Hair dye

Abstract

To provide a hair dye which is excellent in dyeing power and color fastness and causes little scalp contamination.SOLUTION: The hair dye contains (A) a compound represented by formula (1) in the figure or a salt thereof, and (B) an oily component.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a hair dye. [Background technology]

[0002] Traditionally, oxidation dyes have been widely used in hair color products such as hair dyes. Oxidation dyes have the advantage of being superior in dyeing power and color fastness to hair compared to other dyes such as acid dyes, basic dyes, and HC dyes.

[0003] The mainstream hair dyes that use oxidation dyes are two-component hair dyes, consisting of a first component that contains an alkaline agent such as ammonia and an oxidation dye, and a second component that contains an oxidizing agent such as hydrogen peroxide. When dyeing hair, two-component hair dyes mix the first and second components and apply them to the hair, dyeing the hair by oxidative polymerization of the oxidation dye.

[0004] Such conventional hair dyes using oxidation dyes have problems such as skin irritation and odor due to alkaline agents such as ammonia, and hair damage and skin irritation due to oxidizing agents such as hydrogen peroxide.

[0005] In response to this, Patent Documents 1 to 3 propose hair dyes containing oxidized polymers obtained by oxidatively polymerizing an oxidative dye in advance. These hair dyes eliminate the need to use ammonia or hydrogen peroxide during hair dyeing, or can reduce the amount of ammonia or hydrogen peroxide used, and are expected to alleviate problems such as skin irritation, odor, and hair damage. Furthermore, Patent Document 1 describes that the use of a hair dye containing an oxidized polymer results in very little dyeing of the scalp or skin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-145032 [Patent Document 2] Japanese Patent Application Publication No. 6-172146 [Patent Document 3] Japanese Patent Application Publication No. 6-199641 Summary of the Invention [Problem to be solved by the invention]

[0007] However, as a result of investigations by the present inventors, it became clear that when the amount of oxidized polymer contained in a conventional hair dye was increased in order to increase the dyeing power, scalp staining (skin staining) was observed.

[0008] Therefore, an object of the present invention is to provide a hair dye which is excellent in dyeing power and color fastness and causes little scalp staining. [Means for solving the problem]

[0009] A hair dye according to one aspect of the present invention contains (A) a compound represented by the following formula (1) or a salt thereof, and (B) an oily component. This hair dye has excellent dyeing power and color fastness, and causes little scalp staining. Furthermore, this hair dye does not require the use of an alkaline agent such as ammonia or an oxidizing agent such as hydrogen peroxide during hair dyeing, or the amount of these agents can be reduced. [ka]

[0010] The above (B) oily component is preferably at least one selected from the group consisting of higher alcohols, silicones, oils and fats, hydrocarbons, higher fatty acids, waxes, and esters, since this improves dyeing power and reduces scalp staining. Effect of the Invention

[0011] According to the present invention, a hair dye having excellent dyeing power and color fastness and causing little scalp staining can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] An embodiment of the present invention will be described in detail below, however, the present invention is not limited to the following embodiment.

[0013] The hair dye of the present embodiment contains (A) a compound represented by the following formula (1) or a salt thereof, and (B) an oily component. [ka]

[0014] The hair dye of the present embodiment may be a one-component hair dye or a multi-component hair dye. In conventional hair dyes using oxidation dyes, the oxidation dye and the oxidizing agent are reacted with each other during dyeing, so that they need to be multi-component hair dyes that can be stored separately before use. On the other hand, in the hair dye of the present embodiment, the compound represented by formula (A) or a salt thereof can function as a dye as it is, so that it does not necessarily need to be a multi-component hair dye and can be a one-component hair dye.

[0015] The multi-component hair dye of the present embodiment can be made into various types of hair dyes because each component can be given the desired properties. The multi-component hair dye may be a two-component type consisting of a first component and a second component, or a three-component type consisting of three or more components, such as a third component in addition to the first and second components, but from the viewpoint of convenience, it is preferable that the multi-component type is a two-component type or a three-component type.

[0016] The formulation of the hair dye of the present embodiment may be, for example, a gel type, a liquid type, a foam type, a spray type, a cream type, an oil type, a powder type, etc. Depending on the formulation and the desired function, the above-mentioned one-component or multi-component hair dye can be selected.

[0017] The hair dye of the present embodiment can be used for dyeing, for example, human hair, wool, animal hair such as yak, and the like.

[0018] The hair dye of the present embodiment may contain (A) a compound represented by formula (1) or a salt thereof and (B) an oil component, but may contain a conventionally known component for the purpose of improving handling, etc. Each component will be described in detail below.

[0019] <(A) Compound represented by formula (1) or a salt thereof> The compound represented by the above formula (1) (hereinafter sometimes referred to as "compound P1-C1") can be obtained by oxidative copolymerization of 4,5-diamino-1-(2-hydroxyethyl)pyrazole (compound P1) and 2,4-diaminophenoxyethanol (compound C1).

