WO2021084952A1

WO2021084952A1 - Oxidation hair dye

Info

Publication number: WO2021084952A1
Application number: PCT/JP2020/035163
Authority: WO
Inventors: 圭実伊藤; 誠唐渡; 基酒井; 貴子小谷; 裕子篠田; 春佳山田; 朋也園田
Original assignee: ホーユー株式会社
Priority date: 2019-10-31
Filing date: 2020-09-17
Publication date: 2021-05-06
Also published as: CN114667131A; JPWO2021084952A1; TW202118477A

Abstract

The present invention is an oxidation hair dye containing a coupler (A) and characterized in that when the oxidation hair dye contains a dye intermediate (C), the mass ratio (A/C) of the component (A) content to the total dye intermediate (C) content is 2.5 or more. The oxidation hair dye may further contain an alkaline agent (B) and/or an iodine compound (D).

Description

Oxidative hair dye

The present invention relates to an oxidative hair dye containing a coupler.

For example, an oxidative hair dye composed of a first agent containing an alkaline agent and an oxidative dye and a second agent containing an oxidant, for example, hydrogen peroxide is known. The alkaline agent promotes the action of the oxidizing agent contained in the second agent and swells the hair to improve the permeability of the dye to the hair. The oxidant decomposes the melanin pigment in the hair and forms an oxidative dye polymer inside the hair. After the alkaline agent is removed, the hair cuticle closes and the oxidative dye polymer is encapsulated inside the hair.

Since the oxidative dye polymer inside the hair does not easily decompose, the decontamination performance is low. When the hair is dyed with an oxidative hair dye and then re-dyed to another color, the decontamination is performed once. It was necessary to decontaminate with an agent. Furthermore, there were cases where a single decontamination treatment was not sufficient for decontamination.

Conventionally, an oxidative hair dye used for decomposing a dark-colored oxidative dye polymer inside hair without de-staining with a de-staining agent and re-staining (recoloring) the hair to a clear bright color has been used. Are known. For example, the oxidative hair dye disclosed in Patent Document 1 improves the recoloring performance by containing a diamine-based dye intermediate or the like as the main component of the dye.

International Publication No. 2009/05/72228

An object of the present invention is to provide an oxidative hair dye capable of improving decontamination performance and recoloring performance while maintaining hair dyeing performance.

In the present invention, the dye intermediate is not substantially contained as the oxidation dye and only the coupler is contained, or the coupler is contained in a predetermined amount with respect to all the dye intermediates to remove the hair while maintaining the hair dyeing performance. It is based on the finding that the dyeing performance can be improved.

In order to achieve the above object, the oxidative hair dye according to one aspect of the present invention is an oxidative hair dye containing (A) a coupler, and the oxidative hair dye contains (C) a dye intermediate. In the case, the mass ratio (A / C) of the content of the component (A) to the content of the total (C) dye intermediate is 2.5 or more.

The oxidative hair dye may contain (B) an alkaline agent.

The oxidative hair dye may contain (D) an iodine compound.

In the oxidative hair dye, the (B) alkaline agent may contain at least one selected from (B1) carbamic acid ion, carbonate ion, and hydrogen carbonate ion.

According to the present invention, the decontamination performance can be improved and the recoloring performance can be improved while maintaining the hair dyeing performance.

(First Embodiment)
Hereinafter, the first embodiment in which the oxidative hair dye of the present invention is embodied will be described. The oxidative hair dye of the first embodiment is configured as a multi-agent oxidative hair dye, for example, a two-agent oxidative hair dye having a coupler (A) and a second agent containing an oxidant. To. Hereinafter, the components of the two-agent oxidative hair dye will be illustrated. When a solubilizer such as water is used, the value of mass% indicating the content of the component is a value in the dosage form including them.

(The first agent of a two-agent oxidative hair dye)
The first agent of the oxidative hair dye is (A) coupler, (B) alkaline agent, (D) iodine compound, (E) oily component, (F) polyhydric alcohol, and / or (G) surfactant. The agent may be contained. Oxidation dyes are classified into (A) couplers and (C) dye intermediates. Usually, in an oxidative hair dye, color is developed by polymerizing dye intermediates or a dye intermediate and a coupler. In the present invention, it has been found that color can be developed even when (C) the dye intermediate is substantially not contained or the total dye intermediate is not more than a predetermined ratio with respect to the (A) coupler.

Specific examples of the coupler (A) include resorcin, 5-amino-o-cresol, m-aminophenol, α-naphthol (1-naphthol), 5- (2-hydroxyethylamino) -2-methylphenol, and the like. m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, N, N-diethyl-m-aminophenol, phenylmethylpyrazolone, 1,5-dihydroxynaphthalene , Those salts and the like. Specific examples of the salt include, for example, hydrochloride, sulfate and the like. One kind of component (A) may be used alone, or two or more kinds of component (A) may be used in combination. As the coupler (A), preferably 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5- (2-hydroxyethylamino) -2-methylphenol, 1-naphthol, 5-amino-o-cresol, 1,5-Dihydroxynaphthalene, m-aminophenol, and salts thereof can be used.

The lower limit of the content of the coupler (A) in the mixture of the first agent and the second agent, that is, the oxidative hair dye during the hair dyeing treatment applied to the hair is appropriately set, but is preferably 0.5 mass by mass. % Or more, more preferably 0.6% by mass or more, still more preferably 0.7% by mass or more. When the content of the coupler (A) is 0.5% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the coupler (A) in the mixture is appropriately set, but is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and most preferably 3.5% by mass. % Or less. When the content of the coupler (A) is 10% by mass or less, the decontamination performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the coupler (A) is a salt, the content of the coupler (A) is the value in the desalted form.

The first agent of the oxidative hair dye does not prevent the inclusion of the (C) dye intermediate if necessary. Specific examples of the dye intermediate (C) include p-phenylenediamine, p-toluylenediamine (toluene-2,5-diamine), N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, and the like. p-aminophenol, o-aminophenol, p-methylaminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chlor-p-phenylene Examples thereof include diamine, 4-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 1-hydroxyethyl-4,5-diaminopyrazole, and salts thereof. Specific examples of the salt include, for example, hydrochloride, sulfate and the like. One kind of component (C) may be used alone, or two or more kinds of component (C) may be used in combination. The first agent may appropriately contain, for example, an oxidation dye listed in "Quasi-drug Raw Material Standards" (published in June 2006, Yakuji Nippo Co., Ltd.) as a dye other than the specific example of the oxidation dye.

In the mixture, the mass ratio (A / C) of the content of the (A) coupler to the content of the total (C) dye intermediate is 2.5 or more, preferably 5.0 or more, more preferably 7.5. The above is more preferably 10 or more. When the mass ratio (A / C) is 2.5 or more, the decontamination performance can be improved. When the coupler (A) and the dye intermediate (C) are salts, the content used for calculating the mass ratio is the value in the desalted form for both (A) and (C).

