JP7305157B2 - Method for dyeing keratin fibers - Google Patents

Description

The present invention relates to a method for dyeing keratin fibers.

BACKGROUND ART Many fluorescent substance-containing hair dye compositions, hair dye compositions, and the like, which are used for keratin fibers such as hair, have been reported. (For example, see Patent Documents 1 to 4.)
For example, in Patent Document 1, it is reported that hair dyeing with a hair dye composition containing acid dyes of groups (A) and (B) reduces color fading during shampooing after hair dyeing. . In Patent Document 1, Group (A) is one or more acid dyes selected from Green No. 204, Red No. 230 and Yellow No. 202, and Group (B) is other acid dyes. , has been disclosed.

In addition, Patent Document 2 reports an invention in which hair is dyed with a hair dye composition containing a fluorescent brightening dye and a direct dye to make the hair brighter and brighter after dyeing.

Dyeing hair using a hair dye composition or hair dye composition containing a fluorescent substance has been conventionally performed, and various compositions and methods have been proposed according to each purpose.

Japanese Unexamined Patent Application Publication No. 2003-073238 JP-A-2001-294519 JP-A-09-183714 Japanese Patent Publication No. 2001-516706

Conventionally, there has been a demand for hair that emits fluorescence when exposed to light with a wavelength of 305 nm to 400 nm (hereinafter also referred to as black light) in some industries such as the fashion industry and the music industry.
As a technique capable of meeting such demands, dyeing hair with a hair dye composition or the like containing a fluorescent substance has been proposed. Although there are hair dye compositions that emit fluorescent color when exposed to black light, in the prior art, dyes that can be used for hair and emit fluorescent color are limited to yellow, red, etc., and are not black light. The color tone of dyed hair upon irradiation is limited, and the intensity of fluorescent color upon irradiation with black light varies, and improvements have been desired.

Therefore, the present invention provides a dyeing method that enables the color tone of dyed keratin fibers to be arbitrarily controlled when not irradiated with black light, and enables the dyed keratin fibers to emit strong fluorescence when irradiated with black light. The task is to provide

As a result of intensive research by the present inventors, keratin having a step of dyeing keratin fibers dyed with a dye with a preparation containing a specific fluorescent substance in a specific amount or more and having a pH within a specific range The method of dyeing the fibers makes it possible to arbitrarily control the color tone of the keratin fibers after dyeing when not irradiated with black light, and the keratin fibers after dyeing when irradiated with black light are strong. The inventors have found that they can emit fluorescence, and have completed the present invention.

In order to solve the above problems, the present invention is, for example, as follows.
[1] A step (B) of dyeing keratin fibers dyed with a dye with a formulation containing 0.05% by mass or more of Green No. 204 and having a pH of 1.0 to 4.0. , a method of dyeing keratin fibers.
[2] The dyeing method according to [1], wherein the formulation contains 0.05 to 1% by mass of Green No. 204.
[3] The keratin fibers dyed with the dye are keratin fibers dyed with at least one dye selected from acid dyes, basic dyes, HC dyes, nitro dyes and oxidation dyes, [ 1] or the staining method according to [2].
[4] The dyeing method according to either [1] or [2], wherein the keratin fibers dyed with the dye are keratin fibers dyed with an acid dye.
[5] The dyeing method according to any one of [1] to [4], wherein the step (A) of dyeing the keratin fibers with a dye is performed before the step (B).
[6] The dyeing method according to [5], wherein the dye used in the step (A) is at least one selected from acid dyes, basic dyes, HC dyes, nitro dyes and oxidation dyes.
[7] The dyeing method according to [5], wherein the dye used in the step (A) is an acid dye.
[8] The dyeing method according to any one of [1] to [7], wherein the keratin fibers are hair.

The dyeing method of the present invention is a method for dyeing keratin fibers, it is possible to arbitrarily control the color tone of the keratin fibers after dyeing when not irradiated with black light, and the keratin fibers after dyeing when irradiated with black light. has the effect of emitting strong fluorescence.

The present invention will be described in detail below.
The present invention comprises a step (B) of dyeing keratin fibers dyed with a dye with a formulation containing 0.05% by mass or more of Green No. 204 and having a pH of 1.0 to 4.0. A method for dyeing keratin fibers, comprising:

Hereinafter, after explaining the keratin fibers dyed using the dye, which is the target of the step (B) in the dyeing method of the present invention, each step will be explained.