[0020] Here, the term "oxidative copolymerization" refers to copolymerization of two or more compounds by oxidation treatment.

[0021] Examples of the salt of the compound represented by formula (1) include hydrochloride, sulfate, acetate, etc. (A) The compound represented by formula (1) or a salt thereof may be the compound represented by formula (1) or a salt thereof alone, or may be a mixture of the compound represented by formula (1) and a salt thereof.

[0022] The above-mentioned compounds P1 and C1 are both oxidation dyes, that is, compounds in which the oxidized polymer obtained by oxidation treatment develops color. Of these, compound P1 is a "precursor" that can be oxidized alone, and compound C1 is a "coupler" that cannot be oxidized alone but is oxidized by using it in combination with a precursor. These compounds may also be used as salts such as hydrochlorides, sulfates, acetates, etc., or hydrates.

[0023] The method of oxidation treatment is not particularly limited, but for example, a method of adding an oxidizing agent such as hydrogen peroxide water to an aqueous solution containing compound P1 and compound C1, a method of blowing air into an aqueous solution containing compound P1 and compound C1 (aeration) and oxidizing with air, a method of adding compound P1 and compound C1 (e.g., their aqueous solution) to an oxidizing agent (e.g., their aqueous solution), a method of contacting a spray of compound P1 and compound C1 (e.g., their aqueous solution) with a spray of an oxidizing agent (e.g., their aqueous solution), etc. can be applied. When the oxidation treatment is performed in an aqueous solution, the temperature of the oxidation treatment is preferably 10 to 60°C, the reaction time is preferably 1 hour to 5 days, and a catalyst such as iron chloride (II) may be used. The pH of the aqueous solution is preferably 5 to 10. The molar ratio of compound P1 and compound C1 during the oxidation treatment can be appropriately selected, but is preferably 1:0.5 to 1:2. The obtained oxidized polymer may be purified by hot water washing, recrystallization, etc.

[0024] The hair dye of the present invention may contain other by-products produced by the oxidation treatment, as long as the effects of the present invention are not impaired.

[0025] The content of the compound represented by formula (1) (A) or a salt thereof in the hair dye of this embodiment can be, for example, 0.001 to 30% by mass based on the total amount of the hair dye. Among these, from the viewpoint of further improving the dyeing power and further reducing scalp staining, it is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 10% by mass.

[0026] <(B) Oily component> The (B) oily component is not particularly limited as long as it is a hydrophobic or poorly water-soluble compound that can be used in cosmetics. When the hair dye contains the (B) oily component, the hair dye stays on the hair and is less likely to drip onto the scalp, improving dyeing power and reducing scalp contamination. Among the (B) oily components, higher alcohols, silicones, oils and fats, hydrocarbons, higher fatty acids, waxes, or esters are preferred, higher alcohols, silicones, hydrocarbons, esters, or oils and fats are more preferred, and higher alcohols are more preferred, in terms of improving dyeing power and reducing scalp contamination.

[0027] Examples of higher alcohols include linear or branched higher alcohols having a carbon number of 10 to 26. The higher alcohol is preferably a linear or branched higher alcohol having a carbon number of 14 to 22, and more preferably a linear higher alcohol having a carbon number of 14 to 22, in that it improves dyeing power and reduces scalp staining.

[0028] Specific examples of higher alcohols include linear higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, arachyl alcohol, behenyl alcohol, lanolin alcohol, and hydrogenated lanolin alcohol; and branched higher alcohols such as 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, and decyltetradecanol.

[0029] Specific examples of silicones include polyether-modified silicones, amino-modified silicones, alkyl-modified silicones, aminoethylaminopropylmethylsiloxane / dimethylsiloxane, dimethylpolysiloxane, dimethylpolysiloxane with hydroxyl end groups, methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, betaine-modified silicones, alkoxy-modified silicones, mercapto-modified silicones, carboxy-modified silicones, and fluorine-modified silicones.

[0030] The kinetic viscosity of silicone is 5mm because it improves dyeing power and reduces scalp staining. 2 / s~350,000mm 2 / s (at 25°C), and 1,000 mm 2 / s~100,000mm 2 / s (at 25° C.) is more preferable. The kinetic viscosity is measured in accordance with JIS K 7117-1:1999, 4.1 (Brookfield rotational viscometer).

[0031] Examples of silicones having a kinetic viscosity within the above range include polyether-modified silicones, amino-modified silicones, alkyl-modified silicones, decamethylcyclopentasiloxane, dimethylpolysiloxane, and aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymers.

[0032] Specific examples of the oils and fats include jojoba seed oil, almond oil, rice bran oil, shea butter, sunflower seed oil, olive oil, macadamia nut oil, rosehip oil, camellia oil, avocado oil, rapeseed oil, palm oil, meadowfoam oil, mink oil, etc. Among these, jojoba seed oil, almond oil, rice bran oil, shea butter, sunflower seed oil, olive oil, or macadamia nut oil is preferred in terms of improved dyeing power and reduced scalp contamination.