The upper limit of the content of the dye intermediate (C) in the mixture is appropriately set within the range of the mass ratio (A / C) of the above content, but is preferably 1% by mass or less, more preferably 0.5. It is by mass or less, more preferably 0.2% by mass or less, and particularly preferably the mixture is substantially free of the (C) dye intermediate. In the present invention, "substantially free" means that the content is 0.1% by mass or less. When the content of the dye intermediate (C) is 1% by mass or less, the decontamination performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (C) dye intermediate is a salt, the content of the (C) dye intermediate is the value in the desalted form.

The first agent may contain (B) an alkaline agent. (B) The alkaline agent acts to improve the hair dyeing power by promoting the action of the oxidizing agent contained in the second agent. Examples of the alkaline agent include ammonia, alkanolamine, silicate, carbonate, hydrogencarbonate, carbamate, metasilicate, sulfate, chloride, phosphate, organic amine, basic amino acid and the like. .. Specific examples of the alkanolamine include monoethanolamine, triethanolamine and the like. Specific examples of the silicate include sodium silicate, potassium silicate, calcium silicate and the like. Specific examples of the carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate and the like. Specific examples of the hydrogen carbonate include sodium hydrogen carbonate, ammonium hydrogen carbonate and the like. Specific examples of the carbamate include ammonium carbamate and the like. Specific examples of the metasilicate include sodium metasilicate, potassium metasilicate and the like. Specific examples of the sulfate include ammonium sulfate and the like. Specific examples of chlorides include ammonium chloride and the like. Specific examples of the phosphate include ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like. Specific examples of the organic amine include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, guanidine and the like. Specific examples of basic amino acids include arginine, lysine and the like. One kind of component (B) may be used alone, or two or more kinds of component (B) may be used in combination. Among these, carbonates, bicarbonates, carbamates, ammonia, ammonium salts, and alkanolamines are preferably applied from the viewpoint of improving hair dyeing ability. Further, the (B) alkaline agent may be contained as at least one selected from (B1) carbamic acid ion, carbonate ion, and hydrogen carbonate ion from the viewpoint of improving hair dyeing ability.

The content of the (B) alkaline agent in the mixture is preferably such that the lower limit of the pH of the mixture is 7 or more, and more preferably 9 or more. The content of the alkaline agent (B) is preferably such that the upper limit of the pH of the mixture is 12 or less. By setting the pH of the mixture to 7 or more, the action of the oxidizing agent contained in the second agent can be further promoted. By setting the pH of the mixture to 12 or less, damage to the hair can be further suppressed. The pH of the mixture is the pH of a 10% by mass aqueous solution prepared by diluting the mixture of each agent 10 times with water at 25 ° C. The upper limit of the content of the (B) alkaline agent in the mixture is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. The lower limit of the content of the (B) alkaline agent in the mixture is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more.

The (D) iodine compound contained in the first agent improves the hair dyeing power by decomposing hydrogen peroxide by iodine constituting the iodine compound and promoting the polymerization of the oxidative dye. The effect of improving the hair dyeing power of the iodine compound (D) is more strongly exhibited when the amount of the dye intermediate (C) is small or not. Examples of the iodine compound (D) include iodine (I), iodide with a counterion liberated in a solubilizer, and a compound that liberates iodine during use. Specific examples of iodide include alkali metal salts of iodide such as potassium iodide, sodium iodide, lithium iodide and ammonium iodide, hydrogen iodide, cesium iodide, silver iodide and the like. Further, a natural material containing iodine, for example, an extract containing iodide such as garlic iodide extract may be applied. One kind of component (D) may be used alone, or two or more kinds of component (D) may be used in combination.

The lower limit of the content of the (D) iodine compound in the mixture is appropriately set, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more. Most preferably, it is 0.05% by mass or more. When the content of the iodine compound (D) is 0.001% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the (D) iodine compound in the mixture is appropriately set, but is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. When the content of the iodine compound (D) is 5% by mass or less, the decontamination performance can be further improved.

In the mixture, the lower limit of the mass ratio (D / A) of the content of the (D) iodine compound to the content of the (A) coupler is appropriately set, but is preferably 0.01 or more, more preferably 0. It is 05 or more, more preferably 0.1 or more. When the mass ratio (D / A) is 0.01 or more, the hair dyeing power can be improved. The upper limit of the mass ratio (D / A) of the content of the iodine compound (D) to the content of the coupler (A) is appropriately set, but is preferably 1.0 or less, more preferably 0.5 or less, and further. It is preferably 0.25 or less. When the mass ratio (D / A) is 1.0 or less, the decontamination performance can be improved. When the coupler (A) is a salt, the content used for calculating the mass ratio is the value in the desalted type.

The first agent of the present invention may further contain (E) an oily component. (E) When the oily component is contained, the hair dyeing power can be further improved. Examples of the oily component (E) include fats and oils, waxes, higher alcohols, hydrocarbons, higher fatty acids, alkyl glyceryl ethers, esters, silicones and the like.

Specific examples of fats and oils include Argania spinosa kernel oil, lanolin, olive oil, camellia oil, shea butter, almond oil, saflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, corn oil, rapeseed oil, rice bran oil, etc. Examples include rice germ oil, grape seed oil, avocado oil, macadamia nut oil, castor oil, palm oil, evening primrose oil and the like. Specific examples of wax include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin wax and the like. Specific examples of higher alcohols include cetyl alcohol (cetanol), 2-hexyldecanol, stearyl alcohol, isostearyl alcohol, cetostearyl alcohol, oleyl alcohol, araquil alcohol, behenyl alcohol, 2-octyldodecanol, lauryl alcohol, and myristyl alcohol. , Decyltetradecanol, lanolin alcohol and the like.

Specific examples of hydrocarbons include paraffin, olefin oligomer, polyisobutene, hydrogenated polyisobutene, mineral oil, squalane, polybutene, polyethylene, microcrystalline wax, petrolatum and the like. Specific examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, lanolin fatty acid and the like. Specific examples of the alkyl glyceryl ether include batyl alcohol, kimil alcohol, ceracyl alcohol, isostearyl glyceryl ether and the like.

Specific examples of the ester include, for example, diisopropyl adipate, isopropyl myristate, cetyl octanate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, stearyl stearate, myristyl myristate, isotridecyl myristate, 2-ethyl palmitate. Hexil, octyldodecyl ricinolate, fatty acid cholesteryl / lanosteryl having 10 to 30 carbon atoms, cetyl lactate, lanolin acetate, ethylene glycol di-2-ethylhexanoate, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, capric acid Examples thereof include cetyl, glyceryl tricaprylate, diisostearyl malate, dioctyl succinate, and cetyl 2-ethylhexanoate.

