JP5464844B2 - Oxidative hair dye - Google Patents

Description

  The present invention relates to an oxidative hair dye. More specifically, the present invention relates to an oxidative hair dye capable of dyeing hair into a yellow hue. Note that yellow in the present invention represents a Munsell color system hue of 5Y to 10YR, a brightness of 8 or more, and a saturation of 8 or more.

  The oxidative hair dye is generally of a two-component type comprising a first agent containing an alkali agent and an oxidative dye and a second agent containing an oxidant. This two-part oxidative hair dye oxidizes and decomposes the melanin pigment in hair by mixing the first and second agents at the time of use, and oxidatively polymerizes colorless low-molecular oxidative dyes in the hair. To produce pigments of various hues and dye the hair to the desired color.

  However, in recent years, there has been a growing concern about the safety of oxidative dyes blended with oxidative hair dyes, and some oxidative dyes have been refrained from the viewpoint of safety. Especially in European countries, it is becoming prohibited to mix oxidative dyes with safety concerns and oxidative dyes with insufficient safety data into products. For this reason, the use of oxidation dyes with safety concerns has been avoided worldwide.

  Also, ortho-aminophenol, which has been conventionally used for dyeing hair into a yellowish hue, has been regulated in European countries from the viewpoint of safety, so avoid the use of such oxidation dyes. Has come to be. For this reason, there exists a problem that the combination of the oxidation dye which dye | stains hair to a yellowish hue cannot be performed.

  In order to solve this problem, conventionally, a method of dyeing hair into a yellow hue by using a nitro-based direct dye such as p-nitro-o-phenylenediamine has been performed (for example, patents). Reference 1). However, dyeing with a direct dye involves dyeing on the surface of the hair and dyeing it, so that there is a problem that fading is likely to occur due to daily hair washing or the like and the fastness is inferior.

  In addition, as a technique related to the present invention, there has been reported an oxidative hair dye that dyes hair using paramethylaminophenol and resorcin (see, for example, Patent Documents 2 to 6). However, any of these oxidative hair dyes are not intended to dye hair into a yellowish hue, but are merely used as part of various dyes to be mixed.

Japanese Patent Publication No. 3-31191 JP-A-2005-298431 (paragraph numbers [0075], [0078]) Japanese Patent Laying-Open No. 2003-40747 (paragraph number [0044]) JP 2002-193772 A (paragraph number [0039]) JP-A-6-87727 (paragraph number [0029]) Japanese Patent Laid-Open No. 4-31514 (paragraph number [0028])

  The present invention has been made in view of the above-described conventional technology. By combining an oxidative dye with low safety concerns, hair can be obtained without using conventionally used orthoaminophenol. It is an object of the present invention to provide an oxidative hair dye that can be dyed into a yellow hue and that does not fade in the hue of the dyed yellow hair and is excellent in fastness.

That is, the present invention
(1) An oxidative hair dye comprising a first agent containing an alkaline agent excluding carbonate and bicarbonate and an oxidative dye, and a second agent containing an oxidant,
Using paramethylaminophenol and / or a salt thereof as a dye precursor, using resorcin as a coupler,
The total amount of paramethylaminophenol and / or its salt and resorcin is 70 to 100 mole percent of the total amount of the oxidation dye,
The compounding ratio of paramethylaminophenol (A) and resorcin (B) is a molar ratio, A: B = 2: 1 to 1: 5,
An oxidative hair dye characterized by being used by dyeing hair into a yellow hue;
( 2 ) The oxidative hair dye according to (1 ), wherein the alkali agent is at least one selected from the group consisting of ammonia, monoethanolamine, and isopropanolamine,
( 3 ) The oxidative hair dye according to (1) or (2) , further comprising a pH adjuster in the first agent,
( 4 ) The oxidative hair dye according to ( 3 ), wherein the pH adjuster is at least one selected from the group consisting of carbonates, bicarbonates, inorganic acids, and organic acids.
( 5 ) The oxidative hair dye according to any one of (1) to ( 4 ) above, wherein the pH of the system at the time of mixing the first agent and the second agent is pH 9-11.
( 6 ) The oxidative hair dye according to any one of the above (1) to ( 5 ), which does not contain orthoaminophenol as a dye precursor, and ( 7 ) which does not contain a direct dye. The oxidative hair dye according to any one of (1) to ( 6 ).