[0033] Specific examples of hydrocarbons include mineral oil, light isoparaffin, α-olefin oligomer, light liquid isoparaffin, liquid isoparaffin, squalene, squalane, microcrystalline wax, paraffin, petrolatum, polybutene, polyethylene powder, etc. Among these, mineral oil, light liquid isoparaffin, microcrystalline wax, paraffin, or petrolatum is preferred because they provide improved dyeing power and less scalp staining.

[0034] Specific examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, behenic acid, lanolin fatty acid, hydroxystearic acid, 12-hydroxystearic acid, and ricinoleic acid.

[0035] Specific examples of waxes include beeswax, candelilla wax, rice bran wax, sunflower seed wax, carnauba wax, and lanolin wax.

[0036] Specific examples of esters include lanolin acetate, cetyl lactate, cetyl 2-ethylhexanoate, isononyl isononanoate, cetyl caprylate, cetyl caprate, isopropyl myristate, butyl myristate, isotridecyl myristate, octyldodecyl myristate, myristyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, cetyl palmitate, butyl stearate, stearyl stearate, oleyl oleate, and octyldodecyl ricinoleate. , diisostearyl malate, dioctyl succinate, diisopropyl adipate, diisopropyl dimerate, dextrin palmitate, ethylene glycol di-2-ethylhexanoate, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, tri(caprylic acid / capric acid)glyceryl, sorbitan fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, fatty acid cholesteryl / lanosteryl having a carbon number of 10 to 30, etc. Among these, isopropyl myristate, cetyl palmitate, oleyl oleate, diisopropyl dimerate, or dextrin palmitate are preferred in terms of improved dyeing power and reduced scalp staining.

[0037] The blending amount of the (B) oily component is not particularly limited, but from the viewpoints of emulsion stability, ease of application, compatibility with hair, and dyeing power of the hair dye, the blending amount is preferably 0.1 to 99.6 mass%, more preferably 0.5 to 90 mass%, and even more preferably 1 to 70 mass%, based on the total amount of the hair dye.

[0038] <Optional ingredients> In addition to the above-mentioned (A) compound represented by formula (1) or its salt and (B) oil component, optional components can be blended into the hair dye of this embodiment. The optional components include (C) alkaline agents, (D) surfactants, (E) oxidizing agents, (F) chelating agents, (G) water-soluble polymers, (H) preservatives, (I) other dyes, and (J) water-soluble solvents. These components can be appropriately selected according to the formulation of the hair dye and the desired functions. In addition, in a multi-component hair dye, the optional components may be added to any of the first, second, or third agents, etc., as appropriate.

[0039] ((C) component) The component (C) is one or more alkaline agents. The type of alkaline agent is not limited, but examples include ammonia, alkanolamines, organic amines, basic amino acids and their salts, and inorganic alkaline salts.

[0040] Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

[0041] Examples of the organic amine include 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, and guanidine. Examples of basic amino acids include arginine and lysine.

[0042] Examples of inorganic alkali salts include hydroxides such as sodium hydroxide and potassium hydroxide; hydrogen phosphates or phosphates such as disodium hydrogen phosphate and trisodium phosphate; and carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, guanidine carbonate, and guanidine bicarbonate.

[0043] Among these, from the viewpoint of improving the dyeing power of the dye, inorganic alkali salts are preferred, and calcium carbonate or sodium carbonate is more preferred. When an inorganic alkali salt is contained as component (C) in a multi-component hair dye, it is preferred to contain it in the second agent. The second agent may be, for example, composed of an oxidative polymer of an oxidative dye, an inorganic alkali salt, and the oil component.

[0044] The blending amount of component (C) is not particularly limited, but when component (C) is blended in the hair dye, it is preferably contained in an amount of 0.1 to 20.0 mass%, and more preferably 0.3 to 10.0 mass%, based on the total amount of the hair dye.

[0045] ((D) component) The component (D) is one or more surfactants. The type of surfactant is not limited, and various types of cationic, anionic, nonionic and zwitterionic surfactants can be used.

[0046] Examples of nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty acid esters such as polyethylene glycol monostearate, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene propylene glycol fatty acid esters, polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene sorbitol tetra fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene polyglycerin fatty acid esters, polyoxyalkylene sucrose fatty acid esters, and alkyl glycosides such as decyl glucoside.

[0047] Examples of cationic surfactants include alkyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride (cetrimonium chloride), stearyltrimethylammonium chloride (steartrimonium chloride), behenyltrimethylammonium chloride (behentrimonium chloride), distearyldimethylammonium chloride (disteardimonium chloride), dicocoyldimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide (stearyltrimonium bromide), lanolin fatty acid aminopropylethyl dimethylammonium ethyl sulfate, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, behenyltrimethylammonium methyl sulfate, panthenylhydroxypropylsteardimonium chloride, and quaternium-91.