Specific examples of silicone include, for example, dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, terminal hydroxyl group-modified dimethylpolysiloxane, highly polymerized silicone, and polyether-modified silicone (for example,). (PEG / PPG / butylene / dimethicone) copolymer), amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like. One kind of oily component may be used alone, or two or more kinds of oily component may be used in combination.

The first agent of the present invention may further contain (F) a polyhydric alcohol. (F) When a polyhydric alcohol is contained, the stability of the preparation can be improved. Examples of the (F) polyhydric alcohol include glycol, glycerin and the like. Examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, highly polymerized polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, 1,3-butylene glycol and the like. Examples of glycerin include glycerin, diglycerin, polyglycerin and the like. One kind of polyhydric alcohol may be used alone, or two or more kinds of polyhydric alcohols may be used in combination. From the viewpoint of formulation stability, polyethylene glycol is particularly preferable.

The first agent of the present invention may further contain a (G) surfactant. When (G) a surfactant is contained, the stability of the preparation can be further improved. Examples of the (G) surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

Specific examples of anionic surfactants include, for example, alkyl ether sulfate, alkyl sulfate, alkyl ether sulfate, alkenyl ether sulfate, alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated. Fatty acid salt, alkyl or alkenyl ether carboxylate, α-sulfon fatty acid salt, N-acylamino acid type surfactant, phosphate mono or diester type surfactant, sulfosuccinic acid ester, N-alkylmethyl taurine salt, their Derivatives and the like can be mentioned. Specific examples of the counterion of the anion group of these surfactants include sodium ion, potassium ion, triethanolamine and the like. More specifically, examples of the alkyl ether sulfate ester salt include POE sodium lauryl ether sulfate. Specific examples of the alkyl sulfate include sodium lauryl sulfate, sodium cetyl sulfate and the like. Specific examples of the alkyl sulfate derivative include POE sodium lauryl sulfate and the like. Specific examples of the phosphoric acid ester-type surfactant include POE oleyl ether phosphoric acid and the like.

Specific examples of cationic surfactants include, for example, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, Lanolin Ethyl Sulfate Fatty Acid Aminopropyl Ethyldimethylammonium, Stearyltrimethylammonium Saccharin, Cetyltrimethylammonium Saccharin, Methacryloyloxyethyltrimethylammonium Chloride, Behenyltrimethylammonium Methyl Sulfate, Behenyldimethylamine, Diethylaminoethylamide Behenic Acid, Dimethylaminopropylamide Behenate, Examples thereof include behenic acid dimethylaminoethylamide, stearyldimethylamine, palmitoxipropyldimethylamine, stearoxypropyldimethylamine, stearic acid dimethylaminopropylamide and the like. Specific examples of alkyltrimethylammonium chloride include behenyltrimethylammonium chloride, araquiltrimethylammonium chloride and the like.

Specific examples of amphoteric tensides include cocobetaine, lauramidepropyl betaine, cocamidopropyl betaine, sodium lauroanphoacetate, sodium cocoamphoacetate, coconut oil fatty acid amide propyl betaine, lauryl betaine (lauryldimethylaminoacetic acid betaine), and lauryl. Examples thereof include sodium aminopropionate.

Specific examples of the nonionic surfactant include ether type nonionic surfactant, ester type nonionic surfactant, alkyl glucoside and the like. Specific examples of ether-type nonionic surfactants include POE cetyl ether (Cetes), POE stearyl ether (Staires), POE behenyl ether, POE oleyl ether (Ores), POE lauryl ether (Laures), and POE octyldodecyl. Examples thereof include ether, POE hexyl decyl ether, POE isostearyl ether, POE nonyl phenyl ether, POE octyl phenyl ether, POE polyoxypropylene cetyl ether, POE polyoxypropylene decyl tetradecyl ether and the like.

Specific examples of the ester-type nonionic surfactant include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monopalmitate, POE sorbitan monolaurate, POE sorbitan trioleate, and POE glycerin monostearate. POE glycerin monomyristate, POE sorbit tetraoleate, POE sorbit hexastearate, POE sorbit monolaurate, POE sorbit Mitsurou, polyethylene glycol monooleate, polyethylene glycol monostearate, polyethylene glycol monolaurate, monooleic acid prooleate Glycerin, lipophilic glycerin monostearate, self-emulsifying glycerin monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sucrose fatty acid Examples thereof include esters, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monooleate, and decaglyceryl monomyristate.

Specific examples of the alkyl glucoside include alkyl (8 to 16) glucoside, POE methyl glucoside, POE dioleate methyl glucoside and the like. One kind of surfactant may be used alone, or two or more kinds of surfactants may be used in combination.

If necessary, the oxidative hair dye may include components other than those described above, such as solubilizers, water-soluble polymers, pH adjusters other than the above, preservatives, stabilizers, plant extracts, crude drug extracts, vitamins, etc. It may further contain a fragrance, an antioxidant, a chelating agent, an ultraviolet absorber and the like.

The solubilizer is added, for example, when the dosage form is made liquid or the like. Examples of solubilizers used include water and organic solvents (solvents). Specific examples of the organic solvent include, for example, ethanol, n-propanol, isopropanol, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, silica skin alcohol, anis alcohol, and the like. Examples thereof include p-methylbenzyl alcohol, α-dimethylphenethyl alcohol, α-phenylethanol, ethylene glycol phenyl ether (phenoxyethanol), phenoxyisopropanol, 2-benzyloxyethanol, N-alkylpyrrolidone, alkylene carbonate and alkyl ether. One kind of solubilizer may be used alone, or two or more kinds of solubilizers may be used in combination. Among these, water is preferably applied because it has an excellent ability to dissolve other components in the first agent. When water is used as the solvent, the content of water in the mixture (content at the time of use) is preferably 40% by mass or more, more preferably 50% by mass or more.

The water-soluble polymer gives the oxidative hair dye an appropriate viscosity. Therefore, the oxidative hair dye may contain a water-soluble polymer within a range that does not impair the effects of the present invention. Examples of the water-soluble polymer include natural polymers, semi-synthetic polymers, synthetic polymers, and inorganic polymers. Specific examples of natural polymers include guar gum, locust bean gum, quince seed, carrageenan, galactan, arabic gum, tragacanto gum, pectin, mannan, xanthan gum, dextran, succinoglucan, curdran, hyaluronic acid, gelatin, casein, etc. Examples include albumin, collagen, dextrin, triglucopolysaccharide (pullulan) and the like.

Specific examples of the semi-synthetic polymer include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose dimethyldiallyl ammonium chloride, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, cationized cellulose, cationized guar gum, and starch phosphorus. Examples thereof include acid ester, propylene glycol alginate, and alginate.