  The oxidative hair dye of the present invention is capable of dyeing hair into a yellow hue, and has the effect that the hue of the dyed yellow hair does not fade and is excellent in fastness.

  The oxidative hair dye of the present invention comprises a first agent containing an alkali agent and an oxidative dye and a second agent containing an oxidant. First, the 1st agent of this invention is demonstrated.

  As the alkaline agent used in the present invention, an alkaline agent excluding carbonate and bicarbonate is used. The alkali agent that can be used is not particularly limited as long as the effects of the present invention are exhibited. For example, inorganic alkali agents such as ammonia and sodium hydroxide; monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 2-amino-2 -Organic alkali agents, such as methyl-1-propanol, can be illustrated. Of these, ammonia, monoethanolamine, isopropanolamine and the like are preferably used from the viewpoints of sufficiently decolorizing black hair and dyeing the hair vividly yellow.

  The content of the alkali agent in the first agent is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 1% by mass or more, more preferably 3% by mass or more from the viewpoint of dyeability to hair. Moreover, from a viewpoint of irritation to the scalp, 15 mass% or less is preferable and 12 mass% or less is more preferable. From these things, content of the alkaline agent in the 1st agent becomes like this. Preferably it is 1-15 mass%, More preferably, it is 3-12 mass%.

  The oxidative dye in the present invention means both a dye precursor that develops color by its own oxidative polymerization and a coupler that has various hues by reaction with the dye precursor. Examples of the oxidative dye precursor that can be used in the present invention include phenylenediamines, aminophenols, diaminopyridines, and salts thereof such as hydrochlorides and sulfates. Specifically, p-phenylenediamine, toluene-2,5-diamine, toluene-3,4-diamine, 2,5-diaminoanisole, N-phenyl-p-phenylenediamine, N-methyl-p-phenylenediamine N, N-dimethyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N- (hydroxyethyl) -P-phenylenediamine, N- (2-hydroxypropyl) -p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2 -Hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-butyl Phenylenediamines such as mu-p-phenylenediamine; paraaminophenol, orthoaminophenol, paramethylaminophenol, 2,4-diaminophenol, 5-aminosalicylic acid, 2-methyl-4-aminophenol, 3-methyl-4 -Aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2- Examples thereof include aminophenols such as chloro-4-aminophenol and 3-chloro-4-aminophenol; diaminopyridines such as 2,5-diaminopyridine, and salts thereof.

  Examples of the coupler include resorcin, m-aminophenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, 5-amino-o-cresol, 2-methyl-5-hydroxyethylaminophenol, and 2,6-diaminopyridine. And catechol, pyrogallol, gallic acid, tannic acid and the like and salts thereof.

  In the present invention, among these oxidation dyes, at least paramethylaminophenol and / or a salt thereof is used as a dye precursor, and resorcin is used as a coupler. Conventionally, although paramethylaminophenol is an oxidative dye that is not frequently used as an oxidative hair dye, it has been found that hair can be dyed into a yellowish hue by combining both.

  The content of the oxidative dye in the first agent is not particularly limited as long as the effect of the present invention is exhibited. However, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more from the viewpoint of dyeability to hair. Moreover, 10 mass% or less is preferable and 5 mass% or less is more preferable from the viewpoint of dyeing hair in a yellowish hue and the viewpoint of irritation to the scalp. From these things, content of the oxidation dye in the 1st agent becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 1-5 mass%.

  In addition, from the viewpoint of dyeing hair into a yellow hue, the total amount of paramethylaminophenol and / or a salt thereof and resorcin is preferably 70 mol percent or more, and 80 mol percent or more in the total amount of oxidation dye of the first agent. Is more preferable, and 90 mole percent or more is particularly preferable. In particular, when the hair is dyed in a brighter yellow, it may be used as 100 mole percent. From these facts, the total amount of paramethylaminophenol and / or its salt and resorcin is 70 to 100 mole percent in the total amount of the first component oxidation dye.

  Further, the blending ratio of paramethylaminophenol and / or a salt thereof and resorcin is not particularly limited as long as the effect of the present invention is exhibited. However, paramethylaminophenol (from the viewpoint of dyeing hair more vividly yellow) The molar ratio of A) to resorcin (B) is preferably A: B = 2: 1 to 1: 5, and more preferably A: B = 1: 1 to 1: 4.

