JP2007326805A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair cosmetic which can cover hair surfaces with a melanin polymer in a single hair care behavior such as daily styling to eliminate troublesomeness related to an employment place or an employment method, can simply obscure gray hair, and can dye hair by several continuous employments. <P>SOLUTION: This non-washout type hair cosmetic comprises (A) a melanin polymer prepared by polymerizing two or more compounds represented by formula (1) [the broken line shows the presence or absence of a π-bond; R<SP>1</SP>is OH or acetoxy; R<SP>2</SP>is H, -COOR (R is H, CH<SB>3</SB>or C<SB>2</SB>H<SB>5</SB>) or -COO<SP>-</SP>X<SP>+</SP>(X<SP>+</SP>is a cation); R<SP>3</SP>is H, acetyl, CH<SB>3</SB>or C<SB>2</SB>H<SB>5</SB>], (B) a film-forming polymer, (C) an alkali agent, and (D) an antioxidant and has pH8 to 11. <P>COPYRIGHT: (C)2008,JPO&INPIT

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 white hair, it is common to use hair coloring agents such as hair color and hair nail polish. The location is limited due to consideration, the treatment method is complicated, and there are problems such as unnaturalness immediately after hair dyeing due to abrupt changes in hair color 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. In addition, the polymer of the melanin precursor enzyme was unable to control the color, and the color tone was also monotonous.

JP 2002-47144 A

  The object of the present invention is to cover the hair surface with a melanin polymer in a single-use hair care action such as daily styling, so that the troublesomeness in the place of use and the method of use is eliminated and the gray hair is easily made inconspicuous. An object of the present invention is to provide a hair cosmetic that can be dyed by several continuous uses.

  This inventor discovered that the said subject can be solved by using together 2 or more types of melanin precursors, a film-forming polymer, an alkali agent, and antioxidant.

  The present invention provides a hair cosmetic that contains the following components (A) to (D) and has a pH of 8 to 11 and is not washed away.

  (A) 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 ⁺ cation) indicates, R ³ represents a hydrogen atom, an acetyl group, a methyl or ethyl group. ]

(B) Film-forming polymer
(C) Alkaline agent
(D) Antioxidant

  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 of use and method of use. In particular, by producing melanin without using an enzyme, a hair cosmetic with excellent stability can be produced.

  The compound represented by the general formula (1) as the component (A) is an indole derivative or indoline derivative (melanin precursor) that is converted into a melanin pigment by being oxidized, and in the present invention, two or more of them Use a combination of 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. By combining two or more of these, the dyed color can be adjusted. In particular, from the viewpoint of dyeing hair in a natural color, a combination using 5,6-dihydroxyindole is preferable, and a combination of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid is most preferable. 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 can be quantified by reverse phase HPLC.

  The content of the component (A) compound is preferably 0.01 to 10% by weight, more preferably 0.02 to 5.0% by weight in the hair cosmetic composition of the present invention, from the viewpoint of concealment, color transfer and usability of white hair. 0.05 to 2.0% by weight is preferred.

  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 1000cps), 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.

  Examples of the alkaline agent of component (C) include alkanolamines such as monoethanolamine, guanidine salts such as guanidine carbonate, inorganic salts such as sodium hydroxide and calcium hydroxide, sodium carbonate, sodium citrate, and sodium lactate. Organic acid salts and the like are preferred. Ammonia (water) is not preferred in terms of odor. Of these, alkanolamines and guanidine salts are preferable from the viewpoint of melanin production rate, monoethanolamine and guanidine carbonate are particularly preferable, and guanidine carbonate is most preferable from the viewpoint of polymerization rate.

  The alkaline agent of component (C) can be used alone or in combination of two or more, and the content thereof is preferably 0.01 to 10% by weight in the hair cosmetic composition of the present invention, and more preferably 0.02 to 8.0. % By weight, especially 0.05 to 5.0% by weight is preferred.

  As the antioxidant of component (D), an antioxidant used in a normal hair dye can be used, for example, sulfurous acid, ascorbic acid, thioglycolic acid, L-cysteine, N-acetyl-L -Cysteine and their salts are preferred, and ascorbic acid, sulfurous acid and their salts are particularly preferred because they not only contribute to the stabilization of component (A) but also improve the dyeing power.

  The antioxidant of component (D) can be used alone or in combination of two or more, and its content is from the point of dyeing reddish black suitable for concealing Oriental white hair In the hair cosmetic composition of the present invention, 0.01 to 2% by weight, particularly 0.05 to 1% by weight is preferable.

  In addition to component (A), the hair cosmetic composition of the present invention can also contain melanin produced from the melanin precursor (1) by oxidative polymerization as an additional dye component. As this melanin, an oxidation polymer composed of at least one of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid having a molecular weight of 1000 or more is particularly preferable. 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 is preferably 0.01 to 50% by weight of the hair cosmetic composition of the present invention, more preferably 0.1 to 30% by weight, and particularly preferably 0.5 to 20% by weight.

  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.

  The hair cosmetic composition of the present invention may further contain a pigment. As the pigment, organic pigments such as Red No. 221, Red No. 226, Blue No. 404, and Yellow No. 401; and inorganic pigments such as titanium dioxide, brown iron oxide, red iron oxide, bengara, titanium mica, and bismuth oxychloride can be used. .

  The hair cosmetic composition of the present invention may further contain a surfactant in order to make the coatability during use smooth and to disperse the pigment. 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 the content thereof is preferably 0.1 to 15% by weight, particularly 0.5 to 8% by weight in the hair cosmetic composition 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. As thickeners, organic thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, xanthan gum, hydroxypropylxanthan gum, cationized guar gum, and cationized cellulose, and inorganic Bentonite thickeners based on water, hydrous oxides such as boehmite, and the like 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 melanin precursor of component (A) is oxidized by oxygen in the air under basic conditions and converted to a melanin pigment. For this reason, pH of the hair cosmetics of this invention is adjusted to the range of 8-11, Preferably 8.5-11.

  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). .

Examples 1-3 and Comparative Examples 1-2
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 evaluation of the gray hair concealment was made in three stages: three or more people who were good by the evaluation of five professional panelists: ○: good, 2-1 people Δ: normal, 0 people ×: bad.

・ Dyeability:
The tress used for the evaluation of the gray hair hiding property was shampooed, washed with water and air-dried. After repeating this operation 5 times (after repeating application, leaving, shampooing, washing with water, and air drying 5 times), the dyeability was evaluated. The evaluation was made into three stages: ○: good, Δ: normal, ×: poor.

・ Storage stability:
Each aerosol-type hair cosmetic was filled in an aerosol container, and the appearance, discharge performance, and hair dyeability of the composition after storage at 45 ° C. for 2 weeks were compared and evaluated with those immediately after production. Evaluation is carried out by 5 expert panelists. ○: 3 or more people are good (good), △: 2 to 1 people are normal (normal), ×: 0 people are good (bad) ).

Claims (5)

A non-washing-out type hair cosmetic containing the following components (A) to (D) and having a pH of 8 to 11.
(A) 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
(C) Alkaline agent
(D) Antioxidant   The hair cosmetic according to claim 1, wherein component (A) is a combination of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.   The hair cosmetic composition according to claim 1 or 2, wherein the component (B) is an acrylic polymer.   The oxidation polymer comprising at least one of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid, and having a molecular weight of 1000 or more. Hair cosmetics.   The hair cosmetic according to any one of claims 1 to 4, which is in a form enclosed in a pressurized container.