Specific examples of the synthetic polymer include polyvinylcaprolactam, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), vinylpyrrolidone-vinyl acetate (VP / VA) copolymer, polyvinylbutyral, polyvinylmethyl ether, carboxyvinyl polymer, and poly. Soda acrylate, polyacrylamide, polyethylene oxide, ethylene oxide / propylene oxide block copolymer, acrylate / alkyl acrylate copolymer, polydimethyldimethylenepyrrolidinium (polyquantanium-6) (Mercoat 100: manufactured by Merck) , A semi-ester of itaconic acid and polyoxyethylene (hereinafter referred to as "POE") alkyl ether, or an ester of methacrylic acid and POE alkyl ether, and at least one selected from acrylic acid, methacrylic acid and their alkyl esters. Examples thereof include a copolymer composed of a monomer and a monomer. One kind of water-soluble polymer may be used alone, or two or more kinds of water-soluble polymers may be used in combination.

The pH adjuster may be contained to adjust the pH of the oxidative hair dye (mixture). The pH adjuster is appropriately selected from known ones depending on the type of oxidation dye. Specific examples of the pH adjuster include inorganic acids, organic acids, salts thereof, and hydroxides of alkali metals or alkaline earth metals. Examples of the organic acid include citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, malic acid, levulinic acid, acetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, fumaric acid, mandelic acid, acidic amino acids and the like. .. Specific examples of the organic acid salt include sodium salt, potassium salt and the like. Specific examples of the inorganic acid include phosphoric acids such as phosphoric acid and pyrophosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, boric acid and the like. Specific examples of hydroxides of alkali metals or alkaline earth metals include sodium hydroxide, potassium hydroxide and the like.

Specific examples of preservatives include paraben, methylparaben, sodium benzoate and the like. Specific examples of the stabilizer include phenacetin, 8-hydroxyquinoline, acetanilide, sodium pyrophosphate, barbituric acid, uric acid, tannic acid and the like. Specific examples of the antioxidant include ascorbic acids, sulfites and the like. Specific examples of the chelating agent include edetonic acid (ethylenediaminetetraacetic acid (EDTA)), disodium edetate, tetrasodium edetate, diethylenetriaminetetraacetic acid and its salts, hydroxyethylethylenediaminetriacetic acid and its salts, and hydroxyethanedi. Phosphonic acid (HEDP) and salts thereof and the like can be mentioned. As the above-mentioned other components, one kind of other components may be used alone, or two or more kinds of other components may be used in combination.

The dosage form of the first agent is not particularly limited, and specific examples thereof include a liquid form such as an aqueous solution or a milky lotion, a gel form, a foam form, a cream form, and a solid form. In the case of a solid dosage form, a dispersant may be blended. Dosage forms such as aerosols and non-aerosols can be used, and in the case of non-aerosols, various forms such as a squeeze former type and a pump former type can be further taken. In the case of aerosols, known propellants and foaming agents can be applied. Specific examples of the propellant or foaming agent include liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen gas, carbon dioxide gas and the like.

(Second agent of two-agent oxidative hair dye)
In addition to the oxidizing agent, the second agent may also contain components such as the above-mentioned solubilizing agent. Oxidizing agents further improve the decolorization of melanin contained in hair. Specific examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium peroxide, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, potassium persulfate, and sodium persulfate. Sodium peroxide, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, strontium peroxide, hydrogen peroxide adduct of sulfate, hydrogen peroxide adduct of phosphate, hydrogen peroxide of pyrophosphate Additives and the like can be mentioned. One kind of oxidizing agent may be used alone, or two or more kinds of oxidizing agents may be used in combination. The content of the oxidizing agent in the second agent is appropriately set, but is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and further preferably 2.0% by mass or more. Is. When the content of the oxidizing agent is 0.1% by mass or more, the decolorizing property of melanin can be further improved. The content of the oxidizing agent in the second agent is preferably 15.0% by mass or less, more preferably 9.0% by mass or less, and further preferably 6.0% by mass or less. When the content of the oxidizing agent is 15.0% by mass or less, damage to hair and the like can be further suppressed.

When hydrogen peroxide is added to the second agent as an oxidizing agent, in order to improve the stability of hydrogen peroxide, the second agent is preferably a stabilizer such as sodium succinate or ethylene glycol phenyl ether (phenoxyethanol). ), Hydroxyethanediphosphonic acid and / or a salt thereof. Examples of the hydroxyethanediphosphonate include tetrasodium hydroxyetanediphosphonate and disodium hydroxyethanediphosphonate. The second agent may contain each component that is generally contained in the oxidative hair dye and does not inhibit the action of each component described above. For example, the above-mentioned component contained in the first agent may be appropriately contained within a range that does not impair the effects of the present invention.

The dosage form of the second agent is not particularly limited, and specific examples thereof include a liquid form such as an aqueous solution or a milky lotion, a gel form, a foam form, a cream form, and a solid form. Dosage forms such as aerosols and non-aerosols can be used, and in the case of non-aerosols, various forms such as a squeeze former type and a pump former type can be further taken. In the case of aerosols, known propellants and foaming agents can be applied. In the case of a solid dosage form, a dispersant may be blended.

The mixing ratio of the first agent and the second agent of the two-agent oxidative hair dye is appropriately set in consideration of the concentration, miscibility, application method, etc. of each component in the mixture, but is preferably 0.1. It is ~ 10: 1, more preferably 0.5 ~ 2: 1. The dosage form of the mixture is not particularly limited as long as it is a dosage form applicable to hair, and specific examples thereof include a liquid form such as an aqueous solution or a milky lotion, a gel form, a foam form, and a cream form. .. It is preferably in the form of a cream or paste from the viewpoint of being easy to remove with a brush, extending to the hair and adhering to the hair, and being excellent in application operability. Further, the hair dye composition may be further formed into a foam-like or mist-like form. In the case of foaming as described above, even if the hair dye composition is formed by self-foaming by mixing the hair dye composition in the mixing container and the mixing instrument, the hair dye composition is filled in a shaking container and shaken. A known foaming device such as a non-aerosol former or an aerosol former may be used.

As a means for applying the hair dye composition to the hair, it may be applied to the hair using an application tool such as a comb, a brush, a brush, or an applicator. In addition, the hair dye composition may be applied to the hair by hand wearing gloves.

The action and effect of the oxidative hair dye of the first embodiment will be described.

(1-1) In the first embodiment, in the oxidative hair dye, the dye intermediate is not substantially contained and only the coupler is contained as the oxidative dye, or the coupler is contained in a predetermined ratio or more with respect to the total dye intermediate. contains. Therefore, the decontamination performance can be improved and the recoloring performance can be improved while maintaining the hair dyeing performance.

Since the polymer between the dye intermediates or the polymer between the dye intermediate and the coupler has a characteristic that it is not easily decomposed by an alkaline agent or an oxidizing agent, there is a problem that the hair dyeing treatment cannot be performed in a bright color tone from the next time onward. The oxidative hair dye of the first embodiment is alkaline by containing only a coupler as an oxidative dye without substantially containing a dye intermediate, or by containing a coupler in a predetermined ratio or more with respect to all the dye intermediates. Since it forms a polymer that is easily decomposed by the agent, it has excellent decontamination performance and has less influence on the hair color from the next time onward. As a result, you can enjoy various hair colors without considering the next hair color.