[0048] Examples of anionic surfactants include alkyl ether sulfates such as sodium POE lauryl ether sulfate, alkyl sulfates such as sodium lauryl sulfate, sodium cetostearyl sulfate, and sodium cetyl sulfate, alkyl phosphates such as POE lauryl ether phosphate and POE cetyl ether phosphate, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates such as sodium POE lauryl ether acetate, α-sulfonic acid salts, N-acyl amino acid surfactants such as triethanolamine cocoyl glutamate (TEA-cocoyl glutamate) and sodium coconut oil fatty acid acyl glutamate, mono- or diester phosphate surfactants such as monoethyl phosphate and dicetyl phosphate, and sulfosuccinates. Examples of the amphoteric surfactant include the following (1) to (5).

[0049] (1) Fatty acid amidopropyl dimethylaminoacetic betaines such as coconut oil fatty acid amidopropyl dimethylaminoacetic betaine, palm oil fatty acid amidopropyl dimethylaminoacetic betaine, lauric acid amidopropyl dimethylaminoacetic betaine (lauramidopropyl betaine), and ricinoleic acid amidopropyl dimethylaminoacetic betaine, and their sodium salts, potassium salts, or triethanolamine salts.

[0050] (2) Alkyl dimethylaminoacetic acid betaines, such as decyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, cetyl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, oleyl dimethylaminoacetic acid betaine, behenyl dimethylaminoacetic acid betaine, and coconut oil alkyl dimethylaminoacetic acid betaine, as well as their sodium salts, potassium salts, or triethanolamine salts.

[0051] (3) N-acylaminoethyl-N-2-hydroxyethylaminocarboxylates, such as sodium cocoamphoacetate (N-cocoacyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine), sodium cocoamphopropionate (N-cocoacyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine), sodium lauroamphoacetate (N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine), sodium olive amphoacetate, sodium cacao butter amphoacetate, sodium sesame amphoacetate, sodium sweet almond amphoacetate, stearoamphoacetate, sodium palm amphoacetate, sodium peanut amphoacetate, sodium sunflower seed amphoacetate, and sodium cottonseed amphoacetate.

[0052] (4) N-acylaminoethyl-N-carboxymethoxyethylaminocarboxylates such as sodium cocoamphodiacetate, sodium cocoamphodipropionate, and sodium lauroamphodiacetate.

[0053] (5) Hydroxyalkyl (C12-14) hydroxyethyl sarcosine.

[0054] The mass ratio of the blended amounts of the (B) component and the (D) component in the hair dye is preferably (B):(D)=1:1 to 5:1, more preferably 2:1 to 4:1, and even more preferably 3:1 to 4:1, from the viewpoints of emulsion stability, ease of application to hair, and improved dyeing power.

[0055] The blending amount of the (D) component is not particularly limited, but when the (D) component is blended in the hair dye, from the viewpoints of the emulsion stability of the hair dye, ease of application, etc., the blending amount of the (D) component is preferably 0.1 to 30 mass%, and more preferably 1.0 to 25 mass%, based on the total amount of the hair dye.

[0056] ((E) component) Component (E) is one or more oxidizing agents. Examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, potassium persulfate, sodium persulfate, sodium peroxide, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, hydrogen peroxide adducts of nitrates, hydrogen peroxide adducts of phosphates, and hydrogen peroxide adducts of pyrophosphates.

[0057] (Component (F)) The component (F) is one or more chelating agents. Chelating agents include gluconic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), dihydroxyethylethylenediaminediacetic acid (DHEDDA), diethylenetriaminepentaacetic acid (DTPA), 1,3-propanediaminetetraacetic acid (1,3PDTA), triethylenetetraminehexaacetic acid (TTHA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIMDA), and L-aspartic acid. Examples of such compounds include -N,N-diacetic acid (ASDA), aminotrimethylenephosphonic acid (NTMP), 1-hydroxyethane-1,1-diphosphonic acid, tripolyphosphoric acid, ascorbic acid, tartaric acid, citric acid, oxalic acid, lactic acid, glycolic acid, hydroxybutyric acid, glyceric acid, glyceronic acid, succinic acid, malic acid, phytic acid, salicylic acid, benzoic acid, acetic acid, ferulic acid, and maleic acid, salts of these compounds, derivatives of these compounds, and salts of these derivatives.

[0058] When the component (F) is blended in the hair dye, the blending amount of the component (F) is preferably 0.001 to 2.0% by mass based on the total amount of the hair dye from the viewpoints of emulsion stability, dyeing power, and the like.

[0059] ((G) component) The component (G) is one or more water-soluble polymers. Specific examples of the water-soluble polymer include natural organic polymers, semi-synthetic organic polymers, synthetic organic polymers, and inorganic polymers.

[0060] Examples of organic natural polymers include plant-based organic natural polymers such as cellulose, gum arabic, guar gum, locust bean gum, carrageenan, quince seed, starch, glycyrrhizic acid, tragacanth gum, carob gum, pectin, galactan, karaya gum, and algae colloid; microbial organic natural polymers such as xanthan gum, dextran, succinoglucan, pullulan, and hyaluronic acid; and animal-based organic natural polymers such as albumin, glycogen, collagen, chondroitin, chondroitin sulfate, mucoitin sulfate, and hyaluronic acid.

