JP2008208067A - Treating agent of keratinous fiber and method of dyeing treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent of a keratinous fiber, enabling a treatment for dyeing the keratinous fiber again to a desired color tone to be carried out easily, and to provide a method of the dyeing treatment. <P>SOLUTION: The treating agent of the keratinous fiber contains (A) an alkali agent, (B) an organic solvent and (C) an oxidation dye, and is used by mixing the treating agent with an oxidant composition when being used, and applied to the keratinous fiber such as the hair 11 dyed by a direct dye. The method of dyeing treatment is a method of repeating the dyeing treatment of the keratinous fiber by alternately carrying out the oxidation dye treatment and the direct dye treatment. The first keratinous fiber-treating agent used for the oxidation dye treatment is the agent containing (A) the alkali agent, (B) the organic solvent and (C) the oxidation dye, and to be mixed with the oxidant composition when being used. The second keratinous fiber-treating agent used for the direct dye treatment is the agent containing (a) the direct dye and (b) an oxidation dye-reducing agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a keratin fiber treating agent and a keratin fiber dyeing method for dyeing keratin fibers.

  Conventionally, acidic hair dyes and oxidative hair dyes are known as hair dyes for dyeing hair which is a kind of keratin fiber. Acid hair dyes are composed of direct dyes and are also called semi-permanent hair dyes or hair manicures. Such an acidic hair dye dyes hair by directly adsorbing the dye near the surface of the hair. On the other hand, an oxidative hair dye contains an oxidative dye and is also called a permanent hair dye. Such oxidative hair dyes hair by coloring oxidative dye staying in the hair. Thus, the dyeing mechanism is different between the direct dye and the oxidation dye.

Further, removers for directly removing dyes from hair dyed with acidic hair dyes are known, and such removers contain an alkali agent or the like (see, for example, Patent Document 1). Furthermore, a destaining agent for destaining hair dyed with an oxidative hair dye is known, and such a destaining agent contains ascorbic acid or the like (see Patent Document 2). In addition, in the oxidative hair dye containing oxidative dye etc., the structure which mix | blended sodium sulfite etc. is known (for example, refer patent document 3).
JP-A-11-335243 Special Table 2000-504348 JP 2004-149483 A

  For example, when hair dyed with a direct dye comes into contact with water, the dye flows out of the hair directly, and the hair gradually fades. When the fading hair is dyed again with an oxidative dye, the direct dye remaining on the hair may affect the color tone based on the color of the oxidative dye. For this reason, in order to dye such hair to a color tone based on an oxidation dye, first, as shown in FIG. 2, a removal process (step S210) is performed in order to remove the direct dye 21 remaining on the hair 11. Next, an oxidation dye treatment (step S220) using an oxidation hair dye is performed on the hair 10 that has been subjected to the removal treatment (step S210). By such treatment, the hair 12 is dyed to a desired color tone with the colored oxidation dye 22.

  By the way, in the hair dyeing with an oxidative dye, since the oxidative dye enters the hair, the color is good, but since the hair is affected by the oxidizer and the alkali agent, the hair is easily damaged (damaged). . On the other hand, hair dyeing with a direct dye is less likely to cause hair damage, but is more likely to fade than hair dyeing with an oxidative dye. In view of such a situation, the present inventors, from the viewpoint of suppressing hair damage when maintaining the hair dyed state, the oxidation dye treatment (step S220) and the direct dye treatment (step S220) as shown in FIG. Attention was paid to the dyeing method in which S240) is carried out alternately. However, even with such a dyeing method, if the dye 21 and the oxidation dye 22 remain in the hairs 11 and 12 before the treatment, it is difficult to dye them to a desired color tone. Therefore, the direct dye 21 removal process (step S210) is performed prior to the oxidation dye process (step S220), and the decolorization process (step S230) of the oxidation dye 22 is performed prior to the direct dye process (step S240). It will be.

As described above, performing the removal process (step S210) and the decoloring process (step S230) makes the processing operation for re-staining to a desired color tone extremely complicated.
The present invention has been made in view of such conventional circumstances, and an object of the present invention is to provide a keratin fiber treatment agent and a dyeing treatment method capable of simply carrying out a process of dyeing again to a desired color tone. is there.

  In order to achieve the above object, the keratin fiber treatment agent of the invention described in claim 1 contains the following components, and is mixed with an oxidant composition at the time of use and is also dyed with a direct dye. The gist of this is to apply.

(A) Alkaline agent.
(B) Organic solvent.
(C) Oxidative dye.

The gist of the invention described in claim 2 is that the keratin fiber treatment agent according to claim 1 is used for changing the color tone of the keratin fiber dyed with the direct dye.
The invention according to claim 3 is the keratin fiber treatment agent according to claim 1 or 2, further comprising (D) sulfites as a direct dye removing agent, and (C) It is summarized that the mass ratio of D) direct dye remover (mass ratio = (D) mass of direct dye remover / (C) mass of oxidized dye) is 0.6 to 10.

The dyeing method according to claim 4 is a dyeing method for dyeing keratin fibers,
An oxidation dye that dyes the keratin fiber with an oxidation dye by using the first keratin fiber treatment agent that contains the following components (A) to (C) and is mixed with the oxidant composition at the time of use. And a direct dye treatment for dyeing the keratin fibers with a direct dye by using a second keratin fiber treatment agent containing the following components (a) and (b): The gist is to repeat the dyeing treatment of the keratin fiber by alternately performing the treatment and the direct dye treatment.

<First keratin fiber treatment agent>
(A) Alkaline agent.
(B) Organic solvent.

(C) Oxidative dye.
<Second keratin fiber treatment agent>
(A) Direct dye.

  (B) At least one selected from thioglycolic acids, cysteines, sulfites, thiosulfates, dithionites, hydroxymethanesulfinic acids, and ascorbic acids as an oxidizing dye reducing agent.

  According to a fifth aspect of the present invention, in the dyeing treatment method according to the fourth aspect, the first color tone dyed by the oxidation dye treatment and the second color tone dyed by the direct dye treatment are different from each other. It is a summary.

  According to the present invention, it is possible to simply carry out a process of dyeing again to a desired color tone.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 1A schematically shows hair 11 dyed with direct dye 21 and hair 12 dyed with colored oxidative dye 22. The first oxidative hair dye as the keratin fiber treatment agent constitutes the oxidative hair dye together with the second oxidative hair dye as the oxidant composition. And this oxidation hair dye 1st agent is applied to the hair 11 dye | stained with the direct dye 21 while being mixed with the oxidation hair dye 2 agent at the time of use.

<Hair dye>
The hair dye for dyeing the hair 11 directly with the dye 21 will be described. The direct dye contained in the hair dye is a dye that has no reactivity and is colored in an unreacted state. Examples of direct dyes include acid dyes, nitro dyes, basic dyes (cationic dyes), and disperse dyes.

  As the acid dyes, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 201, Red No. 227, Red No. 230 ( 1) Red 230 (2), Red 231, Red 232, Red 401, Red 502, Red 502, Red 503, Red 504, Red 506, Yellow 4, Yellow 5, Yellow 202 (1), yellow 202 (2), yellow 203, yellow 402, yellow 403 (1), yellow 406, yellow 407, orange 205, orange 207, orange 402, green No. 3, Green No. 204, Green No. 205, Green No. 401, Green No. 402, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Black No. 401 No., Acid Blue 1, Acid Bull 3, Acid Blue 62, Acid Black 52, Acid Brown 13, Acid Green 50, Acid Orange 6, Acid Red 14, Acid Red 35, Acid Red 73, Acid Red 184, Brilliant Black 1, and the like.