(1-2) Further, when the oxidative hair dye contains the (D) iodine compound, the polymerization of the oxidative dye can be promoted and the hair dyeing power can be improved.

(1-3) Since the oxidative hair dye does not substantially contain a dye intermediate or its content is very small, it may be used by a subject who is allergic to a specific dye intermediate, for example. is there.

The above embodiment can be modified and implemented as follows. The above embodiment and the following modified examples can be implemented in combination with each other within a technically consistent range.

In the above embodiment, as a dye other than the above-mentioned oxidative dye, a dye that can be contained in the oxidative hair dye, for example, a direct dye, a legal dye, a basic dye, an HC dye, etc., is appropriately used as long as the effect of the present invention is not impaired. It may be contained.

The oxidative hair dye is not limited to the two-agent type, and a part of each component contained in the first agent and the second agent may be composed as a separate agent and may be composed of three or more agents. For example, the first agent of the two-agent type is divided into two, an agent containing a coupler and an alkaline agent which is an optional component, and an agent having a composition other than that, and is configured as a three-agent type oxidative hair dye. May be good. In this case, the formulation stability is further improved.

By using the powdered (A) coupler and the powdered oxidizing agent, a configuration may be adopted in which the (A) coupler and the oxidizing agent are stored in the same agent. When a powdered agent is used, it is dissolved in the above-mentioned solvent at the time of use.

Even when the oxidative hair dye is a composition containing three or more agents or a composition containing a powdered agent, it is still included in the present invention as long as the effects of the present invention are exhibited.

(Second Embodiment)
Hereinafter, a second embodiment in which the oxidative hair dye of the present invention is embodied will be described. The oxidative hair dye of the second embodiment is an oxidative hair dye containing at least one selected from (A) coupler, (B1) carbamate ion, carbonate ion, and hydrogen carbonate ion, and the oxidative hair dye is When the (C) dye intermediate is contained, the mass ratio (A / C) of the content of the component (A) to the content of the total (C) dye intermediate is 2.5 or more.

More specifically, the oxidative hair dye of the second embodiment is a multi-agent oxidative hair dye, for example, (A) coupler, (B1) component, preferably (E) oily component, (F) poly. It is composed of an oxidative hair dye consisting of a valent alcohol, a first agent containing (G) a surfactant, and a second agent containing an oxidizing agent. Hereinafter, the differences from the oxidative hair dye of the first embodiment will be mainly described.

(The first agent of a two-agent oxidative hair dye)
The component (B1) is contained as a polymerization accelerator that promotes the polymerization of the oxidative dye and improves the hair dyeing power.

The carbamic acid ion, carbonate ion, and hydrogen carbonate ion constituting the component (B1) are added to the first agent in the form of carbamic acid salt, carbonate, and bicarbonate with a counter ion liberated in the solubilizer. May be done. As specific examples of the carbamic acid salt, the carbonate, and the hydrogen carbonate, those exemplified in the column of (B) Alkaline agent of the first embodiment can be appropriately adopted. The first agent may contain an (B) alkaline agent other than the (B1) component listed in the first embodiment column.

The lower limit of the content of the component (B1) in the mixture is appropriately set, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more. .. When the content of the component (B1) is 0.01% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the component (B1) in the mixture is appropriately set, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. When the content of (B1) is 20% by mass or less, the decontamination performance can be further improved. The content of (B1) here indicates a value in terms of carbamic acid salt, ammonium carbonate salt, or ammonium hydrogen carbonate salt.

When two or more kinds of (B1) components are contained in the mixture, the lower limit of the total content of the (B1) components is appropriately set, but is preferably 0.01% by mass or more, more preferably 0. It is 1% by mass or more, more preferably 0.5% by mass or more. When the total content is 0.01% by mass or more, the hair dyeing power can be further improved. On the other hand, the upper limit of the total content thereof is appropriately set, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. When the total content is 20% by mass or less, the decontamination performance can be further improved.

As the configuration of the coupler (A), the configuration described in the column of the coupler (A) of the first embodiment can be appropriately adopted.

When the (C) dye intermediate is contained in the first agent, the configuration described in the column of (C) dye intermediate of the first embodiment can be appropriately adopted as the configuration of the (C) dye intermediate. ..

Further, the first agent may further contain a component other than the above-mentioned components, for example, a component contained in the first agent of the oxidative hair dye described in the column of the first embodiment, if necessary.

(Second agent of two-agent oxidative hair dye)
The second agent of the oxidative hair dye has, for example, the same composition as the second agent of the first embodiment.

In addition, the above-described embodiment can appropriately adopt the modified example described in the first embodiment as long as there is no technical contradiction.

The action and effect of the oxidative hair dye of the second embodiment will be described.

(2-1) The polymer between dye intermediates or the polymer between dye intermediates and couplers has the characteristic that it is not easily decomposed by alkaline agents or oxidizing agents, so it is not possible to dye hair in a bright color tone from the next time onward. It was. In the second embodiment, the dye intermediate is substantially not contained and only the coupler is contained as the oxidation dye, or the coupler is contained in a predetermined amount or more with respect to the total dye intermediate, so that the dye is decomposed by the alkaline agent. It forms an easy polymer, has excellent decontamination performance, and has less effect on hair color from the next time onward. That is, the recolor performance can be improved.

Further, the invention in the second embodiment is an invention based on the finding that the component (B1) improves the hair dyeing power. By containing the component (B1) that promotes the polymerization of oxidative dyes, it is possible to achieve hair dyeing performance equivalent to that of oxidative hair dyes containing a high amount of dye intermediates, while maintaining decontamination performance. it can.

(Reference embodiment)
As a reference invention, a reference embodiment embodying the following oxidative hair dye will be described. The oxidative hair dye of the reference embodiment is (A-1) 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5- (2-hydroxyethylamino) -2-methylphenol, 1-naphthol, and the like. When an oxidative hair dye containing at least one coupler selected from a derivative and the oxidative hair dye contains a (C) dye intermediate, (A-) with respect to the content of the total (C) dye intermediate. 1) The mass ratio (A-1) / (C) of the content of the component is 2.5 or more. The oxidative hair dye preferably further contains (B) an alkaline agent.

More specifically, the oxidative hair dye of the reference embodiment is a multi-agent oxidative hair dye, for example, (A-1) component, preferably (B) alkaline agent, (E) oily component, ( F) It is composed of an oxidative hair dye consisting of a first agent containing a polyhydric alcohol, (G) a surfactant and the like, and a second agent containing an oxidizing agent. Hereinafter, the differences from the oxidative hair dye of the first embodiment will be mainly described.