[0061] Examples of organic semi-synthetic polymers include starch-based organic semi-synthetic polymers such as carboxymethyl starch and methyl hydroxypropyl starch; cellulose-based organic semi-synthetic polymers such as cationic cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, crystalline cellulose, methyl hydroxypropyl cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, and cellulose powder; alginic acid-based organic semi-synthetic polymers such as sodium alginate and propylene glycol alginate; and cationized guar gum (for example, guar hydroxypropyltrimonium chloride).

[0062] Examples of the organic synthetic polymer include vinyl-based organic synthetic polymers such as carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl methyl ether; polyethylene-based organic synthetic polymers such as polyethylene glycol; copolymer-based organic synthetic polymers such as polyoxyethylene-polyoxypropylene copolymers and polyvinylpyrrolidone / vinyl acetate (VA) copolymers; acrylic-based organic synthetic polymers such as sodium polyacrylate, polyacrylamide, and polyethyl acrylate; polyethyleneimine; and cationic polymers.

[0063] Examples of inorganic polymers include bentonite, labonite, and silicic anhydride.

[0064] ((H) component) Component (H) is one or more preservatives. Examples of preservatives include amino acids, ethylparaben, propylparaben, sodium benzoate, phenoxyethanol, methylisothiazolinone, methylchloroisothiazolinone, hexanediol, pentanediol, ethylhexylglycerin, salicylic acid, piroctone olamine, and methyl paraoxybenzoate.

[0065] (Component (I)) Component (I) is one or more other dyes. Examples of other dyes include acid dyes, basic dyes, HC dyes, disperse dyes, nitro dyes, and oxidized polymers of oxidized dyes other than Compound P1-C1. Examples of acid dyes include Blue No. 1, Purple No. 401, Black No. 401, Orange No. 205, Red No. 227, Red No. 106, Yellow No. 203, and Acid Orange 3. Examples of basic dyes include Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 76, Basic Red 51, Basic Yellow 57, Basic Yellow 87, and Basic Orange 31. Examples of HC dyes include HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Blue 2, HC Red 1, HC Red 3, HC Red 7, and HC Orange 1. Examples of disperse dyes include Disperse Purple 1, Disperse Blue 11, and Disperse Black 9. Examples of nitro dyes include 4-nitro-o-phenylenediamine, 4-nitro-m-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 2-amino-5-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 3-methylamino-4-nitrophenoxyethanol, 4-amino-3-nitrophenol, and 4-hydroxypropylamino-3-nitrophenol.

[0066] By varying the component (I) in the hair dye or by combining one or more kinds of components, the hair color of the hair dye can be adjusted in various ways.

[0067] ((J) Water-soluble solvent) The component (J) is one or more water-soluble solvents. Specific examples of water-soluble solvents include water; ethanol, isopropanol, propanol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, isoprene glycol, 1,3-butylene glycol (1,3-butanediol), isopentyl diol, dipropylene glycol, glycerin, pentanediol, diethylene glycol, phenethyl alcohol, 2-benzyloxyethanol, phenoxyethanol, ethyl alcohol ... Examples of suitable solvents include alcohol solvents such as ethanol and phenoxyisopropanol; N-alkylpyrrolidone solvents such as N-methylpyrrolidone and N-ethylpyrrolidone; alkylene carbonate solvents such as propylene carbonate; and lactone solvents such as γ-valerolactone and γ-caprolactone. Among these, water, ethanol, isopropanol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butylene glycol, isopentyldiol, dipropylene glycol, and glycerin are preferred.

[0068] (Other Ingredients) In addition to the above-mentioned components, other components can be blended into the hair dye of the present embodiment as long as the effects of the present invention are not impaired. Such other components include peptides, amino acid components, pH buffer components, moisturizers such as sodium pyrrolidone carboxylate, sodium lactate, sorbitol, hyaluronic acid, and urea, stabilizers such as 8-oxyquinoline, antioxidants such as cysteine, thioglycolic acid, sulfites, and ascorbic acid, plant extracts, herbal extracts, disinfectants, vitamins, colorants, fragrances, pigments, ultraviolet absorbers, and body powders such as silica.