  Examples of nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and the like. Salt, HC Blue No.2, HC Blue No.4, HC Blue No.5, HC Blue No.6, HC Blue No.8, HC Blue No.9, HC Blue No.10, HC Blue No.11 , HC Blue No.12, HC Blue No.13, HC Blue No.14, HC Brown No.1, HC Brown No.2, HC Green No.1, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Orange No.5, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.8, HC Red No.9, HC Red No.10, HC Red No .11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.7 HC Yellow No.8, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No.15, etc. Can be mentioned.

  Examples of basic dyes include red 213, red 214, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 99, Basic Brown 4, Basic Brown 16 Basic Brown 17, Basic Brown 1, Basic Brown 4, Basic Orange 1, Basic Orange 1, Basic Orange 2, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11: 1, Basic Violet 14, Basic Violet 16, BASIC Yellow 11, BASIC Yellow 28, BASIC Yellow 57, and the like.

  Examples of disperse dyes include Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 etc. are mentioned.

  Furthermore, as direct dyes, 1-amino-4-methylanthraquinone, 1,4-diaminoanthraquinone, and salts thereof, and "Ministerial Ordinance for Determining Tar Pigments that can be Used in Pharmaceuticals" (1960 Notification, Ministry of Health and Welfare) The direct dyes defined by Direct dyes may be blended singly or in combination of two or more.

  Among these direct dyes, acidic dyes are preferable from the viewpoint that they are easily decolored by the oxidative hair dye of the present embodiment. Red 102, Red 106, Red 227, Yellow 4, Yellow 203, Yellow 403 No. (1), at least one selected from orange 205, purple 401, blue 1 and black 401 is more preferable.

  The content of the direct dye in the hair dye is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass. When the content of the direct dye is less than 0.001% by mass, the hair dyeing effect may not be sufficiently obtained. On the other hand, when the content of the direct dye exceeds 5% by mass, the solubility in the hair dye may not be sufficiently obtained.

  An organic solvent, water, a pH adjuster, a viscosity adjuster, and the like are appropriately blended in the hair dye. Examples of organic solvents include monohydric alcohols such as ethanol, isopropanol, and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, isoprene glycol, glycerin, diglycerin, dipropylene glycol, and ethyl carbitol. N-alkylpyrrolidones such as N-methylpyrrolidone, N-ethylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone, benzyl alcohol, 2-phenylethyl alcohol, cinnamyl alcohol, phenylpropanol, α-methylbenzyl alcohol, Aromatic alcohols such as dimethylbenzyl carbinol, benzyloxyethanol, phenoxyethanol, p-anisyl alcohol, lower alcohols such as ethylene carbonate and propylene carbonate Ren carbonate, and the like. Examples of the pH adjuster include lactic acid, acetic acid, tartaric acid, citric acid, oxalic acid, phosphoric acid, hydrochloric acid, 2-amino-2-methyl-1-propanol and the like. The liquidity of the hair dye is appropriately set according to the type of direct dye. For example, in the case of constituting an acid hair dye mixed with an acid dye as the direct dye, the liquidity of the acid hair dye is in an acidic region, preferably pH 1 to 5, more preferably pH 2 to 4.5. When this pH is less than 1, there is a possibility that the hair or scalp is likely to be damaged. On the other hand, when pH exceeds 5, the tendency for hair dyeing power to fall becomes strong.

If necessary, the hair dye may contain a surfactant, an oil component, an antiseptic, a chelating agent, a stabilizer, a plant extract, a herbal extract, vitamins, a fragrance, an ultraviolet absorber, and the like.
The dosage form of the hair dye is not particularly limited, and examples thereof include an aqueous solution, a dispersion, an emulsion, a gel, a foam, and a cream.

<Oxidative hair dye 1>
The first oxidation hair dye contains (A) an alkali agent, (B) an organic solvent, and (C) an oxidation dye.

  (A) The alkaline agent is a component contained to remove the dye directly from the hair and promote the action of the oxidizing agent to assist the dyeing with the (C) oxidizing dye. Specific examples of the component (A) include ammonia, alkanolamine, ammonium carbonate, ammonium bicarbonate, ammonium acetate, organic amines (guanidine, etc.), inorganic alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) ), Basic amino acids (arginine, lysine, etc.) and their salts. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2 -Amino-2-methyl-1-propanol, 2-amino-2-hydroxymethyl-1,3-propanediol and the like.

  (A) A component may be mix | blended independently and may be mix | blended combining 2 or more types. As the component (A), at least one selected from ammonia and alkanolamine is preferable from the viewpoint of excellent effect of directly removing the dye. The content of the component (A) in the first oxidative hair dye is preferably 0.1 to 10% by mass, more preferably 0.2 to 8.0% by mass, and still more preferably 0.4 to 5.0. % By mass. When the content of the component (A) is less than 0.1% by mass, sufficient leveling may not be obtained. On the other hand, when it exceeds 10 mass%, it may be difficult to obtain a good feel in the hair after treatment.

  (B) The organic solvent is a component for directly dissolving the dye and removing the dye directly from the hair. Specific examples of the component (B) include the organic solvents described in the <hair dyeing> column. (B) A component may be mix | blended independently and may be mix | blended combining 2 or more types. Among the components (B), it is preferable to contain at least one of benzyl alcohol and benzyloxyethanol from the viewpoint of excellent action of directly removing the dye. In addition, when the aromatic alcohol is contained as the component (B), a monohydric alcohol, a polyhydric alcohol is used from the viewpoint of sufficiently exerting the action of directly removing the dye by increasing the compatibility of the aromatic alcohol with water. It is preferable to contain at least one organic solvent selected from alcohol and N-alkylpyrrolidones.

  The content of the component (B) in the first oxidative hair dyeing agent is preferably 1 to 50% by mass, more preferably 1 to 45% by mass, and further preferably 2 to 40% by mass. When the content of the component (B) is 1% by mass or more, sufficient solubility of the direct dye is easily obtained. On the other hand, when (B) component is mix | blended exceeding 50 mass%, it exists in the tendency which is saturated about the improvement of the solubility of a direct dye.

  When the aromatic alcohol is contained as the component (B), the content of the aromatic alcohol in the first agent for oxidative hair dyeing is preferably 1 to 30% by mass, more preferably 3 to 15% by mass.

  (C) The oxidation dye is a compound capable of color development by oxidative polymerization with an oxidant. This component (C) is classified into a main intermediate and a coupler, and at least the main intermediate is contained in the first oxidative hair dye agent.

  Specific examples of the main intermediate include phenylenediamines (excluding metaphenylenediamine), aminophenols (excluding metaaminophenol, 2,4-diaminophenol, and paramethylaminophenol), toluic acid. Range amines (excluding toluene-3,4-diamine and toluene-2,4-diamine), diphenylamines, diaminophenylamines, N-phenylphenylenediamines, diaminopyridines (however, 2,6 -Excluding diaminopyridine) and salts thereof. Examples of the salt include hydrochloride, sulfate, acetate and the like.

  Specific examples of couplers include resorcin, pyrogallol, catechol, metaaminophenol, metaphenylenediamine, 2,4-diaminophenol, 1,2,4-benzenetriol, toluene-3,4-diamine, and toluene-2,4. -Diamine, hydroquinone, α-naphthol, 2,6-diaminopyridine, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, paramethylaminophenol, 2,4-diaminophenoxyethanol, gallic acid, tannic acid, ethyl gallate , Methyl gallate, propyl gallate, pentaploid, 5- (2-hydroxyethylamino) -2-methylphenol and salts thereof.