(The first agent of a two-agent oxidative hair dye)
The component (A-1) is a kind of coupler capable of developing a color due to oxidative polymerization by an oxidizing agent contained in the second agent. In ordinary hair color, color variations are formed by combining with various couplers around the dye intermediate. In the reference embodiment, by applying the component (A-1) as a coupler, it is possible to perform a hair dyeing treatment rich in color variation without using it in combination with a dye intermediate. In particular, by adjusting the type and content of the component (A-1) and the type and content of the alkaline agent (B), the hair dye can be developed into various color tones.

In the above configuration, when a predetermined amount or more of the dye intermediate is further blended, even when the same coupler dye type is used, the color variation even if the dye content, the type and content of the alkaline agent are adjusted. Is scarce. That is, when the dye intermediate is not contained or is contained in a specific ratio or less, abundant color variations can be obtained by adjusting the dye content, the type and content of the alkaline agent.

Derivatives of 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5- (2-hydroxyethylamino) -2-methylphenol, and 1-naphthol include salts thereof. Specific examples of the salt include, for example, hydrochloride, sulfate and the like. One kind of (A-1) component may be used alone, or two or more kinds of (A-1) components may be used in combination.

The lower limit of the content of the component (A-1) in the mixture is appropriately set in consideration of the desired color tone and the like, but is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and further. It is preferably 0.7% by mass or more. When the content of the component (A-1) is 0.5% by mass or more, the hair dyeing power can be further improved.

The upper limit of the content of the component (A-1) in the mixture is appropriately set in consideration of the desired color tone and the like, but is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass. % Or less, most preferably 3.5% by mass or less. When the content of the component (A-1) is 10% by mass or less, the decontamination performance can be further improved, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the component (A-1) is a salt, the content of the component (A-1) is the value in the desalted form.

A coupler other than the component (A-1) may be appropriately blended as long as the effect of the present invention is not impaired. As a specific example of the coupler other than the component (A-1), those exemplified in the column of the coupler of the first embodiment can be appropriately adopted.

The component (A-1) is preferably contained as the main component of all the coupler components from the viewpoint of exerting a color variation effect based on the component (A-1), and specifically, 30% by mass of all the coupler components. The above is preferable, 40% by mass or more is more preferable, 50% by mass or more is further preferable, and 60% by mass or more is most preferable.

When the (C) dye intermediate is contained in the first agent, the configuration described in the column of the first embodiment can be appropriately adopted as the configuration of the (C) dye intermediate.

In the mixture, the mass ratio (A-1) / (C) of the content of the component (A-1) to the content of the total (C) dye intermediate is 2.5 or more, preferably 5.0 or more. It is more preferably 7.5 or more, still more preferably 10 or more. When the mass ratio (A-1) / (C) is 2.5 or more, the color variation action can be exhibited more efficiently. When the component (A-1) and the dye intermediate (C) are salts, the content used for calculating the mass ratio is the value in the desalted form for both (A-1) and (C). And.

The upper limit of the content of the dye intermediate (C) in the mixture is appropriately set within the range of the mass ratio (A-1) / (C) of the above content, but is preferably 1% by mass or less, more preferably. Is 0.5% by mass or less, more preferably 0.2% by mass or less, and particularly preferably the mixture contains substantially no (C) dye intermediate. In the present invention, "substantially free" means that the content is 0.1% by mass or less. When the content of the dye intermediate (C) is 1% by mass or less, the color variation action can be exhibited more efficiently, and when a solubilizer is used, the solubility in the solubilizer can be improved. When the (C) dye intermediate is a salt, the content of the (C) dye intermediate shall be the value in its desalted form.

As the composition of the (B) alkaline agent, the composition described in the column of (B) alkaline agent of the first embodiment can be appropriately adopted.

When (B) contains an alkaline agent, the lower limit of the ratio (B) / (A-1) of the content of (B) to the content of the component (A-1) in the mixture is appropriately set. It is preferably 0.0001 or more, more preferably 0.001 or more, and even more preferably 0.01 or more. The upper limit of the ratio (B) / (A-1) is appropriately set, but is preferably 100 or less, more preferably 75 or less, still more preferably 40 or less, and most preferably 10 or less. By defining it within the range of such a ratio, the color variation action based on the component (A-1) can be more effectively exhibited. When the component (A-1) is a salt, the content of (A-1) used for calculating the above ratio is the value in the desalted form.

In particular, when the (B) alkaline agent is ammonia, the upper limit of the ratio (B) / (A-1) is preferably preferable from the viewpoint of more effectively exerting the color variation action based on the component (A-1). It is 75 or less, more preferably 40 or less, still more preferably 15 or less, and most preferably 7 or less.

In particular, when the (B) alkaline agent is monoethanolamine, the upper limit of the ratio (B) / (A-1) is set from the viewpoint of more effectively exerting the color variation action based on the component (A-1). It is preferably 90 or less, more preferably 60 or less, and even more preferably 40 or less.

In particular, when the (B) alkaline agent is a carbamic acid salt, a carbonate, or a hydrogen carbonate, the ratio (B) / (from the viewpoint of more effectively exerting the color variation action based on the component (A-1)). The upper limit of A-1) is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less.

In addition, as the reference embodiment, the modified example described in the first embodiment can be appropriately adopted as long as there is no technical contradiction.

The action and effect of the oxidative hair dye of the reference embodiment will be described.

(3-1) It is known that in ordinary hair color, color variations are formed by combining with various couplers around a dye intermediate as an axis.

The invention in the reference embodiment is an invention based on the finding that hair dyeing treatment can be performed in various color tones by using the component (A-1) as a coupler.

In the reference embodiment, the hair dyeing treatment rich in color variation can be performed by the above-described configuration. In particular, by adjusting the type and content of (A-1) component and (B) type and content of alkaline agent, various color tones can be developed. Various color variations can be formed even if only one type of coupler is applied.

Next, the embodiment will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the configuration described in the Example column.

<Test Example 1: Decontamination performance>
As the oxidative hair dye, a creamy first agent containing each component shown in Tables 1 and 2 and a milky liquid second agent containing each component shown in Table 3 were prepared. In the following table, the numerical value in the column indicating each component indicates the content of the component in the column, and the unit is mass%. The notation (A) to (D) in the "component" column in each table indicates the compound corresponding to each of the components (A) to (D) described in the claims of the present application.

The 2,4-diaminophenoxyethanol in the table below is obtained by neutralizing the raw material 2,4-diaminophenoxyethanol hydrochloride with NaOH as a pH adjuster. Since 2,4-diaminophenoxyethanol hydrochloride produces 2 mol of hydrochloric acid per mol, it was neutralized by blending 2,4-diaminophenoxyethanol hydrochloride: NaOH = 1: 2 mol. That is, 2,4-diaminophenoxyethanol is contained as a free state in the first agent.