[0069] The viscosity of the hair dye is preferably 10,000 to 160,000 mPa·s, more preferably 10,000 to 80,000 mPa·s, from the viewpoint of dispersion stability of the oxidative polymer of the oxidative dye and improvement of the handleability of the hair dye. The viscosity of the hair dye can be adjusted by appropriately changing the oil component, etc. If the viscosity of the hair dye is less than 40,000 mPa·s, it can be measured with a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) using a No. 4 rotor at 12 rpm and 20°C, and if the viscosity is 40,000 mPa·s or more, it can be measured with a BH type viscometer (manufactured by Toki Sangyo Co., Ltd.) using a No. 7 rotor at 10 rpm and 20°C. EXAMPLES

[0070] The present invention will be further described below with reference to examples, but the present invention is not limited by these examples. In the examples, the unit of blend amount is "parts by mass", and "remaining amount" refers to the remaining amount excluding the blend amounts of other components when the total amount of each agent is 100 parts by mass. In addition, "1,3-BG" stands for 1,3-butylene glycol, "LPG" stands for liquefied petroleum gas, "VA" stands for vinyl acetate, "POE" stands for polyoxyethylene, "DME" stands for dimethyl ether, and "AMP" stands for 2-amino-2-methyl-1-propanol.

[0071] <Measurement of dynamic viscosity> (B) The kinetic viscosity of the oily components, etc. was measured in accordance with JIS K 7117-1:1999, 4.1 (Brookfield rotational viscometer).

[0072] <Analysis of dyes> The dyes synthesized in the synthesis examples were subjected to liquid chromatography mass spectrometry (LC / MS measurement) and high performance liquid chromatography (HPLC measurement) under the following conditions. LC / MS measurement conditions Equipment used: LC1260 (Agilent Technologies) Column: TSKgel ODS-100S column (Tosoh) Condition A: Column temperature 35°C, methanol / water (30 / 70) eluent, flow rate 0.6 ml / min, detector UV = 580 nm, 430 nm and 250 nm Condition B: Column temperature 40°C, acetonitrile / water (35 / 65) eluent, flow rate 0.6 ml / min, detector UV = 430 nm and 280 nm HPLC measurement conditions Equipment used: UltiMate3000 (manufactured by Thermo Fisher SCIENTIFIC) Column: TSKgel ODS-100S column (Tosoh) Condition C: Column temperature 35°C, methanol / water (30 / 70) eluent, flow rate 0.6 ml / min, detector UV = 580 nm, 430 nm and 250 nm Condition D: Column temperature 40°C, acetonitrile / water (35 / 65) eluent, flow rate 1.00 ml / min, detector UV = 430 nm and 280 nm

[0073] The structure of the synthesized dye can be determined by comparing the actual molecular weight measured by LC / MS measurement with the calculated molecular weight of the polymer calculated based on the molecular weight of the monomer.

[0074] <Dye synthesis> Synthesis Example 1 (Synthesis of Compound P1-C1) To 1000mL of distilled water, 3.2g of 4,5-diamino-1-(2-hydroxyethyl)pyrazole sulfate as a precursor and 3.2g of 2,4-diaminophenoxyethanol dihydrochloride as a coupler (the molar ratio of precursor to coupler is 1:1) were added, and 0.32g of iron(II) chloride was added as a catalyst. The mixture was then adjusted to pH 8 with sodium hydroxide and oxidized for 72 hours with aeration at room temperature. The reaction solution was then dried to obtain 5.6g of precipitate (yield 83%). When the precipitate was subjected to HPLC measurement (condition C), a peak was detected at a retention time of 8.6 minutes, accounting for 93% of the total. When LC / MS measurement (condition A) was performed on the peak, the actual measured value was [M+H] += 307, which was confirmed to correspond to the molecular weight of compound P1-C1 (calculated value: 306). The solution of this peak was separated by HPLC, and the solvent was removed to obtain compound P1-C1 with a purity of 100%.

[0075] Synthesis Example 2 (Synthesis of Compound P2-P2) 5.4 g of p-phenylenediamine, a precursor, was added to 2.0 L of distilled water, and the mixture was stirred and oxidized with air at room temperature for one week. The precipitate was then filtered off, and the residue was washed with hot water at 80 to 90°C to obtain 3.44 g (yield 64%) of a purified product. The collected purified product was subjected to HPLC measurement (condition D), and a peak was detected at a retention time of 6.8 minutes, which accounted for 100% of the total. This peak was subjected to LC / MS measurement (condition B), and the measured value was [M+H] + = 319. This corresponds to the molecular weight of the self-polymer (trimer) of p-phenylenediamine (calculated value: 318), and it was confirmed that the peak compound was a self-polymer (trimer). In addition, the precursor, which is the raw material, was not detected in the HPLC measurement.