  (C) component may be mix | blended independently and may be mix | blended combining 2 or more types. Here, when it becomes necessary to return the hair dyed with the oxidative hair dye of the present embodiment to the color before dyeing or to re-dye it to another color, the dyed hair is destained. From the standpoint of ease, it is preferable that the main intermediate is at least one selected from paraphenylenediamine and salts thereof, and the coupler is resorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, metaaminophenol. , Paraaminophenol, α-naphthol, 5-aminoorthocresol, and 5- (2-hydroxyethylamino) -2-methylphenol, and at least one selected from the salts of the respective compounds are preferable.

  Content of (C) component in oxidation hair dye 1st agent becomes like this. Preferably it is 0.01-15.0 mass%. When the content of the component (C) is less than 0.01% by mass, it is difficult to obtain sufficient hair dyeing power. On the other hand, when it exceeds 15.0 mass%, it exists in the tendency which is saturated about the improvement of hair dyeing power.

  The oxidative hair dye first agent preferably contains (D) sulfites as a direct dye remover. These sulfites act on the hair together with (A) the alkali agent and (B) the organic solvent, whereby the direct dye is efficiently removed from the hair. Examples of the sulfites as the component (D) include sulfites, sulfites, and bisulfites. Examples of the sulfites and bisulfites include ammonium salts, sodium salts, and potassium salts. (D) A component may be mix | blended independently and may be mix | blended combining multiple types. Among the components (D), sodium sulfite is preferable from the viewpoint of excellent effect of directly removing the dye.

  The content of component (D) in the first oxidative hair dye is preferably 0.1 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and still more preferably 0.1 to 3%. 0.5% by mass. When the content of the component (D) is 0.1% by mass or more, the effect of directly removing the dye is easily obtained. On the other hand, when it exceeds 10.0 mass%, there is a possibility of inhibiting the color development of the (C) oxidation dye.

  In addition, the content of the component (D) in the first component of oxidative hair dye is (C) the mass ratio of the component (D) to the oxidative dye (mass ratio = (D) mass of the direct dye remover / (C) oxidation. Dye mass) is preferably 0.6 to 10, more preferably 0.8 to 8, and still more preferably 0.9 to 6. When the mass ratio of the component (D) to the oxidation dye (C) is less than 0.6, it may be difficult to react the oxidation dye (C) without waste and to fully exert the effect of the component (D). is there. On the other hand, when the mass ratio exceeds 10, (C) the coloring of the oxidation dye may be inhibited.

  In addition, in the mixture obtained by mixing the oxidative hair dye first agent and the oxidative hair dye second agent from the viewpoint of sufficiently exerting the effect of the component (D) and (C) sufficiently coloring the oxidative dye. In the above, it is preferable that the mass ratio of the component (D) to the oxidizing agent is set within a predetermined range. In the mixture of the oxidative hair coloring agent 1 and the oxidative hair coloring agent 2, the mass ratio of the component (D) to the oxidizer (mass ratio = (D) the mass of the direct dye remover / the mass of the oxidizer) is: Preferably it is 0.06-1, More preferably, it is 0.1-0.8, More preferably, it is 0.1-0.65. When the mass ratio of (D) component with respect to an oxidizing agent is less than 0.06, there exists a possibility that it may become difficult to fully exhibit the effect of (D) component. In this case, when it becomes necessary to return the hair dyed with the oxidative hair dye of this embodiment to the color before dyeing or to re-dye it to another color, There is a risk that it may be difficult to decolorize. On the other hand, when this mass ratio exceeds 1, the coloring of (C) oxidation dye by an oxidizing agent may be inhibited.

  Components other than the above components can be blended as the other components in the first oxidation hair dye agent. Examples of other components include oily components, hydrocarbons, surfactants, pH adjusters and the like.

Examples of the oil component include higher alcohols, fats and oils, waxes, higher fatty acids, esters, and silicones.
Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, aralkyl alcohol, behenyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, oleyl Alcohol, linoleyl alcohol, linolenyl alcohol, lanolin alcohol, etc. are mentioned.

  As fats and oils, olive oil, camellia oil, shea fat, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef fat, cacao butter, corn oil, peanut oil, rapeseed oil, Examples include rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, macadamia nut oil, castor oil, flaxseed oil, coconut oil, mink oil, egg yolk oil and the like.

  Examples of waxes include beeswax, candelilla wax, carnauba wax, jojoba oil, and lanolin. Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid. It is done.

  Esters include diisopropyl adipate, diisobutyl adipate, dioctyl adipate, di-2-hexyldecyl adipate, diisostearyl adipate, isostearyl myristate, isotridecyl myristate, isopropyl myristate, octyldodecyl myristate, Cetyl octoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, diisopropyl sebacate, isopropyl palmitate, hexyl laurate, decyl oleate, hexyl decyl dimethyloctanoate, octyl palmitate, lauryl lactate, octyldodecyl lactate, stearin Isocetyl acid, isocetyl isostearate, ethylene glycol dioctanoate, cetyl caprylate, glyceryl tricaprylate , Neopentyl glycol dicaprate, diisostearyl malate, dipentaerythritol fatty acid ester, oleyl oleate, diethoxyethyl succinate, dioctyl succinate, tri (caprylic-capric acid) glyceryl, and the like.

  Examples of silicones include dimethylpolysiloxane (dimethylsilicone), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, highly-polymerized silicone having an average polymerization degree of 650 to 10,000, and amino-modified silicone. , Betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone, and the like.

  Examples of the hydrocarbon include α-olefin oligomer, light isoparaffin, light liquid isoparaffin, liquid isoparaffin, liquid paraffin, squalane, polybutene, paraffin, polyethylene powder, microcrystalline wax, petrolatum and the like.

  Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Specific examples of the nonionic surfactant include ether type nonionic surfactants and ester type nonionic surfactants. Examples of ether type nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) cetyl ether, POE stearyl ether, POE behenyl ether, POE oleyl ether, POE lauryl ether, POE octyldodecyl ether, POE hexyl decyl ether, POE isostearyl ether, POE nonyl phenyl ether, POE octyl phenyl ether and the like can be mentioned.

  Examples of the ester type nonionic surfactant include POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monopalmitate, POE sorbitan monolaurate, POE sorbitan trioleate, POE glycerine monostearate, POE monomyristate POE Glycerin, tetraoleic acid POE sorbite, hexastearic acid POE sorbit, monolauric acid POE sorbit, POE sorbite beeswax, monooleic acid polyethylene glycol, monostearic acid polyethylene glycol, monolauric acid polyethylene glycol, lipophilic monooleic acid glycerin, lipophilic oil Glyceryl monostearate, self-emulsifying glyceryl monostearate, sorbitan monooleate, sol of sesquioleate Tan, sorbitan trioleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, sucrose fatty acid ester, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl monomyristate, etc. Can be mentioned.

  Cationic surfactants include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, ethyl lanolin sulfate fatty acid Examples thereof include aminopropylethyldimethylammonium, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, and methyl behenyltrimethylammonium sulfate.

  Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate, alkyl ether sulfate salts such as sodium POE lauryl ether sulfate, sodium stearoylmethyl taurate, triethanolamine dodecylbenzenesulfonate, Examples include sodium tetradecene sulfonate, POE lauryl ether phosphate and salts thereof, N-lauroyl glutamates, and N-lauroylmethyl-β-alanine salts.

  Examples of amphoteric surfactants include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, cocoamidopropyl betaine, lauryldimethylaminoacetic acid betaine.