For each Example and Comparative Example 1, the first agent and the second agent were mixed at a mass ratio of 1: 1 to prepare a mixture of oxidative hair dyes of each example. 3 g of the obtained mixture was applied using a brush to 1 g of a white hair bundle sample (manufactured by Bulux Co., Ltd.) (hereinafter, simply referred to as a hair bundle) having a length of 10 cm. Forty minutes after applying the mixture to the hair bundle, rinse the mixture adhering to the hair bundle with water, shampoo (Hoyu's Bigen Treatment Shampoo) twice, and rinse (Hoyu's Bigen Treatment) on the hair bundle. Rinse) was applied once. Subsequently, the hair bundles were dried with warm air to obtain hair dyed hair bundles of each example.

The hair bundles of each example subjected to the hair dyeing treatment were evaluated for decontamination performance or hair dyeing power according to the method shown below on the day after the hair dyeing treatment.

(Evaluation method of decontamination performance)
The hair dyed hair bundles of each example obtained as described above are decontaminated according to a conventional method using "Rece Powder Bleach" (manufactured by Hoyu Co., Ltd.), which is a more general decolorizing / decontaminating agent. A decontamination-treated hair bundle was obtained by the operation.

Then, 10 panelists visually observed whether or not the decontamination property was good by comparing the dyed color tone of the decontaminated hair bundle with that of the untreated white hair bundle under a standard light source. did. The decontamination performance was evaluated by combining the results of comparative observation with these hair bundles, and the judgment was made according to the following criteria. Excellent decontamination performance (5 points), good decontamination performance, good (4 points), slightly good decontamination performance, acceptable (3 points), slightly decontamination performance Bad cases are scored in 5 stages of slightly poor (2 points) and poor decontamination performance is scored in 5 stages of defective (1 point), and the average value is calculated for each panelist's scoring result, and the average value is 4.7 points. The above is "Very excellent: 6", 4.0 points or more and less than 4.7 points is "Excellent: 5", 3.3 points or more and less than 4.0 points is "Good: 4", 2.6 points or more 3 The evaluation results were as follows: "OK: 3" for less than 3 points, "Slightly defective: 2" for 1.9 points or more and less than 2.6 points, and "Defective: 1" for less than 1.9 points. The results are shown in the "Decontamination performance" column of Tables 1 and 2.

As shown in Tables 1 and 2, it was confirmed that each example was a result of the decontamination performance.

Further, in Comparative Example 1 in which (A) the coupler was not contained and the content of the dye intermediate was replaced with the content of the coupler of Example 1, the evaluation of the decontamination performance was significantly inferior to that of each Example. Was confirmed.

<Test Example 2: Effect of improving hair dyeing power by iodine compound>
As the oxidative hair dye, the first agent containing each component shown in Tables 4 and 5 was prepared.

Using the same test method as in Test Example 1, a hair bundle sample of white hair for evaluation was subjected to hair dyeing treatment to obtain a hair dyed hair bundle of each example.

The decontamination performance of each hair bundle that had been dyed was evaluated by the same method as in Test Example 1. The results are shown in the "Decontamination performance" column of Tables 4 and 5. Furthermore, the hair dyeing ability was evaluated by the following evaluation method.

(Evaluation method of hair dyeing power)
For the hair dyed hair bundles of each example obtained as described above, 10 panelists visually observed the dyeing intensity under a standard light source and judged according to the following criteria. Examples 25 to 30 are superior (5 points) when the color tone of the hair bundle is darker than that of Example 4, based on the dyeing intensity of Example 4, and the color tone of the hair bundle is slightly higher than that of Example 4. When it is dark, it is good (4 points), when the color tone of the hair bundle is the same as that of Example 4, it is acceptable (3 points), and when the color tone of the hair bundle is slightly lighter than that of Example 4, it is slightly poor (2 points). ), The case where the color tone of the hair bundle is lighter than that of Example 4 is scored in 5 stages of defective (1 point), the average value is calculated for the scoring result of each paneler, and the average value is 4.6 points or more. Excellent: 5 ”, 3.6 points or more and less than 4.6 points is“ Good: 4 ”, 2.6 points or more and less than 3.6 points is“ OK: 3 ”, 1.6 points or more and less than 2.6 points "Slightly defective: 2" and less than 1.6 points were evaluated as "defective: 1". Examples 31 to 33 were evaluated in the same manner as described above, based on the dyeing intensity of Example 15. Examples 34 to 36 were evaluated in the same manner as described above based on the dyeing intensity of Example 16. The results are shown in the "Hair dyeing power" column of Tables 4 and 5.

As shown in Table 4, it was confirmed that Examples 25 to 30 containing an iodine compound were superior in hair dyeing power to Example 4 containing no iodine compound. As shown in Table 5, it was confirmed that Examples 31 to 33 containing an iodine compound were superior in hair dyeing power to Example 15 containing no iodine compound. As shown in Table 5, it was confirmed that Examples 34 to 36 containing an iodine compound were superior in hair dyeing power to Example 16 containing no iodine compound.

<Test Example 3: Effect of improving hair dyeing power by carbonate>
As the oxidative hair dye, the first agent containing each component shown in Tables 6 and 7 was prepared.

The decontamination performance of each hair bundle that had been dyed was evaluated by the same method as in Test Example 1. The results are shown in the "Decontamination performance" column of Tables 6 and 7.

The hair dyeing power of each of the hair bundles subjected to the hair dyeing treatment was evaluated by the same method as in Test Example 2. In Examples 38 to 40, the evaluation was carried out in the same manner as described above, based on the dyeing intensity of Example 37. Examples 42 to 44 were evaluated in the same manner as described above based on the dyeing intensity of Example 41. Examples 46 to 48 were evaluated in the same manner as described above, based on the dyeing intensity of Example 45. The results are shown in the "Hair dyeing power" column of Tables 6 and 7.

As shown in Table 6, it was confirmed that Examples 38 to 40 containing carbonate were superior in hair dyeing power to Example 37 containing no carbonate. As shown in Table 7, it was confirmed that Examples 42 to 44 containing carbonate were superior in hair dyeing power to Example 41 not containing carbonate. As shown in Table 7, it was confirmed that Examples 46 to 48 containing carbonate were superior in hair dyeing power to Example 45 containing no carbonate.

<Reference test example 1: Color variation>
As the oxidative hair dye, the first agent containing each component shown in Tables 8 to 11 was prepared. The oxidative hair dyes of each of the examples in Tables 8 to 11 were adjusted so that the pH at the time of dilution by 10% by mass was all around 10 to 11. Hair dyeing was performed by the same test method as in Test Example 1.

The color tone of each hair bundle that had been dyed was evaluated according to the method shown below.

(Evaluation method of color tone)
The closest color tone was decided while taking into consideration the sample of JIS Z 8102 compliant JIS color name book (2nd edition). The results are shown in the "Color tone" column of Tables 8-11.