<Keratin fiber dyed with dye>
In the present invention, keratin fibers dyed with a dye are dyed with a formulation described below in step (B).
Keratin fibers refer to fibers containing keratin protein. Specific examples include hair, goat hair, wool, dog hair, and cat hair, and hair includes wigs and extensions using hair. Keratin fibers are preferably goat hair and hair, more preferably hair.

The keratin fibers dyed with a dye to be subjected to the step (B) refer to fibers obtained by dyeing keratin fibers with a dye before the step (B). The keratin fibers dyed with a dye are preferably keratin fibers dyed with at least one dye selected from acid dyes, basic dyes, HC dyes, nitro dyes and oxidation dyes. It is more preferable to use keratin fibers dyed with an acid dye because the change in color is small when (B) is performed. As the dye, the dyes described in the section <<Dyes>> described later can be used. The keratin fibers dyed with a dye may be keratin fibers dyed with one dye or keratin fibers dyed with two or more dyes. In addition, the keratin fibers dyed with a dye may be keratin fibers dyed once with dyes or keratin fibers dyed two or more times with dyes. When dyeing is performed two or more times, the dyes used each time may be the same or different. In the present invention, since the keratin fibers to be subjected to the step (B) are already dyed with a dye, the desired color tone resulting from the dye is imparted to the keratin fibers subjected to the dyeing method of the present invention. can do.

The keratin fibers dyed with a dye may be dyed by others (a person other than the person who performs the step (B)) before the step (B), or they may be dyed by themselves (the person who performs the step (B)). There is no particular limitation. Further, the dyeing with a dye performed before the step (B) may be performed before the step (B), immediately before (for example, several minutes to several hours), or before (for example, one day ~ several months ago). The keratin fibers dyed with a dye are preferably dyed 1 minute to 1 week before the step (B), more preferably 1 minute to 2 hours before the step (B).
Keratin fibers dyed with a dye can be obtained, for example, by the following step (A).

<Step (A)>
In the method for dyeing keratin fibers in the present invention, step (A) of dyeing keratin fibers using a dye may be performed before step (B) described below. The dye used in step (A) is preferably at least one selected from acid dyes, basic dyes, HC dyes, nitro dyes and oxidation dyes, more preferably acid dyes.

≪Dye≫
The dyes used in step (A) are preferably acid dyes, basic dyes, HC dyes, nitro dyes or oxidation dyes, and may be used singly or in combination of two or more. It is more preferable to contain an acid dye from the viewpoint that there is little change in color when the step (B) is performed and the subsequent discoloration properties are similar.

Examples of acid dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 201 and Red No. 213, which are dyes other than Green No. 204. Red No. 227, Red No. 230 (1), Red No. 230 (2), Red No. 231, Red No. 232, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Orange 205 No., Orange No. 207, Orange No. 402, Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Yellow No. 402, Yellow No. 403 (1), Yellow No. 406 , Yellow No. 407, Blue No. 1, Blue No. 2, Blue No. 202, Blue No. 203, Blue No. 205, Green No. 3, Green No. 201, Green No. 205, Green No. 401, Green No. 402, Brown No. 201, Black No. 401 and Murasaki No. 401 can be used. Green No. 204 is generally not used when only one dye is used in step (A). However, when two or more dyes are used in step (A), Green No. 204 may be used as one of the dyes.

Examples of basic dyes include Red No. 213, Red No. 214, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 75, Basic Blue 99, Basic Red 2, Basic Red 22, Basic red 51, basic red 76, basic yellow 57, basic yellow 87, basic orange 31, basic brown 16, basic brown 17, basic purple 3, basic purple 4, basic purple 14 can be used.

Examples of HC dyes include HC blue 2, HC blue 6, HC blue 7, HC blue 8, HC orange 1, HC orange 2, HC orange 3, HC red 1, HC red 3, HC red 7, HC red 10, HC red 13, HC red 14, HC purple 1, HC purple 2, HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, 1-amino-2-methyl-6-nitrobenzene, 1-amino-2- methyl-4-methylaminobenzene, 4-(2-hydroxyethyl)amino-3-nitro-methylbenzene, 1-bis(β-hydroxyethyl)amino-3-nitro-4-amino, 1-amino-2- Benzene(β-hydroxypropylamino)benzene, 1-hydroxy-3-nitro-4-(3-hydroxypropylamino)benzene, 4-hydroxypropylamino-3-nitrophenol can be used.