Examples of the pH adjuster include sulfuric acid, acetic acid, lactic acid, tartaric acid, and citric acid.
In addition, saccharides such as sorbitol and maltose, alkyl glyceryl ethers such as batyl alcohol and chimyl alcohol, gum arabic, karaya gum, tragacanth gum, sodium alginate, xanthan gum, cellulose derivatives, crosslinked polyacrylic acid, polydimethylmethylene pipette Water-soluble polymer compounds such as lithium, preservatives such as parabens, stabilizers such as phenacetin, 8-hydroxyquinoline, acetanilide, sodium pyrophosphate, barbituric acid, uric acid, tannic acid, chelating agents such as EDTA-2Na, plants Extracts, herbal extracts, vitamins, fragrances, ultraviolet absorbers, antibacterial agents and the like can be mentioned. Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

  It is preferable that the pH of the mixture obtained by mixing the oxidation hair dye 1 agent and the oxidation hair dye 2 agent is 8-12. When the pH of the mixture is less than 8, the action of the oxidizing agent may not be sufficiently promoted, and the effect of directly removing the dye may not be sufficiently exhibited. On the other hand, if the pH exceeds 12, problems such as hair damage may easily occur. In addition, pH of a mixture can be easily set with content of the (A) alkaline agent in oxidative hair dye 1st agent.

  By blending a predetermined amount of water into the first oxidation hair dye agent, the first oxidation hair dye agent can be made into a form such as an emulsion, a solution, or a dispersion. The water content is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in the first agent for oxidative hair dyeing. When this compounding quantity is less than 50 mass% or exceeds 99 mass%, it becomes difficult to obtain a stable agent. Moreover, the dosage form of the oxidative hair dye 1st agent is not specifically limited, For example, liquid form, foam form, cream form, gel form etc. are mentioned.

<Oxidative hair dye second agent>
The second agent for oxidative hair dye contains (C) an oxidant in order to cause oxidative polymerization of the oxidative dye to develop a color. Specific examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium peroxide, potassium peroxide, magnesium peroxide, Examples include barium peroxide, calcium peroxide, strontium peroxide, sulfate hydrogen peroxide adduct, phosphate hydrogen peroxide adduct, pyrophosphate hydrogen peroxide adduct, and the like. An oxidizing agent may be mix | blended independently and may be mix | blended in combination of 2 or more types. Among the oxidizing agents, hydrogen peroxide is preferable from the viewpoint of increasing the lightness of the hair.

  The content of the oxidizing agent in the second oxidation hair dye is preferably 0.1 to 4.5 mass%, more preferably 0.8 to 2.0 in the mixture with the first oxidation hair dye. % By mass. When the content of the oxidant is 0.8 to 2.0% by mass, the hair dyed with the oxidative hair dye of this embodiment is returned to the color before dyeing or recolored to another color. When it becomes necessary, it is easy to decolor the dyed hair, and good hair dyeing power is easily exhibited. In addition, when content of an oxidizing agent is less than 0.1 mass%, there exists a possibility that it may become difficult to fully oxidatively polymerize (C) oxidation dye. On the other hand, when it exceeds 4.5 mass%, hair damage may not be reduced.

As the other components, the second hair dye agent may contain water, an oily component, a surfactant and the like described in the section <First hair dye agent>.
The dosage form of the oxidative hair dye second agent is not particularly limited, and examples thereof include an aqueous solution, a dispersion, an emulsion, a gel, a foam, and a cream.

<Mixture>
A mixture is prepared by mixing said oxidation hair dye 1st agent and oxidation hair dye 2 agent at the time of use. The dosage form of the mixture is not particularly limited, and examples thereof include aqueous solutions, dispersions, emulsions, gels, foams, and creams.

  The mixture is then applied to the hair 11 shown in FIG. The mixture can be applied to the hair by attaching it to an applicator such as a brush or a comb. The hair to which the mixture is applied is left in that state for a predetermined time. At this time, the hair 11 is swollen by the alkali agent (A), and the dye 21 is directly dissolved in the organic solvent (B). At this time, the oxidized dye 22 penetrating into the hair is oxidized and polymerized by the oxidizing agent, whereby a colored oxidized dye 22 is generated. Thereafter, the dye 21 and the like are directly removed by washing the mixture from the hair. In this way, the hair 12 is dyed in a desired color tone by the oxidation-polymerized oxidation dye 22.

  For example, when the hair 11 dyed with the direct dye 21 fades with time, the direct dye 21 often remains partially on the hair 11. When such hair 11 is dyed again, the removal treatment (step S210) shown in FIG. 2 can be omitted by applying the first agent for oxidative hair dyeing of this embodiment. In addition, for example, when the color tone of the hair 11 dyed directly by the dye 21 is changed to (C) the color tone based on the color of the oxidation dye, the removal treatment ( Step S210) can be omitted.

<Dyeing method>
As shown in FIG. 1B, the dyeing method of this embodiment includes an oxidation dye treatment (step S110) for dyeing hair with an oxidation dye, and a direct dye treatment (step S120) for dyeing hair with a direct dye. including. For the oxidation dye treatment (step S110), the first hair dyeing agent as the first keratin fiber treatment agent is used. For the direct dye treatment (step S120), a hair dye as a second keratin fiber treatment agent is used. In this dyeing method, the dyeing process for the hairs 11 and 12 is repeated by alternately performing the oxidation dye process (step S110) and the direct dye process (step S120). Here, performing alternately means performing the oxidation dye treatment (step S110) and the direct dye treatment (step S110) at least three times in total.

  The first oxidative hair dye used for the oxidative dye treatment (step S110) is mixed with the second oxidative hair dye as an oxidant composition at the time of use. The first oxidation hair dye contains (A) an alkali agent, (B) an organic solvent, and (C) an oxidation dye. The second oxidative hair dye contains an oxidant. About the oxidation hair dye 1 agent, oxidation hair dye 2 agent, and the mixture of each agent, it described in each column of <oxidation hair dye 1 agent>, <oxidation hair dye 2 agent>, and <mixture>. Therefore, explanation is omitted.

  Next, the hair dye used for the direct dye treatment (step S120) will be described focusing on the parts different from the contents described in the section <Hair dye>. The hair dye contains (a) a direct dye and (b) an oxidizing dye reducing agent. (B) The oxidative dye reducing agent is a component for decolorizing hair dyed with an oxidative dye by depolymerizing or deresonating the colored oxidative dye. (B) The oxidizing dye reducing agent is at least one selected from thioglycolic acids, cysteines, sulfites, thiosulfates, dithionites, hydroxymethanesulfinic acids, and ascorbic acids.

  Examples of the thioglycolic acid include thioglycolic acid, thioglycolate, and thioglycolic acid ester. Examples of the thioglycolate include ammonium thioglycolate and sodium thioglycolate. Examples of the thioglycolic acid ester include glycerin thioglycolate.

Examples of cysteines include cysteine, cysteine hydrochloride, N-acetyl-L-cysteine and the like.
Examples of the sulfites include sulfites, sulfites, and bisulfites. Examples of the sulfites and bisulfites include ammonium salts, sodium salts, and potassium salts.

Examples of the thiosulfuric acid include thiosulfuric acid and thiosulfate, and examples of the thiosulfate include sodium thiosulfate and potassium thiosulfate.
Examples of the dithionites include dithionite and dithionite. Examples of the dithionite include sodium dithionite and potassium dithionite.

  Hydroxymethane sulfinic acids include hydroxymethane sulfinic acid and hydroxymethane sulfinate, and examples of hydroxymethane sulfinate include sodium hydroxymethanesulfinate.