  In the present invention, from the viewpoint of dyeing hair in a brighter yellow, the first agent can contain a pH adjuster in order to adjust the pH of the system during use. The pH adjuster to be used is not particularly limited as long as the effect of the present invention is exhibited. For example, carbonates such as ammonium carbonate, sodium carbonate, and potassium carbonate; bicarbonates such as ammonium bicarbonate, sodium bicarbonate, and potassium bicarbonate. Salts; inorganic acids such as phosphoric acid and hydrochloric acid; and organic acids such as citric acid, lactic acid, oxalic acid, and glycolic acid.

  The content of the pH adjusting agent may be an amount that can adjust the system at the time of mixing (using) the first agent and the second agent to the target pH.

  The 1st agent concerning this invention can contain antioxidant from a viewpoint which prevents the oxidation in the formulation preservation | save of an oxidation dye. Antioxidants include sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, erythorbic acid, sodium erythorbate, magnesium ascorbate phosphate, ascorbyl citrate, ascorbyl acetate, ascorbyl tartrate, ascorbyl palmitate, In addition to ascorbic acid and ascorbic acid derivatives such as ascorbyl stearate and ascorbyl glucoside, sulfites, bisulfites, pyrobisulfites and the like can be mentioned.

  Next, the second agent of the present invention will be described. The second agent according to the present invention contains an oxidizing agent as an essential component in order to oxidatively polymerize the oxidative dye in the first agent in the hair. Examples of the oxidizing agent to be used include hydrogen peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate and the like, and it is preferable to use hydrogen peroxide.

  The content of the oxidizing agent in the second agent is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of dyeability, 0.01% by mass or more is preferable, and 0.1% by mass or more is more preferable. Moreover, from a viewpoint of preventing skin irritation and hair damage, 10 mass% or less is preferable and 6 mass% or less is more preferable. From these things, it is preferable that content of the oxidizing agent in a 2nd agent shall be 0.01-10 mass%, More preferably, it is good to set it as 0.1-6 mass%.

  The second agent of the present invention may contain an oxidizing agent stabilizer. For example, phenacetin, hydroxyethane diphosphonic acid and the like can be exemplified.

  In addition, the first agent and / or the second agent according to the present invention include, in addition to the above components, lower alcohols such as ethanol and isopropanol; lauryl alcohol, myristyl, as long as the effects of the object of the present invention are not impaired. Higher alcohols such as alcohol, cetyl alcohol, stearyl alcohol; higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid; hydrocarbons such as liquid paraffin, liquid isoparaffin, squalane; myristyl myristate, isostearyl myristate, stearin Esters such as stearyl acid; animal and vegetable oils such as avocado oil, olive oil, safflower oil, hydrogenated oil; polyethylene glycol, glycerin, polyglycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-octanediol Etc. Nonionic properties such as alcohol; sorbitan fatty acid ester, glycerin fatty acid ester, and adducts thereof, polyglycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin Surfactant: Higher fatty acid soap, alkyl sulfate ester salt, alkyl phosphate salt, polyoxyethylene alkyl ether sulfate salt, alkyl ether phosphate ester, alkyl ether carboxylate salt, acylmethyl taurate salt, alkyl sulfosuccinic acid and its salt, etc. Anionic surfactants; glycine-type amphoteric surfactants such as alkylglycine salts, carboxymethylglycine salts, N-acylaminoethyl-N-2-hydroxyethylglycine salts Agents, aminopropionic acid type amphoteric surfactants such as alkylaminopropionate and alkyliminodipropionate, aminoacetic acid betaine type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine, alkyl Amphoteric surfactants such as sulfobetaine-type amphoteric surfactants such as hydroxysulfobetaine; alkylamine salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride; dimethylaminoethylamide myristate, diethylamino stearate Cationic surfactants such as fatty acid amide amines such as propylamide; thickeners, anti-inflammatory agents, ultraviolet absorbers, colorants, fragrances, water, etc. can be appropriately contained depending on the purpose. .