Nitro dyes include, for example, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and can be used. Examples of salts include hydrochlorides and sulfates.

Examples of oxidation dyes include p-phenylenediamine, toluene-2,5-diamine, p-aminophenol, 2,2′-[(4-aminophenyl)imino]bisethanol, p-methylaminophenol, 2-chloro -p-phenylenediamine, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, o-aminophenol, 2-hydroxyethyl-p-phenylenediamine, 2-amino-4-hydroxyethylaminoanisole, 2 , 4-diaminophenol, resorcinol, 5-amino-o-cresol, 2,4-diaminophenoxyethanol, m-aminophenol, 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, α- naphthol, 1,5-dihydroxynaphthalene, catechol, pyrogallol, phloglucine, gallic acid, hydroquinone, toluene-3,4-diamine, 2,6-diaminopyridine, diphenylamine, 3,3′-iminodiphenyl, tannic acid, and Salts thereof can be used. Examples of salts include hydrochlorides and sulfates.
When dyeing keratin fibers with a dye, the dye is usually used as a formulation (hair dye, hair dye) in combination with other ingredients.

≪Dyeing method≫
In the step (A), dyeing can be carried out by applying a preparation containing a dye to the keratin fiber and optionally leaving it at 20° C. to 50° C. for 10 seconds to 30 minutes. Since it is easy to penetrate the dye into the keratin fibers, after applying the dye, it is preferably 20 to 50 ° C. for 5 to 30 minutes, more preferably 45 ° C. for 10 minutes or more in the case of a 1-agent type, and in the case of a 2-agent type. Allow to stand at 25°C for 20 minutes. The amount of the formulation used in step (A) is not particularly limited as long as it can be uniformly applied to the keratin fibers. Use 0.5 to 3 g and spread it evenly.

In step (A), one type of dye may be used, or two or more types of dyes may be used. Moreover, step (A) may be performed once or twice or more. When step (A) is performed more than once, the dyes used in each step (A) may be the same or different.

≪Other ingredients≫
The formulation used in step (A) may contain other components in addition to the dye as long as the effects of the present invention are not impaired. Other ingredients include, for example, oily ingredients (hydrocarbons, oils and fats, waxes, higher alcohols, higher fatty acids, esters), thickeners, penetrants, moisturizers, surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants), silicones, chelating agents, antioxidants, stabilizers, pH adjusters, protective agents, solvents, anti-inflammatory agents, fragrances, preservatives, ultraviolet absorbers, propellants, plant extracts, crude drug extracts, vitamins, resins and ion-exchanged water, and may be used singly or in combination of two or more. .

≪Dosage form≫
The dosage form of the formulation used in step (A) includes, for example, cream, gel, liquid, milk, foam and lotion. Specifically, cream or gel may be used. can.

<Step (B)>
In the method of dyeing keratin fibers in the present invention, keratin fibers dyed with a dye are dyed using a formulation containing 0.05% by mass or more of Green No. 204 and having a pH of 1.0 to 4.0. (B).

The amount of the formulation used in step (B) is not particularly limited as long as it can be uniformly applied to the keratin fibers. Use 0.5 to 3 g and spread it evenly.

≪Formulation≫
The formulation used in the present invention contains 0.05% by mass or more, preferably 0.05 to 1% by mass, of Green No. 204 as a dye. Green No. 204 is also called pyranine or trisodium 8-hydroxypyrene-1,3,6-trissulfonate, and has a chemical formula of C ₁₆ H ₇ Na ₃ O ₁₀ S ₃ .

In addition to Green No. 204, the formulation used in step (B) usually contains other ingredients within a range that does not impair the effects of the present invention. Other ingredients include, for example, oily ingredients (hydrocarbons, fats and oils, waxes, higher alcohols, higher fatty acids, esters), thickeners, penetrants, moisturizers, surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants), silicones, chelating agents, antioxidants, stabilizers, pH adjusters, protective agents, solvents, anti-inflammatory agents, fragrances, preservatives, ultraviolet absorbers, propellants, plant extracts, crude drug extracts, vitamins, resins, and ion-exchanged water, and may be used singly or in combination of two or more. good.