  Ascorbic acids include ascorbic acid, ascorbate, ascorbic acid derivatives, erythorbic acid, erythorbate, and erythorbic acid derivatives. Examples of ascorbate and erythorbate include sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, and sodium erythorbate. Ascorbic acid derivatives and erythorbic acid derivatives include, for example, ascorbic acid sulfate disodium, erythorbic acid sulfate disodium, ascorbic acid magnesium phosphate, ascorbyl palmitate, ascorbyl stearate, ascorbyl dipalmitate, tetra-2-hexyldecanoic acid Ascorbyl, Ascorbyl myristate, Ascorbyl laurate, Ascorbyl acetate, Ascorbyl propionate, Ascorbyl tartrate, Ascorbyl citrate, Ascorbyl succinate, Ascorbyl benzoate, (Ascorbyl / tocopheryl) potassium phosphate, Ascorbyl ethyl, Ascorbyl allantoin, Ascorbic acid Chitosan, methylsilanol ascorbate, tetradecylhexyl ascorbyl, Mino propyl ascorbyl phosphate, ascorbic acid poly peptides, ascorbyl glucoside, and the like ascorbyl methylsilanol pectinate, and the like.

  The content of the component (b) in the hair dye is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. When content of this (b) component is less than 1 mass%, there exists a possibility that sufficient decoloring effect may not be acquired. On the other hand, when the content of the component (b) exceeds 40% by mass, the solubility of the component (b) may not be sufficiently obtained.

  The hair dye preferably contains an organic solvent from the viewpoint of (a) enhancing the penetrability of the direct dye into the hair. Examples of the organic solvent include those exemplified as the (B) organic solvent described in the section of <Oxidized hair dye first agent>. An organic solvent may be mix | blended independently and may be mix | blended in combination of 2 or more types. Among organic solvents, it is preferable to contain at least an aromatic alcohol from the viewpoint of increasing hair dyeing power by exerting higher permeability, and it is more preferable to contain at least one of benzyl alcohol and benzyloxyethanol. preferable. It is preferable to contain water as a solvent or a dispersion medium.

  It is preferable that the hair dye contains a reducing sugar from the viewpoint of making it closer to the desired color tone. In hair to which a hair dye is applied, (b) when the oxidative dye decolorized by the oxidative dye reducing agent remains on the hair, the oxidative dye may be gradually discolored by air oxidation. Reducing sugar has the effect of preventing the phenomenon of discoloration by preventing reoxidation of the oxidation dye. The reducing sugar has a free or hemiacetal-bonded aldehyde group or ketone group, and has, for example, Maillard reactivity with amino acids or amino groups of proteins. Examples of reducing sugars include free monosaccharides, reducing disaccharides, and reducing oligosaccharides.

  Examples of free monosaccharides include trioses, tetroses, pentoses, hexoses, and heptoses. Examples of trioses include glyceraldehyde and dihydroxyacetone. Examples of tetroses include erythrose. Examples of pentoses include ribose, xylose, and arabinose. Hexoses include glucose, galactose, mannose, and fructose. Examples of heptoses include sedoheptulose.

  Examples of the reducing disaccharide include homobiose and heterobiose. Examples of homobiose include maltose, cellobiose, isomaltose, and gentiobiose. Examples of heterobiose include melibiose, lactose, maltulose, and lactulose.

  Examples of the reducing oligosaccharide include maltotriose which is an α-amylase degradation product of starch or glycogen. These reducing sugars may be contained alone or in combination of two or more. Among these reducing sugars, free monosaccharides are preferable because they have a high anti-discoloring effect and a high reducing power per unit mass, and xylose or dihydroxyacetone is more effective because they are even more effective in preventing discoloration and are easily available. preferable.

  The content of reducing sugars in hair dyes is determined by measuring the reducing power of constituent sugar residues, ie, reducing end groups (carbonyl groups or functional groups that easily change to carbonyl groups) in reducing sugar molecules. Is done. Further, the content of reducing sugar in the hair dye is also determined by measuring the reducing power per unit mass of reducing sugar. When the reducing sugar is a pentose, for example, xylose, the content of the reducing sugar is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 10% by mass. When the content of reducing sugar is less than 0.5% by mass, the discoloration of hair due to air oxidation may not be sufficiently suppressed. On the other hand, when the content of the reducing sugar exceeds 30% by mass, the hair feel may be lowered due to, for example, the hair becoming sticky. When the reducing sugar is a triose such as dihydroxyacetone, the reducing sugar content is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.2 to 10%. % By mass.

  It is preferable that the hair dye contains a viscosity modifier from the viewpoint of enhancing the adhesion of the hair dye to the hair. Viscosity modifiers include xanthan gum, hydroxyalkyl xanthan gum, gum arabic, carrageenan, galactan, guar gum, quince seed gum, locust bean gum, tragacanth gum, pectin, mannan, starch, dextran, hyaluronic acid, curdlan, succinoglucan, gelatin Natural polymers such as collagen, casein and albumin, cellulose polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, starch polymers such as carboxymethyl starch, methyl starch and soluble starch, alginic acid A semi-synthetic polymer comprising a salt, alginate polymer such as propylene glycol alginate, Synthesis of xylvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid soda, polyethylene oxide, ethylene oxide / propylene oxide block copolymer, polyacrylamide, acrylamide / acrylamide-2-methylpropanesulfonic acid copolymer, etc. Examples thereof include inorganic polymers such as polymers, bentonite, and laponite. These water-soluble polymer compounds may be blended singly or in combination of two or more.

  The hair dye contains (b) a solid hair dye auxiliary agent containing an oxidizing dye reducing agent and (a) a direct dye from the viewpoint of enhancing the storage stability of the (b) oxidizing dye reducing agent. It is preferable to divide the hair dye main agent into a composition and mix the hair dye auxiliary agent and the hair dye main agent at the time of use. In the hair dyeing auxiliary agent, a dispersant or the like can be contained as necessary as a component other than the component (b). Examples of the dispersant include stearic acid metal salts such as calcium stearate and magnesium stearate, talc, crystalline cellulose, low-substituted hydroxypropylcellulose, and dextrin. An organic solvent, water, a pH adjuster, a viscosity adjuster, and the like are appropriately blended with the hair dye main ingredient. The dosage form of the hair dye main ingredient is not particularly limited, and examples thereof include an aqueous solution, a dispersion, an emulsion, a gel, a foam, and a cream.

  As shown in FIG. 1B, in the dyeing method of the present embodiment, for example, the oxidation dye treatment (step S110), the direct dye treatment (step S120), and the oxidation dye treatment (step S110) are performed in this order. Further, for example, the direct dye treatment (step S120), the oxidation dye treatment (step S110), and the direct dye treatment (step S120) are performed in this order.

  When carrying out the oxidation dye treatment (step S110), the above-mentioned first oxidation hair dye agent is used. That is, after preparing the mixture by mixing the oxidative hair dye first agent and the oxidative hair dye second agent at the time of use, the mixture is directly applied to the hair 11 in which the dye 21 remains. In this way, since the dye 21 is directly removed from the hair 12 that has been subjected to the oxidation dye treatment (step S110), the hair 12 is dyed in a desired color tone by the colored oxidation dye 22.

  In order to carry out the direct dye treatment (step S120), the above-mentioned hair dye is used. That is, a hair dye is applied to the hair 12 in which the colored oxidation dye 22 remains. In the hair 11 thus subjected to the direct dye treatment (step S120), the oxidation dye 22 is destained, so that the hair 11 is dyed to a desired color by the direct dye 21.

  Such a dyeing method can be used, for example, as a method of dyeing the hairs 11 and 12 when fading of the hairs 11 and 12 progresses. For example, when changing the color tone of the hairs 11 and 12, the first color tone dyed by the oxidation dye treatment (step S110) is different from the second color tone dyed by the direct dye treatment (step S120). It can be used as a method of repeatedly changing the color tone.

According to the embodiment described in detail above, the following effects are exhibited.
(1) Each component of (A)-(C) is contained in the oxidative hair dye 1st agent of this embodiment. Then, the first hair dyeing agent is applied to hair dyed directly with a dye as a mixture mixed with the second hair coloring agent containing an oxidizing agent. Such a mixture can remove the dye directly from the hair and dye the hair with an oxidative dye. That is, when the hair dyed with the direct dye is dyed again to the color tone based on the oxidation dye, the removal treatment for removing the dye directly from the hair can be omitted. Therefore, it is possible to simply carry out the process of re-staining to the desired color tone.

