolinium bromide, domifene bromide; sodium β-laurylaminopropionate , Lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betai Amphoteric surfactants such as self-emulsifying glyceryl monostearate, lipophilic glyceryl monostearate, lipophilic glyceride monooleate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, monolaurin Sorbitan acid, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sucrose fatty acid ester, undecylenic acid monoethanolamide, lauric acid diethanolamide, coconut oil fatty acid diethanolamide, Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, myristyl lactate, cetyl lactate, poly Xylethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene stearamide, polyoxyethylene monostearate Glycerin, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate (20EO), polyoxyethylene sorbitan monopalmitate (20EO), polyoxyethylene sorbitan monostearate (6EO), polyoxyethylene sorbitan monostearate (20EO) ), Polyoxyethylene sorbite hexastearate, polyoxyethylene sorbitan monooleate (20EO), triole Nonionic surfactants such as polyoxyethylene sorbitan (20EO), polyoxyethylene sorbite tetraoleate, polyoxyethylene sorbite beeswax, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin Can be mentioned.

  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 contains a dye directly, the content thereof is preferably 0.001 to 5% by weight, particularly 0.01 to 3% by weight in the hair cosmetic of the present invention.

  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; beeswax, whale wax, lanolin, carnauba wax, etc. Waxes: Esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; myristyl al Lumpur, cetyl alcohol, stearyl alcohol, behenyl alcohol, 2-octyldodecanol, higher alcohols such as cetostearyl alcohol; Other isostearyl glyceryl ether, polyoxypropylene butyl ether. Of these, higher alcohols are preferable, and myristyl alcohol, cetyl alcohol, and stearyl alcohol are particularly preferable. These oil agents can be used in combination of two or more, and the content thereof is preferably 0.2 to 2% by weight, more preferably 0.3 to 1.8% by weight, particularly 0.5 to 1.5% by weight in the hair cosmetic composition of the present invention. preferable.

  Moreover, the hair cosmetic composition of the present invention may contain a thickener. Thickeners include organic thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, cationized guar gum, and cationized cellulose, and inorganic bentonite thickeners. A hydrous oxide such as an agent and boehmite can be used.

  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 non-washing-type hair cosmetic of the present invention is preferably in the form of a hair styling agent, hair conditioning agent, etc., and it is easy to use in a form filled in a container such as pump spray or pump foam. More preferably, it may be used in a form enclosed in a pressurized container such as aerosol spray or aerosol foam. As an aerosol propellant, it is preferable to use, for example, liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, or a mixture thereof, and in particular, 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 hair cosmetic / propellant mixing weight ratio is (99.5-40) / (0.5-60), particularly (95-80) / (5-20). 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), particularly (20-60) / (80-40). .

Example 1 and Comparative Example 1
An aerosol-type hair cosmetic stock solution is prepared according to the composition 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 (weight ratio) As a propellant, 0.2 MPa dimethyl ether was filled to obtain an aerosol type hair cosmetic.
The obtained hair cosmetics were evaluated as follows. The results are also shown in Table 1.

・ White hair concealment and color:
1 g of hair cosmetic was applied to 5 g of white hair traces of a Chinese woman, and after standing for 15 minutes, the hiding condition of the white hair and its color tone were evaluated without washing away. The gray hair hiding property was evaluated in three stages: ○: good, Δ: normal, and x: poor.

・ Coloring of fingers:
The coloration of the fingers during the treatment was evaluated. The evaluation was made into three stages: ○: no coloring, Δ: slight coloring, x: coloring.

Claims (8)

A non-washing-out type hair cosmetic for concealing white hair, comprising the following components (A) and (B):
(A) Melanin having a molecular weight of 1000 to 3000 obtained by polymerizing 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid in a molar ratio of 80:20 to 99: 1
(B) Film-forming amphoteric polymer The hair cosmetic for concealing gray hair according to claim 1, wherein component (B) is a (meth) acrylic polymer. The hair cosmetic for hiding gray hair according to claim 1 or 2, further comprising an inorganic or organic pigment and a dispersant thereof. Inorganic or organic pigments are carbon black, titanium black, bentonite, black iron oxide, red iron oxide, yellow iron oxide, titanium oxide, titanium mica, kaolin, mica, sericite, talc, gunjo, gunjo pink, red No. 202, red The white hair according to claim 3, wherein the hair is one or more selected from 220, red 226, blue 404, yellow 401, nylon powder, carmine-coated titanium mica, carmine-conjugate-coated mica titanium, and silicic anhydride. Concealment hair cosmetic. The hair cosmetic for hiding white hair according to claim 3 or 4, wherein the dispersing agent is one or more selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. Furthermore, the hair cosmetic for concealing gray hair according to any one of claims 1 to 5, further comprising an oil agent. Furthermore, the hair cosmetic for concealing gray hair according to any one of claims 1 to 6, further comprising a thickener. An aerosol-type hair cosmetic in which the gray hair concealing hair cosmetic according to any one of claims 1 to 7 and a propellant are enclosed in a pressurized container.