≪Dyeing method≫
The method for dyeing keratin fibers of the present invention includes a step (B) of dyeing with a formulation containing 0.05% by mass or more of Green No. 204 and having a pH of 1.0 to 4.0.

As a method of attaching the dye to the keratin fibers, there is a method of immersing the keratin fibers in the prepared sample, or a method of directly applying the formulation to the keratin fibers, followed by optionally heating at 20° C. to 50° C. for 10 seconds to 30 seconds. can be left in minutes. Since the dye is easily permeated into the keratin fibers, the keratin fibers are preferably immersed in the prepared sample and then left at 20 to 50° C. for 15 to 30 minutes, more preferably at 45° C. for 15 minutes.

≪Dosage form≫
Examples of dosage forms of the formulation used in step (B) include liquid, milk, cream, gel and lotion, preferably gel and cream. It may also be applied to keratin fibers as a composition for spraying by using a liquefied product together with a propellant.

<Application>
The keratin fiber dyeing method of the present invention can be performed on the entire keratin fiber or a predetermined portion of the keratin fiber. For example, it can be applied to all or part of a wig using keratin fibers, or to all or part of hair.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

<Sample preparation>
Samples were prepared by mixing each component according to the formulations shown in Tables 1 to 5 below. Formulations A-1 to A-9 are for samples used in step (A) described below, and prescriptions B-1 to B-4 are for samples used in step (B) described below. The samples (formulations) obtained by preparing according to Formulation A-1 to Formulation A-9 and Formulation B-1 to Formulation B-4 were respectively sample A-1 to A-9 and sample B-1. to B-4. Numerical values for formulations in the table represent mass % of each component when each sample is taken as 100 mass %.

In addition, each component of Table 1 and Table 2 used the following commercial items.
<Dye>
・ Red No. 227: “Red No. 227” (Kisumi Kasei Co., Ltd.)
・ Orange No. 205: “Orange No. 205” (Kisumi Kasei Co., Ltd.)
・ Black No. 401: “Purified Black No. 401” (Kisumi Kasei Co., Ltd.)
・ Purple No. 401: “Purified Purple No. 401” (Kisumi Kasei Co., Ltd.)
・ Basic Blue 75: “AHC BLUE SP” (Hodogaya Chemical Industry Co., Ltd.)
・ Basic Red 51: “AHC RED SP” (Hodogaya Chemical Industry Co., Ltd.)
・HC Blue 2: “TM Blue NO.2” (Kisumi Kasei Co., Ltd.)
・ 4-Hydroxypropylamino-3-nitrophenol: “TM Red NO.2” (Kisumi Kasei Co., Ltd.)
・p-Phenylenediamine: “Paraphenylenediamine” (Mitsui Chemicals)
・p-aminophenol: “para-aminophenol” (Mitsui Chemicals)
・ 5-amino-o-cresol: "5-aminoorthocresol" (Mitsui Chemicals)
・ 2,4 Diaminophenoxyethanol Hydrochloride: “2,4 Diaminophenoxyethanol Hydrochloride” (Mitsui Chemicals)
・ Green No. 204: “Green No. 204” (Kisumi Kasei Co., Ltd.)
<Surfactant>
・ Stearyltrimethylammonium chloride: “Catinal STC-70ET” (Toho Chemical)
・Polyoxyethylene cetyl ether: “Nikkor BC-30” (Nikko Chemicals Co., Ltd.)
<Base material/solvent>
・Cetostearyl alcohol: “Calcol 6850” (Kao Corporation)
・ Ethanol: “95% ethanol” (Nippon Synthetic Alcohol Co., Ltd.)
・ Liquid paraffin: “Hicol M-352” (Kaneda Co., Ltd.)
・Polyethylene glycol: "PEG400" (Sanyo Kasei)
<pH adjuster>
・ 90% lactic acid: “90% fermented lactic acid” (Purak)
・ 60% Na lactate: “Fermented lactic acid NAS/HQ60” (Purak)
・ 28% ammonia water: “28% ammonia water” (Taisei Kako)
・ 89% phosphoric acid: “89% phosphoric acid” (Nippon Chemical Industry)
<Thickener>
・(Hydroxyethyl acrylate/Na acryloyldimethyltaurate) copolymer: “Sepinob EMT-10” (SEPPIC)
<Penetrant>
・Benzyl alcohol: “Benzyl alcohol” (Tokyo Ohka Kogyo Co., Ltd.)
<Antioxidant>
・Sodium sulfite: "Sodium sulfite" (Daito Chemical)
<Chelating agent>
・ EDTA-4Na: "SD-2DS" (Chubu Kirest)
<Oxidizing agent>
・ 35% hydrogen peroxide water: "35% hydrogen peroxide water": (Tokai Denka)
<Stabilizer>
・Phenacetin: "Phenacetin" (Yamamoto Chemical Industry)