  For example, when the fading of hair dyed with a direct dye progresses, the process of dyeing again can be carried out easily. For example, the color tone of hair dyed with a direct dye can be easily changed to a color tone different from the color tone.

  Furthermore, the hair treatment using the first oxidation hair dye of the present embodiment can be carried out in a time equivalent to the case where the normal oxidation hair dye first agent is used. That is, with the omission of the removal process, the time for the hair to contact the chemical solution can be shortened. Therefore, damage to the hair caused by the removal process can be avoided.

  (2) The first component of oxidative hair dye further contains sulfites as (D) direct dye remover, and (C) the mass ratio of (D) direct dye remover to oxidative dye is 0.6-10. It is preferable to be in the range. It is presumed that these sulfurous acids act on hair proteins, direct dyes, etc., and (B) the hair is changed to a state in which the direct dyes are easily detached. For this reason, it can dye | stain to the color tone close | similar to the color tone based on the mixing | blending of (C) oxidation dye by removing a dye directly from hair more efficiently.

  (3) As shown in FIG. 1B, the dyeing method repeats the hair dyeing process by alternately performing the oxidation dye process (step S110) and the direct dye process (step S120). In the oxidation dye treatment (step S110), the above-described first oxidation hair dye is used, and in the direct dye treatment (step S120), a dye containing (a) a direct dye and (b) an oxidation dye reducing agent is used. Use hair. According to this dyeing method, the removal process (step S210) and the destaining process (step S230) shown in FIG. 2 can be omitted when the hair is dyed to a desired color tone. For this reason, the process which dye | stains again to a desired color tone can be implemented simply. For example, although fading of hair dyed with a direct dye or an oxidative dye is proceeding, a process of dyeing to a desired color tone can be easily performed at a stage where such dye is not completely detached. Then, by alternately performing the oxidative dye treatment (step S110) and the direct dye treatment (step S120), when maintaining the hair dyed state than when the oxidative dye treatment (step S110) is repeated, Hair damage can be suppressed.

  Furthermore, the time required for the oxidation dye treatment (step S110) and the direct dye treatment (step S120) is equivalent to the normal oxidation dye treatment (step S220) and the ordinary direct dye treatment (step S240). For this reason, with the omission of the removal process (step S210) and the decoloring process (step S230), the time for the hair to come into contact with the chemical solution can be shortened. Therefore, hair damage caused by the removal process (step S210) and the decoloring process (step S230) can be avoided.

  (4) According to the dyeing method of dyeing the first color tone dyed in the oxidation dye treatment (step S110) and the second color tone dyed in the direct dye treatment (step S120) into different color tones, hair The change of the color tone of 11 and 12 can be easily repeated.

  In general, hair dyed with an oxidative dye fades in about one month, and hair dyed with a direct dye fades in about three weeks. Conventionally, when performing a so-called color change to change the dyed hair to a desired color tone, the dye is forcibly removed from the hair as described above, or the color fading period described above is used as a target. The only way to do this was to wait until it completely faded and then re-stain. According to the dyeing method of this embodiment, a desired color change can be performed easily and immediately.

  Further, conventionally, when a desired color change is performed in a short period, for example, the decoloring process (step S230) and the direct dye process (step S240) shown in FIG. It becomes easy to receive. According to the dyeing method of the present embodiment, it is possible to perform a desired color change by omitting the destaining process (step S230) and the like, even if such a color change is performed in a short period of time. Damage can be suppressed.

In addition, the said embodiment can also be changed and comprised as follows.
-The oxidative hair dye second agent may be divided into a plurality of agents and mixed at the time of use.

-The 1st color tone dye | stained by the said oxidation dye process (step S110) and the 2nd color tone dye | stained by a direct dye process (step S120) may be the same color tone.
-You may apply the said oxidation hair dye 1st agent and the dyeing | staining process method to keratin fibers other than hair. Examples of keratin fibers other than hair include wool and feathers.

Next, the technical idea that can be grasped from the above embodiment will be described below.
-(A) Alkaline agent, (B) Organic solvent, and (C) Oxidative dye components are mixed with the oxidant composition at the time of use and applied to keratin fibers dyed directly with the dye. A dyeing treatment method in which the color tone of the keratin fiber is changed to a color tone based on the color of the oxidation dye (C) by applying a fiber treatment agent to the keratin fiber dyed with a direct dye.

-The keratin fiber processing agent which contains at least one of benzyl alcohol and benzyloxyethanol as said (B) organic solvent.
-The keratin fiber processing agent whose pH of the mixture obtained by mixing with the said oxidizing agent composition is the range of 8-12.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
<Oxidative hair dye>
(Examples 1-1 to 1-16, Comparative Examples 1-1 to 1-3)
By mixing each component shown in Table 1 and Table 2, the first hair dye agent as a keratin fiber treatment agent (first keratin fiber treatment agent) and the second hair dye agent as an oxidant composition Was prepared. In Tables 1 and 2, the unit of the numerical value indicating the blending amount is mass%, and in the following tables, the unit of the numerical value indicating the blending amount is also mass%.

  On the other hand, a hair bundle dyed blue with a direct dye was separately prepared. This hair bundle is obtained by applying a conventional acidic hair dye shown in Table 3 to a human hair bundle (Stuffs, medium brown hair), leaving it for 30 minutes, and then washing it with water.

The mixture which mixed the oxidation hair dye 1st agent of each example and the oxidation hair dye 2 agent by mass ratio 1: 1 was prepared. The mixture of each example was applied to the hair bundle, allowed to stand for 30 minutes, and then washed with water, whereby the hair bundle was subjected to an oxidation dye treatment. The following evaluation was performed about the color tone of the hair bundle which performed the oxidation dye process, and the touch of the hair bundle.
<Evaluation of color tone>
Ten panelists evaluated the color tone of the hair bundle subjected to the above-described oxidation dye treatment with the color tone of the blank hair bundle by the following scoring criteria. The blank hair bundle is obtained by performing an oxidation dye treatment in the same manner as in each example except that the above-described human hair bundle is not treated with an acidic hair dye. Moreover, in the <color tone> column of Table 1 and Table 2, the color tone based on the kind of oxidation dye is described, and in the blank hair bundle, the color tone described in the <color tone> column and the hair bundle itself. It is visually recognized as a color tone that overlaps with the color tone.

  Scoring criteria: The color tone is almost the same as the color tone of the blank (excellent: 5 points), the color tone is very close to the color tone of the blank (good: 4 points), and the difference from the color tone of the blank is slight (possible: 3 points), a difference from the color tone of the blank is recognized (slightly poor: 2 points), and a difference in color tone is remarkable (1 point).

For the scoring results of 10 panelists, the average score is calculated, 4.5 points or more are “excellent: 5 points”, 3.5 points or more and less than 4.5 points are “good: 4 points”, 2.5 A score of 3 or more and less than 3.5 was judged as “possible: 3 points”, a score of 1.5 or more and less than 2.5 points was judged as “slightly defective: 2 points”, and a score of less than 1.5 points was judged as “bad: 1 point”. The determination results are also shown in Tables 1 and 2.
<Feel of hair bundle>
Ten panelists evaluated the tactile sensation of the hair bundle that had been subjected to the oxidation dye treatment with the oxidation hair dyes of Examples 1-1 to 1-16 according to the following scoring criteria.

  Scoring criteria: Compared to the hair bundles in each of the above examples, it is most excellent in fingering (excellent: 5 points), slightly inferior in fingering (good: 4 points), and slightly inferior in fingering (possible: 3) Point), the finger passability is inferior (slightly poor: 2 points), and the finger passability is significantly inferior (bad: 1 point).