  In addition, as a dosage form of the 1st agent and 2nd agent which concern on this invention, it can be used with various dosage forms, such as a liquid form, a gel form, and a cream form, and mixes and uses a 1st agent and a 2nd agent To do. What is necessary is just to mix the mixing ratio of the 1st agent and the 2nd agent at the time of use by about 1: 2 to 2: 1 by mass ratio normally.

  Further, the pH of the system (drug) at the time of mixing is not particularly limited as long as the effect of the present invention is exhibited, but pH 8 to 11 is preferable from the viewpoint of dyeing black hair even more vividly, A pH of 9 to 10.5 is more preferred.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. The blending amount is mass% unless otherwise specified. “POE” is an abbreviation for polyoxyethylene, and the number in parentheses represents the number of added moles.

(Sample preparation)
According to the composition shown in Tables 1-2, each 1st agent was prepared by the usual method, the following 2nd agent 40g was mixed with 20 g of 1st agents, and the test sample of each Example and a comparative example was prepared. Each test sample was subjected to the following evaluation test.

(Oxidative hair dye second agent)
Hydrogen peroxide solution (35%) 16.7
Hydroxyethane diphosphonic acid 0.1
Purified water balance part Total 100.0

(Test Example 1: Measurement of pH)
The pH of each test sample of Examples and Comparative Examples was measured with a pH meter (F-23II type, manufactured by Horiba, Ltd.). The results are shown in Tables 3-4.

(Test Example 2: Evaluation of dyeability)
As the test hair bundle, a hair bundle “man hair black hair (level 4) 1 g 10 cm hair bundle” and “yak hair 1 g 10 cm hair bundle” manufactured by Staffus Co., Ltd. were used. In addition, the hair | bristle bundle used what was previously put on 0.5g sodium lauryl sulfate liquid at 50 degreeC and wash | cleaned for 1 hour.
After 2 g of the samples of each Example and each Comparative Example were thoroughly blended with the brush over the entire hair bundle over about 1 minute, the hair bundle was left in a constant temperature and humidity chamber at 30 ° C. and 70% RH for 30 minutes. did. Thereafter, the test hair bundle was taken out from the constant temperature and humidity chamber, washed with tap water at 35 ° C. for about 30 seconds, and then washed with an appropriate amount of a commercially available shampoo for about 30 seconds. Subsequently, an appropriate amount of a commercial conditioner was applied to the washed hair bundle for about 10 seconds, and then rinsed with tap water and air-dried again. The degree of yellow dyeing of the black hair bundle (black hair) and the yak hair bundle (white hair) after drying was evaluated based on the following evaluation criteria. The results are shown in Tables 3-4.

<Evaluation criteria>
◎: Bright yellowish ○: Light yellowish △: Yellowish but strong green ×: Strong greenish and no yellowish

(Test Example 3: Evaluation of fastness)
The yak hair bundle after the evaluation in Test Example 2 was immersed in a 2.5% POE (3) aqueous sodium lauryl ether sulfate solution, subjected to ultrasonic treatment at 40 ° C. for 10 minutes, and air-dried. The obtained hair bundle was measured using a spectrocolorimeter (CM-3610d type, manufactured by Konica Minolta Sensing), and the color difference (ΔE) between the hair bundle before immersion and the hair bundle after immersion treatment was calculated. The fastness was evaluated according to the following evaluation criteria. The results are shown in Tables 3-4. In addition, it shows that robustness is so good that (DELTA) E value is small.

<Evaluation criteria>
◎: ΔE is less than 5 ○: ΔE is 5 or more and less than 6 Δ: ΔE is 6 or more and less than 7 ×: ΔE is 7 or more

(Test Example 4: Evaluation of color transfer)
The hair bundle after the evaluation in Test Example 3 was sandwiched between filter papers, 1 kg was applied for 30 seconds, and the color transfer to the filter papers was evaluated.

<Evaluation criteria>
○: Almost no color transfer was confirmed on the filter paper. Δ: Color transfer was confirmed on the filter paper. X: Dark color transfer was confirmed on the filter paper.

  From the results of Tables 3 to 4, the oxidative hair dye of the present invention can dye hair into a bright yellow hue without using orthoaminophenol conventionally used for dyeing hair into yellow color. In addition, it can be seen that there is no fading of the hue of the dyed yellow hair and it is excellent in fastness.