<Processing method 1>
[Examples 1 to 18, Comparative Examples 1 to 6]
[A process]
2 g of each sample A-1 to A-6 was applied to a 10 cm goat hair bundle (manufactured by Beaulux) of 1 g, and left in a constant temperature layer at 45° C. for 15 minutes.
It was thoroughly washed with water, washed with a 10% POE (3) lauryl ether sulfate aqueous solution, and then thoroughly rinsed.
[B process]
After lightly removing moisture with a towel, it was immersed in samples B-1 to B-4 and allowed to stand in a constant temperature layer at 45° C. for 15 minutes.
It was thoroughly washed with water, washed with a 10% POE (3) lauryl ether sulfate aqueous solution, then thoroughly rinsed and dried with a drier.
The color of the dyed goat hair bundle was visually observed and evaluated according to the following criteria. Tables 6 and 8 show the evaluation results.

<Processing method 2>
[Examples 19 to 24, Comparative Examples 7 and 8]
[A process]
Each sample A-7 or A-8 and sample A-9 were thoroughly mixed at a mixing ratio (mass ratio) of 1:1, respectively, and 2 g of the mixture was applied to a 10 cm goat hair bundle of 1 g. ℃ for 30 minutes.
It was thoroughly washed with water, washed with a 10% POE (3) lauryl ether sulfate aqueous solution, and then thoroughly rinsed.
[B process]
After lightly removing moisture with a towel, it was immersed in samples B-1 to B-4 and allowed to stand in a constant temperature layer at 45° C. for 15 minutes.
It was thoroughly washed with water, washed with a 10% POE (3) lauryl ether sulfate aqueous solution, then thoroughly rinsed and dried with a drier.
The color of the dyed goat hair bundle was visually observed and evaluated according to the following criteria. Tables 7 and 9 show the evaluation results.

[criterion]
Required evaluation items 1. Fluorescence intensity under black light ◎ Emit strong fluorescence.
〇 It emits fluorescence.
x: Fluorescence is not felt.
Optional evaluation item 2. Degree of discoloration in the B process ◎ Almost the same color as before the B process.
O The color has not changed much from before the B process.
Δ: The color is slightly different from that before the B step.
× The color is clearly different from that before the B step.

An essential evaluation item in the present invention is "intensity of fluorescence under black light", and if the criterion is ◯ or ⊚, it is considered as an example.
As an optional evaluation item, "degree of discoloration by step B" is used. Regardless, it was classified as an example.

In the hair dyed in Comparative Examples 1 to 8 of the present invention, sample B-4 having a low content of Green No. 204 was used in the B step, and the intensity of fluorescence under black light was determined. , the results were inferior to those of the examples.

Claims (4)

(A) dyeing the keratin fibers with an acid dye, and
After the step (A), a formulation having a pH of 1.0 to 4.0 containing 0.20 to 1.00% by mass of Green No. 204 is used for keratin fibers dyed with an acid dye. including a step (B) of dyeing with
A method for dyeing keratin fibers. The dyeing method according to claim 1 , wherein the step (A) of dyeing the keratin fibers with an acid dye is performed 1 minute to 2 hours before the step (B). The dyeing method according to claim 1 or 2 , wherein the acid dye used in the step (A) is at least one selected from Red No. 227, Orange No. 205, Purple No. 401, and Black No. 401 . The dyeing method according to any one of claims 1 to 3 , wherein the keratin fibers are hair.