  For the scoring results of 10 panelists, the average score is calculated, 4.5 points or more are “excellent: 5 points”, 3.5 points or more and less than 4.5 points are “good: 4 points”, 2.5 points More than 3.5 and less than 3.5 were judged as “possible: 3 points”, 1.5 and less than 2.5 points as “slightly defective: 2 points”, and less than 1.5 points as “defective: 1 point”. The determination results are also shown in Tables 1 and 2.

表１及び表２の結果から明らかなように、各実施例において色調の判定結果は３点以上であり、所望する色調に再度染色する処理を簡便に実施することができることがわかる。これに対して、比較例１−１及び比較例１−２ではアルカリ剤又は有機溶剤が含有されていないため、色調の判定結果は２点であり、所望する色調に再度染色する処理が困難であることがわかる。なお、比較例１−３では、酸化染料が含有されていないため、直接染料が脱色されるのみであって、染色処理が施されていない毛束の色調を呈した。

As is apparent from the results of Tables 1 and 2, in each example, the determination result of the color tone is 3 points or more, and it can be seen that the process of re-staining to the desired color tone can be easily performed. On the other hand, in Comparative Example 1-1 and Comparative Example 1-2, since the alkali agent or the organic solvent is not contained, the determination result of the color tone is two points, and it is difficult to perform the process of dyeing again to the desired color tone. I know that there is. In Comparative Example 1-3, since the oxidation dye was not contained, only the dye was directly decolored, and the color tone of the hair bundle not subjected to the dyeing treatment was exhibited.

  In Examples 1-1 to 1-5 and Examples 1-7 to 1-15, the mass ratio of (D) direct dye remover to (C) oxidation dye is in the range of 0.6 to 10, and The judgment result was 4 points or more. From this result, if the mass ratio of (D) the direct dye remover to (C) the oxidative dye is in the range of 0.6 to 10, the process of re-dying to the desired color tone can be carried out more easily. Recognize.

From the above results, it can be seen that in each example, the removal treatment for directly removing the dye in advance can be omitted when the oxidative hair dyeing treatment is performed.
Moreover, in Examples 1-1 to 1-14, the determination result of the feel of the hair bundle is 4 points or more, and it is understood that damage to the hair is suppressed.
<Hair dye>
(Examples 2-1 to 2-5)
As the second keratin fiber treatment agent, the first acid hair dye agent and the second acid hair dye agent shown in Table 4 were prepared. A mixture obtained by mixing the acidic hair coloring agent 1 and the acidic hair coloring agent 2 in each example at a mass ratio of 1:10 was used as an acidic hair dye.

  Meanwhile, a hair bundle dyed black with a conventional oxidative hair dye was separately prepared. This hair bundle is obtained by applying the conventional oxidative hair dye shown in Table 5 to human hair bundle (manufactured by Staffus Co., Ltd., medium brown hair), leaving it for 30 minutes, and washing it with water. .

  The acid hair dye of each Example was applied to the hair bundle, left for 30 minutes, and then washed with water, whereby the hair bundle was directly dyed. The color tone was evaluated by comparing the hair bundles of Examples 2-1 to 2-5 with the blank hair bundle in the same manner as in Examples 1-1 to 1-16. The determination results determined for the color tone evaluation results are also shown in Table 4. In the column of <color tone> in Table 4, the color tone based on the type of direct dye is described, and in the case of a blank hair bundle, the color tone described in the <color tone> column and the color tone of the hair bundle itself are shown. It is visually recognized as overlapping colors.

表４の結果から明らかなように、各実施例では、酸化染料に基づく黒色が脱染されることにより、直接染料に基づく色調に染色されていることがわかる。

As is clear from the results in Table 4, it can be seen that in each example, the black color based on the oxidative dye is decolored to dye the color tone based on the direct dye.

Thus, in each Example, since it dyes | stains to a desired color tone, the destaining process which destains an oxidation dye can be abbreviate | omitted.
From the above results, while using the oxidative hair dye and the acid hair dye of this embodiment, the hair dyeing treatment is performed by alternately performing the oxidative dye treatment (step S110) and the direct dye treatment (step S120). According to the dyeing method that repeats the above, it is possible to simply carry out the process of dyeing again to a desired color tone.
<Dyeing method>
(Example 3, Comparative Examples 2 to 4)
In Example 3, as shown in Table 6, the oxidative hair dye first agent of Example 1-7 and Example 1-8 was used as the first keratin treatment agent, and Examples 2-4 and Using the acid hair dye of Example 2-5 as the second keratin treatment agent, the hair dye bundle (manufactured by Stuffs, medium brown hair) of untreated human hair and directly with the oxidation dye treatment (step S110) The dye treatment (step S120) was performed alternately. The oxidation dye treatment (step S110) is performed by applying a mixture of the oxidative hair dye first agent and the oxidative hair dye second agent of each example in a mass ratio of 1: 1 to the hair bundle and leaving it for 30 minutes. It carried out by washing with water. The direct dye treatment (step S120) is performed by applying a mixture obtained by mixing the acidic hair coloring agent 1 and the acidic hair coloring agent 2 at a mass ratio of 1:10 to the hair bundle and leaving it for 30 minutes. It was carried out by washing with water. The interval between each treatment was about 24 hours. The color tone was evaluated by comparing the hair bundle of Example 3 with the blank hair bundle in the same manner as in Examples 1-1 to 1-16. Table 6 shows the determination results determined for the color tone evaluation results. In the <Color tone> column of Table 6, the color tone based on the type of oxidation dye or the type of direct dye is described, and in the case of a blank hair bundle, the color tone and hair described in the <Color tone> column are described. It is visually recognized as a color tone that overlaps the color tone of the bundle itself.

表６の結果から明らかなように、実施例３では、酸化染料処理（ステップＳ１１０）と直接染料処理（ステップＳ１２０）とを交互に実施することにより、各ステップにおいて、毛束の色調を所望の色調に染色することができることがわかる。この結果から本実施形態の染色処理方法によれば、脱染剤等を用いずに所望の色調に染色することができることがわかる。

As is apparent from the results in Table 6, in Example 3, by performing the oxidation dye treatment (step S110) and the direct dye treatment (step S120) alternately, in each step, the desired color tone of the hair bundle is obtained. It can be seen that the color can be dyed. From this result, it can be seen that according to the dyeing method of the present embodiment, it is possible to dye in a desired color tone without using a destaining agent or the like.

  In Comparative Example 2, as shown in Table 7, using the oxidative hair dyes of Examples 1-7 and 1-8, against a hair bundle of human hair (medium brown hair manufactured by Stuffs) The hair bundle was dyed in the same manner as in Example 3 except that only the oxidation dye treatment was repeated. The color tone was evaluated by comparing the hair bundle of Comparative Example 2 with the blank hair bundle in the same manner as in Examples 1-1 to 1-16. The determination results determined for the color tone evaluation results are also shown in Table 7. In the <Color tone> column of Table 7, the color tone based on the type of the oxidative dye is described, and in the blank hair bundle, the color tone described in the <Color tone> column and the color tone of the hair bundle itself are shown. It is visually recognized as overlapping colors.

表７の結果から明らかなように、比較例２の酸化染料処理では、所望の色調に染色することができないことがわかる。すなわち比較例２の方法では、脱染剤等を用いたり、退色するまで放置したりしない限り、所望の色調に染色することができない。

As is apparent from the results in Table 7, it can be seen that the oxidation dye treatment of Comparative Example 2 cannot be dyed to a desired color tone. That is, in the method of Comparative Example 2, it is not possible to dye in a desired color tone unless a destaining agent or the like is used or it is left to stand until it fades.