As shown in Tables 8 to 11, in the composition of the oxidative hair dye using 2,4-diaminophenoxyethanol or the like as the coupler, the content of the coupler, the content of the alkaline agent, or the type of the alkaline agent is changed. It was confirmed that the hair can be dyed in various colors.

An example of prescribing the oxidative hair dye of the present invention is shown below.

(Prescription example 1)
In Formulation Example 1, an oxidative hair dye was prepared, which was discharged as a foam from an aerosol can. The first agent and the second agent shown in Table 12 were filled in an aerosol can, and each agent was discharged on a brush in the form of bubbles. Each agent was discharged at the same time to obtain the same amount. Next, each agent was mixed while being applied to a white human hair bundle with a brush.

As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 1 was excellent in decontamination performance and hair dyeing power.

(Prescription example 2)
In Formulation Example 2, an oxidative hair dye to be discharged as a cream from an aerosol can was prepared. The first agent and the second agent shown in Table 13 were filled in an aerosol can, and each agent was discharged as a cream on a brush. Each agent was discharged at the same time to obtain the same amount. Next, each agent was mixed while being applied to a white human hair bundle with a brush.

As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 2 was excellent in decontamination performance and hair dyeing power.

(Prescription example 3)
In Formulation Example 3, an oxidative hair dye using a first agent composed of a gel emulsion was prepared. The first agent and the liquid second agent shown in Table 14 were mixed at a mixing ratio of 1: 1. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 3 was excellent in decontamination performance and hair dyeing power.

(Prescription example 4)
In Formulation Example 4, an oxidative hair dye using a gel-like first agent was prepared. The first agent and the liquid second agent shown in Table 15 were mixed at a mixing ratio of 1: 1. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 4 was excellent in decontamination performance and hair dyeing power.

(Prescription example 5)
In Formulation Example 5, an oxidative hair dye using a liquid first agent and second agent was prepared. The first agent and the second agent shown in Table 16 were mixed at a mixing ratio of 1: 1. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 5 was excellent in decontamination performance and hair dyeing power.

(Prescription example 6)
In Formulation Example 6, the first agent and the second agent shown in Table 17 are housed in a non-aerosol former container (pump former) at a mass ratio of 1: 1 to prepare a mixed liquid, and the pump head portion thereof is pressed. As a result, the mixed solution was discharged in a foaming form. As the pump former, trade name W-5721 manufactured by Yoshino Kogyosho Co., Ltd., WP former pump L nozzle type (air / liquid mixing ratio: 13/1, discharge amount: 0.9 g (1 push), porous membrane) : Two 90 mesh polyethylene mesh rings) were used. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 6 was excellent in decontamination performance and hair dyeing power.

(Prescription example 7)
In Formulation Example 7, the first agent and the second agent shown in Table 18 were housed in a non-aerosol former container (squeeze former) at a mass ratio of 1: 1 to prepare a mixed liquid, and the first agent and the second agent were discharged in a foam type. As a squeeze former, a discharge head for a former made by Daiwa Kan Co., Ltd. (mesh mesh is 200 mesh on the mixing chamber side, 255 mesh on the discharge port side, both materials are nylon) is attached to a 150 mL container body made of soft plastic material. An S1 squeeze former container (inner diameter of dip tube 2 mm, length 10 cm) was used. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 7 was excellent in decontamination performance and hair dyeing power.

(Prescription example 8)
In Formulation Example 8, an oxidative hair dye using a creamy first agent and second agent was prepared. The first agent and the second agent shown in Table 19 were mixed at a mixing ratio of 1: 1. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 8 was excellent in decontamination performance and hair dyeing power.

(Prescription example 9)
In Formulation Example 9, an oxidative hair dye using the milky first agent and the second agent was prepared. 50 g of the first agent and 50 g of the second agent shown in Table 20 are used in a bottomed tubular container body having a shape in which the opening is wider than the bottom (the inner diameter (diameter) of the opening is 8.5 cm, and the bottom is The container had an inner diameter of 7 cm and a height of 14 cm) and a hemispherical lid that tightly closed the opening of the container body (total capacity: 770 mL). Then, the lid was attached and the container was closed tightly, and the container was shaken up and down 30 times with a swing width of about 30 cm to obtain a foamy oxidative hair dye. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 9 was excellent in decontamination performance and hair dyeing power.

(Prescription example 10)
In Formulation Example 10, an oxidative hair dye using a creamy first agent and second agent was prepared. Multiple liquids that can be sprayed by arranging two aerosol valves in a double-structured container of the same pressure discharge type or one aerosol container in which the first agent and the second agent shown in Table 21 are separated and filled, and the internal solution can be distributed and injected. The aerosol container for distribution was filled, and the same amount was discharged and mixed at the same time. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 10 was excellent in decontamination performance and hair dyeing power.

(Prescription example 11)
In Formulation Example 11, a powder hair dye composition was prepared. 3 g of the powder hair dye composition shown in Table 22 and 30 g of water were put into a mixing container having a volume of 100 mL and mixed using a stirring rod to prepare a hair dye coating solution. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dye of Formulation Example 11 was excellent in decontamination performance and hair dyeing power.

(Prescription Examples 12 to 17)
In Formulation Examples 12 to 17, an oxidative hair dye using a creamy first agent was prepared. The first agent shown in Table 23 and the second agent (2% OX) shown in Table 3 were mixed at a mixing ratio of 1: 1. As a result of evaluation in the same manner as in Example 4, it was confirmed that the oxidative hair dyes of Formulation Examples 12 to 17 were excellent in decontamination performance and hair dyeing power.

Next, the technical idea that can be grasped from the above embodiment and another example will be added below.

(A) (A-1) At least one selected from 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 5- (2-hydroxyethylamino) -2-methylphenol, 1-naphthol, and derivatives thereof. In the case of an oxidative hair dye containing a coupler and the oxidative hair dye contains a (C) dye intermediate, the content of the component (A-1) relative to the content of the total (C) dye intermediate. An oxidative hair dye having a mass ratio (A-1) / (C) of 2.5 or more.

(B) Further (B) The oxidative hair dye containing an alkaline agent.

(C) The oxidative hair dye in which the ratio (B) / (A-1) of the content of the component (B) to the content of the component (A-1) is 0.0001 to 100.

Claims

(A) An oxidative hair dye containing a coupler.
When the oxidative hair dye contains a (C) dye intermediate, the mass ratio (A / C) of the content of the component (A) to the content of the total (C) dye intermediate is 2.5 or more. An oxidative hair dye that is characterized by this.
(B) The oxidative hair dye according to claim 1, which contains an alkaline agent.
(D) The oxidative hair dye according to claim 1 or 2, which contains an iodine compound.
The oxidative hair dye according to claim 2, wherein the (B) alkaline agent contains at least one selected from (B1) carbamic acid ion, carbonate ion, and hydrogen carbonate ion.