[0076] Synthesis Example 3 (Synthesis of Compound P3-C2) 0.20 g of p-aminophenol as a precursor and 0.2 g of 2,6-diaminopyridine as a coupler (the molar ratio of precursor to coupler is 1:1) were added to 100 mL of distilled water, and the mixture was oxidized by stirring for 4 days at room temperature with aeration. After that, the precipitate was filtered and 0.36 g (yield 90%) of precipitate was collected. The collected precipitate was subjected to HPLC measurement (condition D). A first peak, accounting for 9% of the total, was detected at a retention time of 3.2 minutes, and a second peak, accounting for 86% of the total, was detected at a retention time of 4.5 minutes. When LC / MS measurement (condition B) was performed on the first peak, the actual measured value was [M+H] += 320. This corresponds to the molecular weight (calculated value: 319) of a 2:1 copolymer (trimer) of p-aminophenol and 2,6-diaminopyridine, and it was confirmed that the peak compound was a copolymer (trimer). When LC / MS measurement (condition B) was performed on the second peak, the actual measured value was [M+H] + = 322. This corresponds to the molecular weight (calculated value: 321) of a 2:1 copolymer of p-aminophenol and 2,6-diaminopyridine (trimer, an isomer of the first peak compound), and it was confirmed that the peak compound was a copolymer (trimer). In addition, in the HPLC measurement, the raw material precursor and coupler, or self-polymerization of the precursor were not detected. The solution of the second peak was separated by HPLC, and the solvent was removed to obtain compound P3-C2 with 100% purity.

[0077] Synthesis Example 4 (Synthesis of Compound P4-C1) 0.69g of 2,5-diaminotoluene sulfate as a precursor and 0.50g of 2,4-diaminophenoxyethanol hydrochloride as a coupler (the molar ratio of precursor to coupler is 1:1.5) were added to 50mL of distilled water, and 1.61g of 35% aqueous hydrogen peroxide solution was added as an oxidizing agent, and the mixture was adjusted to pH 8 with sodium hydroxide and oxidized by stirring for 4 hours while aerating at room temperature. Magnesium sulfate was then added and the mixture was left for 18 hours to cause salting out, after which the precipitate was filtered and 0.06g (yield 5.0%) of precipitate was collected. The collected precipitate was subjected to HPLC measurement (condition D), and a peak was detected at a retention time of 3.8 minutes, accounting for 78% of the total. When LC / MS measurement (condition B) was performed on this peak, the actual measured value was [M+H] += 287. This corresponds to the molecular weight (calculated value: 286) of a 1:1 copolymer (dimer) of 2,5-diaminotoluene sulfate and 2,4-diaminophenoxyethanol hydrochloride, and it was confirmed that the peak compound was a copolymer (dimer). In addition, the HPLC measurement did not detect the precursor and coupler, which are the raw materials, or the self-polymerization of the precursor. The solution of this peak was separated by HPLC, and the solvent was removed to obtain compound P4-C1 with a purity of 100%.

[0078] Synthesis Example 5 (Synthesis of Compound P1-C3) 1.5 g of 4,5-diamino-1-(2-hydroxyethyl)pyrazole sulfate as a precursor and 0.68 g of m-aminophenol as a coupler (the molar ratio of precursor to coupler is 1:1) were added to 200 mL of distilled water, and 0.12 g of iron(II) chloride was added as a catalyst. The mixture was then adjusted to pH 8 with sodium hydroxide and oxidized for 72 hours with aeration at room temperature. The reaction solution was then dried, and 2.05 g of precipitate (yield 89%) was collected. The collected precipitate was subjected to HPLC measurement (condition C), and a peak was detected at a retention time of 8.2 minutes, accounting for 48% of the total. Since this peak was confirmed at UV=430 nm, where the raw materials 4,5-diamino-1-(2-hydroxyethyl)pyrazole sulfate and m-aminophenol were not detected, it is presumed to be a polymer (dimer) of 4,5-diamino-1-(2-hydroxyethyl)pyrazole sulfate and m-aminophenol. The solution of this peak was separated by HPLC, and the solvent was removed to obtain compound P1-C3 with 100% purity.

[0079] <Prescription Examples> The following prescription example has a dynamic viscosity of 74 to 77 mm. 2 / s (at 25°C), mineral oil with a melting point of 88°C, microcrystalline wax with a melting point of 56°C, kinematic viscosity of 10,000mm 2 Dimethylpolysiloxane of 1000 g / s (at 25°C) was used.

[0080] Formulation examples 1-1 to 1-3 (hair color treatment cream type, single agent formula) A one-part hair dye of hair color treatment cream type was prepared as shown in Table 1. When dyeing hair, 1.5 g of the prepared agent was applied to 1 g of human gray hair bundle, and the hair was left to stand for 15 minutes at 30 to 35°C, after which it was rinsed with water and air-dried.

[0081] [Table 1]

[0082] Formulation examples 2-1 and 2-2 (Hair color treatment oil type 1 agent formula) A one-component hair dye of the hair color treatment oil type was prepared as shown in Table 2. When dyeing hair, 1.5 g of the prepared agent was applied to 1 g of a bundle of human gray hair, and the hair was left to stand for 15 minutes at 30 to 35°C, after which it was rinsed with water and air-dried.

[0083] [Table 2]

[0084] Formulation examples 3-1 and 3-2 (Hair color treatment spray type, single agent type) A one-component hair dye treatment spray type was prepared as shown in Table 3. When dyeing hair, 1.0 g of the prepared agent was applied to 1 g of human gray hair bundle, and the hair was left to stand for 15 minutes at 30 to 35°C, after which it was rinsed with water and air-dried.