  In Comparative Example 3, as shown in Table 8, using the acidic hair dye of Example 2-4 and Example 2-5, against a hair bundle of human hair (medium brown hair manufactured by Stuffs) The hair bundle was dyed in the same manner as in Example 3 except that only the direct dye treatment was repeated. The color tone was evaluated by comparing the hair bundle of Comparative Example 3 with the blank hair bundle in the same manner as in Examples 1-1 to 1-16. The determination results determined for the color tone evaluation results are also shown in Table 8. In the column of <color tone> in Table 8, the color tone based on the type of direct dye is described, and in the case of a blank hair bundle, the color tone described in the <color tone> column and the color tone of the hair bundle itself are shown. It is visually recognized as overlapping colors.

表８の結果から明らかなように、比較例３では、所望の色調に染色することができないことがわかる。すなわち比較例３の方法では、除去剤等を用いたり、退色するまで放置したりしない限り、所望の色調に染色することができない。

As is apparent from the results in Table 8, it can be seen that Comparative Example 3 cannot be dyed to a desired color tone. That is, in the method of Comparative Example 3, it is impossible to dye in a desired color tone unless a remover or the like is used or the colorant is left to fade.

  In Comparative Example 4, the conventional oxidation hair dye and the conventional decoloring agent shown in Table 9 and the conventional acidic hair dye and the conventional removal agent shown in Table 10 were used. Then, as shown in Table 11, each agent is treated with an oxidation dye treatment (Step S220), a destaining treatment (Step S230), and a direct dye treatment (Medium Brown Hair, manufactured by Staffus Co., Ltd.). The hair bundle was dyed in the same manner as in Example 3 except that step S240) and removal processing (step S210) were performed in order. In addition, in the destaining process using the conventional destaining agent shown in Table 9 (step S230), a mixture in which the first agent and the second agent are mixed at a mass ratio of 1:10 is applied to the hair bundle. This was carried out by washing with water after standing for 30 minutes. Moreover, the removal process (step S210) using the conventional removal agent shown in Table 10 was implemented by applying to a hair bundle, leaving it for 30 minutes, and then washing with water. The color tone was evaluated by comparing the hair bundle of Comparative Example 4 with the blank hair bundle in the same manner as in Examples 1-1 to 1-16. The determination results determined for the color tone evaluation results are also shown in Table 11. In the <color tone> column of Table 11, the color tone based on the type of the oxidative dye and the direct dye is described, and in the case of a blank hair bundle, the color tone described in the <color tone> column and the hair bundle itself. It is visually recognized as a color tone that overlaps with the color tone.

表１１の結果から明らかなように、比較例４では、各酸化染料処理（ステップＳ２２０）及び各直接染料処理（ステップＳ２４０）において、所望の色調に染色されているものの、脱染処理（ステップＳ２３０）及び除去処理（ステップＳ２１０）の実施を必要としている。従って、所望の色調に再度染色する処理操作が極めて煩雑である。

As is clear from the results in Table 11, in Comparative Example 4, although each of the oxidation dye treatment (step S220) and each direct dye treatment (step S240) was dyed in a desired color tone, the decoloration treatment (step S230). ) And removal processing (step S210). Therefore, the processing operation for re-dying to a desired color tone is extremely complicated.

  Table 12 shows the result of color change and the result of damage evaluation in Example 3 and Comparative Examples 2 to 4.

表１２には、実施例３及び比較例２〜４から得られた結果と毛髪のダメージについての評価結果を示している。表１２において、「カラーチェンジ回数」の欄には、色調を変化した回数を示し、「処理回数」の欄には、前記カラーチェンジの回数に必要な処理の回数を示している。また、「所望の色調への染色」の欄には、前記カラーチェンジにおいて、所望の色調への染色が可能か否かを示している。

Table 12 shows the results obtained from Example 3 and Comparative Examples 2 to 4 and the evaluation results for hair damage. In Table 12, the “color change count” column indicates the number of times the color tone has been changed, and the “processing count” column indicates the number of times required for the color change. The column “Dyeing to desired color tone” indicates whether or not dyeing to a desired color tone is possible in the color change.

Regarding the damage to the hair bundle, the touch feeling of the hair bundle when 10 panelists completed the final step was evaluated according to the following scoring criteria.
Scoring criteria: The finger passage of the hair bundle is slightly worse than the hair bundle before the treatment (3 points), The finger passage of the hair bundle is worse than the hair bundle before the treatment (2 points) , And the three stages in which the fingering property of the hair bundle is considerably worse than the hair bundle before treatment (one point).

  The average score is calculated for each paneler's scoring result, the average score is 2.5 points or more with very little damage (○), the score is 2.0 points or more and less than 2.5 points (△), and The damage evaluation results are shown in Table 12, with less than 2.0 points indicating a lot of damage (x).

  As is apparent from the results in Table 12, in Example 3, the hair bundle damage was very small. From this result, according to the dyeing method of the present embodiment, hair damage can be suppressed when maintaining the desired color tone of the hair. Moreover, even when the color change of the hair is performed in a short period of time, damage to the hair can be minimized. On the other hand, in Comparative Example 2, since the treatment using the oxidative hair dye is repeated, the desired color change cannot be performed, and in addition, the hair is often damaged. In Comparative Example 3, because of the treatment using the acidic hair dye, hair damage is suppressed, but a desired color change cannot be performed. In Comparative Example 4, it can be seen that as a result of an increase in the treatment time of the hair bundle accompanying an increase in the number of treatments by the decoloring treatment (step S230), hair damage is large.

(A) is the schematic diagram which shows the hair dye | stained with the direct dye, and the hair dye | stained with the colored oxidation dye, (b) is a schematic diagram which shows the dyeing | staining process method. The schematic diagram which shows the conventional dyeing | staining processing method.

Explanation of symbols

  11, 12 ... Hair as keratin fiber, 21 ... Direct dye, 22 ... Oxidative dye.

Claims (5)

A keratin fiber treatment agent comprising the following components, being mixed with an oxidant composition at the time of use, and applied to keratin fibers directly dyed with a dye.
(A) Alkaline agent.
(B) Organic solvent.
(C) Oxidative dye. The keratin fiber treatment agent according to claim 1, wherein the keratin fiber treatment agent is used to change a color tone of a keratin fiber dyed with the direct dye. Further, (D) contains sulfites as a direct dye remover, and (C) a mass ratio of the (D) direct dye remover to the oxidation dye (mass ratio = (D) a mass of the direct dye remover / (C The keratin fiber treating agent according to claim 1 or 2, wherein the mass) of the oxidative dye is from 0.6 to 10. In a dyeing method for dyeing keratin fibers,
An oxidation dye that dyes the keratin fiber with an oxidation dye by using the first keratin fiber treatment agent that contains the following components (A) to (C) and is mixed with the oxidant composition at the time of use. Processing,
A direct dye treatment for dyeing the keratin fiber with a direct dye by using a second keratin fiber treatment agent containing the following components (a) and (b):
A dyeing treatment method comprising repeating the dyeing treatment of the keratin fiber by alternately performing the oxidation dye treatment and the direct dye treatment.
<First keratin fiber treatment agent>
(A) Alkaline agent.
(B) Organic solvent.
(C) Oxidative dye.
<Second keratin fiber treatment agent>
(A) Direct dye.
(B) At least one selected from thioglycolic acids, cysteines, sulfites, thiosulfates, dithionites, hydroxymethanesulfinic acids, and ascorbic acids as an oxidizing dye reducing agent. The dyeing processing method according to claim 4, wherein the first color tone dyed by the oxidation dye treatment and the second color tone dyed by the direct dye treatment are set to different color tones.

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