  Below, the formulation example of the oxidation hair dye of this invention is shown. In addition, a compounding quantity is the mass%.

(Prescription Example 1)
<First Agent>
Polyoxyethylene (20) hydrogenated castor oil 5.0
Polyoxyethylene (20) cetyl ether 3.0
30% stearyltrimethylammonium chloride 3.0
Methylphenylpolysiloxane 1.0
Cetyl alcohol 4.0
Oleyl alcohol 2.0
Glycerin 2.0
28% ammonia water 8.0
Ammonium bicarbonate 2.0
Paramethylaminophenol sulfate 1.0
Resorcin 1.0
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.0
Hydroxyethane diphosphonic acid 0.1
Polyoxyethylene (20) hydrogenated castor oil 0.2
Polyoxyethylene (20) cetyl ether 0.2
Polyoxyethylene (5) cetyl ether 0.2
Cetyl alcohol 0.5
1,3-butylene glycol 5.0
Purified water balance
Total 100.0

(Prescription Example 1)
<First Agent>
Dicetyl phosphate 1.0
Polyoxyethylene (40) cetyl ether 1.0
Polyoxyethylene (20) cetyl ether 1.0
Methylpolysiloxane 1.5
Cetyl alcohol 5.0
Polyethylene glycol 20000 1.0
Xanthan gum 0.1
28% ammonia water 10.0
Phosphoric acid 4.0
Paramethylaminophenol sulfate 0.2
Resorcin 0.4
Toluene sulfate-2,5-diamine 0.2
2,4-Diaminophenoxyethanol hydrochloride 0.03
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.0
Hydroxyethane diphosphonic acid 0.1
Dicetyl phosphate 0.5
Cetyl alcohol 0.5
Purified water balance
Total 100.0

(Prescription Example 1)
<First Agent>
Polyoxyethylene (40) cetyl ether 3.0
Polyoxyethylene (20) stearyl ether 3.0
Polyoxyethylene (5) stearyl ether 1.0
Decamethylcyclopentasiloxane 1.5
Highly polymerized methylpolysiloxane 1.0
Stearyl alcohol 3.0
Dipropylene glycol 5.0
Dimethyl diallylammonium chloride
-Acrylamide copolymer liquid 1.0
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
28% ammonia water 6.0
80% monoethanolamine solution 2.0
Phosphoric acid 4.0
Paramethylaminophenol sulfate 1.5
Resorcin 1.0
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Purified water balance
Total 100.0
<Second agent>
35% hydrogen peroxide solution 16.0
Hydroxyethane diphosphonic acid 0.1
Polyoxyethylene (20) hydrogenated castor oil 0.2
Polyoxyethylene (20) cetyl ether 0.2
Polyoxyethylene (5) cetyl ether 0.2
Cetyl alcohol 0.5
1,3-butylene glycol 5.0
Purified water balance
Total 100.0

Claims (7)

An oxidative hair dye comprising a first agent containing an alkali agent excluding carbonate and bicarbonate and an oxidative dye, and a second agent containing an oxidant,
Using paramethylaminophenol and / or a salt thereof as a dye precursor, using resorcin as a coupler,
The total amount of paramethylaminophenol and / or its salt and resorcin is 70 to 100 mole percent of the total amount of the oxidation dye,
The compounding ratio of paramethylaminophenol (A) and resorcin (B) is a molar ratio, A: B = 2: 1 to 1: 5,
An oxidative hair dye characterized by being used by dyeing hair into a yellow hue. The oxidative hair dye according to claim 1, wherein the alkaline agent is at least one selected from the group consisting of ammonia, monoethanolamine, and isopropanolamine. The oxidative hair dye according to claim 1 or 2 , further comprising a pH adjuster in the first agent. The oxidative hair dye according to claim 3 , wherein the pH adjuster is at least one selected from the group consisting of carbonates, bicarbonates, inorganic acids, and organic acids. The oxidative hair dye according to any one of claims 1 to 4 , wherein the pH of the system when mixing the first agent and the second agent is pH 9-11. The oxidative hair dye according to any one of claims 1 to 5 , which does not contain orthoaminophenol as a dye precursor. The oxidative hair dye according to any one of claims 1 to 6 , which does not contain a direct dye.