[0085] [Table 3]

[0086] Formulation examples 4-1 and 4-2 (foam type hair color treatment) A foam-type hair dye treatment was prepared as shown in Table 4. When dyeing hair, 1.5 g of the prepared agent was applied to 1 g of a bundle of human gray hair, and the hair was left to stand for 30 minutes at 30 to 35°C, after which it was rinsed with water and air-dried.

[0087] [Table 4]

[0088] Formulation examples 5-1 and 5-2 (hair color treatment gel type, single agent formula) A one-part hair dye of hair color treatment gel type was prepared as shown in Table 5. When dyeing hair, 1.5 g of the prepared agent was applied to 1 g of human gray hair bundle, and the hair was left to stand for 30 minutes at 30 to 35°C, after which it was rinsed with water and air-dried.

[0089] [Table 5]

[0090] Formulation example 6 (hair color cream type two-component formula) A two-component cream-type hair dye consisting of the first and second components was prepared according to the formula shown in Table 6. When dyeing hair, the first and second components were mixed in a 1:1 ratio, and 1.5 g of the mixture was applied to 1 g of human gray hair bundle, left for 30 minutes at 30-35°C, then rinsed with water and air-dried.

[0091] [Table 6]

[0092] Formulation examples 7-1 and 7-2 (hair color treatment cream dispersant type) A hair color treatment cream dispersion type hair dye consisting of the first and second agents was prepared according to the formula shown in Table 7. When dyeing hair, the first and second agents were mixed in a ratio of 4:1, and 1.5 g of the mixture was applied to 1 g of human gray hair bundle, left for 15 minutes at 30 to 35°C, then rinsed with water and air-dried.

[0093] [Table 7]

[0094] Formulation examples 8-1 and 8-2 (hair color treatment oil dispersant type) A hair color treatment oil dispersion type hair dye consisting of the first and second agents was prepared according to the formula shown in Table 8. When dyeing hair, the first and second agents were mixed in a ratio of 4:1, and 1.5 g of the dye was applied to 1 g of human gray hair bundle, left for 15 minutes at 30 to 35°C, then rinsed with water and air-dried.

[0095] [Table 8]

[0096] Formulation examples 9-1 and 9-2 (hair coloring cream type 3-component formula) A cream-type three-component hair dye consisting of the first, second, and third agents was prepared according to the formula shown in Table 9. When dyeing hair, the first, second, and third agents were mixed in a ratio of 4:1:5, and 1.5 g of the mixture was applied to 1 g of human gray hair bundle, left for 30 minutes at 30 to 35°C, then rinsed with water and air-dried. In addition, Formulation Example 9-1 was prepared by heating and dissolving the shea butter at 80°C, which is higher than the melting point of the shea butter.

[0097] [Table 9]

[0098] (Examples 1 to 17, Comparative Examples 1 to 26) The following evaluations were carried out on the hair dyes using the formulation examples shown in Tables 1 to 9. The following evaluations were also carried out on the dyes. The results are shown in Tables 11 to 16.

[0099] <Evaluation> Evaluation method 1 (dye density) Each hair dye was mixed and used to dye a strand of hair. The dyeing strength of the strand of hair after dyeing was evaluated by 20 expert panelists according to the following criteria. The darker the dye, the better the dyeing power. ◎: Very dark dye ○: Dyes deeply △: Lightly stained ×: Very lightly stained

[0100] Evaluation method 2 (color fastness) The hair bundle dyed in Evaluation Method 1 was washed with water using the shampoo (2 g per 1 g of hair bundle) shown in Table 10. The shampoo washing was repeated three times, and the dye intensity of the hair bundle before and after washing was evaluated by 20 expert panelists according to the following evaluation criteria. ◎: No fading ○: Little color fading △: Large color fading ×: Very large color fade

[0101] Evaluation method 3 (scalp contamination) Each hair dye was prepared, used to dye human hair, and then washed with water using the shampoo (2 g per 1 g of hair bundle) shown in Table 10. The state of scalp contamination after repeated shampoo washing was evaluated by 20 expert panelists according to the following evaluation criteria. ◎: Almost no scalp contamination with one wash after dyeing ○: Scalp contamination was observed after one wash after dyeing, but there was almost no scalp contamination after two shampoo washes. △: Scalp contamination was observed after washing twice after dyeing, but there was almost no scalp contamination after washing with shampoo 3 to 5 times. ×: Scalp contamination observed after washing with shampoo 6 or more times after dyeing

[0102] [Table 10]

[0103] [Table 11]

[0104] [Table 12]

[0105] [Table 13]

[0106]

Table 14

[0107]

Table 15

[0108]

Table 16

Claims

1. A hair dye comprising (A) a compound represented by the following formula (1) or a salt thereof, and (B) an oil component: 【Chemistry 1】

2. 2. The hair dye according to claim 1, wherein the oily component (B) is at least one member selected from the group consisting of higher alcohols, silicones, fats and oils, hydrocarbons, higher fatty acids, waxes and esters.

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